2020-A Comprehensive Review On The Prospects of Multi-Functional Carbon Nano Onions As An Effective, High - Performance Energy Storage

Carbon 175 (2021) 534e575
Contents lists available at ScienceDirect
Carbon
journal homepage: www.elsevier.com/locate/carbon
Review article
A comprehensive review on the prospects of multi-functional carbon

nano onions as an effective, high- performance energy storage
material
Vivek Dhand a, b, Mithilesh Yadav c, Sang Hoon Kim b, **, Kyong Yop Rhee a, *
a
Department of Mechanical Engineering (BK21 Four), College of Engineering, Kyung Hee University, Yongin, 446-701, Republic of Korea
b
Department of Mechanical Design Engineering, Chonnam National University, 50 Daehak-ro, Yeosu, Jeonnam, 59626, Republic of Korea
c
Department of Chemistry, Prof. Rajendra Singh (Rajju Bhaiya) Institute of Physical Sciences for Study and Research, V.B.S. Purvanchal University, Jaunpur,
222003, India
a r t i c l e i n f o a b s t r a c t
Article history: The present review offers readers with an update over current and novel developments of carbon nano
Received 8 October 2020 onions (CNOs) in recent years. Here we concisely detailed out the synthesis routes, growth mechanism in
Received in revised form different synthetic routes, purification methods, chemical, electronic, optical, electro-magnetic and
21 December 2020
tribological properties, applications in energy storage sectors especially in the field of ion batteries and
Accepted 27 December 2020
Available online 30 December 2020
supercapacitors, polymeric composites of carbon nano onion, publication, patent-research trends data
(1980e2020) and a brief market analysis respectively.
© 2020 Elsevier Ltd. All rights reserved.
Keywords:
Carbon nano onions
Properties
Synthesis
Patent
Energy storage
Purification
Growth mechanism
Market analysis
Contents
1. Introduction: definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

1.1. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
1.2. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
1.3. Features and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
2. Synthesis of carbon nano onions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
3. Growth mechanism of carbon nano onion in different synthesis routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
3.1. Flame synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
3.2. Arc-discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
3.3. Electron beam irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
3.4. Chemical vapor deposition (CVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
3.5. Radiofrequency plasma process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544
3.6. Diamond annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 546
4. Purification of carbon nano onions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 546
5. Properties of carbon nano onions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
5.1. Chemical property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (S.H. Kim), [email protected] (K.Y. Rhee).
https://doi.org/10.1016/j.carbon.2020.12.083
0008-6223/© 2020 Elsevier Ltd. All rights reserved.
V. Dhand, M. Yadav, S.H. Kim et al. Carbon 175 (2021) 534e575
5.2. Electronic property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548

5.3. Optical property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
5.4. Electromagnetic property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
5.5. Tribological property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
6. Application of carbon nano onions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
6.1. Application of carbon nano onions in ion battery systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
6.2. Application of carbon nano onions in supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
6.3. Carbon nano onion based polymer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
7. Global research trends on carbon nano onion and composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
7.1. Publication and citation metrics of carbon nano onions since 1980e2020 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
7.2. Patent analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
7.3. Commercial aspect of carbon nano onion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
8. Outlook and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
1. Introduction: definition 1.2. Structure
Carbon nano onions (CNOs) are multilayered, circular or some- The characteristic onion like symmetry is caused due to the
times non-circular shaped fullerenes. They are especially composed removal of energetic dangling bonds which are present along the
of several stacked layers of sp2 graphene sheets. The arrangement edges of the tiny graphite sheet. This results in inducing the
of such sheets in an onion like fashion has made them earn their conformation (curvature) and the closure of the fullerene molecule
name. They can be otherwise also called as “carbon onions, “carbon [13]. This driving force is the main phenomenon as observed in the
nano onions”, “multi-shelled fullerenes”, “bucky-onions”, “onion formation of other large systems like carbon nanotubes and gra-
like carbons” or “hollow carbon nanospheres” respectively. They phene (graphitic molecules) and giant fullerenes. The extraordinary
are generally in the size range of 2e200 nm depending upon their stability of CNOs suggests that if only a single graphitic shell
synthesis route and conditions. structure is available in a giant molecule, which contains several
thousands of carbon atoms may eventually collapse and become
unstable leading to the formation of multilayered particle. By this
1.1. History
process, the system self stabilizes due to the gain in energy from the
van der Waals interaction amongst atoms of the shells [3,13e15].
The onion-like, semi-spherical, hollow cage with homocentric
Owing to its planar arrangement of layers, graphite is the most
graphene shells, were firstly reported by Ugarte in 1992 by strong stabile allotropic phase of carbon at ambient conditions. Based on
electron irradiation of the carbon soot under harsh environments
the graphitic symmetry and the exceptional strength of the
[1e3]. Carbon nano onions have been bestowed with excellent homocentric architecture of the spherical fullerenes, an hypothesis
properties which generate great research interest which covers a
concluded that carbon particle in the form of quasi-spherical,
large spectrum of applications which will be further elucidated in onion-like-graphitic material is the most stable form of symmetry
the following sections of this article. Based on the various synthesis
[13]. This controversy incited a great deal of research interest in
routes employed, the diameter of the carbon nano onion tends to exploring the nanometric systems bearing planar arrangement of
fluctuate but nevertheless they exhibit high surface area to volume
the sp2 bonding within the large sized graphite and the evident
ratio [2]. Ugarte in his previous work has reported that the inter- spherical shaped particles [16]. The formula (eq. (1)) to know the
stitial distance between each carbon layers is around 0.34 nm
number of atoms (carbon) responsible for creating a corresponding
which is a fingerprint and characteristic signature of graphitic ar- layer is calculated as [17]:
chitecture [1] which we see in the d-spacing of carbon nanotubes,
graphene and other carbon nanomaterials at higher resolution Cx(n) ¼ C60 $ n2 (eq.1)
images and using X-ray diffraction respectively. Ugarte has further
explained and defined that these graphitic structures mimics onion Where n represents the accompanying number of the corre-
like symmetry and is explicitly displayed in a wide range of
sponding layer; x(n) defines the number of carbon atoms contain
carbonaceous structures which includes polyhedral to almost within the layer [17e19]. Carbon nano onion structure is generally
spherical morphologies. Based on all the findings, Ugarte has
comprised of hexagonal or pentagonal concentric rings. The carbon
baptized these nano-graphitic structures as “onion-like-carbons” atoms are located at the apical position forming two single () and
(OLCs) [3]. Prior to Ugarte, the carbon nano onions were discovered one double (¼) bond along its adjacent carbon atom with a delo-
in 1980 by Sumio Ijima and termed them as “polygonized carbon calized pi(p)electron present widely in the molecule [17,20,21]. The
blacks” with layers of graphite organized in closed shells bearing graphitic layers present within the onion structure consist of sub-
polyhedral shapes [4]. This discovery however did not gather much stantial number of holes and defects [17,22]. These can either be
attention as that of carbon nanotubes (CNT) [5e11] which were filled with different ways with the pentagonal or heptagonal car-
discovered at the similar timeline. Later in 1994, Kuznetsov et al. bon rings. Thus the formation of either crystalline or amorphous
successfully synthesized homogeneous, high quantity and small onions with quasi-spherical shape can be materialized [17,23].
carbon nano onions (~2.8 nm) with 5e8 graphitic shells by thermal
annealing process at high temperatures using a tube furnace in
vacuum [12]. By the year 2000, the carbon nano onions started
earning interest and were further explored for its potential.
535
1.3. Features and applications (years 1980e2020). Either one or two reviews are available but are
very old for the application of carbon nano onions or their “com-
Carbon nano onions have been widely used in several applica- posites” for energy conversion or storage respectively.
tions due to their unequalled physico-chemical properties [17]. In this review at first, authors attempt to outline in brief the
These nanomaterials are employed in myriad areas specially in definition, history, structure, and few features based on their(CNOs)
electronics [17,24e26], catalysis [17,27,28], energy storage and applications. Secondly, some important process insight is added to
conversion [17,29e31], optical limiting [17,32], hyper-lubricants the opted major synthesis routes for carbon nano onions by ther-
[17,33e36], sensors [17,37,38], biological and environmental ap- mal annealing of nano diamond, chemical vapor deposition, arc
plications [2,17,39e42] to name a few. The most fascinating phys- discharge, flame synthesis, e-beam irradiation, radiofrequency
ical attribute of carbon nano onions is their conductivity. Carbon plasma etc, which is followed by their growth mechanism during
nano onions synthesized at higher temperatures (~1800 C) by these processes within them. Later, this review discusses the pu-
annealing nano-diamonds has been reported to have the best rification methods in producing impurity free carbon nano onions
conductivity performance [17,43e48]. Since 1980 till date (2020), by simple purification/treatment processes like thermal annealing,
several studies on carbon nano onions have been published based acid/peroxide digestion, ultra-sonication, centrifugation, filtration,
on their shapes and size [17,49e54]. It was found that the synthesis oxidation process etc., later, the following section deals with their
routes determines the carbon nano onion structure and concomi- chemical, electronic, optical, electromagnetic and tribology prop-
tantly decides the physico-chemical properties, which are closely erties respectively. Based on the merits of carbon nano onions and
related to their shape, size, chemistry, layer numbers and its inter the need of energy during the present era, the review takes us to
layer distances [49,54e60]. Based on all these findings, carbon nano further explore carbon nano onion boundaries in the specialized
onions are categorized as (i) small sized (below 10 nm) or big sized application field of energy systems (especially lithium ion battery
(above 10 nm) [12,49,55,56,61]; (ii) Spherical or polygonal shaped and supercapacitors) along with few examples of successfully
[12,49,58,59]; (iii) densely cored or hollow cored (that is empty or synthesized carbon nano onion based polymer composites with
either filled with different metals [1,49,59,62e64]. As observed various applications has been briefly described. In view of its dis-
under the transmission electron microscope Fig. 1 shows different covery and its present day explored merits, it is very important to
types of carbon nano onion morphology. Based on all the resources know the status of its research, publication, patent trends carried
authors have, we found that so far till date few reviews have been out by various researchers from around the globe. This insight may
published (10 year data range 2010e2020) on carbon nano onions be highly helpful for researchers for further exploration of carbon
[2,17,29,65e67], with much emphasis on synthesis, functionaliza- nano onions properties in unexplored fields. Based on its regular
tion, composites and biological applications but so far very less data synthesis, usage amongst different researchers around the globe, a
or none have been published on its citation and patent analysis brief attempt to highlight its prospective commercial aspect is
Fig. 1. High resolution images of carbon nano onions as observed by various researchers: (a) very small spherical shaped carbon nano onion by Ugarte et al. (1995) Ref- [3]; (b)
spherical big sized carbon nano onions by Gan and Banhart (2008) Ref- [58]; (c) mixed carbon nano onion with metal catalyst at the core by Gan and Banhart (2008) Ref- [58]; (d)
hollow core pentagonal shaped carbon nano onion by Gan and Banhart (2008) Ref- [58]; (e) large sized spherical shaped hollow carbon nano onion by Gan and Banhart (2008) Ref-
[58]; (f) Cobalt cored large carbon nano onion by Banhart et al. 1998 Ref- [59]. Reprinted with permission from Elsevier Publishers for Ref [3,59]; and from John Wiley and Sons for
Ref [58]. (A colour version of this figure can be viewed online.)
536
outlined along with the conclusion. In view of these findings and to gets more graphitized with decreased defect density [65]. With
the best of our knowledge, We would like to present this review to further annealing the NDs with increasing temperatures up to
our dynamic students, global researchers, entrepreneurs and sci- 1800 C, the third step ensues with the formation of microscopic
entists to further explore the properties of this unique carbon particles having few layers (6e8 layers) of graphitic shells with
structure and discover more possibilities in synthesis of large scale, diameters ranging from 5 to 6 nm with interlayer spacing of
high purity, economically affordable and eco-friendly feasible ap- 0.35 nm which is a typical signature for bulk graphite (d-spacing:
proaches for various applications. d(002) ¼ 0.334 nm). Such particles are categorized as “small scaled”
carbon nano onions. At step four polyhedral nanostructured onions
are formed when the ND are further annealed up to 1900 C [57].
2. Synthesis of carbon nano onions
Currently, annealing of the NDs is one amongst the most
economical and promising synthesis route for spherical carbon
Till date, there have been several methods published on the
nano onions with huge potential for industrial applications. This
synthesis of carbon nano onions [17], the most opted method of
route produces very high yields close to 98e100% (residual non-
synthesis is the thermal annealing of the nanodiamonds (NDs) [12],
carbon based impurity is 1e2 wt%) [65]. Few layered carbon nano
water submerged graphite electrodes in arc-discharge process
onions synthesis is highly desired due to their significant ability to
[54,55,71], flame synthesis or pyrolysis [11,79] chemical vapor
get transformed by chemical reactions. This type of carbon nano
deposition [72], ion implantation [73], electron beam irradiation
onion has very high surface anatomy and strain energy leading to
[68] respectively. Based on their working and preparatory param-
higher chemical reactivity [52,84]. Sano et al. (2002) proposed
eters the size, shape and structure of onion can be controlled and
another novel route to synthesize carbon nano onions by arc-
achieved as wanted, like small sized [12,57], big sized [55,56],
discharge method. Where, two graphite based electrodes are sub-
spherical shaped [56e58,82], polyhedral shaped [57,78], densely
merged in water with an applied voltage of ~16 V and current at
cored [55e57], hollow cored [58,68,82] respectively. Table .1 shows
30 A [55]. This method resulted in the synthesis of hollow centered,
the listed methods for the synthesis of carbon nano onions. Kuz-
large CNO nanostructures with 20e30 layers of graphene and
netsov's process [12], was based on annealing nanodiamond
15e25 nm in diameter [70]. The other popular method which re-
(average diameter:5 nm) particles at high temperatures under high
searchers opted was ion implantation of carbon ions into silver
vacuum controlled inert conditions. The onion diameter is
[35,77,78] or copper substrates [74e76]. Based on the physico-
connatural to the nanodiamond's diameter and it was reported that
chemical parameters like temperature, implantation dose, sub-
the carbon nano onions were also found to be a major component
strate concentration and grain size, the obtained carbon nano on-
part of the explosion soot of ultradisperse diamond [2,69]. Within
ions can be tuned to have variable size distributions, uniformness
the bulk diamond, the characteristic crystallographic unit param-
and fine microstructures (defects, shape, sphericity etc.). It was
eter for the arrangement of the diamond planes (111) is a standard
found that the higher temperatures contributed to the synthesis of
0.205 nm [69]. A step-wise mechanism of the transformation of
more ideal structure of the carbon nano onions [64]. The only
NDs to carbon nano onion starts occurring from 700 to 800 C
demerit to this process is that the structures are often defective in
during the thermal annealing. This step leads to the stripping of
their shape and are smaller in size(2e5 nm) [61,63].
oxygen bearing groups and the emission of carbon monoxide and
Chemical vapor deposition (CVD) is also another feasible
carbon dioxide gases [83]. In the second step, when the tempera-
method to synthesize carbon nano onions [51,72] in the presence of
ture is in between 1100 and 1300 C, the external graphene layers
Table 1
Synthesis methods for carbon nano onions.
Synthesis Feed fuel/Substrate support Synthesis/catalyst Conditions Size/type of carbon Shape Sample Yield Ref.
Method nano onions
Electron-beam Carbon soot(Amorphous) Data not available Pristine dense-core; Spherical Low yield [1,68]
irradiation 6e50 nm
Annealing NDs 800e2100 C Pristine dense-core; Spherical High yield [12,57,65,69]
5e10 nm
Arc-discharge Carbon soot(Amorphous) Under water arc discharge between two High-quality Spherical Large quantities [55,70]
Ni/Al catalyst graphite electrodes, water hollow-core; 15 Spherical Low yield [54,71]
temperature 5000e6000 K e25 nm
Pristine hollow-
core; 5e50 nm
Chemical vapor CH4/N2/CH4(60 mL/min) Ni/Al catalyst, Ni content >60 wt% Pristine hollow- Spherical Large quantities [51,72]
deposition N2 (540 mL/min) core; 5e50 nm
Ion carbon into Cu/Ni substrate 600e1000 C Pristine dense-core; Spherical Low yield [73e76]
implantation 15e200 nm
Ag >600 C Pristine dense-core; Spherical Low yield [35,77,78]
5e100 nm
Flame Liquefied petroleum gas þ air Propane/Butane mixture 1.4:1; Non- Densely Circular 70% pure (5 g/h yield) in [11]
synthesis/ mixture catalytic, O/F ¼ 0.05e0.1 slpm/slpm, agglomerated, high fairly large quantity
Pyrolysis No support used 800e950 C SSA,
30e40 nm
Phenol-formaldehyde Ferric nitrate catalyst, Pristine dense-core; Mixed Large quantities [79]

1000 C 40 nm morphology
Propane Propane/Oxygen flame (1.8 10e25 nm Mixed Low yield [80]
stoichiometric coefficient), Al morphology
Plastic wastes (polyethylene, Data not available 50e70 nm Mixed Low yield [81]
styrene, ethylene terephthalate morphology
537
a metal catalyst, high pressure and temperature. Large quantities of of carbon nanomaterial. Their shape, microstructure, size and
pristine origin carbon nano onions of well-defined spherical ge- growth mechanisms are totally different from that of other carbon
ometry with size of 5 and 50 nm were synthesized. Chiefly, pyrol- nanomaterials including CNT [11]. Evidently, the carbon nano onion
ysis of propane (diameter of 10e40 nm) [11,80], natural oil [85] or synthesis parameters and conditions can be truly diverse from
plastic waste like ethylene terephthalate (ETP), polyethylene (PE) or those of other carbon nanostructures and CNT [109]. However, the
styrene [81] can produce particles with diameter of 50e70 nm. This growth theory for carbon nano onion synthesis by flame process
offers an effective, eco-friendly and a low-cost approach for syn- was not much documented till year 2013. Dhand et al. in their work
thesis of carbon nano onions respectively. The product may call for [11] theorized the possible vapor solid system type growth mech-
some purification in-view of the existence of impurities and other anism of carbon nano onions within the flames of liquefied pe-
byproducts. Few other methods which can produce carbon nano troleum gas (LPG) and air as proposed for arc process [110,111],
onions are laser ablation [86], thermal dissociation of sodium azide where they proposed (Fig. 2) the growth of the graphitic layers
(NaN3) and hexa-chloro-benzene (C6Cl6) [60], carbonization of from inside out with auto curling mechanism. They showed that
phenolic resin [87], high energy ball mill [88], halogen etching [89], partial decomposition of the hydrocarbon fuel leads to the forma-
high pressure shock compression [90], solvo-thermal [91] to name tion of gaseous vapor phased carbon species. Later the carbon
a few. The synthesis parameters determine the size, layer numbers, species under the influence of higher axial temperature de-
shape, symmetry reactivity physico-chemical properties, and yield composes to carbon atoms leading to the formation of liquefied
of the carbon nano onions [92]. Over the last decade, vacuum carbon droplet. At this stage the growth of carbon nano onions
annealing of NDs at very high temperatures in between 800 C and depends entirely on the parameters like fuel/oxidant flow, tem-
2100 C results in various graphene like nano-morphologies viz: perature gradient, cold quench zones and residence time. Here
spherical, ellipsoidal or polyhedral structures, which were well based on their findings they proposed the vapor-solid system
supported by theoretical calculations and experiments [93e95]. theory. In which the gaseous hot carbon condenses as a droplet and
During the synthesis of carbon nano onion, the temperature im- is deposited at an interface of another hot liquefied droplet. This
parts certain changes in the ND structures which include the process goes on and due to the cooling of the droplet the solid
weight fractions of sp2 carbons, density, average pore size, con- phase materializes into an aromatic arrangement (hexagonal or
ductivity and the specific surface area (SSA) respectively. The de- pentagonal) of carbon atomic shells. This at mass scale promotes
gree of graphitization from 0.39 to 1 (i.e sp2 orderings) increases the formation of onion layers “inside-out”. The continuous depo-
with annealing temperature from 1100 C to 1900 C respectively sition of the carbon atoms at higher rate leads to the appearance of
[17,22,65,96,97], thus resulting in NDs phase transition. Likewise amorphous zones and defects. The aromatic arrangement of carbon
the SSA of the carbon nano onions obtained from gas adsorption (i.e graphitic rings) later stabilizes in a six or five ringed closely
(N2) studies ranges from 400 to 600 m2/g at temperatures within packed structure. Since the presence of dangling bonds and the pi-
1300 C and 1800 C respectively [98,99]. With every rise in tem- pi (p-p) interactions over the edges [112]of the graphitic ridge re-
perature the shape changes from 1300 C to 1800 C (spherical sults in the auto curling of the graphene planes within the shell.
onions) [65], 1900 C (polyhedral onions) [57,100]. The density This results in closing and auto curling of the graphene planes thus
decreases from 3.07 ± 0.02 to 2.03 ± 0.02 g/cm3 with increase in leading to the formation of quasi spherical CNO structure [16,113].
temperature [101]. The phase alteration of NDs to carbon nano Mongwe et al. (2018) used Ghee (clarified Indian butter) as fuel
onions at high temperatures in argon [93,102e106], hydrogen [107] source and a fiber glass wick for the synthesis of carbon nano on-
and helium [70] have been well documented. The annealing in the ions without any catalyst by flame spray pyrolysis approach. The
above listed inert gases at high temperatures leads to higher degree obtained carbon nano onions were annealed at 900 C in 100 mL/
of graphitization with reduction in the ND seed size while in the min of Ar between 1 and 3 h [114]. They also reported similar
oxygen, the oxidation of the carbon rings leads to its denaturation mechanism as theorized by Dhand et al. [11].
when temperature is above 500 C. Whereas in hydrogen envi-
ronment, and ambient conditions, when T > 900 C, it is clearly 3.2. Arc-discharge
linked up with the commencement and ordered arrangement of
the sp2 phase to form onion-like-planar sheets on the diamond For a typical arcing process, Saito et al. [115] proposed the in-
surface with the internal core totally destroyed with few remnants ternal epitaxial growth mechanism which is one of the most
of diamond's sp3 phase in the dry technique (in the presence of acceptable theories for the growth of carbon nano onions (Fig. 3).
CO2) [12,22,65,97,107,108]. The common thought is that the crystallization of carbon atoms
occurs first at the surface when the hot molten carbon atoms are
3. Growth mechanism of carbon nano onion in different cooled after the arcing process. When the carbon atoms are ar-
synthesis routes ranged in a stable and continuous manner the shell formation along
with the layers are formed from outside to the inside layers leading
The present section deals with the growth mechanism of carbon to the formation of irregular carbon nano onion. This phenomenon
nano onions through their synthesis as reported by several re- was later observed by Ugarte et al. (1995) [3]. However the demerit
searchers. A clear understanding of the growth formation further of this model is that it cannot explain the role of catalyst and for-
helps in effectively contributing and enhancing the controlled mation of amorphous phase in the external layers of the onion
synthesis of onions with expected properties and structure pre- structure. Later, few [110e112] tried to establish the vapor liquid
cisely designed for a targeted application. This section further solid (VLS) model with an internal epitaxial co-growth formation.
outlines the mechanism as observed for flame synthesis, arc- This model states that the crystallization starts at the liquid-solid
discharge, chemical vapor deposition (CVD), e-beam irradiation, (LS) and vapor solid (VS) interfaces. During the LS phase, the or-
radiofrequency plasma process and diamond annealing dered crystallization of carbon atoms occurs from outside to inside
respectively. layers. Whereas, during the VS phase, the vapor of carbon atoms re-
deposit at the interface and soon crystallizes into pentagon/hexa-
3.1. Flame synthesis gon shaped shells after their cooling. This way the layer growth
occurs from inside-out. As the external layers keep receiving the
Though, carbon nano onion belongs to a family of fullerene type continuous supply of carbon atoms, the amorphous phases are
538
Fig. 2. Growth mechanism of carbo onions under Flame synthesis by Dhand et al. Adapted, redrawn and modified accordingly from Ref. [11]. (A colour version of this figure can be
viewed online.)
Fig. 3. Growth mechanism of carbon nano onions in arc-discharge process as given by Saito et al. (1993). Adapted, redrawn and modified accordingly from Ref. [115]. (A colour
version of this figure can be viewed online.)
generated. Fig. 4 depicts a novel three step growth mechanism of over the nanoparticle surface resulting in further thickening of the
carbon nano onions in arc-discharge process involving organic shell structure. This makes the outer shell layer to quickly termi-
solvents by Huang et al. (2020) [110]. Huang et al. in their work have nate the further coalescence of the metal nanoparticle at the core.
propounded that the first two mechanisms are similar to the VLS On the other hand, cyclohexane as an organic precursor will not
model where the precursors are in vapor-liquid and solid phase affect the growth of metal nanoparticle by coalescence process,
during coalescence temperature termination stage. In the third hence this results in formation of the external amorphous carbon
stage, the organic hydrocarbon based precursor (benzene) is not layer over the particle which has very negligible presence of
dependent on the above conditions; it directly undergoes contin- graphitic deformed planes. By this process, not only specific metal
uous pyrolysis and directly forms graphitic nano-sized particles core but other metal catalysts can also be directly used for the
539
Fig. 4. Growth mechanism of carbon nano onions in arc-discharge process. (a) Three step growth mechanism by Huang et al. (2020) Ref [110]. Reprinted with permission from
Elsevier publisher for Ref [110]; (b) A general conventional method in the synthesis of carbon nano onion based on the Vapor-liquid-solid (VLS) model. Conceived, adapted, drawn
and modified accordingly from Ref. [110]. (A colour version of this figure can be viewed online.)
synthesis and growth of onion like features without involving the (hexagon or pentagon) flaky pre-onion structure under the cata-
initial two steps respectively. By this merit it has no restriction in lytic reaction of Al nanoparticles. Stage-2, the flaky structure then
preferring the new core metal nanoparticle for the synthesis of modifies into ellipsoidal shells of graphitic origin under continuous
CNOs. Sano et al. explained another growth model for the carbon effect of irradiation. Stage-3, gradual rearrangements of the
nano onion formation under water by the arc process [55]. They graphitic structure into multiple spherical like shells in the pres-
proposed that the temperature gradient between the two graphite ence of Al particle and radiation. The bonds within the graphitic
electrodes under water can reach up to 4000 K (Fig. 5). During the shell expand and slowly wraps off the Al particle. Due to inner
underwater arcing process, the temperature vaporizes the carbon epitaxy the hollow shells are formed by evaporating the Al particle
from graphite and the carbon atoms are instantly captured within leading to the formation of carbon nano onion. This change of shape
the bubbles formed as a result of the dissociation water into oxy- from ellipsoid to spherical is due to the minimization of free energy
gen, hydrogen. The extreme heat gradient within the gas bubble concept leading to formation of stable large onion structures [62].
from the arcing zone (hot plasma) creates a gas-water interface
which plays crucial role in the rapid solidification of the carbon
3.4. Chemical vapor deposition (CVD)
vapor. Due to the high expansion velocity of the bubble, the hot
carbon vapor is readily displaced into the cold zone of the bubble.
Most of the carbon nanomaterials (0D, 1D and 3D) growth
Sano categorized these bubbled cold zones into two types: (i) car-
mechanism, as synthesized by CVD usually follows the vapor liquid
bon vapor quenching zone adjacent to the arcing area and (ii) non-
solid (VLS) model [11,111]. In this model, the atoms of carbon are
thermal and non-ion current region outside the zone-1. In zone-1
adsorbed on the catalyst surface, where the carbon atoms are
due to epitaxial growth in the ion current, elongated structures
continuously diffused, dissolved, and precipitated to create the
are produced (ex: nanotubes). In zone-2, due to lack of directional
multi-layered metal enclosed carbon nano onion particles. The
flow, isotropic growth of 3D symmetry nanoparticles occur (carbon
major demerit of this mechanism is that it could not explain why
nano onions) [55].Since this zone is much cooler the carbon nano
the pure catalytic metal nanoparticles were embedded within
onions coalesce and forms large clusters due to the presence of
different graphite layers?
large van der Waals forces in the crystals which makes them afloat
Kang et al. (2008) proposed that the during the CVD synthesis of
over the water surface.
carbon nano onions [116], the carbon atoms effectively diffuse
through the hot molten substrate or the catalyst particle (transition
3.3. Electron beam irradiation metals: Co, Ni, Fe and their alloys). This dis-
solvediffusionprecipitation (DDP) model Fig. 7, is widely
Ugarte [1] opined that the growth of carbon nano onions was accepted for the growth of carbon nano onions by CVD synthesis
epitaxial under the presence of electron beam energy, where the route [116,117]. Metal carbide forms the initial seed due to the
atoms self-assembled and rearranged over the external layers. Later diffusion, interaction and dissolution of carbon within the metal
Xu and Tanaka (1998) studied the catalytic effect of aluminum (Al) catalyst. They showed that carbon nano onions in their CVD are
particles on the formation of carbon nano onions [62] under the initiated at 600 C. The irregular formation of the onion rings re-
electron beam irradiation of the carbon film. Fig. 6, shows the sembles that of the pre-CNT growth pattern. As the temperature
growth mechanism of carbon nano onions. They categorized the increases to 700 C, the ordering of the rings takes place. They
formation of onions in three stages. Stage-1: The formation of short further proposed that the low interaction between catalyst and its
CeC bond ordered particles which are transformed into ordered copper support at this low temperature, results in lower
540
Fig. 5. Growth mechanism of carbon nano onions in underwater arc-discharge process at postulated by Sano et al. (2002) [55]. Adapted, redrawn and modified accordingly from
Ref. [55]. (A colour version of this figure can be viewed online.)
decomposition rate of methane gas resulting in the heterogenous nano onions [111].
distribution of molten carbon over the catalyst surface. Thus the Zhang et al. (2012) proposed growth mechanism for hollow
effect of diffusion is dependent over the concentration gradient carbon nano onions [53] in the presence of FeeNi alloy by the
with respect to temperature. As the temperature further increases, collective CVD (@850 C) and annealing method (@1100 C). Similar
the diffusion of carbon over the catalyst surface increases consid- to other CVD based mechanisms, the formation of metal carbide
erably thereby decreasing the carbon symmetry. The carbon now (FeeNieC austenite) is the main seed factor for growth of hollow
completely covers the catalyst particle leading to super saturation carbon nano onions Fig. 8. The release of carbon atoms from each
and formation of fluid like layer around it. When the catalyst is carbide particle system helps in production of only two carbon
poisoned, formation of graphite layers takes place over the com- nano onions due to early deactivation of the carbide phased cata-
plete surface of catalyst and the true onion like feature of the car- lyst. Since the carbon in the carbide phase is highly unstable at
bon surfaces. As the graphite rings have defects and voids, the lower temperature, the FeeNieC austenite catalyst decomposes
increasing temperature further evaporate the catalyst particle rapidly, while the excess carbon atoms dissolve inside the alloy
through these defects leading to the formation of hollow carbon particles during the cooling phase. In the second step they annealed
541
Fig. 6. Growth mechanism of carbon nano onions in electron beam irradiation process of carbon film in the presence of aluminum catalyst particles by Xu and Tanaka (1998) [62].
Adapted, redrawn and modified accordingly from Ref. [62]. (A colour version of this figure can be viewed online.)
Fig. 7. Growth mechanism of hollow carbon nano onions by dissolve-diffusion-precipitation in the chemical vapor deposition process in the presence of transition metal(Fe, Co, Ni)
catalyst particles by Kang et al. (2008) [116]. Adapted, redrawn and modified accordingly from Ref. [116]. (A colour version of this figure can be viewed online.)
this as-prepared carbon nano onion sample to 1100 C. Due to the precipitation from the carbide catalyst continues to further initiate
high temperature ambience, the catalyst undergoes melting and multiple series of nucleation, growth and graphite layer modifica-
expansion, while the external carbon layers undergoes cracking tion from the surface. The size of the original alloy particle de-
[118]. The cracking in the outer carbon walls creates a passage for termines the diameter of carbon nano onions (hollow) until all the
the escape of molten alloy particle from within. Meanwhile, at this carbon atoms are completely consumed. Ostwald's ripening and
high temperature stage, the residual, pre-dissolved carbon atom coalescence causes formation of large metal particles which had
within the alloy particle re-establishes its catalytic activity for the previously escaped from the alloy system. This phase leads to the
formation of a carbide system (FeeNieC austenite) to initiate the termination of further synthesis and growth of carbo onions
new growth of carbon nano onions. The cycle of carbon atom [53,119]. In their earlier work they explained a similar mechanism
542
Fig. 8. Growth mechanism for large sized hollow carbon nano onions by a collective synthesis approach involving chemical vapor deposition and annealing process in the presence
of transition metal(Fe, Co, Ni) catalyst particles by Zhang et al. (2012) [53]. Adapted, redrawn and modified accordingly from Ref. [53]. (A colour version of this figure can be viewed
online.)
Fig. 9. Growth mechanism of carbon nano onions and CNT at variable temperatures by chemical vapor deposition method, Zhang et al. (2011) [120]. Adapted, redrawn and modified
accordingly from Ref. [120]. (A colour version of this figure can be viewed online.)
(Fig. 9) for the synthesis of Fe0.64Ni0.36 encapsulated carbon nano growth” and the “root/base growth” are widely accepted principle
onions and carbon nanotubes collectively in a CVD reaction at a theories [121,123]. Velasquez et al. (2016) suggested [121] that
temperature range of 750e850 C in the presence of FeeNi alloy decomposition of the hydrocarbon carbon source
(Fe0.64Ni0.36) system [120] respectively. (glycerol þ ethanol) occurs on the metal catalyst (NieFe) surface
Several theories have been propounded regarding the growth leading to the diffusion of the carbon atoms into the catalyst lattice
mechanism of other carbon nanostructures [121,122]. In spite of all structure. In their case the carbide formation doesn't take place
the explanations, still the final conclusions over these mechanisms unlike other reported mechanisms. Soon the carbon saturation
are yet to be universally accepted. Two major theories the “tip- occurs and the carbon atoms segregate and start crystallizing
543
leading to the formation of first single layered graphene over the (2007) believes that their carbon nano onion formation mechanism
supported catalyst particle. With the continuous supply of carbon (Fig. 11) is totally different from that of the high-temperature
atoms the diffusion and crystallization cycle repeats and several hydro-pyrolysis of coal [125,126]. They found that unlike other
graphene layers are formed around the catalyst leading to the mechanisms, short-scaled, ordered, crystalline carbon was formed
formation of carbon nano onion. Up to this stage, the growth during the growth process. Though in other mechanism, this type
mechanism (Fig. 10) is alike to the one suggested for carbon nano of carbon (not purely of graphitic crystallinity) is generally formed
onions [124]. The closure of onion layers occurs on account of during the process temperature range and pressure parameters, but
higher interaction between the catalyst particle and the support in their case, the carbon has a high degree of graphitization.
layer [120]. During the solid-liquid phase changeover, the graphene Consequently they showed that RFP plays a crucial role in the for-
layer creates an asymmetric pressure on the catalyst surface, as a mation of pentagonal rings, which is in agreement with their
result forces the partially formed carbon nano onion to escape. As synthesis and mechanism, as these rings are very important in
soon as the catalyst particle is freed from the onion like structure, stabilizing the structure and the formation of fullerenes
the interconnected layers shape themselves accordingly, so that the [125,127e132]. Within the coal, certain metallic minerals (Si, Fe, Al,
catalyst particle surface is free for receiving the next supply of and their oxide minerals), form active support surface where the
carbon atoms and henceforth repeats the catalytic cycle for the energetic, broken aromatic units nucleate and reorganize on the
formation of another set of carbon nano onion layers. support catalytic surface. They start curving up because of initiation
of pentagonal rings. The central void will be smaller if the small
sized aromatic units (C1 or C2), acts as building block present inside
3.5. Radiofrequency plasma process the innermost shell. During the post nucleation process the aro-
matic units in the vapor, go on to bond with other nucleating
Du et al. (2007) states that radio frequency plasma (RFP) is an agents. This leads to the potential formation of concentric and
asymmetrical type plasma with an electron temperature up to defect free graphite/polyhedral cages with uni-axial orientation
104 K, whereas the heavy particles like atoms, ions reach up to having flawlessly superimposed pentagonal corners. Alignment of
300 Ke500 K when the reaction starts. Under an inert atmosphere the pentagons in the concentric shells is utmost important to
(mostly argon gas) the argon (Ar) plasma provides enough energy maintain the final shape of the onions. If not the final product will
to completely destroy the chemical bonds of coal. This results in the have the quasi-spherical morphology [3,125]. In the continuous
destruction of weak bonds of the aromatic moieties. Over the time, process, the RFP keeps decomposing the larger aromatic fragments
large amounts of aromatic fractions like naphthalene, anthracene, to curve and close for the formation of onion like fullerenes (OLF)
biphenyl, biphenylene and pyrene are released [125]. Formation of inside the vapor, due to the temperature gradient, the OLFs are
abundant C1 or C2 carbon units from few other dominant aromatic deposited on the quartz chamber wall. Presence of any amorphous
fractions is seen due to intense bombardment of the high energy phase around the OLF suggests that the curving and growth initi-
electrons. This mechanism is also seen in the CNT synthesis from ates from center to the external surface. The OLF growth ceases
coal. It is believed that fullerene formation is not dependent on once the temperature and other experimental conditions are not
denaturation of all bonds within the coal derived carbons. Du et al.
Fig. 10. Growth mechanism of carbon nano onions by a non-carbide based root growth model in chemical vapor deposition, Velasquez et al. (2016) [121]. Adapted, redrawn and
modified accordingly from Ref. [121]. (A colour version of this figure can be viewed online.)
544
Fig. 11. Growth mechanism of carbon nano onions from coal by radio frequency plasma by Du et al. (2007) [125]. Adapted, redrawn and modified accordingly from Ref. [125]. (A
colour version of this figure can be viewed online.)
ambient. Eventually the multilayered OLFs are formed when the They categorized different stages for understanding the growth
single graphitic layer containing several thousands of unstable mechanism of carbon nano onions (Fig. 12). Stage-1: the semi-
atoms collapse and rearrange themselves as multi layered particles. circular hollow fragment of one C60 or C70 molecule initiates the
Due to van der Waals interaction between the shells, the energy formation of the nucleus, Stage-2: by the addition of hexagons and
minimization stabilizes the system converting the arrangement pentagons, formed due to the supply of carbon atoms, the nucleus
into stable, concentric, graphene layers [3,125]. transforms into a cage like structure. Stage-3: the first cage acts as a
In 2001, a similar mechanism was proposed by Chen et al. 2001 substrate for the newly nucleating second cage, Stage-4: the newly
[72] by employing RFP equipped CVD. In their work they explained formed secondary cage gets encapsulated by the third, fourth, fifth
the non-catalytic growth mechanism of carbon nano onions and cages and so on. This leads to the formation of several large
the importance of aromatic units and their role in the formation of concentric layers of closed shell cages with a small central hollow.
heptagon and hexagonal rings for stabilizing carbon nano onions. When several pentagons, hexagons and septagons are implanted
Fig. 12. Growth mechanism of carbon nano onions using radio frequency plasma enhanced chemical vapor deposition method by Chen et al. (2001) [72]. Adapted, redrawn and
modified accordingly from Ref. [72]. (A colour version of this figure can be viewed online.)
545
with different extents of epitaxial continuity, curvy type carbon compact agglomerates, smaller grains are generally covered with
sheets are formed. Such events during the growth mechanism leads either thin graphite-carbon layers or linked covalently due to
to the formation of open shelled onions. functionalization [102,135,140]. Moreover the diamond grain mass
is directly associated with the nitrogen, hydrogen and oxygen
3.6. Diamond annealing atoms instead of carbon [102,135]. Studies show that the trans-
formation of nano-diamonds to CNOs occurs when the carbon
The modification process of carbon nano onions from NDs is phase transforms from sp3 to sp2 around 600 C by forming non-
outlined as follows. Kuznetsov et al. (1999) proposed the Zipper crystalline carbon [102,141]. Gradually when the temperature in-
mechanism for the growth of carbon nano onions by high tem- creases between 900 C and 1100 C, the non-crystalline carbon
perature annealing of nano and micron sized diamonds at begins to graphitize further from outside towards the core thereby
1200e1800 K [108]. They found that the central plane, out of all continuing with further sp3 to sp2 transformation [102,142].
three {111} diamond planes, moves into the bulk of the diamond Morphological investigations show that even small sized diamond
crystal [12]. Due to this movement, two graphitic sheets are formed particles be transformed to sp2 phase carbon easily leading to co-
because of the equi-distribution of atoms in the central diamond synthesis and existence of both small and bigger CNOs with
layer. Fig. 13demonstrates the process, which mimics the unwind- partly changed nano-diamonds [101,102,143,144]. The presence of
ing of a zipper. Every marked group of carbon atoms facilitates the any functional groups on the surface plays significant role in the
formation of an extra graphitic row with six folded rings. With temperature action for the transformation of nano-diamond to
sequential insertion of two carbon atoms per two six folded rings, CNOs [102,144]. During this phase, the pre-CNO displays dramatic
the process proceeds in developing of the sheets with moderate modifications within the crystal structure which develops sym-
formation and subsequent refabrication of eightfolded rings. Qiao metrically bent circular graphitic lattice planes. Analysis shows that
et al. (2006) [133], demonstrated that the small irregular chunks of with increase in temperature gradient, the graphitization and
graphite units first covers the top layer of NDs, later on they asso- ordering of the walls also increases directly [102,145e148]. The
ciate together to remove the dangling bonds for fabrication of the volume of the (002) graphitic lattice plane spacing (0.344 nm
closed graphite shells (Fig. 14). Most of the time the initial forma- which radially extends from center to the exteriors) of a single
tion, linking and curving of the graphite fragments occur on the particle, shows significant increase after transformation in com-
edge of the ND surface having {1 1 1} planes. Initial shape of the parison to that of the starting CeC bond spacing(0.154 nm) of dia-
diamond's sustained inner core minifies slowly due to the course of mond respectively. Buildup of mechanical stress/strain during
graphitization. At this stage the evolution of concentric graphitic synthesis also results in the formation of d-spacing smaller than
layers occurs on the surface of the original NDs leading to the for- 0.344 nm at the center of the CNOs [102,146]. TEM analysis reveals
mation of carbon nano onions within. Finally the ordered graphitic that the expansion of the d-spacing planes and the size of CNOs
layers evolve and shape the carbon nano onion similar to that of the depends on the ratio of sp3-to-sp2, which has been observed
diamond’s form [133,134]. theoretically (by reactive force field modeling) [143] and experi-
According to Zeiger et al. (2015) [102], nano-diamond is the mentally where the size of CNOs have expanded from 5 nm to
most fascinating precursor for synthesis of CNOs in gram quantities 10 nm respectively. Further information on the mechanism, ki-
by the thermal annealing approach [135]. This process has good netics precursor effects and synthesis of the CNOs from nano-
control over the structure, shape, size and properties of the diamonds has been extensively reviewed by Kuznetsov and
resulting CNOs [98,102]. The most widely used size of nano- Butenko [149]. The inter relationship between the particle density,
diamond for the synthesis of CNOs is around 5 nm [102,135]. porosity and size largely dictates the specific surface area (SSA) of
These usually have surface dangling bonds which are stabilized by nano-diamonds and CNOs. It has been observed that during sp3-to-
adding mostly carboxylic functional groups [102,135,136]. The car- sp2 transition as the particle size(diameter) increases the density
bon is mostly sp2 hybridized which locally terminates on the sur- dramatically decreases which consequently increases the SSA [101].
face [102,137e139]. These two surface aspects lead to As the temperature increases >1800 C, the CNOs undergoes sin-
agglomeration of every single nano-diamond particles to clusters of tering process which results in compact agglomeration [146],
size between 10 and 100's of nanometers [102,140]. Within the which later leads to the release of reactive gases from the surface
functional groups and contributes to the fabrication of large poly-
hedral onion crystals [150]. The common range of the SSA of CNOs
as reported are in the range of 200e600 m2/g [98,151] which is
lower than their other carbon counterparts like porous carbon,
activated carbon, CNTs, graphene etc., (1200e2630 m2/g)
[102,152,153] which is purely dependent on the synthesis
condition.
4. Purification of carbon nano onions
Several efforts are being made to develop novel techniques for

the purification of as-prepared carbon nano onions which majorly
contains amorphous carbon phase, defective carbon nanotubes and
metal catalysts. These impurities greatly affect and decrease the
properties, quality and application of the sample. Hence it is
important to purify the carbon nano onions before any assessment
of sample property and their related application [17,154e156]. Till
date majority of the purification and modification protocols for
Fig. 13. Zipper based growth mechanism and formation of carbon nano onions from
diamond to graphitic phase by nanodiamond annealing method, Kuznetsov et al.
carbon nano onions reported are related to the methods applied for
(1999) [108]. Adapted, redrawn and modified accordingly from Ref. [108]. (A colour CNT and C60. Most of the methods employed are physical, non-
version of this figure can be viewed online.) destructive or chemically separated which have their own merits
546
Fig. 14. Growth mechanism and formation of carbon nano onions from nanodiamond annealing method by Qiao et al. (2006) [163]. Adapted, redrawn and modified accordingly
from Ref. [163]. (A colour version of this figure can be viewed online.)
and demerits to achieve the best results. The physical purification good quality, yields and purity of carbon nano onions. Moreover,
protocol category involves methods like thermal, ultrasonic, cen- these methods did not influence the architecture of the carbon
trifugal separation, sublimation and concussion based on their size, nano onions. This prospect may lay the cornerstone for advanced
sublimation temperature of onions and impurities, solubility in purification processes in future by improving ex-situ and incorpo-
polar and nonpolar organic solvents to name a few. The chemical rating in-situ methods to effectively get highly pure, crystalline
category consists of oxidative reactions between the carbon nano carbon nano onions for advanced and applied applications
onions and the oxidizing acid and the reactivity of the catalyst to- respectively.
wards it based on their susceptibility. In few cases the non-catalytic
synthesis leads to major phase of carbon nano onion with very less
5. Properties of carbon nano onions
impurities like amorphous phase. These impurities can be removed
either with physical or chemical treatments. Whereas, the catalyst
5.1. Chemical property
enclosed carbon nano onion have to undergo chemical oxidation
and digestion protocol to remove the enclosed metal catalyst. Few
CNOs have certain unique side which includes advantageous
standard purification procedures like acid refluxing, calcination,
physico-chemical, optical, electronics and magnetic properties. This
ultrasonic etc., have proved to be successful in converting metal
allows them to explore the boundaries of different disciplines. One
encapsulated carbon nano onions to Hollow carbon nano onion-
such chemical property of CNO is that it is extremely hydrophobic
s(HCOs) [53,154,157,158] respectively. Under few circumstances,
in nature, with low solubility in the presence of both aqueous and
HCOs were at times obtained during the synthesis of other carbon
organic solvents, hence in order to enhance its solubility/dispersion
nanomaterials [159], but all are difficult to scale up. Borgohain et al.
and the only way to activate CNOs chemically, is that its surface
(2014) purified arc synthesized carbon nano onions using the four
should be functionalized with various groups [165]. Zhai et al.
step process which started with sonication in phosphor-tungstic
(2020) successfully carried out the hydrogenation of CNO by facile
acid followed by centrifugation, filtration, hydrofluoric (HF) acid
solvo/hydro thermal process [91]. They believe that hydrogenation
curing and annealing at 450 C for 2 h [154]. Certain other steps
may improve different properties. The precursors in the form of
have been reported for purification of carbon nano onions like the
carbon nano-spheres when hydrothermally reacted with potas-
two-step method of boiling in aromatic liquid solvents and later
sium metal produced CNOs initially and later as the reaction time
oxidation using hydrogen peroxide [60], thermal treatment in air
further increased, the hydrogenation further continued due to the
followed by acid (HCl) digestion then followed by ultra-sonication
attack of C-radicals evolving from to the cleavage of CeCl and CeH
and filtration [160], HCl oxidation followed by ultra-sonication
from the precursor. The C-radical initiates fragmentation and
and centrifugation [52,161], air oxidization and hydrochloric acid
reconstruction of the curved sp2 carbon fragments and later as-
(HCl) refluxing [162,163], carbon disulfide (CS2) and toluene soni-
sembles the same to form CNOs. Similar to other forms of nano-
cation [79], HNO3 refluxing followed by calcination in air [156], or
carbons, as synthesized CNOs hardly disperses in the polar/non
only HNO3 refluxing [164] respectively. Sometimes resistant large
polar solvents. The presence of strong van der Waals and pi(p)-
onions require four step method of purification protocol, involving
stacking intermolecular forces within the CNOs leads to non-
thermal heating in air followed by HCl refluxing, centrifugation and
dispersible agglomerations [166]. To tackle this challenge, surface
ultra-sonication in sodium cholate solution [155]. Based on the
functionalization using supra-molecular compounds or other
purification process results, the samples purified by the physical,
chemicals are important to modify the outer surface layers of CNOs
chemical methods effectively removed the impurities, leading to
[2,166]. Presence of surface functionalization helps promoting the
547
solute-solvent interactions which leads to good dispersion and (345 nm) and emission (450 nm) bands demonstrating a typical n-
negligible agglomeration within different kinds of polar and non- p* electronic transition of C]O bond in CNOs respectively [174].
polar solvents respectively [52,86,166,167]. Kharissova et al. Under the UV illumination, a strong blue emission of CNOs in DI
(2018) have extensively reviewed solubility and dispersion of water is also observed. Whereas, the fluorescence dependent
functionalization allotropes of carbon including CNOs in various emission spectra displayed red (bathochromic) shift from 440 nm
organic and inorganic polar/non-polar solvents respectively [168]. to 575 nm with an excitation band in the range of 300 nme50 nm
The utility and application of functionalized CNOs is highly prom- respectively. The emission maxima at 350 nm may be because of
ising for biological and electrochemical applications, Bartelmess defective crystalline phase and synergistic effect within the core
and Giordani (2014) and Mykhailiv et al. (2017) have extensively carbogenic framework of the carbon moiety [172].
reviewed different types of surface modification/functionalization
pathways of CNOs which includes hetero atom and metal doping 5.4. Electromagnetic property
[2,17]. Few other properties of CNOs are discussed as below.
CNOs also exhibit good protective barrier like properties even if
5.2. Electronic property they have any nanoparticle encapsulated within, this also helps in
having good electro-magnetic protection. Few reports have shown
CNOs were prepared from the highly oriented pyrolytic graphite that the CNOs exhibit magnetic property when transitional metals
(HOPG) by using a DC arc-charge method. The obtained CNOs were like Fe, Ni, Co etc., are encapsulated. Saini et al. (2020) demon-
analyzed for their electronic property using an ultra-high vacuum strated high saturation magnetization (Ms) ~25.2 emu/g for Ni
atomic force microscopy (UHV-AFM) and scanning tunneling mi- encapsulated CNO annealed at 850 C even in the presence of a
croscopy (STM). Results demonstrates that the CNOs tend to non-magnetic graphitic shell layer [175]. They observed that the
agglomerate as clusters on the surface of HOPG yielding in samples with endohedral like geometries displayed both super-
normalized conductance with six characteristic peaks between -1 V paramagnetic and soft-magnetic nature, demonstrating magnetic
and þ1 V, where the origin was not based on zero. This indicates property akin to that of the bulk nickel and thus, establishing CNOs/
that the CNOs electronic structure ranges between graphite and metal composites appropriate for various magnetic applications
single shelled fullerenes [112,169]. Tomita et al. (2001) found that like: catalysis, ferrofluid, magnetic sensors, EM absorption, data
the Electron spin resonance (ESR) of the spherical CNOs displays a storage and clinical drug delivery etc. [175,176]. Jiang et al. (2015),
very fine and narrow signal with a “g-value” of 2.0020 which is demonstrated that the reflection loss (RL) value for CNO/paraffin
attributed to the presence of dangling bonds spins related to the composite was lower than 10dB in the working frequency range
underlying structural and framework defects [57]. They found that of 2e18 GHz, whereas the defective composite exceeded 10dB RL
the localized spins in a spherical CNOs has an assembly of 3.9 1019 value if the thickness is managed between 1.4mm and 3.4 mm
spins/g which is 10 dangling bonds/spherical CNO respectively. On respectively. The presence of large numbers of imperfect sites
the other hand HRTEM, Raman and electron energy-loss spectros- within CNOs yields out enhanced microwave absorption property.
copy (EELS) study suggests the presence of pi(p)-electrons, sug- They also found that composites performed better and had good
gesting the presence of miniature graphitic sp2 domains with microwave-absorption efficiency in low frequency range (5e8 GHz)
peripheral dangling bond defects [170]. They observed that the respectively [177]. Li et al. (2018) synthesized CNOs encapsulated
defects (in form of dangling bonds) decreased with increasing permalloy (FeeNi) by detonation method with different FeeNi ra-
graphitization during their annealing process at 1900 C due to de- tios from 1:1 and 1:4. The sample, thickness was 2 mm and it
localization of the pi(p)-electrons [57]. exhibited an absorption peak value of 30 dB at 12.88 GHz and
14.6 dB at 9.7 GHz respectively. They observed that the 1:1 ratio
5.3. Optical property based sample had higher electromagnetic-wave-absorption capa-
bility than the sample with atomic ratio of 1:4 respectively [178].
Chhowalla et al. (2003) found that UV absorption of CNOs and
that of the inter-stellar dust concurs each other at an absorption 5.5. Tribological property
band of 217.5 nm (4.6 mm1, 5.7eV) which is due to the pi(p)-plas-
mon resonance energy of the sp2 carbon [171]. On the other hand, CNOs in comparison to their other carbon counterparts like
synthesis of CNOs by implantation of carbon ions in substrates like fullerenes, nanotubes, nano wires etc, are more tribologically active
copper (Cu) and silver (Ag) has garnered immense interest in due to their specific spherical shape, small size and chemically inert
spectroscopic investigations. The EELS transmittance of the CNO nature [112]. CNOs are often used as additives and blended in
layer in Ag demonstrated very low transmittance (i.e higher ab- synthetic base oil matrix system resulting in excellent friction less
sorption) at 4.4 mm1 which is lower than the isolated pure CNO. anti-wear and tear properties. Cabioc'h et al. (2002) in their work
This Bathochromic Effect observed is due to the agglomeration of showed that of the silver substrate coated with CNO layers greatly
onions and presence of graphitization and greater de-localization improved its wear behavior [35]. Street et al. (2004) demonstrated
of the pi(p)-electrons [171]. Tomita et al. (2002) investigated the that the CNOs when synthesized by induction of carbon black and
optical extinction properties of their CNOs, synthesized from nano- used as an adjuvant in base oil, yielded graphite type similar
diamonds using optical transmission spectroscopy. Their samples lubrication but only under ambient conditions. They used this
(spherical and polyhedral CNOs dispersed in water) demonstrated a lubricant for aero-space application [82]. Hirata et al. (2004)
broad extinction peak at 3.9 mm1 for spherical CNOs, whereas the observed that the CNOs synthesized by thermal treatment of the
two peaks were observed for polyhedral CNOs at 3.9 and 4.6 mm1 diamond clusters/particles on Si wafer, resulted in friction coeffi-
respectively [32]. Panda et al. (2021) analyzed the optical property cient value below 0.1 under normal air pressure and under vacuum
of CNOs at neutral pH ¼ 7 in the presence of DI water. The UVevis at room temperature, when tested by ball-on-disc type friction test
spectroscopy results show that CNOs exhibited a very strong ab- machine. It was also observed that larger CNOs exhibited decreased
sorption signal at 275 nm attributed to the distinctive p-p* electron frictional property on the rough exterior of the Si-discs [33]. Mat-
transition of C]C within the poly-cyclic, aromatic configuration of sumoto et al. (2007) used ultra-high vacuum (UHV)-atomic force
the graphitic carbon loop [172,173]. On the other hand, the pho- microscope (AFM) to investigate the tribological and frictional
toluminescence (PL) spectra displayed two strong excitation properties of CNOs mixed in poly-alpha-olefin (PAO) oil at nano
548
level. They also evaluated the use of CNOs as molecular additives to means that, higher the temperature higher is the degree of crys-
understand its low friction, lubricant behavior. Results show that tallinity, graphitization based on carbon arrangement. This post-
the friction coefficient value under UHV for CNOs was 0.05, this annealing treatment enhances the graphitization and makes
value is very much lower enough to be employed in either vacuum transport channels for more electrical conductance. Whereas, CNOs
or in space ambience. They also observed that the AFM and scan- synthesis routes determines extensively the electro-chemical
ning tunneling microscope (STM) exhibited a typical structure of properties in comparison to the other carbon counterparts. To the
steady state low friction film as low as 0.07 in PAO on 52100 steel best of our knowledge, non-diamond (other carbon sources) syn-
substrate [179]. Pottuz et al. (2008) observed the effect in the thesized CNOs have been very poorly studied and there is huge
presence of remnant diamond within the core of the CNOs as lacunae of characterization and their electrochemical data respec-
detrimental to the tribological property. They also observed that tively [65]. There are few meritorious points to highlight related to
the raw CNOs in 0.1 wt % of PAO demonstrated very low friction CNOs produced from thermal annealing of nano-diamonds viz:
even at pressures of 1 GPa thus inferring that CNOs in general are
far better than the diamond cored CNOs [34] respectively. CNOs synthesized at temperatures greater than 1500 C displays
higher carbon ordering, electrochemical stability, potential,
6. Application of carbon nano onions differential capacitance, conductivity and superior rate handling
capacity.
Generally, carbon nano onions demonstrate fascinating prop- If synthesized below 1500 C, CNOs shows only high SSA,
erties akin to those of CNT and Buckyballs [48] and are continuously capacitance due to redistribution of carbon during the minimal
being explored at present with a faster pace. These novel carbo- sintering process.
naceous nanomaterials can now be synthesized in bulk quantities Thirdly, minimizing sintering process by rapid cooling and
with intriguing properties. Due to their attributes of orbicular heating yields high conductivity, and upon further annealing at
shape, nanometeric size, several contours of concentric shells of sp2 1700 C yields high SSA, better electrical conductivity, and rate
graphitic carbon, controlled surface qualities, high conductivities handling capacity. By using argon rather than vacuum, during
[180], are endowed with potentially broad applications in several the annealing process, CNOs achieve excellent electro-chemical
fields like, Nonlinear optical limiting [48,181], catalysis stability.
[48,182e184], environmental remediation [185,186], energy Surface chemical activation of CNOs by KOH, paves way for
[187,188], electronics and sensors [189e191], biomedical engi- roughening their external shells which leads to the formation of
neering [39,165,192e195] and tribology or lubrication internal pores, improves the SSA and leads to enhancement of
[33e36,48,82,196] to name a few. capacitance.
Absence of sub-nanometer sized smaller pores over the com- During the fabrication of the electrodes, the packing density and
plete surface of the CNOs is one peculiar characteristic feature, most the thickness greatly determines the rate handling activity of
of the pores are equal in size and the exterior surface is completely both CNOs and other components and materials used during the
approachable to the ions from the electrolyte. This enables easy, fabrication. This may help for further comparison of data based
quick and increased capability for energy delivery from the stored on their electrochemical performance [65] respectively.
systems. In comparison, the CNO cell delivers two-times more
capacitance in comparison to that of the multi-walled carbon To the best of our knowledge, few reviews are available on
nanotube (MWNT). The loss of capacitance is less than 10% and the carbon nano onions which cover vast areas of biomedical, tribo-
current density reaches as high as 800 mA cm2 if the CNOs are logical, and energy storage applications, but are highly limited up to
synthesized above 1800 C. Moreover the time constant (<1s) is ten year 2018e2019 [17,48,49,65,112,165,196,206]. We in this review,
times smaller for CNOs to that of the nano-diamonds annealed attempt to cover research carried out in the field of capacitors and
beyond 1800 C, and for activated carbon. The value is approxi- ion battery post 2019 so that reader can get more info in line by
mately close to MWNTs. These properties make CNOs as promising studying rest of the previous reviews followed by the present re-
candidate for their use in energy systems like supercapacitors [197]. view to be updated with present research trends for the above
As stated in the previous section, CNOs are small sized, concentric listed applications. Moreover, it will be very interesting to see how
layers of defective and highly disordered, graphitic shells wrapped this potential material will pave its way to open doors for pro-
similar to “Russian doll” model [65,198]. The active and most spective development and broad spectrum applications. Though
preferred size for various applications is around 10 nm. Due to their buckminsterfullerene's possible applications have been moving
small size they have extremely large outer active surface area, slow, it is anticipated that carbon nano onions will plausibly evoke
higher conductivity [17,43e48], extraordinary exohedral affine interesting and unrivaled applications in the coming time.
curvature with multi-lamellar structural anatomy, large
approachable surface for electrolyte ion assimilation, high surface 6.1. Application of carbon nano onions in ion battery systems
area, high rate capability, corrosion resistance, thermal stability,
electrical conductivity, micro porosity, and energy density of the Global energy demand and its increasing deficit units is a major
fabricated supercapacitor system [199e205] respectively. As an problem for concern. Parallelly, the environmental damage is the
electrode material, CNOs offers quick and easy charge-discharge biggest and the most grievous challenge for survival of the fittest
rates with higher specific power but lacks comparative value for (for all life forms: flora, fauna and humanity). The major environ-
the specific energy [65]. Addition of CNOs as conductive compo- mental concern is the high battery production rate and pollution
nent, significantly improves the performance of the carbon elec- related to the discarding and its recycling. The only promising so-
trodes and demonstrates as an effective substrate to achieve redox- lution to this growing problem is to focus on development of clean
active properties in materials. It should be noted that the electrodes renewable form of energy and extenuate the environmental and
made of CNOs is greatly influenced by the material's inherent energy dearth conditions. In order to have redundant supply of
electrical conductivity, compaction, particle crystallinity and energy for increased consumption, the delivery medium inten-
arrangement, degree of sintering and methodology opted for pre- sively requires high-tech energy storage technologies [207e211].
paring the electrodes (i.e either binder free or with binder) [65]. By Various rechargeable electro-chemical energy based storage(EES)
annealing one can alter the inherent conductivity of CNOs which devices like lithium-ion based batteries, nickel-metal hydride (Ni-
549
Fig. 15. Schematic representation of a typical lithium ion battery and its charge-discharge process. MCBC represents: meso-porous carbon(MC), beaded carbons(BC) (A colour
MH), lead (Pb)eacid batteries, flow batteries and nickel-cadmium unfortunately, they still cannot compete to the mark when
(NieCd) batteries and so on are found to be the most viable and compared to that of carbon based post ion battery devices [207].
effective storage solutions till date [212e214]. Fig. 15 depicts a Firstly, this is because their current development is at the incipient
typical schematic of a lithium ion battery. The policies imple- stage and incurs high-cost for the above listed elements for the
mented by several countries to develop clean energy system are synthesis and fabrication of positive electrodes. Secondly, the de-
specifically compelled by the EES device productivity, which is also vices are not able to demonstrate the wide voltage window because
found to be growing exponentially. It is projected that the global the anodes are not properly inducing the high energy storage po-
market for storage devices will surpass $152.3 billion by 2025 at a tential. Thirdly, the liquid electrolytes have a fundamental demerit
Compound annual growth rate (CAGR) of 10.6% [215]. Where, Pb- of a narrow electrochemical window which largely restricts their
acid battery amidst other systems still holds a significant market energy density [207]. The increasing rate of miniaturization and
share due to its low cost and trustworthy performance [216]. manifold approach towards functionalization of electrode materials
Whereas, lithium-ion batteries (LIBs) are expected to touch $32 for mobile electronic devices, calls for exhibiting high power den-
billion by 2020 in the global market survey where all rechargeable sity with long-term cycling efficiencies. The major drawback is due
batteries are expected to have the highest growth rate [217]. In to graphite's lower theoretical anode capacity of 372 mAh/g, which
another report published by UBS AG, (the merger of the Union Bank the conventional lithium ion battery (LIBs) cannot continue
of Switzerland and the Swiss Bank Corporation in 1998) estimates without advancement of mobile electronic devices [208]. EES de-
that by the coming decade (by 2030), the cost of energy storage will vices utilizing carbon material as electrode displays good conduc-
decrease between 66% and 80% and the global market will grow as tivity, efficient ion diffusion pathways and high structural stability.
much by US$ 134e426 billion at a rate of 13% of global power ca- Though there are variations in the type of EES devices, the gist of
pacity opposed to only 3% for the expected financial year 2020 energy utilization and storage is the storage of charged ions within
[218]. Most of the electrode composition of these rechargeable the electrode material. The carbonaceous structure and the applied
batteries contains heavy metals like cobalt (Co), nickel (Ni), and voltage determines the mechanism of ion storage in the material.
lead (Pb). World Health Organization (WHO) has classified all of For example, the layered structure and the high specific surface
them as potential carcinogenic and mutagenic substances [219]. As area (SSA) of graphene can store energy either by intercalation or
the metal in the electrode material is a non-renewable source, the adsorption of ions [231]. When compared to activated carbon,
over exploitation will eventually lead to the depletion of reserves graphene has lower SSA, and as a result the EES is very small
and increase in their prices [214]. It is estimated that by 2050, the specially when used with organic electrolytes. The energy stored in
consumption of lithium will reach 1/3rd of the total lithium reserves graphene anodes with defects is highly complex and commercially
due to increased lithium's demand vs supply [220]. Whilst there are inferior when compared with that of commercially available
other useable and widely researched, low e cost series of graphite anodes. Consequently this section shall attempt to present
rechargeable battery alternatives to that of conventional LIBs like: distinctive capacitor and battery fabricated and tested with one
alkali ion batteries (sodium/potassium) [221e223], polyvalent such type carbonaceous material. Therefore it is highly critical to
metal ion batteries (calcium, magnesium, aluminum, zinc) seek for low-cost, green, and high capacity electrode materials for
[224e228] and their related aqueous batteries [229,230], the development of eco-friendly EES devices for the prospective
550
energy dependent society. range (0.01 V and 2 V). The coin cell with NeC@m-Si electrodes
Prasanna et al. (2019) synthesized porous onion like, nitrogen initially showed lower capacity and columbic efficiency for the first
containing carbon (NeC) and their composite in the presence of cycle but the values stabilized after few cycles at slow Columbic
silicon (m-Si) by employing a simple hydrothermal method at rate. The NeC@m-Si electrode after 100 cycles at 1C delivers
180 C for 12 h which was followed by carbonization, silicon was ~852 mAh g1 of reversible capacity and an areal discharge capacity
ball milled for 24 h to reduce its size before the hydrothermal of ~2.9 mAh cm2 (Fig. 16). This improvement in capacities is
process. The NeC@m-Si composite material was made into an attributed to the presence of carbon material with nitrogen func-
electrode for Lithium ion battery application (LIB). The fabricated tional groups. These groups within the carbonaceous structure
electrode demonstrated superior cycling performance when improves the transport of electrons between the electrodes.
compared to that of bare Si-electrode(m-Si). The charge-discharge Moreover, a large irreversible capacity obtained at first cycle is
cycles were studied at a current rate of 0.1C between the voltage because of the solid electrolyte interphase (SEI) layer formation and
Fig. 16. Lithium ion battery and its charge-discharge performance evaluated by Prasanna et al. (2019) [232]. Charge-discharge graph of (a) NeC@m-Si; (b) NeC; (c) Percentage of
discharge capacity retention at different Coulombic rates for NeC@m-Si and NeC electrodes. (d) Specific capacity and columbic efficiency at different cycles for m-Si and NeC@m-
Si,(e) NeC electrodes, and (f) Areal capacity and specific capacity of NeC@m-Si electrode at 1C. Data reprinted from Ref. [232] published by Springer Nature Publishers copyright©
2019; with article licensed for open access under Creative Commons Attribution (CC BY) 4.0 International License: http://creativecommons.org/licenses/by/4.0/. (A colour version of
this figure can be viewed online.)
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usage of lithium ions. The higher columbic efficiency and capacity maintains the electrical conductivity around the active phase of a-
of the NeC@m-Si electrode is due to strong interactions and stable MnO2 particles formed during the electrode pulverization. The
network between the articles and the current collector. Addition- ameliorated electro-chemical performance of the a-MnO2/CNO
ally the nitrogen doped carbon nano onion layers surrounding the nanocomposite is ascribed to the higher electrical conductivity
ball-milled silicon particle enhances the electronic conductivities (2e4 S cm1) and surface area (247 m2/g) of the carbon nano onions
by creating excessive electrons. Existence of nitrogen improves the [233]. Zhang et al. (2019) synthesized core-shelled composite
ionic interaction between the CeLi which results in further in-situ structures of phosphorous doped carbon nano onion layers
intercalation of the electrode. They found that the NeC@m-Si covering the FeP nanoparticles (FeP@PeCNO) [208]. The composite
electrode retains 62% (@0.2C) of the incurred initial capacity. Ni- was fabricated as an anode material for LIB, after 500 cycles it
trogen in the carbon structure helps in creating numerous active shows a stable and a high capacity of 915 mAh/g at 0.1 A/g. The
sites which helps in acquiring more Li-ions, resulting in superior Li- composite possessed an initial high capacity of 1306 mAh/g at
ion storage capability [232]. 0.1 A/g, with an initial high coulombic efficiency (CE) of 79.8%. Their
Palaniyandy et al. (2019) fabricated a potential cathode material sample also displayed an outstanding rate capacity averaged at
for high-performance zinc-ion batteries (ZIBs) composed of CNOs 379 mAh/g at 8.0 A/g and 237 mAh/g at 10.0 A/g, respectively
integrated metal oxide (a-MnO2 nanorods) nanocomposite (a- (Fig. 18). This enhancement in the capacity and efficiency is
MnO2/CNO) by one-pot molten salt method. The anode utilized attributed to the cooperative effect of the optimized composition
here was zinc metal foil and the electrolyte was a mixture of Zn/ and the microarchitecture. PeCNO shells facilitate the assembling
MnSO4. Results show that the composite displayed stable and high of FeP nanoparticles by offering efficient ions and electron chan-
reversible specific capacity of 168 mAh/g with 93% capacity reten- neling route. This minimizes the volumetric expansion of the FeP
tion compared to a-MnO2 with 104 mAh/g (81% capacity retention) particles during the continuous Li-ion insertion and removal pro-
respectively (Fig. 17). For the a-MnO2/CNO sample the initial cess leading to superior lithium ion storage. This partially prevents
discharge and charge capacities of 175 and 190 mAh/g was pulverization of the anode, thus improving the cyclic stability [208].
observed. All the results obtained were post-100 cycles, at fixed Similarly from the same group, Liu et al. (2019) fabricated carbon
current density of 246 mA/g (0.8C), between the potential range of nano onion encapsulated Fe3C wrapped with porous carbon
1.0e1.8 V vs Zn respectively. They found that the increased capacity nanocomposite particles (Fe3C@CNO/PC). The composite was tested
is due to an in-situ formation of super-fine nanoparticles of a-MnO2 as an anode material for high performance LIB. Their sample dis-
and re-formation of a-MnO2/CNO. Besides that, carbon nano onion played a high reversible capacity of 582 mAh/g after 500 cycles at a
acts as an efficient mechanical stress absorber during the charge e current density of 0.2 A/g with a remarkable retention efficiency of
discharge cycles, while the carbon nano onion network structure ~100% from current density of 16 to 0.2 A/g respectively [234].
Fig. 17. Zinc ion battery and its charge-discharge performance evaluated by Palaniyandy et al. (2019) [233]. Selected charge-discharge cycles of 1, 2, 5, 10, 15 and 20 and assessment
of its Specific capacity vs. Voltage plot for (a) a-MnO2 and (b) a-MnO2/CNO composite; (c) Cycling performance studies of MnO2/CNO (1:1) (blue); MnO2 (red) and MnO2/CNO (1:0.5)
(green) electrodes in 1 M ZnSO4/0.1 M MnSO4 electrolyte, also MnO2 (black) alone was assessed for its performance in 1 M ZnSO4 at current density of 246 mA/g; (d) Rate capability
assessment and evaluation at different current densities of 123, 246, 369, 462 and 615 mA/g respectively in 1 M ZnSO4/0.1 M MnSO4 electrolyte for only two specific nanorod based
electrodes of (a-MnO2) and (a-MnO2/CNO-1:1) composite which were cycled between 1.0 and 1.8 V, (Ch.Cap represents Charge capacity; Dis.Cap represents Discharge capacity)
respectively. Reprinted with permission from Elsevier Publishers for Ref [233]. (A colour version of this figure can be viewed online.)
552
Fig. 18. Charge-discharge and ion storage performance of (FeP@PeCO) core-shell structured nanoparticles evaluated for Lithium ion battery application by Zhang et al. (2019) [208].
(a) Cycle life and stability at lower current density of 0.1 A/g; (b) rate capability assessment at different rates of current densities ranging from 0.1 to 10 A/g; (c) Galvanostatic charge-
discharge (GCD) capacity vs Voltage profiles at current density of 0.1 A/g. Reprinted with permission from Elsevier Publishers for Ref [208]. (A colour version of this figure can be
viewed online.)
Samanta and Raj (2020) fabricated nitrogen doped CoFe electrochemical performance is due to the higher structural sta-
encapsulated carbon nano onion hybrid nanocomposite material bility with good framework of the onion structure around the Si-
(CoFe@CNO) as a cathode for rechargeable zinc-air battery (ZAB) particle. Their charge-discharge curves show that the initial CE
application. The cathode demonstrated an impressive open circuit increases from 73% to 84.5% because of the decrease in the layers of
voltage of 1.58 V, with high power density peak of 102 mW cm-2, carbon nano onion covering the Si-particle, this reduces the initi-
the initial voltaic efficiency of their battery was 59% with 5% loss ation of any defects and by consuming less number of Li-ions from
after 288 cycles but later stabilized without any loss and had a the electrolyte to create the SEI layer [47]. Xie et al. (2020) syn-
stable long term cycling process >48 h. The fabricated coin cell thesized onion like bubbles of nitrogen rich graphitic carbon by
battery (ZAB) could light up 32 red colored LED's up to 1.5 h graphitization of EDTA-Fe(III) sodium complex (ethyl-
respectively. They found that the carbon nano onion played an enediaminetetraacetic acid ferric sodium salt) at 700 C for 2 h in
important role in enhancing the gross performance of the battery the inert argon atmosphere. The Fe-metal core surrounded by on-
[235]. ion layers was acid digested to create the hollow bubble like
Wang et al. (2020) successfully synthesized carbon nano onions structure of layered carbon. The as-prepared N-rich bubble like
encapsulating silicon (Si) at 900 C using a vertical carbonization carbon nano onion (NeBeCNO) was fabricated as an anode mate-
furnace (Fig. 19). Where samples P3, P5, P10 and P20 represents 3, rial for LIB. The results display superior reversible specific capacity
5, 10 and 20 mL of pyridine dosage with 0.5 g Si precursor before (505 mAh/g) at different current densities of 100 mA/g, 150 mAh/g
pyrolysis. The encapsulated Si nanoparticle (CNO@Si) was used as and 1600 mA/g at more than 150 discharge/charge cycles respec-
an anode material for LIB. Initial results show that, the primary tively. The material also displays superior cyclic performance,
discharge capacities of samples P3 and P5 were 1638.3 and enhanced conductivity with real good rate capability, which is due
1533 mAh/g but when the theoretically calculated value for the to the distinctive nature of porous construct of the bubble like
capacity of P3 and P5 it was found to be around 2105 and carbon layers. In summary, they concluded that the degree of
1910 mAh/g, when the current density was increased from 0.05 to graphitization, strength of graphitic layers, crystallinity, N-doping,
2 A/g respectively. The results obtained shows superior Li-storage specific surface area and pore size volume, all accounted for
activity, when the cycling performances for the samples P3, P5, improved conductivity, capacity, higher discharge-charge cycles,
P10 and P20 were assessed at a constant current density of 0.2 A/g active Liþ storage reservoir sites, carbon-lithium interaction and
in between the voltage scan rates of 3.0 and 0.01 V respectively. extra energy storing capacity via pseudo-capacitance chemistry
Where, P3, P5, P10 and P20 maintained their initial reversible which greatly improves LIB performance [236]. Liu et al. (2020)
charge capacities at 1391 mAh/g, 1015 mAh/g, 649 mAh/g and recycled donkey hide gelatin mass in the presence of FeCl3 and
538.4 mAh/g even after 400 cycles, respectively. When they hydrothermally synthesized onion like hollow carbon nano-
increased the current density between 2 A/g to 200 mA/g they spheres (HCN) which were in-situly co-doped with nitrogen and
observed 63.9% rate capacity retention. This improvement in the sulfur. They utilized the as-prepared hollow carbon as an effective
553
Fig. 19. Lithium ion storage performance of onion like spherical Si/C composites (CO@Si)by Wang et al. (2020) [47]. (a) TEM image of the onion-like Si/C spheres (CO@Si) with
hollow carbon shells after etching away silicon using NaOH; (b) HRTEM image of sample onion-like Si/C with Si-core and layers of carbons around it; (c) charge-discharge curves at
different voltages and different cycles for CO@Si composite; (d) rate performance studies of composite; (e) Cycle performance studies and Coulombic efficiency (CE) of the (CO@Si)
electrodes (Where P3, P5, P10 and P20 represents 3, 5, 10 and 20 mL of pyridine dosage with 0.5 g Si precursor before pyrolysis). Reprinted with permission from Elsevier Publishers
for Ref [47]. (A colour version of this figure can be viewed online.)
anode for sodium ion battery (SIB). The improved electrochemical shells may decrease the ionic diffusion route and put up a large
Na-storage performance was attributed to unified effect of the N/S electrode-electrolyte interface region which helps in easy elec-
doping with the thin shells of the hollow sphere. The N/S doped HC tronic/ionic transport. Electronegativity accounts for secondary
(NSeHCN) powders showed an electrical conductivity of 7.9 S cm1 phenomenon, whereas, the large atomic radius and the growing
which was higher than the un-doped HCN (3.5 S cm1). The elec- interlayer distance facilitates the Naþ insertion/extraction. The ef-
tronegativity of N and S atoms commences charge distribution fect of doping in carbon, results in formation of large structural
which increases the conductivity. The battery evaluation showed defects and disorders arising due to the difference in bond lengths,
412/662 mAh/g and 62% of initial specific charge-discharge capac- electronegativity, atomic radius amongst the C, S, and N atoms,
ities with lower Coulombic efficiency (CE). 2nd cycle exhibited 404/ which additionally helps in accessing additional active site zones
405 mAh/g with high CE (99.8%) and an initial irreversible capaci- for Naþ storage [237]. Ma et al. (2020) coated CNO layers on mes-
ty(IIC) loss of 38.8%. The higher IIC loss and lower CE is due to the oporous Co9S8 nanoparticles sustained on reduced graphene oxide
formation of SEI layer and irreversible, incomplete Naþ insertion (rGO) by solvothermal method where the material was heated in
into the carbon system. For 500 and 1000 cycles at current densities between 150 and 200 C for 20 h and was later annealed at 650 C
of 0.5 A/g and 2 A/g, the NS-HCN anode exhibited stable specific for 6 h in the presence of H2/Ar (5/95, vol%) mix to obtain the
discharge capacities of 266 and 174 mAh/g respectively, followed by transition metal chalcogenide (TMC) based composite (CNO@-
>90% of high capacity retentions. They hypothesized that the thin Co9S8/rGO). The composite was evaluated as an anode for its
554
efficiency and performance in potassium-ion batteries (KIB). The electrochemical capacitors (ECs), particularly because of their
performance results shows that the specific capacity of the com- intermediary relation between the conventional batteries and
posite after 100 cycles was 407.9 mAh/g at current density of 0.2 A/g electrical double layer capacitors (EDLCs). A thematic scheme is
with 83.8% of the charge capacity at the end of 3rd cycle and depicted in Fig. 20 representing a charged capacitor with its ion
215.1 mAh/g at 5 A/g respectively. After 1200 cycles the composite flow and reservoir. That is, one can relate that ECs function as an
maintains a steady capacity of 210.8 mAh/g at a current density of entity between physical capacitors (high power with very low en-
1.0 A/g respectively. The composite was later doped with sulfur for ergy density) and batteries (medium power with high energy
exploring the electrochemical performance studies in lithium sul- density); where, they completely occupy the void amongst both
fur battery application. They found that their sulfur composite variants of electrical storage devices. In this system, the charges are
(CNO@Co9S8/rGO/S) after 800 cycles at 3 C maintained a specific stored at the interface of electrodes and electrolytes [199]. Super-
capacity of 431.8 mAh/g with loss of 0.052% per cycle. They found capacitors are another type of high power density based electro-
that the layers of carbon surrounding their TMC composite pro- chemical energy storage devices which has extremely lengthier
vided a protective cover to reduce the chemical reaction between cycling spans (>1 million cycles). To actualize possibilities being
the TMC and electrolyte. The carbon layers also aids in the fortifi- contributed for the development of ECs, one should examine the
cation of structural entirety, enhances and maintains the stability specific power vs specific energy Ragone plot for various energy
during the cycling process. Moreover, rGO creates a 3D network for devices (Fig. 21). In general, the power density is 100 times higher
facile charge transportation whilst inhibiting the mobility of par- but the energy density of supercapacitors is approximately ~10% in
ticles during the cycling process [238]. Mao et al. (2020) though comparison with the conventional batteries. Furthermore, capaci-
their work does not show any relationship to the carbon nano onion tors are an alternative and a reliable power source for a particular
based sample, but they fabricated an amorphous, porous carbon need and circumstances, due to their excellent adaptability in po-
coated ultrafine Li3P/C composite with several nano-metric do- wer/energy profiles. Nonetheless, it is highly important to note
mains for lithium ion battery application. Due to the unique micro that, the governing standard rule for any electrochemical capacitor
and nano-architecture of their composite, the porous carbon layer within a device is to perpetually deliver the stored electric charge
framework provided rapid electron transfer by conductive immediately [240]. Thus more research in this field is being
pathway. They found that any volumetric differences between the P explored for improving the energy density of the supercapacitors.
and Li3P were mostly confined to the nano-pores of carbon. This This holds a very high commitment in solving the most critical and
enhanced the structural integrity of the whole Li3P/C composite challenging problems related to energy storage applications
particles. The composite demonstrated a high initial specific ca- including mobile electric vehicles [241]. Contrasting to this,
pacity of 791 mAh/g during the initial de-lithiation process at a pseudo-capacitors belongs to another subclass of the super-
current density of 0.1C respectively. The composite showed a spe- capacitor family, which stores energy charges by way of Faradaic
cific capacity of 620 mAh/g at current density of 0.5C during the reactions occurring at the surface of electrodes [242] and delivers
lithiation process. The composite (Li3P/C), demonstrated stable instant surge of energy and power. Fig. 22 illustrates the capacitive
cycleability with 75% and 82% at 0.5C of capacity retention at cur- energy and Faradaic storage of different kinds of materials and
rent density of 4 and 6C respectively [239]. devices. The figure briefly depicts the summary of distinctive de-
vice characteristic functions of cyclic voltametry, galvanostatic
6.2. Application of carbon nano onions in supercapacitors charge discharge (GCD) profiles, mechanisms involved, devices
which typically utilizes the depicted charge-storage mechanisms
Since few years on, there has been a significant growing interest [242] respectively. This type of system exhibits very high specific
in the field of supercapacitors which are also known as capacitance in contrast to the carbon based EDLCs counterparts
[243,244]. Supercapacitors find their way in several important
application fields like wearable, portable and flexible electronics,
power bank units, kinetic energy recovery systems (KERS) or
regenerative braking systems (RBS) and electric vehicles (EVs)
[199,243e245]. Recently efforts are on way in improving the cyclic
stability by integrating Faradaic and non-Faradaic procedures for
long-run charge/discharge efficiencies [246,247]. Few potential
candidates of carbon based composite with transition metal oxides
(TMO) [248e250], metal hydroxides (MOH) [251e253] and con-
ducting polymers [254e257] have demonstrated promising energy
storage results. Several challenges were encountered in the devel-
opment of efficient and durable hybrid pseudo-capacitors. Often it
is found that during the cycling process, the undesirable lower shelf
life and electrode deterioration is caused by the volume expansion
[258,259]. Incorporation of carbon based micro/meso or nano-
materials have shown to boost the structural constancy and longer
shelf life based cycling efficiency [200e202,260e262].
Recently, carbon nano onions have emerged as a potential
candidate for the high performance electrodes for the super-
capacitor application. This sudden interest is due to their extraor-
dinary exohedral affine curvature with multi-lamellar structural
anatomy, large approachable surface for electrolyte ion assimila-
tion, high surface area, high rate capability, corrosion resistance,
Fig. 20. Generalized schematic of a supercapacitor displaying the electron flow and
migration towards their electrolyte soaked respective electrodes during the electro-
thermal stability, electrical conductivity, micro porosity, and energy
chemical charging. Adapted, redrawn and modified accordingly from Ref. [240]. (A density of the fabricated supercapacitor system [199e205]
colour version of this figure can be viewed online.) respectively. Nonetheless, several forms of nanocarbons with their
555
Fig. 21. A typical Ragone plot representing Specific Energy (Energy Density) vs. Specific power for various energy based devices. Adapted, redrawn and modified accordingly from
inherent low energy density and capacitance are major choke- conductivity, stability capacitance and its electrochemical perfor-
points for the development and market value upgradation for mance for a given capacitor. Based on the need and the type of
supercapacitor industry [200,203]. Therefore, it is necessary to capacitor fabricated, electrolytes are categorized in three major
introduce modifications like intercalation, functionalization, groups: aqueous (liquid); organic and ionic/conducting liquids
doping, polymer grafting etc to pristine carbon materials for sub- respectively. (Fig. 23), describes the capacitor's inter-relationship
stantially ameliorating the electrochemical and electrical proper- between electrolytic properties and their electrochemical fea-
ties [200,203,263]. Doping with heteroatoms like boron (B), tures. For a specific choice of an electrolyte, the size of ions and
nitrogen (N) and sulfur (S) into the host carbon matrix is a highly their matching counter parts (solvated ions) with pore size greatly
opted strategy for designing pristine carbonaceous candidates. By affects the pore accessibility [240,280,281]. Parameters like oper-
designing these, the surface wettability, electronic, structure and ating voltage window and the operational temperature range of the
electrochemical properties of the doped carbonaceous electrodes capacitor are dependent heavily on the type of electrolyte used.
are altered. These alterations enhance the pseudocapacitive Whereas, the capacitance and time constant of the device are
behavior. Several studies have already been reported for heteroat- determined by the concentration and the conductive properties of
om utilization in carbon matrix for energy applications the electrolyte. Nonetheless, the standard requisite for having
[200,203,241,261,263e274]. Reports have indicated the value of longer shelf-life with innumerable cycling capability is directly
maximum specific capacitance to range between 20 and 100 F/g in related to the electrochemical stability of the electrolyte. Tradi-
acidic/alkalic electrolytes even after complexing with polymers, tionally, by using organic electrolytes, the potential voltage window
metals and redox active metal compounds [203,275e279]. Pres- can be increased but the major demerit is their low ionic conduc-
ently, low-cost, in-situ synthesis methods are being developed for tivity. Due to this, the equivalent series resistance (ESR) increases
the fabrication of carbon nano onion based composite materials for and reduces the specific power of the system. In addition, these
supercapacitor application. The doped CNO can be conceived as a electrolytes are highly toxic, expensive, inflammable, pose health
potential electrode material to demonstrate fascinating super- and safety risk, adding to inadequate practical relevance. Ionic
capacitive properties and applications respectively. For an asym- liquids were later opted and trials were carried out to assess the
metric assembly, coupling of doped CNOs with red-ox active metal capacitive properties for the expansion of OVF, but due to its in-
oxides may expand the operating voltage frame (OVF) for a given efficiency in generating any high interfacial charge they were later
electrolyte and thereby enhancing the energy density of the sys- not tried [203]. Another method of expanding the OVF is to employ
tem. Generally, for an asymmetric supercapacitor (ASC) device, the an asymmetric arrangement, where the liquid electrolyte's poten-
negative electrode (power source) is often favored to be carbon tial window can be enhanced beyond its own thermodynamic
based, whereas the positive electrode (energy source) is transition boundary (i.e oxygen evolution at 1.23 V). This causes the energy
metal oxide (TMO) based. The general formula for calculating the density to increase beyond the limits of symmetric supercapacitor
energy density of a supercapacitor is given by equation E ¼ 0.5 CV2. [203]. Based on all the above information, Fig. 24 shows the clas-
Therefore, for an opted electrolyte the energy density is directly sification of the types of supercapacitors. The following section
proportional to the capacitance and the operating voltage frame. further describes the current work done since last one year
Electrolyte choice is an important factor in improving the (2019e2020) in the field of carbon nano onions in this subject area.
556
Fig. 22. Tabulated image of different electrochemical devices with their respective energy storage mechanisms involved based on the faradaic and capacitive routes, and a succinct
outline of their characteristic graphical metrics involving cyclic Voltammetry and Galvanostatic profiles. Data reprinted from Ref. [242] published by Springer Nature Publishers
copyright© 2016; with article licensed for open access under Creative Commons Attribution (CC BY) 4.0 International License: http://creativecommons.org/licenses/by/4.0/. (A
colour version of this figure can be viewed online.)
With the best of our knowledge, Authors have tried to briefly cover agent (142.3 F/g) was 28.4% higher than that of the supercapacitor
the importance of carbon nano onions and their efficiency as an using Super-P as conductive agent. From data it was found that the
effective electrode material for supercapacitor application. specific capacity was decreased to 86.9% of the initial one by
Zhang et al. (2019) synthesized supercapacitor by using carbon applying 5000 cycles at constant current density of 0.5 A/g. They
nano onions (CNO) as a conductive agent. The used graphitized found that the voids (1e3 nm) present in the CNO were beneficial
carbon nano onions have been fabricated by chemical vapor for ions to migrate and lead to the improvement of supercapacitor
deposition (CVD) using methane as carbon source. They purified functions. Further, the electrical conductivity of COs was found
carbon nano onions by calcination and commercial super-P were better than that of Super-P due to its high degree of graphitization
employed as conductive agents of electrochemical supercapacitors [156]. Mohapatra et al. (2019) in-situly synthesized sulfur doped
with the same proportion and dosage. Their sample at lower carbon nano onions (SeCNOs) by flame pyrolysis method. The
scanning rate (Fig. 25), exhibits a typical rectangular plot with good obtained SeCNOs, sample was hydrophilic, graphitic, and porous
symmetry with zero red-ox peaks inferring that the device mech- with high SSA (950 m2 g1) in nature. The obtained sample was
anism for energy storage represents the EDLC type conformation. It later fabricated as a high performance symmetric supercapacitor
was also found that at different scan rates of 10, 20, 50, 100 and electrode and assessed its performance in 1 M Na2SO4 electrolyte.
200 mV/s, the cyclic Voltagrams preserved their rectangular shaped Due to the direct and in-situ doping of sulfur into host carbon
plot even during the increasing scan rates respectively. Thus, con- matrix created a highly polarized surface, well dispersed reversible
firming the superior and stable galvanostatic charge and discharge pseudo-sites, overall improvement in conductivity and enhanced
(GCD) properties of carbon nano onions. Results confirmed that the electrolyte-electrode interaction respectively. The electrode dis-
specific capacity of the supercapacitor using CNO as conductive played specific capacitance of 305 F g1, energy and power density
557
Fig. 23. A thematic representation of interdependence between electrochemical capacitor features and electrolyte properties. Adapted, redrawn and modified accordingly from
of 10.6 Wh/kg, and 1004 W/kg respectively at an applied current doped carbon nano-onions (N-CNO). Their sample electrode
density of 2 A/g for the symmetrical two-electrode cell conforma- (NPGeN-CNO) based device demonstrated areal capacitance of
tion. On comparison, this cell conformation electrochemical pa- 1.16 mF/cm2 and gravimetric capacitance (259 F/g) at a maximum
rameters are three folds higher than that the pristine carbon nano energy density and power density of 0.16 mWh/cm2 and 24.87 mW/
onion based devices with similar testing environment. The cm2, at the scan rate of 10 mV/s1 and 200 mV/s respectively. The
SeCNOjjSeCNO system at a current density of 11 A/g yielded device showed good cycling stability with 80% retention in capac-
6.1 Wh/kg of energy density and power density of 5.5 kW/kg with itance up to 10,000 cycles. This is attributed to high surface area
discharge of good rate capability, power management and stability. and electrical conductivity within the network of interconnected
The same at an applied current density of 5 A/g, displayed high pores of the three dimensional NPG which offers active loading
value electrochemical reversibility with 95% retention of its initial sites for the carbon nano onions or any other alternative material.
capacitance even after 10,000 repetitive charge cycles during the They also found that the graphene rings in the nitrogen doped
experimental process [200]. carbon nano onions plays a crucial role in improving the energy
Jin et al. (2019) fabricated electrode materials with porous car- density and the capacitance of carbon bound alternative materials
bon nano-onions (PCNO) derived from rice husk for super- [263]. Mohapatra et al. (2020) synthesized asymmetric super-
capacitors. The synthesis of PCNO was performed by a facile nickel capacitor (ASC) electrodes by using highly graphitic, mesoporous
assisted graphitization, followed by an activation procedure with nitrogen-doped carbon nano-onions (NeCNO) with NiO particles.
renewable and sustainable rice husk as carbon precursor. The The prepared electrodes anatomy shows several interconnected
sorption of nitrogen stated that the sample (CNO-700) showed a network of NeCNO, which are highly graphitized and hierarchically
porous structure and a high specific surface area (3831 m2/g). CNO- mesoporous which potentially improved the supercapacitor per-
700 shows a high specific capacitance of 350 F/g at the current formance. It was observed that after applying the voltage of 1.8 V
density of 0.1 A/g, good rate performance (288 F/g at 20 A/g), and of (in the electrolyte 1 M Na2SO4) on the ASC device, it generated a
the capacitance retention(99%) over continuous 10,000 cycles at a maximum specific capacitance of 113 F/g and energy density of
current density of 20 A/g in the aqueous electrolyte of 6 M KOH 51 Wh/kg at a current density of 4 A/g. In addition, the fabricated
with zero attenuation [43]. Singh et al. (2019) developed a portable, ASC showed best electrochemical cyclic stability beyond 10,000
minimized, solid-state micro-supercapacitor as an energy storage cycles, thereby retaining 98% of its specific capacitance with
device on a silicon wafer by using nanoporous gold (NPG)enitrogen excellent coulombic efficiency of 99% at a high current density of 20
558
Fig. 24. A general classification of the supercapacitor family. (A colour version of this figure can be viewed online.)
A/g respectively. The excellent performance behavior of the ASC were functionalized with Lysine by two routes (i) amidation (lys-
device is attributed to the exo-hedral curvature, high SSA (842 m2/ CNO) and (ii) outer shell aliphatic carbocation and formation of
g), additional capacitive sites, mesoporous hierarchy, nitrogen and diazonium salts (slys-CNO). They observed an increased specific
NiO presence, high graphitization of carbon nano onions, increased capacitance of CNO in the presence of lysine. Prior to functionali-
electron transport and uninterrupted rapid ionic diffusion, zation of p-CNO, the oxidation procedure was carried out on the p-
improved electrode wettability and electrical conductivity [203] CNOs, where the fabricated electrodes displayed increased charge
respectively. Bhaumik et al. (2020) fabricated an asymmetric transfer resistance. On the other hand, the electrochemical per-
supercapacitor with Ni(OH)2@PANI composite with CNO synthe- formance evaluated by the Electrochemical Impedance Spectros-
sized from waste car tyres as an anode material. The results (Fig. 26) copy (EIS) in the presence of 1 M Na2SO4 as an electrolyte, showed
show very good specific capacitance of 622 F/g and an excellent that the electrodes exhibited specific capacitance of 16.49 F/g for p-
capacity retention > 97% at high current density of 2 A/g. At 5 A/g of CNOs, 4.03 F/g for lys-COs and 32.72 F/g for slys-CNOs, respectively.
current density, the cycling process is clearly stable even after They found that oxidation of CNOs, greatly influences the electrical
continuous 10,000 charge-discharge cycles in a 3 M KOH electrolyte properties and the capacitance of the electrodes [204]. Shanmu-
with 97% of capacity retention. The asymmetric device electrodes gapriya et al. (2019) fabricated onion like porous carbon super-
discharged very high energy and power densities of 70 Wh/kg and capacitor electrodes (J-800) from an invasive weed Prosopis juliflora
136 kW/kg and the symmetric device delivers energy density of by hydrothermal approach and later chemically treated it by KOH.
23 Wh/kg and power density of 292 kW/kg respectively. It was The obtained sample has a SSA of 967 m2/g. They made a symmetric
further demonstrated that Ni(OH)2@PANI/CNO composite showed EDLC and electrochemically tested it in H2SO4 aqueous electrolyte.
a high specific capacitance value of 166 F/g at a higher current To further increase the performance, they introduced KI as a redox
density of 5 A/g. The mechanism behind the extend prolonged cycle additive agent into their electrolyte along with their porous carbon.
stability might be due to the synergistic effect of 3D-nanosponge- The device demonstrated specific capacitance of 274 F/g at a cur-
like Ni(OH)2 on PANI nanotubes surface, stabilizing the volume rent density of 1.3 A/g in a conventional non-redox H2SO4 elec-
changes upon cycling [199]. trolyte. Whereas, when the electrolyte was mixed with KI, they
Velasquez et al. (2020) functionalized pristine carbon nano on- observed superior energy density of 35.7 Wh/kg at an elevated
ions (p-CNO) synthesized by annealing nanodiamonds under he- power density of 971 W/kg. Interestingly, when the cell voltage was
lium atmosphere at 1600 C. Pristine carbon nano onions (p-CNO) increased to 1.4 V, they observed an enhanced cell capacitance of
559
Fig. 25. Enhanced capacitance in the carbon nano onion based supercapacitor by Zhang et al. (2019) [156]. (a) Cyclic Voltagrams of EDLC device with carbon nano onions (CNO) and
Super-P at scan rate of 10 mV/s; (b) Cyclic Voltagrams of EDLC device with carbon nano onions (CNO) as conductive agent at different scan rates and (c) Specific capacitances of EDLC
based devices with Super-P and CNO as conductive agents at constant current density of 0.5 A/g with cycling over 5000 cycles. Reprinted with permission from Elsevier Publishers
588 F/g. The KI mixed aqueous electrolyte also exhibited superior density of 16.1 Wh/L as depicted in Ragone plot (Fig. 27-d)
cycling stability till 10,000 cycles and had 96% of capacitance respectively. The a-CNO electrodes presented gravimetric capaci-
retention [282] respectively. tance of 71 F/g at a current density of 2 A/g (Fig. 27-b), in an organic
Jung et al. (2020) synthesized carbon nano onions from wick electrolyte medium of 1 M Tetra-ethyl-ammonium-tetrafluoro-
pyrolysis of waste cooking/frying oil and fabricated KOH-activated borate (TEABF4) in acetonitrile. Whereas, non-activated carbon
carbon nano onion (a-CNO) electrodes for supercapacitor applica- nano onions had a specific capacitance of ~30 F/g. The electrodes
tion. Fig. 27a shows a typical capacitive nature and higher rate additionally presented a comparative and productive volumetric
capability due to the almost rectangular curve obtained at different capacitance of 63 F cm3 and expressing high packing density
scan rates range from 0.1 to 1 V/s respectively. The triangular sha- around 0.89 g/cm3 in comparison to that of the commercially
ped curves in Fig. 27b demonstrates superior electrochemical available activated carbon. Moreover, the electrodes even at higher
reversibility and coulombic efficiency of the a-CNO obtained at current density of 8 A/g displayed over 80% of capacitance retention
different current density values from 2 to 8 A/g respectively. The a- post 10,000 Galvanostatic charge and discharge (GCD) cycles
CNO based supercapacitor exhibited a maximum gravimetric en- respectively (Fig. 27-e). The superior performance of the a-CNOs, is
ergy density Fig. 27c of 18 Wh/kg and a maximum gravimetric attributed to good interconnected network of carbon chains, effi-
power density of 132 kW/kg respectively. This enhancement in the cient and accelerated pathway for ion-transport, lower resistance
capacitive power led to higher performance with reaching highest for electron transfers and presence of active charge storage sites
volumetric power density of 118 kW/L and volumetric energy [283] respectively. Zhang et al. (2019) synthesized onion like 3D
560
Fig. 26. Electrochemical performance evaluation of asymmetric supercapacitor fabricated with Ni(OH)2@PANI/CNO in 3 M KOH electrolyte by Bhaumik et al. (2020) [199]. (a)
Specific capacitance versus current density plot for Ni(OH)2@PANI/CNO composite electrode; (b) Ragone plot of Ni(OH)2@PANI/CNO based asymmetric device; (ced) Capacity
percent retention tests over 10,000 consecutive cycles at a constant current density of 5 A/g and (d-inset) variable voltage range. Reprinted with permission from Elsevier Publishers
Fig. 27. Electrochemical performance of KOH activated (a-CNO) in organic electrolytes by Jung et al. 2020 [283]. (a) Cyclic Voltammetry curves at various scan rates (0.1e1.0 V/s). (b)
GCD curves obtained at variable current densities of 2, 4 and 8 A/g. (c) Specific (gravimetric and volumetric) capacitance of a-CNO electrodes obtained at different current densities
(d) Ragone plot of a-CNO electrodes. (e) Percent capacitance retention and their cycling stability over 10,000 cycles at a current density of 8 A/g. Reproduced from Ref. [283] with
permission from the Royal Society of Chemistry. (A colour version of this figure can be viewed online.)
561
porous carbon from waste xylose mother liquor by hydrothermal carbon (C60/NFO/HE-LVP/SC is represented as CNLS hereafter) by
approach. The product acquired had self-doped oxygen and nitro- freeze drying and thermal reduction of carbon method respectively.
gen as hetero atoms. The product was utilized for the construction The CNLS material was evaluated for its electrochemical perfor-
and assembly of two electrode type symmetrical supercapacitor. mance in a battery-supercapacitor hybrid (BSH) device as a cathode
The supercapacitor with onion like 3D porous carbon exhibited in a mixed LieNa electrolyte throughout a potential range of
superior performance with heightened specific capacitance of 0.01e4.3 V respectively. The CNLS and LVP/C composite electrodes
544 F/g at the current density of 0.5 A/g. The supercapacitor dis- were fabricated for the BSH device. Results indicates (Fig. 29) un-
played superior rate performance (260 F/g) at higher current den- usual, but highly novel electrochemical performance like the self-
sity of 20 A/g with longer cycle stability. The system even after enhanced specific capacity, ultra-high capacity retention(204.2%),
10,000 charge cycles showed 90.2% retention in capacitance at the at a very high energy density of 405 Wh/kg, power density of
current density of 10 A/g in an aqueous inorganic electrolyte (6 M 413 W/kg even after 300 charge cycles at current rate of 10 C
KOH) with three electrode systems respectively. Particularly, the respectively. The electrodes exhibited an initial specific capacity of
symmetric capacitors displayed 22.3 Wh/kg of energy density at 108.1 mAh/g and later stabilized to 98.4 mAh/g at current density
448 W/kg of power density in the presence of aqueous Na2SO4 as rate of 0.1 C within a potential window of 2.5e4.2 V respectively. On
electrolyte. Moreover, higher extent of specific energy density of the similar current density of 0.1C and wide voltage window range
42.8 Wh/kg at higher power density of 749.8 W/kg was respectively of 1.5e4.3 V, the electrodes displayed a specific capacity of
attained using Tetraethylammonium tetrafluoroborate (Et4NBF4) in 180 mAh/g for two cycles. The difference of charge-discharge be-
an organic electrolyte [284] respectively. Yang et al. (2020), suc- tween the two cycles shows decrease in the voltage from 3.7 to
cessfully synthesized molybdenum disulfide (MoS2) coated hybrid 3.08 V, but alternatively increases its charge capacity by 41%
hollow carbon nano onion like spheres (HCNOS) by supramolecular (89 mAH/g) which is due to the secondary storage mechanism.
assembly and hard template protocols. The hybrid composite Furthermore the graph of CNLS shows a close rectangular shape CV
(MoS2@HCS) displays SSA of 119 m2/g. The composite was curve devoid of any red-ox peaks which displays an electro-
employed in the construction of an asymmetric supercapacitor chemical nature which is very similar to the electric double layer
electrode and the system respectively. The electrochemical result (EDL) capacitors type device phenomenon. This type of curve is due
shows that the composite electrode reaches a maximum specific to the surface enclosed charge-transfer action which confirms the
capacitance of 314.5 F/g at current density of 1 A/g at 50 mV/s scan presence of EDL mechanism over the surface controlled process
speed. At this rate, the specific capacity retention of the system was within the CNLS electrodes respectively. The electrode also exhibits
maintained at 87% even after 4000 charge cycles with high system almost 100% of coulombic efficiency along with active redox re-
stability. On the other hand, they also fabricated a flexible asym- actions involving Fe2þ/Fe3þ and V3þ/V4þ ions in NFO and LVP
metric supercapacitor assembled with MnO2//MoS2@HCNOS elec- respectively. All the enhanced electrochemical property is attrib-
trodes. This system displays an energy density of 34.0 Wh/kg at uted to joint and cooperative effects of the multi-components of
power density of 611.6 W/kg. This asymmetric supercapacitor is the electrode material, higher crystallinity, exceptional Liþ inter-
highly flexible, when it was bent to 180 , the device showed high calation affinity, pseudo-capacitance and conductivity of the car-
functional stability and capacitive performance with 93% capacity bon nanocages, multiple presence of redox couples of V3þ/V4þ and
retention, even after 2000 charge cycles respectively [285]. Vela s- Fe2þ/Fe3þ ions and beginning of external faradaic reactions in C60
quez et al. (2020) synthesized pristine carbon nano onions (p-CNO) respectively [288].
by thermal annealing of nanodiamonds which were oxidized (ox- Habib et al. (2019) synthesized hybrid composite of MXene
CNO) and later covalently functionalized by pyrene molecules (Pyr- (Ti2CTX) doped with CNOs to evaluate its super-capacitive proper-
CNO). The obtained carbon nano onions (p-, ox- and pyr-CNO) were ties. All the electrochemical tests for the fabricated electrodes were
later assessed for their supercapacitor applications (Fig. 28) as carried out at 1 A/g of constant current density in the presence of
electrodes in 1 M Na2SO4 solution as the electrolyte. The results 1 M H2SO4 with a symmetric bi-electrode T-type Swagelok capac-
show that the highest specific capacitance obtained at scan rate of itor configuration. They found that by doping CNO into the host
30 mV/s for functionalized carbon nano onion was 62.2 F/g. Simi- (MXene) layered structure; electrode samples showed enhance-
larly, at scan rate of 100 mV/s the pyr-CNO electrode displayed ment and stability in the extended cycling capability. The samples
longer cycling stability even after 1000 charge cycles with 99% of showed increased specific capacitance of 106e147 F/g for MXene
initial capacity retention between the current density of 3.7 to with 5 wt % CNO concentration and decreased capacitance of 104 to
2.9 A/g respectively. They found that the pyrene functionalization 92 F/g for 10 wt % CNO concentrations respectively. The electrodes
was highly beneficial in improving the specific capacitance by 138% showed stable higher capacitance retention from ~80% to >95% up
in comparison to their p-CNO [286]. to 10,000 charge-discharge cycles. The enhancement in super-
Kim et al. (2020) synthesized three dimensional (3D) turbos- capacitive property may be due to the surface area, active sites,
tratic onion like hierarchical porous carbon materials (PCMs) by conductivity, increased sp2 ordering of graphene planes of CNO,
hard template method of acid reactive meso-porous ZnO/Zn(OH)2 structural support to the multilayered MXene architecture and
spheres. The obtained sample had a SSA of 1013 m2/g, and exhibited physicochemical nature of CNO [289] respectively. Sanchez et al.
high gravimetric specific capacitance of 329.5 F/g at the current (2020) synthesized endohedral carbon nano onion like nano-
density of 0.1 A/g based on the galvanostatic charge/discharge structures with Ni (II) and Fe(II) core. The samples were synthe-
(GCD) study. They found that the sample was highly stable with sized by direct pyrolysis of Ni(II) and Fe(II) phthalocyanines. The
117% capacitance retention post 10,000 charge cycles at a given electrochemical analysis was carried out in 2 M H2SO4 aqueous
current density of 5 A/g. secondly they constructed another sym- electrolyte. The sample electrodes which have CNOs were pro-
metric bi-electrode supercapacitor system which exhibited specific tected from any damage/degeneration by the acidic medium of
capacitance of 338.9 F/g at current density of 0.108 A/g, with su- electrolyte. The samples demonstrated high rate capabilities till
perior capacitance retention (98.18%) even after 10,000 GCD cycles 1 V/s, higher cycling stability, capacitance retention up to 99% at a
at a slightly higher current density of 2.16 A/g respectively [287]. current density of 5 A/g above the 10,000 marked charge discharge
Zhang et al. (2020), synthesized a super-structured hybrid quater- cycles respectively. Different sample electrodes displayed a range of
nary composite material composed of CNO nanocages (C60 rings), energy densities from 1.7 to 1.2 W h/kg, under the power density of
Na4FeO3 (NFO), high-energy (HE) Li3V2(PO4)3: (LVP) with soft 140.3e6537.5 W/kg respectively. Additionally, at current density of
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Fig. 28. Supercapacitor performance assessment of carbon nano onions (CNO) with pyrene as a surface functionalized molecules by Velasquez et al. (2020) [286]. (a) Obtained cyclic
Voltammetry (CV) plots of glassy carbon electrodes coated with functionalized and non-functionalized CNO in 1 M Na2SO4 electrolyte with a sweep rate of 30 mV/s. (b) Percentage
capacitance retention values as a function of cycle numbers. Cyclic stability measurement studies of pyr-CNO based on function of time for 1000 cycles: (c) represents the first 8
cycles and (d) the last 8 cycles. Data reprinted from Ref. [286] published by MDPI, Basel, Switzerland Publishers copyright© 2020; with article licensed for open access under
Creative Commons Attribution (CC BY) 4.0 License: http://creativecommons.org/licenses/by/4.0/. (A colour version of this figure can be viewed online.)
0.2 A/g, the samples exhibited highest capacitance of 15 F/g and the studying the merits of electrochemical properties have been thor-
lowest at 6 F/g. They attributed this improvement in the electro- oughly researched on global scale and can be summarized on their
chemical performance of the onion like endohedral (Ni, Fe) carbon merits as follows: (i) facile routes for the carbon nano onion based
due to the graphitic nature and the pseudocapacitance mechanism composite synthesis and assessment of their electrochemical and
occurring between the surface groups like oxygen and nitrogen ion exchange properties for capacitor application. (ii) Improved
through the faradaic reaction on the surface of the electrode CNOs dispersion in various inorganic/organic solvents to yield ho-
respectively [290]. Thus based on the results observed from the mogeneous combination of organic and inorganic material com-
above listed research reports, it was determined that by intro- posites, (iii) improving composite porosity and study the effects of
ducing carbon nano onions with other materials including organic CNOs concentration within the host matrix and its effects on the
and inorganic moieties increases the materials specific capacitance composite's capacitance and conductivity. (iv) Improving the
quality which is advantageous for the electrochemical based composite's affinity and its proactivity towards faradaic reactions
supercapacitor application [291e293]. Henceforth, in order to such that the composite exhibits greater specific capacitance with
achieve an optimized electrode composite material, several factors high degree of stability including their undoped (either polymer
should be considered before altercating the carbon nanostructure’s based or inorganic) composite counterparts respectively.
anatomy. As an example to understand this, factors like, crystal-
linity, hydration reaction, wettability, degradation of the host ma-
terial, ionic conductivity of the material, degree of graphitization, 6.3. Carbon nano onion based polymer composites
diffusion of ions, rate/reversibility of ions [294], pore volume and
composite's specific surface area to name a few should be taken Nanomaterials are used in several fields which require con-
into serious consideration. Henceforth, the composite hybrid trolling their unique properties like structural, physico-chemical,
electrode materials fabricated with carbon nano onions (CNOs) for mechanical, electronic etc., at macro and microscopic levels. Simi-
larly, functional alterations of carbon nano onions improve the
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Fig. 29. Electrochemical performance studies of battery-supercapacitor hybrid devices (BSH) by Zhang et al. (2020) [288]. (a) Charge/discharge plots of BSH configured with C60/
NFO/HE-LVP/SC hybrid electrode after different cycles in various voltage range of 1.5e4.3 V at 0.1 C; (b) Inset image of charge/discharge capacity versus cycle number obtained at
0.1 C; (c) Rate capacities of C60/NFO/HE-LVP/SC hybrid electrode at various current rates for 320 cycles and their corresponding coulombic efficiencies; (d) Comparison of CV curves
of C60/NFO/HE-LVP/SC and LVP/C electrodes between the voltage range of 0.0e1.2 V at 0.1 mV/s of scan rate; (e) Charge/discharge plot of C60/NFO/HE-LVP/SC between energy density
and cycle numbers (>320 cycles) at various current rates. Data reprinted from Ref. [288] published by Springer Nature Publishers copyright© 2020; with article licensed for open
access under Creative. Commons Attribution 4.0 International License: http://creativecommons.org/licenses/by/4.0/. (A colour version of this figure can be viewed online.)
blending characteristics which help them in mixing thoroughly electrons on the surface prone to oxidation as CNT. Nevertheless
without much of agglomerations within the polymer matrix. This the di-radical creation and reactivity of other oligomers and bis-o-
helps in facile fabrication methods of carbon nano onion based diynyl arene (BODA) monomer demonstrates good number of
polymeric nanocomposites with myriad applications. The present possibilities to directly functionalize the less oxidizable large-sized
section tries to deal with the polymer based nanocomposites carbon nano onions [296]. Taking the tunable conjugation length,
fabricated with carbon nano onions so far and their applications thermal reactivity, and functional group content of the Bis-O-
explored by various researchers. This may also help prospective and Diynyl Arene (BODA) strategy, processing, and fabrication of
entrepreneurial researchers and scientists to further explore other novel CNO composites may now be possible for a variety of appli-
possibilities of the composites in different fields and subject areas. cations. This resolve helped them in successfully synthesizing the
Georgakilas et al. in 2003 were the first to functionalize carbon BODAcarbon nano onion composite. Hence most researchers
nano onions with a mixture of nitrogen doped amino acid and prefer smaller onion size for having greater reactivity over larger
paraformaldehyde [295]. Three years later on Rettenbacher et al. onions. Su et al. synthesized carbon nano onions by CVD at 800 C
(2006) and Rettenbacher et al. (2007) laid the foundations for un- from methane. After purification the carbon nano onions were
derstanding the chemical based solubility of the carbon nano on- mixed within the paraffin matrix and was assessed for its EMI
ions in various organic/inorganic solvents, which later paved its performance in the frequency range of 8.2e12.4 GHz. Their nano-
way in exploring the possibilities of surface functionalization and composites demonstrated a minimum reflection coefficient (RC)
fabrication of carbon nano onion-polymers based composites of 42.04 dB at 9.02 GHz [297]. Similarly, Jiang et al. also synthe-
[52,296]. They successfully functionalized (exohedral nature) car- sized arc discharged induced defective carbon nano onions (CNOs)
bon nano onions where they were able to oxidize and generate from Hexane and ethanol as carbon precursors. They fabricated a
active defective sites and functionalization aided by conversion into 1.4e3.4 mm thick CNOs/paraffin composite for electromagnetic
various derivatives like amides and PEGylation. They also directly applications [177]. Several reports on the use of carbon nano onions
functionalized carbon nano onions by 1,3-dipolar cycloaddition or CNOs with polymer as composites have been reported for elec-
reactions on azomethine-ylides [52]. Based on their methods, it tromagnetic applications like CNOs/vaseline composites [298],
was envisioned that a parallel can be drawn with the carbon CNOs/polymethyl metacrylate (PMMA) [299], CNOs/poly-
nanotubes (CNT) chemistry. For example, the direct method of aryl dimethylsiloxane (PDMSO) [300], and CNOs/polyurethane (PU)
diazonium salt reduction producing radicals is widely employed on [301], CNOs/PMMA thin films [302,303]. Macutkevic et al. (2008)
CNT, but the same approach (either solvent based or solvent free) presented the spectral forms of carbon nano onion-polymethyl
failed for carbon nano onions. This may be due to the decreased methacrylate CNOs-PMMA composite films in the terahertz fre-
surface chemical reactivity, because of defects and shrinkage within quencies up to 3 THz. The electromagnetic (EM) shielding of CNOs-
the graphite sheet and its curvature. Parallelly as the particle size PMMA films showed quasi-resonant behavior in the frequency
increases the sp2 carbon surface stability also increases resulting in range near 0.3e0.5 THz. The obtained resonant character of the
non-reactive surface sites and a decrease in reactivity [70,296] composite films depends on the used concentration of CNOs. The
respectively. Similarly the diazonium chemistry also fails for carbon obtained absorption bands are also related with excitation of
nano onions. It is thought to be due to the lack of any existing free plasmon modes. They observed that the use of CNOs in the polymer
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impacts on the dielectric properties in the THz frequency range signature for double-layer capacitors. They found that the amount
which opens a new route for potential applications [303]. Shen- of CNOs in the polymer matrix influenced the porosity and the
derova et al. demonstrated that the fabrication of detonation orig- capacitance of the composite systems. Both composites displayed
inated CNOs/polydimethylsiloxane (PDMSO) and CNOs/ relatively similar capacitance in the presence of CNOs. Whereas, in
polyurethane (PU) composites by simple mixing of the onions in a the absence of CNOs, the capacitances of neat Chitosan and PDDA
suitable solvent. They primarily mixed carbon nano onions in a films were very low [308]. Bhaumik et al. (2020) fabricated sulfur
suitable solvent so as to avoid any agglomerations when mixed in treated polyaniline (PANI) nanotubes modified with Ni(OH)2 nano-
the polymer matrix. They found that by increasing the onion con- sponge and carbon nano onions (CNOs) produced from used car
centration, loss tangent (tan (d) and dielectric constant: εr) of the tyres. The carbon nano onions were synthesized from waste tyres
composites also increases [304]. They concluded that carbon nano by modified Hummers protocol before being annealed at high
onions are an important additive for the synthesis of multifunc- temperatures. SeNi(OH)2@PANI/CNOs composites were modified
tional polymer composites especially in the field of microelec- as an anode material for supercapacitor application [199]. Mamidi
tronics. Gavrilov et al. (2009) fabricated Polystyrene (PS)/CNOs et al. (2020-a) fabricated Gelatin(GL)/poly 4-hydroxyphenyl meth-
composites by rolling PS satiated CNO powder, obtained by acrylated (PHPMA)-carbon nano onions (CNOs) based composite
annealing of NDs from the detonation process at 2140 K (1867 C). hydrogels via sonochemical method. The GL-PHPMA-CNO com-
Their studies showed that the uniformity of CNOs dispersion in PS posite displayed stable colloidal dispersion in water for more than
matrix was dependent on the cycles of rolling stages. The perco- 12 months. With increasing GL-PHPMA-CNOs concentration as
lation threshold in the composite was achieved with CNOs pro- filler within the hydrogel matrix, the water swelling decreased due
portions of 35e40 wt % [305]. Du et al. (2003) and Kuzhir et al. to increased physi-sorption because of the physical crosslinking
(2009) successfully fabricated CNOs/PMMA composites via coagu- sites available in the polymer chains of the gel matrix. This swelling
lation technique [306,307]. Kuzhir et al. 2009 additionally fabri- phenomenon is coherent with some nanofiller added composite
cated CNOS/epoxy composites along with CNOs/PMMA hydrogels. Mechanical properties like fracture toughness, yield
respectively. The CNOs content was kept constant at 10 wt % in their strength, tensile strength and elastic modulus of the hydrogel
studies. They also reported that the CNOs/PMMA showed increased composite improved to a greater extent. The composite showed
EM reflection than their CNOs/epoxy counterparts. This was high quality interaction with osteoblast cells with good adhesion,
attributed to the better adhesion and percolation of CNOs as filler cell viability and growth. The composite hydrogel was conjugated
within the polymer host matrix. The PMMA showed homogeneous with 5-fluorouracil which displayed pH-sensitive, persistent drug
and stable dispersion of CNOs unlike the epoxy which had ag- release for over 15 days. Thus the functionality of the carbon nano
glomerations within their matrix which resulted in decreased EM onions is highly dependent on their physico-chemical aspect and
reflection for epoxy composites [307]. Mamidi et al. (2019) reported surface modification, which grants substantial control over its
the first covalently functionalized nanocomposites of carbon nano properties. Such materials are believed to be a great boon for the
onions with mercaptophenyl methacrylate (MPMA) and the ultra- biomedical industry especially the cartilage tissue engineering and
high molecular weight-polyethylene/functionalized carbon nano in theranostics [193]. Mamidi et al. (2020-b) synthesized poly4-
onion (U-HMW-PE/f-CNOs) respectively. The U-HMW-PE/f-CNOs mercaptophenyl-methacrylated-carbon nano onions (PMPMA-
nanocomposites were synthesized by solution mixing succeeded CNOs) composites which were then loaded with poly-ε-capro-
by hydraulic pressing. They assessed the biocompatibility of these lactone (PCL) nanofibers and later were coated with chemothera-
composites with the human-osteoblast cells, where they demon- peutic drug doxorubicin hydro chloride(DOX). The nanocomposite
strated excellent viability and cell growth in-vitro for over 14 days fibers of DOX@PCL-PMPMA-COs were formed by Forcespinning®
without any cytotoxicity. They found that as the concentration of f- (FS) technique. pH 6.5 showed 87%, and pH 5.0, the composite was
CNOs (0.1 wt%) increased within the U-HMW-PE composite, freely releasing the drug with 99% efficiency in a controlled state. As
biocompatibility towards the surface of the bone cells also the composite is pH sensitive the control of the drug can be tuned
increased. Apart from this the mechanical strength (yield, elastic accordingly. The controlled release of the DOX drug from the PCL-
modulus, tensile and fracture toughness) improved greatly over PMPMA-CNOs nanofibers is attributed to the stacking inter-
83% in comparison with neat U-HMW-PE. This remarkable actions(p-p type) between the polymerized/functionalized CNOs
improvement in the property is attributed to the degree of and DOX. Similar to other research reports, the carbon nano onion
dispersion and polymer wrapping of the carbon nano onions, its as a filler has improved the mechanical, colloidal dispersion, bio-
axis orientation in matrix and the interfacial strength between the compatibilty and thermal properties of the sample [194]. Recently,
host and matrix respectively. They emphasized that these non-toxic zein protein reinforced poly 4-mercaptophenyl methacrylate-
U-HMW-PE/f-CNOs composites holds promising scope in the field carbon nano onions (PMPMA-CNOs) hydrogel composites have
of manufacturing artificial biomedical implants with great pros- been developed by the acoustic cavitation technique. The com-
pects in arthroplasty [192]. Breczko et al. (2012) reported the posites were assessed for the controlled release of 5-fluorouracil
fabrication of small carbon nano onions (CNOs)/poly(- under gastric and intestinal pH conditions, for which the authors
diallyldimethylammonium chloride) (PDDA) nanocomposite films believe this composite system could be a potential candidate for
as the first sensor to detect low dopamine levels between 5 105 pH-responsive drug conveyor for a colon theranostics system [309].
and 4 103 mol/L, range respectively, in the presence of uric and Kuzhir et al. (2012) fabricated carbon nano onion (CNO)-based
ascorbic acids respectively. The sensor also demonstrated simul- polymer composite for electromagnetic (EM) shielding properties.
taneous assessment for all three molecules in the solution. They CNOs are obtained by the annealing of detonated nanodiamond
fabricated the CNO/PDDA composites by solution mixing process under an inert atmosphere. Efficacy of EM shielding was tested in
followed by drop coating method on to the electrode surface as the frequency range of 26e37 GHz. The maximum EM attenuation
described in their earlier work [38,308]. In 2010 Breczko et al. had at 36.6 GHz reaching 34 dB was detected for poly-
also fabricated CNO/Chitosan and CNO/PDDA nanocomposite films methylmethacrylate films comprising 20 wt% of CNOs. Experi-
using the above stated methods and employed them to test their mental data confirmed that CNOs EM shielding capacity can be
electrochemical properties. The films were stable after exposing to optimized by varying the nano onion cluster size and nanodiamond
prolonged potential cycles. The voltammetry studies showed that annealing temperature so that effective EM coatings can be pro-
the films display a pseudo-rectangular profile which is a typical duced. On the basis of observations it was proved that small
565
amount additions of CNOs particles to a polymer host can notice- improves the biocompatibility and water reabsorption of the films,
ably modify the composite response to EM radiation [310]. a fact that stimulates tissue regeneration. The degradation of films
Olejnik et al. (2018) fabricated polyaniline nanotube (PANINT)e in stimulated body fluid (SBF) showed losses between 14% and 16%
carbon nano-onion (CNO) composites for solid-state super- of the initial weight after 25 days of treatment. Still, a faster
capacitors by using the template method. Specially, the nano- degradation (weight loss and pH changes) were obtained with
structural properties of both the mentioned components and the composites of CS-g-CNO due to a higher SBF interaction by
unique perpendicular organization of the conducting nanotubes hydrogen bonding. The stability of the samples were found to
relative to the surface electrode affected the unusual electro- decrease with higher concentration of chitosan (CS). The lower
chemical properties of these materials. The electrochemical per- stability was due to higher CS proportion, which alleviates the
formance of the composites is affected by the mass of carbon bonding of hydrogen with water leading to the decrease in water-
nanostructures. The PANINT/CNOox composites exhibited a high resistance capacity. A lower dispersion of CNOs within the matrix
specific capacitance ca. 950 F/g. The most important benefit of was recorded because of hydrogen bonding with CS/PVA chains,
composites is their potential application as a conductive material in which is also confirmed by histological studies and SBF hydrolytic
solid-state supercapacitors [311] respectively. Macutkevic et al. degradation respectively. For the hydrolytic degradation, composite
(2009) studied the dielectric behavior in terms of complex samples with CS-g-CNO lost 14e16% of their initial weight after 25
permittivity of polymethylmethacrylate (PMMA) thin films with days, due to higher affinity with water. This result correlates well
embedded CNO within a frequency range from 20 Hz to 1 MHz with in-vivo studies carried out after 30 days of subdermal im-
[312]. It is found that the observed beta transition in CNOs/PMMA plantation in Wistar rats with no further immune response [316].
films is practically independent on CNOs concentration. It indicates Macutkevic et al. (2010) studied the dielectric properties of carbon
that the loaded CNOs do not represent any effect of the rotation nano onion (CNOs)/polyurethane composite in the frequency range
degree of freedom of the ester groups along the polymer chains. up to 1 MHz. It was determined that the cured samples which were
Further, it is also noted that increase in concentration of the CNOs annealed at temperatures near to the melting point (450 K),
affects the glass and melting temperatures of the composites. On exhibited significantly higher electrical conductivity and dielectric
the basis of the structural properties of the CNOs/PMMA composite, permittivity in comparison with the untreated samples. The electric
it is concluded that CNOs based composite can be used as elec- conductivity, dielectric permittivity and increased critical fre-
tromagnetic materials [299,312]. Izadi et al. (2019) demonstrated quency of an untreated sample tend to increase with increasing
the elastic properties of fullerene (C60) and carbon nano onion temperature, whereas, aggregate size of CNOs and the
(C60@C240) reinforced poly methyl methacrylate (PMMA) and the MaxwelleWagner average relaxation time decreases. Composites
simulation using molecular dynamic (MD). The polymer compos- after annealing close to melting temperatures, helps in achieving
ites are fabricated by embedding C60 and the C60@C240 into polymer homogeneous dispersion of CNOs within its matrix. It was found
matrix. The young's modulus of the polymer composite increases that, the weak positive temperature coefficient in the homoge-
with increasing weight fractions of the additives, which is consis- neous sample induced temperature dependent conductivity [317]
tent with experimental observations. The composite containing respectively.
4 wt% of C60 exhibits Young's modulus of 3.774 GPa that is 24%
higher than pure PMMA. The validity of the simulation is verified by 7. Global research trends on carbon nano onion and
the comparing it with the experimental results [313]. Bobrowska composites
et al. (2017) fabricated a composite based on carbon nano-onions
(CNO) and polyethylene glycol (PEG 400) as a carrier of 1,2,3,4,6- Since the discovery, several research articles have been pub-
penta-b-O-galloyl-D-glucopyranose (b-PGG) for biomedical appli- lished. Owing to carbon nano onion's unusual anatomy and
cations. The designed biocompatible nanostructures can be applied arrangement of the sp2 graphene concentric rings, which garnered
for bio sensing of the particular peptides [314]. Papathanassiou a global spark in knowing its potential in parallel to the carbon
et al. (2015) studied the dielectric permittivity and fabricated nanotubes. Several researchers around the globe started synthe-
electrically conducting carbon nano-onion/polyaniline (CNO/PANI) sizing this novel and revolutionizing carbon nanomaterial but the
composites. The Broadband Dielectric Spectroscopy (BDS) showed only hindrance was its low yield. Then in 1994, breakthrough
a ColeeCole relaxation mechanism by applying temperature (from occurred in the large scale synthesis of carbon nano onions by
16 K to 298 K) in the frequency range between 1 mHz and 1 MHz. Kuznetsov et al. [12]. Soon after Kuznetsov's novel synthesis
Relaxation intensity is comparable with the observed large static approach, the research in this field exponentially grew by several
dielectric constant, and showed a relationship between relaxation Universities, R&D institutions, and other private and governmental
and intense capacitance effects. The obtained relaxation dynamics establishments all around the world. Research on carbon nano
require single or two phonon assisted tunneling of the relaxing onions is found in every scientific discipline, as of today. In the
electric charge carriers (protons and electrons) at low tempera- present section, we look into the past and current prospects, with
tures, which changes to multi-phonon assisted tunneling relaxa- an overview of a number of research work published, highlighting
tion above 100 K. Also, MotteDavis model showed phonon-assisted the global thrust in carbon nano onion research respectively. The
tunneling relaxation in unordered media, the typical spatial scale following sections attempts to address the present scenario and the
relaxation was found to be in agreement with the size of carbon prominence of carbon nano onion research. The research and re-
nano onions. Whereas, the capacitance was in agreement with the view articles published since the last decade shows the quality,
carbon nano onion's large and effective surface areas [315]. quantity and the intensity of carbon nano onion research on the
Recently, Tovar et al. (2020) fabricated scaffolds based on bio- basis of its publications along with an aim towards patenting. Here,
compatible nanocomposite films of chitosan/polyvinyl alcohol/ the authors attempt to update this trend related to the current
chitosan-grafted-carbon-onions (CS/PVA/CS-g-CNO) and it was growth of its publications and patents respectively.
used for injury based biomedical applications. Successful prepara-
tion of CS/PVA/CS-g-CNO was confirmed from the mechanical, 7.1. Publication and citation metrics of carbon nano onions since
chemical, subdermal implantation and thermal tests. Thermal and 1980e2020
mechanical stability were found to be lower in the fabricated
composite films. Carbon nano onion grafting with chitosan Search engine like Web of Science (WoS) was utilized for
566
analyzing the publication and citation metrics [318] for the search contribute to majority share of the publications followed by all
string “carbon onion” as “title” within the year range from 1980- other countries contributing from 0.1% to 7.5% of publications
present (April 2020). String “carbon onion” as only “title” also around the globe (data not shown). Fig. 30e shows the subject wise
showed results of all nanocomposites of carbon onion. It should be distribution, it is evident that the carbon nano onion based research
noted that the point of using the staring year as 1980 for search was is highly multi-disciplinary and majority of the data published re-
to fetch data related to earlier publications but due to the string it lates to the fields of chemistry (68%), material science (68%), physics
showed only 656 results from 1992 highlighting Ugarte's discovery (62%); science technology topics (50%); engineering(38%) and so
and its naming as “onion” as main source. We avoided the use of on. This indicates the significance given to carbon nano onion
string carbon onion as “topic” category because the search had research based on its quantity and quality of research around the
yielded several un-related articles to different category of onion as globe. Based on the present scenario, it is forecasted that by the
in vegetable/farming. Hence only “title” category containing “car- year's end (2020), the research and application based competition
bon onion” as a single word string was employed which yielded will intensify amongst several countries for the applications,
only 656 publication records. From the (Fig. 30a) we can observe quality, commercial products and patents, highest position, and
that there was a steady rise in the research and publication of ar- future markets for carbon nano onion based products respectively.
ticles related to carbon nano onions along with their composites.
Within the last 5 year we can observe that there has been some
growing interest amongst the researchers in exploring the further 7.2. Patent analysis
use of carbon nano onions for their respective applications. For the
years 2018e2019 there have been a total of 133 publications and by A successful outcome of a research work in the form of Patents
the mid of April 2020 the publication reached almost halfway with often plays an important and prime role for the scientific and in-
respect to the year 2019. Authors believe that there would be more dustrial platform [318]. Scopus search tool was employed here to
and double publications yet to be recorded in the coming year end. search and analyze the patent metrics. Fig. 31a, shows the year wise
All these publications (656), were cited (Fig. 30b) heavily and patent analysis for the years 1992e2020. As discussed in the pre-
overall citations recorded till April 2020 were 19,683, off which vious section patents similar to the publication results related to
4505 were self-cited. Year 2019 marked the highest citations with a onion as title were observed only from 1994 onwards post Ugarte's
record of 2766 times. For the present year (April 2020), 810 cita- 1992 publication. As the years passed a steady rise in patents can be
tions were recorded, which is almost 1/3rd times the previous year. seen with the highest number of patents granted in 2016(69 pat-
Fig. 30c shows document wise distribution where majority of them ents). With the trend decreasing now shows that a lot of unex-
are related to research articles contributing to almost 95% of the plored application is to be researched so as to get the patents
total documents published where only 2% of the documents are granted in for the coming years under various applications. Fig. 31b,
related to review articles. Fig. 30d shows top 20 countries actively shows distribution of patents issued by different patent offices
involved in carbon nano onion research where China (192 publi- around the world. Based on the string “carbon onion” we can see
cations; 29% of total publication), USA(25%) and Russia(12%) that United States Patent and Trademark Office (USPTO) has the
most patents registered through them followed by Japan Patent
Fig. 30. Metrics data of carbon nano onions from 1992 to 2020. (a) Year wise publication data; (b) Year wise citation data; (c) Pie diagram of document wise distribution; (d) Pie
diagram of top 20 country based publications; (e) Pie diagram of subject wise distribution. (A colour version of this figure can be viewed online.)
567
Fig. 31. Patent metrics of carbon nano onion published from 1992 to 2020. (a) Year wise patents published; (b) Number of patents issued by different patent offices. (A colour
Office (JPO), World Intellectual Property Organization (WIPO), Eu- their peculiar structure. Though, carbon nano onions were
ropean Patent Office (EPO) and United Kingdom Intellectual Prop- discovered a decade earlier than carbon nanotubes, these highly
erty Office (UKIPO) respectively over the period from 1980 till attractive structures gained attention much later but were highly
present day(April 2020) respectively. limited. It should be noted that carbon nano onions have proved
their unusual niche in this scientific universe. They offer myriad,
7.3. Commercial aspect of carbon nano onion applied opportunities with realistic applications. This small, ringed
nanostructured carbon has demonstrated some very interesting
According to Liu et al. (2019), the cost of a ton of carbon nano applications which includes electromagnetic shielding, super-
onions would be valued more than $1million [319]. Few researchers lubricity, biomedical, anti-corrosion, catalysis etc. In this review
are working round the clock to ease the cost burden to $1000 per an attempt has also been done to showcase their capacity as a
ton by introducing novel chemical routes for the synthesis of CNOs potential candidate in electrochemical storage applications as well.
by molten carbonate electrolysis (exclusive of anode costs) this It was presented with two major areas outlining their applications
alternative can prove beneficial with several orders of magnitude in the field of metal ion battery and supercapacitors respectively. In
[319]. Liu et al. (2019) in their review, reported that the challenges order to render extra perception and flavor, patent analysis, market
faced for the bulk production has limited the commercial avail- outcome and literature citation metrics data, since the discovery of
ability of the carbon nano onions. According to Liu, one of the carbon nano onions is included to understand the emphasis given
producer sells quasi-spherical carbon nano onions(40 ± 20 nm) in on this beautiful nanostructure till date since its discovery.
gram quantities inclusive of the academic discount, with a stag- Furthermore, authors believe that, once the commitment of an
gering rate extrapolated to $195 million per ton and another sells endless, green energy demand is materialized with the help of
37 ± 7 nm with 50e55 layers for 0.1 g unit to a very high price of storage devices fabricated with these materials (carbon nano on-
$3350 million per ton [319] respectively. ions and any other structures with high energy output), it will
prove to be a great achievement and a scientific boon in mitigating
8. Outlook and conclusion the serious effects of pollution on our environment. Hence it is
highly important to explore further research boundaries in opti-
In this review, we have investigated carbon nano onion syn- mizing the properties of carbon nano onions for future research and
thesis, history, morphology and structure, growth mechanism in development of clean energy, biomedical and intelligence bound
different synthesis routes, purification strategies, chemical, elec- smart devices respectively to name a few.
tronic, optical, electromagnetic and tribological properties followed
by their electrochemical based energy storage applications, poly-
Declaration of competing interest
mer composites of carbon nano onions with various applications,
global research, publication and patent trends with some brief in-
The authors declare that they have no known competing
formation on the commercial aspect of CNOs respectively.
financial interests or personal relationships that could have
Evidently in the present era, the research activities in carbon, in-
appeared to influence the work reported in this paper.
troduces us with its intriguing challenges, new allotropic states,
phenomenal discoveries, novel routes in design and preparation of
fascinating new structures, and also exploration of prospective Acknowledgement
material application. Nanostructured carbonaceous materials and
carbon nano onion in specific has shown some higher possibilities This work was supported by the Basic Science Research Program
of hybrid, better dispersibility, possession of extraordinary physico- through the National Research Foundation of Korea (NRF) funded
chemical properties, good nano-porous features, electrical con- by the Ministry of Education, Science and Technology (Project
ductivity, chemical interactions, stability and other scientific for- Number: 2020R1A2B5B02002203) and (Project Number: NRF-
mations and phenomenons than their other counterparts owing to 2020R1I1A3071046).
568
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Contents lists available at ScienceDirect

A comprehensive review on the prospects of multi-functional carbon

1. Introduction: definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

5.2. Electronic property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548

1. Introduction: deﬁnition 1.2. Structure

4. Puriﬁcation of carbon nano onions

Several efforts are being made to develop novel techniques for

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