Journal of Alloys and Compounds 961 (2023) 170885

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Review

Preparation of graphene by exfoliation and its application in lithium-ion

batteries ]]
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⁎ ⁎⁎
Ya Wen a, Huimin Liu b,c, , Xunyong Jiang a,d,e,
a
School of Materials Science and Engineering, Tianjin University of Technology,Tianjin, China
b
Tianjin Key Lab of Film Electronics and Communication Devices, China
c
School of Integrated Circuit Science and Engineering, Tianjin University of Technology, China
d
Key Laboratory of Display Materials and Photoelectric Devices, Ministry of Education, China
e
Tianjin Key Laboratory for Photoelectric Materials and Devices,China

a r t i cl e i nfo a bstr ac t

Article history: The two-dimensional material graphene has excellent electrical, optical, and mechanical properties. Since
Received 19 January 2023 its successful preparation, graphene has been used in many applications in energy, environment, electro­
Received in revised form 9 May 2023 nics, or biomedicine fields. Graphene can be prepared on a large scale using top-down strategies, such as
Accepted 6 June 2023
using mechanical shear force. Shear force is also used for the preparation of electrode slurry. This paper
Available online 7 June 2023
summarizes the current status of research on integrating the graphene preparation process with electrode
slurry preparation. The article starts with a systematic introduction to the principles of the top-down
Keywords:
Mechanical exfoliation method from the strategy of top-down graphene preparation, followed by a summary of the top-down
Graphene process classified by the source of external forces. Comparing the top-down process, it was found that the
Lithium-ion battery graphene prepared by using mechanical shear force is simple and can be used for mass production. The
paper overviews the mechanical techniques utilized to create graphene on a big scale. The use of me­
chanically exfoliated graphene in lithium-ion batteries is considered. Graphene prepared by mechanical
exfoliation method is more beneficial to improve the electrochemical performance of lithium-ion batteries.
Prospects for their utilization are reviewed together with developments in process approaches that in­
tegrate the manufacture of electrode slurry with the preparation of graphene.
© 2023 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 2

2. Top-down method for graphene preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 3
2.1. Preparation of graphene by chemical redox force exfoliation. . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 3
2.2. Preparation of graphene by mechanochemical mixed force exfoliation . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 4
2.3. Preparation of graphene by mechanical exfoliation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 4
2.3.1. Graphene preparation using wet exfoliation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 4
2.3.2. Graphene preparation by dry exfoliation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 4
3. Large-scale production of graphene by mechanical force liquid phase method . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 6
3.1. Ultrasonic exfoliation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 6
3.2. High-speed shear stripping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 7
3.3. High-pressure homogenization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 8
3.4. Mechanical ball mill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 9
4. Application of graphene prepared by mechanical exfoliation in lithium-ion batteries. . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 9
4.1. Lithium-ion battery electrode preparation process and two ways of adding graphene . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 10
4.2. Graphene used as a conductive additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 10

⁎
Corresponding author at: Tianjin Key Lab of Film Electronics and Communication Devices, China.
⁎⁎
Corresponding author at: School of Materials Science and Engineering, Tianjin University of Technology,Tianjin, China.
E-mail addresses: [email protected] (H. Liu), [email protected] (X. Jiang).

https://doi.org/10.1016/j.jallcom.2023.170885
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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

4.3. Graphene composite with active material prepared by the shearing method for lithium-ion battery anode . . . ..... . ..... . ..... . ..... . 11
4.4. Graphene composite with active material prepared by the shearing method for lithium-ion battery cathode. . ..... . ..... . ..... . ..... . 11
5. Discussion on the integration of graphene preparation and electrode slurry preparation process . . .............. . ..... . ..... . ..... . ..... 12
6. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .............. . ..... . ..... . ..... . ..... 12
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .............. . ..... . ..... . ..... . ..... 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .............. . ..... . ..... . ..... . ..... 13

1. Introduction manufacturing is not feasible due to the complicated, energy-in­

tensive, and environmentally hazardous circumstances of the ne­
The new two-dimensional material graphene was first exfoliated cessary facilities and operational conditions.
from graphite by mechanical exfoliation in 2004 by Novoselov and Top-down methods obtain graphene from bulk graphite by
Geim [1]. Graphene has an ortho-hexagonal honeycomb two-di­ breaking the van der Waals forces between graphite layer sheets
mensional crystalline structure with internal atoms arranged in a with the help of external forces. The top-down methods mainly in­
bonding pattern with SP2 hybrid orbitals. The coordination number clude ultrasonic exfoliation [21], ball milling exfoliation[22], high
of carbon atoms in graphene is 3, the bond length between every shear exfoliation [23], high pressure homogeneous exfoliation [24],
two adjacent carbon atoms is 1.42 x 10-10 m, and the bond angle is microfluidic [25], Hummers method [26], electrochemical exfolia­
120°. In addition to the σ-bonds, which are connected to other tion[27], etc. Top-down produced graphene has several flaws, and
carbon atoms in a honeycomb laminar structure of hexagonal rings, the number of layers is challenging to manage. Top-down prepared
the Pz-orbitals of each carbon atom perpendicular to the plane of the graphene is inexpensive, easy to operate, energy-saving, and simple
layer can form polyatomic π-bonds that run through the entire layer. to produce on a big scale. It can be used in conductive coatings [28],
Because of its particular structure, graphene has a high electron leap anti-corrosion coatings [10], multifunctional composite materials
rate by a factor of 15,000 cm2 ▪ V-1 ▪ S-1[2]. Graphene is one of the [9], capacitors [15], batteries[29], etc.
most robust known materials, with good toughness, a tensile There have been some review articles on graphene from different
strength of 130 GPa, and Young’s modulus of 1.0 TPa[3]. Graphene perspectives. Some focus on graphene preparation methods—some
has excellent optical properties, with absorption of about 2.3% over a on the choice of solution, and some on applying graphene in various
wide wavelength range and an increase of 2.3% for each additional fields. For example, Ahmad Amiri [30] highlights recent advances in
layer of thickness through out several graphene layers. Graphene has liquid-phase exfoliation technology for graphene production from
a stable carbon-carbon bond structure, good thermal conductivity 2008 to 2018. Methods for shear exfoliation, wet ball milling, ex­
[4], and a large specific surface area [5]. The chemical properties of foliation based on stabilizers, exfoliation helped by functionaliza­
graphene are similar to graphite, which can adsorb and desorption tion, exfoliation based on electrochemistry, and novel exfoliation
various atoms and molecules. Because of its excellent physical and based on the supercritical fluid are highlighted. The article described
chemical properties, graphene is widely studied and used in elec­ the advantages and disadvantages of the different liquid phase ex­
tronic devices [6], photonic devices [7], photocatalysis [8], advanced foliation methods. Ma [31] summarized the latest research on the
composite materials [9], coatings [10], printing [11], sensors [12], exfoliation of graphene nanosheets in water. It highlighted graphene
biology, biomedicine [13], batteries [14], supercapacitors [15], mili­ nanosheets’ exfoliation and stabilization mechanisms in various
tary, aerospace[16] and other fields. aqueous media. It reviewed water-based exfoliation methods such as
There are two main types of graphene preparation methods, liquid phase exfoliation and electrochemical exfoliation. Kartika A.
bottom-up and top-down, as shown in Fig. 1(a). Bottom-up is Madurani [32] highlighted the applications of graphene in the fields
growing graphene continuously by breaking the chemical bonds of of environment, energy, biomedicine, sensors, biosensors, and heat
carbon-containing compounds and depositing carbon atoms on the sinks. Luca Lavagna [33] provides a comprehensive overview of re­
substrate by certain methods. Bottom-up methods include chemical cent advances in lithium-ion battery anodes using graphene and
vapor deposition [17], epitaxial growth [18], plasma synthesis [19], related 1D materials doped into lithium-ion batteries. Ahmed A.
etc. Bottom-up methods for graphene preparation allow for control Moosa [34] summarise the most commonly used methods for the
of the growth process and good control of thickness and quality. preparation of graphene, focusing on exfoliation methods and their
Bottom-up methods can prepare graphene with excellent optoelec­ progress. The unique structure of graphene, its high electron leap
tronic and electronic applications for applications such as touchsc­ rate, good electrical conductivity, and its large specific surface area
reens [20], OLEDs, solar panels, etc. However, Large-scale industrial reduce internal resistance. It improves the cycling and diversity

Fig. 1. (a) Schematic diagram of the top-down and bottom-up methods; (b) Schematic diagram of graphite structure.

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Fig. 2. (a) The process of Hummers method [41].Copyright 2013 World Scientific; (b) Electrochemical exfoliation of bulk graphite in the presence of acids; (c) The suggested
mechanism for electrochemical exfoliation [42].Copyright 2013 American Chemical Society NANO; (d)Schematic diagram of electrochemical/mechanical hybrid exfoliation
equipment [43]. Copyright 2019 Springer; (e) Photograph of the microfluidizer; (f) Schematic of the reaction chamber, where the diameter of the channel is 87 µm.; (g) Illustration
of flow profile in channel, with the maximum fluid velocity ∼220 m/s [60]. Copyright 2017 IOP Science; (h)The illustrative procedure of Scotch-tape based micromechanical
cleavage of HOPG [62].Copyright 2015 The Royal Society of Chemistry.

characteristics of lithium-ion batteries. Santosh K. Tiwari [35] sum­ Graphene can be prepared on a large scale using top-down
marize the latest research results on the application of graphene and strategies, such as using mechanical shear force. Can the graphene
graphene-based materials in different fields. First, some funda­ preparation process be integrated with the battery slurry prepara­
mental aspects of graphene, graphene oxide, graphene quantum tion process? If this process is possible, this reduces the cost and
dots, graphene nanoribbon, etc. are discussed in brief. Then, recent solves the problem of graphene agglomeration. There are few review
signs of progress in Materials Engineering concerning 3 graphene- articles in this area. This paper summarizes the literature from the
covering materials fabrication, properties, and applications are perspective of the fusion of graphene preparation and the prepara­
pointed out in detail. Sun [36] recent progresses on the structural tion process of lithium-ion battery electrode material slurry. This
design and interfacial modification of graphene to regulate the paper starts with the strategy of top-down preparation of graphene,
charge transport in LIBs have been summarized. The structure-per­ systematically introduces the principle of the top-down method, and
formance relationships between the structure of the graphene and then classifies and summarizes the top-down process according to
its dedicated applications for LIBs have also been clarified in detail. the source of external force. This article provides a synopsis of the
The reviews that have been published on graphene are sum­ mechanical techniques used to manufacture graphene at a massive
marized in two main areas: a discussion of graphene preparation scale. Lithium-ion batteries that use graphene produced through
methods or the direct use of graphene in lithium-ion batteries. In mechanical exfoliation are addressed. The advantages and future
applying graphene to electrode materials, there are two ways to add potential of a process approach that combines graphene preparation
graphene. One is to use graphene powder as raw material and mix it and electrode slurry preparation are explored.
with active substances to prepare electrodes. Wang [37] first gen­
erated a few layers of graphene powder using the AC arc plasma 2. Top-down method for graphene preparation
process for manufacturing electrodes. They investigated the elec­
trochemical performance of graphene as a cathode conductive ad­ Graphite is a hexagonal crystal system where each layer of flakes
ditive for LiFePO4 lithium-ion batteries. The issue of graphene is bonded together by van der Waals forces. Fig. 1(b) is a schematic
agglomeration may still arise despite improvements in capacity and diagram of the graphite structure. The top-down method starts from
multiplicative performance. Another approach is to disperse the pre- the bulk graphite. It breaks the van der Waals forces between the
prepared graphene powder in the solution and add the graphene graphite layer flakes by an external strength, thereby stripping the
solution while preparing the electrode. Wang [38] first designed graphene from the graphite. Depending on the external force, there
graphene powder by jet cavitation. Then the graphene powder was are chemical and mechanical forces. It can mechanically exfoliate
put into an NMP solution and sonicated for 2 h. Finally, it was mixed graphene from bulk graphite by breaking the van der Waals forces
with acetylene black as a conductive additive for the lithium iron between the graphite sheets due to the shear forces generated or
phosphate cathode. Although this method overcomes the agglom­ chemically exfoliated by intercalating ions in solution between the
eration problem of graphene to a certain extent, the preparation graphite layers and expansion. According to external pressure, the
process is long and more complicated. top-down method can be categorized as chemical redox exfoliation,
The preparation process of the lithium-ion battery electrode is to mechanical-chemical mixed party, and mechanical exfoliation.
put the conductive agent, binder, and active material into the NMP
solution. Then the solution is stirred uniformly to obtain the elec­ 2.1. Preparation of graphene by chemical redox force exfoliation
trode material slurry and dry it on copper or aluminum foil to get the
electrode piece. During the preparation of the electrode slurry, the Typical chemical methods for producing graphene include the
active substance is uniformly mixed in the solution by mechanical Hummers method [26], electrochemical exfoliation [27], etc. The
shear force. Hummer process (Fig. 2(a)) combines graphite with solid acids and

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

oxidizing agents. Ions swell graphite by intercalation. Then a redu­ Coleman Finds graphene exfoliation theory similar to nanoma­
cing agent such as hydrazine hydrate is added to remove the oxygen- terial dispersion Theory. As the surface energy of graphite is similar
containing functional groups. The layer spacing between graphite is to that of carbon nanotubes (∼68 mJ/m2), carbon nanotubes can ef­
increased. Finally, graphene can be obtained by ultrasonic treatment fectively disperse in solutions with surface energies matching those
[39]. The preparation of graphene using this method is simple, of carbon nanotubes. It has been found through research that the
convenient, and quick. Still, oxygen-containing functional groups same approach applies to graphite. Graphene can exfoliate from
remain on the surface of the prepared graphene. Electrochemical graphite solutions with similar surface energies[49,50].
exfoliation (Fig. 2(b),(c)) involves using graphite as the anode and
platinum as the cathode. Graphene is prepared by electrolytic re­
2.3.1. Graphene preparation using wet exfoliation
action in an acidic, alkaline, or salt solution electrolyte [40]. The O-
Wet exfoliation produces graphene by exfoliating graphite with
and OH- ions in the electrolyte enter between the graphite layer
shear force in a fluid with similar surface energy as graphite. The
sheets by intercalation. Make the graphite swell. After increasing the
technique used for exfoliation can be classified as ultrasonic ex­
graphite layer spacing, SO42- ions enter between graphite layers to
foliation [51], wet ball milling exfoliation [52], high shear exfoliation
exfoliate graphene. The method is low-cost. The prepared graphene
[53], high-pressure homogeneous exfoliation [54], microfluidics
has high physicochemical properties and no defects.
[55], etc. Ultrasonic exfoliation is the preparation of graphene by
putting graphite and solvent into the ultrasonic generator. Ultrasonic
2.2. Preparation of graphene by mechanochemical mixed force vibration produces shear force through the rupture of microbubbles
exfoliation generated by compression when the ultrasonic waves propagate in
the medium. Ultrasonic exfoliation is superficial but takes a long
Mechanochemical mix force exfoliation prepares few-layer gra­ time, consumes energy, and produces graphene with a few defects.
phene by combining mechanical exfoliation with a redox exfoliation Ball milling involves placing graphite, a grinding aid, and steel balls
process. Shear-assisted electrochemical exfoliation [43,44], ultra­ into a ball milling tank. During the rotation of the tank, the kinetic
sound-assisted liquid phase exfoliation combined with redox [45], energy gained by the steel balls is transferred to the graphite as they
high-pressure homogenization combined with redox[46], etc., are collide with the graphite and other steel balls, thus exfoliating the
examples of mechanochemical mixed-force exfoliation. Teng [43] graphene. High shear exfoliation involves placing the graphite into a
produced graphene using a combination of electrochemical inter­ solvent with similar surface energy, generating shear forces during
calation and mechanical exfoliation, as shown in Fig. 2(d). A rotating the high-speed rotation of the drill, and destroying the van der
tool was used as the electrode cathode and platinum as the anode. Waals force between graphite by shear force. This method allows for
Graphite powder was put into a mixer. The graphite powder was the mass production of high-quality graphene with few defects. The
electrochemically intercalated using the ions in the electrolyte. Then high-pressure homogenization method involves placing graphite in
the expanded graphite powder is mechanically exfoliated. Finally, a solution, which is pressurized so that the solution flows into a tiny
several layers of graphene flakes were obtained. Although the gra­ valve. Graphene is prepared through an impact ring using the energy
phene produced by mechanical chemical force mixing has a low generated by the high rotation speed. The graphene prepared by this
number of layers, good quality, and a high yield, the solution em­ method is usually more stable. Microfluidics (Fig. 2(e-g)) involves
ployed in this process must be electrically conductive. Therefore the putting a mixture of graphite, water, and surfactant under pressure
method has limitations. Qi [45] used a combination of ultrasound- into a microchannel. Shear forces are generated in the mix as it
assisted liquid-phase exfoliation and oxidation-deoxidation to pre­ passes through the microchannel. Due to pressure release, cavitation
pare large-size graphene. Expanded graphite was used as raw ma­ causes bubbles around the graphite to burst. Micro-jet action is
terial and put into DMP for sonication. The sonicated graphite was formed on the graphite surface. Stress waves propagate throughout
prepared into graphite oxide by a modified Hummers method. Fi­ the graphite. Tensile stress exfoliates the graphite into graphene
nally, graphene was successfully prepared by a simple redox re­ [56]. The preparation of graphene using this method consumes low
action. energy and can be produced on a large scale.

2.3. Preparation of graphene by mechanical exfoliation

2.3.2. Graphene preparation by dry exfoliation
Graphene is prepared by dry exfoliation without using a solution
The mechanical force exfoliation (physical approach) for gra­
as a medium. Applying mechanical forces can directly exfoliate the
phene preparation is applying shear forces to graphite to disrupt the
graphite, including the transparent tape method [1], dry ball mill
van der Waals forces between graphite layer sheets. Based on the
[61], etc. The transparent tape method (Fig. 2(h)) involves stripping
exfoliation medium can be subdivided into wet and dry exfoliation.
graphite flakes from highly oriented pyrolytic graphite, gluing the
By drawing on the strengths between nanoparticles, we can estimate
fragments on both sides to a special tape, tearing the video, splitting
the power required to obtain graphene by exfoliation from bulk
the pieces in two, and repeating the operation, with the flakes be­
graphite.
coming thinner and thinner, resulting in a layer of carbon atoms, i.e.,
In 2007, Huang [47] first quantified the van der Waals force be­
graphene. This method prepares graphene with an uncontrollable
tween nanoparticles by calculating the Hamaker constant.
size and low yield, which makes it challenging to meet the needs of
FA = AD/(24H2) (1) industrial production. The dry ball milling method involves mixing
graphite with a solid grinding aid that assists ball milling in a spe­
where A is the Hamaker constant, D is the particle diameter, and H is cific ratio. During the ball milling process, the mutual extrusion and
the particle spacing. collision of the balls and graphite generate impact, shear, and fric­
In 2009, Coleman [48] found that carbon nanotubes attract each tion energy. This process results in grinding and van der Waals forces
other due to van der Waals force interactions between neighboring being destroyed between graphite. Although the graphene prepared
carbon atoms. The potential energy of these pairwise interactions by this method is simple and efficient, the way releases a large
satisfies the following: amount of heat during the preparation process. The prepared gra­
phene is prone to aggregation and has a few defects.
Vr = C /r 6 (2)
Table 1 summarizes the three strategic methods used to obtain
Where r is the atomic spacing and C is the constant（A = 2 2 C）. graphene for the top-down method. It can produce all graphene

4
 Y. Wen, H. Liu and X. Jiang

Table 1
Summary of preparation methods of graphene.

Classify Method Principle Characteristics

Mechanical force Wet Ultrasonic exfoliation [51,57] Ultrasound propagates through the medium and the compression Simple handling, long stripping time, few defects in graphene
exfoliation method produces microbubbles that rupture
Wet ball milll exfoliation [52,58] During rotation, the kinetic energy gained by the steel ball is transferred Simple operation and low grinding costs
to the graphite when the ball collides with graphite and other steel balls
High shear exfoliation [53] Disruption of van der Waals forces between graphite by shear forces Graphene has high yield and few defects
High pressure homogeneous High speed rotation generates energy to break van der Waals forces in Graphene is stable
exfoliation [55] graphite materials to obtain graphene
Microfluidics [55,56] A mixture of graphite, water and surfactant is pressurised into a Low energy, can be mass produced
microchannel, through which shear forces, pressure release and
cavitation occur, causing bubbles around the graphite to burst, creating a
microjet effect on the graphite surface and exfoliating the graphene.
Dry method Scotch tape method [1] The graphite flakes are peeled from the highly oriented pyrolytic graphite, Uncontrolled product size and low yield
the flakes are glued on both sides to a special tape, the tape is peeled off
and the flakes are split in two, the operation is repeated and the flakes
become thinner and thinner, resulting in a flake of one layer of carbon
atoms, i.e. graphene.
Dry ball mill Mixing graphite with solid grinding aids in a certain ratio, the mutual High efficiency, simple operation, large amount of heat released

5
extrusion and collision between the balls and graphite during the ball during the grinding process and agglomeration of the graphene
milling process generates impact energy, shear energy and friction energy obtained.
to grind and destroy the van der Waals force between graphite
Chemical redox exfoliation Hummers [26,39] Graphene is obtained by dispersing graphite with strong acids and Simple and easy, less time consuming, few defects in graphene,
oxidizing substances under the action of ultrasound and then adding environmental pollution
reducing agents to remove the oxygen-containing functional groups.
Electrochemical exfoliation [27,40,59] Preparation of graphene in an acidic, alkaline or salt solution electrolyte Low cost, simple handling, high physic- ochemical properties of
using graphite as the anode and platinum as the cathode graphene, no defects
Mechanochemical mixing force Shear-assisted electrochemical Electrochemical intercalation of graphite powder using ions in the High quality, high yield
exfoliation exfoliation [43,44] electrolyte followed by mechanical exfoliation of the expanded graphite
powder
Ultrasound-assisted liquid phase Graphene was prepared from ultrasonically treated expanded graphite by Preparation of large size graphene, Limitations exist
exfoliation combined with redox [45] a simple redox reaction
High-pressure homogenization Preparation of graphene oxide by hummer method and structural Smaller graphene size, fewer layers and improved electro-
combined with redox [46] modification of graphene oxide (GO) by high pressure homogenization chemical properties
Journal of Alloys and Compounds 961 (2023) 170885
Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Fig. 3. (a) Illustration of the possible mechanism of graphite exfoliation [68].Copyright 2017 MDPI; FESEM images of GNs from graphene DMF-H2O (9:1, v-v) after 6.5 h sonication
at various powers: (b) 80 W, (c) 120 W, (d) 80 W, after preservation for 2 months, and (e) EG as a comparison. These samples were obtained by depositing graphene DMF-H2O
solutions onto glass substrates and drying under vacuum at 40 ℃ [65].Copyright 2013 ELSEVIER.; (f) A schematic diagram of the high speed homogeneous disperser [10].Copyright
2019 ELSEVIER; (g) Characterization of LDG by SEM [74].Copyright 2020 MDPI.

prepared by mechanical exfoliation on a large scale with simple ultrasound [30]. The ultrasonic treatment generates tiny bubbles by
operations and high yield efficiency. creating zones of high and low density by vibration, bubbles in a
liquid contract, and expand under high and low pressure. Due to the
3. Large-scale production of graphene by mechanical force liquid rapid change in force and the tension generated, the bubbles vio­
phase method lently blow up on the graphite surface. The graphite in the solution
shattered, as shown in Fig. 3(a), as the principle diagram of ultra­
The chemical preparation of graphene involves using strong acid sonic exfoliation. Ultrasonic exfoliation usually involves three steps:
or alkali solutions, and the graphene prepared will be mixed with in the first step, graphite is mixed with a solvent to prepare a gra­
oxygen-containing functional groups. Mechanical graphene pre­ phite dispersion; in the second step, the graphene dispersion is
paration reduces environmental pollution, is simple, and produces exfoliated by ultrasonication; and in the third step, it is centrifuged
high-quality graphene with no impurities. The liquid phase exfolia­ and purified. Commonly used solvents for ultrasonic exfoliation are
tion method is one of the most feasible methods for industrial gra­ N-methyl-pyrrolidone (NMP), N, N-dimethylformamide (DMF),
phene production due to its low cost, simple operation, good 1,1,3,3- Tetramethylurea (TMU), naphthalene, dimethyl sulfoxide
scalability, and the small number of graphene layers prepared [63]. (DMSO), ionic liquids, etc. As early as 2008, Yenny Hernandez [64]
Graphene slurries are organized directly by the liquid phase method. used N-methyl pyrrolidone (NMP) as a dispersion solvent. After so­
The solvent used can be the same as in preparing electrode slurries. nication, they obtained a graphene dispersion with a 0.01 mg/mL
The technique of graphene preparation by liquid phase has the po­ concentration. Zhu [65] prepared graphene dispersions by ultrasonic
tential to be integrated with existing electrode material slurry pre­ stripping expanded graphite using a co-solvent of N, N-di­
paration, thus simplifying the electrode slurry preparation process. methylformamide (DMF), and water. The morphology of the pre­
The following section outlines the current research status of several pared graphene is shown in Fig. 3(b-e). The graphene layers
widely utilized mainstream approaches for generating graphene via composed of too high ultrasonic power crossed each other. They had
liquid-phase exfoliation. small dimensions. The graphene layers made with too low ultrasonic
energy were multilayered and thick. So a suitable power is required
3.1. Ultrasonic exfoliation to prepare high-quality graphene. The graphene flakes obtained
using DMF solvent were thin. The maximum size of the graphene
Ultrasonic exfoliation involves placing graphite into a solution flakes was about two μm, with high yield strength. The graphene
and exfoliating graphene by creating shear forces through ultra­ prepared by this method had no obvious structural defects. Xu [66]
sound. Ultrasonic exfoliation is available as bath ultrasound or tip produced graphene by adding naphthalene exfoliation to an organic

6
Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Fig.4. (a) Schematic illustration for the preparation of graphene in DMF and graphite nanosheets in water through high pressure homogenization; (b)SEM images of graphite. (c,d)
FE-SEM images of exfoliated graphite nanosheets [75].Copyright 2015 The Royal Society of Chemistry.

solvent. Under sonication, the addition of naphthalene to NMP im­ head to rotate at high speed. The gap between the rotor and the
proved the graphene yield. The yield of dispersed graphene in NMP stator generates a massive shear force. The graphite particles in the
was as high as 0.15 mg/mL after 90 min of sonication. The graphene solution collide. Under the shear force, the van der Waals between
produced by this method can be well used in thin films and com­ the graphite forces breaks down [53]. The graphite is exfoliated into
posites. Wan [67] explored mixtures of renewable solvent water and graphene. The van der Waals energy between two adjacent flakes in
1,1,3,3 -tetramethylurea (TMU) as solvent-stripped graphene. It graphite crystals is approximately 2ev/nm2. It is easy to peel gra­
found that a mix of water and TUM was an effective solvent for the phene from graphite by mechanical force. Graphene can be ex­
preparation of multilayer graphene. When the volume ratio of water foliated from graphite by shear forces in a suitable solution. The
was 0.3, the yield of graphene prepared was 4.5 times higher than solution promotes the exfoliation of the graphite flakes, prevents
graphene prepared using pure NMP as the solvent. The preparation graphene agglomeration, and provides stability to the graphene [69].
of graphene by this method solves the problem of environmental Eswaraiah Varrla [70] produced large amounts of defect-free
safety. It provides a reference for how to improve the yield and graphene using kitchen blenders as exfoliating instruments and
stability of graphene. Adding organic substances and surfactants household detergents as solvents. It found that the yield did not
without chemical reactions can enhance efficiency during ultrasonic change with increasing mixing time but increased with increasing
exfoliation. However, this method’s graphene preparation has a re­ mixing volume. For such a simple system, the concentration of
latively long ultrasonic time. graphene in the solution was as high as 1 mg/mL after a few hours of
exfoliation. Nicklas Blomquist [71] proposed a new process with low
3.2. High-speed shear stripping energy consumption and easy control. Nano-graphite was exfoliated
from graphite in an aqueous environment. The process produces
The method involves the preparation of graphene by breaking very thin graphite nanoparticles that can be mixed with nano cel­
graphite through the high shear force generated by the high-speed lulose to form highly conductive composites. It can be used in su­
rotation of the disperser drill in the solution. The exercise consists of percapacitors, solar cells, etc. However, when the surface tension of
two drill bits of different sizes inside and outside, driven by a motor. the solvent used (40–50 mJ/m2) is close to that of graphene, e.g., N-
two drill bits inside and out run at high speeds with varying rotation methyl -pyrrolidone (NMP), N-dimethylformamide (DMF), ethanol,
speeds. The structure of the device is shown in Fig.3(f). The graphite etc., it is possible to exfoliate graphene with fewer layers and
solution enters the disperser head when the motor drives the rotor without defects more quickly. HongJun Park [72] put graphite into an

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Fig.5. (a)Principle of ball milling method [79].Copyright 2016 John Wiley & Sons, Ltd; (b) Illustration of the mechanical mechanism for exfoliation via ball milling [62].Copyright
2015 The Royal Society of Chemistry; SEM images of (c) pristine graphite and (d) milled GNS, (e-f) milled NGNS [78].Copyright 2017 ELSEVIER; SEM images: (g) Pristine graphite
and (h) G-MA (inset was the dispersion of samples in water after standing for 3 weeks, the concentration was 1 mg·mL-1)；(i) Digital images of G-MA conductive coating
[52].Copyright 2020 The Royal Society of Chemistry.

NMP solution and prepared graphene using graphite’s hydro­ 3.3. High-pressure homogenization
dynamic induction shear peeling method. The graphene prepared by
this method was ultra-thin and defect-free, with a graphene yield of The high-pressure homogenization method puts graphite in the
23.8%, better than other solution-based methods. Sodium cholate solution through pressurization [75]. The solution flows into the
and urea can accelerate graphene’s exfoliation and increase gra­ valve. Using the energy generated by the high-speed rotation of the
phene’s stability. They effectively prevent the stacking of graphene homogenization valve and preparing graphene through the impact
layer sheets, which leads to better preparation of defect-free few- ring and the schematic diagram of the activation process is shown in
layer or single-layer graphene. Sara Lund [73] proposed a method for Fig.4(a). The homogenization process occurs in the valve, which
rapidly synthesizing graphene using sodium cholate as a surfactant. consists of the impact ring and valve seat. Homogenizer exfoliation
After shearing and peeling in water for 2 h, the graphene con­ preparation of graphene uses the energy generated by high-speed
centration in the solution was as high as 3 mg/mL. Yield is 3%. Most rotation to subject the graphite material to a combination of solid
of the graphene produced was less than five layers thick. With the mechanical shear, high-speed impact exfoliation, centrifugal
increasing number of areas where graphene has been used in recent squeezing pressure, liquid layer friction, cavitation, etc. The graphite
years, the mass production of graphene is of great significance for layer-to-layer horizontal dislocation and slip motion is generated.
commercial and industrial applications. Chang-Seak Lee [74] shear The graphite is exfoliated rapidly. After the high-frequency cycle,
exfoliated graphene in NMP with the help of urea as a stabilizer. stable graphene is finally obtained. Shang [75] put graphite into DMF
Many high-quality, low-defect graphene nanosheets (LDG) could be solution through a high-pressure homogenization method to pre­
prepared under this condition. Most of the graphene nanosheets by pare multilayer graphene on a large scale and with a high yield. The
optimization were monolayers or a few layers, as shown in Fig.3(g). thickness of Fig.4(c) and (d) is significantly smaller compared to the
The size and thickness of graphene were significantly smaller than original graphite in Fig.4(b). Graphite is successfully exfoliated into
that of graphite. Low-defect graphene has a thin, flat structure with thin graphene nanosheets. Qi [76] proposed to combine the ex­
curled and uneven edges, which may be utilized in sectors such as foliation of first-stage Fecl3-based graphite intercalation compounds
electrochemical sensors. The preparation of graphene by shear ex­ (GICs) through a high-pressure homogenization method, which fa­
foliation is usually a simple and controlled process. It allows the cilitates graphene exfoliation due to the sizeable interlayer spacing
preparation of high-quality defect-free monolayer or few-layer gra­ of Fecl3-GICs. This method can produce graphene on a large scale. In
phene in large quantities. It is a basic method for achieving gra­ addition, thermal annealing can prepare αFe2O3/low-layer graphene
phene’s commercial and industrial production. hybrids with a sandwich structure. The high-pressure

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

homogenization method is expected to produce high-performance put graphite and maleic anhydride (MA) into NMP solvent. The
graphene-based energy storage materials as the material shows functionalized graphene was prepared by the ball milling method.
excellent performance in the anode of lithium-ion batteries. Li [46] Compared with the new graphite (Fig.5(g)), the functionalized gra­
used high-pressure homogenization to treat graphene oxide pre­ phene (Fig.5(h)) has similar lateral dimensions to the pure graphite
pared by the Hummers method to obtain graphene with better but with fewer layers. It shows good dispersion in water and polar
electrochemical properties. After characterization by a series of tests solvents. The functionalized graphene coating can be prepared
such as UV-Vis spectroscopy, X-ray diffraction, and Raman, it was without any binder, as shown in Fig.5(i). The surface of the layer is
found that the high-pressure homogenization treatment could re­ flat and smooth, as can be seen by observing the image. Moreover,
duce the number of layers of graphene oxide, resulting in better the coating has a conductivity of 769 S ▪ m-1 at room temperature
dispersion and homogeneity of the graphene oxide solution. The and 2000 S ▪ m-1 after heat treatment at 200 °C for two hours,
electrochemical properties of graphene were significantly improved providing a good strategy for the reversibility of the electronic
after further treatment by high-pressure homogenization. Although properties of graphene. However, wet ball milling with the addition
the preparation of graphene by high-pressure homogenization is of a grinding aid followed by drying will increase the cost of the
relatively energy intensive, this method has a strong refinement experiment. Agglomeration may also occur after drying. However, in
effect and keeps the material properties unchanged. most cases, the sample size obtained by wet ball milling will be
smaller and more uniformly distributed. They will reduce some of
3.4. Mechanical ball mill the heat generated during grinding.
The liquid phase method can prepare graphene dispersion by
Ball milling involves placing graphite, solvents, or solid grinding mechanical force. Generally, the solution used in the preparation
aids with stainless steel balls in a ball milling tank. Centrifugal force process of lithium-ion battery electrodes is NMP. When the resolu­
through the high-speed rotation of the balls in the tank exfoliates tion of graphene exfoliation is NMP, we can combine graphene dis­
the graphene(Fig.5(a)). Two types exist for the ball milling process: persion preparation with lithium-ion battery electrode sheet
dry ball milling and wet ball milling. The dry ball milling process fabrication. This process shortens the process, improves the utili­
involves mixing the graphite with a solid grinding aid in a specific zation rate of graphene, and solves the problem of graphene ag­
ratio. The principle of ball milling to obtain graphene is shown in glomeration. Huang [81] prepared a graphene paste by putting
Fig.5(b), where a rotating steel ball interacts with graphite and ex­ microcrystalline graphite, micron-sized ZrO2 microbeads into an
erts a shear force on the graphite. The shear forces break the van der NMP solution for ball milling. The graphene was exfoliated from the
Waals forces between the graphite layers to obtain graphene. These microcrystalline graphite using mutual shear friction between gra­
collisions occur as the balls roll or create a vertical impact that phite particles. This method increases the yield of graphene ex­
shatters the graphite. Dry ball milling is relatively efficient and foliation to 100% and enables the preparation of graphene on a
simple to operate. Zhu [77] proposed producing high-quality gra­ kilogram scale. The graphene nanosheets prepared had a lateral size
phene by dry ice ball milling of pristine graphite. The study found of 298 nm and good electrical conductivity. They diluted the gra­
that Graphene flakes with a higher specific surface area and a phene paste. Then it is used as a conductive agent for lithium-ion
shorter milling time were obtained by adjusting the milling time, batteries added directly during the preparation of electrode sheets. It
milling speed, and stainless steel ball size. These graphene flakes enhances the specific capacity and cycling stability of lithium-ion
also show advantages such as good storage capacity and excellent batteries. Graphene prepared by the liquid phase method is often
cycling stability in lithium-ion batteries. Using a specific ratio of used in batteries [82–84], capacitors [85], conductive films [86,87],
graphite to urea, Liu [78] found that nitrogen-doped graphene na­ composite materials [88], optical electronics [89], and other fields.
nosheets could be produced using ball milling. As shown in the SEM
image in Fig.5(c-f), ball milling significantly reduced the particle 4. Application of graphene prepared by mechanical exfoliation in
size, successfully creating graphene nanosheets with less than ten lithium-ion batteries
layers and enabling N elements’ doping on graphene. Unlike the
undoped graphene nanosheets, the N-doped graphene nanosheets Researchers have received significant attention from lithium-ion
were more inclined to the aggregated state. The graphene prepared batteries for their excellent properties, including no memory effect,
by this method is low-cost and has good water solubility. The ma­ environmental friendliness, and low self-discharge. The develop­
terial was tested and found to have solid electronic conductivity and ment of information electronics, electric vehicles, and smart grids
lithium-ion storage capacity. The graphene exhibits good cycling has created an enormous demand for lithium-ion batteries with high
stability and multiplicative properties in the negative electrode of energy density, long cycle life, and low cost. The preparation of
lithium-ion batteries. Therefore, it can be used as a promising anode graphene by the shear exfoliation method only undergoes physical
material for lithium-ion batteries. In dry ball milling, graphene is changes during the exfoliation process, not chemical changes. There
prone to "agglomeration" during the ball milling process. It gen­ is no damage to the graphene surface. Graphene is widely used in
erates more heat. The dead corner of the ball mill tank is difficult to lithium-ion batteries due to its good electrical conductivity, large
grind. specific surface area, and high electron leap rate. There are three
Wet ball milling involves putting graphite and solution into a ball main directions for applying graphene in lithium-ion batteries: (1)
milling tank for ball milling. Wet ball milling is an excellent solution Using graphene as an active electrode material. For instance, gra­
to the problems of aggregation and the generation of large amounts phene can serve as a negative electrode. It provides reversible sto­
of heat. Tang [80] put graphite into N-methyl pyrrolidone (NMP) rage space for lithium ions and improves specific capacity and fast
solvent, ball milling for 6 h. Then the supernatant was separated by charging and discharging efficiency [90–92]. As a cathode material,
centrifugation. The graphene concentration in the graphene solution the oxygen-containing functional groups on the surface of graphene
obtained after centrifugation was up to 2.6 mg/mL. The graphene in can undergo a reversible redox reaction with lithium ions to achieve
this solution was large, defect-free, and with few layers. Graphene a high rate of charge and discharge [93,94]. (2) Graphene is com­
paper was created from the exfoliated graphene dispersion using pounded with cathode or anode electrode materials to improve the
fast filtration, heat treatment, and mechanical compression. The electrode material’s performance. For example, graphene com­
graphene paper has an electrical conductivity of 2231 S ▪ cm-1 and a pounded with cathode active material enhances good electrode
thermal conductivity of 1529 W ▪ m-1 ▪ K-1, which has great po­ conductivity [95]. Graphene is compounded with anode active ma­
tential for applications in electronic devices and other fields. Xu [52] terials to build a three-dimensional structure, providing room for

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Fig.6. (a)Flow chart of pole piece preparation; (b) Two ways of incorporating graphene into electrode slurries; (c) Schematic diagram of graphene powder and graphene slurry
when added to a lithium-ion battery.

volume expansion [96–100]. (3) Graphene is used as a conductive use it directly to prepare electrodes, which shortens the process.
additive to provide a fast channel for electron transmission and Graphene can be used in lithium-ion batteries to reduce the internal
improve the conductivity of the electrode [101]. resistance of lithium-ion batteries and improve cycle stability, spe­
cific capacity, and rate performance. Good graphene dispersion is
essential in Li-ion batteries. The second doping method performs
4.1. Lithium-ion battery electrode preparation process and two ways of better than the first in Li-ion batteries. The subsequent section de­
adding graphene scribes the application of graphene in Li-ion batteries using the li­
quid phase mechanical exfoliation method.
The general lithium-ion battery electrode manufacturing process
is shown in Fig.6(a). The primary approach is to dissolve the binder
in NMP, add the conductive additive and electrode material, and mix 4.2. Graphene used as a conductive additive
well. Then the stirred slurry is coated and dried to stamp the elec­
trode sheet. The most basic function of the conductive agent is to penetrate
At present, there are currently two ways of adding graphene to between the particles of the active material, provide a fast channel
lithium-ion electrodes: 1) when preparing the electrode slurry, the for electron transport, and improve the conductivity of the electrode.
graphene powder is directly mixed with the active material, and In addition, the conductive agent can also enhance the electrode
another stirring or the graphene is first dispersed in a solution such sheet’s processability and improve the electrolyte’s wettability. It
as ethanol and then mixed into the electrode slurry; 2) the graphene effectively enhances the migration rate of lithium ions in the elec­
slurry is prepared by the liquid phase method, The graphene slurry trode material and reduces polarization. Ultimately, an improved
prepared by the liquid phase method is mixed directly with the battery charging and discharging efficiency and an extension of the
electrode slurry. The flow chart of the two methods is shown in lithium-ion battery’s service life is accomplished. Currently, the
Fig.6(b). Adding graphene directly as a powder increases the dis­ market’s conductive agents mainly include conductive carbon black,
persion cost and makes it prone to aggregation. Chen[102] in­ conductive graphite, carbon nanotubes, etc [103]. The gap between
vestigated the effect of graphene nanosheets introduced as N-methyl the various properties of traditional conductive agent materials and
pyrrolidone (NMP) dispersions in electrode pastes as conductive graphene is large. There are many advantages of graphene as a
additives on the performance of lithium-ion batteries containing conductive agent. For example, graphene’s excellent conductivity
92 wt% Li1.1(Mn0.6Ni0.4)0.9O2 cathode. The specific capacity and rate can improve lithium-ion batteries’ multiplicative properties
performance of lithium-ion batteries were found to be significantly [104,105]. The high specific surface area of graphene can improve the
improved. It showed that the graphene dispersion prepared by the charge/discharge efficiency of Li- ion batteries [106,107]. The ex­
exfoliation method is stable, well dispersed, and less prone to ag­ cellent thermal conductivity of graphene can improve the thermal
gregation. Thus the graphene slurry process can be compounded stability of lithium-ion batteries. The "surface-dot" contact between
directly with the active material by combining the exfoliation graphene and electrode materials can improve the conductivity of
method with the preparation of electrode slurry. This saves the cost lithium-ion batteries [108].
of dispersing graphene in solution and prevents the aggregation of Norihiro Shimoi[109] used a biaxially independently controlled
graphene flakes. Fig.6(c) illustrates the process of preparing elec­ three-dimensional rotating ball mill to exfoliate graphene with a
trode slurry from graphene using two methods. One method is to unique shape, as shown in Fig.7(a),(b). The exfoliated graphene was a
put graphene powder into the solution for ultrasonic dispersion. thin sheet layer attached to the Si surface. It uniformly dispersed in
Then it is mixed with active material, binder (or conductive agent) to the electrode without stacking using a wet dispersion technique
prepare the slurry for use in lithium-ion batteries. This method takes with a homogenizer and airflow mill. The study of the multiplier
a long time and fails to ensure uniform graphene dispersion. The performance of lithium-ion batteries using silicon powder as the
other is to prepare graphene dispersion by liquid phase method and negative electrode and exfoliated graphene as the conductive

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Fig. 7. (a)SEM images of exfoliated graphene dispersion, (b) magnified SEM [104].Copyright 2021 ELSEVIER; Comparison of the charge/discharge cycle characteristics of exfoliated
graphene, Ketjenblack, and graphite at a rate 0.3 C (c) and 1.5 C (d) [104].Copyright 2021 ELSEVIER; (e) Schematic diagram of the ultrahigh concentration, stable dispersion of RGO
paste as conductive additive for LIB; (f) Charge/discharge curves with the rate 0.1 C of the LFP@CB and LFP@RGO; (g) The charge/discharge profiles at different rate for the; (h) The
rate capacity property of the LFP@CB and LFP@RGO; (i) The cycling performance at the rate of 0.5 C of the LFP@CB and LFP@RGO[105].Copyright 2021 ELSEVIER; (j) Schematic
preparation process and applications of LEGr@SnS heterojunctions; (k) CV curves of LEGr@SnS2-60; (l) Galvanostatic discharge–charge curves of LEGr@SnS2-60 anode in 1st, 2nd,
and 100th cycles; (m) Cycling performance of SnS2, and LEGr@SnS2-X anodes at 300 mA g-1 current density; (n) Rate performance of SnS2, and LEGr@SnS2-X anodes at different
current densities [106].Copyright 2019 American Chemical Society.

additive is shown in Fig.7(c),(d). At a rate of 0.3 C, the capacities of anode materials. The flexible graphene layer can effectively inhibit
exfoliated graphene, Ketjenblack, and graphite at the 30th cycle the volume expansion during lithium-ion batterie’s charging and
were 1500 mAh/g, 460 mAh/g, and 200 mAh/g, respectively. At a rate discharging process. Excellent electrical conductivity can build a
of 1.5 C, the capacities at the 10th cycle were 1700 mAh/g, 800 mAh/ conductive bridge between particles. The high specific surface area
g, and 150 mAh/g, respectively. This method has been tested to de­ of graphene can increase the storage capacity of lithium. Graphene’s
monstrate that graphene as a conductive agent improves the rate high porosity allows for complete electrolyte infiltration. The high
property of Li-ion batteries. It is superior to commonly used con­ porosity of graphene can make the electrolyte thoroughly infiltrated.
ductive agents like carbon black or graphite. Therefore, the application of graphene and its composites in the
The graphene slurry is prepared by wet ball milling and added anode of lithium-ion batteries dramatically enhances the perfor­
directly during the electrode preparation as a conductive agent for mance of lithium-ion batteries[111–117].
lithium-ion battery cathodes. As shown in Fig.7(e), Teng [110] pre­ SnS2 is popular in lithium-ion battery anode materials due to its
pared monolayer reduced graphene oxide powder utilizing swelling- high theoretical capacity and low cost. Still, it receives limitations in
oxidation-swelling of expandable graphite. Reduced graphene oxide terms of poor cycling stability and rate. As shown in Fig.7(j), Li [118]
was put into an NMP solution with PVP in the ratio of 10:1. The prepared graphene sonication by adding graphite and sodium citrate
reduced graphene oxide slurry was prepared to utilize high-speed to NMP. Then LEGr@SnS2 was prepared by microwave-assisted sol­
ball milling, which was used with carbon black conductive additives vothermal method. It was used as an anode for lithium-ion batteries.
for lithium-ion batteries with LiFePO4 as the active cathode material. Its conductivity was improved. The diffusion rate of lithium ions was
The electrode performance was greatly improved. Experimental re­ accelerated. As depicted in Fig.7(k-n), through the cyclic voltam­
sults indicate that the charge/discharge capacity, rate performance, metric curve test, constant current charge/discharge test, cycle test,
and cycling performance of lithium-ion batteries, including gra­ and rate performance test, it is proved that the addition of graphene
phene, are superior to those using solely carbon black as a con­ successfully solves the problems of poor stability and poor rate
ductive addition (Fig.7(f-i)). Adding only a tiny graphene electrode performance. Zhang[119] first prepared multilayer graphene by mi­
material to the electrode significantly improves performance. Huang cromechanical exfoliation followed by ball milling to prepare SiOx/
[81] used microbeads as grinding media in microcrystalline graphite graphene composites. The optimized SiOx/graphene composites
to prepare a high-yield graphene conductive slurry in NMP solution were used as anodes for lithium-ion batteries with excellent elec­
by mechanical force through mutual shear friction between graphite trical conductivity. The initial reversible capacity was 1325.7 mAh/g,
particles. This conductive slurry was diluted and used as a con­ and the capacity was 1269.7 mAh/g after 120 cycles, with a retention
ductive additive for lithium-ion batteries with an active material of rate of 95.8%. Compounding graphene with the active anode material
LiNi0.8Co0.1Mn0.1O2 and improved the specific capacity and cycling can significantly improve capacity, cycle stability, and rate perfor­
stability of the batteries with better performance than other carbon- mance.
based conductive agents.
4.4. Graphene composite with active material prepared by the shearing
4.3. Graphene composite with active material prepared by the shearing method for lithium-ion battery cathode
method for lithium-ion battery anode
For lithium-ion battery cathodes, it is necessary to meet high
The graphite anode of lithium-ion battery is it easy to form li­ reversible capacity, high potential and stability, non-toxicity, and
thium dendrites during the charging and discharging process. It low cost[120]. Most cathode materials are lithium iron phosphate,
causes dead reasoning, poor stability, and difficulty achieving high cobaltate, etc. The rupture of the structure during the charging and
rate charge and discharge. Therefore, it is urgent to develop new discharging process can limit its application in functional materials.

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

Table 2
Application of liquid-phase exfoliation graphene in lithium-ion batteries.

Application direction Preparation method of graphene Electrochemical performance effect

Conductive agent Ball milling method [109,110] Rate performance improvement; Capacity improvement
Jet cavitation [38] Capacity improvement
Hummers [104] Rate performance improvement
Hydrothermal method [105] Rate performance improvement
anode Ultrasonic [118,122] Rate performance improvement; Capacity improvement; Cycling stability improvement
Micromechanical stripping [119] Rate performance improvement; Capacity improvement
Hydrothermal method [123] High specific capacity; Long cycle life; Rate performance improvement
High pressure homogenization [76] Cycling stability improvement; High reversible capacity
Hummers [113,124,125] Reversible capacity improvement; Rate performance improvement; Cycling Stability improvement

On the other hand, graphene’s unique properties significantly con­ well; (3) the stirred slurry is coated and (4) the stamped electrode
tribute to the positive electrode of lithium-ion batteries. However, sheet is dried.
there needs to be more research on the mechanical exfoliation of Mechanical liquid-phase preparation of graphene uses mechan­
graphene in the form of slurry for direct incorporation into lithium- ical shear forces to exfoliate graphite in the liquid phase to obtain
ion battery cathodes. graphene. The process of preparing electrode slurry for lithium-ion
Chen[102] dispersed graphene in an NMP solution. battery is to prepare electrode slurry by mixing active substance,
Li1.1(Mn0.6Ni0.4)0.9O2 powder, PVDF binder, and carbon black were conductive agent, and binder by mechanical force. The method of
stirred well in the NMP solution with graphene dispersion to prepare preparing graphene in the liquid phase and the process of preparing
the electrodes for lithium-ion battery cathodes. A small amount of electrode slurry all require mechanical shear force. Then there is the
graphene additive can significantly increase the overall electrode possibility of integrating the graphene preparation process with the
electronic conductivity and the specific capacity of lithium-ion electrode paste preparation process. Suppose the preparation of
batteries. Chen[121] synthesized V2O5 microspheres by hydro­ graphene can be integrated with the preparation of the electrode
thermal method. The V2O5/graphene composite was prepared by slurry. In that case, this shortens the process of preparing the elec­
ball milling method. This composite was used in lithium-ion battery trode slurry. As shown in Fig.8(b), graphite and binder PVDF are put
cathodes. The capacity was 313.65 mA h g-1 at a current of 150 mA g- into the NMP solution to form a graphite dispersion, which is stirred
1
. The capacity exceeded 150 mA h g-1 at a current of 3 A g-1. The high uniformly using shear force to form the electrode slurry. A small
conductivity of graphene effectively improves the conductivity and amount of graphene is successfully exfoliated during the shear force
cycling stability of V2O5 at high current densities. mixing of the slurry. The exfoliated graphene acts as a conductive
Table 2 provides a summary of the application of liquid-phase agent in the electrode. From the current research status of graphene,
preparation of graphene in lithium-ion batteries. The liquid phase there has yet to be a report on the preparation process of graphene
method for the preparation of graphene is a simple and non-pol­ directly integrated with the preparation process of lithium-ion bat­
luting process, which allows the preparation of high-quality gra­ tery electrodes. This may be a development direction for applying
phene. The liquid phase method enables the preparation of graphene graphene in lithium-ion batteries.
slurry, which is added directly to the electrode preparation process
without any other treatment. As shown in Table 2, when graphene is 6. Summary and outlook
added to lithium-ion batteries as a conductive agent for positive and
negative electrodes or compounded with active anode materials, it In recent years, graphene has been widely used in many fields.
can effectively improve the rate characteristics of lithium-ion bat­ The preparation of graphene on a large scale and with high quality is
teries. There is also a significant improvement in performance, such an essential requirement to enable its development in various areas.
as cycle stability. Top-down method of graphene preparation obtains graphene from
bulk graphite by breaking the van der Waals forces between graphite
5. Discussion on the integration of graphene preparation and layers and sheets with the help of external forces. This paper sys­
electrode slurry preparation process tematically summarizes the preparation of graphene by mechanical
exfoliation. The preparation process of the lithium-ion battery
The graphene preparation procedure consists of three primary electrode is to put the conductive agent, binder, and active material
steps(Fig.8(a)): (1) graphite mixed with a solvent (or grinding aid) to into the NMP solution. Then the solution is stirred uniformly to
prepare the graphite dispersion; (2) exfoliation of the graphene obtain the electrode material slurry and dry it on copper or alu­
dispersion by shear force; (3) centrifugation and purification. minum foil to get the electrode piece. During the preparation of the
Four steps comprise the electrode slurry preparation procedure electrode slurry, the active substance is uniformly mixed in the so­
(as shown in Fig.6(a)): (1) the binder is dissolved in NMP; (2) the lution by mechanical shear force. This paper summarizes the lit­
conductive additives and electrode materials are added and stirred erature from the perspective of the fusion of graphene preparation

Fig. 8. (a) Graphene preparation flow chart; (b) Graphene preparation and electrode slurry preparation process integration diagram.

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Y. Wen, H. Liu and X. Jiang Journal of Alloys and Compounds 961 (2023) 170885

and the preparation process of lithium-ion battery electrode mate­ Tianjin University of Technology. Wen Ya reports financial support
rial slurry. was provided by Tianjin University of Technology. Huimin Liu re­
This paper systematically introduces the principle of the top- ports financial support was provided by Tianjin University of
down method, and then classifies and summarizes the top-down Technology.
process according to the source of external force. This article pro­
vides a synopsis of the mechanical techniques used to manufacture References
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relationships which may be considered as potential competing deposition graphene for transparent and flexible touch screen with low sheet-
interests:Xunyong Jiang reports financial support was provided by

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