Sustainable Materials and Technologies 39 (2024) e00852

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Sustainable Materials and Technologies

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

Reliable test by accelerating for gas evolution in cathode materials of

lithium-ion batteries
Sungmin Na a, Chanjoo Park a, Hyunjin An a, Kwangjin Park a, b, c, *
a
Department of Mechanical Engineering, Gachon University, 1342 Seongnamdaero, Sujeong-gu, Seongnam-si, Gyeonggi-do 13120, Republic of Korea
b
Department of Battery Engineering, Gachon University, 1342 Seongnamdaero, Sujeong-gu, Seongnam-si, Gyeonggi-do 13120, Republic of Korea
c
Koulomb, 1342 Seongnamdaero, Sujeong-gu, Seongnam-si, Gyeonggi-do 13120, Republic of Korea

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

Keywords: Lithium-ion batteries are widely used in modern electronic devices and Electric Vehicles (EVs) and play an
Gas evolution mechanism important role in various applications, but fire and explosion accidents continue to occur in Energy Storage
Lithium-ion battery Systems (ESSs) and EVs, which is an issue. Due to the material characteristics of the Li-ion battery, when
High-voltage
charging and discharging are repeated, gas is generated not only due to structural changes inside the cell, but
High-temperature
H2O injection
also due to various external factors. This can lead to an explosion accident of the battery cell. Therefore, gas
Pouch type cell generation in batteries is considered an essential problem to be solved for battery safety. However, accurate gas
generation comparisons are possible only when the gas generation conditions and processes of the battery are
established, and the conditions under which gas can be uniformly generated in the battery have not yet been
investigated. According to previous studies, the main causes of gas generation are considered as follows. 1)
Operating at high voltage range, 2) Operating at high temperature and 3) H2O present inside the cell. Therefore,
this study conducted a study on the possibility of reproducing the above tree gas generations, which are
considered to be a major cause of gas generation. Gas generation in high voltage operation and high temperature
operation was confirmed, but there was no reliable reproducibility. On the other hand, it was confirmed that H2O
inside the cell reproducibly generates gas. In addition, compared to the Al coating sample, a surface treatment
that suppresses gas generation caused by HF generation by H2O, it was reliably confirmed that more than 10% of
gas generation by H2O was prevented.

1. Introduction predict the gas generation environment [5,6]. To solve this issue, re­
searchers have explored the conditions under which gas generation
The increasing demand for high-capacity lithium-ion batteries, occurs in battery. These studies have revealed that gas generation does
driven by the growing use of electronic devices and electric mobility, not uniformly manifest under varying conditions. This variability pre­
underscores the necessity to enhance battery safety while advancing sents a challenge in detecting minor changes associated with gas gen­
their energy storage capabilities [1–3,65]. eration in the cell. To overcome this limitation, researchers have
The issue of gas generation in lithium-ion batteries has emerged as a employed specialized cells like DEMS (Differential Electrochemical Mass
crucial subject in the study of advancing high-capacity batteries while Spectroscopy) or OEMS (Online Electrochemical Mass Spectroscopy) to
enhancing their safety [4,5,63,64]. With the rise in mobility and elec­ experimentally analyze gas generation under controlled but unrealistic
tronic device usage in contemporary society, the demand for high- conditions [7,8]. However, an absolute predictive model for under­
capacity batteries has increased. As a result, research has been focused standing and analyzing gas generation in real-world, high-capacity cells
on materials like NCM a ternary compound, to meet this demand. that performed real cycling remains absent.
However, despite its high capacity, NCM faces limitations due to rapid So, we need tools to capture the gas generation inside the cycled
performance degradation and gas generation. So, there is a need for a battery cell in a real-world environment and conduct quantitative and
model that can identify the gas generation mechanism and accurately qualitative analysis. Our study addresses this by investigating gas

* Corresponding author at: Department of Mechanical Engineering, Gachon University, 1342 Seongnamdaero, Sujeong-gu, Seongnam-si, Gyeonggi-do 13120,
Republic of Korea.
E-mail addresses: [email protected] (S. Na), [email protected] (K. Park).

https://doi.org/10.1016/j.susmat.2024.e00852
Received 20 November 2023; Received in revised form 9 January 2024; Accepted 31 January 2024
Available online 8 February 2024
2214-9937/© 2024 Published by Elsevier B.V.
S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

Fig. 1. A schematic image of the gas measurement method.

generation under conditions known to accelerate the process, such as anode, respectively, using the welding machine (Wellcos, WC-TW-
high temperature and high voltage. Y kim et al. investigated that Li2CO3 300SJ). The z-folded electrode-separator compound was sealed in a
and LiOH, a type of lithium residuals presents on the surface when the pouch after adding 400 μL of electrolyte. The electrolyte for the pouch
internal temperature increases due to electrochemical cycling in a high- cell was composed of 1.0 M LiPF6 in EC:DEC (1:1 vol%) and added FEC 5
capacity Ni-rich NCM cell, decompose to cause an HF mediated reaction wt%. Manufacture of gas capture part for safe H2O injection and gas
[9,10]. collection in areas without electrodes as shown in SI. 8.
By comparing and analyzing results obtained under these conditions,
we gain insights into the scenarios in which gas generation occurs. In 2.2. Electrochemical performance
addition, the gas generation was compared and analyzed after acceler­
ating gas generation by injecting substances such as H2O present inside The charging/discharging process of the cell cycling sequence as
the cathodes and electrolytes directly from the outside. Through this, the shown in SI. 10. After stacking and sealing, a rest process was performed
direct effect on gas generation in the cell was identified. And also, R W for 12 h for electrolyte wetting. Thereafter, charging was performed at
Lindstrom et al. investigated that the generation of CO2 is highly related 0.1C for 3 h, and the gas generated in this process was removed and then
to the rise in the cell’s operating voltage. In particular, it was accelerated sealed again. This process is represented by degassing. After degassing,
from 4.15 V and reacted with the electrolyte from 4.2 V to 4.3 V to charging and discharging was performed at 0.2C to stabilize the cell, and
accelerate the ethylene evolution rate, which leads to acceleration of at this time, it was confirmed whether the cell was operating normally.
CO2 generation. It was also investigated that the generation of CO2 is This process is indicated by capacity check. After completing all the
acceleration by the reaction of oxygen generated from the cathode previous processes, the formation process was performed at a rate of
materials with the electrolyte during high voltage operation started 0.1C, and then the cycle was performed at 1C.
onset 4.55 V [ 11].
The generation of gas in Li-ion batteries lacks standardization. 2.3. Gas generation method
Despite numerous prior studies, gas generation does not always occur,
even when various conditions known to contribute to it, such as me­ The design of the gas generation and measurement method was
chanical cell failure, electrolyte decomposition, cathode oxygen release, implemented as shown in Fig. 1.
and Solid Electrolyte Interphase (SEI) layer form and breakdown, are
present [ 8,12–19,66]. However, a comprehensive analysis, both quan­ 2.3.1. High-voltage experimental
titatively and qualitatively, of potential gas compositions arising from It is difficult to experiment with high voltage in the existing charger
changing cell status due to charge/discharge cycles under typical and discharger because of safety conditions, so a charger and discharger
operating conditions is imperative. This necessitates the establishment was built directly based on ODA technologies (Battery Charge Discharge
of a consistent evaluation methodology that can be applied across Demo Software Ver 1.0.2). The voltage of the cell was observed through
various cell states [ 20]. the DC loader in real time by connecting the DC loader (LF 300-A), the
So, this study provides insight into the scenarios in which gas gen­ DC power supply (U8001A), and the charge/discharge jig. A cycle was
eration occurs within actual battery cells with gas generation tools, and carried out after setting a charging voltage•current (CV•CC), discharge
this study is expected to provide information for improving the safety voltage (CV), and time, and the thickness of the cell was checked every
and performance of high-capacity batteries. cycle whether gas was generated in the cell. In addition, the temperature
of the cell was measured through an infrared thermometer (GIS 500)
2. Experimental every cycle to prevent side reactions caused by a surge in temperature
within the cell. The charge was stopped at the point where the cell
2.1. Sample preparation thickness reached 5 mm.

LiNi0.88Co0.08Mn0.04O2, the cathode active material, was pur­ 2.3.2. High-voltage experimental
chased from Reshine New Material Co., Ltd. Single-sided coated NCM88 In order to increase the temperature, charging and discharging was
electrode composed of the active material (92 wt%), Super P (Timcal, 4 conducted in an oven that could increase the temperature up to 120 ◦ C.
wt%), and polyvinylidene difluoride (PVDF, 4 wt%) are cast on an The pouch cell volume was confirmed by increasing the temperature by
aluminum foil and used as the current collector. Graphite coated on 10 degrees, and charging and discharging stopped when the thickness
double-sides of copper foil was used as an anode. The N/P ratio reached 5 mm. In the high-temperature and high-voltage experiment,
(Negative / Positive) was set at 1.05. The separators and electrodes were the cut-off of each cell was set to 4.2, 4.35, 4.5, 4.65, 4.8, and 4.95 V in a
stacked with a z-folding machine (Wellcos WCR-ZS-M). Each cell con­ 0.15 V unit in a charger and discharger chamber at 55 ◦ C. To accurately
tained two cathode sheets, one anode sheet, and a 15 μm separator. check the amount of gas generated according to the voltage, the voltage
Aluminum and copper tabs were welded on top of the cathode and interval was set to 0.15 V.

2
S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

Table 1
The mechanism by which gas is generated by (a) the influence of water inside the pouch cell and (b) reaction with electrolyte or SEI layer.

(a)

2C3 H4 O3 (ECEC) + 2Li+ + 2e− →(CH2 OCO2 Li)2 + C2 H4 (1.1)

C3 H4 O3 (ECEC) + 2Li+ + 2e− →Li2 CO3 + C2 H4 (1.2)
2C3 H4 O3 (ECEC) + Li+ + 2e− + H+ →(CH2 OCO2 Li)2 + 2CO + CH4 (1.3)
(b) C5 H10 O3 (DECDEC) + 2Li+ + 2e− →Li2 CO3 + C2 H4 + C2 H6 (2)
2Li+ + (CH2 OCO2 Li)2 →2Li2 CO3 + C2 H4 (3)
Li2 CO3 + 2H+ →2Li+ + H2 O + CO2 ↑ (4.1)
Li2 CO3 + 2HF→2LiF + H2 O + CO2 ↑ (4.2)

2.3.3. H2O injection experimental 1260 ppm, 4535 ppm, 790 ppm, and 75 ppm, respectively. C2H4 and
To inject 50 μL H2O, it was directly injected into a pouch-type cell for C2H6 were generated through their reaction with H2 after the reduction
analysis using a syringe of 50 μL volume. To prevent the inflow and of electrolytes (e.g., Ethylene Carbonate (EC), Diethyl Carbonate (DEC)).
outflow of gas to the outside of the pouch after injection, the insulating While, Fig. 2(b) shows the Thermal Conductivity Detector (TCD) anal­
tape was attached back and front to the injection area. After injecting ysis graph, and N2, CH4, CO, and CO2 were detected 455 ppm, 1145
H2O, the insulating tape was attached again, and the syringe was pulled ppm, 2560 ppm, and 20,660 ppm, respectively. Co and CO2 were
out to prevent the electrolyte and gas from leaking as shown in SI. 9. generated together with a very small amount of hydrocarbons (e.g.,
After that, it was stored in a 45 ◦ C chamber for 2 h to generate gas. The C2H4O2− 2 , C2H4, C2H6) through the decomposition of EC and DEC, which
volume of the gas-generating cell was measured using the Archimedes act as additives within the electrolyte as shown in Table 1 (b) 1.1, 1.2, 2.
method, and then the gas was extracted and collected. The collected gas However, they have a large error bar due to the high difference in gas
was injected into GC (GC-2030, Shimadzu scientific.) and analyzed generated between cells as shown in Fig. 2 (a, b). Therefore, gas analysis
through TCD and FID detector. in the gas-generated cells was possible, but uniform evaluation of the
cells is difficult.
The main cause of gas generation was the decomposition of elec­
2.4. Coating process
trolyte and SEI layers. When the voltage exceeded 4.7 V, the electro­
lyte’s organic carbonates (EC, Propylene Carbonate (PC), Diethyl
The LiNi0.88Co0.08Mn0.04O2 (Reshine New Material Co., Ltd.) mate­
Carbonate (DMC), Ethyl Methyl Carbonate (EMC), etc.) were decom­
rial was coated with Al2O3 nano sized powder (Sigma-Aldrich) using a
posed and oxidized on the cathode surface during charging process
Spheric Coater (KM Tech, Korea), in which a rotating four-way coating
[6,23–25]. Since, these organic carbonate have a significantly higher
blade was placed 5 mm away from the wall. At a high rotational speed of
Highest Occupied Molecular Orbital (HOMO) potential at 4.7 V
3000 rpm, the 1.0 wt% Al2CO3 and Ni-rich NCM were subjected to shear
compared to Li/Li+ and a correspondingly reduced Lowest Occupied
stress and compressive force as they passed through the gap between the
Molecular Orbital (LUMO) potential at 1 V compared to Li/Li+. As a
container and blade. Owing to such force, the Al2CO3 acquired sufficient
result, they were caused to decompose at a cathode of a voltage of 4.7 V
thermal energy to fuse onto the surfaces of the NCM particles, thereby
or more, while being reduced at an anode of a voltage of 1 V or less
enabling coating.
[22,26,27].
To compare the material characteristics generated inside the cell
3. Results when gas is generated due to the high voltage operation, the rested cell
without an electrochemical test (refer to non-gassing cell) and the gas
3.1. Operating condition at high voltage range generated by the 6 V charge (refer to gassing cell) were disassembled
and analyzed as shown in Fig. 2 (c, d). Ni, CO, and Mn, which are NCM
The pouch-type cell was charged with a constant current until gas elements, were detected equally in non-gassing cells and gassing cells as
was generated. Due to the gradual rise of the voltage generated in the shown in SI. 2 (a, b). In addition to NCM, P and F elements were
charging cycle, it swelled to a thickness of 5 mm of the cell with gas detected, which can be expected to be generated due to the decompo­
generation. The pouch-type cell was not burst and sufficient gas for sition of Li2CO3 and LiF, which were major components of the SEI layer
analysis was generated, and charging was continued until it was swollen [7,28]. However, it was difficult to see it as an accurate gas generation
to a thickness of 5 mm. As shown in SI. 1, The shape of the pouch cell factor because it overlapped with the elements of active material (NCM),
was initially flat at a low voltage (3.0–4.0 V), but as the charging voltage carbon additive (Super P), and binder (Polyvinylidene fluoride (PVdF)
increased, the pouch cell began to swell in 23 min as shown in SI. 1. To that make up the cathode. In contrast, aluminum (Al) was an element
investigate the range and factors of gas generation at high voltage, as demonstrating a distinct differentiation between non-gas and gas cell.
known in previously studied gas generation, gas generation was When the voltage exceeded 5 V, aluminum (Al), the substrate, partici­
confirmed and analyzed while gradually increasing the charging voltage pated in the reaction and acted as one of the causes of gas generation as
from 3.0 V of the pouch cell [5,21,22]. The gas generation voltage shown in SI. 2 (b) [29]. Xueyuan Zhang et al. investigated that
confirmed through the DC loader was 5.76 V as shown in SI. Table 1 and aluminum current collectors are susceptible to localized corrosion in
it was also checked that the voltage range was consistently maintained LiPF6 battery electrolytes because aluminum is susceptible F [29].
between 5.75 V and 5.78 V. The gas generated voltage was higher than
the previously known gas generated voltage [21,22]. The generated gas PF6 − →PF5 + F− (1)
was captured and analyzed to find the cause of the gas generation by Gas
Chromatography (GC). Fig. 2(a) shows the Flame Ionization Detector PF5 + H2 O→PF3 + 2HF (2)
(FID) analysis graph, and CH4, C2H6, C2H4, and C3H8 were detected

3
S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

High concentration of HF in the electrolyte of the microcaps pro­ reducing the gas generation time by more than 1/3 compared to the 25
duced from Eq. 1, 2 causes aluminum to corrode [13,30,31]. The anode ◦
C. It has been confirmed that gassing is accelerated at high tempera­
was mainly composed of carbon (Super P) as shown in SI. 3, and the F tures, which greatly affects the gassing of actual pouch cells. However,
content increased by 9.9% due to the emergence of impurities in gassing when the same experiment was repeated, there was a problem in that it
cell compared to non-gassing cell. Specifically, it was increased due to was difficult to quantify the amount of gas generation because the gas
the formation of lithium ethylene carbonate (LEDC) and lithium fluoride generation time was not constant. Therefore, additional experiments
(LiF) generated by decomposition of the EC and LiPF6 [7,8]. LEDC, a were conducted under high-temperature and high-voltage conditions to
fundamental element of the SEI layer formed within the anode, origi­ quantify gas evolution. Fig. 3 (a) exhibit the amount of gas generated
nated from the reduction of the electrolyte as shown in Table 1 (b), 1.1 according to voltage at high temperatures (55 ◦ C) by using Archimedes’
[5,32]. Similarly, Li2CO3, a critical element of the SEI, derived from principle as shown in SI. 6 [12]. The voltage range was set in 0.15 V
electrolyte reduction as shown in Table 1 (b), 1.2 [33,34]. The SEI layer intervals, starting from the standard NCM battery operating condition of
decomposed and regenerated during the initial charge/discharge cycle 4.2 V up to the battery’s stable voltage of 4.95 V [21,28]. Gas was
was found to induce gas generation as shown in Table 1 (b), 3, 4.1, 4.2 generated as the voltage increased, especially from 4.65 V. SI. 7 (a-c)
[35]. Furthermore, the oxygen content exhibited a 48.9% increase in shows the charge profiles of the 4.65, 4.8 and 4.95 V samples with a
gassing cell compared to non-gassing cell, it was attributed to the for­ sharp increase in gas volume. All samples were charged in CV mode for a
mation of oxide-derived impurities (Li2O, Li2CO3, TMO) simultaneous longer time than CC during charging and excessive gassing was observed
with gas production [36]. As shown in SI. 4, in the separator, the dif­ in real time. This is because the electrolyte 1 M LiPF6 in EC:DEC = 1: 1
ference between non-gassing cells and gassing cells was evident. The used to fabricate the pouch cell as electrolyte was electrochemically
separator of the gas cell was blackened by the formation of many im­ decomposed exceeding its decomposition voltage of 4.5 V [45]. As a
purities on the surface. The composition of impurities was mainly rep­ result, the decomposition of the electrolyte shows remarkable gas gen­
resented by C, O, and F, which were generated by SEI decomposition eration at 4.65, 4.8, and 4.95 V.
containing Li2CO3 and LECD, and CH4 and C2H4 are generated as Fig. 3 (b-d) show the charge-discharge profile at 4.2 V, 4.35 V, and
charge/discharge progress as shown in Table 1 (b), 1–3 [37]. The Al and 4.5 V. In these voltage ranges, the cycling processes proceeded normally
O elements were detected by coating the separator for the purpose of without problems related to electrolyte decomposition. However, as the
cycle enhancement. cycle progressed, the sample at 4.5 V showed rapid morphological
As a result, it was demonstrated in the experiment that gas was changes. Fig. 3 (b-d) presents the dq/dv plot employed to investigate the
generated through the interaction of electrolyte, SEI layer, and Al-based root cause of the degradation resulting from this voltage elevation. In
oxidation as voltage increases. It was noteworthy that gas generation Fig. 3 (b-d), depending on each voltage area, four distinct peaks can be
appeared in a voltage range exceeded the established electrolyte discerned. The initial peak results from the lithium intercalation into
decomposition voltage (4.7 V). The trends in voltage and gas generation graphite [46,47]. Following that, the next three peaks correspond to the
did not exhibit linearity, displaying significant variability among cells. phase transitions in the positive electrode: from hexagonal (H1) to
However, it is difficult to distinguish gas generation by voltage range, monoclinic (M), then M to H2, and finally H2 to H3, respectively
and accurate gas analysis inside the cell is difficult because most of the [46,47]. Among them, the H2-H3 phase transition is uniquely observed
gas generation is due to other incidental reactions caused by high in Ni-rich NCM where nickel exceeds 80%. This specific phase transition
voltage range. induces detrimental lattice contraction along the c-axis [16,46]. This
contraction not only leads to capacity/voltage degradation and irre­
versible structural damage resulting in anisotropic lattice volume
3.2. Operating condition at high temperature changes and subsequent micro-cracking but also has implications for
safety, as it can trigger oxygen release due to degradation, potentially
The Arrhenius equation, one of the fundamental principles of elec­ leading to internal gas generation and battery explosion risks [48]. In
trochemistry, is given by Eq. (1) [38,39]. the dq/dv plot, no significant change was found with cycle progression
for the 4.2 V and 4.35 V samples as shown in Fig. 3 (b-d). However, in
k = Ae− Ea /RT
. (1)
the 4.5 V sample, it was clearly observed that the H2-H3 peak shifted
k is the reaction rate constant. A is the pre-exponential factor (or toward the higher voltage as the cycle progressed, and its intensity also
frequency factor), which represents the reaction rate when all the decreased. While evident change occurred in the H2-H3 peaks, the
molecules collide. Ea is the activation energy, which represents the initial peak associated with the anode remained relatively stable. This
minimum energy required for the reaction to proceed, R is the gas deterioration of the cathode causes gas generation by the following
constant (8.314 J•mol− 1•K− 1) and T is the absolute temperature, equation [8,49].
expressed in Kelvin (K). In this equation, the key factor is the correlation
2Li2 CO3 →4Li+ + e− + 2CO2 + 1 O2
between the reaction rate and temperature. As the temperature rises, the
reaction rate increases, whereas a decrease in temperature results in a
21 O2 + (CH2 O)2 CO→2CO2 + CO + H2 O
reduced rate of reaction. In this regard, an increase in the temperature of
the battery leads to an increase in the electrochemical reaction rate, Deterioration of the cathode causes release of oxygen within the
which accelerates the decomposition of the SEI/CEI layer and side re­ structure, which exists as active oxygen inside the battery. These active
actions at the anode/cathode [7,40]. Therefore, elevated temperatures oxygens cause CO and CO2 gas generation by reaction with EC and can
can cause thermal runaway in batteries due to amplified gas formation be a source of additional gas generation through H2O formation
and accelerated reactions, increasing the risk of explosion [41–43]. In [8,32,50]. Therefore, excessive CO and CO2 generation can be expected
practice, tests are mainly conducted at 45 ◦ C and 1C to evaluate the cycle to be caused by the deterioration of the cathode. This indicates that the
retention and safety in practical applications such as electric vehicles cathode degradation was the main factor to the observed performance.
[44]. However, in this study, a temperature of 55 ◦ C was selected to However, as demonstrated in Fig. 3 (a), although electrochemical
achieve more dramatic results. SI. 5 shows the gas evolution results by changes due to cathode degradation are evident, it is difficult to deter­
temperature at 25, 55 ◦ C. The gas generation time was measured based mine the effect of the cathode on gas generation due to decomposition of
on the time when the gas bag thickness of the battery was 5 mm, and it the electrolyte.
was confirmed that the gas generation time was 1 h 45 min and 32 min
for the samples at 25 ◦ C and 55 ◦ C, respectively. It was confirmed that
the 55 ◦ C sample accelerated gas generation at high temperatures by

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S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

3.3. H2O injection 3.4. Al coating on the surface of the cathode materials

Most previous studies emphasize the electrolyte - H2O reaction as the Analysis was performed using the H2O injection tool mentioned
main factor of gas generation in Li-ion batteries due to H2O that may above to determine how the composition change according to the
exist inside the cell, however other factors like the release of oxygen due electrochemical reaction occurring inside the cell after the charge/
to cathode degradation as indicated in Table 1 (a), and reactions discharge cycle affects the generation of gas. To analyze the effect of
resulting from the formation and disintegration of the Cathode Elec­ composition change inside the cell on gas production, conducted coating
trolyte Interphase (CEI) layer as depicted in Table 1 (b) are equally on the surface of the Ni-rich NCM. There are many methods such as
important [5,31,51–53]. Especially in Ni-rich NCM, the presence of doping, electrolyte additive, etc. [28,56–60] that suppress the gas gen­
lithium residual, such as Li2CO3, on the cathode material’s surface, eration of the Ni-rich NCM cathode cell, but among them, Al2O3 surface
which can form from the manufacturing or storage, may initiate elec­ coating is known to form stable AlF3 on the surface of the active mate­
trochemical collapse around an onset potential of approximately 3.8 V, rials to prevent HF formation, which is one of the most fatal problems for
leading to gas production [14,15,54]. In Li-ion cells using Ni-rich NCM Ni-rich NCM [56,58]. In addition, Al2O3 surface coating is reported to
as a cathode for various reasons above, gas is generated by reacting with have a great effect on reducing the generation of gas inside the cell by
H2O in various ways. As shown in SI. 8, in order to collect gas, a gas suppressing side reactions that may occur when the Ni-rich NCM active
collection bag was made by ensuring a sufficient space in a part without material and the electrolyte directly meet, thereby effectively
an electrode of the pouch cell to charge/discharge cycling. comparing gas generation with Pristine Ni-rich NCM materials.
An investigation into the optimal conditions for gas generation in Fig. 5 (a, b) demonstrates the SEM images of pristine Ni-rich NCM
cathode materials at various States of Charge (SOC) was carried out by and Al coated NCM particles. As shown in Fig. 5 (a), in the Pristine
introducing H2O. Therefore, we generated gas by injecting a stoichio­ sample, there are many spaces between primary particles that can cause
metric amount of 50 μL of H2O to react sufficiently well with EC, DEC side reactions due to the penetration of electrolyte into the cathode
and FEC contained in the internal electrolyte [31,51,55]. Fig. 4 (a) active material surface. On the other hand, as might be seen from Fig. 5
shows the amount of gas generated according to the SOC of the after (b), it might be seen that Al2O3 material is well coated on the surface of
capacity check cycled, 1st cycled and 50th cycled samples, respectively, the active material, and the surface of the active material is sooth by
when H2O is injected by using Archimedes’ principle [12]. Many pre­ using a mechano-fusion method. This prevents direct contact of the
vious studies have investigated that a higher voltage accelerates gas active material with the electrolyte and suppressed a side reaction and
generation in the Li-ion batteries [21,22,26]. Correspondingly, at a formed AlF3 on a surface, thereby preventing HF that might be produced
100% SOC with the highest voltage potential, after capacity check by Ni-rich NCM reaction with the electrolyte [58].
cycled, 1st cycled samples generated the most gas. However, gas was not Fig. 5 (c) depicts the electrochemical capacity check cycle profiles of
generated in the after 50th cycled sample, whereas a relatively small pouch-type cell cycled between 3.0 and 4.2 V under 0.2C / 0.2C con­
amount of gas was generated in SOC 0%, but gas was generated in all ditions. The discharge capacity of Pristine sample was 107.72 mAh and
samples, so all subsequent cells were injected with H2O at SOC 0% to Al 1.0 wt% coated sample was 106.92 mAh, it might be thought that
generate gas [55]. Moreover, this approach provides insight into the Al2O3 was coated on the surface of the active material and acted as a
cathode materials in the fully intercalated state of Li+ ions. It facilitates resistance layer, affecting the electrochemical performance [58,60].
the evaluation of how by-products from surface degradation, CEI gen­ Fig. 5 (d) shows the cycling performance under 1.0C / 1.0C at 45 ◦ C.
eration and degradation at the cathode affect the magnitude and Pristine exhibit 88.25% after 50th cycles, whereas the Al2O3 coating Ni-
composition of the generated gas [8,44]. rich NCM sample exhibit 90.97% of cycle retention. Coated sample show
As shown in Fig. 4 (b, c), in order to analysis the composition of gas superior electrochemical performance, and it is widely known through
generated in accordance with the cell charge/discharge cycle, the gas previous studies that Al present on the surface reacts with lithium re­
generated by injecting H2O at SOC 0% state after capacity check cycle, siduals on the surface of the Ni-rich NCM to form ion conductive lithium
1st cycled and 50th cycled samples were collected, and GC analyzed. aluminate, which facilitates efficient ion transfer. The effective protec­
Fig. 4 (b) shown a FID analysis graph, and it can be seen that CH4, C2H6 tion of the surface layer has further been confirmed with pouch type cell
and C2H4 in the after 50th cycled sample were 616 ppm, 1900 ppm and electrochemical test [59,60].
3400 ppm, respectively, and CH4, C2H6 and C2H4 generated in the cell Many previous studies have shown that Al coating effectively pre­
after 1st cycled increased by almost over 100% compared to 643.3 ppm, vents HF generation compared to Pristine Ni-rich NCM, resulting in less
900 ppm and 2570 ppm, respectively. In addition, in the TCD analysis gas generation. However, both pristine and Al coating samples did not
shown in Fig. 4 (c) investigated a 500% increase in CO2 gas generation generate gas after 50th cycles, so the effect of coating could not be
from 14,580 ppm to 70,950 ppm in after 50th cycled sample compared confirmed. Thus, the H2O injection method mentioned above was used
to after 1st cycled sample, respectively. In Li-ion batteries, the effect of to analyze the degree of gas generation depending on the active mate­
H2O has mostly been evaluated to be the effect of SEI layer formed on rials. Gas was forcibly generated by injecting 50 μL of H2O after 50th
the anode materials during cell formation cycle. However not only that, cycles using Pristine and Al coating samples in pouch cells. As can be
but a factor that may significantly affect both the gas generation seen from Fig. 6 (a) using Archimedes’ principle, Al coating samples
mechanism and the degree of the gas generation chain reaction is the showed a 12% decrease in gas generation compared to Pristine samples,
type and status of cathode materials in the Li-ion batteries, particularly while Pristine samples generated 4.17 mL of gas on average and Al
the electrocatalyst activity on the surface of the oxide [17,46]. Fig. 4 (b, coating samples generated 3.69 mL of gas on average, respectively. It
c), which analyzed the gas after the electrochemical of the real-world Li- can be seen that Al coating, known to prevent HF generation inside the
ion battery cell, not just a special cell for analyzing the composition of cell, acts effectively on the surface of Ni-rich NCM, dramatically
gas generated during the initial charge and discharge cycle, supports this reducing the amount of gas generated even though H2O, which accel­
as evidence. erates gas generation, was injected [8,31,32,58]. In addition, when
In the high voltage and high temperature conditions, which are the comparing the composition of the forced gas of the cells through GC
operation conditions set to determine the cause of gas generation analysis, as shown in Fig. 6 (b, c), it was confirmed that most of the gases
mentioned above, gas generation was not uniform due to various were reduced in Al coating sample compared to pristine in both FID and
problems as well as cathode problems, whereas in the samples generated TCD analysis. In particular, C2H6 and C2H4 produced by reacting with a
by injecting DI water, gas was generated in a tendency as shown in Fig. 4 carbonate-based electrolyte were reduced by 24.6% and 15.9%,
(a-c). Through this, it was confirmed that gas analysis with small de­ respectively, compared to Pristine, and CO2 generated by the influence
viations between cells is possible. of active oxygen released from the surface of Ni-rich NCM was reduced

5
S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

Fig. 2. Components of gas generated at high voltage (a) FID, (b) TCD and images of internal electrode, substrate and separator of pouch cell (c) only rest (non-gassing
cell), (d) after 6.0 V charge (gassing cell).

by 50% [5,8,31,32,61,62]. Through DI water injection, gas could be 4. Conclusion

generated and analyzed in a short cycled cells that gas was not generated
naturally, and through this, the difference in gas generation character­ In this study, high-temperature and high-voltage operating condi­
istics between samples could be compared. tions known to generate gas evolution based on the previous studies
were performed to quantify gas evolution for battery gas analysis. As

Fig. 3. (a) Pouch cell volume change plot according to the voltage range, First charge/discharge curves and dq/dv plot of the pouch cell, (b) Cut-off at 3.0–4.2 V, (c)
Cut-off at 3.0–4.35 V, (d) Cut-off at 3.0–4.5 V.

6
S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

Fig. 4. (a) Amount of gas generation after 50th cycles according to SOC 100, 50 and 0% and the content of gas compositions from the cycled and H2O injected pouch
cell after 50th cycles analyzed by (a) FID, (b) TCD.

Fig. 5. SEM images of (a) pristine (b) Al coating samples and EDS mapping of Al, Electrochemical performance testing of pouch cell. (c) charge-discharge plot of
Pristine and 1 wt% Al coating samples at 45 ◦ C in the voltage range of 3.0–4.2 V at 0.2 / 0.2C rate for capacity check, (d) cycle retention of Pristine and 1 wt% Al
coating samples at 45 ◦ C in the voltage range of 3.0–4.2 V at 1.0 / 1.0C rate.

reported in the previous studies, accelerated gas generation was battery cell to induce gas generation serves as an effective method for
observed in high-temperature and high-voltage operating conditions. expediting reactions involving trace amounts of water within the cell.
However, repeated experiments have revealed that gas evolution is not This technique enables a comprehensive comparison and analysis of the
uniformly consistent, suggesting the need for a tool to quantify gas diverse range of gases that may be generated through various by-product
evolution for accurate battery gas analysis. pathways at each component of the Li-ion battery. These pathways
The approach involving controlled water injection into a Li-ion encompass oxidation reactions as well as processes involving the CEI

Fig. 6. (a) Amount of gas generation after 50th cycles of Pristine and Al coating and the content of gas compositions from the cycled and H2O injected pouch cell
after 50th cycles analyzed by (a) FID, (b) TCD.

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S. Na et al. Sustainable Materials and Technologies 39 (2024) e00852

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