eScience 3 (2023) 100091

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Research Paper

Rejuvenating LiNi0.5Co0.2Mn0.3O2 cathode directly from battery scraps

Yaqing Guo a, b, 1, Chi Guo c, 1, Pengjie Huang b, Qigao Han b, Fuhe Wang b, Hao Zhang a,
Honghao Liu c, Yuan-Cheng Cao b, *, Yonggang Yao a, *, Yunhui Huang a, *
a
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology,
Wuhan, 430074 China
b
State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and
Technology, Wuhan 430074, China
c
Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, School of Optoelectronic Materials & Technology, Jianghan University, Wuhan
430056, 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

Cathode materials are recycled from

battery scraps produced during
manufacturing.

The failure and regeneration mecha-
nisms of air-degraded battery scraps are
studied.

A 1.2 Ah pouch cell of regenerated
NCM523 can retain 92.7% capacity after
1000 cycles.

Scrap recycling and regeneration offer
~10x higher profit than other recycling
methods.

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

Keywords: Battery recycling is indispensable for alleviating critical material shortages and enabling sustainable battery
Battery scrap applications. However, current methods mostly focus on spent batteries, which not only require sophisticated
Battery recycling disassembly and material extraction but also have unknown chemistries and states of health, resulting in high
Air degradation
costs and extreme challenges to achieve regeneration. Here, we propose the direct recycling and effective
Cathode regeneration
Techno-economic analysis
regeneration of air-degraded LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode directly from battery scraps generated
during battery manufacturing. The NCM523 shows surface degradation only a few nanometers deep and
accordingly can be regenerated without adding Li, achieving restored properties (170 mAh g1 at 0.1 C, 92.7%
retention after 1000 cycles) similar to those of fresh commercial materials. EverBatt analysis shows that scrap
recycling has a profit of $1.984 kg1, which is ~10 times higher than conventional recycling, making it practical
and economical to rejuvenate slightly degraded electrode materials for sustainable battery manufacturing.

1. Introduction
With the booming electric vehicle (EV) industry, lithium-ion batteries
(LIBs) are rapidly becoming mainstream electrical energy storage devices
[1]. With LIBs widely employed, more than 25 billion used batteries
(approximately 500,000 tons) are being generated annually since 2020
[2]. Considering surging prices of raw materials and the potential haz-
ards of LIBs at their end of life, effective recycling of LIBs will be indis-
pensable for addressing raw material shortages as well as the
environmental problems associated with LIB disposal [3,4].

* Corresponding authors.
E-mail addresses: yccao@hust.edu.cn (Y.-C. Cao), yaoyg@hust.edu.cn (Y. Yao), huangyh@hust.edu.cn (Y. Huang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.esci.2023.100091
Received 6 November 2022; Received in revised form 18 December 2022; Accepted 4 January 2023
Available online 7 January 2023
2667-1417/© 2023 The Authors. Published by Elsevier B.V. on behalf of Nankai University. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
Y. Guo et al.
In recent years, the sustainable recycling of spent batteries by direct
recycling methods has gained much attention due to the potential eco-
nomic and environmental benefits [5–7]. Direct recycling can maintain
the chemical structure of materials during recycling and then regenerate
those materials to restore their electrochemical properties for reuse in
batteries [8,9]. This is in sharp contrast to traditional pyrometallurgical
and hydrometallurgical processes, which break spent materials down
into elements and require new synthesis [10–12]. In addition, the cath-
ode material can be upcycled to prepare catalysts for air batteries and
other uses [13]. However, direct recycling requires battery collection and
disassembly; automation of these processes has not yet been achieved,
and manual disassembly is slow and very risky (Fig. 1a). In addition, the
current labeling system for recycled batteries is imperfect, making it
difficult to determine the composition of recovered materials. Impor-
tantly, we often do not know the state of health of spent batteries and
materials (i.e., the cycling history and cell age), which makes targeted
regeneration almost impossible [14].
Alternatively, battery production yields a large amount of electrode
scraps (~5–15%, called battery scraps) from electrode cutting and
failures during manufacturing [15,16]. Because these scrap materials
have not experienced electrochemical cycles of charge and discharge,
they are of high quality, with very few defects. Compared with spent
batteries, the electrode materials in battery scraps are easily gathered
(no need for battery collection and disassembly) and have intact
structures and known compositions, thus presenting a readily available
resource and a much higher-value asset that needs to be recycled
(Figs. 1b–d) [16].
Fig. 1. Regeneration of battery scraps. (a) EV battery disassembly process to obtain spent battery materials [21]. (b) Electrode cutting process and (c) online pro-
duction lead to large amounts of battery scraps. (d) Actual battery scraps and (e) cathode materials recycled from scraps after regeneration. (f) Comparison of different
LIB recycling methods.
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eScience 3 (2023) 100091
Despite the above advantages, the cathodes in battery scraps often
undergo shallow degradation due to air exposure, particularly cathodes
with high Ni content. Ni3þ can easily react with CO2 and H2O in the air to
produce Li-poor phases on the surface, thereby greatly reducing lithium-
ion transport and electrochemical performance [17]. In addition, in a
scrap electrode, cathode materials are covered with polyvinylidene
difluoride (PVDF) binder and carbon black after electrode manufacture,
which must be removed for effective regeneration. Yet little has been
reported about the failure mechanisms of battery scraps, and there is
some controversy about contaminant species on the surface [18]. What is
more, in terms of regeneration, the binder (PVDF) and the conductive
carbon on the cathode surface are difficult to remove, and they often can
seriously affect recovery efficiency and cathode quality if not handled
properly [19,20]. Indeed, we have found that the often-used direct
high-temperature regeneration method is not practically applicable to
air-degraded electrode scraps, and pretreatment is required to minimize
adverse effects from the binder and conductive carbon black and achieve
effective regeneration.
In this work, we focus on the direct recycling and regeneration of
shallowly degraded cathodes from battery scraps (Figs. 1b–e). We sys-
tematically investigated the degradation and regeneration mechanisms
for NCM523 powders. Atomic resolution electron microscopy imaging
and electron energy loss spectroscopy together showed that surface
degradation of NCM523 occurs only to a few nanometers in depth, in
contrast to the bulk structural failure found in spent batteries. Surface-
degraded NCM523 was facilely regenerated using a simple and low-
cost calcination method, without the need to add extra lithium. Based
Y. Guo et al.
on this understanding, we demonstrated the direct recycling of NCM523
cathode from actual battery scraps and its complete regeneration in terms
of structural and electrochemical properties (170 mAh g1 at 0.1 C).
Further, a 1.2 Ah pouch cell retained 92.7% capacity after 1000 cycles,
behaving similarly to fresh commercial materials. Compared with major
regeneration methods using spent batteries (Fig. 1f; see also the EverBatt
analysis later in the paper), our direct recycling strategy based on battery
scraps has great advantages in terms of material readiness, process
simplicity, waste reduction, energy efficiency, and economic benefits,
making it a high priority for development, and practical for industrial
applications.
2. Materials and methods
Preparation of degraded NCM523 powder and cathode electrodes:
Commercial LiNi0.5Co0.2Mn0.3O2 powder (NCM523) was supplied by
Hefei Kejing. NCM523 powder, Super-P, and PVDF were added to 1-
Methyl-2-pyrrolidinone (NMP) solvent in a mass ratio of 96.2:2.0:1.8
to obtain a cathode slurry and stirred overnight. The slurry was loaded on
aluminum foil with a coating machine and dried in a vacuum oven at 120

C for 24 h to yield electrodes with a loading of about 22 mg cm2. To
obtain degraded NCM523, the powder, as well as the electrode materials,
were directly exposed to air conditions for a time lag of one year (or
accelerated aging in an oven). The accelerated aging process can be
performed in an oven with controlled temperature and humidity (50  C,
80% RH, 30 days).
Preparation of cathode/anode electrodes for half-cells and full cells:
Li||NCM523 half-cells were used to evaluate the electrochemical per-
formance of commercial NCM523, degraded NCM523, pretreated-
degraded NCM523, and regenerated NCM523 materials. The percent-
age of active substance was 80%, and the loading was 2–3 mg cm2. High
loadings of graphite and repaired NCM523 electrodes were used for
pouch cell testing. For the anode, graphite:Carboxymethyl Cellulose:-
LA133:Super-P ¼ 95%:1%:2.5%:1.5%. The solvent was water (in which
NMP accounted for 1%). The mixture was stirred for 2 h and coated on
copper foil with an active substance loading of about 11.3 mg cm2, then
dried overnight at 120  C under vacuum. For the cathode, the percentage
of active substance was 96.2%, the loading was about 22 mg cm2, and
the N/P ratio was controlled at about 1.1.
Pre-treatment of degraded NCM523 electrodes.
(a) Mechanical crushing: Degraded NCM523 electrodes were
sequentially processed through a shredder and a cyclone to obtain
millimeter-level debris, which were used as test subjects by
sieving or further pretreatment.
(b) NMP immersion: The NMP was added in a solid-to-liquid mass
ratio of 1:5 and stirred at room temperature (25  C), 80  C, and
120  C for 30 min. The upper layer of liquid in the beaker was
collected after resting for 1 h, and the aluminum foil was removed
after cooling. The powder was obtained by centrifugation and
dried at 120  C. The powder was ground and sieved as battery
cathode active material for testing.
(c) High-temperature calcination: The samples were calcined in a
tube furnace at a temperature of 350–600  C, and the reaction was
carried out under air conditions with a heating rate of 5  C min1
and a holding time of 1 h. Due to the decomposition of PVDF, the
material was easily detached from the aluminum foil with manual
assistance. After further milling, the material was used for testing.
Materials characterization: Scanning electron microscope (SEM) im-
ages of samples were attained using a Hitachi SU8010 scanning electron
microscope, and energy-dispersive X-ray spectra (EDS) images were ob-
tained with a XFlash610-H at an acceleration voltage of 20 kV. High-
resolution transmission electron microscopy (HRTEM) characterizations
were achieved with a Titan G260-300, and X-ray diffraction (XRD) mea-
surements were conducted with a D8 Discover X-ray diffractometer using a
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eScience 3 (2023) 100091
Cu Kα X-ray source with 2θ ranging from 10 to 90 . Particle size distri-
bution was measured by a laser distribution instrument (Battersize 2600).
X-ray photoelectron spectroscopy (XPS) measurements were performed
with an EscaLab Xi þ instrument. Dual electron energy loss spectroscopy
(EELS) was taken with a spectrometer dispersion chosen for simultaneous
visualization of zero loss, O K-edges, Ni K-edges, Co K-edges, and Mn L-
edges. Inductively coupled plasma optical emission spectroscopy (ICP-
OES) was carried out in an ARCOS II MV (Spectro, Germany).
Electrochemical characterization: Battery charge/discharge charac-
teristic curves were performed in a LAND Test Cabinet (CT3002A) and
tested with a coin-type cell. A lithium metal anode, separator (Celgard
2400), organic electrolyte (1 M LiPF6, EC/DMC/EMC 1:1:1 vol%), and
NCM523 cathode were sequentially added to the cell case (CR2025), and
the cell assembly was conducted in an argon-filled glove box. Cyclic
voltammetry (CV), galvanostatic intermittent titration technique (GITT),
and in situ electrochemical impedance spectroscopy (EIS) tests were
performed on an electrochemical workstation (Autolab 302 at a room
temperature of 25  C). CV and GITT tests were performed from 2.8 to
4.35 V, with a sweep rate of 0.1 mV s1 for CV and a current density of
0.5 A g1 for GITT. For in situ EIS, the cell was investigated with a voltage
in the range of 2.7–4.35 V, the test potential was set at 5 mV, and the
adapted frequency range was 100 kHz to 0.01 Hz.
3. Results and discussion
3.1. Degradation mechanism of NCM523 powder
In actual electrodes, PVDF and conductive Super P can have large
effects on the surface appearance of degraded NCM523 material. Hence,
we first employed NCM523 powders stored in air (i.e., without surface
coatings of PVDF and Super P) to investigate the degradation mechanism
of the NCM523 material. Commercial NCM523 powder was used for
comparison. The fresh commercial NCM523 powders showed a smooth
and impurity-free surface (Fig. 2a), while air-degraded NCM523 powders
exhibited a large number of impurities on the surface; these were
particularly aggregated at the interface or accumulated at the particle
boundaries to reduce the interfacial energy (Fig. 2b) [22]. Interestingly,
both materials showed a typical α-NaFeO2 structure in the XRD pattern,
without an observable impurity phase, which may be because the surface
of air-degraded NCM523 contained few impurities (Fig. 2c) [23]. In the
XRD pattern, the highest peak of the (003) crystal plane underwent an
insignificant shift in its peak position after air degradation, suggesting
the degraded NCM523 was still a layered structure with a similar lattice
spacing. However, it is noteworthy that the degraded NCM523 material
showed a decrease in the splitting of the (006)/(102) peak near 38 ,
indicating some disruption of the layered structure [24].
Since impurities were not clearly reflected in the XRD peaks, spherical
aberration-corrected scanning transmission electron microscopy (STEM)
was used for further structural analysis of the material. As shown in
Fig. S1a, the material's rough surface had obvious graininess, visible in
low-magnification TEM images. At the same time, distinct Moire fringes
appeared in the region at the edge of the powder. Irregular fringes cor-
responded to crystal structures that had undergone atomic rearrange-
ment and had chaotic small-angle grain boundaries, indicating the
presence of a large number of crystal defects in the material (Fig. S1b).
In order to further analyze the changes in the surface crystal structure
of the material, a focused ion beam (FIB) was applied to shape the
samples along the cross-section. As shown in Fig. 2d, a coating layer was
present on the surface of the degraded material; from the outside to the
inside of a degraded particle (Figs. 2e and S2), we found a reconstructed
rock-salt phase (several atomic layers, lattice spacing of 0.25 nm), a
disordered phase (near the surface), and a primitive layered structure
(lattice spacing of 0.49 nm). Moreover, Ni, Co, Mn, and O elements were
uniformly distributed on the surface of the material. However, C
appeared to be enriched on the surface; this was related to impurity
phases (such as LiHCO3 and Li2CO3) generated there (Fig. 2f).
Y. Guo et al. eScience 3 (2023) 100091

Fig. 2. Degradation mechanism of NCM523 in air. SEM images of (a) commercial NCM523 and (b) shallowly degraded NCM523 in air. (c) XRD patterns of commercial
and degraded NCM523 particles. (d) BF STEM image and (e) high-resolution HAADF STEM image, focusing on the surface of shallowly degraded NCM523. (f)
Corresponding EDS elemental mappings of shallowly degraded NCM523. (g) Ni 2p, C 1s, and O 1s high-resolution XPS spectra of shallowly degraded NCM523. (h)
Schematic representation of surface degradation mechanism, showing NCM523 reacting with H2O and CO2.

XPS measurements were used to probe the composition of impurities
on the surface of shallowly degraded NCM523 crystals. As presented in
Fig. 2g, the Ni 2p spectrum showed two dominant peaks, at 855.1 eV
(2p3/2) and 872.7 eV (2p1/3), respectively. After deconvolution, the
peaks at 855.1, 872.6, 861.3, and 879.0 eV confirmed the presence of
Ni2þ, while the peaks at 856.9, 864.3, 875.2, and 881.5 eV confirmed the
presence of Ni3þ [25]. It is worth noting that the material had not un-
dergone the cycling process, so the surface did not contain electrolyte
decomposition products, and elemental F was not detected (Fig. S3). As
for elemental C, the C 1s spectrum could be divided into three peaks at
284.8, 286.4, and 288.9 eV, corresponding to C–C/C–H, C–O, and C¼O
bonds, respectively [26,27]. This further implies that the material

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Y. Guo et al.
reacted with CO2 and H2O in the air to form C-containing salts such as
LiHCO3 and Li2CO3. In addition, the high salt content on the surface of
the long-term stored commercial NCM523 cathode material resulted in a
high surface oxygen content and a low O 1s lattice oxygen content [28].
EELS was applied to analyze the valence states of the chemical ele-
ments in the degraded NCM523 crystals (Fig. S4). The EELS spectra of the
O K-edge show that the O 1s were excited to unoccupied 2p orbitals
above the Fermi level, which is associated with hybridization between
the oxygen 2p and transition metal 3d and 4sp states [29,30]. In addition,
the O K-edge is related to the hybridization between O 2p and C 2p states,
which was mainly influenced by the lithium salt on the material's surface.
Furthermore, the EELS spectra of Ni, Co, and Mn L-edge exhibited a blue
shift of the absolute energy from the surface to the center region, indi-
cating a lower oxidation state on the surface [31–33].
Based on the above results, we can conclude that the NMC523
degradation was caused by a reaction with H2O and CO2 in the air. Liþ
diffused out of the crystal lattice, reacting with H2O and CO2 to form
lithium salts, such as LiHCO3, Li2CO3, and LiOH, on the surface of the
material. In addition, a Li-poor rock-salts phase was formed, accompa-
nied by the reduction of Ni3þ to Ni2þ with the simultaneous precipitation
of oxygen at the material's surface (Fig. 2h), which hindered the charge
transfer process during charging and discharging (Fig. S5). Hence, the
degradation mechanism of NCM523 storage in air is summarized as
follows [17]:
LiNi0.5Co0.2Mn0.3O2 þ xCO2 → xLi2CO3 þ yNiO þ Li1-2xNi0.5-yCo0.2
Mn0.3O2-m þ 0.5(m-x-y)O2 (1)
LiNi0.5Co0.2Mn0.3O2 þ xH2O → 2xLiOH þ yNiO þ Li1-2xNi0.5-yCo0.2
Mn0.3O2-m þ 0.5(m-x-y)O2 (2)
3.2. Direct regeneration of degraded NCM523 powder
It is obvious that the shallow degradation of NCM523 is mainly
caused by the formation of lithium salts (such as LiOH, Li2CO3, and
LiHCO3) and Li-poor phases as surface impurities. In other words, the
NCM523 components are still at the surface, but the phase structure is
not right. If we can resynthesize these lithium salt with the Li-poor
phases, then the surface structure of the degraded cathode can be
restored, leading to performance regeneration. To investigate the po-
tential for achieving this, a TG-DSC test of degraded NCM523 was con-
ducted in air. As shown in Fig. S6, the degraded NCM523 powder lost the
adsorbed water at around 100  C (about 0.25 wt%); slight weight loss
then continued due to the volatilization of crystallized water and the
decomposition of Li salts (such as LiHCO3). Finally, when the tempera-
ture was higher than 800  C, there was a large decrease in mass, caused
by the reaction of the lithium salts (LiOH and Li2CO3) on the surface with
the Li-poor phases to produce gas volatilization, thus offering the possi-
bility of material regeneration.
Accordingly, we annealed the degraded NCM523 cathode powder
directly under an air atmosphere at 800–950  C for 6 h (named
regenerated-T NCM523) to verify structural regeneration. SEM images of
these powders are shown in Fig. S7. It can be observed that the NCM523
cathode material calcined at different temperatures exhibited smooth
grains, and the impurity phases in the crystal interstices were completely
reacted. At the same time, there was no obvious structural breakage of
the material. In addition, all samples showed distinct (006)/(102) as well
as (018)/(110) peaks in their XRD profiles, indicating that the samples
maintained an intact layer structure (Fig. 3a). Compared to degraded
NCM523, the (003) peak of the NCM523 cathode material annealed at
850  C (regenerated-850 NCM523) shifted to the right, indicating a
smaller layer spacing and therefore fewer Li-poor phases. Further in-
crease in the calcination temperature (900–950  C) led to a leftward shift
of the (003) peak, indicating the occurrence of side reactions such as
lattice phase change and lithium loss. Lithium loss was also verified in
ICP tests (Fig. 3b and Table S1), which showed that higher-temperature
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eScience 3 (2023) 100091
calcination led to a lower Li/metal content ratio. Hence, as shown in
Fig. 3c, the regeneration of degraded NCM523 can be summarized as Li-
poor phases reacting with surface Li salts to form a layered material at
optimal temperature: with calcination at/below 800  C, it was difficult to
completely regenerate the cathode, while calcination at or above 900  C
led to loss of lithium in the structure. The reaction/regeneration equation
(Equation (3)) is as follows [34,35]:
Li1-2xNi0.5-yCo0.2Mn0.3O2-m þ xLi2CO3 þ yNiO þ 0.5(m-x-y)O2 →
LiNi0.5Co0.2Mn0.3O2 þ xCO2 (3)
We also employed STEM to directly observe structural regeneration in
the regenerated-850 NCM523 sample. It exhibited a clear layered
structure and uniform lattice spacing at both the center and the surface
(0.487 nm, Figs. 3d and e), and no surface heterogeneity. At the same
time, the C element content in the EDS mapping decreased after high-
temperature calcination (Fig. 3f), further implying the conversion of
surface components such as Li2CO3 into layered cathode materials. The
EELS spectra of the Ni L-edge and Mn L-edge showed similar peak shapes
from the exterior to the interior of regenerated-850 NCM523, indicating
that the compositions and valence states of the materials were homoge-
neous after regeneration (Fig. 3g). The above results demonstrated that
the regenerated-850 NCM523 had a completely regenerated layered
structure and composition.
To further understand the effect of the regeneration process, the
electrochemical performance of commercial, degraded, and regenerated
NCM523 were measured and compared, including CV, GITT, and rate
performance. Fig. S8 shows that the degraded NCM523 displayed a larger
polarization voltage (0.07 V) and a smaller peak current in the CV
compared to commercial NCM523 (0.039 V), which had a direct impact
on their respective redox kinetics. The CV curves of NCM523 regenerated
at different temperatures all showed better reversibility with smaller
polarization voltages (0.04–0.06 V), implying improved redox kinetics
after regeneration. In particular, the regenerated-850 sample had the
lowest polarization and was comparable to the commercial NCM523
sample.
GITT was used to further explore the Liþ intercalation and dein-
tercalation behavior of degraded, commercial, and regenerated NCM523.
As shown in Fig. S9, the poor symmetry in the GITT results demonstrated
low Columbic efficiency in charging and discharging, while the large
voltage decay in the resting relaxation phase also indicated large
impedance and severe polarization in degraded NCM523. In addition, the
Liþ diffusion coefficients during charging and discharging showed an
order of magnitude difference between degraded and commercial
NCM523 (4.735  1011 and 1.744  1010 cm2 s1, respectively). The
GITT curve of the regenerated-850 sample (Fig. S10) was also measured,
and the Liþ diffusion coefficient during charging and discharging (2.410
 1010 cm2 s1) exhibited values comparable to commercial NCM523.
Such a high Liþ transport capability also led to better rate performance in
regenerated NCM523 (Fig. 3h). In particular, the regenerated-850 sam-
ple demonstrated better performance at a high rate (e.g., 5 C). These
results all suggest that the poorer kinetics of degraded NCM523 can be
attributed to surface impurities (LiOH, LiHCO3, and Li2CO3) and phase
changes (rock salt or spinel phases), which can be structurally and
electrochemically restored by regeneration (calcination at 850  C) to
achieve an intact surface–bulk layered structure and good electro-
chemical properties.
3.3. Recycling of NCM523 with practical electrode scraps
The degradation mechanism of NCM523 electrode scraps is similar to
that of NCM523 powder, with CO2 and H2O molecules diffusing through
the pores of the electrode and reacting with NCM523. Accordingly, the
recycling of NCM523 electrodes from practical battery scraps generally
involves two steps: (1) pretreatment to effectively remove the surface
binder and conductive carbon, and (2) regeneration to restore the
Y. Guo et al. eScience 3 (2023) 100091

Fig. 3. Direct regeneration of degraded NCM523 powder. (a) XRD and (b) Li/Me (Me ¼ Ni, Co, and Mn) ratios of degraded NCM523 and regenerated NCM523
annealing in air. (c) Schematic representation of degraded and regenerated NCM523 annealed at different temperatures. (d, e) High-resolution HAADF STEM images
focusing on the surface and the center of the regenerated-850 NCM523. (f) The corresponding EDS elemental mappings of regenerated-850 NCM523. (g) HAADF
STEM image and the corresponding EELS low-loss spectra between the surface and the interior for regenerated-850 NCM523. (h) Rate performance of degraded
NCM523 and regenerated NCM523.

structural and electrochemical properties of the cathode materials. The
surface binder and conductive carbon are difficult to remove due to the
compacting process used to obtain high energy density. Moreover, the
residual binder PVDF and conductive carbon can be very harmful to the
cathode material during regeneration or re-synthesis. For example, sim-
ple high-temperature calcination can generate harmful gases (such as HF
from PVDF) and induce carbon reduction of the cathode (generating
oxygen vacancies and reduced metals), which easily damage the
NCM523 crystal structure and greatly undermine its electrochemical
properties (Figs. S11 and S12).
We thoroughly studied the effects of different pretreatment methods
and finally employed a combination of methods to effectively remove
impurities (PVDF and Super P) without damaging the electrochemical
properties: mechanical crushing, NMP immersion, and thermal annealing
(Fig. 4a). Mechanical crushing accelerates the detachment of the cathode
material from the current collector (aluminum foil) and effectively
loosens compacted particles to increase their contact with the atmo-
sphere, thus benefiting the later processes. Note that crushing does not
cause structural damage or electrochemical degradation to NCM523
(Fig. S13) but inevitably introduces small amounts of aluminum impu-
rities (860 ppm, Table S2).
In the subsequent NMP immersion treatment, we studied the effect of
the soaking temperature (25, 80, and 120  C) on the binder removal
efficiency and material purity (Figs. S14 and S15). The results indicated
that the yield of cathode material increased with the increase in soaking
temperature. SEM images showed that all samples still had numerous
impurities adhering to their surface (Figs. S14a–c), undetectable by XRD
(Fig. S14d). XPS was used to determine the surface composition, and the
peak intensity of F 1s at 688 eV indicated the PVDF content
(Figs. S14e–h). It was found that increasing the soaking temperature was
favorable for the dissolution of PVDF, but the PVDF solubility reached
saturation at 120  C. Lastly, the Al content in NCM523 after NMP im-
mersion was quite low (29–43 ppm), while the lithium content remained
at 1.05–1.06 (Li/Me, Me ¼ Ni, Co, and Mn), as can be seen from the ICP
results (Table S3). Electrochemically, after NMP immersion, all samples
showed similar polarization voltages, despite the different soaking tem-
peratures used (Figs. S15a–e). In addition, there were no significant
differences in the multiplicative characteristics when different soaking

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Y. Guo et al.
Fig. 4. Recycling of NCM523 from electrode scraps. (a) Schematic diagram of the pretreatment process. SEM images of (b) the pretreated (NMP, 400  C) NCM523 and
(c) regenerated NCM523. (d) The C content of pretreated NCM523 and regenerated NCM523. (e) C 1s, (f) F 1s, and (g) O 1s high-resolution XPS spectra of degraded
NCM523 electrode and regenerated NCM523.
temperatures were used (Fig. S16). To reuse the NMP, we used filtration
to separate out NCM523 as well as a large amount of NMP. The separated
NMP could be used directly for NCM523 pretreatment or dealt with by
reduced pressure distillation; even if the NMP was adsorbed on the sur-
face of NCM523 particles, it could be reused by reduced pressure distil-
lation. We therefore chose to soak in NMP at 120  C to increase the
cathode yield and accelerate the process.
Lastly, thermal annealing was used to remove the remaining PVDF
and carbon black. TG testing was applied to the degraded NCM523
electrodes (Fig. S17), which started to decompose at 340  C and lasted
until 510  C [36,37]. With the increase in annealing temperature, the
yield of cathode materials gradually increased (Table S4). However, we
found that excessive annealing (> 500  C) brought about large amounts
of additional Al impurities, which was reflected in the ICP analysis
(Table S5). On the other hand, lower-temperature annealing (350  C)
resulted in largely incomplete decomposition of the PVDF and a lower
collection rate (Fig. S18a, Table S4). To find the optimal annealing
temperature, recycled materials after thermal annealing at different
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temperatures (350–600  C) were characterized by XRD (Fig. S18b), XPS
(Figs. S18c–f), and SEM (Fig. S19), and their electrochemical properties
were compared (Figs. S20–25 and Table S6). We concluded that thermal
annealing at 400  C was appropriate in terms of material purity and
energy efficiency.
Based on the above experiments, we determined that combinatorial
pretreatment methods are necessary to remove impurities and obtain
cathode materials with the least deterioration to their structural and
electrochemical properties. The optimal pretreatments are mechanical
crushing, NMP immersion at 120  C, and thermal annealing at 400  C.
After these pretreatments, we obtained materials with relatively clean
surfaces (Fig. 4b), yet still some residue. These degraded NCM523 par-
ticles were then regenerated (calcined at 850  C) in accordance with our
understanding of the failure and regeneration mechanisms. Of course,
the two steps of annealing could be performed simultaneously without
cooling. As shown in Fig. 4c, the NCM523 particles after high-
temperature calcination had a smooth surface without observable im-
purities. Moreover, the surface carbon was drastically reduced after high-
Y. Guo et al.
temperature calcination, indicating there was a reaction between Li2CO3
and rock salt phases that led to surface regeneration or decomposition
during calcination (Fig. 4d). Correspondingly, the XPS results show that
the PVDF content on the surface of the material decreased substantially
after calcination at high temperatures: this can be observed from the peak
positions in the XPS spectra at F 1s (687.6 eV) and C 1s (289 eV; Figs. 4e
and f). It is noteworthy that the decomposition of PVDF generated a LiF-
rich interfacial layer and a small portion of fluorine-doped carbon ma-
terials, which closely adhered to the surface of the regenerated material
to optimize its surface electronic structure and help suppress side re-
actions. As a result, the activation process of the material during charging
and discharging was reduced, and the symmetry of the GITT was
improved (Fig. S24). In addition, the O XPS spectrum showed a reduction
in the impurities on the surface of the high-temperature treated material
(Fig. 4g). Through the above pretreatment and regeneration process, we
thus successfully obtained LiF-coated NCM523 with a restored structure,
directly from electrode scraps.
3.4. Electrochemical performance of regenerated NCM523
The structurally restored NCM523 materials were then evaluated for
their electrochemical properties. CV tests indicated that the regener-
ated NCM523 exhibited reversibility comparable to that of commercial
materials (Figs. 5a and S7b). Fig. 5b shows the in situ EIS and fitting
Fig. 5. Electrochemical performance of regenerated NCM523. (a) CV curves of regenerated NCM523. (b) In situ EIS and fitting data of regenerated NCM523. (c) Rate
performance. (d) Cycling performance of degraded NCM523 electrode after pretreatment, and of commercial NCM523. (e) Cycling performance of regenerated
NCM523 (pouch cell 1.2 Ah). (f) Pouch cell powering an LED and undergoing flexibility testing. (g) Wireless charging of a cell phone by three pouch cells connected
in series.
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results for regenerated NCM523. Typically, resistance (ohmic resis-
tance (Rohm)) comes from the cell ohmic resistance and is related to the
electronic conductivity of the electrode material. This was around 2–3
Ω, similar to that of commercial materials. At low potentials, the
dominant role is played by the desolvation reaction process, in which
lithium ions diffuse into the bulk phase of the material. The charge-
transfer resistance (Rct) refers to the charge-transfer resistance of the
oxidation–reduction reaction. The charge-transfer impedance under the
reaction platform (3.75 V) was 29.73 Ω, similar to that of commercial
NCM523 material (Fig. S5) [38].
The pretreated NCM523 sample showed a specific capacity of 166.1
mAh g1 at 0.1 C and 120.7 mAh g1 at 5 C, better than the original
degraded NCM523 electrode, indicating that suitable pretreatment was
beneficial (Fig. 5c). However, due to the absence of further regeneration,
the surface impurity phases (Li2CO3, rock-salt phase, conductive carbon,
etc.) still affected the performance of the pretreated NCM523, as re-
flected in lower specific capacity and inferior capacity retention in long
cycles compared with fresh commercial NCM523 (Figs. 5c and d). Spe-
cifically, the commercial material had 94.5% capacity retention, while
the pretreated degraded material retained 93.6% capacity after 500 cy-
cles (cycled with a potential of 3.0–4.2 V at 1 C).
The regenerated NCM523 exhibited a specific capacity of 170 mAh
g1 at 0.1 C and 131.7 mAh g1 at 5 C (Fig. 5c), values comparable to
those of fresh commercial materials. Moreover, it achieved a very high
Y. Guo et al.
capacity retention of 96.3% in long cycle testing of a 1.2 Ah pouch cell at
1 C for 500 cycles, and 92.7% for 1000 cycles (Fig. 5e and Table S7). The
highly consistent voltage plateau during cycling (inset) also implied
excellent material reversibility, further proving that the regenerated
material had structural stability comparable to that of commercial ma-
terials and low impurity content on the surface. In fact, during thermal
annealing (400  C), a small amount of lithium salt reacted with PVDF to
form LiF, as verified in the XPS results. LiF can act as a stable CEI
component to protect NCM523 during the cycling process [38,39]. To
demonstrate its utility, the regenerated NCM523 pouch cell was used to
light up an LED, even after folding, indicating that the regenerated
NCM523 pouch cell had a high level of safety. In addition, connecting
three soft pouch batteries in series provided a high output voltage for the
wireless charging of a phone (Fig. 5g), indicating the regenerated
NCM523 material could be used in practical applications.
3.5. Techno-economic analysis of scrap recycling
We then compared the different recycling processes for spent bat-
teries and battery scraps. As shown in Fig. 6a, the pyrometallurgical
process recovers valuable metals from degraded LIBs at high tempera-
tures [40]. While the process is relatively simple, it consumes a
considerable amount of energy and produces abundant exhaust gases
[41–43]. The wet metallurgy process dismantles the waste battery and
adds chemical reagents to leach out the impurity elements, finally
yielding a high concentration of transition metal salt solution for pre-
paring ternary precursors [44]. The whole process is sophisticated and
consumes a large amount of leachate, generating significant wastewater
Fig. 6. Economic analysis of the regeneration of degraded NCM523. (a) A brief comparison of the different recycling processes. (b) GHG emissions, (c) total energy
consumption, and (d) the potential benefits of the different recycling processes.
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and environmental burden [45]. Direct recycling requires manual
disassembly of spent batteries to obtain low-impurity cathode powder,
which is then regenerated by various methods to replenish the lithium
[46,47]. Typically, the regeneration of battery scraps has significantly
fewer steps than spent battery recycling, mainly because the materials
are readily available and tedious processes such as battery disassembly
are not required; the materials also have known compositions and
chemistries that are easily regenerated.
We made a quantitative comparison of the direct regeneration of
NCM523 scraps and the current pyrometallurgical, hydrometallurgical,
and direct recycling of spent batteries in terms of greenhouse gas (GHG)
emissions, energy consumption, cost, and potential benefits, based on the
EverBatt 2020 model [48,49]. Since the regeneration of scraps is similar
to the direct recycling of degraded cathodes but excludes the lithium
replenishment and disassembly processes required for spent batteries,
the GHG emissions and energy consumption are similar for scrap
regeneration (9.159 kg kg1 and 134.34 MJ kg1) and direct recycling
(9.292 kg kg1 and 136.27 MJ kg1, Figs. 6b and c). In addition, since
neither scrap regeneration nor direct recycling involve acid treatment
and pyrometallurgy, they have lower GHG emissions and energy con-
sumption than pyrometallurgical and hydrometallurgical processes.
Importantly, scrap regeneration requires only 59.97% of the energy used
to produce cathodes from new materials, indicating the importance of
recycling.
While direct recycling of spent batteries and scrap regeneration both
have advantages in terms of environmental protection and energy con-
sumption reduction [35,50], direct recycling of spent batteries requires
careful dismantling of the battery, identification of the collected cathode
Y. Guo et al.
powder's composition, and assessment of its condition; these steps not
only significantly increase the cost (around $1.83 kg1) and process so-
phistication (Fig. 6d) but also mean industrialization will be slow,
because battery disassembly and material separation are not yet auto-
mated. Taking into account the cost, the potential profit for direct recy-
cling is about $0.16 kg1, similar to that of pyrometallurgical ($0.26
kg1) and hydrometallurgical ($0.14 kg1) processes. Scrap materials, on
the other hand, come mainly from factory production, so the source
consumption of the materials is much lower than in direct recycling. As
both processes command the same selling price for the regenerated
material, the cost savings in scrap recycling can be converted into profit.
Since scrap regeneration does not require battery collection and disas-
sembly, only pre-treatment and high-temperature regeneration, the
profit from this approach can reach $1.984 kg1 (Fig. 6d), almost 10
times higher than other recycling methods using spent batteries. EverBatt
analysis thus makes clear that battery scraps represent a significantly
higher-value asset than spent batteries, and their efficient recycling and
regeneration can lead to further applications of these materials.
4. Conclusions
We have focused on the recycling and regeneration of battery scraps
produced during battery manufacturing, which are readily available
materials, do not require battery disassembly, and have known compo-
sitions and chemistries, making them much more valuable to recycle.
Taking NCM523 as an example, we explored the slow degradation of
NCM523 in air, which generated Li2CO3, LiHCO3, and LiOH impurity
phases on the surface (5 nm), along with Li-poor rock-salt phases,
resulting in inferior performance. Based on the degradation mechanism,
lightly degraded NCM523 was effectively regenerated into a complete
layered structure by calcination at 850  C in air without adding extra Li.
We found that to extract the NCM523 in practical battery scraps,
combinatorial and optimized pretreatments were critical to effectively
remove binder PVDF and conductive carbon and thereby improve the
cathode yield, as well as significantly decrease the potential impurities
and structural deterioration. After pretreatment and regeneration, the
recycled cathode NCM523 exhibited excellent electrochemical perfor-
mance in both coin cells (170 mAh g1 at 0.1 C) and pouch cells (92.7%
retention after 1000 cycles). EverBatt analysis showed that our process
has better energy efficiency, fewer emissions, and a much higher profit
yield than pyrometallurgic, hydrometallurgic, and direct recycling
methods. This work deepens researchers’ understanding of the degra-
dation and recovery mechanisms of shallowly degraded cathode mate-
rials and facilitates the practical recycling of scrap materials to achieve
more sustainable battery manufacturing.
Author contributions
Y.C. Cao, Y.H. Huang, and Y.G. Yao proposed the concept and pro-
vided supervision. Y.Q. Guo and C. Guo performed the experiments. Y.Q.
Guo and C. Guo co-wrote the manuscript. All authors participated in data
analysis and manuscript discussion.
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.
Acknowledgments
This project was supported by the fund from the National Key R&D
Program of China (2022YFB2404303, 2021YFA1202300), the National
Natural Science Foundation of China (NSFC No. 5202780089,
52107224), and the Fundamental Research Funds for the Central Uni-
versities, HUST: 2021GCRC046. The authors thank test support from the
10
eScience 3 (2023) 100091
Analytical and Testing Center of Huazhong University of Science &
Technology and the State Key Laboratory of Materials Processing and Die
& Mould Technology.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.esci.2023.100091.
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