Regeneration of Spent Lithium-Ion Battery Materials

Journal of Energy Storage 51 (2022) 104470
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Journal of Energy Storage

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Research papers
Regeneration of spent lithium-ion battery materials

Jianfeng Wan a, Jianan Lyu a, Wenyan Bi b, *, Qiang Zhou b, Pengxun Li b, Haiyan Li c, Yingjie Li b
a
School of Mechanical and Power Engineering, Henan Polytechnic University, Jiaozuo, Henan 454000, China
b
School of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, Henan 454000, China
c
School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo, Henan 454000, China
A R T I C L E I N F O A B S T R A C T
Keywords: Lithium-ion batteries (LiBs) have excellent electrical properties and are widely used in many application do
Lithium-ion batteries (LiBs) mains. With the remarkable development of the LiBs industry, the number of spent LiBs has dramatically
Recycling increased. To reduce environmental pollution and resource depletion, several technologies for recycling and
Regeneration
regenerating LiBs have been developed, especially for valuable metals, such as lithium, manganese, cobalt,
Electrode materials
nickel, and copper. The reuse of LiB materials via regeneration is one of the cleanest and cheapest approaches.
Normalised transformation method
Assessment This study first analyses the structure and composition of a typical LiBs and classifies the regeneration methods
based on their structure. Owing to the varied measurement conditions of different regeneration methods, which
cannot be compared directly, a normalised transformation method for LiBs is proposed to calculate and compare
the results under different discharge current rates (Crates) and cycles. Furthermore, the degradation mechanism of
LiB materials is analysed. Finally, novel green regeneration technologies are summarised. This review aims to
develop a deep understanding of regeneration methods through comparison and analysis and identify the most
promising regeneration methods. The analysis shows that designing a fully recyclable and regenerative LiB is the
most promising method to solve the problem of spent LiBs.
1. Introduction [11]. Considering the economy, environment, and resources, regenera

tion is a promising approach for solving the problem of spent LiBs.
Lithium-ion batteries (LiBs) are used in various electronic products The typical structure and components of LiBs [15–17] are shown in
and vehicles on a large scale owing to their excellent performance and Fig. 2. Scientists have successfully explored different technologies to
large battery charge and discharge capacities [1–4]. The consumption of improve the regeneration of spent LiBs. The general regeneration
LiBs is growing remarkably at over 20% per year [5]. The global demand method of spent LiBs requires the regeneration of battery materials ac
for LiBs has increased dramatically, resulting in a proportional increase cording to their composition [18–39]. The processes include disman
in the demand for raw materials (Fig. 1) [5–10]. Consequently, a large tling, crushing, leaching, impurity removal, co-precipitation, and solid-
number of spent LiBs are produced every year, which causes environ state synthesis [40–43]. Some researchers have also studied the direct
mental pollution and resource depletion [2,11]. regeneration of spent LiBs.
To address these issues, many studies have been conducted on spent In this study, different regeneration methods were investigated, and
LiBs, including recycling technologies, regeneration methods [3,12], the degradation mechanism of the electrode was analysed. Further, few
analytical techniques [13], lifetime prediction [14], environmental novel green regeneration technologies have been summarised. These
impact assessment, and economic evaluation [11]. Most recycling technologies include (1) closed-loop regeneration process
technologies require the introduction of leaching agents, acids, and al [17,28,30,31,44–47], (2) lithium reconstruction through lithium
kalis, which cause environmental pollution and increase the recovery replenishment de-lithiation and/or re-lithiation [18,37,46,48–52], (3)
cost. Compared to pyrometallurgical recycling and hydrometallurgical coupling regeneration with other wastes to improve the performance
recycling in terms of environmental impacts and economic performance, [53,54], (4) exploration of a new application field [55,56], and (5)
direct physical regeneration has the greatest potential for reducing designing directly renewable and regenerative batteries [57].
greenhouse gas emissions, water pollution, and manufacturing costs
* Corresponding author.
E-mail address: biwenyan@hpu.edu.cn (W. Bi).
https://doi.org/10.1016/j.est.2022.104470
Received 17 September 2021; Received in revised form 10 March 2022; Accepted 18 March 2022
Available online 6 April 2022
2352-152X/© 2022 Elsevier Ltd. All rights reserved.
J. Wan et al. Journal of Energy Storage 51 (2022) 104470
2250 20000 1000 +1600

a Battery Capacity Demand b
Battery Capacity Demand
2000 18000 Lithium Demand +1400
Total Chemical Components
Battery Capacity Demand (GWh)
Lithium Supply/Demand (kt LCE)

800
Total Chemical Components (kt)
Battery Capacity Demand (GWh)

1750 16000 Lithium Supply
+1200
1500 14000 600
+1000
1250 12000
400
1000 10000 +800
750 8000 200 +600

500 6000
0 +400
250 4000
0 2000 +200
-200
-250 0 0
2020 2022 2024 2026 2028 2030 2014 2016 2018 2020 2022 2024 2026
Year Year
Fig. 1. Relation between battery capacity demand and raw materials. (a) Demand for total chemical components (lithium, nickel, manganese, cobalt, copper,
aluminium, iron, phosphorus, and graphite), (b) lithium demand and supply.
the initial discharge efficiency (ηini) and (ii) the normalised discharge
capacity (NDC) to compare and assess the different regeneration
methods.
2.1. Initial discharge ratio, ηini
To compare the initial discharge capacity of different batteries, the

initial discharge ratio (ηini) has been defined as Eq. (1),
ηini = QI /QT (1)
where QI is the initial discharge capacity, and QT is the theoretical

capacity.
The above equation shows that the initial discharge performance of a
battery. Although the QI was measured by different researchers under
different conditions (Crate and cycles), experimental data and model
[69] indicate that QI is barely affected by the discharge rate for a robust
battery. Therefore, the data provided by researchers can be directly used
in the calculation without any conversion. QT is constant for the selected
material.
2.2. Normalised discharge capacity, NDC
Fig. 3 is capacity degradation curve of typical LiBs, includes lithium

cobalt acid battery (LCO) (Fig. 3a), lithium nickel manganese cobalt
Fig. 2. The component of LiBs.
battery (NMC) (Fig. 3b), lithium iron phosphate battery (LFP) (Fig. 3c),
and lithium manganate battery (LMO) (Fig. 3d).
2. Calculation and assessment methods of the performance of
The general model to describe NDC of LiBs is expressed as the Eq. (2),
regenerated battery materials
which is based on the Popular Empirical Model–Single Power Law [58].
The effectiveness of the regeneration method for spent batteries NDCNC ,Crate = 1 − K1 NC b1 − K2 NC b2 (2)
needs to be evaluated based on the battery performance using the re
generated materials. Presently, researchers use the following two pa where NDC is the normalised discharge capacity, defined as the ratio of
rameters to measure battery performance: (i) initial discharge capacity the battery capacity at a given cycle count and Crate to its initial
and (ii) capacity retention rate at a certain discharge current rate (Crate) discharge capacity, Nc is the number of cycles, Crate represents the
and number of cycles. The initial discharge capacity of different studies discharge current rate, and K1, K2, b1, and b2 are the model coefficients.
can be directly compared, as it is barely affected by Crate for a robust LiB, The expression for NDCNC, Crate consists of three terms: 1, K1 NC b1 , and
especially when the Crate is less than 1C [58–69]. However, capacity K2 NC b2 . The first term is a constant 1, which indicates the starting point
retention is affected by the discharge rate and number of cycles. As of the NDC curve is at (0,1). The second term K1 NC b1 represents the
different researchers use different conditions to test the performance of initial part of the experimental curve, i.e., the first degradation stage,
regenerative batteries, the capacity retention cannot be directly and the concave part of the second slow degradation stage (shown in
compared under different Crates and number of cycles. In this study, Fig. 3c). The value of b1 is between 0 and 1. If it is close to 1, the concave
based on existing models and general experimental results, a normalised shape is not obvious (Fig. 3b). The third term K2 NC b2 represents the
transformation method for LiBs with different Crates and cycles is pro convex part of the tail of the experimental curve. The value of b2 is much
posed. The capacity retention rates measured under different conditions greater than 1, and since K2 is small, this part is significant only when NC
were converted into the normalised discharge capacity at the same Crate is large. When NC is large, the normalised capacity drops rapidly, similar
and number of cycles. Here, we adopted two evaluation parameters: (i) to a bent knee (shown in Fig. 3a and b). When K1, K2, b1, and b2 change,
2
a LCO b NMC
1.0 1.0
Normolized Capacity
Normolized Capacity
0.9 0.9
1.0 0.8 1.0

0.8 LCO NMC
Normolized Capacity
Normolized Capacity
0.7
0.7 0.9 0.9
0.6
0.6 50 100 150 200 250 300 50 100 150 200 250 300
Cycle Number Cycle Number
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
c LFP d LMO
1.0 1.0
Normolized Capacity
Normolized Capacity
0.9
0.9
1.0 LFP 0.8

Normolized Capacity
1.0 LMO
Normolized Capacity
0.8
0.7
0.9
0.9
0.7
100 200 300 400 500 600 700 800 900 1000 0.6 50 100 150 200 250 300
0.6
0 500 1000 1500 2000 0 100 200 300 400 500
Fig. 3. Typical capacity degradation curve for (a) LCO [58,59], (b) NMC [60,61], (c) LFP [60,62–67], (d) LMO [68,70].
Ultrasonic technology Solid-phase calcination

Hydrothermal
treatment
Electrochemical method Annealing
Fig. 4. Hydrothermal treatments combined with other techniques.
Table 1
Battery performance regenerated by hydrothermal method.
No. Regeneration Reaction condition Regeneration initial the first the capacity Commercial/ theoretical Reference
method material discharge charge retention pristine capacity capacity
capacity the capacity
1# Ultrasonic 800 W LiCoO2 131.8 mAh/g 132.8 97.3%, at C/5 274 mAh/g [72]
technology 2.0 mol/L LiOH, 120 ◦ C, mAh/g after 40 cycles
-Hydrothermal 6h
treatment
2# Hydrothermal 4 h, 220 ◦ C LiCoO2 153.1 mAh/g, 91.2% at 1C 274 mAh/g [73]
treatment 800 ◦ C at 0.1C after 100
- Annealing cycles
3# Aqueous solution Galvanostatic method LiCoO2 134.8 mAh/g, 95.9% at C/5 274 mAh/g [74]
reaction (between 0.001 and at C/5 after 50 cycles
- Electrochemical 1.00 mA/cm2)
reactions Etoile-Rebatt
- Hydrothermal
reactions
4# Hydrothermal Concentrated LiOH at LiCoO2 144.0 mAh/g 92.2% after 40 274 mAh/g [75]
method 200 ◦ C, 20 h cycles
#
5 Ultrasonic 1050 W LiCoO2 131.0 mAh/g 132.1 127.8 mAh/g 274 mAh/g [29]
technology 90 ◦ C, 6 h, 1 mL of at 0.2C mAh/g, at 0.2C after
-Hydrothermal H2O2, 0.5 MPa Ar gas 0.2C 50 cycles
technology
6# Hydrothermal 150 ◦ C LiFePO4 144.0 mAh/g 92.4% at 0.2C 170 mAh/g [43]
treatment 600 ◦ C, 4 h, in nitrogen at 0.1C after 100
- Annealing atmosphere cycles
3
1.0 1.0 (i) Influence of temperature

ηini
NDC100,0.2C
0.9 In the temperature range of 10–60 ◦ C, if the number of cycles is less
than 300 and Crate < 1, the influence of temperature is negligible
0.9
LFP
(especially at 10–45 ◦ C) [58]. In this study, most of the regeneration
Normalized Capacity
0.8
0.8 performance was measured at ambient temperature; therefore, the in
fluence of temperature can be ignored.
0.7
ηini
0.7
(ii) Uniformity of cycles: transformation of NDCNC, Crate to NDC100,
0.6
LCO Crate.
LCO 0.6
LCO
0.5 LCO LCO The slope of NDC vs Nc curve is:
0.5 dNDCNc
0.4 = − β0 *exp(β1 *Crate )*b*Ncb− 1
dNC
)
0.3 0.4 ( − β0 *exp(β1 *Crate )*Ncb *b
1# 2# 3# 4# 5# 6# = (7)
Nc
No.
(NDCNc − 1)*b
=
Fig. 5. Comparison of cathode materials' performance regenerated by hydro Nc
thermal method.
As Nc = 100 is located in the middle of the linear area of the NDC vs
Nc curve (Fig. 3), the slope is higher in this region compared to that of
different forms of the results are produced, which indicates the univer
the edge region. Considering the slope at Nc = 100 as the average slope
sality of the model. For example, when the value of b1 is close to 1, no
of this curve, the relationship between NDCN and NDC100 at any point is
concavity is observed in the normalised capacity curve (Fig. 3b). Simi
as follows:
larly, when K2 is too small, or when b2 approaches 1, no convexity is
⃒
observed at the tail of the curve (Fig. 3c and d). dNDC⃒⃒
NDC100 = NDCN + (100 − N) (8)
A thorough analysis of a large amount of experimental data suggests dN ⃒N=100
that between concave and convex regions, the curve is almost linear (e.
Substituting Eq. (7) in Eq. (8),
g., the middle part in Fig. 3), which is difficult to understand directly
using the general model (Eq. (2)). The value of b1 is usually close to 1 (NDC100 − 1)*b
NDC100 = NDCN + (100 − N) (9)
(0.5–1); therefore, the middle region of the power function becomes 100
close to a straight line. The cycles to be converted in this study are
Therefore,
located in the linear or approximately linear region (the red rectangle
part in Fig. 3), which is far from the knee point. The third term of the 100*NDCN − (100 − N)b 100*NDCN + N*b − 100*b
NDC100 = = (10)
model represents the convex region after the knee point of the curve. 100 − (100 − N)b 100 + N*b − 100*b
Therefore, ignoring the third term, Eq. (2) becomes:
Using Eq. (10), NDCNC, Crate can be transformed to NDC100, Crate
NDC = 1 − K1 *N b (3)
(iii) Uniformity of Crate: transformation of NDC100, Crate to NDC100,0.2C
Saxena et al. [69] proposed a more accurate version of Eq. (3) as
follows:
In Eq. (6), β0 and β1 are constants corresponding to the material and
NDC = 1 − K*Nc b (4) structure of the battery (independent of Crate). To facilitate the deriva
tion, we define expβ1 = γ; then, Eq. (5) becomes
where K is expressed as:
NDCNC ,Crate = 1 − β0 *γCrate *NC b (11)
{ ( ) }
B D
K = A*Tα *exp − + C + *g(Crate ) (5) According to the research results and models, when Crate < 0.2, the
T T
NDC vs Nc curve under different Crate nearly overlaps, and NDC becomes
where T is the temperature in Kelvin, α, A, B, C, and D are model co close to 1. For a robust battery, the error is very small (<2%). Consid
efficients that are independent of T and Crate. As the researches discussed ering the maximum allowable error of 5%, which is permitted in engi
in this study are performed at a constant temperature, Eq. (4) can be neering practice, we can assume that the error of the discharge capacity
simplified as loss, Dloss < 5%, to estimate the value range of γ.
Dloss = 1–NDC.
NDC = 1 − β0 *exp(β1 *Crate )*Nc b (6)
1 − NDC0.2C
1< < 1.05 (12)
where β0 and β1 are model coefficients. 1 − NDC0.01C
Eq. (6) is consistent with Eq. (3) and contains the parameter Crate. Eq. From Eqs. (11) and (12),
(6) was adopted to calculate the NDC, using b = 0.50, 1.0, and 0.774 for
LFP [63], NCM [60], and LCO [58], respectively. 1 < γCrate < 1.05 (13)
As the performance of the regenerated materials in different regen
1 < γ < 1.276 (14)
eration methods was measured under different conditions, the results
cannot be compared directly. Therefore, it is necessary to convert the Using Eq. (11), NDC100,0.2C and NDC100, Crate can be written as
NDC into the same cycles and the same Crate before comparison. Since
most studies use Nc = 100 and Crate = 0.2, the normalised discharge NDC100,0.2C = 1 − β0 *γ0.2 *NC b (15)
capacity NDCNC, Crate was uniformly transformed into NDC100,0.2C. The
transformation includes three steps: NDC100,Crate = 1 − β0 *γCrate *NC b (16)
4
Table 2
Battery performance regenerated by thermal method.
No. Regeneration Reaction condition Regeneration Initial The first The Commercial/ Theoretical Reference
method material discharge charge capacity pristine capacity capacity
capacity capacity retention
7# Solid-state synthesis 850 ◦ C, 12 h LiCoO2 152.1 135.4 274 mAh/g [73]

mAh/g at mAh/g at
0.1C 1C after
100 cycles
8# Thermal and Nitric acid and hydrogen LiCoO2 154. mAh/ 165 >90% after 274 mAh/g [76]
mechanical peroxide media citric g mAh/g 30 cycles
treatment acid, LiNO3
-Leaching technique 950 ◦ C, 24 h
-Calcination/
amorphous citrate
precursor process
9# roasting approach Molten ammonium LiCoO2 154 mAh/g 94% at 1C 274 mAh/g [77]
sulfate, 400 ◦ C, 2 h at 1C after 100
cycles
10# Ultrasonic N-methylpyrrolidone, LiCoO2. 153 mAh/g good cycle 274 mAh/g [78]
treatment, 40 ◦ C, 15 min at 0.1C ability
-Acid dissolution, 3 mol/L H2SO4, 1.5 mol/
-Precipitation L H2O2, 70 ◦ C, 1 h.
1 mol/L Na2C2O4
11# Direct regeneration 650 ◦ C LiFePO4 147.3 95.32% 170 mAh/g [79]
process mAh/g at after 100
0.2C cycles
12# Mechanical 650 ◦ C, 10 h, LiFePO4 139 mAh/g 95% at 170 mAh/g [80]
separation Under N2 flow at 0.2C 0.2C after
-High-temperature 100 cycles
pyrolysis
13# Solid-phase 650 ◦ C, 12 h LiFePO4 135.1 89.5% at 170 mAh/g [43]
calcination. mAh/g at 0.2C after
0.1C 100 cycles,
14# Hydrothermal 150 ◦ C LiFePO4 144.0 92.36% at 170 mAh/g [43]
treatment 600 ◦ C, 4 h, mAh/g 0.2C after
- Annealing In nitrogen atmosphere. 0.1C 100 cycles,
15# Direct pulverization 300 ◦ C, 2 h and 750 ◦ C, LiFePO4 129.4 92.96% at 170 mAh/g [81]
- Solid state reaction 7 h in high purity N2 mAh/g at 0.5C after
atmosphere 0.5C 1000
cycles
16# Peroxidation 500 ◦ C, 3 h, in air LiFePO4/C 151.9 99.1%. at 170 mAh/g [82]
-vanadium doping mAh/g at 1C after
0.1C 200 cycle
17# Pyrometallurgical NMP, 60 ◦ C, 50 min LiMn2O4 136.6 93 mAh/g 148 mAh/g [83]
techniques 500 ◦ C, 12 h mAh/g at after 50
- Calcination 0.1C cycles
18a# Hydrothermal LiNi1/3Co1/3Mn1/ 158.4 – 122.6 145.1 mAh/g in 278 mAh/g [71]
treatment 3O2 mAh/g at mAh/g, at the first cycle at
- Thermal annealing 1C 1C, after 1C, 85% after 100
100 cycles cycles
18b# LiNi0.5Co0.2Mn0.3O2 – – 128.3 146.6 mAh/g, in 278 mAh/g
mAh/g the first cycle at
1C and 89% after
100 cycles
(Pristine)
19a# Direct solid-state Mixing with Li salt, in air LiNi1/3Co1/3Mn1/ 153.3 – 125.4 278 mAh/g [71]
sintering 3O2 mAh/g at mAh/g, at
1C 1C, after
100 cycles
19b# Mixing with Li salt, in LiNi1/3Co1/3Mn1/ 157.4 – 123.8 278 mAh/g [71]
oxygen 3O2 mAh/g at mAh/g, at
1C 1C, after
100 cycles
19c# LiNi0.5Co0.2Mn0.3O2 – – 127.4 278 mAh/g
mAh/g
20# Supplementing 450 ◦ C for 5 h, LiNi0.5Co0.2Mn0.3O2 189.8 83.2% at <189.mAh/g, 278 mAh/g [44]
metal ions- 850 ◦ C, 15 h under O2 mAh/g at 1C after 0.1C
granulation, atmosphere with PO43− 0.1C 300 cycles (Commercial)
-Ion doping doping
-Heat treatment
21# calcining The mixture of LiNi0.5Co0.2Mn0.3O2 161.3 95.29% at 278 mAh/g [84]
LiOH⋅H2O and the spent mAh/g at 0.5C after
LiNi0.5Co0.2Mn0.3O2 0.1C 50 cycles
materials
22a# Solvent dissolution NMP Li(Ni1/3Co1/3Mn1/3) 278 mAh/g [85]
-Heat treatment at 800 ◦ C O2
(continued on next page)
5
Table 2 (continued )
157.9 95.1% at
mAh/g at 0.2C after
0.2C 100 cycles
22b# Basic solution Li(Ni1/3Co1/3Mn1/3) 122.7 mA 278 mAh/g
At 800 ◦ C O2 h/g at 0.2C
after 100
cycles
23 Direct calcination At 600 ◦ C Li(Ni1/ 145.4 96.7% at 0.2C 278
3Co1/3Mn1/ mAh/g at after 100 cycles mAh/g
3)O2 0.2C
[85]
24 Pre-heating 800 ◦ C for 1 h LiNi0.5Co0.2Mn0.3O2 140 mAh/g 97%at 147 mAh/g in the 278 mAh/g [86]
-High energy ball 950 ◦ C at 0.2C 0.2C after first cycle. 91%, at
milling 50 cycle 0.2C after 50 cycle
- Sintering (commercial)
25 Acid leached 2-Hydroxy-5-nonyl LiNi0.8Co0.15Al0.05 162 mAh/g 248.7 92% after 264 mAh/g [21]
-Extraction salicylaldehyde oxime O2 mAh/g, 50 cycles
-Calcination 800 ◦ C for 15 h
Pre-heating -high-energy ball-milling

Sintering
Spray drying
Hydrothermal treatment Annealing
Thermal and mechanical
Calcination Leaching Precursor technique

Acid-leached -
Ultrasonic treatment acid dissolution precipitation
molten ammonium Roasting
Mechanical separation Pyrolysis
Direct pulverization Solid-state synthesis
Solvent dissolution (NMP)

Heat treatment
Basic solution
Fig. 6. Thermal treatment combined with other techniques.
Eliminating β0 NC b from Eqs. (15) and (16), 3. Regeneration of cathode materials

( )
NDC100,0.2C = 1 − 1 − NDC100,Crate *γ0.2− Crate (17) The cathode of LiBs mainly includes a cathode current collector
Substituting Eq. (16) into Eq. (17), (aluminium foil) and active cathode materials such as LiCoO2, LiMnO2,
When Crate>0.2C, LiFePO4 and LiCoxNiyMnzO2 [15]. The cathode materials directly
( ) determine the electrochemical performance and cost of LiBs. The failure
NDC100,Crate > NDC100,0.2C > 1 − 1 − NDC100,Crate 1.2760.2− Crate
(18) and degeneration of spent LiBs can be attributed to structural and phase
changes, impurities, and Li+ losses [44,71]. According to the failure and
When Crate = 0.2C, no conversion is required,
degeneration, many methods can be used to regenerate cathode mate
When Crate < 0.2C,
rials from spent LiBs [18–20,22–29,43,72].
( )
1 − 1 − NDC100,Crate 1.2760.2− Crate > NDC100,0.2C > NDC100,Crate (19)
3.1. Thermal method
Based on the above research results, we adopted Eq. (6) to calculate
the approximate normalisation capacity for different cycles under
3.1.1. Hydrothermal method
different Crate and comparatively evaluate different regeneration
Hydrothermal synthesis is a clean and environmentally friendly
methods.
regeneration method for spent LiBs. It is a reaction in an aqueous solu
tion under a specific temperature and pressure. This method can easily
combine with other technologies to increase regeneration efficiency
(shown in Fig. 4). Table 1 summarises the results of the research on
6
ηini cations become more ordered. The specific capacity of the LiB recovered
fully and the electrochemical performance improved considerably.
1.0 1.0
NDC100,0.2C
Therefore, it is a promising method and can be widely applied across
industries.
0.9 LFP
LFP 0.9
LFP
Normalized Capacity
LFP
0.8
LFP 3.1.2. High-temperature thermal method
0.8
Many researchers have studied the regeneration of spent LiB mate
0.7 NCM
rials using high-temperature thermal methods, as listed in Table 2. To
ηini
NCM-Al
0.7 achieve better regeneration efficiency, researchers couple the thermal
0.6
LCO LCO NCM
NCM
NCM NCM
NCM method with many other technologies (shown in Fig. 6). The perfor
NCM 0.6 mance of the material regenerated by the thermal method is shown in
NCM
0.5 NCM Fig. 7.
Fig. 7 shows that average ηini is 0.56, 0.83, and 0.56 for LCO (com
0.5
0.4 mercial is 0.52), LFP (commercial is 0.99) and NMC (commercial is
0.73), respectively. The average NDC100,0.2C is 0.92, 0.95, and 0.90 for
0.3 0.4 LCO, LFP, and NMC, respectively. These results indicate that the thermal
7# 9# 11# 13# 14# 15# 16# 18a#19a#19b# 20# 21# 22a#22b# 23# 24# 25#
method provides good regeneration for spent LiBs when coupled with
No. various methods. The NDC is related to the initial discharge ratio (ηini).
Fig. 7. Comparison of the performance of cathode materials regenerated by
Generally, when the initial discharge capacity is high, the NDC is high;
thermal method. however, the opposite is not true. The regenerated material quality is
considered high, i.e., the discharge performance and cycle stability are
good when both ηini and NDC are high. In the thermal regeneration
cathode materials regenerated by the hydrothermal method. Fig. 5
method, a higher initial discharge ratio usually results in better battery
shows that the average ηini of LCO is 0.51, which is nearly the same as
performance, including cycle stability.
that of pristine LCO (ηini = 0.54REF). The deviation ratio of ηini in the five
samples is less than 1%. The average NDC100,0.2C was 0.92. This in
3.1.3. Thermal reduction method
dicates that the hydrothermal method is a stable and effective regen
The thermal reduction method reduces the metal from its compound
eration method for LCO. For LFP, ηini was 0.85, which was slightly lower
using reducing agents by a redox reaction. Thermal reduction methods
than that of pristine LFP (0.94), and the NDC was over 90% after 100
typically include carbon thermal reduction and hydrogen reduction.
cycles. These results show that the hydrothermal method has high
reactivity because of good dispersibility and uniformity in solution.
Additionally, the reaction conditions are mild, which is beneficial for 3.1.3.1. Carbon thermal reduction. The carbon thermal reduction
maintaining the electrochemical properties of the electrode materials. method reduces metal oxides at a specific temperature using carbon as
Therefore, it has a great advantage for regenerating spent LiBs materials. the reducing agent. This is an economical regeneration method and can
Hydrothermal regeneration is a non-destructive and energy-efficient conveniently improve product purity. Wang et al. [87] combined
method with few side reactions. Owing to the simple steps, the hydro mechanochemical extraction and thermal carbon reduction to regen
thermal method is easy to perform compared to leaching, precipitation, erate Li2CO3 from spent LiCoO2. Tang et al. [88] combined the multi-
or solid-state synthesis, which involve complicated processing steps. vacuum pyrolysis and carbon thermal reduction method to regenerate
Therefore, hydrothermal regeneration has been widely used to process Li2CO3 and Co0, and the capacity retention of the regenerated cathode
various spent LiBs. More importantly, the original morphology, struc was 93% after 100 cycles. Carbon thermal reduction is a prominent
ture, and size distribution were retained and improved during the hy green method for the recovery and regeneration of spent LiBs.
drothermal regeneration process [73].
Hydrothermal technique combined with other techniques, such as 3.1.3.2. Hydrogen reduction. Hydrogen reduction is a method for pro
annealing treatment [43], ultrasonic technology [29], and electro ducing metals by reducing metal oxides with hydrogen at high tem
chemical treatment [74] (Fig. 5), results in more uniform lithium peratures (Table 3). The hydrogen reduction method is widely used for
replenishment, a smaller charge transfer resistance, and a larger Li+ metal production and renders products with higher purity and easily
diffusion coefficient. The capacity retention improves because the controllable properties compared to the carbon reduction method. The
Table 3
Battery performance regenerated by hydrogen reduction.
No. Regeneration Reaction Regeneration Initial The first The capacity Commercial/pristine Theoretical Reference
method condition material discharge charge retention capacity capacity
capacity capacity
26# Hydrogen Using LiFePO4/C 156.7 mAh/ 99.0% at 1C after Discharge capacity 170 mAh/g [89]
reduction FePO4⋅2H2O g at 0.1C 25 cycles 168.5 mAh/g at 0.1C,
precipitated discharge capacity
700 ◦ C in 5% H2 retention 99.4% at 1C
and 95% Ar for after 25 cycles
8h (LiFePO4/C prepared
with Commercial
FePO4⋅2H2O)
27# Hydrogen H2 reduction at LiNi0.8Co0.1Mn0.1O2 The capacity The capacity retention 275 mAh/g [90]
reduction 500 ◦ C within retention at 10C at 10C is 75% of at 0.1C
method 15 min is 63% of at 0.1C (Synthesized from
- Water (Synthesized commercial LiOH⋅H2O)
leaching from regenerated
-LiOH⋅H2O LiOH⋅H2O)
crystallization
7
Table 4
Battery performance regenerated by solid–liquid extraction method.
No. Regeneration Reaction condition Regeneration material Initial The first The capacity Commercial/ Theoretical Reference
method discharge charge retention pristine capacity
capacity capacity capacity
the
28# Leaching process Sulfuric acid and LiCoO2 61.5 mAh/g 274 mAh/g [91]
- Precipitation hydrogen peroxide for discharge
- Thermal synthesis Potassium hydroxide time of 4.4 h
at 800 ◦ C for 5 h. in the 4th
cycle,
32.5 mAh/g
in the 15th
cycle for
discharge
time of 2 h.
29# Leaching process Ammonium oxalate, at LiCoO2 119.7 124.9 105.3 mAh/g 274 mAh/g [92]
- Precipitation pH = 2.0, 55 ◦ C, 40 mAh/g at mAh/g at 0.2C after
- Solid phase method min 0.2C 50 cycles
ammonium oxalate
900 ◦ C, 20 h
30# Leaching process 0.9 vol%H2O2, 1 mol/ LiCoO2 138.6 150.8 86% at 0.2C 274 mAh/g [22]
L methanesulfonic mAh/g mAh/g after 200
acid, 70 ◦ C cycles
31# Leaching 2- LiCoO2 The 121.2 mAh/g 274 mAh/g [93]
-Precipitation Naphthalenesulfonic coulombic at 0.1C,
process acid efficiency
was
maintained
at 99% after
100 cycles
32# Dismantling 800 ◦ C for 2 h. LiCoO2 127.2 130.8 >96.6%, at 274 mAh/g [41]
-Detachment N-methylpyrrolidone mAh/g at mAh/g, 0.1C after 30
-Acid leaching (NMP) 0.1C at 0.1C cycles
-Electrochemical 1 mol/L HNO3, 1.0 vol rate
deposition % H2O2, 80 ◦ C, 1 h
technology 1.0 mA/cm2, 100 ◦ C,
20 h
33# Hydrometallurgical N-methyl-2- LiMn2O4 123.7 67.3% at 148 mAh/g [94]
method pyrrolidone solution mAh/g at 0.1C after 50
- Calcination 500 ◦ C, 12 h 0.1C cycles
34# Leaching H2SO4 and H2O2 LiNi1/3Mn1/3Co1/3O2 158 mAh/ 178 80% at 0.5C 278 mAh/g [95]
-Co-precipitation NaOH and NH3⋅H2O g at 0.1C mAh/g after 50
process 900 ◦ C, in air, 12 h. at 0.1C cycles
- Solid-phase
calcination
35# Leaching Concentrated sulfuric LiNi1/3Co1/3Mn1/3O2 165.7 85.9% at 1C 170 mAh at 278 mAh/g 28
– Precipitation acid, 1 h, 80 ◦ C mAh at after 200 0.1C
- Calcined H2O2 0.1C, cycles. (Commercial)
36# Leaching Tartaric acid and LiNi1/3Co1/3Mn1/3O2 159 mAh/ 98.7% at 278 mAh/g [96]
-Co-extraction hydrogen peroxide g at 0.1C 0.5C after 50
-Calcination sodium hydroxide, cycles
saturated hot sodium
carbonate, NH3⋅H2O
900 ◦ C
37# Leaching 3 mol/L HCl, di-(2- LiNi1/3Co1/3Mn1/3O2 151.0 182.4, 95.0% at 2C 278 mAh/g [24]
- Co-extraction ethylhexyl) mAh/g at mAh/g
- Co-precipitation phosphinic acid, 0.5C at 0.5C
- Calcination oxalic acid
in air, 900 ◦ C, 12 h
38# Leaching oxalic acid Li(Ni1/3Co1/3Mn1/3)O2 168 mAh/ 91.5% at 278 mAh/g [35]
-Calcination g at 0.2C 0.2C after
150 cycles
39# Leaching Ascorbic acid LiNi1/3Co1/3Mn1/3O2 164.9 91.3% at 157.4 mAh/g 278 mAh/g [97]
-Coprecipitation Oxalic acid mAh/g at 0.2C after at 0.2C
- Heat treatment 900 ◦ C 0.2C 100 cycles (commercial
NCM)
40# Dismantling- D2EHPA, sulfuric Li[(Ni1/3Co1/3Mn1/3)(1- 152.7 175.4 94% at 1C [54]
-Ball milling, solution x)Mgx]O2 mAh/g at mAh/g, after 50
-Leaching and NaF, 550 ◦ C, 5 h 0.2C at 0.2C cycles,
impurity removing,
-Solid-state synthesis
41# Leaching 2 mol/L HNO3 and 5 Li1.2[Mn0.56Ni0.16Co0.08]O2 239.4 81.0% at 377 mAh/g [98]
-Coprecipitation. vol% H2O2 at 75 ◦ C mAh/g at 0.1C after
2 mol/L Na2CO3, 2 0.1C 100 cycles
mol/L NH3⋅H2O
solution
8
No. Regeneration Reaction condition Regeneration material Initial The first The capacity Commercial/ Theoretical Reference
method discharge charge retention pristine capacity
capacity capacity capacity
the
42# Leaching 2-Hydroxy-5-nonyl LiNi0.8Co0.15Al0.05 O2 162 mAh/ 248.7 92% at 0.5C 264 mAh/g [21]
- Calcination salicylaldehyde oxime g at 0.5C. mAh/g after 50
800C for 15 h at 0.5C. cycles
43# Acid leaching 0.1 mol/L H2SO4, 0.5 LiNi0.6Co0.2Mn0.2O2 180.6 86% at 1C 276 mAh/g [42]
- Co-precipitation mol/L citric acid mAh/g at after 100
- Solid-phase 0.5 mol/L oxalic acid 0.1C cycles
reaction 120 ◦ C, 10 h,
500 ◦ C, 5 h, and
800 ◦ C for 12 h
Extraction Precipitation Calcination
Detachment
Dismantling Electrochemical deposition
Leaching
Ball milling
Calcination
Solid-phase calcination
Precipitation
Thermal synthesis
Fig. 8. Solid–liquid extraction method combined with other techniques.
be applied as an alternative technology for recycling spent LiB materials.

0.9
ηini 1.0
NDC100,0.2C
3.2. Extraction
0.8
0.8
NCM
3.2.1. Solid–liquid extraction (leaching)
Normalized Capacity
0.7 Solid–liquid extraction, also referred to as leaching, is a method that

NCM
NCM
0.6 separates components from a solid mixture using solvents. Leaching is a
NCM NCM NCM typical regeneration method for electrode materials. It adopts an inor
ηini
0.6 NCM ganic or organic acid as the leaching agent to recycle and regenerate
NCM-Mg
0.4 active cathode materials from spent LiBs (Table 4). The solid–liquid
LCO
0.5 extraction method can be combined with many other technologies
(Fig. 8). The performance of the materials regenerated by the solid
LCO LCO
0.2 –liquid extraction method is shown in Fig. 9. Table 4 and Fig. 9 show
0.4
that some solid–liquid extraction methods can realise high capacity
retention (NDC100,0.2C > 0.9) while some realise low (NDC100,0.2C < 0.8).
0.3 0.0 The average ηini and NDC100,0.2C of LCO are 0.48 (commercial is 0.52)
29# 30# 32# 34# 35# 36# 38# 39# 40# 41# 43# and 0.86, respectively, while the average ηini and NDC100,0.2C of NMC are
No. 0.61 (commercial is 0.73) and 0.86, respectively.
Solid–liquid extraction involves simple metal recycling procedures to
Fig. 9. Performance comparison of cathode materials regenerated by solid
realise gradient recycling and regeneration, which has many advan
–liquid extraction method.
tages, such as high selectivity and yields, low chemical consumption,
and enhanced closed-loop [93]. Moreover, the leaching method can
average ηini and NDC100,0.2C of LFP are 0.92 (commercial is 0.99), and
regenerate micro/nanostructured LiCoO2 cathode and Co3O4 anode
0.99, respectively.
materials [97]. The cathode material LiCoO2 with micro/nanostructures
LiFePO4/C can be synthesized with regenerated FePO4⋅2H2O by the
exhibits excellent electrochemical properties. Using comparative ex
hydrogen reduction method [89]. LiNi0.8Co0.1Mn0.1O2 can also be syn
periments, Wang et al. showed that methane sulfonic acid has better
thesized with regenerated LiOH⋅H2O by the one-step hydrogen reduc
leaching performance compared to citric acid, malonic acid, succinic
tion method [90]. Hence, the hydrogen reduction method can
acid, and oxalic acid. Additionally, owing to its biodegradable and low-
regenerate the spent LiB materials in a simple and environment-friendly
toxic nature, methane sulfonic acid is a preferred leaching agent in the
way.
LiB regeneration industry [22].
The thermal method regenerates spent LiBs by heating, and the re
generated materials show good electrochemical performance similar to
3.2.2. Liquid–liquid extraction
pristine materials. The primary reasons for the degradation of the ca
Liquid–liquid extraction, also referred to as solvent extraction, is a
pacity are the loss of Li+, the change in the electrolyte, crystal structure,
unit operation in chemical engineering, which separates mixtures ac
microphase, and thickening of the solid, or interface (SEI). The phase
cording to the different solubilities of different components in the same
change of Li+ increases the charge transfer resistance. The thermal
solvent (Table 5). It transfers a solute substance from one solvent to
method facilitates Li+ phase to regain its layered structure. Hence, the
another by employing the difference in the solubility or distribution
thermal method is a direct, green, low-cost, and facile method that can
coefficient between two incompatible solvents. Liquid–liquid extraction
9
Table 5
Battery performance regenerated by liquid–liquid extraction method.
No. Regeneration Reaction condition Regeneration Initial The first The capacity Commercial/ Theoretical Reference
method material discharge charge retention pristine capacity
capacity the capacity capacity
44# Leaching Ammonia, ammonium LiNi0.5Co0.5O2 162.8 mAh/g 174.9 145.8 mAh⋅/g 274 mAh/g [99]
-Extraction sulfite and ammonium at 0.1C mAh/g, at at 0.1C after
-Co- bicarbonate 0.1C 100 cycles
precipitation LIX984, 25 ◦ C 10 min;
-Calcination H2SO4 1.5 mol/L
NaOH at 55 ◦ C pH =
11.25
800 ◦ C, 12 h
45# Leaching Tartaric acid and LiNi1/3Co1/3Mn1/ 159 mAh/g at 98.7% at 0.5C 278 mAh/g [96]
-Co-extraction hydrogen peroxide 3O2 0.1C after 50 cycles
-Calcination Sodium hydroxide and
saturated hot sodium
carbonate, NH3⋅H2O
900 ◦ C
46# Leaching Sulfuric acid and LiNi1/3Co1/3Mn1/ 150 mAh/g at 96.3% at 1C 278 mAh/g [100]
-Precipitation hydrogen peroxide. 3O2 0.5C after 50 cycles
–Co-extraction 4 mol/L NaOH, pH = 4.8,
10% D2EHPA, 90%
sulfonated kerosene, pH
=2
47# Leaching 3 mol/L HCl LiNi1/3Co1/3Mn1/ 151.0 mAh/g 182.4 95.03% at 2C 278 mAh/g [24]
- Co-extraction Di-(2-ethylhexyl) 3O2 at 0.5C mAh/g at
- Co- phosphinic acid oxalic 0.5C
precipitation acid
- Calcination In air, 900 ◦ C, 12 h
48# Acid leached 2-Hydroxy-5-nonyl LiNi0.8Co0.15Al0.05 162 mAh/g at 248.7 92% at 0.5C 264 mAh/g [72]
-Extraction salicylaldehyde oxime O2 0.5C mAh/g, at after 50 cycles
-Calcination 800 ◦ C for 15 h 0.5C
The performance of the materials regenerated by the liquid–liquid

Precipitation Calcination extraction method is shown in Fig. 11. Fig. 11 shows that the average ηini
of NC is 0.53; average NDC100,0.2C of NC is 0.89; average ηini of NMC is
Leaching Extraction
0.55 (commercial is 0.73), and average NDC100,0.2C of NMC is 0.88. The
Calcination
average ηini of NMC-Al is 0.61 (commercial is 0.73), and average
NDC100,0.2C of NMC-Al is 0.85. The addition of aluminium increases the
Leaching
initial discharge ratio of NCM, however, the cycle stability decreases
Precipitation Extraction
slightly.
Furthermore, co-extraction, combined with leaching (45#) and
Fig. 10. Liquid–liquid extraction combined with other techniques.
calcination, can achieve a high initial discharge ratio (0.57) and good
cycle stability (NDC100,0.2C > 0.96).
The structure of the cathode materials regenerated by liquid–liquid
ηini
extraction is stable, indicating that liquid–liquid extraction is an effec
NDC100,0.2C
0.9 tive method for regenerating cathode materials [99] for LiBs.
0.7
3.3. Precipitation method

Normalized Capacity
NCM-Al 0.8
0.6
NCM Using the precipitation method, ions can be separated from the so
NCM NCM lution via a precipitation reaction. Different types of co-existing soluble
ηini
NC 0.7
ions are precipitated together in this method. The regeneration of active
materials from spent LiBs using the precipitation method is popular
0.5
0.6 because the process is simple, fast, inexpensive, and easy to control
(Table 6). The precipitation method can be combined with other tech
0.4
0.5 nologies (Fig. 12). The performances of the materials regenerated by the
precipitation method are shown in Fig. 13. The composition of regen
erated materials influences the performance of regenerated batteries.
0.3 0.4 Fig. 13 shows that the average ηini and NDC100,0.2C of NC are 0.64, and
44# 45# 46# 47# 48#
0.83, whereas the average ηini and NDC100,0.2C of NMC are 0.64 (com
No. mercial is 0.73) and 0.82, respectively. The ηini decreases with
decreasing nickel content (Fig. 13 55a#,55b#,55c#), while the tendency
of NDC100,0.2C is different.
liquid–liquid extraction method.
During the precipitation process, diffusion can affect the reaction
rate of the materials. Lou et al. [25] found that the phase transformation
is combined with other recycling technologies to improve the extraction
from amorphous to crystalline during the precipitation process can
efficiency (Fig. 10), and the improved technique is widely used in the
improve precipitation efficiency and accelerate morphology evolution
recovery and regeneration of spent LiBs.
and composition change.
10
Table 6
Battery performance regenerated by precipitation method.
No. Regeneration Reaction Regeneration material Initial The first The Commercial/pristine Theoretical Reference
method condition discharge charge capacity capacity capacity
the
49a# Leaching 2 mol/L sulfuric Li (Ni0.9Co0.05Mn0.05) O2 192.5 72.5% at 207.9 mAh/g at 275 mAh/g [26]
Coprecipitation acid, 75 ◦ C, 0.5 h. (NCM50) mAh/g at 0.2C after 0.2C,
calcination 1.8 mol/L NaOH, 0.2C 100 cycles 81.2% at 0.2C after
49b# 1.8 mol/L Li (Ni0.9Co0.05Mn0.05) O2 173.9 mAh 75.2% at 100 cycles (pristine)
ammonia, pH = (NCM100) at 0.2C 0.2C after
11.3, Ar 100 cycles
atmosphere
500 ◦ C 6 h and
720 ◦ C 12 h at O2
atmosphere.
50# Dismantling- D2EHPA, sulfuric Li[(Ni1/3Co1/3Mn1/3)(1- 152.7 175.4 94% at 1C [54]
-Ball milling, solution x)Mgx]O2 mAh/g at mAh/gat after 50
-Leaching and NaF 0.2C 0.2C cycles
impurity 550 ◦ C for 5 h
removing,
-Solid-state
synthesis
51# Dissolving 1-M H2SO4 and LiNi1/3Co1/3Mn1/3O2 163.5 198.9 94.1% at 94.5% at 1C after 50 278 mAh/g [61]
-Co-precipitation 1 vol% H2O2. mAh/g at mAh/g at 1C after 50 cycles, (synthesized
sintering 1.8 mol/L 0.1C 0.1C cycles from fresh material)
Na2CO3,
NH3⋅H2O, 60 ◦ C,
12 h, pH = 7.5
in air, 900 ◦ C, 12
h
52# Leaching Ammonia, LiNi0.5Co0.5O2 162.8 174.9 145.8 274 mAh/g [99]
-Extraction ammonium mAh/g at mAh/gat mAh/g at
sulfite, and 0.1C 0.1C 0.1C after
-Co-precipitation ammonium 100 cycles,
-Calcination bicarbonate
LIX984, 25 ◦ C, 10
min; H2SO4 1.5
mol/L
NaOH, 55 ◦ C, pH
= 11.25
800 ◦ C, 12 h
53# Acid leaching, H2C2O4 LiNi0.5Co0.2Mn0.3O2 149.5 85.45% 278 mAh/g [101]
-Co-precipitation 850 ◦ C, 12 h mAh/g at after 100
solid-phase 0.2C cycles
calcination
54# Reduction Carbon black was LiNi0.5Co0.2Mn0.3O2 172.9 198.4 93.8% at Initial charge 278 mAh/g [102]
roasting, heated at 600 ◦ C mAh/g at mAh/g at 0.2C after capacity 204.9 mAh/
-Two-step for 0.5 h in an 0.2C 0.2C 50 cycles g and discharge
leaching, argon atmosphere capacity 179.6 mAh/
-Co-precipitation, Water leaching g at 0.2C
solid-state and sulfuric acid (commercial)
reaction leaching solution
(7 mol/L)
Ammonia (7.5
mol/L) at
nitrogen
atmosphere at
55 ◦ C and pH
10.7–10.8
500 ◦ C, 5 h and
850 ◦ C, 15 h
55a# Leaching 4 mol/L H2SO4, LiNi0.8Co0.1Mn0.1O2 197.7 86.3%, 275 mAh/g [103]
Hydroxide Co- 4% H2O2, 90 ◦ C, mAh/g after 50
precipitation 2 h, cycles
55b# ammonia, pH = LiNi0.5Co0.2Mn0.3O2 174.3 95% after 278 mAh/g
10.5 mAh/g 50 cycles
#
55c LiNi0.33Co0.33Mn0.33O2 168.3 96%, after 279 mAh/g
mAh/g 50 cycles
#
56 Leaching 2 mol L1 HNO3, 5 Li1.2[Mn0.56Ni0.16Co0.08] 239.4 81.0% at 377 mAh/g [98]
-Coprecipitation. vol% H2O2, 75 ◦ C O2 mAh/g at 0.1C after
0.1C 100 cycles
3.4. Sol-gel method reactants in the liquid phase. The system forms a stable three-
dimensional network structure of the gel via a condensation reaction.
In the sol-gel regeneration process, precursors and compounds con The sol-gel method is an environmentally friendly method for regener
taining highly chemically active components are mixed with the ating active cathode materials from spent LiBs, especially lithium,
11
Dissolving Solid-phase synthesis
Precipitation Calcination
Dismantling Ball milling
Leaching Extraction Precipitation Calcination
Reduction roasting
Fig. 12. Precipitation combined with other techniques.
shown in Fig. 17. The average ηini and NDC100,0.2C of LCO are 0.48
1.0
ηini (commercial is 0.52) and 0.92, respectively. The ηini is stable because the
NDC100,0.2C 0.9 deviation is less than 0.4%. The normalized capacity increases with an
0.9 increase in the ηini.
0.8 0.8
Normalized Capacity
3.6. Electrochemical method
NCM
NCM NCM
0.7
0.7 Electrochemical regeneration methods include electrolysis, electro
ηini
NCM NC NCM
NCM
NCM NCM osmosis, and electrochemical high-voltage pulse methods. This process
0.6
NCM uses voltage, high-voltage pulses, and electric fields to conduct the redox
0.6
reaction, discharge, and dialysis, respectively. The electrochemical
method can be combined with other regeneration technologies, as
0.5
0.5 shown in Fig. 18. He et al. extracted lithium ions from spent cathodes by
0.4 applying a direct-current electric field. The electrochemical regenera
tion is fast, highly efficient, and clean. A few results of electrochemical
0.3 0.4 regeneration are listed in Table 9. The average ηini of LCO is 0.46
49a# 49b# 51# 52# 53# 54# 55a# 55b# 55c# 56#
(commercial is 0.52), NDC100,0.2C of LCO is 0.92, and the average ηini of
No.
NMC is 0.65 (commercial is 0.73).
Fig. 13. Comparison of the performance of cathode materials regenerated by Using the electrochemical method [80] to separate active materials
precipitation method. from Al foil is a closed-loop regeneration method and has a significant
prospect in the LiBs industry [110].
nickel, cobalt, and manganese. Several studies (Table 7) have been
performed to regenerate spent LiBs using the sol-gel method. The sol-gel 3.6.1. Electrolytic method
method usually combines leaching, calcination, and thermal and me In the electrolysis process, the redox reaction occurs under a current.
chanical methods (Fig. 14). The performance of materials regenerated The electrical energy is converted into chemical energy. Wang et al.
by the sol-gel method is shown in Fig. 15. Fig. 15 shows that average ηini [111] adopted the suspension electrolysis method to directly regenerate
and NDC100,0.2C of LCO are 0.50 (commercial is 0.52) and 0.85; average LiCoO2 and achieved a recovery rate of 75 wt%.
ηini and NDC100,0.2C of LMO are 0.47 and 0.92; average ηini and
NDC100,0.2C of NMC are 0.51 (commercial is 0.73) and 0.91; average ηini 3.6.2. High-voltage pulsed discharge
and NDC100,0.2C of NMC-Al are 0.53 (commercial is 0.73) and 0.96, Tokoro et al. [37] adopted a high-voltage pulsed discharge method to
respectively. The materials regenerated by the sol-gel method exhibited strip cathode active substances from an aluminium foil. Joule heating of
good battery performance (NDC100,0.2C > 0.85). The ηini increased with Al foil at 19.0 kA and 25 kV melted the polyvinylidene fluoride binder
an increasing Al content (Fig. 14 66a#, 66b#,66c#); however, the ten and separated 93.9% of the cathode active substances. More impor
dency of NDC100,0.2C was different. The addition of Al increases the ηini tantly, 99% of the regenerated active substances recovered their
and cycle stability (NDC100,0.2C. > 0.93). chemical composition. Hence, this novel high-voltage pulsed discharge
The sol-gel method can yield regenerated cathode materials with electrical method is efficient, clean, and prospective.
good performance [107], and, more importantly, the pollution and
produced side products of this method are negligible [104]. Li et al. 3.6.3. Electrodialysis
found that maleic acid esterifies and establishes a stable network to Electrodialysis can transport salt ions from one solution to another
chelate metal ions [108]. Zhang et al. found that doping a small amount through ion-exchange membranes under an applied electrical potential
of Al3+ improves the discharge capacity of LiNi1/3Co1/3Mn1/3O2, en difference. This method can solve the problem of lithium-ion loss. Jung
hances the ionic and electronic conductivities, and improves the lithium et al. [45] reported a novel hydrometallurgical electrodialysis method to
storage properties [109]. regenerate spent lithium cathode materials with lithium hydroxide
(LiOH) or lithium carbonate (Li2CO3) to replace the impurities and used
a three-compartment electrodialysis cell to regenerate LiOH and sulfuric
3.5. Ultrasonic method acid (H2SO4) in recovering lithium. Electrodialysis is an environment-
friendly closed-loop process as LiOH and H2SO4 are regenerated and
The acoustic cavitation effect plays a key role in the ultrasonic can be used as reactants in the new hydrometallurgical recycling
regeneration process. In this method, cavitation bubbles form in a liquid, process.
grow, and collapse. When the bubbles collapse, they are associated with A comparison of different regeneration methods indicates that for
a firm pressure pulse, which can accelerate the recovery and regenera LiCoO2 initial discharge capacity of the thermal method is higher than
tion of electrode materials (Table 8). When the ultrasonic method is that of the leaching method. When the leaching method is coupled with
combined with other technologies (Fig. 16), the regenerated cathode the sol-gel method, calcination, ultrasonic enhancement, and spray
materials display good electrochemical performance and cycle ability. drying, the initial discharge capacity of LiCoO2 barely changes. The
The performance of the material regenerated by the ultrasonic method is results show that the thermal method has a significant advantage in
12
Table 7
Battery performance regenerated by sol-gel method.
57# Thermal and Nitric acid-hydrogen LiCoO2 154 mAh/g 165 mAh/g >90% after 274 mAh/g [76]
mechanical peroxide media 30 cycles.
treatment citric acid, LiNO3,
-Leaching 950 ◦ C, 24 h
technique
-Amorphous
gelatinous
precursor
-Calcination/
58# Leaching Citric acid, C2H3LiO2, LiCoO2 137 mAh/g at 94.38% at 142.5 mAh/g at 274 mAh/g [104]
-Sol-gel method NH3⋅H2O, ethylene 0.1C 0.1C after 20 0.1C
-Calcination glycol cycles 97.98% after 20
cycles at 0.1C
(commercial)
59# Leaching Citric acid, glucose LiMn2O4 130 mAh/g 91.1% at 1C 274 mAh/g [105]
-Sol-gel method 750 ◦ C after 100
-Calcination cycles
60# Leaching 1.0 mol/L Citric acid, LiNi1/3Co1/3Mn1/ 147 mAh/g at 93% after 50 150 mAh/g 278 mAh/g [106]
- Sol-gel method 12 vol% H2O2, 60 ◦ C, 3O2 1C cycles (pristine)
-Calcination 40 min
Aqueous ammonia
350 ◦ C, 2 h, in
atmosphere, at
750 ◦ C, 12 h
61# Acid leaching 1.5 vol%, H2O2, 0.5 LiCo1/3Ni1/3Mn1/ 149.8 mAh/g 140.7 mA h/g 152.8 mAh/g at 278 mAh/g [107]
-Sol–gel method mol/L citric acid, 3 O2 at 0.2C after 160 0.2C
-Calcination 90 ◦ C,60 min cycles 79.31% after
at 900 ◦ C for 12 h 160 cycles
(pristine)
62a#- Leaching Maleic acid LiNi1/3Co1/3Mn1/ 151.6 mAh/g 84.0% at 278 mAh/g [108]
1 - Sol-gel process pH = 7 3O2 at 0.2C 0.2C, after
-Calcination 450 ◦ C, 4 h and 150 cycles,
900 ◦ C, 12 h
62b# Acetic acid LiNi1/3Co1/3Mn1/ 115.0 mAh/g 85.0% at 0.2C 278 mAh/g
pH = 7 3O2 at 0.2C after 150
450 ◦ C, 4 h and cycles
900 ◦ C, 12 h
63a# Leaching 1.0 mol/L D, L-malic LiNi1/3-0Co1/ 141.1 mAh/g 99.6% at 0.2C 278 mAh/g [109]
- Sol-gel method acid, 8 vol% H2O2, 3Mn1/3Al0.00O2 at 0.2C after 100
-Calcination 80 ◦ C, 80 min cycles
63b# Ammonia, pH = 8 LiNi1/3-0.02Co1/ 148.0 mAh/g 92.5% at 0.2C 280 mAh/g
450 ◦ C, 6 h 3Mn1/3Al0.02O2 at 0.2C after 100
cycles
63c# LiNi1/3-0.004Co1/ 154.4 mAh/g 95.9% at 0.2C 281 mAh/g
3Mn1/3Al0.04O2 at 0.2C after 100
cycles
Thermal and mechanical treatment Leaching Sol-gel method Calcination
Fig. 14. Sol-gel methods combined with other techniques.
regenerating LiCoO2 from spent LiBs. good. The average ηini and NDC100,0.2C of C are 0.94 (commercial is 0.98)
and 0.93, respectively which are close to 1. These results confirm that
4. Regeneration of anode materials the anode materials regenerated from spent LiBs can be reused as new
anode materials.
The anode of a LiB includes carbon active materials (graphite), an
anode current collector (copper foil), and others. The degradation of the
anode active material is attributed to the deterioration of the graphite 4.1. Thermal method
structure, volume expansion, graphite content reduction, and impurities
[112]. The stabilised EG structure provides a buffer zone, further 4.1.1. Carbon thermal reduction
reducing volume expansion during lithiation/delithiation [113]. The Kayakool et al. [117] regenerated graphite from spent LiBs. This
regeneration of anode materials requires a combination of different method can be applied to Li-ion-based-all-carbon-dual-ion batteries. Liu
methods (Fig. 19). Table 10 shows a typical regeneration method of et al. removed impurities and reconstructed the graphite structure
anode active materials. Fig. 20 shows the performance of the regener through acid treatment and carbon thermal reduction. The reconstruc
ated anode materials. Fig. 20 shows that the ηini of the anode materials tion strengthens the force between the interlayers, shortens the inter
regenerated from spent LiBs is very large. The cycling stability was also layer lattice distance, and makes the layered structure more stable.
Carbon thermal reduction can be applied not only in LiBs but also in
13
0.70 4.3. Electrolysis method

ηini 1.0
NDC100,0.2C
0.65 Electrolysis can directly recycle graphite, without introducing im
purities. More importantly, regenerated graphite possesses a high spe
0.60 0.9 cific capacity, and exhibits a stable discharge platform at low voltage
[33].
Normalized Capacity
0.55 NCM NCM NCM-Al
NCM NCM-Al 0.8
LCO NCM-Al
ηini
0.50
LMO
0.45 0.7
NCM Hydrothermal renovation
0.40
0.6 Separation
0.35 Ultrasonic treatment
Leaching Spray drying
0.30 0.5
# # # # # # # # #
58 59 60 61 62a 62b 63a 63b 63c
Acid dissolution Precipitation
No.
Fig. 15. Comparison of the performance of cathode materials regenerated by Fig. 16. Ultrasonic method combined with other techniques.
sol-gel method.
0.6 1.0
sodium-ion batteries [118]. ηini
Compared to Ar and He, the N2 atmosphere is better for carbon NDC100,0.2C
activation [115]. The high-performance silicon-graphite composite 0.9
synthesized by the thermal method from spent graphite has a porous

structure and can reduce volume expansion [116]. 0.8
Normalized Capacity
0.5
LCO LCO LCO
4.1.2. Hydrothermal method 0.7
The hydrothermal method is an efficient method for regenerating
ηini
anode materials from spent LiBs [18,119]. Li, et al. combined a two-step 0.6
hydrothermal method with the calcination method to regenerate TiO2/ 0.4
C/FeS2 with a high discharge capacity (1270 mAh/g at 0.2 A/g). 0.5
4.2. Leaching 0.4
In addition to the cathode materials, leaching is also used to regen 0.3 0.3
erate the anode materials. For example, Pegorettia et al. [91] regener 65# 67# 68#
ated graphite anode materials by leaching with sulfuric acid, hydrogen No.
peroxide, and filtration.
ultrasonic method.
Table 8
Battery performance regenerated by ultrasonic method.
64# Ultrasonic 120 ◦ C, ultrasonic power LiCoO2 131.5 mAh/g 132.6 98.1%. after 274 mAh/g [20]
-Hydrothermal 999 W,10 h under mAh/g 20 cycles
hydrothermal conditions
65# Ultrasonic 1.5 mol/L DL-malic acid - 3 LiCoO2 131.2 mAh/g 84.5% at 1C 274 mAh/g [27]
enhanced leaching vol% H2O2, 95 W, 80 ◦ C 25 at 1C after 100
-Spray drying min cycles
66# Ultrasonic 270 W, 75 ◦ C, Argon LiCoO2 166.3 mAh/g 167.0 98%, after 274 mAh/g [28]
separation and atmosphere mAh/g 50 cycles
renovation
67# Ultrasonic 1 mL H2O2, 1050 W, 90 ◦ C, LiCoO2 131.0 mAh/g 132.1 96.74% 274 mAh/g [29]
hydrothermal 6 h, 0.5 MPa Ar gas at 0.2C mAh/g after 50
renovation At 0.2C cycles
68# Ultrasonic 800 W LiCoO2 131.8 mAh/g 132.8 97.3% at C/ 274 mAh/g [72]
technology 2.0 mol/L LiOH, 120 ◦ C,6 h mAh/g 5 after 40
-Hydrothermal cycles
treatment
69# Ultrasonic N-methylpyrrolidone (NMP) LiCoO2. 153 mAh/g Good cycle 274 mAh/g [78]
treatment, at 40 ◦ C for 15 min at 0.1C ability
-Acid dissolution, 3 mol/L H2SO4, 1.5 mol/L
-Precipitation H2O2, 70 ◦ C, 1 h.
1 mol/L Na2C2O4
14
Electrochemical deposition
Dismantling Detachment Acid leaching
Electrolytic method
Fig. 18. Electrochemical methods combined with other techniques.
Table 9
Battery performance regenerated by electrochemical method.
70# Dismantling 800 ◦ C for 2 h LiCoO2 127.2 mAh/ 130.8 >96.6% at 274 mAh/g [41]
-Detachment N-methylpyrrolidone g, at 0.1C mAh/g, at 0.1C after
-Acid leaching 1 mol/L HNO3,1.0 0.1C 30 cycles
-Electrochemical mol/L H2O2, 80 ◦ C, 1 h
deposition 1.0 mA/cm2, 100 ◦ C,
technology 20 h.
71# Electrolytic method sodium sulfate LiNi0.6Co0.2Mn0.2O2 179.0 mAh/ 198.9, 276 mAh/g [110]
g, at 0.2C mAh/g, at
0.2C,
Solvothermal
Reduction Leachin Oxidation Calcinatio method
g n
Smelting Ultrasonic vibration and sieving
Direct regeneration Calcination Acid leaching
Leaching Microwave irradiation
Heat-treatment Coated
Leaching Calcination
Thermal method
Calcination
Acid-treatment Carbon-thermal reduction

Anode regeneration
Healing and doping Annealing
Hydrothermal method
Calcination
Mechanically separating washing

Leaching
Hummers method
Electrolysis method Precipitation
Fig. 19. Anode regeneration methods.
4.4. Microwave-assisted method scrapped LiFePO4 batteries, including cathode active substances
(LiFePO4, acetylene black), anode active substances (graphite, acetylene
Graphite regenerated by the microwave-assisted reconstruction black), and others (Al foil, Cu foil, shell, etc.).
method possesses more open sites or channels, which allows Li+ to store,
transfer, and diffuse quickly during LiB operation [32]. 5. Regeneration of separator, binder, and current collector
4.5. Direct regeneration method 5.1. Regeneration of separators
Direct regeneration is a green, economical, and feasible method that In a LiB, the separator is an inner porous organic material that sep
uses a physical method to directly regenerate the active substance of the arates the cathode and anode components to prevent the occurrence of a
cathode. In an efficient, green, and sustainable strategy [112], Markey short circuit. The separator allows lithium ions, and prevents electrons,
et al. [18] used boric acid to regenerate graphite with a fine structure to pass freely during the charging–discharging process. The performance
directly from spent LiBs and found that B doping can significantly of the separator determines the battery interface structure and the in
improve the electrochemical activity and cycling stability. Li et al. [79] ternal resistance. Furthermore, it affects the capacity, cycle ability, rate
reported a direct regeneration method to recycle all components of performance, life span, and battery safety. Therefore, suitable separators
15
Table 10
Regeneration methods of anode materials.
capacity capacity
72# Direct Nitrogen atmosphere, Graphite 360.8 mAh/g 424.9 100% at 1C 372 mAh/g, [33]
regeneration 1673 K, 4 h. at 0.1C mAh/g at after 100
Smelting deionized water for 0.1C cycles
-Ultrasonic 15 min
vibration and
sieving
73# Direct 400 ◦ C, 1 h, in argon Graphite 172.6 mAh/g, 97.9% at 372 mAh/g, [31]
regeneration atmosphere at 372 mA/g 372 mA/g
two-stage 500 ◦ C, 1 h, in air after 100
calcination atmosphere cycles,
-Acid leaching 1 mol/L hydrochloric
acid, 4% hydrogen
peroxide solution,
80C, 2 h.
74# Direct 550 ◦ C,60 min, in air Graphite 428.3 mAh/g 87% at 0.05 300 mAh/g 372 mAh/g, [32]
regeneration 1 mol/L H2SO4 at 0.05 A/g A/g after (Commercial)
heat 800 W, in air 0–40 s 100 cycles,
-Leaching
-Microwave
irradiation
75# Heat-treatment In air with pyrolytic Graphite(with 377.1 mAh/g 347.2 98.8% after 364.1 mAh/g 372 mAh/g, [112]
-Coated carbon coating layer, mAh/g 50 cycles (discharge);
residual AB and CMC 354.7 mAh/g
pyrolysis product) (charge)
(Pristine)
76# Direct H2SO4 and CoO/CoFe2O4/ 890 mAh/g 372 mAh/g, [114]
regeneration FeSO4⋅7H2O expanded Graphite at 1 A/g after
Reduction-acid Ar atmosphere, 700 cycles
leaching 700 ◦ C, 1 h
-Oxidation
-Intercalation
- Calcination
-Solvothermal
method
77# Thermal Nitrogen atmosphere, Graphite 675.4 mAh/g 424.9 100% at 1C 372 mAh/g [33]
treatment 1673 K, 4 h. at 0.1 mAh/g at after 100
-Smelting deionized water, 15 0.1C cycles
-Ultrasonic min
vibration and
sieving
78# Thermal 3000 ◦ C, 6 h, under Graphite 351.9 97.42% at 302.0 mAh/g 372 mAh/g, [115]
treatment the N2 atmosphere mAh/g at 0.1 A/g after (commercial)
0.1 A/g 100 cycles
79# Thermal 1 mol/L sulfuric acid Silicon-graphite 434.1 mAh/g 92.47% at 372 mAh/g, [116]
treatment Under N2 condition, composite at a current 500 mA/g
-Leaching 1000 ◦ C,2 h density of 500 after 300
-Calcination mA/g cycles
80# Carbon-thermal 800 ◦ C, 5 h, under Graphite 657 mAh/g at 352 mAh/ >90% at 100 372 mAh/g, [117]
reduction argon atmosphere 100 mA/g g at 100 mA/g
annealing mA/g
81# Acid-treatment concentrated H2SO4 Graphite 130.2 mAh/g 396.5 121.6 mAh/g [118]
-Carbon-thermal 750 ◦ C,8 h, under N2 at 50 mA/g mAh/g at at 50 mA/g
reduction atmosphere 0.5C, after 150
800 ◦ C, 8 h, under N2 cycles
atmosphere
82# Hydrothermal Boric acid Graphite 362 mAh/g at 333 mAh/g [18]
method C/3 at C/3 after
-Healing and 100 cycles
doping
-Annealing
83# Two-step 10 mol/L NaOH, TiO2/C/FeS2 1270 mAh/g at 916.1 1057.5 mAh/ [119]
hydrothermal 150 ◦ C, 24 h 0.2 A/g mAh/g at g at 0.2 A/g
method 1 mmol 0.2 A/g after 100
- Calcination thioacetamide, cycles
200 ◦ C,12 h
N2 atmosphere.
84# Mechanically With deionized water Graphite 446.5 mAh/g 338.9 75% after 401.6 mAh/g 372 mAh/g, [120]
separating, for 5 times dried in an mAh/g 100 cycles (discharge)
-Leaching oven at 60 ◦ C 346 mAh/g
-Washing overnight (charge)
86%, after 100
16
capacity capacity
cycles
(commercial)
#
85 Hummers NaNO3, concentrated LiFePO4/reduced 163.3 mAh/g 99.63% at 372 mAh/g, [30]
method H2SO4, MnO4, 30 vol graphene oxide at 0.2C 0.2C after
% H2O2 100 cycles
86# Electrolysis Na2SO4 Graphite (purity 409.15 mAh/g 350.5 87.4% at 372 mAh/g, [121]
method 95%)-copper foil at 0.2C mAh/g at a 0.5C after
-Precipitation rate of 100 cycles
method 0.1C
5.3. Regeneration of current collector

1.8
ηini 1.0
The function of the current collector in the LiBs is to collect the
NDC100,0.2C
1.6 current generated by the active substance and form a larger current
0.9 output. The current collectors are commonly made of metals and should
1.4 contact the active substance completely. The internal resistance of the
current controllers is required to be as small as possible. Primarily, Al
Normalized Capacity
C
0.8
1.2 C C C and Cu foils are used as the cathode and anode current collector,
respectively. Cu and Al usually account for considerable weight per
ηini
centages of 6.88% and 8.11% in spent LiBs, respectively. Regeneration

C C C C
1.0 C 0.7
methods of the current controller typically include solvent dissolution of
0.8 the binder, mechanical and thermal treatment, and pneumatic separa
0.6
tion [3]. The pneumatic separation is eco-friendly and highly efficient
0.6 [122].
0.5
C
0.4 5.3.1. Regeneration of Al
C
0.4
Separating the cathode active substances from the current collector
72# 73# 74# 75# 77# 79# 81# 82# 84# 85# 86# (Al foil) is challenging owing to the strong bonding force between the
No. active cathode materials and Al foil. Chu et al. [110] reported an elec
trolytic method to separate and regenerate an Al-LiNi0.6Co0.2Mn0.2O2
Fig. 20. Comparison of the performances of regenerated anode materials. cathode substance and achieved good electrochemical performance
(initial discharge capacity of 179 mAh/g at 0.2C). Chen et al. [123]
can improve the overall performance of batteries. The separator mate adopted an ultrasonic-assisted acid (sulfuric and oxalic acidic media)
rials are primarily polyolefin materials with excellent mechanical and scrubbing method for in-situ recycling of Al foils and coating materials
chemical properties, compatibility, and stability. Recycled separators from spent LiBs. The purity of the Al foils regenerated in sulfuric acid,
can be used in many applications. Natarajan et al. [34] reported a simple oxalic acid, and pure water media was 98%, 99%, and 15%, respec
and green method to recover used separators from spent LiBs by tively. Tokoro et al. [37] adopted a high-voltage pulsed discharge
cleaning with deionized water. The physical and chemical properties of method to separate aluminium foil and cathode particles in water from
the recovered separator materials (tensile strength, ionic conductivity, spent LiBs. High-voltage pulsed discharge at 25 kV melts PVDF but does
electrolyte uptake, and interfacial resistance) are similar to those of the not result in pyrolysis. This method peels cathode particles from the Al
commercial separators and, therefore, can be reused in new batteries foil maintaining Al foil's pristine shape. Therefore, pulsed discharge can
without any further modification. The regenerated separator displayed be applied for the regeneration of spent LiBs. Li et al. [79] directly re
an approximately equal capacity of 123 mAh/g at 25 mA/g and better generated Al foil from LiFePO4 batteries. Fan et al. [38] recovered Al
cycle life compared to those of commercial separators under the same foils and cathode materials from LiBs using concentrated sulfuric acid
conditions. (18.4 M H2SO4) solution as a separation and leaching agent. In this
method, H2SO4 destroys the structures of cathode materials and
5.2. Regeneration of binder weakens the adhesion between cathode materials and PVDF. Al disso
lution is prevented owing to the formation of the passivation film which
The function of the binder in LiBs is to hold the active substance improved the separation efficiency of the Al foils. Zhao et al. [28] re
particles uniformly within the current collector. Hence, small ohmic ported a sustainable recycling method for the separation of lithium co
resistance and stable performance of the binders are required in the balt oxide (LiCoO2) and aluminium foil from spent LiBs by ultrasonic
electrolyte. The binder material is primarily composed of PVDF/NMP or cavitation in an H2O2 solution. Chen et al. [123] reported an in-situ
PVA [17]. The binder dosage in the LiB is large and can be regenerated method to regenerate Al foils using an acid scrubbing method coupled
by the organic solvent dissolution method [35,36]. Sarkar et al. [36] with the ultrasonic technique. They obtained 98% pure Al foil with
reported a regeneration method to regenerate polyvinylidene fluoride sulfuric acid and 99% pure Al foil with oxalic acid. He et al. [122] used
(PVDF) binders of high purity using a mixture of tetrahydrofuran and N- AEES to weaken the mechanical interlocking force and Coulomb force
methyl-2- pyrrolidone at 90 ◦ C. The regenerated PVDF displayed almost between cathode materials and foils, which facilitate exfoliation of the
the same performance as pristine PVDF. The solubility of PVDF depends cathode material from the Al foil. This method can be employed
on its physical state (i.e., isolated powders or composite films). This industrially owing to the high efficiency of Al recovery (99.0%),
research provides a promising approach for the recycling of binders. restricted infiltration of impurities into the electrode materials, and eco-
friendly approach. He et al. [15] recycled cathode materials and Al foil
from spent LiBs by ultrasonic cleaning, which dissolved PVDF because of
17
Table 11
Battery performance regenerated by closed-loop regeneration process.
capacity the capacity retention
87# Ultrasonic 270 W, 75 ◦ C, 120 LiCoO2 aluminium 166.3 mAh/ 167.0 98% after 274 mAh/g [28]
cavitation min, Argon foils g mAh/g 50 cycles
-Leaching atmosphere
88# Supplementing 450 ◦ C, 5 h, LiNi0.5Co0.2Mn0.3O2 189.8 mAh/ 83.2% at 1C <189 mAh/g at 278 mAh/g [44]
metal ions, 850 ◦ C, 15 h, under g at 0.1C after 300 0.1C
-Granulation, O2 atmosphere cycles (Commercial)
-Ion doping PO43− doping
-Heat treatment
89# Ionothermal D-NCM black LiNi1/3Co1/3Mn1/3O2 173.6 the first charge 278 mAh/g [126]
synthesis powder mAh/g capacity 175.3
calcination Li halide ionic mAh/g (pristine)
liquids
500 ◦ C, 4 h.
90# Leaching tartaric acid, LiNi1/3Co1/3Mn1/3O2 159 mAh/g 98.7% at 278 mAh/g [96]
-Co-extraction hydrogen peroxide at 0.1C 0.5C after
-Calcination sodium hydroxide, 50 cycles
saturated hot
sodium carbonate,
NH3⋅H2O
900 ◦ C
91# Dismantling NaOH LiNixCoyMn(1-x-y) O2 148.8 mAh/ 97.0% at 150.3 mAh/g at [17]
-Crushing sulfuric acid, H2O2 g at 0.2C 0.2C after 0.2C
-Leaching (30 wt%) 100 cycle 97.1% at 0.2C at
-Impurity Ammonium 100th cycle
removing hydroxide (Commercial raw
-Co-precipitation 350 ◦ C, under an material)
-Solid-state argon atmosphere,
synthesis 4 h.
750 ◦ C, under an air
atmosphere, 10 h
92a# Leaching 0.5 mol/L H2SO4, Li1-xNaxNi0.6Co0.2 176.4 mAh/ 93.07% at 275 mAh/g [127]
-Co-doping 0.1 mol/L Na2SO3, Mn0.2 O2-xFx g at 0.1C 0.2C after
-Co-precipitation 20 g/L, 120 ◦ C, 8 h (x = 0.02) 100 cycles
92b# Na-F Li1-xNaxNi0.6Co0.2 165.5 mAh/ 81.7%, at 274 mAh/g
Mn0.2 O2-xFx g 0.2C after
(x = 0.04) 100 cycles
batteries using a direct regeneration method. He et al. used AEES to

0.8 1.0 regenerate Cu foil. This process meets industry requirements because of
ηini
its high efficiency (recovery efficiency of 100%) and environment-
NDC100,0.2C
friendly nature. Dutta et al. [125] reported a green and close-loop
0.7 NCM
0.9
regeneration method using LIX 84 IC solvent extraction reagent to
NCM-Na-F separate Cu (in solution) from spent LiBs. The above studies suggest that
Normalized Capacity
0.8 if the battery components are regenerated separately, a good recovery

NCM-Na-F
0.6
NCM
rate and battery performance can be achieved, but the recovery cost is
high.
ηini
NCM 0.7
0.5 6. Novel green regeneration technology

0.6
With the development of regeneration technologies, a few new green
0.4 approaches have emerged.
0.5
0.3 0.4 6.1. Closed-loop regeneration process

88# 90# 91# 92a# 92b#
No. Researchers have developed closed-loop regeneration processes to
reduce environmental pollution and resource depletion, as presented in
Fig. 21. Comparison of the performance of cathode materials regenerated by Table 11. Jung et al. reported a green closed-loop regeneration method
closed-loop regeneration process.
to recover lithium by electrodialysis using LiOH and Li2CO3 as the
extractants and precipitants, respectively. The ionothermal lithiation
ultrasound cavitation. The obtained cathode material displayed a low method can directly regenerate spent LiBs. This is a green closed-loop
degree of agglomeration. process as ionic liquids can be reused. Zhao et al. separated lithium
cobalt oxide and aluminium foil by the ultrasonic method. They re
5.3.2. Regeneration of Cu ported a separation efficiency of 99.98%.
Mechanical methods can easily separate and regenerate active anode The performance of the material regenerated by the closed-loop
substances from spent LiBs owing to the weak [124] bond between regeneration processes is shown in Fig. 21. Fig. 21 shows that the
graphite and Cu foil. Li et al. [79,122] exfoliated Cu foils from LiFePO4 average ηini and NDC100,0.2C of NMC are 0.60 (commercial is 0.73) and
18
Table 12
Electrode reconstruction through replenishing lithium, de-lithiation, re-lithium.
93a# Calcination Li2CO3 at 800 ◦ C LCoO2(Al2O3-coated) 136.8 mAh/ 90.1% after 94.2% after 30 274 mAh/g [46]
g 100 cycles cycles
93b# LCoO2 132.5 mAh/ 90.2% after (commercial) 274 mAh/g
g 100 cycles
94# Target healing Molten salt LiOH, LiCoO2 149.1 mAh/ 93%.at 0.2C 147.3 mAh/g in 274 mAh/g [48]
method KOH,LiNO3, g at 0.2C. after 100 the first cycle at
Two-stage heating 300 ◦ C,8 h 500 ◦ C, cycles 0.2C,
process 16 h in O2, 91% at 0.2C
after 100 cycles.
95# Electrochemical Li2SO4 LiCoO2 136 mAh/ 140 mAh/g at C/ 274 mAh/g [52]
Relithiation 700 ◦ C, in air. g at C/5 5 (commercial)
Calcination
96# Thermal-chemical Molten LiOH,KOH, LiCoO2 144 mAh/g 92.5% at 0.2C 274 mAh/g [51]
treatment Li2CO3 500 ◦ C, at 0.2C after 200
under air cycles
atmosphere
97a# Low-temperature, 15 min LiFePO4 145 mAh/g 96% capacity 170 mAh/g [128]
rapid microwave at 1C retention at
process 5C for 300
cycles.
97b# NaFePO4 138 mAh/g 85% at C/15 154 mAh/g
at C/15 after 150
cycles
98# Defect targeted Lithium salt, LiFePO4 159 mAh/g 99% at 0.5C 161 mAh/g at 170 mAh/g [30]
Healing method 600 ◦ C, 2 h at 0.5C after 100 0.5C,
Thermal annealing cycles; 100% after 100
94% at 0.5C cycles
after 1000 (Pristine)
cycles
99# Hummers method NaNO3, LiFePO4/reduced 163.3 mAh/ 99.63% at 170 mAh/g [50]
concentrated graphene oxide g at 0.2C 0.2C after
H2SO4,KMnO4, 100 cycles
30% vol. H2O2
100# One-pot molten salt- LiOH: LiNO3 molar LiNi0.5Co0.2Mn0.3O2 152.5 mAh/ 86% at 0.2C 278 mAh/g [50]
assisted ratio is 3: 2 g at 0.2C after 100
regeneration cycles
101# Solid-state sintering 600 ◦ C, 2 h LiNi0.5Co0.2Mn0.3O2 162.0 mAh/ 91.9% at 1C Fresh is same 278 mAh/g [129]
850 ◦ C,12 h g at 0.1C. after 100 with
cycles regeneration
102# Blending lithium acetate, LiNi0.5Co0.2Mn0.3O2 164.6 mAh/ 89.12%, at 1C 278 mAh/g [130]
-Sintered 500 ◦ C, 5 h g at 0.1C after 100
900 ◦ C, 12 h cycles
103# Supplementing 450 ◦ C, 5 h LiNi0.5Co0.2Mn0.3O2 189.8 mAh/ 83.2% at 1C <189.mAh/g at 277 mAh/g [44]
metal ions, 850 ◦ C, 15 h, under g at 0.1C after 300 0.1C
-granulation, O2 atmosphere cycles (Commercial)
-Ion doping PO43− dopingg
-Heat treatment
104# Thermochemical molten salt LiNi0.5Co0.2Mn0.3O2 160 mAh/g 95.5% after 159.6 mA h/g, at 277 mAh/g [131]
process medium, acetylene at 0.2C 100 cycles. 0.2C
black (Commercial)
105# Ionothermal D-NCM black LiNi1/3Co1/3Mn1/3O2 173.6 175.3 mAh/g 278 mAh/g [126]
synthesis powder mAh/g (pristine)
Calcination Li halide
ionic liquids
500 ◦ C, 4 h.
106# Molten Salts Method eutectic molten LiNi0.5Co0.2Mn0.3O2 146.3 mAh/ 89.1% at 1C 278 mAh/g [49]
salts, LiOH, Li2CO3 g at 1C after 200
cycles
107a# Solid-state synthesis 850 ◦ C,12 h, in air Li1-xNaxCoO2 151.5 mAh/ 87.6% at 10C [57]
g at 1C after 100
cycles
107b# Regenerated LiCoO2 149.4 mAh/ 63.2% at 10C 54.2% at 10C, 274 mAh/g
g at 1C after 100 after 100 cycle
cycles (Commercial)s
0.97, whereas the average ηini and NDC100,0.2C of NMC-Na-F are 0.62 and friendly method for the regeneration of spent LiBs.
0.87, respectively. Both ηini and NDC100,0.2C decrease with increasing Na
and F contents (Fig. 21 92a#,92b#). The Na and F contents influence the
initial discharge ratio and cycle stability. Na-F co-doping helps achieve a 6.2. Reconstruction through replenishing lithium, de-lithiation, re-
fast rate, improved cycle ability, and discharge capacity. lithiation
Therefore, the closed-loop process is a promising and environment-
The reason for the deterioration of spent LiBs is the phase change
19
1.1 ηini 1.0 The performance of the materials regenerated by closed-loop

NDC100,0.2C regeneration processes is shown in Fig. 22. Materials regenerated
1.0 using reconstruction by replenishing lithium, de-lithiation, and re-
LFP
LFP 0.9 lithiation from spent LiBs have a high initial discharge ratio and good
0.9 LFP cycling stability. The average ηini and NDC100,0.2C of LCO are 0.53
Normalized Capacity
(commercial is 0.52), and 0.94, average ηini and NDC100,0.2C of LFP are
LFP
0.8
0.8 0.91 and 0.96 (commercial is 0.99), and average ηini and NDC100,0.2C of
NMC are 0.59 (commercial is 0.73) and 0.92, respectively. These studies
ηini
showed the LiB electrode can be reconstructed by adding lithium and

0.7 NCM 0.7
NCM NCM
removing impurities. Therefore, reconstruction via replenishing lithium,
0.6 NCM
LCO NCM 0.6 de-lithiation, and re-lithiation is an economical and effective regenera
LCO
tion method.
NCM
0.5
6.3. Coupling regeneration of spent LiBs with other wastes

0.5
0.4
0.3 0.4 The addition of a few special materials can significantly improve the
94# 96# 97a# 97b# 98# 99# 100# 101# 102# 103# 104# 106# performance of LiBs. Wang et al. studied the role of graphene-supported
No. Si-TiO2 nanospheres [133], SnO2 modified Li4Ti5O12 [134] and SiO2
aerogel-supported C/TiO2 [135] to improve battery performance. Meng
closed-loop regeneration process. et al. [53] regenerated LiNi1/3Co1/3Mn1/3O2-V2O5 by combining spent
LiBs and vanadium-bearing slag and achieved excellent electrochemical
performance. The vanadium oxide layer effectively improves the elec
(pore blocking, surface interface failure, structural collapse, or trans
trochemical performance of the cathode. Therefore, coupling regener
formation) and Li+ loss due to thickening of the solid and electrolyte
ation with other wastes improves the performance of regenerated LiBs
interface (SEI) [44,71]. The regeneration by electrode reconstruction is
and provides a new green approach to regenerate LiB materials.
an effective method and includes replenishing lithium with molten salt
containing lithium [46,48–51], de-lithiation [18,37], or re-lithiation
6.4. Use of the spent LiB material in other fields
through electroosmosis [46] and electrochemical methods [52]
(Table 12).
Another promising approach to solve the issue of spent LiBs is to use
The molten salt containing lithium [48] is targeted by an applied
regenerated materials from spent LiBs in other applications. Li et al. [55]
electric field [132], and the lithium ions can be replenished in the crystal
used a retired battery energy storage system in a photovoltaic power
lattice. An improved electrochemical performance (Table 12) indicates
station and significantly improved the photovoltaic self-utilisation rate.
effective regeneration via reconstruction. Ma et al. [50] studied the re
Liu et al. [118] applied regenerated (by acid treatment) graphite from
covery capacity by restoring the lattice structure using molten salt and
spent LiBs in sodium-ion batteries as an anode material and achieved a
obtained a high capacity of 133.4 mAh/g at 5C, with a small charge
high reversible capacity and high capacity retention [118]. Weng et al.
transfer resistance. Zhou et al. [130] reported reconstruction of the
[56] used activated microporous carbon spheres regenerated from spent
lattice using solid-state sintering. The electrochemical performance
LiBs as electrodes for capacitive deionisation (CDI) and reported high
improved as the insulating film was removed, which facilitated the
performance. They reported a specific capacitance of 196.9 F/g, low
diffusion of lithium and made the lattice more complete. Gao et al. [46]
charge transfer resistance, the electro-sorption capacity of 12.7 mg/g,
regenerated LiCoO2 coated with Al2O3 using a calcination method; the
the salt adsorption rate of 2.6 mg/(g⋅min) at 1.2 V with excellent
coated Al2O3 improved the discharge capacity and stability of the
repeatability. The electrode can be used as a high-performance CDI
electrode structure during the charge–discharge process. Sloop et al. [3]
electrode. Lv et al. [132] used an external direct electric field to extract
reported that during use, the crystal became disordered in the NCM
Li+ from spent NCM cathode materials. The specific surface area and
cathode caused by cation (Ni2+ and Li+) mixing and results in degra
pore volume increased and the morphology and chemical structure
dation of electrochemical performance. Using the cathode healing
(including the composition, electronic structure, and valence state) were
method in which lithium and oxygen are introduced, a layered ordered
changed after extraction. Therefore, it has a high OCR catalytic activity
structure is formed and the specific capacity increases. Deng et al. [131]
and excellent durability. These results provided us with a new approach
found that intrinsic network structures increased the reliability of the re-
to solve the problems associated with spent LiBs.
lithiation process. Xu et al. [128] used the defect target healing method
by annealing at 600 ◦ C and achieved high capacity and high stability
6.5. Design a fully recyclable and regenerated LiB
with regenerated LiFePO4 cathode material. Zhang et al. [52] used an
electrochemical method to regenerate LiCoO2 by lithiation and obtained
With the significant increase in LiB production and consumption, the
a crystal structure similar to that of pristine LiCoO2. The electrochemical
environmental pollution and depletion of natural resources have grown
properties were fully recovered.
significantly. To solve the problem of spent LiBs from the stems,
The molten salt has a good dissolving capacity and high ion diffusion
Thompson et al. [136] developed a sustainable general regeneration
rate, and it provides homogeneous thermal conditions with plentiful Li+.
strategy for next-generation all-solid-state batteries. This is a direct
Therefore, the damaged structure of spent LiBs is repaired by dissolution
regeneration process where the spent LiB materials are separated, re
and recrystallisation processes. Yang et al. [51] regenerated LiCoO2 with
generated, and used as electrodes and solid electrolytes in a new battery
good electrochemical performance using a molten salt thermal chemical
without any damage to their chemical structure. This work provides one
method from spent LiCoO2. Deng et al. [131] reported a low-
of the most promising approaches to design renewable batteries directly
temperature microwave-assisted lithiation and sodiation method to
in the future.
rapidly regenerate LiFePO4 and NaFePO4 from spent LiFePO4. Wu et al.
[57] regenerated Li1-xNaxCoO2 from a spent LiCoO2 cathode via solid-
7. Comprehensive comparison of various regeneration methods
state synthesis through lithiation and modification. As Na+ has a
larger atomic radius, doping with Na+, expands the spacing between the
The discharge performance of a regenerative battery depends on two
lithium layers, and increases the diffusion rate of Li+.
aspects: the initial discharge capacity and cycle stability. These two
20
Average ηini Regenerated LCO Average ηini Regenerated LFP

Average NDC(100凞 0.2C) Average NDC(100凞 0.2C)
1.0 α 1.0 α
Battery perfprmence
Battery perfprmence
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11
Generation method No. Generation method No.
Average ηini Regenerated LMO Average ηini Regenerated NMC

1.2 Average NDC(100凞 0.2C) 1.2 Average NDC(100凞 0.2C)
α α
1.0 1.0
Battery perfprmence
Battery perfprmence
0.8 0.8
0.6 0.6
0.4 0.4
0.2
0.2
0.0
0.0 1 2 3 4 5 6 7 8 9 10 11
1 2 3 4 5 6 7 8 9 10 11
Generation method No. Generation method No.
Average ηini Regenerated C

Average NDC(100凞 0.2C)
1.0 α
Battery perfprmence
0.8
0.6
0.4
0.2
0.0
1 2 3 4 5 6 7 8 9 10 11
Generation method No.
Fig. 23. Performance of batteries regenerated by different methods.

1-Hydrothermal method; 2-Thermal method, 3-Hydrogen reduction, 4-Solid-liquid extraction method, 5-Liquid-liquid extraction method, 6-Precipitation method, 7-
Sol-gel method, 8-Ultrasonic method, 9-Electrochemical method, 10-Anode material regeneration method, 11-Closed-loop regeneration process, 12-Electrode
reconstruction through replenishing lithium, de-lithiation, re-lithiation.
parameters are equally important in LiBs. To achieve uniformity in regeneration. For LCO, the maximum evaluation factor α (approxi
comparison, a comprehensive evaluation factor α was introduced to mately 0.74) was achieved using the thermal method (2), closed-loop
evaluate the efficiency of the batteries regenerated by different methods. regeneration method (10), and reconstruction method by replenishing
This comprehensive evaluation factor is defined as: lithium, de-lithiation, and re-lithiation (11). For LFP, the maximum
evaluation factor α (approximately 0.95) was achieved using hydrogen
α = 0.5*ηini + 0.5*NDC(100,0.2 C) (20)
reduction (3), closed-loop regeneration process (10), and electrode
The average discharge performance of the batteries regenerated by reconstruction method by replenishing lithium, de-lithiation, and re-
different methods (ηini and NDC (100, 0.2c)) and the evaluation factor α are lithiation (11). For LMO, an evaluation factor of 0.70 was obtained
shown in Fig. 23. As shown in Fig. 23, the comprehensive evaluation using the sol-gel method (7). For NMC, the maximum evaluation factor α
factors for LCO, LFP, LMO, NMC, and C were all above 0.67, indicating (approximately 0.76) was achieved by the closed-loop regeneration
that these materials regained good battery performance after process (10) and electrode reconstruction by replenishing lithium, de-
21
lithiation, and re-lithiation (11). For the carbon anode material, the and the Key Scientific and Technological Project of Henan Province
maximum evaluation factor (approximately 1.03) was obtained using (162102210067 and 162102310152).
ultrasonic methods (7). Among all the above-mentioned materials, re
generated C (α = 1.03) and LFP (α = 0.95) from spent LiBs can be reused References
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Regeneration of Spent Lithium-Ion Battery Materials

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Journal of Energy Storage 51 (2022) 104470

Contents lists available at ScienceDirect

Journal of Energy Storage

Regeneration of spent lithium-ion battery materials

1. Introduction [11]. Considering the economy, environment, and resources, regenera­

2250 20000 1000 +1600

Battery Capacity Demand (GWh)

Lithium Supply/Demand (kt LCE)

Total Chemical Components (kt)

Battery Capacity Demand (GWh)

750 8000 200 +600

2.1. Initial discharge ratio, ηini

To compare the initial discharge capacity of different batteries, the

where QI is the initial discharge capacity, and QT is the theoretical

2.2. Normalised discharge capacity, NDC

Fig. 3 is capacity degradation curve of typical LiBs, includes lithium

1.0 0.8 1.0

1.0 LFP 0.8

Ultrasonic technology Solid-phase calcination

Fig. 4. Hydrothermal treatments combined with other techniques.

1.0 1.0 (i) Influence of temperature

7# Solid-state synthesis 850 ◦ C, 12 h LiCoO2 152.1 135.4 274 mAh/g [73]

Pre-heating -high-energy ball-milling

Hydrothermal treatment Annealing

Thermal and mechanical

Calcination Leaching Precursor technique

Ultrasonic treatment acid dissolution precipitation

molten ammonium Roasting

Mechanical separation Pyrolysis

Direct pulverization Solid-state synthesis

Solvent dissolution (NMP)

Fig. 6. Thermal treatment combined with other techniques.

Eliminating β0 NC b from Eqs. (15) and (16), 3. Regeneration of cathode materials

Extraction Precipitation Calcination

Fig. 8. Solid–liquid extraction method combined with other techniques.

be applied as an alternative technology for recycling spent LiB materials.

0.7 Solid–liquid extraction, also referred to as leaching, is a method that

The performance of the materials regenerated by the liquid–liquid

3.3. Precipitation method

Dissolving Solid-phase synthesis

Fig. 12. Precipitation combined with other techniques.

Thermal and mechanical treatment Leaching Sol-gel method Calcination

Fig. 14. Sol-gel methods combined with other techniques.

0.70 4.3. Electrolysis method

synthesized by the thermal method from spent graphite has a porous

4.2. Leaching 0.4

Fig. 18. Electrochemical methods combined with other techniques.

Direct regeneration Calcination Acid leaching

Leaching Microwave irradiation

Acid-treatment Carbon-thermal reduction

Mechanically separating washing

Electrolysis method Precipitation

Fig. 19. Anode regeneration methods.

4.5. Direct regeneration method 5.1. Regeneration of separators

5.3. Regeneration of current collector

centages of 6.88% and 8.11% in spent LiBs, respectively. Regeneration

batteries using a direct regeneration method. He et al. used AEES to

0.8 if the battery components are regenerated separately, a good recovery

0.5 6. Novel green regeneration technology

0.3 0.4 6.1. Closed-loop regeneration process

1.1 ηini 1.0 The performance of the materials regenerated by closed-loop

showed the LiB electrode can be reconstructed by adding lithium and

1. Introduction [11]. Considering the economy, environment, and resources, regenera