Journal of Cleaner Production 359 (2022) 132116

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

Comparative study of chemical discharge strategy to pretreat spent

lithium-ion batteries for safe, efficient, and environmentally
friendly recycling
Zheng Fang , Qiangling Duan , Qingkui Peng , Zesen Wei , Huiqi Cao , Jinhua Sun **,
Qingsong Wang *
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, 230026, China

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

Handling Editor: Prof. Jiri Jaromir Klemeš The residual electricity contained in spent lithium-ion batteries probably triggers the thermal runaway and re­
sults in irreparable disaster during recycling. Chemical discharge is a common method to eliminate hazards by
Keywords: immersing batteries in an aqueous solution to release the remnant energy. However, a high-efficiency discharge
Lithium-ion battery safety solution usually causes severe corrosion of the battery shell, inducing safety accidents. In this work, theoretical
Recycling pretreatment
and experimental studies are carried out in various solutions to investigate the efficiency and corrosion of
Chemical discharge
chemical discharge strategy. The results suggest that zinc acetate solution is a potential discharge medium with
Corrosion resistance
Adsorption theory excellent comprehensive properties compared with NaCl, MnSO4, FeSO4, and KAc solutions. Electrolytic re­
actions and external short circuit have been proved to be the essential causes of high discharge efficiency.
Adsorption theory and Kolbe reaction are used to explain the low corrosion of battery shells in acetate solutions.
Besides, the thermal stability of treated spent batteries also validates our discharge strategy’s feasibility and
ensures safety during transportation, storage, and recycling.

1. Introduction pollution without proper disposal (Karnchanawong and Limpitee­

Lithium-ion batteries (LIB) have been widely used in widespread
portable electrical devices (laptops, mobile phones, wearable devices,
etc.) since Sony commercialized lithium-ion batteries in 1991 (Good­
enough and Park, 2013; Tarascon and Armand, 2001). With the rapid
development of Hybrid Electric/Electric vehicles (HEV/EV) and energy
storage industries, the demand for lithium-ion batteries has ushered in a
new peak (Harper et al., 2019; Liu et al., 2019; Wang et al., 2021).
However, the sharply increasing use of LIBs will introduce a large
number of spent LIBs within an 8–10 year span (Chen, M. et al., 2019).
Considering that the applications of LIBs are becoming more and more
diversified, we should foresee that the recycling of spent LIBs will be the
primary source of raw materials rather than mining in the immediate
future (Chen, Z. et al., 2019; Huang et al., 2018). On the other hand,
occupying at least 60% of LIB’s entire mass, electrodes and external
shells contain a lot of heavy metals that can leach slowly into soil,
groundwater, or surface water and thus result in environmental
prakan, 2009; Li et al., 2010). More seriously, the inflammable and toxic
compounds include electrolytes and their transformation products, such
as carbonic esters and fluoride, which may be generated and released
during the recycling procedures (Li et al., 2016; Sun et al., 2016). Hence,
the recycling of spent LIBs will be imperative from both resource cir­
culation and environmental protection.
In order to separate and enrich high purity metallic materials, proper
pretreating technology is essential (Zhang et al., 2021). Nevertheless,
the research on the pretreatment stage of spent LIBs is relatively less.
Compared with using stage of LIBs, the potential safety risks of spent
LIBs have been ignored for a long time, until the recent frequent fire and
explosion accidents in the recycling process sounded the alarm for the
whole industry (Deng, 2021; Liu, 2021). Typically, pretreatment pro­
cedures are divided into four steps: discharging, dismantling, sepa­
rating, and dissolving (Kim et al., 2021). Discharging is the first step of
the entire recycling process, which releases the residual electricity in the
spent LIBs to ensure the safety of subsequent procedures. Although the

* Corresponding author. State Key Laboratory of Fire Science, University of Science and Technology of China, No.96, JinZhai Road, Hefei, 230026, China.
** Corresponding author. State Key Laboratory of Fire Science, University of Science and Technology of China, No.96, JinZhai Road, Hefei, 230026, China.
E-mail addresses: sunjh@ustc.edu.cn (J. Sun), pinew@ustc.edu.cn (Q. Wang).

https://doi.org/10.1016/j.jclepro.2022.132116
Received 1 December 2021; Received in revised form 2 May 2022; Accepted 2 May 2022
Available online 5 May 2022
0959-6526/© 2022 Elsevier Ltd. All rights reserved.
Z. Fang et al. Journal of Cleaner Production 359 (2022) 132116

discharge process has been widely used in industrial treatment, its

feasibility and impacts have not been intensively investigated.
The discharge methods can be categorized as cryogenic freezing,
physical discharging, and chemical discharging (Yao et al., 2020).
Among them, chemical discharging has attracted much attention
because of its high efficiency and exemplary safety. Ojanen et al.
compared the voltage fluctuations and corrosion characteristics of spent
LIBs by direct immersion or connecting poles with external platinum
wire in salt solutions (NaCl, Na2SO4, FeSO4, and ZnSO4). Although the
external platinum wire can prevent the batteries from corrosion, it is
compensated by prolonging the treatment time (Ojanen et al., 2018).
Shaw-Stewart et al. systematically studied discharge efficiency and
corrosion behaviors of halides salts (Cl− , Br− , and I− ), and various salts
with inorganic acid radicals (SO−4 , S2O2− 2− 3−
3 , CO3 , HCO3 , PO4 , and
−

H2PO−4 , etc.). Among them, mildly acidic dihydrogen phosphates

(H2PO−4 ) exhibited uniform corrosion-free positive terminals, but un­
satisfactory discharge efficiency (residual voltage >3.0 V after 24 h)
(Shaw-Stewart et al., 2019). Xiao and Yao et al. investigated the effects
of different salt solutions (NaCl, FeSO4, MnSO4, etc.) on pole corrosion
and rate of discharge during immersing treatment, and presented
"O2-control mechanism" to explain the anti-corrosive phenomenon of
battery in MnSO4 solution (Xiao et al., 2020; Yao et al., 2020). Unfor­
tunately, excellent discharge efficiency always seems to be accompanied
by severe corrosion in previous literature. The electrolyte leakage
caused by corrosion hampers the valuable metals’ recoveries and brings
high waste liquid treatment costs. More seriously, several researchers
have reported a phenomenon of voltage increase after discharge process,
which is called "voltage relaxation" in electrochemistry (Nembhard,
2020; Rouhi et al., 2021). Although many researchers have studied some
salt solutions, most of them focused on the apparent voltage change
instead of the actual thermal safety of subsequent procedures. To the Fig. 1. Structure and composition of 18650 cylindrical batteries.
best knowledge of authors, none of the current discharge strategies is
optimal, considering the balance among some comprehensive factors, In order to the experimental variables and simulate the fast charging-
such as safety, efficiency, and environmental impacts. discharging usage scenario, accelerating aging procedures were con­
Above all, our work aims to systematically investigate chemical ducted. And then, capacity test procedures are carried out in the stan­
discharge strategy and develop an optimized discharge medium that dard cycle mode stipulated by the manufacturer. The detailed cycling
considers both high efficiency and low corrosion. The discharge effi­ parameters are listed in Table S1. Finally, the tested batteries continued
ciency and corrosion behavior of spent LIBs immersed in different so­ to degrade until their SOH decreased to approximately 50%.
lutions (NaCl, MnSO4, FeSO4, KAc, and Zn(Ac)2 solutions)) will be
studied in detail. Meanwhile, the nail penetration and extended volume
2.2. Discharge solutions
accelerating rate calorimeter (EV-ARC) tests were conducted to manifest
the thermal stability and hazards of spent LIBs after immersing treat­
All along, NaCl solution has been widely utilized to pretreat spent
ment. Finally, the corrosion behaviors of positive cap in various
LIBs in industrial processing, owing to its low cost and easy availability.
discharge solutions were presented by apparent analysis and electro­
MnSO4 and FeSO4 solutions were considered as latent discharge solu­
chemical tests.
tions with comprehensive performance, according to recent works (Xiao
et al., 2020; Yao et al., 2020). Considering the corrosion of the battery
2. Experimental
shell caused by solution immersion, a milder neutral solution is urgently
required as the discharge medium. Acetate solution, being a conjugate
2.1. Spent LIBs
base of weak acid, has been frequently investigated to prevent corrosion
of metal materials (Kılınççeker, 2008). Given the cost and solubility of
The studies mentioned above did not consider the impacts of several
acetate solutions, KAc and Zn(Ac)2 solutions were selected as repre­
vital factors on their experiments, including the battery types, compo­
sentatives for discharging spent LIBs. In this work, various discharge
sitions, state of charge (SOC), state of health (SOH), and detailed
solutions (NaCl, MnSO4, FeSO4, KAc, and Zn(Ac)2 solutions) were
degradation history (Ren et al., 2019). To compare and evaluate
investigated systematically to evaluate the chemical discharge strategy.
different discharge solutions as objectively as possible, 18650 cylindri­
NaCl, MnSO4⋅H2O, FeSO4⋅7H2O, KAc, and Zn(Ac)2⋅2H2O were pur­
cal batteries (cathode: Li(Ni0.5Co0.2Mn0.3)O2, anode: natural graphite)
chased from Sinopharm Chemical Reagent Co., Ltd. All the reagents used
manufactured by Far East First New Energy Co., Ltd. were used in this
in the experiment were analytical grade and directly used without
work, as shown in Fig. 1. The battery has a nominal capacity of 2.5 Ah
further treatment.
and voltage of 3.7 V. Herein, 50% SOH is defined as the filter criteria for
spent battery recycling, which indicates the current capacity of the aging
battery has shrunk to half of the initial capacity. Eq. (1) defines the SOH 2.3. Discharge test
of batteries, where Q is the current discharge capacity, and Q0 is the
initial capacity of the cycled battery. A paperless recorder (SIN-R5000C, Sinomeasure Corp., Hangzhou)
was applied to monitor the residual voltage of spent LIBs during the
Q
SOH = (1) discharge process. The discharge experiments were conducted in a
Q0
beaker containing 200 mL aqueous solutions. All discharge solutions

2
Z. Fang et al.
were prepared at the same concentration (0.8 mol/L) to ensure the
comparability of results. The residual voltage variations with time were
detected to represent the discharge efficiency by connecting spent LIB’s
poles and paperless recorder with platinum wires, whose chemical
inertness can avoid the influence caused by the impurities (Fig. S1). In
order to investigate the mechanisms and characteristics of the discharge
process, qualitative analysis of precipitated powder was carried out by
X-ray Diffractometer (XRD, Smartlab, Rigaku Corp., Japan), Scanning
Electron Microscope (SEM, GeminiSEM 500, Zeiss Corp., Germany), and
X-ray photoelectron spectroscopy (XPS, Axis supra+, Kratos Corp.,
Japan). Quantitative analysis of the supernatant after discharge was
carried out by Inductively Coupled Plasma-Optical Emission Spectrom­
etry (ICP-OES, Opmita 7300 DV, PerkinElmer Corp., U.S.).
2.4. Thermal stability test
A nail penetration test was used to investigate the thermal stability of
treated batteries, which was performed using the battery penetration
machine (Beier Experiment Apparatus Co., Ltd, Dongguan) with a 3 mm
diameter stainless-steel nail (Mao et al., 2018). The cylindrical battery
was horizontally fixed by a clamp to prevent offset during the penetra­
tion. The stainless-steel nail was completely punctured in the diameter
direction from the middle of the battery shell. A moderate penetration
speed (20 mm/s) was employed to simulate accidental crush or puncture
Fig. 2. (a) The fluctuation of residual voltage versus immersion time of spent LIBs immersed in different solutions. (b) the photos of discharge solutions before and
after immersion.
3
Journal of Cleaner Production 359 (2022) 132116
of the battery by foreign objects during transportation, storage, and
recycling. The surface temperatures of the tested battery were detected
by 5 K-type thermocouples (1 mm in diameter) attached to the battery
shell at equal intervals (16.25 mm), as shown in Fig. S2. Additionally,
the internal mechanisms of the thermal stability of batteries were
studied by EV-ARC. The experimental setup and results are shown in the
Supplementary Materials (Figs. S6 and S7).
2.5. Electrochemical measurements
In order to intensively investigate the corrosion behavior of LIB’s
shell, especially the positive cap, in various discharge solutions, elec­
trochemical tests were used here. The electrochemical tests were per­
formed on a CHI 660E electrochemical workstation (CH Instruments,
Inc., Shanghai) in a three-electrode beaker cell. The working electrodes
(5 mm × 5 mm × 0.5 mm) were prepared by manually disassembling
spent LIBs’ positive caps, embedded in epoxy resin, and only 0.25 cm2
area was exposed. A platinum foil (10 mm × 10 mm × 0.1 mm) was used
as a counter electrode, whereas an Ag/AgCl/KCl (sat) electrode with a
saturated KCl salt bridge was utilized as a reference electrode.
The open-circuit potential (OCP), potentiodynamic polarization tests
were conducted to evaluate the corrosion behavior of spent LIB’s posi­
tive cap in various discharge solutions (0.8 mol/L) at 25 ◦ C. The OCP
values, Eocp, were recorded during 30 min of immersion in various
Z. Fang et al. Journal of Cleaner Production 359 (2022) 132116

discharge solutions. For potentiodynamic polarization tests, slow scan literature (Bhaskara et al., 2021).
rate (1 mV/s) and narrow potential range (from − 400 to 200 mV vs.
Eocp) were used to obtain the steady-state polarization curve and 3. Results and discussions
investigate the self-corrosion behavior of LIB’s positive cap. Further­
more, anodic polarization curves were performed by a higher scan rate 3.1. Discharge efficiency
(10 mV/s) and wider potential range (from Eocp − 0.2 V to 4.2 V) to
investigate the dynamic corrosion behavior of the positive cap under The curves of residual voltage with immersion time during the
external voltage, which has been proved to be acceptable in previous discharge process of spent LIBs submerged in various solutions are

Fig. 3. Surface temperature versus time of spent batteries during penetration in different conditions: (a) 100% SOC battery; (b) 50% SOC battery; (c) 0% SOC
battery; and after 24 h immersing treatments in (d) NaCl solution, (e) FeSO4 solution, (f) Zn(Ac)2 solution, (g) KAc solution, (h) MnSO4 solution.

4
Z. Fang et al. Journal of Cleaner Production 359 (2022) 132116

recorded in Fig. 2(a). The discharge curve of NaCl solution shows an
irregularly multi-stage drop, indicating that the battery was substan­
tially damaged due to gradual corrosion of battery shell. As shown in
Fig. 2(b), the turbid liquid, sediment at the bottom, and exposed jelly
roll confirmed that the battery had been critically corroded. NaCl so­
lution has been widely utilized in industrial procedures to release
remnant energy from spent LIBs. Nevertheless, the electrolyte leakage
caused by corrosion will bring out serious secondary pollution and in­
crease the treatment costs (Xiao et al., 2020). The discharge curves of
FeSO4 and Zn(Ac)2 solutions fluctuated significantly with time, and the
electricity of spent LIBs were rapidly consumed to 0 V within an hour,
which undoubtedly satisfied high discharge efficiency. In KAc solution, a
smooth discharge curve and mild discharge behavior can be observed,
but the residual voltage was still above 3.0 V after 24 h, which may lead
to potential thermal hazards. Besides, as shown in Fig. 2(b), the limpid
and transparent liquid in KAc and Zn(Ac)2 solutions indicates that the
immersed batteries were not corroded. And the brown floccule in the
bottom of FeSO4 solution is probably Fe(OH)3, which is the hydrolytic
product of iron ions (Refait et al., 2018; Xiao et al., 2020). However, the
discharge efficiency of the MnSO4 solution is not as excellent as that
described in current studies (Xiao et al., 2020; Yao et al., 2020). In
contrast, the residual voltage of spent LIB immersed in MnSO4 solution
for 24 h basically did not decline, which was still higher than 4.0 V.
Moreover, most heavy metal ions were precipitated in the form of metal
or metallic oxide powder after 24 h discharging process, and then the
residual wastewater will be collected for centralized treatment by
chemical precipitation (Chakraborty et al., 2019).
3.2. Thermal stability of treated spent LIBs
battery.
3.3. Discharge mechanisms and characteristics
In previous works, the electrolytic reactions were generally consid­
ered the main reason for the voltage drop of spent LIBs. However, the
electrolytic potential windows limit the minimum achievable discharge
voltage in aqueous solutions (Shaw-Stewart et al., 2019). The sudden
drop and extremely low voltage (close to 0 V) are not simply caused by
electrolytic reactions. Herein, theoretical electrolytic reactions and
experimental results will be offered to investigate the discharge mech­
anisms and characteristics. It should be noted that the positive pole
mentioned in this paper is the anode for aqueous solution oxidation
reaction, and negative pole is the opposite. The following electrolytic
reactions and standard electrode potentials (SEP, vs. SHE) are derived
from the CRC Handbook of Chemistry and Physics (90th edition) (Lide
and Haynes, 2010).
In general, water splitting reaction widely exists in the electrolytic
process of aqueous solutions, producing oxygen and hydrogen at the
positive and negative terminals, respectively. Eqs. (2)–(7) express the
specific reactions and their theoretical potentials of water dissociation.
Due to the kinetic barrier caused by the over-potential, the actual po­
tential required is higher than the theoretical value (Ojanen et al.,
2018). In addition to the water splitting reaction, other anions or cations
in salt solutions may also undergo redox reactions on the electrode
surface. Herein, possible competitive reactions of anode and cathode are
shown in Table 1 and Table 2.
In acidic solution:
Anode (positive pole, oxidation):

In order to check up the feasibility and validity of the discharge 2H2O – 4e− ⇌ O2(g) + 4H+ Eϴ = − 1.23V (2)
strategy, nail penetration test was utilized to reveal the thermal stability
Cathode (negative pole, reduction):
and hazards of spent LIBs after immersing treatment. The surface tem­
perature fluctuations of spent LIBs during penetration at different SOCs 2H+ + 2e− ⇌ H2(g) Eϴ = 0 V (3)
(100%, 50%, and 0%) are presented in Fig. 3(a)–(c), which are consid­
ered the control groups, indicating the potential thermal hazards of end- Total reaction:
of-life LIBs. As shown in Fig. S3(a), violent sparks and flame could be 2H2O ⇌ 2H2(g) + O2(g) Eϴ = − 1.23V (4)
observed during the penetration process of 100% SOC spent LIB, which
suggests the battery got into thermal runaway. Although there was no In alkaline solution:
combustion for spent LIBs with 50% and 0% SOC, the maximum surface Anode (positive pole, oxidation):
temperatures reached 137.58 and 84.13 ◦ C, respectively (Fig. 3(b) and
4OH− – 4e− ⇌ O2(g) + 2H2O Eϴ = − 0.4 V (5)
(c)). Furthermore, Fig. 3(d)–(h) present the surface temperature varia­
tions of spent LIBs during penetration after immersing in various salt Cathode (negative pole, reduction):
solutions for 24 h. The surface temperatures of spent LIBs immersed in
NaCl, FeSO4, and Zn(Ac)2 solutions did not change significantly during H2O + 2e− ⇌ H2(g) + 2OH− Eϴ = − 0.83 V (6)
penetration (Fig. 3(d)–(f)), which indicates that the residual electricity
Total reaction:
has been drained completely, and thus the thermal safety of subsequent
procedures can be ensured. Despite the electrolytic reactions that 2H2O ⇌ 2H2(g) + O2(g) Eϴ = − 1.23V (7)
occurred in KAc solution releasing a part of electricity in spent LIB, the
residual voltage (above 3.0 V) still resulted in the peak temperature of As shown in Fig. 1, the positive cap and safety valve materials are
90.46 ◦ C during penetration (Fig. 3(g)). As mentioned in section 3.1, the nickel-plated steel and aluminum, respectively. Eqs. (8)-(11) describe
residual voltage of spent LIB did not substantially decrease after soaking the possible oxidation reactions of the positive terminal, which explain
in MnSO4 solution for 24 h, meaning that it does not eliminate the
thermal hazards, which can be reflected by the peak temperature Table 1
(535.27 ◦ C) during penetration (Fig. 3(h)). Moreover, Figs. S3(b) and (c) The possible competitive oxidation reactions at the positive pole and their
visually present the penetration process of the spent batteries after theoretical potentials.
immersing treatment in MnSO4 and Zn(Ac)2 solutions, and compare Anodic half reaction Eϴ vs. SHE (V)
them with 100% SOC battery. As for the EV-ARC test results, both 100% (8) Fe – 2e– ⇌ Fe2+ 0.447
and 50% SOC batteries went into thermal runaway during the experi­ (9) Fe – 3e– ⇌ Fe3+ 0.037
ment, while the battery with 0% SOC and another immersed in Zn(Ac)2 (10) Al – 3e– ⇌ Al3+ 1.662
(11) Ni – 2e– ⇌ Ni2+ 0.257
solution were not ignited even higher than the terminated temperature
(12) 2Cl− − 2e− ⇌ Cl2(g) − 1.358
(450 ◦ C). As shown in Fig. S7(c), the longest experimental period and (13) Mn2+ − e− ⇌ Mn3+ − 1.542
lowest temperature increasing rate (dT/dt) indicate that the immersing (14) Mn2+ + 2H2O – 2e– ⇌ MnO2 + 2H+ − 1.224
treatment reduced the reactivity of materials in spent LIBs, ensuring the (15) 2Mn2+ + 3H2O – e– ⇌ Mn2O3 + 6H+ − 1.485
safety of subsequent recycling processes. In general, the more thor­ (16) Mn2+ + 4H2O – 5e– ⇌ MnO−4 + 8H+ − 1.507
(17) 2CH3COO− – 2e– ⇌ C2H6(g) + 2CO2(g) 0.396 (Vijh and Conway, 1967)
oughly the electricity is released, the higher the thermal safety of the

5
Z. Fang et al. Journal of Cleaner Production 359 (2022) 132116

Table 2 still regarded as effective competitive reactions for hydrogen evolution

The possible competitive reduction reactions at the negative pole and their because the residual voltage of spent LIBs can compensate for the po­
theoretical potentials. tential gap. Fig. 4(c) and (d) show that the nano-size particles were
Cathodic half reaction Eϴ vs. SHE (V) agglomerated into larger powder during the batteries immersed in
(18) 2+
Fe + 2e ⇌ Fe
–
− 0.447
FeSO4 and Zn(Ac)2 solutions. We designed an experiment to measure the
(19) Fe3+ + 3e– ⇌ Fe − 0.037 battery terminal voltage and surface temperature concurrently, as
(20) Zn2+ + 2e– ⇌ Zn(s) − 0.762 shown in Fig. S4. It is noteworthy that the violent fluctuation of spent
(21) Mn2+ + 2e– ⇌ Mn(s) − 1.185 LIBs’ terminal voltage occurred simultaneously with the temperature
(22) SO2−
4 + 4H + 2e ⇌ H2SO3 + H2O
+ –
0.172
rise (Fig. 5). Due to the structural characteristics of the cylindrical bat­
(23) H2SO3 + 4H+ + 4e– ⇌ S + 3H2O 0.449
tery, the whole iron shell is negative pole and separated from the posi­
tive pole by an insulating gasket (Fig. 1). As shown in the inset of Fig. 5,
corrosion behaviors of the battery shell. All corrosion reactions have there were flashing sparks between the positive and negative terminals,
significantly higher potentials than water oxidation, meaning they indicating that metallic powder caused an external short circuit, which
would be dominant compared with oxygen evolution (Eq. (2)). How­ converted electricity into Joule heat. The peak temperature of Zn(Ac)2
ever, Eq. (10) is difficult to occur because the dense passivation layer of
aluminum oxide formed on metallic aluminum’s surface will protect it
from further oxidation and corrosion. The spent LIB immersed in NaCl
solution was destroyed entirely. Previous studies have confirmed that
the product composition is complex, mainly iron rust and solid salt (Xiao
et al., 2020). The theoretical potential of Cl− oxidation to chlorine gas
(Cl2) is close to that of water oxidation in acidic solution (Eqs. (12) and
(2)). Mixed gases of Cl2 and O2 may be expected to be the product at the
positive terminal. The products in NaCl solution have been analysed in
previous studies, which will not be the focus of this work.
A considerable amount of precipitation can be observed in FeSO4, Zn
(Ac)2, and MnSO4 solutions. By filtering and drying, the precipitate was
obtained from the solutions, whose crystalline structure and micro­
morphology were further analysed by XRD and SEM, respectively. As
shown in Fig. 4(a), the results of XRD detection of sediments in FeSO4
solutions show that the powder generated from the negative terminal is
metallic Fe, which is consistent with the description of Eqs. (18) and
(19) (The iron oxides were formed during drying). The diffraction peaks
of metallic Zn appear in Fig. 4(b), indicating the reduction reaction that
Zn2+ gain electrons to form metallic Zn was occurred in Zn(Ac)2 solution
(Eq. (20)). Although the theoretical potentials of Eqs. (18)-(20) are Fig. 5. The residual voltage and surface temperature variation curves versus
more negative than water reduction in acidic solution (Eq. (3)), they are time of spent LIBs immersed in FeSO4 and Zn(Ac)2 solutions.

Fig. 4. The XRD pattern and SEM photos of the precipitated powder generated from (a), (c) FeSO4 solution; (b), (d) Zn(Ac)2 solution.

6
Z. Fang et al.
solution is much lower than that of FeSO4 solution, which suggests that
chemical energy is the main conversion form of electricity in Zn(Ac)2
solution, showing a mild discharge phenomenon. The voltage oscillation
is related to the intermittent connection and disconnection of the posi­
tive and negative terminals by conductive metallic powders. Moreover,
the discharge process in KAc solution did not produce precipitation, but
the continuous release of gas bubbles from the electrode surface was
always accompanied by the procedure, which was probably generated
by water dissociation and Kolbe reaction (Eq. (17)) (Holzhäuser et al.,
2020).
As described in section 3.1, the voltage of spent LIBs did not change
obviously after immersing in MnSO4 solution for 24 h. As shown in Fig. 6
(a) and the inset, a black precipitation layer is attached to the surface of
the positive cap, and the characteristic amorphous diffraction peaks
appear in the XRD pattern of precipitation from MnSO4 solution. Ac­
cording to Eqs. (13)-(16), the products are expected to be mixtures of
many complex oxidation reactions because of the various oxidation
states of manganese. Xiao et al. (2020) considered that the main pre­
cipitation is probably MnO2, which was validated by our similar XPS
results in Fig. 6(b). As shown in Fig. 6(c) and (d), the micromorphology
of the precipitate is significantly different from the above agglomerated
powder, the sheet structure indicates it should come from the MnO2
isolation layer attached to the positive cap. As a common semiconductor
and electrode material, manganese dioxide (MnO2) has high theoretical
specific capacitance (~1370 F/g) and excellent chemical stability
(Huang et al., 2015; Pielichowski and Majka, 2018), but poor conduc­
tivity (10− 6–103 Ω− 1⋅cm− 1) (Liu et al., 2017). Therefore, incorporating
inorganic materials (e.g., MnO2) into organic conducting polymers (e.g.,
polyaniline, PANI) can obtain composites with better mechanical,
thermal, electrical and electrochemical properties, which are widely
utilized in secondary batteries, solar cells, and supercapacitors (Kannan
et al., 2020; Reddy et al., 2010). It should be noted that, due to the poor
conductivity of MnO2 isolation layer, false reading was probably ob­
tained by directly connecting the positive cap with the voltmeter,
resulting in the misinterpretation of the spent LIBs’ residual electricity.
Fig. 6. (a) The XRD pattern and (b) XPS results of the precipitated powder generated from MnSO4 solution; (c) and (d) is the SEM photos of sediments (Mag: 1 kX and
10 kX).
7
Journal of Cleaner Production 359 (2022) 132116
The voltage measurement method is not made clear in previous litera­
ture, some errors caused by poor contact will greatly affect the mea­
surement results. In this work, as shown in Fig. S1, the current lead,
platinum wire passed through the pressure relief hole of the positive cap
and directly contacted the clean aluminum safety valve, ensuring the
authenticity of voltage measurement results.
Based on the above, it could be deduced that high discharge effi­
ciency could be achieved if electrolytic reactions produce conductive
powder precipitation. Hence, the chemical discharge mechanisms of
spent LIB can be concluded into two aspects: 1) Electrolytic reaction: the
electricity is converted into chemical energy by electrolytic reactions. 2)
External short circuit: the conductive powders produced by the elec­
trolytic reactions leads to the external short circuit between the positive
and negative poles, which converts electricity into thermal energy.
Meanwhile, released heat can be absorbed by aqueous solution, which
eliminates the potential thermal hazards of operational process.
3.4. Apparent corrosion analysis of battery shells
Two types of ordinary corrosion of metals occur in salt solutions: 1)
chemical corrosion, which is usually caused by the chemical properties
of solutions, such as strong acidity or alkalinity, and aggressive halide
ions. 2) galvanic corrosion, which occurs due to electrochemical re­
actions of two electrically connected dissimilar metals immersed in a
conductive solution (Homma et al., 2000; Kondo et al., 2000). Through
the characterization of surface micromorphology, the corrosion
behavior of the positive cap can be observed intuitively, which is usually
used for qualitative analysis. Moreover, the concentrations of metal el­
ements in supernatants after immersion were obtained by ICP-OES,
which is supporting evidence to estimate corrosion degree
quantitatively.
Firstly, the pH fluctuations of various salt solutions during discharge
are recorded in Fig. S5, reflecting the strength of chemical corrosion.
Although NaCl solution is neutral, the pitting effect of Cl− is also an
important reason for chemical corrosion (Amar et al., 2003). According
Z. Fang et al.
to the hydrolysis reactions of salts, the solutions of MnSO4 and FeSO4 are
acidic, and the solution of KAc is alkaline. In MnSO4 and FeSO4 solu­
tions, the pH dropped significantly within the first 6 h, implying that the
reduction reaction of H+ ions into hydrogen was inhibited at the nega­
tive pole, and the hydrolysis of metal ions will cause a decrease in pH.
Besides, SO2−4 tends to reduce at the negative pole to produce H2SO3 and
S, as demonstrated by the positive reduction potentials in Eqs. (22) and
(23). The strong acidity with pH near 2.5 not only has non-negligible
chemical corrosion to spent LIBs, but metal equipment in this environ­
ment will be seriously damaged, limiting their industrial application. In
alkaline KAc solution, the corrosion of the positive cap is relatively light,
but rubber insulating gasket is more easily degraded in a basic envi­
ronment (Shaw-Stewart et al., 2019). Zn(Ac)2 is a weak-acid and
weak-base salt, whose pH depends on the hydrolytic equilibrium of Zn2+
and CH3COO− . In this work, Zn(Ac)2 solution shows weak acidity with
pH near 6.0, reflecting a mild corrosion behavior of the battery shell.
Fig. 7 shows the micrographs of spent LIBs’ positive caps after 24 h
immersion in various discharge solutions, except for NaCl solution,
whose positive terminal was severely corroded and totally damaged
(Fig. 7(f)). Table 3 shows the concentrations of supernatants of various
discharge solutions after 24 h immersion. The concentrations of lithium,
nickel, and manganese in NaCl solution are significantly higher than
those in other solutions. Especially, lithium, as the characteristic
element, exists only in the interior of LIB, which indicates a terrible
Fig. 7. Micrographs of spent LIBs’ positive caps after 24 h immersion in various discharge solutions, (a) fresh positive cap, (b) FeSO4 solution, (c) MnSO4 solution (d)
KAc solution (e) Zn(Ac)2 solution; (f) photo of totally destroyed positive cap in NaCl solution.
8
Journal of Cleaner Production 359 (2022) 132116
leakage of electrolyte was caused by serious corrosion of the battery
shell. The new positive cap seems complete and smooth (Fig. 7(a)),
setting as the control group. Fig. 7(b) shows hierarchical corrosion of
positive cap after immersing in FeSO4 solution, which indicates the
nickel coating layer has been partially corroded. The relatively high
concentrations of nickel (3.116 mg/L) and aluminium (10.227 mg/L) in
FeSO4 supernatant confirm the statement. In Fig. 7(c), obvious attach­
ments can be observed on the surface of positive cap immersed in MnSO4
solution after 24 h, which should be the MnO2 isolation layer described
in section 3.3. However, the analysis of supernatant demonstrates that
the corrosion in MnSO4 solution should not be underestimated, owing to
high concentrations of nickel (22.412 mg/L), aluminium (4.002 mg/L),
and iron (3.799 mg/L). It is probably that the metal corrosion reactions
(Eqs. (8)-(11)) are dominant as the formation reaction of MnO2 (Eq.
(14)) is less thermodynamically favorable, and the corrosion may have
occurred until the isolation layer was covered entirely. Inspiringly, this
is no visible corrosion traces on the positive cap after immersing in ac­
etate solutions for 24 h, and a relatively complete nickel coating can still
be observed in the micrographs (Fig. 7(d) and (e)). The low concentra­
tions of nickel, iron, and aluminium in supernatants again indicate that
the battery shell is well protected from corrosion. Acetate aqueous so­
lutions are chosen as the discharge medium because of a special kind of
electrolytic reaction, the Kolbe reaction. As shown in Fig. 8, the reaction
intermediates generated in the process of carboxylate electrolysis will
Z. Fang et al. Journal of Cleaner Production 359 (2022) 132116

Table 3
Concentrations of metallic elements in supernatant after discharging treatment. (mg/L).
Solution Li Ni Co Mn Fe Al Cu

NaCl 14.127 26.556 13.733 22.450 57.551 9.249 1.235

MnSO4 0.051 22.412 0.049 258.600 3.799 4.002 N/A
FeSO4 0.050 3.116 0.014 17.634 349.494 10.227 0.063
KAc 0.063 0.103 N/A 0.001 0.033 0.276 N/A
Zn(Ac)2 N/A 0.171 0.004 N/A 0.052 0.025 N/A

dioxide (Vijh and Conway, 1967). The high theoretical potential (0.396
V) of Kolbe reaction in Eq. (17) validates the above statement, which
promotes the excellent corrosion inhibition effect of acetate solutions
(Vijh and Conway, 1967).

3.5. Electrochemical analysis of corrosion behaviors

In order to intensively investigate the corrosion behaviors of LIB’s

shell, especially the positive pole, in various discharge solutions, several
electrochemical tests of the positive cap were performed here. The
corrosion behaviors of the specimens were evaluated by performing OCP
and potentiodynamic polarization tests. The OCP evaluation of the
specimens submerged in various salt solutions as a function of immer­
sion time is presented in Fig. 9(a). The slight fluctuations of Eocp at the
initial immersion stage are related to the interaction between the elec­
trolyte and the metal surface (Bordbar-Khiabani et al., 2020). And then,
Fig. 8. The corrosion inhibition and adsorption mechanism of battery shell in
the stable potentials were achieved after 30 min. The Eocp can reflect the
acetate solution.
self-corrosion tendency of metal in a certain solution. Specifically, the
lower Eocp of the specimen in the solution, the more prone it to
absorb and cover the surface of the anode electrode, so as to inhibit some
self-corrosion, revealing a deteriorated corrosion resistance. The Eocp of
anodic oxidation reactions, such as oxygen evolution and metal disso­
positive cap in various salt solutions follows the sequence Zn(Ac)2 >
lution, which will alleviate the corrosion of the anode metal, and the
KAc > MnSO4 > FeSO4 > NaCl, which is in accordance with the
reaction intermediates may further generate hydrocarbons and carbon
corrosion degrees obtained by SEM measurement and ICP-OES data.

Fig. 9. (a) OCP value versus time; (b) steady-state polarization curves, (c) anodic polarization curves of the specimen disassembled from positive cap; (d) is a
standard anodic polarization curve with the indication of the characteristic parameters and the specific regions.

9
Z. Fang et al.
The steady-state polarization curves of the positive caps in various
salt solutions are depicted in Fig. 9(b). For a steady-state system, the
open-circuit corrosion potential (Ecorr) and corrosion current density
(icorr) are usually utilized to evaluate the corrosion characteristics
(El-Taib Heakal et al., 2009; Zhang et al., 2009). The Ecorr is directly
obtained from the log i vs. E curve, which is the potential where the
current density equals zero. Then, icorr can be determined by extrapo­
lating the anodic and cathodic Tafel lines to the Ecorr (Zhang et al.,
2009). This work performs the curve fitting and extrapolation calcula­
tion of experimental data using "CHI Electrochemical Analyzer" software
(version 15.03). Table 4 presents the electrochemical parameters of the
steady-state polarization test for positive caps in various salt solutions.
The specimen has the lowest stability in NaCl solution compared to other
salt solutions, which displays the lowest Ecorr (− 0.946 V) and highest
icorr (379.33 μA/cm2). Therefore, it can be inferred that pitting corrosion
destroyed the positive cap could be ascribed to competitive adsorption
between Cl− and passive species (OH− and H2O dipoles) (Amar et al.,
2003; Hoar et al., 1965). In FeSO4 and MnSO4 solutions, the specimens
show roughly similar corrosion tendencies as given by the values of Ecorr
and icorr presented in Table 4. Moreover, it can be deduced from the icorr
values that the positive caps immersed in Zn(Ac)2 and KAc solutions
present excellent corrosion protection (2.52 and 10.56 μA/cm2,
respectively).
In the actual application of chemical discharge, the residual voltage
of the spent LIBs will accelerate the corrosion of the positive cap during
the immersion. Herein, an anodic polarization test was performed with a
higher scan rate (10 mV/s) and wider potential range (from Eocp − 0.2 V
to 4.2 V) to reveal the dynamic corrosion behavior of the positive cap
under external voltage. Fig. 9(c) shows the anodic polarization curves of
the positive caps in various salt solutions. As shown in Fig. 9(d), a
standard anodic polarization curve is divided into five parts, which
describe the active-passive transition of the specimen (Bellezze et al.,
2018). Some vital characteristic parameters can be obtained from this
schematic plot: 1) the critical passivation current density (icp) and cor­
responding critical passivation potential (Epp), where the transition from
the active to the passive state occurs and current density starts to decline
with the formation of the passive film. 2) the passivation current (ip) and
corresponding passivation potential (Ep), where the current density
decreases from icp to the lowest value ip, and basically does not change
with the increase of potential, indicating a state of complete passivation.
3) the transpassivation potential (Etr), where the current density begins
to rise again as the potential increases toward more positive values,
which is attributed to the breakdown of passive film or other anodic
reactions.
The above critical parameters are determined as suggested in (Bel­
lezze et al., 2018) and listed in Table 5. As shown in Fig. 9(c), the anodic
polarization curves of specimens immersed in NaCl, MnSO4, and FeSO4
solutions have an apparent active-passive transition. In NaCl solution,
the active-passive transition occurred at the most negative potential
(Epp: − 0.545 V), indicating the poor corrosion inhibition of the spec­
imen, and the violent fluctuation of the current density in the passivity
region implies the instability of the passive film. Similar corrosion trends
are observed between MnSO4 and FeSO4 solutions, which are demon­
strated by similarly characteristic parameters of passivation. Neverthe­
less, the passivation state of the specimen in MnSO4 solution seems
Table 4
Electrochemical parameters of steady-state polarization test for specimens in
various salt solutions.
Solution βa (mV/dec) βb (mV/dec) Ecorr (V) icorr (μA/cm2)
NaCl 279 115 − 0.946 379.33
MnSO4 85 492 − 0.654 132.96
FeSO4 81 51 − 0.734 107.28
KAc 217 216 − 0.090 10.56
Zn(Ac)2 187 214 0.259 2.52
10
Journal of Cleaner Production 359 (2022) 132116
Table 5
Critical parameters in anodic polarization test for specimens in various salt
solutions.
Solution Epp (V) Ep (V) Etr (V) log icp (A/cm) log ip (A/cm)
NaCl − 0.545 − 0.534 − 0.235 − 1.831 − 2.274
MnSO4 0.460 0.738 1.418 − 0.666 − 2.344
FeSO4 0.407 0.702 1.451 − 0.657 − 2.011
KAc N/A 0.476 0.737 N/A − 3.828
Zn(Ac)2 N/A 0.468 1.032 N/A 4.615
−
unstable, showing that there is no steady passivity region, and the pas­
sive film is fragile. This result explains the non-negligible corrosion of
the positive cap in MnSO4 solution, which is consistent with the above
discussion. Whereas the anodic polarization curves of the specimens
immersed in KAc and Zn(Ac)2 solutions exhibit a pure passive region
without active-passive transition, which indicates the adsorption of
alkyl and alkoxy radicals on the specimen surface forms a protective
layer to inhibit metal dissolution (Holzhäuser et al., 2020; Kılınççeker,
2008). Moreover, when the potential exceeds Etr, continuous release of
gas bubbles can be observed from the specimen surface instead of the
passive film breakdown caused by localized corrosion. This observation
shows mixed-type inhibition with predominant anodic reactions
(Prabhu et al., 2021). Thus the increase of current density in corre­
spondence of Etr is determined by Kolbe reaction and oxygen evolution
(Koutsaftis et al., 2012). That is probably the reason for the excellent
corrosion inhibition of acetate solutions compared to other salt
solutions.
4. Conclusions
Chemical discharge is an effective pretreatment to eliminate the re­
sidual electricity and ensure the safety of subsequent recycling pro­
cesses. This work investigated the discharge efficiency and the corrosion
behavior of the spent LIBs immersed in several discharge mediums
(NaCl, MnSO4, FeSO4, KAc, and Zn(Ac)2 solutions). Through the nail
penetration and EV-ARC tests, the thermal stability of treated batteries
validates the feasibility of discharge strategy. This study provided some
conclusions as follows:
(1) NaCl solution can effectively consume the residual electricity of
spent LIBs but at the expense of serious corrosion and electrolyte
leakage. The additional pollution and corresponding treatment
costs will limit its industrial application.
(2) MnSO4 solution is not suitable for the discharge pretreatment of
spent LIBs because the MnO2 isolation layer deposited at the
positive cap inhibits the further electrolytic reaction. The residual
voltage of the battery immersed in KAc solution for 24 h was
above 3.0 V, which cannot guarantee the safety of subsequent
operations.
(3) The spent LIBs in FeSO4 and Zn(Ac)2 solutions performed excel­
lent discharge efficiency, and the residual voltage decreased to 0
V within an hour. According to the nail penetration and EV-ARC
test results, electricity consumption and material deactivation are
the essential reasons for the high safety of the spent LIBs after
immersion. Moreover, Zn(Ac)2 solution showed better corrosion
resistance to the battery shell, attributed to the adsorption layer
formed by acetate radical on the metal surface during electrolysis
and Kolbe reaction, protecting the battery shell from corrosion.
(4) Through qualitative and quantitative analysis of precipitated
powder and supernatant during the discharge process, the
chemical discharge mechanisms of spent LIB can be concluded
into two aspects: electrolysis and external short circuit. There­
fore, a high discharge efficiency could be achieved if electrolytic
reactions produce conductive powder precipitation.
Z. Fang et al.
Furthermore, recycling the nano-size zinc powder precipitated by
electrolysis as a high-grade chemical material can further reduce the
treatment cost. The above results show that Zn(Ac)2 solution is a po­
tential discharge medium because of its superiorities in discharge effi­
ciency, prevention of corrosion, and total cost. The performance of Zn
(Ac)2 solution is promising for establishing industrial applications and
realizing a safe, rapid, and environmentally friendly discharge pre­
treatment for spent LIBs. In addition, the modules composed of many
single batteries have a higher voltage, whose feasibility and safety of
chemical discharge strategy need to study in future work.
CRediT authorship contribution statement
Zheng Fang: Conceptualization, Methodology, Writing – original
draft, Writing – review & editing. Qiangling Duan: Methodology,
Writing – original draft, Writing – review & editing. Qingkui Peng:
Methodology, Writing – review & editing. Zesen Wei: Methodology,
Writing – review & editing. Huiqi Cao: Writing – review & editing.
Jinhua Sun: Conceptualization, Funding acquisition, Writing – review
& editing. Qingsong Wang: Conceptualization, Funding acquisition,
Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work is supported by the National Natural Science Foundation
of China (No. 51976209) and the Key R&D Plan of Anhui Province (No.
202104a07020003). Dr. Q.S Wang is supported by Youth Innovation
Promotion Association CAS (No.Y201768).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2022.132116.
References
Amar, H., Benzakour, J., Derja, A., Villemin, D., Moreau, B., 2003. A corrosion inhibition
study of iron by phosphonic acids in sodium chloride solution. J. Electroanal. Chem.
558, 131–139.
Bellezze, T., Giuliani, G., Roventi, G., 2018. Study of stainless steels corrosion in a strong
acid mixture. Part 1: cyclic potentiodynamic polarization curves examined by means
of an analytical method. Corrosion Sci. 130, 113–125.
Bhaskara, S., Fakrudeen, S.P., Raju, V.B., Murthy, H.C.A., Raghu, A.V., 2021.
Comparative studies of inhibitive effects of diamines on corrosion of aluminium
alloy in presence of acid media. Rasayan J. Chem. 72–82.
Bordbar-Khiabani, A., Ebrahimi, S., Yarmand, B., 2020. In-vitro corrosion and bioactivity
behavior of tailored calcium phosphate-containing zinc oxide coating prepared by
plasma electrolytic oxidation. Corrosion Sci. 173, 108781.
Chakraborty, D., Shelvapulle, S., Reddy, K.R., Kulkarni, R.V., Puttaiahgowda, Y.M.,
Naveen, S., Raghu, A.V., 2019. Integration of biological pre-treatment methods for
increased energy recovery from paper and pulp biosludge. J. Microbiol. Methods
160, 93–100.
Chen, M., Ma, X., Chen, B., Arsenault, R., Karlson, P., Simon, N., Wang, Y., 2019.
Recycling end-of-life electric vehicle lithium-ion batteries. Joule 3 (11), 2622–2646.
Chen, Z., Zhang, L., Xu, Z., 2019. Tracking and quantifying the cobalt flows in mainland
China during 1994-2016: insights into use, trade and prospective demand. Sci. Total
Environ. 672, 752–762.
Deng, L., 2021. CATL’ Factory Exploded to 1 Dead and 20 Injured, Officials Responded.
https://baijiahao.baidu.com/s?id=1688582650375756402&wfr=spider&for=pc.
(Accessed 11 January 2021).
El-Taib Heakal, F., Fekry, A.M., Fatayerji, M.Z., 2009. Influence of halides on the
dissolution and passivation behavior of AZ91D magnesium alloy in aqueous
solutions. Electrochim. Acta 54 (5), 1545–1557.
Goodenough, J.B., Park, K.S., 2013. The Li-ion rechargeable battery: a perspective.
J. Am. Chem. Soc. 135 (4), 1167–1176.
Harper, G., Sommerville, R., Kendrick, E., Driscoll, L., Slater, P., Stolkin, R., Walton, A.,
Christensen, P., Heidrich, O., Lambert, S., Abbott, A., Ryder, K., Gaines, L.,
11
Journal of Cleaner Production 359 (2022) 132116
Anderson, P., 2019. Recycling lithium-ion batteries from electric vehicles. Nature
575 (7781), 75–86.
Hoar, T.P., Mears, D.C., Rothwell, G.P., 1965. The relationships between anodic
passivity, brightening and pitting. Corrosion Sci. 5 (4), 279–289.
Holzhäuser, F.J., Mensah, J.B., Palkovits, R., 2020. (Non-)Kolbe electrolysis in biomass
valorization – a discussion of potential applications. Green Chem. 22 (2), 286–301.
Homma, Y., Kondo, S., Sakuma, N., Hinode, K., Noguchi, J., Ohashi, N., Yamaguchi, H.,
Owada, N., 2000. Control of photocorrosion in the copper damascene process.
J. Electrochem. Soc. 147 (3), 1193–1198.
Huang, B., Pan, Z., Su, X., An, L., 2018. Recycling of lithium-ion batteries: recent
advances and perspectives. J. Power Sources 399, 274–286.
Huang, M., Li, F., Dong, F., Zhang, Y.X., Zhang, L.L., 2015. MnO2-based nanostructures
for high-performance supercapacitors. J. Mater. Chem. 3 (43), 21380–21423.
Kannan, K., Radhika, D., Nesaraj, A.S., Kumar Sadasivuni, K., Reddy, K.R., Kasai, D.,
Raghu, A.V., 2020. Photocatalytic, antibacterial and electrochemical properties of
novel rare earth metal oxides-based nanohybrids. Mater. Sci. Energy Technol. 3,
853–861.
Karnchanawong, S., Limpiteeprakan, P., 2009. Evaluation of heavy metal leaching from
spent household batteries disposed in municipal solid waste. Waste Manag. 29 (2),
550–558.
Kılınççeker, G., 2008. The effects of acetate ions on electrochemical behaviour of brass in
chloride solutions. Colloids Surf. A Physicochem. Eng. Asp. 329 (1–2), 112–118.
Kim, S., Bang, J., Yoo, J., Shin, Y., Bae, J., Jeong, J., Kim, K., Dong, P., Kwon, K., 2021.
A comprehensive review on the pretreatment process in lithium-ion battery
recycling. J. Clean. Prod. 294, 126329.
Kondo, S., Sakuma, N., Homma, Y., Ohashi, N., 2000. Slurry chemical corrosion and
galvanic corrosion during copper chemical mechanical polishing. Jpn. J. Appl. Phys.
39 (Part 1, No. 11), 6216–6222.
Koutsaftis, D., Marinis, D., Karantonis, A., 2012. Bubble dynamics during Kolbe
electrolysis of trifluoroacetic acid at Pt electrodes. Electrochim. Acta 59, 376–381.
Li, J., Wang, G., Xu, Z., 2016. Generation and detection of metal ions and volatile organic
compounds (VOCs) emissions from the pretreatment processes for recycling spent
lithium-ion batteries. Waste Manag. 52, 221–227.
Li, L., Ge, J., Chen, R., Wu, F., Chen, S., Zhang, X., 2010. Environmental friendly leaching
reagent for cobalt and lithium recovery from spent lithium-ion batteries. Waste
Manag. 30 (12), 2615–2621.
Lide, D.R., Haynes, W.M., 2010. CRC Handbook of Chemistry and Physics, 90th ed. CRC
press, Boca Raton, FL.
Liu, C., Lin, J., Cao, H., Zhang, Y., Sun, Z., 2019. Recycling of spent lithium-ion batteries
in view of lithium recovery: a critical review. J. Clean. Prod. 228, 801–813.
Liu, L., 2021. A Truck Full of Waste Batteries Suddenly Caught Fire in Huai’an.
https://baijiahao.baidu.com/s?id=1663396611484152368&wfr=spider&for=pc.
(Accessed 16 April 2020).
Liu, W., Wang, Z., Su, Y., Li, Q., Zhao, Z., Geng, F., 2017. Molecularly stacking
manganese dioxide/titanium carbide sheets to produce highly flexible and
conductive film electrodes with improved pseudocapacitive performances. Adv.
Energy Mater. 7 (22), 1602834.
Mao, B., Chen, H., Cui, Z., Wu, T., Wang, Q., 2018. Failure mechanism of the lithium ion
battery during nail penetration. Int. J. Heat Mass Tran. 122, 1103–1115.
Nembhard, N., 2020. Safe, Sustainable Discharge of Electric Vehicle Batteries as a Pre-
treatment Step to Crushing in the Recycling Process. Universitat Politècnica de
Catalunya.
Ojanen, S., Lundstrom, M., Santasalo-Aarnio, A., Serna-Guerrero, R., 2018. Challenging
the concept of electrochemical discharge using salt solutions for lithium-ion batteries
recycling. Waste Manag. 76, 242–249.
Pielichowski, K., Majka, T.M., 2018. Polymer Composites with Functionalized
Nanoparticles: Synthesis, Properties, and Applications. Woodhead Publishing.
Prabhu, R., Roopashree, B., Jeevananda, T., Rao, S., Raghava Reddy, K., Raghu, A.V.,
2021. Synthesis and corrosion resistance properties of novel conjugated polymer-
Cu2Cl4L3 composites. Mater. Sci. Energy Technol. 4, 92–99.
Reddy, K.R., Jeong, H.M., Lee, Y., Raghu, A.V., 2010. Synthesis of MWCNTs-core/
thiophene polymer-sheath composite nanocables by a cationic surfactant-assisted
chemical oxidative polymerization and their structural properties. J. Polym. Sci.
Polym. Chem. 48 (7), 1477–1484.
Refait, P., Grolleau, A.M., Jeannin, M., François, E., Sabot, R., 2018. Corrosion of mild
steel at the seawater/sediments interface: mechanisms and kinetics. Corrosion Sci.
130, 76–84.
Ren, D., Hsu, H., Li, R., Feng, X., Guo, D., Han, X., Lu, L., He, X., Gao, S., Hou, J., Li, Y.,
Wang, Y., Ouyang, M., 2019. A comparative investigation of aging effects on thermal
runaway behavior of lithium-ion batteries. eTransportation 2, 100034.
Rouhi, H., Karola, E., Serna-Guerrero, R., Santasalo-Aarnio, A., 2021. Voltage behavior in
lithium-ion batteries after electrochemical discharge and its implications on the
safety of recycling processes. J. Energy Storage 35, 102323.
Shaw-Stewart, J., Alvarez-Reguera, A., Greszta, A., Marco, J., Masood, M.,
Sommerville, R., Kendrick, E., 2019. Aqueous solution discharge of cylindrical
lithium-ion cells. Sustain. Mater. Technol. 22, e00110.
Sun, J., Li, J., Zhou, T., Yang, K., Wei, S., Tang, N., Dang, N., Li, H., Qiu, X., Chen, L.,
2016. Toxicity, a serious concern of thermal runaway from commercial Li-ion
battery. Nano Energy 27, 313–319.
Tarascon, J.M., Armand, M., 2001. Issues and challenges facing rechargeable lithium
batteries. Nature 414 (6861), 359–367.
Vijh, A.K., Conway, B.E., 1967. Electrode kinetic aspects of the Kolbe reaction. Chem.
Rev. 67 (6), 623–664.
Wang, F., Harindintwali, J.D., Yuan, Z., 2021. Technologies and perspectives for
achieving carbon neutrality. Innovation 2 (4), 100180.
Z. Fang et al.
Xiao, J., Guo, J., Zhan, L., Xu, Z., 2020. A cleaner approach to the discharge process of
spent lithium ion batteries in different solutions. J. Clean. Prod. 255, 120064.
Yao, L.P., Zeng, Q., Qi, T., Li, J., 2020. An environmentally friendly discharge technology
to pretreat spent lithium-ion batteries. J. Clean. Prod. 245, 118820.
12
Journal of Cleaner Production 359 (2022) 132116
Zhang, G., Yuan, X., He, Y., Wang, H., Zhang, T., Xie, W., 2021. Recent advances in
pretreating technology for recycling valuable metals from spent lithium-ion
batteries. J. Hazard Mater. 406, 124332.
Zhang, X.L., Jiang, Z.H., Yao, Z.P., Song, Y., Wu, Z.D., 2009. Effects of scan rate on the
potentiodynamic polarization curve obtained to determine the Tafel slopes and
corrosion current density. Corrosion Sci. 51 (3), 581–587.