SCIENCE

RES EARCH
◥ capacitance, and diffusion-limited inter-

REVIEW SUMMARY calation processes. The development of new
high-performance materials, such as redox-
NANOMATERIALS active transition-metal carbides (MXenes) with
conductivity exceeding that of carbons and
Energy storage: The future enabled by nanomaterials other conventional electrode materials by at
least an order of magnitude, open the door
Ekaterina Pomerantseva*, Francesco Bonaccorso*, Xinliang Feng*, Yi Cui*, Yury Gogotsi* to the design of current collector–free and
high-power next-generation energy storage
devices. The combination of nanomaterials in
BACKGROUND: Nanomaterials offer greatly im- oxides, chalcogenides, and carbides to carbon hybrid architectures, such as carbon-silicon
proved ionic transport and electronic conduc- and elements forming alloys with lithium. This and carbon-sulfur, together with the develop-
tivity compared with conventional battery and library includes various particle morphologies, ◥
ment of versatile methods
supercapacitor materials. They also enable the such as zero-dimensional (0D) nanoparticles ON OUR WEBSITE of nanostructuring, over-
occupation of all intercalation sites available and quantum dots; 1D nanowires, nanotubes, and Read the full article come challenges related
in the particle volume, leading to high specific nanobelts; 2D nanoflakes and nanosheets; at http://dx.doi. to large volume change
capacities and fast ion diffusion. These fea- and 3D porous nanonetworks. Combined with org/10.1126/ typical for alloying and
tures make nanomaterial-based electrodes lithium and beyond lithium ions, these chem- science.aan8285 conversion materials. These
..................................................
able to tolerate high currents, offering a pro- ically diverse nanoscale building blocks are examples indicate that
mising solution for high-energy and high- available for creating energy storage solutions nanostructured materials and nanoarchitectured
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power energy storage. However, there are such as wearable and structural energy stor- electrodes can provide solutions for designing
still many challenges associated with their age technology, which are not achievable with and realizing high-energy, high-power, and
use in energy storage technology and, with conventional materials. long-lasting energy storage devices.
the exception of multiwall carbon-nanotube
additives and carbon coatings on silicon par- ADVANCES: The success of nanomaterials in OUTLOOK: The limitations of nanomaterials in
ticles in lithium-ion battery electrodes, the use energy storage applications has manifold as- energy storage devices are related to their high
of nanomaterials in commercial devices is very pects. Nanostructuring is becoming key in con- surface area—which causes parasitic reactions
limited. After decades of development, a lib- trolling the electrochemical performance and with the electrolyte, especially during the first
rary of nanomaterials with versatile chemical exploiting various charge storage mechanisms, cycle, known as the first cycle irreversibility—
compositions and shapes exists, ranging from such as surface-based ion adsorption, pseudo- as well as their agglomeration. Therefore, fu-
ture strategies aim to develop smart assembly
of nanomaterials into architectures with con-
1D materials trolled geometry. Moreover, combining nano-
materials with complementary functionalities,
such as high electronic conductivity of gra-
phene or MXenes with high operating voltage
and high redox activity of oxides, is necessary.
Building sophisticated electrode architectures
requires innovative manufacturing approaches,
such as printing, knitting, spray deposition,
and so on. Already-developed techniques such
Applications
as 3D printing, roll-to-roll manufacturing, self-
assembly from solutions, atomic layer deposi-
tion, and other advanced techniques should be
Spray coating, used to manufacture devices from nanomate-
ink-jet printing 3D printing, electrospinning rials that cannot be made by conventional
slurry-based methods. Such manufacturing
approaches can also enable long-sought flex-
ible, stretchable, wearable, and structural
energy storage and harvesting solutions
for Internet of Things and other disruptive
0D materials 2D materials technologies.
▪
The list of author affiliations is available in the full article online.
*Corresponding author. Email: [email protected] (E.P.);
Roll-to-roll manufacturing [email protected] (F.B.); xinliang.feng@tu-dresden.
Self-assembly into complex architectures de (X.F.); [email protected] (Y.C.); [email protected] (Y.G.)
Cite this article as E. Pomerantseva et al., Science 366,
eaan8285 (2019). DOI: 10.1126/science.aan8285
Nanomaterials for energy storage applications. The high surface-to-volume ratio and short diffusion
pathways typical of nanomaterials provide a solution for simultaneously achieving high energy and power
density. Furthermore, the compatibility of nanomaterials with advanced manufacturing techniques—such TOMORROW’S EARTH
as printing, spray coating, roll-to-roll assembly, and so on—allows for the design and realization of wearable, Read more articles online
flexible, and foldable energy storage devices. at scim.ag/TomorrowsEarth
Pomerantseva et al., Science 366, 969 (2019) 22 November 2019 1 of 1

RES EARCH
◥ large volume expansion and contraction (19, 20),

REVIEW which can cause mechanical and chemomech-
anical instability across the length scales of
NANOMATERIALS individual nanoparticles, electrodes, and full
electrochemical cells (21, 22). Coatings with
Energy storage: The future enabled by nanomaterials nanoscale thickness obtained via atomic or
molecular layer deposition may be needed to
Ekaterina Pomerantseva1,2*, Francesco Bonaccorso3,4*, Xinliang Feng5,6*, Yi Cui7*, Yury Gogotsi1,2* suppress parasitic interfacial reactions, includ-
ing the growth of metal dendrites, and/or
Lithium-ion batteries, which power portable electronics, electric vehicles, and stationary storage, have form an artificial solid-electrolyte interphase
been recognized with the 2019 Nobel Prize in chemistry. The development of nanomaterials and their (SEI) layer leading to the improved stability of
related processing into electrodes and devices can improve the performance and/or development of the electrochemical cells (23–27). Achieving future
existing energy storage systems. We provide a perspective on recent progress in the application of advancements in this research area will re-
nanomaterials in energy storage devices, such as supercapacitors and batteries. The versatility of quire broadening the compositional chemistry
nanomaterials can lead to power sources for portable, flexible, foldable, and distributable electronics; of interfacial layers and developing nano-
electric transportation; and grid-scale storage, as well as integration in living environments and technology approaches that would allow for
biomedical systems. To overcome limitations of nanomaterials related to high reactivity and chemical pinhole-free coating of 3D architectures with
instability caused by their high surface area, nanoparticles with different functionalities should be varying porosity. Advances in the develop-
combined in smart architectures on nano- and microscales. The integration of nanomaterials into ment of autonomous microsystems and micro-
functional architectures and devices requires the development of advanced manufacturing approaches. devices call for smaller power sources. As a

We discuss successful strategies and outline a roadmap for the exploitation of nanomaterials for result, many of the future energy storage de-
enabling future energy storage applications, such as powering distributed sensor networks and flexible vices need to be just several microns or even
and wearable electronics. tens of nanometers thick. Therefore, thin film
electrode and electrolyte layers need to be
E
grown or printed not only on flat chips but
nergy usage is experiencing a large and The short diffusion path can enable the use also on surfaces of various shapes, such as
fast shift toward electricity as the main of nonflammable solid electrolytes, leading to packaging materials, or created as wearable
power source. Reversible storage and re- safer batteries, and large or multivalent ions tattoos, requiring manufacturing processes
lease of electricity is an essential technol- for more affordable grid-scale applications. which differ drastically from the current bat-
ogy, driven by the needs of portable In addition to active energy-storing nanomate- tery manufacturing practice.
consumer electronics and medical devices, rials, passive components can benefit from the This review takes a holistic approach to en-
electric vehicles, and electric grids, as well as use of nanomaterials as well. For example, ergy storage, considering battery materials
the emerging Internet of Things and wearable ultrathin hexagonal boron nitride (h-BN) and that exhibit bulk redox reactions and super-
technologies. These applications and the need metal oxide separators and graphene or two- capacitor materials that store charge owing
to store energy harvested by triboelectric and dimensional (2D) transition-metal carbide to the surface processes together, because
piezoelectric generators (e.g., from muscle move- (MXene) current collectors can decrease nanostructuring often leads to erasing boun-
ments), as well as solar panels, wind power the size and weight of the batteries (4, 5). daries between these two energy storage solu-
generators, heat sources, and moving machin- Today, we possess a large library of nano- tions. We explain how the variety of 0D, 1D,
ery, call for considerable improvement and particles and nanostructured materials with a 2D, and 3D nanoscale materials available
diversification of energy storage technology. variety of compositions, electrochemical prop- today can be used as building blocks to create
In this context, materials with nanometer- erties, and morphologies ranging from 0D functional energy-storing architectures and
sized structural features and a large electro- nanoparticles and quantum dots (6, 7) to 1D what fundamental and engineering problems
chemically active surface can change the nanowires, nanotubes, and nanobelts (8, 9), to need to be resolved to enable the distributed
paradigm for energy storage from within the 2D nanoflakes and nanosheets (10–13), and to energy storage required by the technologies of
electrode bulk to surface redox processes that 3D porous networks (14–17) (Fig. 1). the next decade.
occur orders of magnitude faster and allow a However, some of the challenges related to
greatly improved power and cycle life (1–3). the reactivity of nanomaterials are due to their Nanomaterials platform
High electronic and ionic conductivities com- high specific surface area (SSA), which leads to Figure 1 shows the variety of available 0D to
bined with intrinsic strength and flexibility of parasitic, and often irreversible, reactions and 3D nanomaterials (nanoscale building blocks).
low-dimensional materials allow ultrathin, flex- strong interaction with electrolyte (1, 2); in What emerges is the large family of carbon
ible, and structural energy storage solutions. addition, cost and manufacturability of nano- nanomaterials (Fig. 1, top row). Carbon is
materials make the battery community skepti- invaluable for energy storage owing to its
cal about their promise for practical applications. properties, such as low specific weight and
1
A.J. Drexel Nanomaterials Institute, Drexel University, Although the number of studies of various high abundance, coupled with the high elec-
Philadelphia, PA 19104, USA. 2Department of Materials phenomena related to the performance of tronic conductivity of graphitic carbons. More-
Science and Engineering, Drexel University, Philadelphia, PA
19104, USA. 3Graphene Labs, Istituto Italiano di Tecnologia,
nanomaterials in energy storage is increasing over, because of sp/sp2/sp3 hybridization,
16163 Genova, Italy. 4BeDimensional Spa, 16163 Genova, year by year, only a few of them—such as multiple carbon structures and morpholo-
Italy. 5Center for Advancing Electronics Dresden (CFAED), graphene sheets, carbon nanotubes (CNTs), gies are available. However, nanostructured
Technische Universität Dresden, 01062 Dresden, Germany.
6
Faculty of Chemistry and Food Chemistry, Technische
carbon black, and silicon nanoparticles—are carbons usually provide limited, if any, redox
Universität Dresden, 01062 Dresden, Germany. 7Department currently used in commercial devices, primar- capacity and only after functionalization
of Materials Science and Engineering, Stanford University, ily as additives (18). (28, 29). Therefore, they are usually used as
Stanford, CA 94305, USA.
High-capacity conversion (sulfur and fluo- a double-layer capacitor material, or as a con-
*Corresponding author. Email: [email protected] (E.P.);
[email protected] (F.B.); [email protected] rides) and alloying (Si and Sn) materials un- ducting support backbone (28, 29), rather than
(X.F.); [email protected] (Y.C.); [email protected] (Y.G.) dergo considerable structure changes and as active material for energy storage devices.
Pomerantseva et al., Science 366, eaan8285 (2019) 22 November 2019 1 of 12

RES EARCH | R E V I E W
0D 1D 2D 3D
Carbon Onion Single Wall Carbon Nanotube Graphene Pillared Graphene
Nanoparticles Multiwall Nanotube Multielement 2D Compounds Metal-Organic Frameworks

Quantum Dots Nanowires Nanoflakes Aerogels
Advantages
Small in all dimensions Mechanical reliability Open 2D channels for ion Can be used to create
Surfaces on all sites are Possibility to integrate with transport; all surface is thick electrodes with
accessible to electrolytes wearable devices accessible enabling fast large areal and
No bulk solid-state diffusion Porous flexible freestanding charge storage volumetric storage
Can be integrated into films Compatible with flexible properties
multiple systems devices
Can be used in stable inks Small nanoflakes can be
for printing used in inks for printing
Limitations
Agglomeration Low packing density; cannot Re-stacking Design
Do not densify and form only exhibit high volumetric Low out-of-plane electronic Stability
low density non-uniform performance and ionic conductivity Manufacturing
structures Low yield and high cost of High cost of synthesis
Numerous points of contact synthesis
lead to high resistance Diffusion pathways can be
Poor chemical stability relatively long
Fig. 1. Overview of 0D, 1D, 2D, and 3D nanomaterials. An illustration of the chemical, structural, and morphological diversity of the available nanoscale building
blocks that can be used to create complex functional architectures for next-generation energy storage devices with improved performance compared with the
currently available ones. The advantages and challenges related to the application of each class of nanomaterials are summarized in the last two rows. [Metal organic
frameworks, pillared graphene, quantum dots, and aerogels images reproduced with permission from (140–143), respectively; nanowires and nanoflakes images by
Yayuan Liu/Stanford University and Meng-Qiang Zhao/Drexel University, respectively.]
The exception is graphite, which consists of an state diffusion limitations. More recently, high- electrodes for energy storage but can also be
ordered stack of graphene layers and exhibits ly crystalline conductive materials—such as used as precursors to develop carbon-rich mate-
a specific capacity of 372 mA·hour g−1 for lith- metal organic frameworks (33–35), covalent rials for energy storage (38).
ium ion storage in between the layers (30). organic frameworks (36), MXenes, and their In addition to chemical diversity, advances
A more conventional approach to achieving composites, which form both 2D and 3D in nanomaterial synthesis enable control of
high specific capacity is to exploit redox re- structures—have been used as electrodes for morphological dimensionality, ranging from
actions in nanomaterials and thus utilize energy storage. They show promise to deliver 0D to 3D nanostructures (Fig. 1), each of which
materials beyond carbons. High surface area high areal capacity owing to their high porosity, has both advantages and limitations for en-
of transition-metal compounds (oxides, sul- thus allowing the construction of thick elec- ergy storage applications. To benefit from
fides, carbides, nitrides, etc.) and pure elements trodes (37). Organic nanomaterials, especially their useful properties and alleviate short-
forming alloys with Li (Si, Ge, Sn, etc.) (31, 32) heteroatom-rich molecules and porous organic comings, redox-active 0D nanoparticles can
allow those reactions to occur without solid- materials, not only can be directly used as be decorated on the surface of conductive 1D

and 2D materials with a double function— are less prone to catching fire (8). The empty the intrinsic electronic and electrochemical
that is, preventing their aggregation and space between 1D structures allows the design properties. Moreover, restacking of 2D struc-
restacking—while at the same time contrib- of zero-expansion electrodes, leading to in- tures limits electrolyte penetration and ionic
uting to charge storage. Examples of such creased lifetime and decreased mechanical, transport (57). Smart architectures should have
structures are demonstrated by graphene- thermal, and resistive losses. This property is sufficient porosity and enlarged interlayer dis-
oxide (6, 39, 40) or MXene-oxide hybrids with particularly important for alloying anodes, tance, as well as vertical alignment of 2D sheets
enhanced energy storage capabilities enabled such as Si, Ge, or Sn, in accommodating vol- enabling fast electrolyte penetration, while still
by the redox activity of oxide nanoparticles ume changes associated with interaction with enabling dense packing of nanoflakes. Hybrid-
and the high electronic conductivity of graphene up to 4.4 Li+ ions per atom (3). The downside of ization of 2D sheets with 0D and 1D nano-
(41) or MXene (42). When produced as nano- 1D nanostructures is their low packing density, materials can either minimize or completely
scale particles, even typical battery materials which makes the design and realization of eliminate the restacking issue. Preventing re-
can show pseudocapacitive behavior (pseudo- 1D nanomaterial–based electrodes with high stacking is also important to boost the per-
linear charge-discharge), as was demonstrated volumetric performance challenging (3). A formance of catalytically active 2D materials
for 6-nm nanoparticles of LiCoO2 (43) and will strategy to overcome this limitation could be in order to make their surface accessible to
be discussed in detail later. The self-assembly combining 1D nanostructures with 0D nano- reagents and increase the number of reaction
of 0D nanoparticles into denser systems is particles, thereby filling gaps between the sites. Layered materials and pillared clays of-
possible if the particles are monodisperse, as nanotubes or nanowires and increasing the fer opportunities for a tailored nanodesign,
shown by the assembly of oxide nanoparticles volumetric performance. The large-scale pro- including tunable interlayer spacing and mod-
on dichalcogenide sheets into ordered struc- duction of 1D nanostructures is another chal- ification of the interlayer chemistry often ac-
tures (44). Another limitation of 0D nanopar- lenge. 1D nanomaterials such as single-wall companied by improved stability, leading to

ticle electrodes is a low electrical conductivity, CNTs or silicon nanowires are difficult to pro- their diverse applications as multifunctional
owing to the contact resistance created by duce in large quantities at low cost. Another catalysts (59). Efficient strategies demonstra-
each contact point. An electrode containing limitation of 1D nanomaterials is their intrin- ted in the catalysis area can also be explored
multiple nanoparticle contact points can be sic structure-morphology relationship, which for energy storage application and vice versa.
considered as many resistors in series. If affects the electrochemical performances. For Many 3D nanomaterials, such as carbon
nanoparticles are conductive, as in the case example, for tunnel manganese oxide nano- (graphene) aerogels (14) and metal organic
of carbon onions, this problem is mitigated, wires (9, 50), the diffusion pathways are oriented frameworks (MOFs), are a result of the assem-
but for most less conductive materials, this along the length, not across the 1D nanowire, bly process of nanoparticles. Few 3D nanoma-
represents a severe limitation. Even in the and can be relatively long, up to 100 mm. terials have intrinsic nanoscale features (e.g.,
case of conducting particles, Schottky junc- For 2D nanomaterials, their primary advan- thin walls of porous templated or carbide-
tions can form (45). In addition, nanopar- tage is related to their intrinsic structure, that derived carbons); most of them are built by
ticles of certain material classes, such as is, the entire 2D surface can be accessible to combining 0D, 1D, and 2D nanomaterials of
dichalcogenides, are not very stable (46) and electrolyte ions, enabling fast charge storage the same kind (carbons). To produce thick
require protective treatment during both syn- (11, 42). Similar to 1D nanostructures, 2D electrodes (e.g., 100 to 200 mm) with large areal
thesis and handling. Many semiconductor and sheets can form flexible electrodes without and volumetric storage properties, it is neces-
metal nanoparticles form a passivating coat- binders (51) or other additives, but they have sary to develop 3D architectures optimized
ing layer on the surface (47), creating a barrier the added value of achieving a much higher for both ion and electron transport. These
for the charge transport, which either requires packing density and volumetric performance architectures would minimize the amount of
a further annealing step or encapsulation. compared with the 1D counterparts. Although passive materials in cells, such as current col-
A key feature of 1D structures relies on the 2D sheets can be grown on some metal sub- lectors and separators that occupy additional
possibility of forming highly conducting con- strates, and progress is being made toward volume and add dead weight. Examples of 3D
tinuous networks, by assembling conducting large-area single crystals (52), the large-scale electrodes with porous architectures that en-
1D nanomaterials (e.g., CNTs and metallic nano- bottom-up production of 2D materials is too able advances in energy storage have already
wires) over a large area and thickness of the expensive for the majority of energy storage been reported in literature (60–62). Building
electrode, leading to fast electron transport (20). applications, with the exception of small on- on these approaches, as well as developing
CNTs are already widely used as conductive chip devices. By contrast, the direct liquid- new ones, is important for moving closer to
additives in battery electrodes (20). Addition- phase exfoliation (LPE) of bulk layered crystals nanomaterials-enabled energy storage.
ally, many of the 1D nanostructures, especial- (53–55), wet chemical synthesis, and selective Despite exciting diversity, none of the avail-
ly CNTs, provide high mechanical strength etching and dealloying (transformative syn- able nanomaterials are perfect, and none of
(e.g., Young’s modulus of 0.6 TPa) (48), en- thesis) are much more relevant strategies for them can solve all the problems of the current
suring mechanical integrity of the electrodes the scalable production and processing of 2D energy storage technologies. Carbon materials
(20). Unlike the 0D particles, 1D nanomate- nanomaterials (56). The LPE process enables offer high electrical conductivity and chemical
rials do not require a binder to produce flex- the formulation of inks of 2D materials in dif- stability but a limited charge-storage capabil-
ible structures, a feature that is particularly ferent solvents (10) for printing devices (10, 11). ity. Transition-metal oxides and redox-active
attractive for wearable applications. More- 2D structures can provide high electronic con- organic materials can often offer much larger
over, although 1D nanomaterials form bundles ductivity in-plane, but there might be low elec- charge storage, but most of them have low
(49), they still produce porous electrodes en- tronic conductivity and slow transport of ions electrical conductivity. The latter issue can be
abling electrolyte penetration (20, 35). Porous in the out-of-plane direction (57, 58). Thus, the overcome by combining the aforementioned
free-standing membranes were formed using 2D morphology hinders the achievement of active materials in a physical mixture or a
Al2O3 nanowires through direct transforma- high (electro)chemical performance of thick hybrid structure with carbon or other conduct-
tion of bulk aluminum alloy into alkoxide planar electrodes with 2D sheets aligned along ing materials (20). 2D transition-metal car-
nanowires, followed by heating in air (8). the surface of the current collector (37). In bides, nitrides, and carbonitrides, classified
These membranes were used to produce cera- this respect, defect (pinhole) generation in as MXenes, possess high electronic and high
mic separators for high-rate batteries, which 2D sheets would help, if it did not sacrifice ionic conductivities (42). However, for this

class of materials, cost, stability, and an under- anism between MXene nanosheets (65). The pects is important to gain knowledge of the
standing of the electrochemical mechanisms presence of confined water or electrolyte within role of confined water in charge storage prop-
are still open issues. This field is rapidly grow- nanochannels is known to facilitate the trans- erties of nanomaterials.
ing, with more than 30 highly conductive port of ions (66), including large or multiva- It is also necessary to study the transport of
materials available, of which Ti3C2 has already lent ions, such as Mg2+ and Al3+ (67). Water or electrons, because for some low-dimensional
demonstrated exceptional values of capaci- electrolyte confinement also allows the trans- materials—such as CNTs, graphene, or Nb2C—
tance in aqueous electrolytes and excellent port of complex ions—for example, AlCl4− or quantum capacitance (74) can become a lim-
performance at rates up to 1000 V s−1 (57). Over- organic ions—which is challenging and/or iting factor. The quantum capacitance is linked
all, the availability of nanoscale building blocks cannot be achieved in conventional battery with the variation of the density of states of the
is continuously increasing. This provides a port- electrodes (68), at least not for the intercala- materials (i.e., the effect of band filling and
folio of materials with properties not achieva- tion mechanism. In the case of nanomaterials, band emptying), which modifies the capaci-
ble with the conventional materials used for we can explore fast storage mechanisms, such tance, imitating a second capacitor in series
batteries and supercapacitors. as intercalation pseudocapacitance, which is a (74). More severely, many nanomaterials, such
process determined as non–diffusion-limited as oxides, are poor electronic conductors, rais-
Fundamental processes governing insertion of ions into the active electrode mate- ing multiple questions. How can we wire them?
energy storage rial (69). Confined structural water can be bene- How can we inject electrons? Can electrons
The fundamental processes that control electro- ficial to improving charge-transfer resistance, tunnel through thin mono-, double-, or triple-
chemical performance can be somewhat differ- especially in the case of aqueous energy stor- layers of ions of electrolyte between the sheets?
ent from bulk battery materials. For example, age systems (70, 71). Moreover, it was shown What are the rate-limiting factors?
the transport of ions in nanoscale systems that there was no detrimental effect on the Hybridization of dissimilar nanomaterials—

typically occurs in confinement between or performance of nonaqueous Li-ion cells over that is, the combination of oxide nanoparticles
at the surfaces of electrode materials (Fig. 2A), several hundreds of cycles when a small amount and carbons—maximizes heterointerfaces at
as in supercapacitors with porous carbon elec- of water was added to the electrolyte (72). which new phenomena can occur, as schemat-
trodes (63), instead of the transport in bulk However, a considerable amount of water pres- ically illustrated in Fig. 2B. As a result of dif-
electrolyte and solid electrodes in conven- ent in the electrode structure can be harmful ferent work functions of carbon (e.g., graphene,
tional batteries. Examples of extreme confine- to the device operation by causing parasitic CNTs, or carbon onions) and oxide nanopar-
ment could be narrow 2D slit pores between reactions, which lead to irreversible chemical ticles (e.g., MnO2 or Nb2O5), electrons may be
2D sheets or narrow 1D channels in the struc- transformations of the device components (73). injected from the carbon into the oxide, in-
ture of tunnel oxides or nanotubes. Although As of now, there is no clear understanding of creasing the electrical conductivity of the
an understanding of such transport properties how the kind of confinement or the amount latter. Consequently, formation of holes in
is largely missing thus far, there are data that of water in the material structure, the strength graphene leads to an increase in the number
show anomalous fast transport of water in of bonds, crystallographic positions, and other of charge carriers and its quantum capaci-
hydrophobic channels of CNTs (64) or fast parameters affect the electrochemical storage tance. Faster ionic transport and different ion-
transport of protons by the Grotthuss mech- properties. A more in-depth study of these as- insertion potentials have been reported for
hybrid 2D materials (75), such as graphene
A Transport of Ions B Transport of Electrons and MoS2 (76) and graphene and Ti3C2 com-
pared with the individual components (77).
Therefore, the synergistic effects between dif-
ferent nanomaterials can be achieved by com-
+ + + bining materials with different properties.
Apex
One challenge is the avoidance of unwanted
chemical reactions associated with the high
+ + + SSA of nanomaterials, which reaches to more
than 2000 m2 g−1 for porous carbon and
graphene and is between 100 and 1000 m2 g−1
for most other nanomaterials, such as CNTs,
C Surface Electrode/Electrolyte Interactions D Assembly into 3D architectures
dichalcogenides, or MXenes (42). High SSA
+ + favors chemical interactions and the forma-
+ +
+ tion of SEI-like structures, often resulting in
a very large first-cycle irreversible capacity
+ + + or parasitic reactions during cycling, limiting
+ + + + + the device’s lifetime (Fig. 2C). Therefore, reac-
e– tions between nanoparticles and electrolyte
+
+ during cycling need to be studied in depth to
+ + +
fully understand and control them. An effec-
+ tive strategy to solve this problem is to as-
semble small nanostructures into secondary
+ +
particles—that is, aggregates or clusters—of
+ + Electrolyte
larger dimensions. In these structures, the
electrolyte only contacts the outer surface of
Fig. 2. Fundamental properties governing the performance of nanostructured materials for energy the secondary particles, thus reducing the ef-
storage application. (A) Transport of ions. (B) Transport of electrons. (C) SEI formation and parasitic reactions fective contact surface area without losing
between electrode and electrolyte. Blurry areas represent reaction products, such as SEI. (D) Connectivity and the advantages of nanoscale dimensions of
transport in 3D space. electrode material. This has been seen in

A B
Coating Coating
Conversion Conversion
or alloying or alloying Conversion
material material or alloying
material

Fig. 3. Strategies developed to overcome performance limitations of nanomaterials in energy storage applications. (A) Nanoscale coatings on the surface
of conversion and alloying electrode materials need to avoid mechanical instability caused by large-volume change and loss of the surface area as a result of
agglomeration (78). D, diameter of pomegranate microparticle; t, thickness of the conducting framework; 2a, void dimension; d, diameter of the active material
primary particles. (B) Nanostructured 3D electrode architecture can be realized through a scalable block-copolymer self-assembly process (86). [Images adapted with
permission from (78, 86)]
pomegranate-like Si nanoparticle–assembly native strategy relies on the infiltration of a 3D theoretical capacity of up to 3579 mA·hour g−1,
anode materials (78) (Fig. 3A) and concentration- scaffold that has a macroporous structure—for considering Li15Si4 formation, cannot work as
gradient LiNiMnCoO2 cathode materials (79). example, aerogel, graphene, or CNTs—with stand-alone anode in a Li-ion battery. The life
Finally, assembly into interconnected 3D nanoparticles of active material. However, cycle of silicon-based anodes is limited by the
electrode architectures with different length this approach has a number of limitations, pulverization of the active material, which is
scales (from nanometers to microscale) can such as limited volumetric performance. Fun- determined by the volume swelling of silicon
provide electronic and ionic conductivity in damentally, it is necessary to learn how to upon lithiation (up to 400 volume %) and
three dimensions. This requires pore engineer- build 3D architectures by self-assembly during subsequent shrinkage upon delithiation (87).
ing (80) and controllable assembly of different electrode manufacturing. Relatively little has However, reducing the particle size below
classes of nanomaterials (Fig. 2D). A goal is been done in this direction, but there are al- ~150 nm (3) limits the electrode cracking upon
to generate a self-assembled 3D bicontinuous ready encouraging demonstrations of truly the insertion of Li+ ions, which mitigates the
nanoarchitecture consisting of electrochemi- integrated 3D electrodes (86) (Fig. 3B). Electro- anode mechanical failure (Fig. 4A). There have
cally active material with rapid ion and elec- chemical or vapor-phase deposition of a sepa- been designs proposed to overcome the issues
tron transport pathways (81). For building truly rator and a counter electrode on a meso- or of large volume expansion and mechanical
3D architectures that integrate anode, cathode, macroporous scaffold is promising as well. failure, including the use of nanowires (1, 8),
and electrolyte together, which shortens the nanotubes (88), graphene flakes (19), hollow
ionic diffusion length compared with conven- Advances and phenomena enabled by spheres, and core-shell and yolk-shell struc-
tional electrodes, the interdigitated types of nanomaterials in energy storage tures (89). To build a stable SEI for nano-
electrode configurations have been proposed Nanostructuring often enables the use of con- materials with large volume change, the concept
(82), although their experimental realization ventional materials that cannot be used in the of nanoscale double-walled hollowed struc-
at a large scale is still challenging. A true 3D microcrystalline state as either cathodes or tures was demonstrated. In this structure, the
architecture was demonstrated using layer-by- anodes. Classical examples are alloying anodes— outer wall confines the expansion of the inner
layer self-assembly of interdigitated thin films such as silicon, germanium, or tin—that ex- wall toward the hollow space inside and
on the surface of an open-cell aerogel sub- perience large structure and volume changes therefore generates a static outer surface for
strate and other examples (83–85). An alter- during cycling (31, 32). Bulk silicon, which has a stable SEI formation (31).

A B
Potential (V vs Li/Li+)
6.0 nm 8.2 nm 17 nm bulk
11 nm 15 nm
Capacity (mAh/g)
Silicon LiCoO2
Fig. 4. Effect of nanostructuring on the electrochemical performance of energy storage materials in Li-ion batteries. (A) Schematic showing the effect of

particle size on the lithiation of silicon anode material (144). (B) Effect of grain size on the galvanostatic discharge curve of LiCoO2 cathode material (43).
[Images adapted with permission from (43, 144)]
A large family of conversion materials—such separator. Encapsulation of sulfur in mesopo- ing, and fire hazard (100). The interfacial sta-
as oxides, sulfides, and fluorides—offer poten- rous carbon or MXene (95), S-TiO2 yolk-shell bility was recently improved with additives or
tial for storing a large amount of charge, but structures (89), hollow sulfur spheres, and am- coatings of nanodiamonds, h-BN, and other
they have poor cyclability coupled with phase phiphilic binding of sulfur and lithium sulfide nanomaterials (4, 101). The issue of large vol-
transformation and large volume change (90). species by oxide and nitrides offer solutions. ume change can be addressed by designing
Benefits of nanostructures have been fully de- In the case of metal-S batteries, nanomaterials host materials to house Li metal plating and
monstrated on these materials as well (20). with strong affinity to Li-polysulfides, such as striping, including hollow carbon nanospheres,
For example, through a conversion reaction, carbides and nitrides of transition metals with graphene oxide, MXene, and polymer nano-
lithiation and sodiation of FeF2 electrodes high metallic conductivity (97), are preferred fiber scaffolds (102).
generate a composite material consisting of for building a scaffold for sulfur. The same Many conventional cathode materials, such
ultrafine (1 to 4 nm) Fe nanoparticles, which materials with nanofiber or nanosheet mor- as LiFePO4 or LiCoO2, when downsized to the
are further fused into a continuous conduc- phology can be used for coating separators to nanometer scale, can provide faster energy
tive network, and a fluoride phase. Metal nano- prevent polysulfide shuttle. Another type of storage compared with the bulk counterparts
particle networks in the resulting structures nanomaterial in the form of 0D or 2D particles (43). However, the energy storage mechanism
enable fast electron transport during further or porous scaffolds can be used to prevent Li changes, with the surface redox reaction be-
cycling (91, 92). A similar effect is observed dendrite growth on the anode side (98, 99). coming a dominant process. Large surface area
during lithiation of a Ag2VO2PO4 cathode (93). Such battery architecture highlights the im- creates a variety of sites for redox reactions, eli-
High rate capability demonstrated by this portance of the use of nanomaterials in all minates diffusion, and very often leads to changes
material is attributed to the 15,000-fold in- the battery components but also requires in the electrochemical behavior, as has been
crease in electronic conductivity associated with a holistic approach toward selecting nano- shown, for example, for LiCoO2 (43) (Fig. 4B). A
in situ formation of Ag nanoparticles during materials that can perform different functions decrease in the particle size leads to capacitor-
electrochemical reduction of Ag2VO2PO4 (93). within an energy storage device. This area of like behavior, almost linear (supercapacitor-like)
The sulfur cathode is another important ex- research is currently under active investigation, galvanostatic charge-discharge curves, and a
ample (94). Sulfur has a high theoretical ca- and specific material solutions are yet to be decrease in capacity (43). Changes in electro-
pacity of 1673 mA·hour g−1 and offers a high found for each individual energy storage sys- chemical behavior induced by nanostructuring,
theoretical specific energy of 2500 W·hour kg−1 tem. Nevertheless, MXenes and graphene have similar to those observed for LiCoO2, are likely
for Li-S batteries. However, sulfur cathodes already shown promise in all the three key to be exhibited by other intercalation cathodes,
have three critical problems: (i) dissolution of aforementioned battery components. including high-capacity materials from the
lithium or sodium polysulfides into the or- The continued pursuit of high–energy den- lithium nickel cobalt aluminum oxide (com-
ganic electrolyte and their shuttling across the sity battery chemistries, such as Li-S, recent- monly LiNi0.8Co0.15Al0.05O2 or NCA) and lith-
separator, (ii) lack of the electronic and ionic ly revived considerable interest in Li metal ium nickel cobalt manganese oxide (often
conductivity of sulfur and lithium sulfide re- anodes. Li metal has the theoretical specific LiNi0.6Co0.2Mn0.2O2 or LiNi0.8Co0.1Mn0.1O2 or
sulting in poor utilization of active material, capacity of 3860 mA·hour g−1 and the lowest NCM) families. This behavior is not neces-
and (iii) large (80%) volume expansion of sul- potential as an anode, which maximizes the sarily exhibited by all nanomaterials, but it is
fur upon lithiation. The nanomaterials ap- specific energy. However, Li metal has a long necessary to consider that capacity can be both
proach represents the most powerful solution list of problems, including extremely high increased or decreased, with the shrinking of
to the aforementioned problems (89, 95). Thin chemical reactivity and large volume changes crystal or particle size, depending on the type
layers of 2D materials, such as MXene (42), or during Li metal plating and stripping, which of material and charge-storage mechanism.
electrospun carbon nanofibers (96) at the create phenomenological problems of Li metal Examples are the increase in capacity in the
separator on the cathode side can serve as dendrites and mossy Li formation, instability case of silicon (3) and the decrease in capacity
barriers for polysulfide transfer across the of SEI, low coulombic efficiency, battery short- in the case of LiCoO2 (43) (Fig. 4B).

Solid-state batteries, exhibiting substantially fast biodegradation when exposed to water and trodes with tens of milligrams per square cen-
improved safety compared with the traditional air. However, it is important to study the timeter. In this context, thickness-independent
ones, are considered to be one of the most toxicity and environmental fate of new nano- (up to 200 mm) capacitance of vertically aligned
promising storage technologies. In this con- materials to ensure that they can safely be MXene flakes has been demonstrated (37).
text, there are a few considerations that make introduced into large-volume manufacturing. In many cases, however, it is necessary to
nanomaterials important for advancing this Minimization of the side reactions caused by a combine different materials to achieve fast
technology. First, in case of the solid-state bat- large surface area of many nanomaterials is transport of both electrons and ions. A good
teries with planar geometry, nanostructuring another major challenge. Surface chemistry example is the design and realization of hybrid
promises to control 2D interfaces between passivation, electrode materials design that structures, which have been reported for num-
battery components by means of the incorpo- minimizes exposed SSA (e.g., yolk-shell par- erous oxides (Nb2O5, TiO2, MoO3, etc.) on a
ration of specifically designed interface layers ticles), preconditioning of electrodes, and use variety of carbon supports, such as nanotubes,
with nanoscale thickness and the ability to of electrolytes that produce stable SEI can be graphene-based materials, and porous carbons
suppress parasitic reactions between electrode used separately or together to mitigate the (13). The carbon affects the electronic proper-
and electrolyte or metal dendrite growth negative effects of side reactions. ties of both materials because it not only acts
(23–27). Additionally, nanomaterials can be as a channel for electrons but also forms a
used to create specific battery components. For Nanomaterials with fast ion and heterojunction between the oxide and car-
example, nanoflakes of conductive 2D mate- electron transport bon surface. As a result, a higher capacity
rials, such as graphene or MXene, can be as- Low-dimensional materials can combine high (~1000 mA·hour g−1) has been achieved for
sembled to form an exceptionally thin current electronic and ionic conductivities by using a graphene–iron oxide electrode compared
collector layer (103). An exciting opportunity a mechanism that is usually referred to as with both only oxide (~600 mA·hour g−1),

exists in the area of creating a highly conduc- pseudocapacitive or surface redox energy stor- which cannot operate at high rates, and only
tive, uniform, and pinhole-free solid-state elec- age (69). It was realized more than 20 years carbon material (~400 mA·hour g−1) (111)
trolyte layer with nanoscale thickness, which ago by Conway et al. that ruthenium oxide (Fig. 5C). When combined, these materials
can potentially be achieved, for example, by (RuO2), having a capacitor-like behavior, has can operate at current densities exceeding
using atomic layer deposition (104). Alterna- redox energy storage (faradaic process) be- several amperes per gram. Moreover, with the
tively, Li-conducting nanofibers or nanowires hind its large capacitance values (108). But correct design of the electrode architecture, a
could be embedded into the Li-conducting the cost of the rare element ruthenium coupled very high rate performance can also be achieved,
polymer matrix to produce a hybrid reinforced with the fact that this material can only ope- as demonstrated for Nb2O5 supported on gra-
electrolyte layer with both high ionic conduc- rate in very thin layers has limited its prac- phene or MXene (112). Building such compo-
tivity and improved mechanical properties com- tical use (109). Additionally, the amount of site architectures can also allow the use of
pared with the pristine one (105). Second, in structural water in ruthenium oxide is a key conversion electrode materials, such as FeF3,
case of the solid-state batteries with 3D archi- factor for its electrochemical performance CuCl2, or S undergoing phase transforma-
tectures, the aforementioned nanomaterials- (Fig. 5A), and its control during device ope- tions (21).
enabled advances are also important. However, ration represents a major challenge (110). Another way to enable fast transport of
in this case, nanomaterials can be used to con- Transition-metal atoms on the surface of electrons and ions is through the creation of
struct 3D electrodes. Indeed, 3D elements in MXenes can participate in redox reactions 2D heterostructures (12), which allow the
electrodes, such as pillars or cavities, often have with fully electrochemically reversible redox combination of highly conducting and high–
micron-sized geometry to ensure mechanical wave in cyclic voltammetry curves overlaid energy density 2D materials. Because at least
stability. However, they can be hierarchically on the large rectangular area corresponding one material in the hybrid structure should
built out of nanoscale particles of various to the double-layer capacitive charge storage have good electronic conductivity, graphene
geometries to form pores for electrolyte pene- mechanism (57) (Fig. 5B). The example of has been the primary material of choice. This
tration and to shorten diffusion distances to MXenes (42, 57) has shown that both double- approach is rather universal, with a very large
achieve fast transport of ions and electrons layer and redox capacitance can be used at number of metallically conductive and redox-
(106). Of course, building such architectures very high current rates, with just ~20% elec- active materials available (113). It has been im-
would require advanced manufacturing ap- trochemical performance loss when going plemented in several different systems for
proaches, which we discuss below. from 10 to 100,000 mV s−1 cycling (Fig. 5B). applications ranging from pseudocapacitors
In addition to higher cost, compared with This rate would be impossible for conven- to Li-ion and Li-S batteries (113). As of now,
conventional materials, the remaining chal- tional redox electrodes, which have low the governing assembly principles of integrat-
lenges related to the use of nanomaterials in conductivity and a diffusion-limited charge- ing dissimilar nanomaterials into desired arc-
energy storage devices include dealing with storage mechanism. MXenes have shown a hitectures are poorly understood. Moreover, it
the sloping charge-discharge and the toxicity. charging time in the 1- to 10-ms range (57). is not yet known how the transport of electrons
For the former, the supercapacitor community At the same time, the capacitance of MXenes and ions occurs between dissimilar 2D sheets
knows how to handle this issue (107). Concern- (up to 500 F g−1 and 1500 F cm−3 in thin and through the separating electrolyte or
ing the toxicity, it is important to ensure that films in acidic electrolyte, Fig. 5B) exceeds confined fluid. What is the optimal spacing
nanomaterials have no or low toxicity and will the capacitance of double-layer capacitor between the sheets? Is the physical contact
not be harmful either during manufacturing materials, such as carbons, which have 100 between the particles an essential requirement
or in the environment, once disposed. Nano- to 200 F g−1 or F cm−3, while volumetrically for electron transport or can the hopping or
materials, such as carbons, silicon, MXenes, or rivaling that of ruthenium oxide thin films tunneling serve as the dominant transport
TiO2, are nontoxic. Moreover, nanomaterials (1500 F cm−3) (110). Thick electrodes can also mechanism? Machine learning should allow
can be degraded in the environment faster work well, if restacking of the 2D sheets is for optimization of those systems and for
than macroscopic materials with the same com- prevented. In fact, vertical alignment of 2D understanding the guiding principles for the
position. For example, Ti3C2 degradation pro- sheets, achieved by exploiting their liquid selection of the optimum combinations of 2D
duces TiO2 and CO2, both nontoxic products, crystalline behavior or through templating, materials to achieve the best electrochemical
and the 2D morphology of MXene will lead to would allow the development of MXene elec- performance (114).

A HIGH LOW RuO2·0.5H 2O

600 B Transition Metal Oxide Surface 1000
RuO2·0.5H2O 10 mV s-1
‘Fast’ Protons and Intercalated Water

(Redox-Active Centers) 750
100 mV s-1
-1
400 500 mV s-1
(g-RuO2)
1,000 mV s-1
Conductive Carbide Core

500
Capacitance (F g-1)
(Rapid Electron Supply)
e- conduction 200 250
H+ mobility
RuO2·0.3H 2O
-1
0
0
/CV
500
200 -250
50 5,000 mV s-1
-1
-200 -500
10,000 mV s-1
dQ dE
20
-750
20,000 mV s-1
50,000 mV s-1
RuO2 -400 5 100,000 mV s-1
-1000
2 mV s -1.0 -0.8 -0.6 -0.4 -0.2
-600 M C O H
0.2 0.4 0.6 0.8 1.0 1.2 Potential (V vs Hg/Hg2SO4)
E / V vs. RHE
LOW HIGH MXene
Ruthenium Oxide
C Graphene Layers D NDG/MoS2 van der Waals

1200 Commercial Fe3O4
Decorated with Fe3O 4 35 mAg-1
GNS/Fe3O4 Heterostructure
Capacity (mAh g-1)
Bare Fe3O4
g-1)
1000
Nanoparticles 105 mAg-1 Nitrogen-Doped
350 mAg-1
Specific Capacity (mAh

800 175 mAg-1 Graphene Polysulfide 1600 0.1 A/g Charge Capacity

1050 mAg-1 MoS2 0.2 A/g Discharge Capacity
600 700 mAg-1 1200
Nitrogen-Doped 0.5 A/g
400 1750 mAg-1
Graphene 800 1 A/g 1 A/g
200
MoS2 2 A/g
- 400 5 A/g
Nitrogen-Doped e
0 Graphene - 0
0 10 20 30 40 50 60 70 e 0 20 40 60 80 100
MoS2
Cycle Number Cycle Number
Graphene/Oxide Composites 2D Heterostructures
Fig. 5. Achieving fast transport of both electrons and ions in nanomaterials. (A) Schematic illustration of RuO2·nH2O demonstrating the ability to control
electronic conductivity and proton transport by tuning the material hydration and cyclic voltammetry (CV) data obtained at scan rates from 2 to 500 mV s−1 (145).
dQ dE−1, capacitance; RHE, reversible hydrogen electrode. (B) Schematic illustration of a typical M3C2 MXene structure and cyclic voltammetry data collected
at scan rates from 10 to 100,000 mV s−1 for a 90-nm-thick Ti3C2Tx film. Ti3C2Tx possesses excellent electronic conductivity owing to an electronically conductive
transition metal carbide layer. Intercalated water molecules enable accessibility of protons to the redox-active TiO2-like surface (57). (C) Schematic illustration
of a composite material synthesized via decoration of graphene sheets with Fe3O4 nanoparticles and rate performance of the obtained material at current densities
ranging from 35 to 1750 mA g−1 as compared with that of commercial Fe3O4 particles and nanoparticles of Fe3O4 synthesized using a similar approach but
without the addition of graphene sheets (146). GNS, graphene nanosheets. (D) Schematic illustration of a 2D heterostructure consisting of the alternate MoS2 and
nitrogen-doped graphene (NDG) layers and its rate performance in a Li-S battery at current densities ranging from 0.1 to 5 A g−1 (147). [Images adapted with
permission from (57, 145–147)]
Manufacturing of the nanomaterial-enabled these properties can be achieved by using 1D been established by (i) using flexible substrates
energy storage devices and 2D materials with high mechanical prop- (117) and separators (118); (ii) designing new
For large-scale applications, we need to build erties and electronic conductivity. Beyond con- device patterns (119) and configurations—for
batteries and supercapacitors in a convent- ventional energy storage devices for portable example, fiber-like and spring-like devices (120);
ional format, but exploiting nanomaterials electronics and vehicles, there is increasing (iii) compositing electrode materials into flex-
will allow faster operation, higher power, and demand for flexible energy storage devices ible matrices (32, 121), and so on. Flexible energy
longer lifetime compared with the current needed to power flexible electronics, including storage devices, including Li-ion battery (122),
technology. For example, replacing graphite bendable, compressible, foldable, and stretch- Na-ion battery (7), and Zn-air battery (123);
with nanostructured silicon (115) can lead to able devices. Wearable electronics (116) will flexible supercapacitors, including all-solid-state
a substantial increase in the energy density require the incorporation of energy storage devices (124); and in-plane and fiber-like micro-
over conventional batteries. One of the key devices. This means that we need energy stor- supercapacitors (125) have been reported. How-
advantages of nanoscale materials is that they age fibers, fabrics, and textiles and the ability ever, the packaged microdevice performance is
can be used to manufacture electrodes of any to incorporate energy-storing materials into usually inferior in terms of total volumetric or
size, shape, or form factor. For example, we are clothes. This involves the manufacture of non- gravimetric energy density compared with con-
used to seeing conventional batteries as sepa- toxic, strong, stretchable, and even washable ventional batteries of supercapacitors. Nano-
rate units. But there is no reason why they conductive fibers, capable of both ionic and materials will use different manufacturing
cannot be combined with structural elements electronic transport. For the implantable de- methods (Fig. 6). Spray coating and other high-
and distributed, when electrodes can conform vices, instead of traditionally used coin cells or throughput manufacturing techniques (e.g.,
to any shape and be made strong, robust, and patches, stretchable and biodegradable or bio- doctor blade, dip coating, electrodeposition,
flexible. As a result, instead of occupying space compatible batteries could be incorporated in- layer-by-layer deposition, vacuum filtration, and
under the car body or in a trunk, they can be- side the human body or battery-powered devices. ink-jet printing) (10) may make these devices
come part of the automobile structure per se, The design and realization of these devices sufficiently inexpensive for commodity appli-
for example, forming the car body or filling the require the incorporation of nanomaterials into cations. For example, electrochemically exfo-
empty space in doors and under the hood. All functional architectures. Several strategies have liated graphene has been used to formulate


Fig. 6. Nanomaterials enable the production of next-generation energy storage systems by different manufacturing methods. [Supercapacitor array image
by Husam N. Alshareef/King Abdullah University of Science and Technology (KAUST); figure wearing smart textiles image by Kristi Jost/Drexel University]
inks and manufacture in-plane micro-super- the anode and cathode materials, respectively framework graphene- and MXene-based in-
capacitors on flexible substrates and wafers (128). This approach can produce distributed plane micro-supercapacitors with ac line-
by spray coating (126). Ink-jet printing has energy storage devices integrated with other filtering performance were fabricated by in
shown promise in the fabrication of flexible electronic components. situ layer-by-layer growth of active material
thin-film energy devices with large area and The use of structural or printable energy stor- on prefabricated current collectors (34). Such
readily controllable thickness (127). Centrifu- age (Fig. 6) adds additional requirements to the an approach, coupled with the exploitation of
gal casting can produce large-area sheets of 2D environmental and temperature stability of all 2D materials, offers a pathway for the scalable
materials much faster than vacuum-assisted components of the device. If a battery is loca- fabrication of in-plane micro-supercapacitors.
filtration. Roll-to-roll manufacturing can trans- ted close to the hot part of an engine or in- Smart energy storage devices, which can de-
form the assembly of battery-powered devices corporated into a part of the car body that will liver extra functions under external stimuli
into a process similar to printing a newspaper. be subjected to sunshine over a prolonged beyond energy storage, enable a wide range
It is important to mention that conducting period of time, the use of thermally stable of applications. In particular, electrochromic
current collectors and insulating separators electrolytes (e.g., ionic liquids) and other com- (130), photoresponsive (131), self-healing (132),
(in the case of sandwich-device architecture) ponents (e.g., ceramic separators, such as cera- thermally responsive supercapacitors and bat-
need to be printed by the same method. Also, mic nanofibers, boron nitride, or clay) may be teries have been demonstrated. However, the
interdigitated and other non-sandwich energy required. In printable devices for Internet of fade of the performance under stimuli still
storage device architectures become possible Things and future miniaturized electronics, hinders their practical applications. Another
with printing technologies and polymer gel the use of nanomaterials should be considered pathway to achieve stimuli is manipulating
electrolytes, which both conduct ions and not only as active components but also as electrolyte—for example, by using thermally
separate the electrodes. binders, current collectors, sealants, and en- responsive polymer gels—to control the ion
The quality of printed films depends on the capsulating elements. For example, the latter transport between the electrodes, which can
stability of active nanomaterial-based inks (10). can be constructed using micrometer-thick eventually cause the on and off switching
In this context, functionalized nanoparticles polymer films with insulating 2D nanopar- of the device. Although several prototypes
are typically used for ink formulation because ticles, decreasing water and oxygen permeability. have already been demonstrated, consid-
of their good dispersibility in solvents (both In-plane micro-supercapacitors made of erable challenges—for example, balance of
aqueous and organic). To increase the areal carbide-derived carbons and 2D materials— high performance and extra functions and
energy density of devices and their capacitance including graphene, MXene, metal oxides, and the integration of such smart devices into
or capacity, it is necessary to build 3D devices conductive MOFs—are among the most pop- fully functioning systems—still need to be
with increased thickness and hierarchy of the ular flexible and integrated energy storage resolved (133).
electrodes. Therefore, it is necessary to develop devices. Carbide-derived carbon films that Parasitic reactions between electrode nano-
3D printing techniques and adjust them to possess a high SSA and narrow pore size can materials and electrolytes (3) can cause the
specific conditions; for example, 0D particles also be fabricated on a silicon wafer without decomposition of electrolyte and metal consump-
and 2D sheets are easier to print compared cracking by two key steps: sputtering of metal tion for metal-ion batteries and consequently
with CNTs, but the latter can be more readily carbides and chlorine-gas etching (129). 2D result in poor energy storage performance,
incorporated into fibers, providing mechanical heterostructures can provide improved electron- including low Coulombic efficiency, cycle life,
strength and electrical conductivity required and ion-transport pathways (12). However, and energy density, compromised safety, and
in this application. A 3D printed, interdigi- most 2D materials–based in-plane micro- so on. Many efforts—such as the development
tated Li-ion microbattery was demonstrated supercapacitors are fabricated by photo- of coated electrode materials (134), electrolytes
using Li4Ti5O12 (LTO) and LiFePO4 (LFP) as lithography. 2D metal–organic coordination and additives (135), membranes (136), and

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Energy storage: The future enabled by nanomaterials
Ekaterina Pomerantseva, Francesco Bonaccorso, Xinliang Feng, Yi Cui and Yury Gogotsi
Science 366 (6468), eaan8285.

DOI: 10.1126/science.aan8285
Thinking small to store more

From mobile devices to the power grid, the needs for high-energy density or high-power density energy storage
materials continue to grow. Materials that have at least one dimension on the nanometer scale offer opportunities for
enhanced energy storage, although there are also challenges relating to, for example, stability and manufacturing. In this

context, Pomerantseva et al. review fundamental processes of charge storage that apply specifically to nanostructured
materials and briefly explore potential manufacturing processes. The authors also consider some of the skepticism, such
as that found in the battery community, to the use of these materials.
Science, this issue p. eaan8285
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Science, 1200 New York Avenue NW, Washington, DC 20005. The title Science is a registered trademark of AAAS.
Copyright © 2019, American Association for the Advancement of Science

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RES EARCH

◥ capacitance, and diffusion-limited inter-

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◥ large volume expansion and contraction (19, 20),

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Carbon Onion Single Wall Carbon Nanotube Graphene Pillared Graphene

Nanoparticles Multiwall Nanotube Multielement 2D Compounds Metal-Organic Frameworks

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A HIGH LOW RuO2·0.5H 2O

‘Fast’ Protons and Intercalated Water

Conductive Carbide Core

C Graphene Layers D NDG/MoS2 van der Waals

Specific Capacity (mAh

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Graphene/Oxide Composites 2D Heterostructures

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Science 366 (6468), eaan8285.

Thinking small to store more

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