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High-efficiency, self-grinding exfoliation of small graphene nanosheets from

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mater.scichina.com link.springer.com Published online 25 April 2022 | https://doi.org/10.1007/s40843-021-2015-8
Sci China Mater 2022, 65(9): 2463–2471

High-efficiency, self-grinding exfoliation of small graphene nanosheets

from microcrystalline graphite driven by microbead milling as conductive
additives
Limei Huang1, Hao Li2, Xinxin Wang1, Yuanli Ding1, Jianfeng Wang1* and Lei Jiang3

ABSTRACT Direct mass exfoliation of graphene from bulk between layers to promote exfoliation in solvents. However,
graphite with high yield and productivity for commercial ap- rGO is defective with an ID/IG larger than 1 and a C/O atomic
plications is challenging. This work proposes self-grinding ratio less than 10 [15,17–19]. Given its defects, rGO is a non-
exfoliation using the mutual shear friction of graphite parti- viable alternative to graphene. Although chemical oxidation can
cles to fabricate graphene from microcrystalline graphite. The be scaled up potentially, this process involves multiple steps of
concept is implemented using microbeads as the grinding oxidation, purification, and reduction, inevitably generating
medium to drive the shear friction between graphite nano- huge acidic wastewater and causing environmental pollution.
crystals in a high-concentration paste. The proposed approach Another widely studied strategy is liquid-based direct exfo-
substantially improves graphene yield from 6.3% to 100% and liation, which involves a series of approaches for the direct
simultaneously generates a record productivity of 7.5 g h−1 L−1, delamination of graphite in liquids into graphene without any
achieving total graphite-to-graphene conversion on the kilo- chemical reaction to maintain the in-plane atomic order [20–
gram scale. The as-prepared graphene nanosheets have an 26]. Delamination is driven by shear force, which is typically
average lateral size of 298 nm and the same C/O atomic ratio provided in a mixture of low-concentration graphite and a
as the pristine graphite. In addition, the well-exfoliated, small solvent by a sonicator, a high-shear mixer, or a ball mill. Liquid-
nanosheets display good electrical conductivity and exhibit based direct exfoliation can produce large-volume, few-layer
significant potential as conductive additives that improve the graphene dispersion, and the graphene obtained from this
specific capacity and cyclic stability of Li-ion batteries better process has fewer defects (ID/IG < 0.25) and a higher C/O ratio
than commercial carbon-based conductive particles. (>20) than that of the graphene from chemical exfoliation.
However, this strategy has low exfoliation efficiency and yield,
Keywords: self-grinding exfoliation, microcrystalline graphite, which seriously restricts the applications of graphene. A detailed
graphene, conductive additive literature survey (Table S1) reveals that a productivity above
2 g h−1 L−1 and a yield above 80% have yet to be achieved. In
fact, 90% of the studies surveyed achieve productivity below
INTRODUCTION 1 g h−1 L−1, which is considerably low for commercial produc-
Given its unique two-dimensional (2D) structure and unprece- tion. These problems are ascribed to the limited shear working
dented mechanical, electrical, and thermal properties, graphene area of mechanical equipment components that exert shear force
promises a wide range of applications in many fields, including on graphite particles. For example, the mixed head of a
mechanical reinforcements [1–4], gas barrier coatings [5,6], laboratory high-shear mixer only provides a working area of a
transparent conductive films [7,8], thermal management [9,10], few square centimeters per gram of graphite. The grinding
and energy storage devices [11–13]. In layered bulk graphite, medium of a laboratory ball mill can provide a working area of a
strong in-plane covalent bonds but weak out-of-plane van der few tens of square centimeters per gram of graphite at most.
Waals force enable top-down delamination into thin nanosheets Hence, even after 15 years of progress in graphene technology, a
at nanometer or even atomic thickness. In the last 15 years, physical exfoliation approach for the high-efficiency and high-
many laboratory protocols to extract graphene from cheap and yield production of graphene on a large scale remains to be
abundant graphite resources have emerged; among these pro- developed.
tocols, chemical exfoliation has shown considerable achieve- In this study, we propose self-grinding exfoliation through the
ments [14]. Strong acids or oxidants are usually used to produce mutual grinding of graphite particles to extract graphene from
a graphene oxide (GO) precursor for the scalable production of microcrystalline graphite. The concept takes the surface area of
reduced GO (rGO) [15]. In general, oxygen-containing groups microcrystalline graphite particles as the shear working area to
introduced by oxidation reaction widen the interlayer distance greatly improve the efficiency and yield of graphite exfoliation.
from 0.335 to 0.7 nm [16] and weaken the attractive force Microcrystalline graphite contains numerous graphite nano-

1
College of Materials Science and Engineering, Hunan University, Changsha 410082, China
2
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
3
CAS Key Laboratory of Bio-Inspired Materials and Interface Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing
100190, China
*
Corresponding author (email: [email protected])

September 2022 | Vol. 65 No. 9 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2022 2463
ARTICLES SCIENCE CHINA Materials
crystals with a lateral size of several hundreds of nanometers and weighing. The concentration ratios after and before centrifuga-
a thickness of 50–100 nm, which corresponds to a theoretical tion were determined to be the yield.
surface area of 8.7–17.4 m2 g−1. The utilization of the large
surface area of microcrystalline graphite particles as the shear Characterizations
working area would overcome the limitation of traditional X-ray diffraction (XRD) curves were obtained on an X-ray dif-
liquid-based direct exfoliation strategies (e.g., probe ultra- fractometer under the scanning rate of 10° min−1 (Rigaku,
sonication, high-shear mixing, and ball milling) that only MiniFlex). Raman spectra were obtained on a micro-confocal
depend on the working area of equipment components (ultra- Raman spectrometer (Renishaw, inVia) with a 532-nm laser
sonic probe, mixing head, and grinding ball). To implement the excitation. X-ray photoelectron spectroscopy (XPS) was per-
concept, we use mechanical stirring as the energy source and formed on an X-ray photoelectron spectrometer (Thermo Fisher
microbeads as the medium to drive the rotation of graphite Scientific, ESCALAB 250XI). Rheological properties were mea-
nanocrystals. The mutual shear friction between rotated graphite sured with an HAAKE Mars60 rheometer at 25°C. The mor-
nanocrystals is achieved by decreasing the interparticle distance phology and microstructure of the samples were characterized
by increasing graphite concentration in the solvent to a paste. by a field-emission scanning electron microscope (SEM, Hitachi,
Indeed, the self-grinding exfoliation greatly contributes to the S-4800) and a transmission electron microscope (TEM, FEI,
yield and productivity of thin, small graphene nanosheets. In Tecnai G2 F20 S-TWIN). The surface morphology was obtained
addition, self-grinding exfoliation inherits the advantages of by an atomic force microscope (AFM, Veeco, NanoManVS). The
traditional liquid-based direct exfoliation. That is, this strategy small graphene exfoliated from microcrystalline graphite as a
does not introduce heteroatoms or decrease the C/O ratio conductive additive was evaluated through the electrochemical
because it is a direct exfoliation process without any chemical measurement of the assembled button cell. The weight ratio of
reaction. Moreover, the as-prepared small graphene nanosheets NCM811, graphene, and PVDF in the cathode was 90:5:5. The
are suitable as conductive additives for Li-ion batteries and assembled cell was cycled galvanostatically with a Neware BTS
display obvious advantages over commercial carbon-based 4008 tester at 25°C. The cyclic voltammogram curve was tested
conductive additives in improving specific capacity and cyclic at 0.1 mV s−1 on an electrochemical workstation (Corrtest CS
stability because of their unique 2D structure and excellent 2350). Electrochemical impedance measurements were con-
electron conduction. ducted over the frequency range of 0.01–100 kHz.

EXPERIMENTAL SECTION RESULTS AND DISCUSSION

We designed a microbead milling process of high-concentration
Materials microcrystalline graphite paste in a solvent to implement self-
Microcrystalline graphite (Hunan Chenzhou Lutang Micro- grinding exfoliation. The microcrystalline graphite appeared as
crystalline Graphite Carbon CO., Ltd., 200 mesh, purified by microscale powder with a size of several tens of micrometers and
10% HF acid), ZrO2 beads (0.5 mm in diameter, Saint-Gobain), contained numerous graphite nanocrystals with a thickness of
N-methyl-2-pyrrolidone (99.0%, Aladdin), LiNi0.8Co0.1Mn0.1O2 several tens of nanometers and a size of several hundreds of
(NCM811, Hunan Shanshan New Energy Technology CO., nanometers (Fig. 1a). N-methyl-2-pyrrolidone was selected as
Ltd.), carbon black (SP, Saibo Electrochemical Material Net- the solvent because its surface energy matches that of graphene
work), polyvinylidene fluoride (PVDF, HSV900, Saibo Electro- (70.9 versus 71.0 mJ m−2). Thermodynamically, their small dif-
chemical Material Network), and 1 mol L−1 LiPF6 (ethylene ference of surface energy would decrease their mixing enthalpy
carbonate:dimethyl carbonate (EC:DMC) = 1:1 volume ratio and thus facilitate the direct exfoliation of graphene from
with 5% fluoroethylene carbonate (FEC), Duoduo Reagent microcrystalline graphite [27–29]. A schematic of bead milling is
Network) were used without further purification. shown in Fig. 1b. A dumbbell-shaped agitator connected to a
high-speed motor was used to stir ZrO2 beads. Microscale ZrO2
Self-grinding exfoliation of graphene from microcrystalline beads with the diameter of 500 μm, which are one or two orders
graphite of magnitude smaller than the balls widely used in traditional
The self-grinding exfoliation concept was implemented by the ball milling, were employed to facilitate the formation of fast
microbead milling of a viscous microcrystalline graphite paste. A turbulent flow and homogenize the whole mixed system [30,31].
high concentration facilitated the physical contact and shear With the same ZrO2 bead loading, small beads would have a
friction between graphite particles during grinding. Micron-size large surface area to contact with graphite particles and a small
beads as the grinding medium helped homogenize the whole inter-bead distance to shear the ground mixture uniformly, both
mixed system, forming a fast turbulent flow. Microcrystalline of which increase the exfoliation yield and productivity (Fig. S1).
graphite powder, ZrO2, and N-methyl-2-pyrrolidone microbeads Meanwhile, the initial concentration of microcrystalline graphite
with a weight ratio of 1:72.2:15.7 were added to a grinding tank was set to be as high as 6%, forming a viscous paste to ensure
and then ground at a peripheral speed of 23 m s−1. A fine and mutual physical contact between graphite particles. After
smooth graphene paste with a mass concentration of 6% was grinding for several hours, the paste obviously becomes fine and
obtained after grinding. The ZrO2 beads were separated from the smooth. Such exfoliation was achieved at ambient temperature
graphene paste through vacuum-assisted filtration with a 60- without the use of any reactive agents, such as oxidated acid,
mesh stainless steel screen. The paste was diluted into a dis- strong alkali, and intercalant. Moreover, the microbead milling-
persion with a low concentration of 0.5 mg mL−1 for the yield driven, self-grinding exfoliation is easily scaled up proportion-
test. The dispersion was centrifuged at 500 r min−1 (centrifugal ally for the kilogram scale production of graphene paste
force: 28 ×g) for 45 min. Then, the supernatant was collected, (Fig. 1c). The graphene paste is stable for a long storage period.
and its concentration was tested by filtration, drying, and After storing for a year, the paste can be directly diluted with N-

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SCIENCE CHINA Materials ARTICLES

Figure 1 High-efficiency preparation of graphene paste from micro-

crystalline graphite mineral through self-grinding exfoliation driven by mi-
crobead milling. (a) Natural microcrystalline graphite. (b) Schematic of
exfoliation. (c) As-prepared 11 kg graphene paste with a mass concentration Figure 2 SEM images of microcrystalline graphite before (a) and after (b)
of 6%. (d) Change in graphene yield with grinding time. (e) Comparison of grinding for 30 min. SEM images of macrocrystalline graphite before (c) and
yield and productivity of graphene prepared by self-grinding and other ex- after (d) grinding for 30 min. (e) Total yield of graphene at an increasing
foliation approaches. Reference data are listed in Table S1. initial concentration of microcrystalline graphite from 0.1% to 6% after
grinding for 8 h, proving significant self-grinding exfoliation at a con-
centration above 0.7%. (f) Contribution of self-grinding to yield at an in-
creasing initial concentration. (g) Total productivity of graphene at an
methyl-2-pyrrolidone by 1000 times into a uniform dispersion increasing initial concentration. (h) Dependence of G′ and G′′ of the ground
without aggregation (Fig. S2). mixture on the oscillation strain.
The self-grinding exfoliation approach can produce graphene
with high yield and productivity. Fig. 1d shows the change in
graphene yield with grinding time. In specific, the yield sharply interlayer distance of 0.337 nm (Fig. S4). Moreover, it has an
increases at the initial stage and then reaches 84.3% within only obvious D band at 1348 cm−1 in the Raman spectra, indicating
2 h, indicating that most of the microcrystalline graphite parti- the existence of non-negligible defects (Fig. S5). After grinding
cles are delaminated into graphene at this stage. The yield is for only 30 min, large pristine microparticles are crushed into
increased to 100% when the grinding time is prolonged to 8 h. several small graphite nanoparticles (Fig. 2a, b). For comparison,
Productivity is another critical factor that determines the feasi- natural macrocrystalline graphite is ground for the same dura-
bility of the industrial production of graphene. The change in tion, but the crushed graphite particles are still large, i.e., more
productivity with grinding time is shown in Fig. S3. The pro- than 10 μm (Fig. 2c, d). XRD shows that it has a sharp diffrac-
ductivity is as high as 81.8 g h−1 L−1 within 20 min. The pro- tion peak at 26.4°, indicating high crystallinity (Fig. S4). Raman
ductivity that corresponds to a yield of 100% is still up to spectrum shows that it has a slight D band at 1348 cm−1, sug-
7.5 g h−1 L−1, although the grinding time is prolonged to 8 h. The gesting few defects (Fig. S5). The comparison indicates that the
yield and productivity are far higher than previously reported inherent structural defects facilitate the crushing of micro-
values achieved by liquid-based direct exfoliation strategies crystalline graphite particles into graphite nanocrystals by ZrO2
(Fig. 1e), such as ultrasonics (12.5%, 0.025 g h−1 L−1) [20], high- microbeads.
speed shearing (0.1%, 0.017 g h−1 L−1) [32], and ball milling The high efficiency of exfoliation is closely related to the self-
(26%, 0.43 g h−1 L−1) [25]. grinding of graphite nanocrystals, as proven by the influence of
The exfoliation process involves the fracture of natural the initial concentration of microcrystalline graphite on gra-
microcrystalline graphite by numerous ZrO2 microbeads. phene yield (Fig. 2e). In the low concentration range of 0.1%–
Microcrystalline graphite consists of many nanocrystals and 0.7%, which was widely adopted in previous liquid-based direct
exhibits a wide XRD peak at 26.4°, which corresponds to an exfoliation, the yield is always stabilized at a low level of

September 2022 | Vol. 65 No. 9 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2022 2465
ARTICLES SCIENCE CHINA Materials
approximately 6.3%. This result indicates that the exfoliation
arising from the shear friction between microbeads and graphite
particles is insufficient. This phenomenon is further confirmed
by increasing the loading weight of grinding microbeads in a
wide range, which only generates a marginal increase in yield
(Fig. S6). Remarkably, graphene yield begins to increase sub-
stantially when the initial concentration is larger than 0.7%.
Increasing the initial concentration from 0.7% to 6% sharply
improves the yield from approximately 6.3% to 100%. This result
indicates that a high-concentration facilitates self-grinding
delamination between rotating graphite nanocrystals because of
a decreased interparticle distance. We assume that the con-
tribution of microbead-graphite grinding to yield is the same as
that in the low initial concentration range. The contribution of
graphite-graphite grinding to yield was calculated, as shown in
Fig. 2f. The contribution of self-grinding to yield sharply
increases from 0% at 0.7% initial graphite concentration to
93.7% at 6% initial graphite concentration. Aside from its yield,
the productivity of graphene also increases sharply when the
initial concentration is larger than 0.7%. Increasing the initial
concentration from 0.7% to 6% results in a 136.4-fold
improvement in productivity from 0.055 to 7.5 g h−1 L−1
(Fig. 2g). The sharp improvement in yield and productivity
indicates that self-grinding plays a critical role in the graphene
exfoliation.
We measured the rheological property of the ground mixture
to prove that the interparticle distance decreases at a high
concentration for self-grinding. Fig. S7a shows the elastic and
viscous moduli as a function of frequency at a fixed shear strain
of 0.1%. The elastic modulus is one order of magnitude higher
than the viscous modulus over the frequency range of
0.1–100 Hz. This result indicates that the elastic behavior is
dominant, and the ground graphite nanocrystals form a jammed Figure 3 Morphology and size of graphene exfoliated from microcrystal-
network (Fig. S7b) [33,34]. Fig. 2h shows the elastic (G′) and line graphite. (a) SEM and (b) TEM images after grinding for 8 h. (c) High-
resolution TEM image at the edge of a graphene nanosheet. (d) Statistical
viscous (G′′) moduli as a function of shear strain at a fixed
histogram of the lateral size of graphene nanosheets extracted from TEM.
frequency of 1 Hz. When the shear strain is less than 10%, the (e) AFM image of graphene nanosheets. (f) Height profiles. (g) Statistical
elastic modulus is the main response, and the paste shows a histogram of the thickness of graphene nanosheets extracted from AFM.
solid-like behavior. By contrast, when the shear strain is more (h) Statistical histogram of the lateral size of graphene nanosheets extracted
than 10%, the viscous modulus is the main response, and the from AFM.
paste shows fluid-like behavior. The change indicates that the
jammed network can be disturbed and flow under shear stress.
The thixotropy is also proved by a steady rheology test. As information of graphene, we diluted the paste with N-methyl-2-
shown in Fig. S8, the paste shows a non-Newtonian fluid pyrrolidone solvent for TEM observation. Low-magnification
behavior [35], that is, the higher the shear rate, the lower the image reveals that the graphene sheets are transparent and
viscosity. The viscosity decreases sharply under shear from ultrathin (Fig. 3b). It is also observed that adjacent nanosheets
449 mPa s at 100 s−1 to 76 mPa s at 1000 s−1. The shear-induced are overlapped locally, which is due to the aggregation during
flow is also visually reflected by manual stirring (Fig. S8, the drying for sample preparation. High-resolution image at the
inset). After stirring with a glass rod, the viscous graphene paste edge of the nanosheet exhibits six parallel lines with a total
placed in a syringe starts to flow out. The shear thinning is thickness of about 2 nm (Fig. 3c). Their average lateral size is
attributed to the rotation, mutual shear friction, and the orien- 258 nm by statistics analysis of 150 nanosheets (Fig. 3d). To
tation of graphite particles in the jammed physical network, further testify that the paste does not contain graphite particles,
improving the fluidity of the paste. Such thixotropic behavior we dilute the paste and then centrifugate it at a high speed
enables the smooth exfoliation of microcrystalline graphite (1500 r min−1) for TEM observation of the sediment. It is con-
during microbead milling. firmed that the sediment is composed of thin nanosheets with a
The morphology and size of the graphene within the paste are thickness of several atomic layers (Fig. S10). AFM was also
characterized by SEM, TEM and AFM. We directly dried the performed to determine the thickness and lateral size of the
paste to remove N-methyl-2-pyrrolidone solvent and observed graphene nanosheets. The representative AFM image presents
the morphology of graphene. Many thin nanosheets were many uniformly distributed bright spots (Fig. 3e). The corre-
observed from SEM images, suggesting that the self-grinding sponding height profiles extracted from the topographical image
predominantly peels off graphene along the basal plane of gra- are shown in Fig. 3f. Enlarged view also shows that the
phite nanocrystals (Fig. 3a and Fig. S9). To acquire the size nanosheet height is less than 3 nm (Fig. S11). It can be found

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SCIENCE CHINA Materials ARTICLES
that the thickness of all graphene nanosheets is less than 3 nm, the pristine graphite to 2689.0 cm−1 for the exfoliated graphene.
implying that the thickest nanosheet consists of nine atomic The position of the 2D band can reflect the exfoliation of
layers. The thickness distribution obtained by statistical analysis graphene nanosheets. In general, decreasing the number of
of 100 sheets is in the range from 0.35 to 3 nm with an average graphene layers would cause the red-shift of the 2D band [38].
value of 1.8 nm (less than 10 atomic layers on average) (Fig. 3g). Fig. 4c, d show the XPS spectra of the pristine microcrystalline
The lateral size distribution is in the range from 150 to 600 nm graphite and the exfoliated graphene. Pristine graphite has a C/O
with an average value of 298 nm (Fig. 3e), consistent with the atomic ratio of 17.2:1. After exfoliation, no heteroatoms are
result from TEM (Fig. 3b). In a word, small-size graphene introduced, and the C/O ratio slightly changes, confirming that
nanosheets are successfully exfoliated from microcrystalline the bead milling-driven, self-grinding exfoliation is a purely
graphite by the self-grinding exfoliation approach. physical process without any chemical reaction (Table S2). This
The structure of the exfoliated graphene was characterized by process is different from chemical intercalation exfoliation and
XRD, Raman spectroscopy, and XPS. Fig. 4a shows the XRD chemical oxidation exfoliation, which inevitably introduce het-
patterns of the pristine microcrystalline graphite and the exfo- eroatoms and/or decrease the C/O ratio. Deconvolution of the C
liated graphene. Their (002) reflection peak is located at 26.4°, 1s peak reveals that the sp2-C structure arising from the hon-
which corresponds to an interlayer distance of 0.337 nm. By eycomb lattice in the basal plane of graphene is predominant.
contrast, the peak width at half height broadens and the dif- The peak areas of C=O and C–O show no changes compared
fraction intensity weakens after exfoliation, indicating a with those of the pristine graphite. The only change is the peak
decreased order in the c axis. This change arises from the suc- area of C–C increases, which is probably ascribed to the
cessful exfoliation along the basal plane of graphite nanocrystals. increased edge defect introduced by the ball milling-caused
Fig. 4b shows the Raman spectra of the pristine microcrystalline fractures of microcrystalline particles. The result is consistent
graphite and the exfoliated graphene. The spectrum of pristine with the effect that the intensity of the D band in the Raman
graphite was characterized by a typical D band at 1345.2 cm−1, a spectrum increases after exfoliation.
G band at 1576.5 cm−1, and a 2D band at 2696.2 cm−1. After The high C/O atomic ratio and moderate ID/IG ratio endow
exfoliation, the spectrum of graphene presents two changes. One graphene with good electron conduction ability. The graphene
is that the D band becomes strong, enabling the intensity ratio of paper prepared through filtration of a diluted dispersion has an
the D peak to the G peak (ID/IG) to increase from 0.36 for the electrical conductivity of 7700 S m−1, which is comparable to
pristine graphite to 0.65 for the exfoliated graphene. This change that of chemical rGO paper (7200 S m−1) [39] and solvent-
indicates that self-grinding increases the degree of defect. Our exfoliated graphene paper from macrocrystalline graphite
previous work proved that microbead milling generates defects (6500 S m−1) [24]. Our graphene features good electrical con-
only at edges through crushing large graphite particles into small ductivity and small size and allows high-efficiency and high-
pieces [36,37]. The defect type is different from the plane defect concentration production on a large scale. Thus, we attempted
generated by the conventional strong acid oxidation exfoliation. to evaluate the graphene paste as a conductive additive in a
The other change is that the 2D band shifts from 2696.2 cm−1 for commercial LiNi0.8Co0.1Mn0.1O2 cathode electrode of Li-ion

Figure 4 (a) XRD curves; (b) Raman spectra of the microcrystalline graphite and exfoliated graphene. (c) XPS spectra of the microcrystalline graphite and
the deconvolution of C 1s peak. (d) XPS spectra of exfoliated graphene and the deconvolution of C 1s peak.

September 2022 | Vol. 65 No. 9 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2022 2467
ARTICLES SCIENCE CHINA Materials
batteries (Fig. S12). Fig. 5a presents the initial three galvanostatic increasing the potential difference by 0.085 V (Fig. S14). The
charge-discharge profiles of the graphene-containing electrode increased potential difference is probably related to serious
at a current density of 20 mA g−1. The discharge capacity polarization of the cathode because 0D carbon black particles
increases from 196 mA h g−1 for the first cycle to 203 mA h g−1 offer a worse electron conduction path than 2D graphene
for the second cycle and then stabilizes at 204 mA h g−1. The nanosheets [40].
slight rise implies that the Li+ is released completely from the Electrochemical impedance spectroscopy was performed for
graphene-coated electrode because of the formation of a solid the two types of cells containing the graphene-coated and carbon
electrolyte interphase film at the first cycle. The stable discharge black-coated electrodes before cycling to understand the effect of
capacity is 21 mA h g−1 higher than that of the electrode coated graphene additive on the electrochemical kinetics of the elec-
by Super P, a type of commercial carbon black (Fig. S13). The trode. They display typical Nyquist plots, and the corresponding
cyclic voltammogram curves of the graphene-coated electrode equivalent circuit model is shown in Fig. 5c. The two types of
for the initial three cycles are shown in Fig. 5b. The main cells have the same constant phase-angle element that describes
cathode and anode peaks are located at 3.794 and 3.688 V, which the nonideal capacitance of the surface layer and the same
correspond to a potential difference of 0.106 V. Under the same contact resistance (Rc) that reflects an uncompensated Ohmic
condition, the main cathode peak for the carbon black-coated resistance between the working and reference electrodes [40].
electrode is shifted toward a higher voltage (3.896 V), thereby However, the charge-transfer resistance (Rct) of the graphene-

Figure 5 Electrochemical performance of the cell with the exfoliated graphene as a conductive additive. (a) Charge-discharge profiles for the initial three
cycles at a rate of 0.1 C (1 C = 200 mA g−1). (b) Cyclic voltammogram curves of three cycles at a sweep rate of 0.1 mV s−1. (c) Comparison of electrochemical
impedance spectra of the graphene-containing cells with the carbon black-containing cells. (d) Comparison of rate performance of the graphene-containing
cells with the carbon black-containing cells when increasing the current rate from 0.1 to 5 C. (e) Discharge capacity and Coulombic efficiency of the graphene-
containing cells versus carbon black-containing cells at 1 C (1 C = 200 mA h g−1).

2468 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2022 September 2022 | Vol. 65 No. 9
SCIENCE CHINA Materials ARTICLES
coated electrode manifested by the semicircle size at the high-
frequency region of electrochemical impedance spectra is
235 Ω cm−2, which is lower than that of the carbon black-coated
electrode (265 Ω cm−2). The Warburg impedance (Zw) related to
Li-ion diffusion resistance is reflected from the tail in Nyquist
plots at a low frequency [41]. The graphene-coated electrode
shows a steeper tail than the carbon black-coated electrode. The
smaller semicircle and steeper tail suggest that the graphene
additive offers a better electron conduction pathway than carbon
black, thus causing the effective diffusivity and transfer of Li ions
from the interior of the electrode to the electrolyte.
The rate capability at increasing current density from 20 to
1000 mA g−1 is shown in Fig. 5d. The graphene-coated electrode
exhibits excellent rate performance with a discharge capacity of
209.4 mA h g−1 at 0.1 C, 195.7 mA h g−1 at 0.5 C, 188.1 mA h g−1
at 1 C, 176.8 mA h g−1 at 2 C, and 136.5 mA h g−1 at 5 C. These
values are obviously higher than those of the carbon black-
coated electrode. Moreover, their capacity difference becomes
more apparent with increasing current density. This result
suggests that the massively exfoliated small graphene has a
prominent advantage over the commercial carbon-based parti-
cles in applications requiring fast charge/discharge. Fig. 5e
depicts the representative cycle performance of the graphene-
containing cell at the current rate of 1 C. After cycling 500 times,
its capacity is still up to 152.2 mA h g−1, retaining 83.2% capacity
relative to its initial value. Moreover, the Coulombic efficiency is
always more than 99%, indicating that the graphene conductive
network coated on the electrode is stable during long-term
charge-discharge cycles. The carbon black-containing cell shows
a fading capacity with a relatively poor capacity retention of 46% Figure 6 Morphology of the graphene-coated and carbon black-coated
after cycling 500 times. In addition, the rate capability and electrodes before and after charge-discharge cycle. Graphene-coated elec-
capacity retention of the small graphene-coated electrode is trode before (a, b), and after (c, d) 500 cycles; carbon black-coated electrode
before (e, f), and after (g, h) 500 cycles.
superior to those of the normal large graphene-coated electrode
(Table S3). Large graphene reportedly protracts the diffusion
distance of Li+ transfer, thereby increasing impedance [42].
The morphologies of the graphene-coated electrode before CONCLUSION
and after cycling for 500 times were observed via SEM to elu- High-efficiency, total-conversion exfoliation from microcrystal-
cidate the excellent electrochemical performance. The low- line graphite to small graphene is achieved through a self-
magnification image shows the uniform distribution of graphene grinding process driven by the microbead milling of high-con-
nanosheets without aggregation in the as-prepared electrode centration graphite paste. The mutual shear friction between
(Fig. 6a). The enlarged image reveals that the LiNi0.8Co0.1Mn0.1O2 graphite nanocrystals plays a critical role in the high-efficiency
microparticles are coated by many small graphene nanosheets, exfoliation, generating a record combination of up to 100% yield
different from the pristine active particle with bare morphology and 7.5 g h−1 L−1 productivity. Such self-grinding exfoliation
(Fig. 6b and Fig. S12). After long-term cycling, the morphology does not introduce heteroatoms or decrease the C/O ratio
is maintained without obvious changes (Fig. 6c, d). By contrast, because of the absence of any chemical reaction. The small
the carbon black-coated electrode presents a separation mor- graphene nanosheets with good electrical conductivity are
phology with carbon black nanoparticles filling the gap of potential conductive additives that can decrease the polarization
LiNi0.8Co0.1Mn0.1O2 microparticles (Fig. 6e, f). The same long- and resistance of the cathode of Li-ion batteries, generating
term cycling generates the breakage of most active micro- higher capacity than commercial spherical carbon-based con-
particles (Fig. 6g, h). Their different structural changes could be ductive additives. Moreover, the small graphene nanosheets
related to the electron conduction path of the formed carbon- prevent the premature breakage of active electrode particles
based network. Well-dispersed graphene nanosheets constitute during long-term charge-discharge cycling and endow the cell
an interconnective network and contact with the active particles with high cyclic stability. These findings offer a new method to
in a face-to-face form, promoting the uniform intercalation/ effectively exfoliate graphene on a large scale and widen the
deintercalation of Li ions from the active particles. However, practical applications of graphene in Li-ion batteries.
spherical carbon black constitutes an aggregation network and
contacts with the active particles in a point-to-point form, Received 8 December 2021; accepted 28 February 2022;
causing the local intercalation/deintercalation of Li ions from published online 25 April 2022
the active particles. The local electrochemical reaction results in
stress concentration in the interior of the active particles, thus 1 Wang B, Li Z, Wang C, et al. Folding large graphene‐on‐polymer films
promoting their breakage. yields laminated composites with enhanced mechanical performance.

September 2022 | Vol. 65 No. 9 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2022 2469
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quantities of defect-free few-layer graphene by shear exfoliation in li-
project, and wrote the manuscript. Li H participated in the investigation and
quids. Nat Mater, 2014, 13: 624–630
21 Phiri J, Gane P, Maloney TC. High-concentration shear-exfoliated drew the schematic diagram. Wang X and Ding Y participated in the in-
colloidal dispersion of surfactant-polymer-stabilized few-layer graphene vestigation. Wang J and Jiang L supervised the experiments and provided
sheets. J Mater Sci, 2017, 52: 8321–8337 theoretical guidance. All authors contributed to the general discussion.
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foliation of graphene. Small, 2010, 6: 864–871 Conflict of interest The authors declare that they have no conflict of
23 De S, King PJ, Lotya M, et al. Flexible, transparent, conducting films of interest.
randomly stacked graphene from surfactant‐stabilized, oxide‐free gra-
phene dispersions. Small, 2010, 6: 458–464 Supplementary information Supporting data are available in the online
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based on ball-milling exfoliated graphene. Adv Funct Mater, 2017, 27:

2470 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2022 September 2022 | Vol. 65 No. 9
SCIENCE CHINA Materials ARTICLES
Limei Huang is currently a PhD candidate at the College
of Materials Science and Engineering, Hunan University. 珠磨驱动微晶石墨自研磨高效制备小尺寸石墨烯作
Her research interest focuses on 2D nanomaterial ex- 为导电添加剂
foliation from layered bulk materials.
黄丽梅1, 李豪2, 王新新1, 丁元力1, 王建锋1*, 江雷3
摘要 在过去十五年, 将块状石墨直接高产率、高效率地剥离为石墨
烯一直是一个重大挑战. 针对这一问题, 本文提出了一种自研磨剥离新
概念, 即利用石墨颗粒之间相互剪切摩擦, 从微晶石墨矿中剥离石墨烯.
Jianfeng Wang received his PhD degree from Beihang 实验中通过微珠作为研磨介质驱动高浓度石墨晶体颗粒相互研磨的过
University in 2013. Afterward, he worked as an assistant 程成功执行了这一概念. 经证实, 自研磨大幅提高了石墨烯的剥离产率
professor at the School of Chemistry, Beihang University. (从6.3%提高至100%), 并获得了破纪录的剥离效率(7.5 g h−1 L −1), 在实
He worked as a visiting scholar at Nanotech Institute, 验室实现了从微晶石墨到石墨烯的公斤级转化. 所制备的石墨烯纳米
University of Texas at Dallas in 2015. He joined Hunan 片横向尺寸小(298 nm), C/O原子比与起始微晶石墨相同, 导电性良好.
University in 2017 and is now a professor at the College of
该小尺寸石墨烯适合作为锂离子电池的导电添加剂, 在改善电池的比
Materials Science and Engineering. His research interest
focuses on exfoliation of 2D nanomaterials and their 容量和循环稳定性方面优于商用碳基导电颗粒.
bioinspired assembly.

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