Journal of Power Sources 518 (2022) 230767

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Journal of Power Sources

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

A systematic investigation of internal physical and chemical changes of

lithium-ion batteries during overcharge
Ning Mao a, b, Teng Zhang c, Zhirong Wang a, *, Qiong Cai b, **
a
Jiangsu Key Laboratory of Urban and Industrial Safety, College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 210009, China
b
Department of Chemical and Process Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, GU2 7XH, United Kingdom
c
Department of Mechanical Engineering Science, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, GU2 7XH, United Kingdom

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

• A comprehensive and systematic inves­

tigation of LIB overcharge behavior is
presented.
• The decomposition mechanism of the
NMC311 cathode during overcharge is
speculated.
• The evolution of the electrode crystal
structure during LIB overcharge is
examined.
• A four-stage degradation and failure
process during LIB overcharge is
revealed.
• The findings help to understand the
thermal runaway behavior during LIB
overcharge.

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

Keywords: The overcharge of lithium-ion batteries (LIBs) can not only cause irreversible battery degradation and failure but
Lithium-ion batteries also trigger detrimental thermal runaway. This paper presents a systematic investigation of the electrical and
Overcharge thermal behaviors of LIBs during overcharge up to thermal runaway, and reveals the underlying physical,
Physical structure
structural, and chemical changes at each electrode at different stages of overcharge using microscopic and
Chemical reaction
Thermal runaway
spectroscopy characterizations. The overcharge process of LIBs with Li(Ni0.6Mn0.2Co0.2)O2 cathodes can be
divided into four stages. Stage I involves the decomposition of LiMnO2 and LiNiO2 to MnO and NiO, respectively,
accompanied by a slight collapse of the cathode. During stage II, the cathode forms a relatively stable hexagonal
phase H3 while Li plating occurs at the anode surface. Moreover, NiO and Ni(OH)2 decompose into metallic Ni
and release a large amount of heat. During stage III, MnO2 is formed on the cathode, which is irreversibly
damaged, and unstable substance LiH is formed on the anode, which accelerates thermal runaway onset. During
stage IV, the battery ruptures at approximately 174% state of charge (SOC), followed by thermal runaway in just
20 s. During overcharge, the crystallinity of the cathode decreases with the increase of SOC.

* Corresponding author.
** Corresponding author.
E-mail addresses: wangzhirong@njtech.edu.cn (Z. Wang), q.cai@surrey.ac.uk (Q. Cai).

https://doi.org/10.1016/j.jpowsour.2021.230767
Received 29 March 2021; Received in revised form 5 November 2021; Accepted 11 November 2021
Available online 18 November 2021
0378-7753/© 2021 Elsevier B.V. All rights reserved.
N. Mao et al.
1. Introduction
Lithium-ion batteries (LIBs) have been widely used in portable
electronics, hybrid and electric vehicles, as well as large-scale energy
storage systems because of their high energy density, long cycle life, low
memory effects, and self-discharge rate [1–3]. However, the safety
concerns of LIBs, especially thermal runaway, still hinder their
large-scale application [4–6]. Thermal runaway can be triggered by
abuse, such as overcharging, overdischarge, short-circuiting [7], over­
heating, nail penetrating the battery [8]. Among these factors, over­
charge commonly occurs in battery packs because of improper design,
battery management system (BMS) or charger failure [9], and mis­
matched resistance, temperature, and capacity between cells [10].
Overcharging triggers many detrimental processes in LIBs, including
side reactions, such as Li plating, and the decomposition of the active
materials and the electrolyte, causing irreversible battery degradation
[11–14]. Moreover, overcharging can trigger thermal runaway, which
can propagate among batteries, causing catastrophic fires or explosions
[15,16]. Hence, understanding the overcharge-induced physical and
chemical changes in LIBs is important for the development of safer
batteries and BMS.
Research on the overcharging mechanisms of LIBs has led to a
rudimentary understanding of the electrochemical and thermal pro­
cesses that occur during overcharging. When LIBs are overcharged,
excess Li ions are extracted from the cathode and inserted into the
anode. At the cathode, overdelithiation causes structural changes [16],
decomposition of active materials, and exothermic reactions with the
electrolyte [17]. These reactions generate significant amounts of O2 and
heat [10,15,16], leading to electrolyte oxidation and promoting thermal
runaway [4]. At the anode, excess Li inevitably sink into the carbon
crystal structure [18,19]. Consequently, Li deposits on the carbon
instead of intercalating into it, promoting Li dendrite growth, which is
one of the main causes of internal short-circuit and thermal runaway
[20]. Initially, the uncontrolled growth of Li dendrites leads to an in­
crease in the active surface area of Li metal, accelerating irreversible
side reactions between the electrolyte and Li metal, and resulting in
rapid consumption of the electrolyte and active Li metal [21]. Subse­
quently, the active Li dendrites wrapped around the insulating solid
electrolyte interface (SEI) film become electrochemically inert dead Li
[22]. Furthermore, the growth and uneven structure of the Li dendrites
increase the diffusion path length, resulting in significant polarization
[23]. Lastly, Li dendrites can penetrate the separator and cause battery
internal short circuit until thermal runaway occurs [24]. Additionally,
dendrite growth is typically accompanied by gas release into the battery
packaging, including CO2, H2, CO, and CH4, resulting in battery
expansion and potential packaging rupture [25]. The thermal runaway
behavior and mechanisms of battery triggered by overcharging have
been studied as above. However, the exact mechanisms of the relevant
side reactions are still being intensively investigated.
Many scholars have conducted overcharge experiments on LIBs with
LiCoO2 cathodes. Lin et al. [26] demonstrated that the temperature of
the cathode increased when the voltage reached 4.16 V, whereas the
temperature of the anode increased only when the cell was charged at
voltages higher than 4.58 V, indicating that the reaction occurred first at
the cathode side and released heat. Furthermore, Ohsaki et al. [27] re­
ported that a rapid exothermic reaction between the delithiated cathode
and the electrolyte accelerated the reaction between the anode (depos­
ited Li) and electrolyte solvent, which can cause thermal runaway.
Similar results were reported by Maleki et al. [28]. Belov et al. [29]
suggested that the separator was a critical component leading to thermal
runaway. LIB thermal runaway during overcharging can be micro-­
shorting– initiated by the electro-conducting growth penetrating
through the separator. However, the aforementioned studies did not
clarify the reaction mechanisms required to optimize battery chemistry.
MacNeil et al. [30] studied the decomposition reaction of an over­
charged LiCoO2 cathode and concluded that the reaction of Li0.5CoO2
2
Journal of Power Sources 518 (2022) 230767
with the solvent proceeded to CoO through a Co3O4 intermediate.
Owing to the high energy density and wide use of ternary batteries
using Ni–Mn–Co oxides (NMC) as cathodes, an increasing number of
scholars have focused their attention on the overcharge mechanisms of
NMC batteries. He et al. [31] indicated that the increase in battery total
resistance generated a large amount of Joule heat, which accelerated
thermal runaway. However, Joule heat is not a critical factor during
thermal runaway. Wang et al. [32] used differential scanning calorim­
etry and thermal gravimetric analysis to demonstrate the critical role of
the reaction of electrolytes with the evolved O2 in thermal runaway. Ye
et al. [33] further confirmed this conclusion. However, a more system­
atic and detailed analysis of battery components is required to provide
an in-depth understanding of the overcharging behavior and its under­
lying mechanisms. Rago et al. [21] and Bareño et al. [34] studied the
overcharge behavior of the NMC cathode and the graphite anode;
however, they mainly focused on the changes in structure and did not
evaluate the changes in chemical composition, which hindered the un­
derstanding of the intrinsic causes of thermal runaway caused by battery
overcharge.
Despite these recent advances, a comprehensive understanding of
the degradation mechanisms of LIBs during overcharge is still lacking,
especially in terms of crystal structure changes, chemical reactions, and
decomposition mechanisms at both electrodes of LIBs with ternary
cathodes, such as Li(Ni0.6Mn0.2Co0.2)O2.
This work presents a comprehensive and systematic investigation of
electrical and thermal behaviors of LIB overcharge until thermal
runaway, as well as comprehensive characterization of structural and
chemical changes in overcharged cathode and anode. By analyzing the
voltage, temperature, and physical changes of LIBs during overcharging
and thermal runaway, we identified four stages of overcharging
behavior. To understand the underlying mechanisms of these stages,
LIBs with LiNi0.6Co0.2Mn0.2O2 cathodes were overcharged to different
state of charge (SOC; 110%–165%), followed by disassembly in a glove
box for material characterization. Scanning electron microscopy (SEM),
energy dispersive spectrometry (EDS), X-Ray diffraction (XRD), and X-
ray photoelectron spectroscopy (XPS) experiments were performed to
evaluate the changes in the physical structure and chemical composition
of LIBs during overcharging. Our findings helped to elucidate the
mechanisms of the degradation and failure processes during LIB over­
charge leading to thermal runaway. We believe that our study can
promote the development of new methods for improving battery safety
using more suitable battery monitoring and control approaches.
2. Experimental
2.1. Commercial 1.2 Ah pouch LIBs
In this study, we used commercial 1.2 Ah pouch LIBs comprising Li
(Ni0.6Mn0.2Co0.2)O2 (NMC622) cathodes, polyethylene separators and
graphite anodes. The double-side laminate cathode consisted of 89.5 wt
% NMC622, 5 wt% carbon black, and 5.5 wt% polyvinylidene fluoride
(PVDF) binder. The double-side laminate anode consisted of 90 wt%
graphite, 3 wt% carbon black and 7 wt% PVDF binder. The electrolyte is
a 1 M solution of LiPF6 in a mixture of ethylene carbonate (EC) and
diethylcarbonate (DEC) (3:7 by wt%). The schematic of the LIBs is
presented in Fig. 1. LIBs performance tests were performed before the
overcharging experiments. Detailed information on the performance
tests is provided in the Supplementary material.
2.2. Dynamic overcharge tests
A battery test system (Neware BTS-10V20A, China) was used to
analyze the electrical and thermal behaviors of the LIBs during over­
charging in an explosion-proof chamber. Seven LIBs were used to
analyze the effect of the overcharging C-rate on thermal runaway. An
eighth LIB was overcharged at 0.5C to evaluate the battery internal
N. Mao et al.
Fig. 1. The schematic of the 1.2Ah pouch lithium-ion battery.
resistance. All the experiments were performed at 25 ◦ C. During the
experiment, a thermocouple was connected to the center of the battery
surface to measure the temperature, which was also considered to be the
highest temperature at the battery surface [33,35]. A hybrid pulse
power characterization method was used to estimate the internal resis­
tance of the battery during overcharging. The battery was overcharged
at 0.5C in 5 min increments, and charging was paused after each over­
charging step to determine internal resistance (Fig. 2). The internal
resistance of the battery was calculated using Eqns. (1)–(3), [14].
Therein, RT, RO and RP represent the total resistance, ohmic resistance
and polarization resistance of the battery, respectively.
RT = (V(t3) ─ V(t1))/(I(t3) ─ I(t1))
Fig. 2. Overcharge test curve. The charging current was intermittently inter­
rupted to measure resistance.
Journal of Power Sources 518 (2022) 230767
RO = (V(t2) ─ V(t1))/(I(t2) ─ I(t1)) (2)
Rp = RT ─ RO (3)
2.3. Material characterization
Each LIB was overcharged to 110%, 120%, 130%, 140%, 150%,
155%, 160% and 165% SOC respectively. The 100%, 110%, 120%,
130%, 140%, 150%, 155%, 160% and 165% SOC were defined as Full-
Stage SOCs. After overcharging, all the cells were disassembled in an Ar-
filled glove box (Nine Door JMS-S1X, China, water content <0.1 ppm
(1)
and the O2 < 2 ppm). The cathodes were lightly washed three times via
gentle swirling for 2 min at a time, in excess dimethyl carbonate (DMC)
to remove the electrolyte residue and salt deposits (LiPF6) from their
surfaces. Thereafter, the cathode samples were transferred to a vacuum
chamber to evaporate residual DMC.
SEM–EDS was used to analyze the surface morphology, internal
microstructure, and composition changes of the battery components.
First, the electrode samples were placed on the SEM sample stage in a
glove box to minimize air contact. Thereafter, the samples were trans­
ferred to the SEM–EDS (Quanta FEG 250, USA; VANTAGE DSI, USA)
system for detailed examination.
XRD analysis was used to detect crystal structure changes. The
electrode samples were loaded into self-made closed XRD sample slots
(Fig. S2) in a glove box to prevent air contact. Subsequently, the samples
were placed inside the XRD (Smartlab, Japan) instrument for structural
analysis. The XRD patterns were constructed using the Jade 6 software,
and the structural parameters were calculated using the Jade 6 profile
matching refinement method for XRD diagrams [31].
XPS analysis was used to evaluate the chemical characteristics of the
cycled LIB materials. The washed cathode samples were transferred to
the main chamber of the XPS (AXIS SUPRA, Japan) device, which was
purged with high-purity Ar to prevent air exposure. The obtained
spectra were analyzed using XPS Peak Fit software. The binding energy
scale was calibrated to the C1s peak at 284.8 eV [36].
3. Results and discussion
3.1. Overcharge behavior of the LIBs
The voltage and temperature curves of the LIBs overcharged at
different C rates are presented in Fig. 3. All the experiments were per­
formed in triplicate, and the results are illustrated in Fig. S3. Thermal
runaway did not occur when LIBs were overcharged at 0.1, 0.2, and
0.3C. The highest temperature reached at 0.1C was only 36 ◦ C, indi­
cating low Joule heating and self-heating rates from side reactions. The
temperature of the LIBs overcharged at 0.2 and 0.3C reached 107 and
115 ◦ C respectively, and the LIBs visibly expanded owing to the gas
3
N. Mao et al.
Fig. 3. Voltage and temperature profiles of batteries with different charging rate during overcharge (a: 0.1C, 0.2C, 0.3C; b: 0.4C, 0.5C, 1C, 2C).
generated during the side reactions. According to the definition of
thermal runaway in IWG GTR EVS (= Informal Working Group for
developing a Global Technical Regulation for Electric Vehicle Safety,
now also referred as GTR 20), the temperature increase rate (dT/dt)
should be ≥ 1 ◦ C/s [37,38]. In addition, according to the hazard level
classification of the European Council for Automotive Research and
Development, thermal runaway should be accompanied by fire, flame,
rupture, and explosion [37,39]. However, it can be seen from Fig. S4
that dT/dt was < 1 ◦ C/s, and no rupture, combustion, or explosion
occurred. It was concluded that thermal runaway did not occur when the
LIBs were overcharged at 0.2 and 0.3C. Thermal runaway follows a
chain reaction mechanism during which the decomposition reactions of
the battery component materials occur sequentially [40]. When the LIBs
were overcharged at a low rate (0.1, 0.2 and 0.3C), the amount of heat
generated inside the battery, including Joule, polarization, side reaction
heat, was low. In addition, the growth rate of Li dendrites was low, and
the formation of large-area internal short-circuits was hindered.
Therefore, the LIBs could not generate a large amount of heat in a short
period of time to trigger the next reaction. Consequently, the chain re­
action was stopped and the battery did not undergo thermal runaway.
Therefore, owing to the low charging and reaction rates, the heat
generated by these LIBs was not sufficient to cause thermal runaway in a
short time, providing ample time for heat dissipation. BMS can use the
charging rate as the detection object during the monitoring of battery
operation. At charge rates higher than 0.3C, the risk of overcharging is
high, and an alarm should be triggered.
Upon overcharging the LIBs at 0.4, 0.5, 1, and 2C, thermal runaway
occurred. The maximum battery voltage increased with increasing
charging rate, which was attributed to the higher polarization. For all
the thermal runaway experiments, the cathode tab detached and fell off
but the anode one did not. The cathode and anode tabs were fabricated
of aluminum and nickel, respectively. These results indicated that,
during thermal runaway, the internal temperature of the LIBs was
greater than 660 ◦ C (melting point of aluminum) and less than 1453 ◦ C
(melting point of nickel). The venting time (tv) values are presented in
Fig. 3, and listed in Table 1 together with venting temperature (Tv), and
venting voltage (Vv) values of the LIBs at different charge rates during
overcharging. As the overcharging rate was increased, the time required
for the battery to rupture and vent, as well as the Tv values decreased,
indicating that the LIBs were more prone to catastrophic accidents when
they were overcharged at high rates. This was attributed to battery
venting causing large amount of high-temperature mixed combustibles
Table 1
The tv, Tv, and Vv for different charge rates during overcharge.
Charging rate tv/s Tv/◦ C
0.4C 16350 101.1
0.5C 12570 97.9
1C 5770 90.3
2C 2900 91.9
Journal of Power Sources 518 (2022) 230767
to be sprayed into the air, followed by combustion and explosion [41,
42].
Considering the thermal and electrical behaviors of the LIBs over­
charged at 0.5C as an example, four stages (I-IV) of overcharging
behavior were identified, as shown in Fig. 4a. The characteristics of the
points of interest in Fig. 4a, namely points (A)–(G), are summarized in
Table 2.
During Stage I, the battery was gradually overcharged from 3.34 to
4.74 V (point C), where an inflection point (Vi-p) occurred in the voltage
curve and the SOC reached 136%. The appearance of point C indicated
the occurrence of Li plating [43]. Moreover, during Stage I, dT/dt <
0.15 ◦ C min− 1. At the end of Stage I, the battery swelled slightly.
During Stage II, the voltage increased rapidly and the highest voltage
(Vmax = 5.07 V) was reached at point D. The temperature increased
quickly from 31 to 39 ◦ C. Noting that the inflection point of the tem­
perature curve appeared at 39 ◦ C. Typically, the increase in temperature
during this stage is primarily caused by an increase in battery internal
resistance. The battery continued to expand during stage II, which was
ascribed to the production of internal gas, such as H2, CO2, and CH4
[44].
Stage III was the critical stage for determining whether the battery
would undergo thermal runaway. SOC increased from 147% to 173%;
however, the voltage decreased to 4.47 V (point E). This was attributed
to the consumption of the charge current during electrolyte oxidation
and severe destruction of the cathode and anode. The temperature
increased to 89.5 ◦ C, whilst dT/dt reached 0.75 ◦ C min− 1. During this
stage, the battery swelled severely, whilst numerous irreversible re­
actions occurred.
During Stage IV, the voltage rose back to 4.93 V (point F) and the
temperature reached 97.9 ◦ C. Battery ruptured at 174% SOC, and a large
amount of gray smoke was ejected from the top (area near the tabs) of
the battery. Thereafter, the battery burned at 174.33% SOC, and the
voltage dropped to 0 V (point G). Only 20 s elapsed between point F and
thermal runaway.
Based on these results, it was concluded that, to prevent thermal
runaway it is critical to prevent battery rupture and avoid entering Stage
IV, which leads to combustion and explosion. The time elapsed between
point D and thermal runaway was approximately 32 min. However, only
46 s elapsed between point E and thermal runaway. Therefore, point E,
the peak in overcharge voltage, was considered the cut-off point for
preventing thermal runaway.
The changes in the internal resistance of the battery during the 0.5C
overcharging test are presented in Fig. 4b. Overall, during overcharge,
the ohmic resistance of the battery changed slightly, whereas the po­
larization resistance varied significantly. This was attributed to the
ohmic resistance depending on the battery materials rather than the
Vv/V
electrode kinetics. The battery polarization resistance did not increase
4.805 until the SOC exceeded 120%, which was consistent with the results of
4.926 Ouyang et al. [14]. As the battery expanded, the internal resistance
4.886
increased significantly, primarily because of the electrical separation of
4.985
4
N. Mao et al. Journal of Power Sources 518 (2022) 230767

Fig. 4. The curves of lithium-ion battery under 0.5C overcharge test: (a) Thermal behavior; (b) Internal resistance change.

the cathode and anode caused by the significant battery swelling. The
Table 2
maximum internal resistance and Vmax occurred at approximately the
Description of the characteristic points of battery No. 8 during overcharge.
same SOC. Subsequently, the battery polarization resistance decreased
Point SOC/% Voltage/V Temperature/◦ C Cell structure as the voltage decreased.
A 0 3.34 27.7 No changes The negative/positive (N/P) ratio, which is one of the most impor­
B 96.75 4.2 29.1 No changes tant parameters used to determine battery performance, significantly
C 136 4.74 31 Slight swelling
affects the failure behavior of LIBs. Typically, N/P ranges between 1.04
D 147 5.07 39 Moderate swelling
E 173 4.74 89.5 Sever swelling
and 1.2. The N/P ratio of the LIBs in this study was approximately 1.1. If
F 174 4.93 97.9 Rupture the N/P ratio is too high or too low it can cause different failure be­
G 174.33 0 103.3 Burning haviors [45,46]. If the N/P ratio is too high, the active material of
cathode is separated from the current collector and the battery internal
resistance increases, causing the temperature and potential safety haz­
ard to increase. If the N/P ratio is too low, the anode is more likely to

Fig. 5. SEM diagrams of LIBs with different SOCs: (a) SEM: cathode samples with Full-Stage SOCs; (b) SEM: anode samples with Full-Stage SOCs.

5
N. Mao et al.
become overcharged, causing internal short circuits and thermal
runaway. Therefore, the N/P ratio should be within a certain range to
ensure adequate battery performance and safety.
3.2. Physical structural changes of LIBs during overcharge
3.2.1. Changes in electrode morphology with different SOCs
The surface morphologies of the cathode of the LIBs overcharged at
different SOCs are presented in Fig. 5(a). Cathode material morphology
changes were negligible up to 120% SOC. Irregular white spots appeared
at SOC ≥ 130% (marked by the areas encircled in yellow), which were
attributed to cathode decomposition. In addition, noticeable holes
(marked by the red circles) were observed at 140% SOC, indicating that
the structure of NCM622 cathode collapsed significantly.
The surface morphologies of the anode of the LIBs overcharged at
different SOCs are illustrated in Fig. 5(b). Anode material morphology
changes were negligible up to 120% SOC. As overcharge progressed
above 130% SOC, powder-like substances began to adhere to the anode
surface, indicating Li deposition. Furthermore, the agglomerated Li de­
posits (illustrated by the area encircled in blue) observed on the surface
of the anode at 150% SOC were considered to be Li dendrites. The
presence of dendrites at 150% SOC indicated that compared with the Li
intercalation in the anode, Li deposition on the anode surface was faster.
This suggested that battery internal short circuit can occur at SOC ≥
150%. At 155% SOC, the precipitated Li occupied most of the anode
surface. It was worth noting that the bumps resembling the shape of hills
were seen at 160% SOC, which were much larger than Li dendrites. This
Fig. 6. XRD diffraction patterns of the cathodes with different SOCs: (a) 10–90◦ ; (b) (003) peak; (c) (104) peak; (d) (101) peak; (e) Intensity ratio of (003) peak and
(104) peak as a function of SOC; (f) Crystallinity as a function of SOC; (g) Lattice constants as a function of SOC.
6
Journal of Power Sources 518 (2022) 230767
should be the product of the deposited Li reacting with the electrolyte
and anode, as can be confirmed with the anode SEM image at 165% SOC.
The holes on the surface were caused by the deposited Li reaction.
The SEM images revealed that as the progress of overcharging, the
cathode has undergone obvious decomposition reactions, whereas the
anode primarily produced Li dendrites and further reacted with the
electrolyte to produce Li compounds.
3.2.2. Changes in cathode crystal structures with different SOCs
The XRD patterns of the overcharged LIBs are illustrated in Fig. 6.
The cathode material underwent significant structural changes during
overcharging (Fig. 6a–e). A typical hexagonal structure with an R-3m
symmetry was observed at 100% SOC [47]. However, as overcharging
continued, the (003) peak and (104) peak position moved to a higher 2θ
value, as shown in Fig. 6b and c. The changes in lattice constant (Fig. 6g)
indicated that the slight increase in parameter a and considerable
decrease in parameter c caused the (003) and (104) peaks to upshift,
suggesting that the cathode underwent deformation during over­
charging. The significant decrease in parameter c indicated that the
layer spacing of O, Li and ordered Ni–Mn–Co decreased. This was
attributed to a fraction of Li being irreversibly deposited on the anode
surface during battery overcharging. In addition, the Li(Ni0.6Co0.2Mn0.2)
O2 cathode material was significantly delithiated, which caused the
collapse of the layered structure and resulted in a decrease in parameter
c. As shown in Fig. 6d, the (101) peak moved to the lower 2θ angels with
increasing charge SOC, and then kept stable between 130 and 150%
SOC, which corresponded to the H3 phase of Li(Ni0.6Co0.2Mn0.2)O2 [26].
N. Mao et al.
This indicated that the cathode material underwent a phase change
before 130% SOC and the structure remained stable for a short time.
Upon increasing the SOC beyond 155%, the H3 phase of Li(Ni0.6C­
o0.2Mn0.2)O2 was destroyed, indicating that the side reaction shifted this
balance.
As the SOC was increased, the intensity ratio of the (003) and (104)
peaks (I(003)/I(104)) decreased (Fig. 6e). This suggested that the cation
mixing progressed significantly. It is commonly accepted that an I(003)/
I(104) ratio greater than 1.2 is a good indicator of a layered structure.
Upon increasing the SOC beyond 150%, I(003)/I(104) decreased below
1.2, indicating that the cathode suffered significant damage. A simple
linear fitting demonstrated that I(003)/I(104) linearly depended on SOC,
as follows:
|I(003) / I(104)| = 3.389–0.015 |SOC|, r2 = 0.963
The crystallinity of the cathode material decreased linearly with
increasing SOC, as indicated by Eqn. (5) and illustrated in Fig. 6f. |
Crystallinity| and |SOC| are non-dimensional numbers and represent the
absolute values of Crystallinity and SOC, respectively. At 165% SOC, the
crystallinity was only 19.36%.
|Crystallinity| = 160.81–0.848 |SOC|, r2 = 0.9475
3.3. Chemical composition changes of LIBs during overcharge
3.3.1. Chemical changes at anode with different SOCs
The EDS results of the overcharged anode samples (see Fig. S5)
mainly detected the chemical elements C, O, Li, P and F. The presence of
O was attributed to lithium-oxide and the SEI, the presence of F was
ascribed to the PVDF binder and several SEI components, and the
presence of P was attributed to the SEI component of the carbon surface
[42].
The XRD patterns of the anode samples at 120%, 140%, 155% and
165% SOC and their corresponding photographs are presented in Fig. 7.
A small amount of metallic Li was deposited at 120% SOC. At 140% SOC,
more metallic Li precipitated and formed a Li plating layer, which
supported the emergence of point C in Fig. 4. The abundant holes similar
to “pinholes” observed on the surface of the Li plating layer at 155% SOC
were attributed to the consumption of Li. At 155% SOC, the temperature
at the battery surface was 56.7 ◦ C (Fig. 4). Considering that before
thermal runaway the temperature difference between the inside and
outside of the battery was approximately 20 ◦ C [47] and that Li reacted
with the electrolyte at approximately 68 ◦ C [4], we can deduce that, Li
might have reacted with the electrolyte to produce Li2CO3 at 155% SOC.
Furthermore, the SEI layer could have already undergone breakdown
owing to overheating [4,43]. The following chemical reactions have
occurred [4,47]:
2Li + C3H4O3 (EC)→Li2CO3 + C2H4
Fig. 7. XRD diffraction patterns of the anode with different SOCs.
Journal of Power Sources 518 (2022) 230767
2Li + C5H10O3 (DEC)→Li2CO3 + C4H10 (7)
It is worth noting that a large amount of black compound was pro­
duced at 165% SOC, which was assumed to be impurity-containing Li3N
or LiH. The EDS images indicated that N was absent from the anode
(Fig. S5). In addition, according to Kong et al. [48], no N2 was generated
inside the battery before rupture. Therefore, the presence of Li3N was
preliminarily ruled out. The (111) and (200) peaks in the XRD patterns
of the 165% SOC sample (Fig. 7b) corresponded to LiH (PDF #:
01-075-9538) [49,50]. Hence, we concluded that the black compound
was LiH, which might be a result of Li reaction with H2. H2 was pre­
sumed to originate from the reaction of the binder with LixC6, as shown
in Eqn. (8). We considered that LiH was formed via the hypothetical
reaction described by Eqn. (9). In addition, the metastable components
(4) of SEI can decompose exothermically at 90–120 ◦ C [4,51], according to
the reaction described by Eqn. (10).
–CH2–CF2 + Li→LiF + –CH = CF– + 0.5H2 (8)
2Li + H2→2LiH → (9)
(CH2OCO2Li)2→Li2CO3 + C2H4 + CO2 + 1/2O2 (10)
(5) When the side reactions progressed to a certain extent during over­
charging, the carbonate solvents underwent oxidation to produce H2O
[4,24], according to the reactions described by Eqns. (11) and (12).
2.5O2 + C3H4O3 (EC)→3CO2 + 2H2O (11)
6O2 + C5H10O3 (DEC)→5CO2 + 5H2O (12)
LiH is an unstable product that can react with H2O to produce
flammable H2 gas and release abundant heat during overcharging, ac­
cording to the reaction described by Eqn. (13). This can also be the
reason for the thermal runaway of LIBs.
2LiH + H2O→LiOH + H2 (13)
3.3.2. Chemical changes at cathode with different SOCs
The EDS mapping of the cathode overcharged at different SOCs
revealed the presence of C, O, F, Li, Ni, Mn, and Co (Fig. S6). C origi­
nated primarily from carbon black. The presence of O was primarily
attributed to the O atoms of NMC itself and the components of the
cathode electrolyte interfacial (CEI). The presence of F was ascribed to
the lithium salt in the electrolyte, which reacted with the cathode ma­
terial to form the CEI on the cathode surface. At SOC ≥ 150%, F was no
longer detected in the EDS mappings of the cathodes, indicating that the
CEI was destroyed, and the F-containing substances were dissolved in
the electrolyte. In addition, the presence of Be, which was observed in
the EDS mappings of the cathodes overcharged at 150% and 165% SOC,
was ascribed to the impurities in the electrolyte. When the battery was
(6) overcharged to a certain extent, the electrolyte reacted, and the Be-
7
N. Mao et al.
containing impurities could be adsorbed on the cathode surface. The
EDS mappings of Ni, Co and Mn revealed that at a SOC > 140%, the
transition metal content of the cathode decreased, especially at 165%
SOC. This was attributed to Ni, Co, and Mn compounds dissolving in the
electrolyte and reaching the anode during prolonged over-
deintercalation at high operating voltages [52].
The XPS spectra of the cathodes overcharged at different SOCs are
illustrated in Fig. 8. The atomic content of the cathodes is included in the
inset of table of Fig. 8a. The elements of battery with different SOCs
shifted, indicating that new chemical bonds and substances were pro­
duced during overcharging at different SOCs. Moreover, the Li content
decreased with increasing SOC, and the Li content was only 0.2 mol% at
165% SOC. This was attributed to the deposition of Li on the anode,
which caused a loss of Li at the cathode. This can lead to structural
damage, deintercalation, and a decrease in battery capacity. Most of the
changes in the XPS spectrum of the cathode occurred in the O1s and C1s
regions. Upon increasing the SOC, the F content decreased from 12.6 to
10.3 mol%, whereas the O content increased from 10.8 to 26.8 mol%.
These results indicated that organic solvents were more easily decom­
posed than Li salts during overcharging, which led to a decrease in the
intensities of the XPS signals of the F-containing compounds. Comparing
Ni2p, Co2p, and Mn2p, the atomic concentration of Co was relatively
low, which was attributed to the low sensitivity of the XPS instrument
for Co. Compared to Mn2p and Co2p, Ni2p had a more obvious shift with
different SOCs. Therefore, it was inferred that Ni ions were more reac­
tive than Co or Mn ions during overcharging.
The Ni2p, Mn2p and O2p XPS profiles of the cathode are presented in
Fig. 8b–d, respectively. The primary peaks at 875.51, 857.08, and
853.34 eV in the Ni2p XPS profile of the cathode overcharged at 100%
SOC were attributed to Ni3+, namely LiNiO2 [53,54]. The peaks at 651.1
and 639.6 eV in the Mn2p XPS profile of the cathode overcharged at
100% SOC were ascribed to Mn3+, which could be related to the pres­
ence of LiMnO2 [55], whereas the peaks at 649.3 and 639.3eV could be
attributed to MnO [56]. Therefore, the decomposition mechanism of
LiMnO2 during overcharging may be as shown in Eqn. (14).
LiMnO2→2MnO + 2Li + O2 +
(14)
Fig. 8. XPS spectra of cathodes with different SOCs: (a): full spectra; (b): Ni2p; (c): Mn2p; (d): O1s; (e): Li1s; (f): Co2p core levels.
8
Journal of Power Sources 518 (2022) 230767
The peaks at 533.8 eV and 531 eV in the O1s XPS profile of the
cathodes indicated the presence of R–CH2OCO2Li and LiOH, respec­
tively [57], which were the primary components of the CEI layer [4,20].
The distinct peak at 856 eV in the Ni2p XPS profile of the cathode
overcharged at 120% SOC was attributed to Ni2+ [58], whereas the peak
at 529.2 eV in the O1s XPS profile of the cathode overcharged at 120%
SOC corresponded to O–Ni2+ [59]. These results indicated that NiO
present in the cathode material, and we hypothesized that LiNiO2
decomposed according to the reaction described in Eqn. (15):
LiNiO2→2NiO + 2Li+ + O2 (15)
In addition, the small peak at 873.2 eV in the Ni2p XPS profile of the
cathode overcharged at 120% SOC could be attributed to Ni(OH)2 [60].
The peak at 531.2 eV in the O1s XPS profile of the cathode overcharged
at 120% SOC, which was ascribed to –OH groups, further confirmed the
presence of Ni(OH)2. It was hypothesized that Ni(OH)2 was the product
of the reaction of LiOH with NiO described by Eqn. (16):
4LiOH + 2NiO→ 2Ni(OH)2 + 4Li + O2 (16)
This indicated that the CEI film at the cathode underwent a side
reaction at 120% SOC.
The amount of Mn3+ converted into Mn2+ at 120% SOC was higher
than that at 100%, indicating that overcharging accelerated the
decomposition of LiMnO2.
It is worth noting that in the Ni2p spectrum of 140% SOC, in addition
to the peaks of Ni2+ and Ni3+, a peak of 870.3 eV appears, which could
be attributed to Ni0 (i.e., metallic Ni [61]). We hypothesize that the
metallic Ni could originate from reactions of Ni(OH)2 or NiO with
reducing gases such as hydrogen that come from reactions at anode [62,
63]. The possible reactions were proposed by Eqns. (17) and (18).
2Ni(OH)2 + 2H2→2Ni + 4H2O + Heat (17)
NiO + H2→Ni + H2O + Heat (18)
In conjunction with Fig. 4, it was found that after overcharging to
140% SOC, the battery temperature increased significantly. Therefore,
N. Mao et al.
the decomposition reactions of Ni(OH)2 were likely to generate abun­
dant heat and accelerate the rate of the side reactions. The Mn2p XPS
profile of the cathode overcharged at 140% SOC indicated that the
amount of Mn3+ that was converted into Mn2+ was higher than that of
the cathodes overcharged at lower SOCs, suggesting that overcharging
accelerated the decomposition of LiMnO2. The peaks at 529.25 and
530.43 eV in the O1s XPS profile of the cathode overcharged at 140%
SOC were ascribed to NiO [64] and Co–O [65], respectively, suggesting
that Co underwent an oxidation reaction and formed an oxide. The small
peak at 526.6 eV in the O1s XPS profile of the cathode overcharged at
140% SOC could be attributed to O–metal bonds. This finding combined
with the Mn2p XPS profile of the cathode overcharged at 140% SOC
suggested that MnO was present in the cathode material.
The peaks at 869.72 and 846.9 eV in the Ni2p XPS profile of the
cathode overcharged at 165% SOC revealed that the amount of NiO that
was reduced to metallic Ni increased as the SOC was increased from
140% to 165% [66,67]. Generally, metallic Ni is a catalyst that can
accelerate the subsequent reactions, such as the decomposition reaction
of the cathode and the reaction between the cathode and the electrolyte
[4,17,25]. The possible reactions are speculated in Eqns. (19)–(21):
LixCoO2→xLiCoO2 + 1/3(1-x)Co3O4 + 1/3(1-x)O2 (19)
2.5O2 + C3H4O3 (EC)→3CO2 +2H2O (20)
Li0.5CoO2 + 0.1C3H4O3→0.5LiCoO2 + 0.5CoO + 0.3CO2 + 0.2H2O (21)
Such reactions can release abundant heat and O2 to accelerate the
side reactions at the anode, leading to thermal runaway.
The primary peaks at 653.56 and 642.19 eV in the Mn2p XPS profile
of the cathode overcharged at 165% SOC were attributed to Mn4+ [68,
69]. In addition, the peak at 530.2 eV in the O1s XPS profile of the
cathode overcharged at 165% SOC [70] further suggested that MnO2
was produced. The side reactions associated with the production of
MnO2, could be described as follows:
2MnO + O2→2MnO2 (22)
LiMnO2→MnO2 + Li +
(23)
We hypothesized that MnO2 was produced via the reaction of MnO
with O2 or the decomposition of LiMnO2 at a large overpotential. In
addition, the disproportionation reaction of Mn3+ to Mn4+ and Mn2+
described by Eqn. (24) has been previously mentioned in the literature
[48]:
2MnIII→MnIV + MnII (24)
The XPS was less sensitive to the presence of Li and Co in the cathode
material, especially Co (Fig. 8e and f). The O1s XPS profiles of the
cathodes indicated that Co could be oxidized during overcharging,
which was consistent with the presence of CoO2 and CoO species re­
ported by MacNeil et al. [17,30]. Although there are noises in the Li1s
XPS signal, we can still see from Fig. 8e that the cathodes with 100% and
120% SOC should have Li1s peaks at 53.5 ev and 52.9 ev. The presence
of Li1s peaks at 53.5 ev and 52.9 ev are ensured when considering the
following aspects. Firstly, it can be seen from the O1s spectrum in Fig. 8d
that there were R–CH2OCO2Li and R–CH2OLi (both of which are part of
SEI film) which are Li-containing compounds at 100% and 120% SOC.
Secondly, in our previous research [71], we used inductively coupled
plasma optical emission spectrometry (ICP-OES) to quantitatively detect
the Li content of cathode materials after the overcharge of the ternary
battery (NCM). The Li content in the cathode material with 100% and
120% SOC was 25,236.8 ppm and 18912.4 ppm, respectively. However,
it is difficult to define which substance 53.5ev is attributed to, which
seems to be somewhere between metallic lithium and lithium ion [72,
73]. The binding energy of the peak shifts to 52.9 eV at 120% SOC,
which could be related to Li interstitials corresponding to the valence
state of incomplete oxidation [72,74]. No distinct Li peaks were
9
Journal of Power Sources 518 (2022) 230767
observed in the Li1s XPS profile of the cathode overcharged at higher
SOCs. This indicated that excess Li was deposited on the anode surface,
resulting in the consumption of the Li at the cathode. In addition,
because the detection depth of the XPS instrument for metals did not
exceed 3 nm, it was suggested that the Li compounds at the cathode were
present in deeper layers and could not be detected.
4. Conclusion
We systematically analyzed the physical and chemical changes of
LIBs during overcharging, including their thermal and electrical be­
haviors and the internal chemical reaction mechanisms.
Our results demonstrated that the charge rate directly affected the
thermal runaway behavior. Owing to the low amount of self-generated
heat at low charging rates, thermal runaway only occurred at charge
rates higher than 0.3C. The entire overcharge-to-thermal runaway pro­
cess was divided into four stages.
During Stage I, the voltage increased to 4.74 V, and the temperature
increased slowly to 31 ◦ C. The battery began to swell at SOC > 136%
SOC. During Stage II, the voltage increased to the Vmax (5.07 V) and the
temperature increased quickly to 39 ◦ C. Moreover, the battery under­
went significant expansion because of the production of gas. During
Stage III, the voltage decreased to 4.47 V because of the severe damage
to the electrodes. Furthermore, the battery temperature increased to
89.5 ◦ C because of the abundant heat released during the violent side
reactions. During Stage IV, the voltage increased to 4.93 V and the
temperature reached 97.9 ◦ C. Lastly, the battery ruptured at approxi­
mately 174% SOC and subsequently caught fire at 174.33% SOC. It only
took 20 s from rupture to thermal runaway. During overcharging, the
increase in battery internal resistance was primarily ascribed to the in­
crease in polarization resistance. The internal resistance increased
significantly at SOC > 120%.
Significant internal structural and chemical changes occurred at both
electrodes during overcharging. At 100% SOC, the LiMnO2 in the
cathode decomposed into MnO and Li+, however, the changes at the
anode were negligible. At 120% SOC, the LiNiO2 in the cathode
decomposed into NiO and Li+, and then NiO and LiOH reacted to pro­
duce Ni(OH)2. A small amount of Li precipitated on the surface of the
anode. Subsequently, at 140% SOC, metallic Ni was present in the
cathode material. This was the decomposition product of Ni(OH)2, and
the decomposition reaction generated a large amount of heat. Moreover,
a Li-plating layer emerged on the anode surface. Subsequently, the
precipitated Li reacted with the electrolyte at 155% SOC to form Li2CO3.
When the SOC reaches, the amount of more metallic Ni in the cathode
was higher than at 155% SOC, and LiMnO2 decomposed into MnO2. At
this high SOC, the anode underwent significant changes. The precipi­
tated metal Li reacted with H2 to produce LiH. LiH and metallic Ni
accelerated the side reactions and generated abundant heat and
combustible gas, which eventually led to thermal runaway.
This work provides a comprehensive experimental examination of
the behaviors and underlying mechanisms of LIBs overcharged at
different SOCs. The highest Vmax value should be regarded as the cut-off
point to prevent thermal runaway. During the design stage, battery
packaging material that can prevent rupture and effective additives can
be used to prevent the production of excess LiH and metallic Ni. Based
on this, BMS can optimize the design and operation of LIBs to reduce or
eliminate thermal runaway.
CRediT authorship contribution statement
Ning Mao: Conceptualization, Methodology, Validation, Investiga­
tion, Writing – original draft, Data curation. Teng Zhang: Formal
analysis, Writing – review & editing. Zhirong Wang: Methodology,
Writing – review & editing, Funding acquisition, Project administration.
Qiong Cai: Methodology, Writing – review & editing, Funding acqui­
sition, Project administration.
N. Mao et al.
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.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China [grant numbers 51874184], the Key R & D programs (Social
Development) in Jiangsu Province [grant number BE2016771], the Key
Natural Science Foundation in Jiangsu Province [grant number
18KJA620003], the Jiangsu Project Plan for Outstanding Talents Team
in Six Research Fields [grant number TD-XNYQC-002]. Teng Zhang and
Qiong Cai would like to acknowledge the funding support from Faraday
Institution LiSTAR Programme (EP/S003053/1, Grant FIRG014).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2021.230767.
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