Powder Technology 411 (2022) 117921

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Powder Technology
journal homepage: www.journals.elsevier.com/powder-technology

Enhanced electrochemical performance of the fluidization separation

graphite powders from waste power lithium-ion batteries by phenolic resin
carbon coated
Changliang Shi a, b, c, Silong Zhang a, Zhendong Jiang a, c, *, Haozhi Sun a, Chuanxiang Zhang a, c,
Fengfeng Xue b
a
College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454003, China
b
Do-Fluoride Chemical Co., LTD, Jiaozuo 454003, China
c
Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo 454003, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Recovery and reuse graphite powders

from waste lithium batteries is studied.
• A column fluidized bed can recover the
grade of graphite powders with 96.42%
• Phenolic resin carbon coating technol­
ogy can repair the pores and defects.
• Repaired graphite powders have a high
capacity and first coulomb efficiency.

A R T I C L E I N F O A B S T R A C T

Keywords: The recycling of waste lithium batteries (LIBs) is important for the healthy development of the LIBs industry. In
Waste lithium-ion batteries this work, a column fluidized bed was designed to recover graphite powder from waste LIBs, and the phenolic
Graphite powders resin-coated recovered graphite powder composites ware prepared by liquid-phase impregnation-carburization
Fluidization separation
method, which effectively repaired the pores and defects on the surface of recycled graphite powders. The
Phenolic resin carbon coated
Electrochemical performance
composites exhibited better Li storage performance than the recovered graphite powders. When the current
density was 0.05 A/g, the composite obtained at 5% phenolic resin coating displayed a high reversible capacity
of 451.0 mAh/g and an initial coulombic efficiency of 68.0%. The specific capacity was maintained at 131.9
mAh/g at a higher current density 1.0 A/g, the reversible capacity gradually increased from 464.4 to 546.1 mAh/
g after 100 cycles at a current density of 0.1 A/g, indicating outstanding rate performance and excellent cycling
stability.

* Corresponding author at: College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454003, China.
E-mail address: 18623855902@163.com (Z. Jiang).

https://doi.org/10.1016/j.powtec.2022.117921
Received 28 April 2022; Received in revised form 7 August 2022; Accepted 6 September 2022
Available online 10 September 2022
0032-5910/© 2022 Elsevier B.V. All rights reserved.
C. Shi et al.
1. Introduction
Currently, global energy and environmental systems are facing sig­
nificant challenges. Fuel vehicles, as the major contributor to oil con­
sumption and CO2 emissions, need to be revolutionized changes, while
the electric vehicle market is on a rapid growth trend. As the core
component of electric vehicle, the output of power lithium-ion batteries
(LIBs) also maintains a rapid increase in the long momentum [1].
However, large-scale utilization of electric vehicles results in power
lithium battery disposal [2]. It is reported that the cumulative decom­
missioning of power LIBs in China will reach approximately 200,000 t
(approximately 25.0 GWh) in 2022 and is expected to reach 780,000 t
(approximately 116.0 GWh) by 2025 [3]. Heavy metals such as Co, Mn,
and Ni in waste power LIBs are not only harmful to humans but also
damage the ecological environment [4,5]. Moreover, waste power LIBs
contain various valuable and in shortage components. The recovery and
reuse of valuable components of waste power LIBs have high environ­
mental protection and economic value.
At present, the recovery of waste power LIBs is mainly achieved
through the treatment of cathode materials, through core technologies
of pyrometallurgy and hydrometallurgy; however, the recovery rate is
only 3.0% of the total amount of materials. The recovery of graphite
powder (GP), the main component of waste power LIBs, contained in the
anode materials can be achieved through three processes: pretreatment,
secondary treatment, and advanced treatment. Pretreatment and sec­
ondary treatment are mainly based on crushing, grinding, and separa­
tion. In particular, separation can be performed by employing the
fluidization separation technology, which is based on the density dif­
ference between copper foil and the GP, or the flotation technology,
which is based on the floatability of the GP. Nonetheless, the ultimate
purpose of separation is the achievement of high-grade GP. Yu, Liu, and
Zhang, et al. [6–8] mainly carried out the GP recovery test based on the
flotation technology, using diesel as the flotation collector and methyl
isobutyl methanol as the foaming agent and achieved a GP recovery rate
of 98.0%. Anna et al. [9] conducted Fenton-reagent-assisted flotation at
an Fe2+/H2O2 ratio of 1:120 and a liquid/solid ratio of 75:1 to effec­
tively recover GP from a − 0.25 mm crushed product.
Advanced treatment is mainly used to further purify recovered GP
and confer excellent electrochemical properties to it. Zhu et al. [10]
adopted a green and environmentally friendly low-temperature fluori­
nation roasting-water leaching process to obtain GP with a purity of
99.98%. Yang et al. [11] collected GP from waste LIBs through two-stage
calcination; acid-leached it with hydrochloric acid to remove impurities
such as lithium, copper, and aluminum; and removed aluminum and
copper through pH adjustment to obtain regenerated GP with enhanced
electrochemical performance. Xiao et al. [12] ensured the electro­
chemical performance of GP with large layer spacing through purifica­
tion via acidification and the oxidation of ammonium persulfate. Gao
et al. [13] found that using a sulfuric acid curing-acid leaching method
to remove impurities from waste graphite in LIBs allowed the regener­
ation of GP with a purity of 99.6%. They also found that impurity
removal efficiency was much higher than that through direct acid
leaching. Regenerated GP showed excellent characteristics, with
morphology and structure similar to those of commercial graphite. Ruan
et al. [14] treated graphite recovered from waste LIBs by pyrolysis, acid
leaching, graphitization, and amorphous carbon coating to obtain re­
generated graphite. Compared with recovered graphite, regenerated
graphite had a smaller specific surface area, fewer pore defects, and a
higher graphitization degree, making it more beneficial. It exhibited
excellent rate performance and cycling stability when used as an anode
material for LIBs, with an initial Coulombic efficiency (ICE) of 90.64%
and a specific capacity of 344.0 mAh/g at a current density of 0.2 A/g.
Regenerated graphite was stable over 250 cycles of cycling performance
tests at 0.5 A/g. Although the successful application of carbon coating as
a modification technology has been verified, there are only a few reports
on the carbon coating modification technology of LIB waste graphite
2
Powder Technology 411 (2022) 117921
after the advanced treatment. Xu, Wang, and Wang et al. [15–17] suc­
cessfully synthesized new composite materials by using different carbon
sources and by employing a one-step solution combustion method and a
vapor deposition method; and they have higher reversible capacity and
excellent rate performance than the recycled GP mentioned in Sabisch
et al. [18]. The carbon coating technology for the advanced treatment of
GP is of great significance for improving the electrochemical perfor­
mance of LIB anode material recycling [19–21].
Waste power LIBs contain 12.0%–21.0% (wt%) graphite. With the
rapid increase in demand for graphite in aerospace, national defense
science and technology, and other fields (estimated at 250,000 t/year),
graphite has gradually become an important resource and, thus, has
become increasingly expensive [22–25]. Upon long-term usage and
storage, although the chemical composition of GP does not change, its
chemical activity significantly degrades; thus, its charge and discharge
performances do not meet the vehicle power demand [26,27]. Recov­
ered graphite has the properties of conductivity, heat conduction, high-
temperature and low-temperature resistance, corrosion resistance, ra­
diation resistance and self-lubrication. Thus, it can be commercially
used in fields such as production of nuclear energy, development of new
materials and derivation of electronic information. In addition, the
echelon utilization technology can be implemented for GP from waste
power LIBs [22,28,29].
In this study, we applied the high-grade GP recovered from waste
power LIB anode materials by optimizing the separation conditions for
fluidization; the anode materials were used as a precursor and phenolic
resin (PR) was selected as the encapsulated carbon source. Recovered GP
was modified through PR carbon coating via liquid-phase impregnation-
carburization and reapplied as a LIB anode material. The effects of the
PR proportion on the microstructure and electrochemical properties of
recovered GP were investigated. The results of this study can provide a
reference for the separation, recovery, and material utilization of GP in
waste power LIBs, and is conducive to the formation of a complete
technical system suitable for the recycling of graphite materials in waste
power LIBs.
2. Experimental section
2.1. Experimental process
A cylindrical fluidized bed was used, and the qualified products
(grade measurement) were mixed with asphalt carbon. The experi­
mental process is shown in Fig. 1.
The complete preparation process of recycled GP coated with PR
carbon is shown in Fig. 1c. The PR and recycled GP were weighed in
proportions of 3:97, 5:95 and 8:92. The content of PR in each composite
sample were 3%, 5% and 8% (wt%). PR was dissolved in a certain
amount of absolute ethanol and the GP proportion was added. The
mixture was placed in a water bath pot, stirred at a constant temperature
of 50.0 ◦ C, solidified at 120.0 ◦ C, and cooled to room temperature before
being ground into a powder. Carbonization was then carried out in a
nitrogen atmosphere, and the temperature was raised to 400.0 ◦ C at a
rate of 5.0 ◦ C/min for 1.0 h. The mixture was then heated to 850.0 ◦ C at
the same rate and carbonized for 2.0 h. After cooling, a PR‑carbon-
coated recycled graphite powder (denoted as GP/C) was obtained. Ac­
cording to the different proportions of PR, the composite samples were
recorded as GP/Cx (x = 3, 5, 8), and the recycled GP samples that were
not subjected to the coating treatment was recorded as GP.
2.2. Experimental raw materials
The anode materials of waste power LIBs were acquired from waste
anode materials after industrial application in an enterprise in Henan (as
shown in Fig. 1a). PR was obtained from Shanghai McLean Biochemical
Technology Co., Ltd.
C. Shi et al. Powder Technology 411 (2022) 117921

2.3. Fluidization separation and recovery experiment polypropylene film as the diaphragm, and a 1 mol/L LiPF6/EC-DMC
(1:1, v/v) solution as the electrolyte.
In this experiment, the waste anode materials were pretreated by a Galvanostatic charge-discharge (0.01–3.0 V at multiple current
combination of shear crushing and hammer crushing. The fluidization densities) measurements were performed on a Neware Battery Testing
separation of crushed materials with different particle sizes was then System CT-4008 (Shenzhen, China). Electron impedance spectroscopy
carried out by using a cylindrical fluidized bed (Fig. 2) to obtain high- (EIS, between 100.0 kHz and 0.01 Hz) and cyclic voltammetry (scan rate
quality GP by optimizing the particle size and air velocity.
The microstructures of the samples were characterized by X-ray
diffraction (XRD) analysis using a Cu Kα (λ = 1.5406 Å) Smart Lab X-ray
diffraction analyzer (Shimadzu Corporation, Japan). The tube voltage
was 40.0 kV, the scanning range was 10.0◦ -80.0◦ , and the scanning rate
was 10.0◦ /min. Field-emission scanning electron microscopy (SEM;
Hitachi SU8020) was used to observe the surface morphology of the
samples.

2.4. Re-preparation and electrochemical performance test of anode

materials

The electrode materials (GP/C3, GP/C5, GP/C8, and GP), conductive

carbon black, and polyvinylidene fluoride (PVDF) were fully mixed in a
mass ratio of 8:1:1 and stirred in N-methylpyrrolidone (NMP) solution to
obtain a slurry, before being evenly coated on a 0.2 mm copper foil,
dried at 100.0 ◦ C in a vacuum drying oven, and stamped into a circular
electrode sheet with a diameter of 15.0 mm. The average loading mass of
the anode materials was about 0.9 mg. The button battery was assem­
bled with an electrode plate made in an argon glove box as the working
Fig. 2. Structure of the cylindrical fluidized bed.
electrode, Li metal as the counter electrode, Celgard 2400

Fig. 1. Research content frame diagram.

3
C. Shi et al.
of 0.5 mV/s) were conducted using a CHI 660D Electrochemical
Workstation (Shanghai Chenhua Corp.) to analyze the performance of
the batteries.
3. Results and discussion
3.1. Column fluidized bed separation test results
After the waste LIB anode materials were treated by a hammer
crusher and a universal crusher, the material shown in Fig. 1b was ob­
tained after a screening test. The grade relationship of copper and GP
with different particle sizes measured by ICP is shown in Fig. 3. The
evaluation indices of the sorted products are shown in Eqs. (1) to (4). For
the separation test, 100 g of the sample was weighed. The grade and
recovery of recovered GP under the influence of different wind speeds
are shown in Fig. 4.
DCu
RCu (%) = × 100%
DCu ± dCu
dC
RC (%) = × 100%
DC ± dC
MCu (g)
LCu (i) = × 100%
Mi (g)
MC (g)
LC (i) = × 100%
Mi (g)
where RCu and RCare the recoveries (%) of the copper powder and GP,
respectively. DCu and dCu are the masses (g) of copper in the heavy
component and copper in the light component. LCu(i) and LC(i) are the
grades (%) of the copper powder and GP in the i-th grade material. MCu
and MC represent the masses (g) of the copper powder and GP of each
grade, respectively, and Mi is the total mass (g) of the crushed material at
each stage.
Figs. 3 and 4 show that as the particle size of the pulverized anode
materials decreases, the grade of the copper powder gradually de­
creases, while that of the GP gradually increases. The grade of the GP,
with a particle size of <0.074 mm, reached 97.9%, and the amount of
copper mixed in it was very small. The samples with particle size of
>0.5 mm is mainly composed of copper, and the GP content is low. The
samples with particle sizes of <0.074 mm and > 0.5 mm can be recycled
directly. 0.074–0.5 mm sized particles are found in mixed samples of GP
Fig. 3. Grade distribution of the GP and copper powder of different parti­
cle sizes
Powder Technology 411 (2022) 117921
(1)
(2)
Fig. 4. Recovered graphite grade and recovery rate under the influence of
(3) different wind speeds.
and copper powder; 0.074–0.5 mm is the particle size suitable for col­
(4) umn air separation. Fig. 4 shows that with an increase in wind speed, the
overall quality of light components improved, but the grade value de­
creases significantly owing to the high copper content of the samples.
When the wind speed was low, the grade of GP reached 96.42%, but the
recovery rate was low. This study focuses on the grade value; thus, the
light products after classification at a wind speed is 0.5 m/s are selected
and mixed with the sieved samples having a particle size of <0.074 mm
for use as coating raw materials.
3.2. Structure and surface morphology of GP/Cx
The XRD patterns of GP and GP/Cx are shown in Fig. 5. As seen in
Fig. 5, the characteristic peaks of the (002), (100), (101), (004), and
(110) crystal planes representing the graphite microcrystalline structure
appear at approximately 26.6◦ , 42.5◦ , 44.6◦ , 54.7◦ , and 77.5◦ for GP,
GP/C3, GP/C5, and GP/C8, respectively. The peak positions do not
change significantly, indicating that the PR-coating carbonization
treatment does not change the crystal structure of the recycled GP raw
materials [30,31]. However, the characteristic peak corresponding to
amorphous carbon formed after the PR-coating carbonization treatment
was not observed in the XRD pattern, because the amount of PR was very
low. However, the changes in the crystal structure of the samples before
and after coating could still be observed in the corresponding XRD
patterns. The apparent change is that the intensities of the (002), (101),
and (004) diffraction peaks of GP/Cx are significantly lower than those
of the uncoated recycled GP, and the intensities of the XRD peaks
decrease gradually with an increase in the proportion of PR. This shows
that with the carbon coating process, the crystallinity of the samples
decreases and the disordered structure is more readily formed, which
indicates that PR carbon is successfully coated on the surface of recycled
GP [32].
To further investigate the surface morphology characteristics of the
GP/Cx, the SEM images of GP and GP/Cx are shown in Fig. 6. As shown
in Fig. 6a, the surface of GP is relatively rough, and there are many pores
and defects. This is mainly because Li ions are repeatedly embedded and
separated from the graphite layer during multiple charge-discharge
processes in the LIB, resulting in the irregular expansion of the
graphite crystal structure and causing serious damage to the graphite
crystal structure [33]. As shown in Fig. 6 (b-d), PR carbon is coated on
the surface of recycled GP, which effectively repairs the pore and defect
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C. Shi et al. Powder Technology 411 (2022) 117921

Fig. 5. XRD patterns of GP and GP/Cx.

structures on the surface of recycled GP, thereby significantly improving
surface morphology of recycled GP. With an increase in the PR pro­
portion, the surface of recycled GP gradually becomes smoother, and the
pores and defects disappear slowly. When the PR proportion is 5.0%, the
pores and defects on the surface of recovered GP disappear. As shown in
Fig. 6c, a uniform amorphous carbon layer is formed on the surface of
recovered GP. The existence of the amorphous carbon layer can effec­
tively inhibit the decomposition of the electrolyte and improve the
electrochemical performance of recovered GP. When the PR proportion
continues to increase, excess PR will independently form a large amount
of pyrolysis carbon, which reduce the overall Li storage capacity of the
material [32].
3.3. Electrochemical properties of GP/Cx
The first constant current charge-discharge curves of GP and GP/C
anode materials at 0.05 A/g current density are shown in Fig. 7. In Fig. 7,
the charge–discharge curves of GP, GP/C3, GP/C5, and GP/C8 show a
long and gentle potential platform below 0.2 V, which corresponds to
the intercalation reaction process of Li ions between graphite layers
[34]. A voltage plateau also appears in the discharge curves at approx­
imately 0.75 V, which corresponds to the formation of the solid

Fig. 6. SEM images of GP and GP/Cx: (a) GP; (b) GP/C3; (c) GP/C5; (d) GP/C8.

5
C. Shi et al.
Fig. 7. The first constant current charge-discharge curves of GP and GP/Cx
anode materials at 0.05 A/g current density.
Table 1
First charge-discharge specific capacities and ICEs of GP and GP/Cx anode
materials.
Sample Discharge specific Charge specific Irreversible specific
capacity/(mAh/g) capacity /(mAh/ capacity /(mAh/g)
g)
GP 583.4 386.3 197.1
GP/C3 649.7 430.9 218.8
GP/C5 663.1 451.0 212.1
GP/C8 657.4 429.1 228.3
electrolyte interphase (SEI) film [35]. According to the constant current
charge-discharge test results, the first charge-discharge specific capacity
and ICE of the GP and GP/Cx anode materials were calculated. The re­
sults are listed in Table 1. The reversible capacity of GP is higher than
the theoretical specific capacity of modified graphite; however, the first
charge-discharge efficiency is low. It may be because more pores and
defects on the surface of recovered GP generate more Li storage active
sites, while numerous Li ions are consumed to form the SEI film,
resulting in a lower ICE [36]. The charge-discharge specific capacities of
GP/Cx were higher than that of GP. This is because carbon coating al­
lows the repair of the pores and defects on the GP surface and
strengthens the affinity between the surface of GP and the electrolyte. In
contrast, PR produces many micropores owing to the escape of small
molecules during carbonization, thereby increasing the storage space of
Li ions [37]. With an increase in the PR proportion, the specific capac­
ities and first charge-discharge efficiencies of GP/Cx first increased and
then decreased.
When the PR proportion was 5.0%, the first charge-discharge specific
capacity of GP/C5 was the highest, the first discharge specific capacity
was 663.1 mAh/g, the first charge specific capacity was 451.0 mAh/g,
and the ICE was 68.0%. However, when the PR proportion continued to
increase, the charge-discharge specific capacity and ICE of GP/C5
showed a downward trend. This may be because the carbon layer of GP
is too thick, which hinders the insertion of Li ions into the graphite layer,
thus reducing its charge-discharge specific capacity. When too much PR
is carbonized, more micropores are produced; thus, more Li ions need to
be consumed to form the SEI film, the irreversible capacity increases,
and the ICE decreases [38].
The rate performances of GP and GP/Cx are shown in Fig. 8; their
average specific charging capacities at different current densities are
listed in Table 2. As shown in Fig. 8, compared with GP, the charging
specific capacities and stabilities of GP/Cx at different current densities
had significantly improved, and GP/C5 showed the highest rate per­
formance. When the current density was 0.05 A/g, the charging specific
Powder Technology 411 (2022) 117921
capacity of GP/C5 was 453.2 mAh/g (averaging the values for 10 cy­
cles), and the specific capacity gradually decreased with the increase in
current density. When the current density increased to 1.0 A/g, its
specific capacity was maintained at 131.9 mAh/g, and the higher spe­
cific capacity at high current density may be attributed to the PR carbon
coated on the surface of recycled GP that served as a Li ion diffusion
buffer layer, which improves the high current charge–discharge char­
acteristics of anode materials [39]. In addition, after 60 cycles, when the
current density was restored to 0.1 A/g, the specific capacity increased
to 442.7 mAh/g, which is essentially completely restored, further indi­
cating that the GP/C5 anode material has high electrochemical stability.
The cycling performances of the GP and GP/Cx anode materials at
0.1 A/g current density are shown in Fig. 9. As shown in Fig. 9, with the
increase in the number of charge and discharge cycles, the capacity of
GP decreased significantly, while the cycling performances of GP/Cx
significantly improved, and the capacity increased gradually. Among
them, GP/C5 demonstrated the highest cycling performance. After 100
charge-discharge cycles, the reversible capacity increased from the
initial 464.4 mAh/g (the average of the first 10 reversible capacities) to
546.1 mAh/g (the average of the last 10 reversible capacities), which is
much higher than the reversible capacity of GP. This is because an
appropriate amount of PR is coated on the surface of GP to form an
amorphous carbon coating layer with high mechanical strength, which
effectively prevents structural breaking caused by the repeated insertion
ICE and removal of Li ions from graphite microcrystals, and improves the
(%)
cycling stability of the anode materials of recycled GP [40]. At the same
time, with the increase in cycle times, the surface of electrode materials
66.2 is further activated, and more active sites are added to improve the
66.3
68.0
lithium storage capacity [41].
65.3 To further analyze the reaction process on the electrode, cyclic vol­
tammetry (CV) was carried out on the GP and GP/C5 negative electrode
materials. The CV curves for the first three cycles of the GP and GP/C5
anode materials at a 0.5 mV/s scanning rate are shown in Fig. 10. In
graphs (a) and (b), the recovery curves of GP before and after coating
(1st cycle) show apparent reduction peaks at the voltage platforms of
approximately 1.2, 0.5, and 0.01 V, which correspond to the Li inter­
calation of ultrafine micropores, the formation of SEI film, and the Li
intercalation of graphite crystallites and nanopores [42]. Simulta­
neously, the apparent oxidation peaks are observed at the voltage
platforms of approximately 0.34 and 0.31 V for GP and GP/C5,
respectively, corresponding to the reversible Li removal of graphite
microcrystals [43]. It is worth noting that the voltage platform for GP/
C5 is smaller than that for GP, indicating that PR carbon coating reduced
the delirium potential of recycled GP in GP/C5. This suggests that the
polarization of the electrode is reduced, which is conducive to the
progress of the electrode reaction. This can also explain the excellent
rate performance of recycled GP after carbon coating, which is mainly
due to the improvement in the Li ion diffusion coefficient of the GP
anode material after carbon coating [44]. In addition, the second and
third cycle curves of recovered GP before and after coating coincide,
indicating that both anode materials have good cycling reversibility and
high electrochemical stability.
Fig. 11 shows the AC impedance spectra of the GP and GP/Cx anode
materials after different cycles. In Fig. 11, the curves of the GP and GP/
Cx anode materials are composed of semi-circular arcs in the middle-
frequency and high-frequency regions, and a slash in the low-
frequency region. The high-frequency semi-circular arc corresponds to
the formation of SEI film and contact resistance (Rf), while the medium-
frequency semi-circular arc corresponds to the charge transfer resistance
(Rct) between the electrode and the electrolyte surface; the slash rep­
resents the Warburg resistance (Re) of the limited transfer of Li ions in
the negative electrode material [45]. From Fig. 11(a), the impedance
spectra of GP/C5 with fresh uncycle and after three cycles are obviously
different. The radii of the semi-circular arcs in the medium-frequency
and high-frequency regions of GP/C5 after three cycles are smaller
than that of GP/C5 with fresh uncycle, indicating the resistance of
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C. Shi et al. Powder Technology 411 (2022) 117921

Fig. 8. Rate performances of GP and GP/Cx anode materials.

electrode material decreases and the conductivity improves after

Table 2
cycling. From Fig. 11(b), the radii of the semi-circular arcs in the
Average specific charging capacities of GP and GP/Cx anode materials at
medium-frequency and high-frequency regions for GP/C3 and GP/C5
different current densities.
are both smaller than that of GP, with GP/C5 showing the smallest radii.
Sample Current density (A/g)
The radius of the semi-circular arc in the medium-frequency and high-
0.05 0.1 0.3 0.5 0.7 1.0 0.1 frequency regions of GP/C8, is larger than that of the uncoated recy­
GP 317.9 218.8 178.9 103.0 73.4 51.6 268.4 cled GP, indicating that when the coating amount was small, the PR
GP/C3 430.0 436.1 288.4 152.9 115.8 92.7 435.0 carbon coating reduced the resistance of the anode material of recycled
GP/C5 453.2 452.3 347.0 278.9 207.7 131.9 442.7 GP. When PR proportion was high, PR carbon coating caused an increase
GP/C8 436.9 410.6 202.2 109.7 89.8 62.6 411.7
in the resistance value. This is because when the PR proportion is low,
PR carbon can be well coated on the surface of recycled GP to reduce the

Fig. 9. Cycling performances of GP and GP/Cx anode materials.

7
C. Shi et al.
Fig. 10. CV curves of (a) GP and (b) GP/C5 anode materials (scanning rate: 0.5 mV/s).
Fig. 11. EIS profiles of GP and GP/Cx anode materials after different cycles: (a) GP/C5 with fresh uncycle and after three cycles; (b) GP and GP/Cx after three cycles.
number of defects, so as to avoid the formation of excessive SEI film and
reduce the contact resistance and charge transfer resistance. In contrast,
when the PR proportion is high, more SEI film will be formed, which
increases the contact resistance and charge transfer resistance. Never­
theless, too much amorphous carbon increases the resistivity of the GP
anode materials, thereby increasing the internal resistance of the battery
[46]. Therefore, PR proportion is an important factor affecting the
electrochemical performance of the GP anode materials. The small
radius of the semi-circular arc in the middle-and high-frequency regions
of GP/C5 indicates that it has low resistance and exhibits excellent
electrochemical performance.
4. Conclusion
The effective separation of GP and copper powder was achieved by
columnar fluidized bed separation with anode materials of waste power
LIBs in this work. It was found that wind speed and particle size are
important factors in fluidization separation efficiency. With a particle
size of 0.074–0.50 mm and a wind speed of 0.5 m/s, the grade of the GP
recovered by column fluidized bed separation was 96.42%. On this
basis, the GP was modified with PR carbon coating by the liquid-phase
impregnation carbonization method using GP as the raw material and
PR as the coating carbon source. Phenolic resin carbon coating could
repair the pores and defects on the GP surface and significantly improve
the morphology of GP, making it's surface smoother without changing
the crystal structure of GP. GP/C5 with a PR ratio of 5.0% exhibited
excellent lithium storage properties when used as an anode material for
Li-ion batteries, with a reversible capacity of up to 451.0 mAh/g at a
current density of 0.05 A/g, and the ICE of 68.0%, both higher than
8
Powder Technology 411 (2022) 117921
those of GP (386.3 mAh/g, 66.2%). At a high current density of 1.0 A/g,
the specific capacity was maintained at 131.9 mAh/g. At a current
density of 0.1 A/g, the reversible capacity gradually increased from
464.4 to 546.1 mAh/g after 100 cycles, showing high-rate performance
and excellent cycling stability. This work is of guiding significance both
to alleviate the shortage of graphite resources and to improve the
recycling system of waste power lithium batteries.
CRediT authorship contribution statement
Changliang Shi: Conceptualization, Methodology, Formal analysis,
Writing – original draft. Silong Zhang: Methodology, Resources.
Zhendong Jiang: Methodology, Validation, Supervision. Haozhi Sun:
Investigation. Chuanxiang Zhang: Writing – review & editing, Vali­
dation. Fengfeng Xue: Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This paper was financially supported by China Postdoctoral Science
C. Shi et al.
Foundation (Grant No. 2020M672180), the key project of science and
technology innovation of the education department, Henan Province
(Grant No.21A440012), the young backbone teachers funding of Henan
polytechnic University(2019XQG-05), and the fundamental research
funds for the universities of Henan Province (NSFRF200311).
References
[1] L. Hou, B. Xing, H. Zeng, W. Kang, H. Guo, S. Cheng, G. Huang, Y. Cao, Z. Chen,
C. Zhang, Aluminothermic reduction synthesis of Si/C composite nanosheets from
waste vermiculite as high-performance anode materials for lithium-ion batteries,
J. Alloys Compd. 922 (2022), 166134.
[2] M. Fan, X. Chang, Q. Meng, L.-J. Wan, Y.-G. Guo, Progress in the sustainable
recycling of spent lithium-ion batteries, SusMat 1 (2021) 241–254.
[3] C. Wang, Z. Yuan, Y. Wang, W. Cao, F. Jiang, Overview of key technologies for
echelon utilization of decommissioned power batteries, Adv. New Renewable
Energy 9 (2021) 327–341.
[4] S. Natarajan, V. Aravindan, Burgeoning prospects of spent lithium-ion batteries in
multifarious applications, Adv. Energy Mater. 8 (2018) 1802303.
[5] Y. Zhang, N. Song, J. He, R. Chen, X. Li, Lithiation-aided conversion of end-of-life
lithium-ion battery anodes to high-quality graphene and graphene oxide, Nano
Lett. 19 (2019) 512–519.
[6] J. Yu, Y. He, Z. Ge, H. Li, W. Xie, S. Wang, A promising physical method for
recovery of LiCoO2 and graphite from spent lithium-ion batteries: Grinding
flotation, Sep. Purif. Technol. 190 (2018) 45–52.
[7] J. Liu, H. Wang, T. Hu, X. Bai, S. Wang, W. Xie, J. Hao, Y. He, Recovery of LiCoO2
and graphite from spent lithium-ion batteries by cryogenic grinding and froth
flotation, Miner. Eng. 148 (2020), 106223.
[8] G. Zhang, Y. He, H. Wang, Y. Feng, W. Xie, X. Zhu, Application of mechanical
crushing combined with pyrolysis-enhanced flotation technology to recover
graphite and LiCoO2 from spent lithium-ion batteries, J. Clean. Prod. 231 (2019)
1418–1427.
[9] V. Anna, S. Johanna, R. Martin, S.-G. Rodrigo, A contribution to understanding the
flotation behavior of lithium metal oxides and spheroidized graphite for lithium-
ion battery recycling, Colloids Surf. A Physicochem. Eng. Asp. 626 (2021), 127111.
[10] X. Zhu, J. Xiao, Q. Mao, Z. Zhang, Z. You, L. Tang, Q. Zhong, A promising
regeneration of waste carbon residue from spent Lithium-ion batteries via low-
temperature fluorination roasting and water leaching, Chem. Eng. J. 430 (2022),
132703.
[11] Y. Yang, S. Song, S. Lei, W. Sun, H. Hou, F. Jiang, X. Ji, W. Zhao, Y. Hu, A process
for combination of recycling lithium and regenerating graphite from spent lithium-
ion battery, Waste Manag. 85 (2019) 529–537.
[12] H. Xiao, G. Ji, L. Ye, Y. Li, J. Zhang, L. Ming, B. Zhang, X. Ou, Efficient regeneration
and reutilization of degraded graphite as advanced anode for lithium-ion batteries,
J. Alloys Compd. 888 (2021), 161593.
[13] Y. Gao, C. Wang, J. Zhang, Q. Jing, B. Ma, Y. Chen, W. Zhang, Graphite recycling
from the spent lithium-ion batteries by sulfuric acid curing-leaching combined with
high-temperature calcination, ACS Sustain. Chem. Eng. 8 (2020) 9447–9455.
[14] D. Ruan, F. Wang, L. Wu, K. Du, Z. Zhang, K. Zou, X. Wu, G. Hu, A high-
performance regenerated graphite extracted from discarded lithium-ion batteries,
New J. Chem. 45 (2021) 1535–1540.
[15] C. Xu, Y. Li, R.A. Adams, V.G. Pol, Y. Xiao, A. Varma, P. Chen, One-step combustion
synthesis of carbon-coated NiO/Ni composites for lithium and sodium storage,
J. Alloys Compd. 884 (2021), 160927.
[16] B. Wang, G. Wang, Z. Zheng, H. Wang, J. Bai, J. Bai, Carbon coated Fe3O4 hybrid
material prepared by chemical vapor deposition for high performance lithium-ion
batteries, Electrochim. Acta 106 (2013) 235–243.
[17] Z. Wang, L. Kong, Z. Guo, X. Zhang, X. Wang, X. Zhang, Bamboo-like SiOx/C
nanotubes with carbon coating as a durable and high-performance anode for
lithium-ion battery, Chem. Eng. J. 428 (2022), 131060.
[18] J.E.C. Sabisch, A. Anapolsky, G. Liu, A.M. Minor, Evaluation of using pre-lithiated
graphite from recycled Li-ion batteries for new LiB anodes, Resour. Conserv.
Recycl. 129 (2018) 129–134.
[19] S.-J. Park, H. Zhao, G. Ai, C. Wang, X. Song, N. Yuca, V.S. Battaglia, W. Yang,
G. Liu, Side-chain conducting and phase-separated polymeric binders for high-
performance silicon anodes in lithium-ion batteries, J. Am. Chem. Soc. 137 (2015)
2565–2571.
[20] H. Zhong, Y. Zhao, T. Zhang, G. Liu, Controlled lithium deposition on Alq3 coated
substrate, Batteries Supercaps 4 (2021) 98–105.
[21] S. Fang, N. Li, T. Zheng, Y. Fu, X. Song, T. Zhang, S. Li, B. Wang, X. Zhang, G. Liu,
Highly graphitized carbon coating on SiO with a π–π stacking precursor polymer
for high performance lithium-ion batteries, Polymers 10 (2018) 610.
[22] S. Natarajan, V. Aravindan, An urgent call to spent LIB recycling: whys and
wherefores for graphite recovery, Adv. Energy Mater. 10 (2020) 2002238.
Powder Technology 411 (2022) 117921
[23] B. Xing, C. Zhang, L. Chen, G. Huang, H. Guo, X. Liu, R. Yuan, C. Zhang, S. Yuan,
Preparation of high performance coal-based graphite anode materials and their
lithium storage properties, J. China Univ. Min. Technol. 48 (2019) 1133–1142.
[24] H. Zeng, B. Xing, Y. Cao, B. Xu, L. Hou, H. Guo, S. Cheng, G. Huang, C. Zhang,
Q. Sun, Insight into the microstructural evolution of anthracite during
carbonization-graphitization process from the perspective of materialization, Int. J.
Min. Sci. Technol. (2022), https://doi.org/10.1016/j.ijmst.2022.06.009.
[25] R. Gao, M. Yu, H. Xu, L. Li, M. Deng, Y. Wu, Z. Chen, Open-structured
oxyfluorinated titanium phosphate nanosheets synthesized with the assistance of
an ionic liquid and their use as an anode in lithium-ion batteries, Energy Fuel 35
(2021) 15213–15222.
[26] K. Dai, Z. Wang, G. Ai, H. Zhao, W. Yuan, X. Song, V. Battaglia, C. Sun, K. Wu,
G. Liu, The transformation of graphite electrode materials in lithium-ion batteries
after cycling, J. Power Sources 298 (2015) 349–354.
[27] N. Lin, Z. Jia, Z. Wang, H. Zhao, G. Ai, X. Song, Y. Bai, V. Battaglia, C. Sun, J. Qiao,
K. Wu, G. Liu, Understanding the crack formation of graphite particles in cycled
commercial lithium-ion batteries by focused ion beam-scanning electron
microscopy, J. Power Sources 365 (2017) 235–239.
[28] J. Li, Y. Li, C. Lv, W. Zhao, J. Zhou, Analysis on key technologies and current
situation of echelon utilization of retired power batteries, Automat. Elect. Power
Syst. 44 (2020) 172–183.
[29] D. Ruan, K. Zou, K. Du, F. Wang, L. Wu, Z. Zhang, X. Wu, G. Hu, Recycling of
graphite anode from spent lithium-ion batteries for preparing Fe-N-doped carbon
ORR catalyst, Chemcatchem 13 (2021) 2025–2033.
[30] A.D. Jara, J.Y. Kim, Chemical purification processes of the natural crystalline flake
graphite for Li-ion Battery anodes, Mater. Today Commun. 25 (2020), 101437.
[31] C. Wang, G. Gai, Y. Yang, Shape modification and size classification of
microcrystalline graphite powder as anode material for lithium-ion batteries, Jom
70 (2018) 1392–1397.
[32] X. Jiang, H.C. Fang, P. Xiao, T. Liu, J.M. Zhu, Y.C. Wang, P.F. Liu, Y. Li, Influence
of carbon coating with phenolic resin in natural graphite on the microstructures
and properties of graphite/copper composites, J. Alloys Compd. 744 (2018)
165–173.
[33] Y. Lee, S.M.N. Jeghan, G. Lee, Boost charging lithium-ion battery using expanded
graphite anode with enhanced performance, Mater. Lett. 299 (2021), 130077.
[34] B. Xing, C. Zhang, Y. Cao, G. Huang, Q. Liu, C. Zhang, Z. Chen, G. Yi, L. Chen, J. Yu,
Preparation of synthetic graphite from bituminous coal as anode materials for high
performance lithium-ion batteries, Fuel Process. Technol. 172 (2018) 162–171.
[35] Z. Wang, B. Xing, X. Han, H. Zeng, L. Hou, H. Guo, C. Zhang, Z. Yue, Preparation of
coal tar pitch-based microcrystal carbons and their lithium storage properties,
Chem. Indust. Eng. Prog. 40 (2021) 313–323.
[36] C. Yi, Y. Yang, T. Zhang, X. Wu, W. Sun, L. Yi, A green and facile approach for
regeneration of graphite from spent lithium ion battery, J. Clean. Prod. 277 (2020),
123585.
[37] L. Xu, H. Liu, F. Li, Y. He, Effect of PF resin-coating on nature microcrystalline
graphite used as anode materials of Li-ion batteries, Non-Metallic Mines 33 (2010)
24–27.
[38] Y. Matsumura, S. Wang, C. Yamaguchi, J. Mondori, H. Matsui, A study of the
surface morphology of a disordered carbon electrode, J. Power Sources 74 (1998)
246–251.
[39] C. Wang, H. Zhao, J. Wang, J. Wang, P. Lv, Modification on artificial graphite
anode material by coating with organic pyrolytic carbon, J. Function. Mater. 43
(2012) 3208–3212.
[40] B. Xing, T. Bao, X. Li, C. Shi, H. Guo, Z. Wang, L. Hou, C. Zhang, Z. Yue, Research
progress on structure regulation and surface modification of graphite anode
materials for lithium ion batteries, Mater. Rep. 34 (2020) 15063–15068.
[41] D.W. Kim, S.M. Jung, C. Senthil, S.-S. Kim, B.-K. Ju, H.Y. Jung, Understanding
excess Li storage beyond LiC6 in reduced dimensional scale graphene, ACS Nano 15
(2021) 797–808.
[42] Z. Wang, B. Xing, H. Zeng, G. Huang, X. Liu, H. Guo, C. Zhang, Y. Cao, Z. Chen,
Space-confined carbonization strategy for synthesis of carbon nanosheets from
glucose and coal tar pitch for high-performance lithium-ion batteries, Appl. Surf.
Sci. 547 (2021), 149228.
[43] H. Zeng, B. Xing, B. Xu, L. Chen, C. Zhang, X. Liu, B. Zhang, Q. Sun, Y. Zhang,
Microstructural regulation of coal-based carbon nanosheets and their
electrochemical performance, J. China Coal Soc. 46 (2021) 1182–1193.
[44] L. Xu, The Research on Natural Microcrystallion Graphite as Anode Materials for
Li-Ion Batteries, Changsha University of Science & Technology, 2010.
[45] B. Xing, C. Zhang, Q. Liu, C. Zhang, G. Huang, H. Guo, J. Cao, Y. Cao, J. Yu,
Z. Chen, Green synthesis of porous graphitic carbons from coal tar pitch templated
by nano-CaCO3 for high-performance lithium-ion batteries, J. Alloys Compd. 795
(2019) 91–102.
[46] F. Li, Study on the Pitch Carbon Coated Graphite Anode Materials by Vacuum-
Liquid Phase Method, Hunan University, 2015.