Journal of Energy Storage 56 (2022) 105905

Contents lists available at ScienceDirect

Journal of Energy Storage

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

Research papers

In situ Raman investigation on gas components and explosion risk of

thermal runaway emission from lithium-ion battery
Qingsong Zhang a, Tiantian Liu a, *, Chaolong Hao a, Yirun Qu a, Jianghao Niu a, Qiong Wang b,
Da Chen a, *
a
Aircraft Fire and Emergency Research Institute, Civil Aviation University of China, Tianjin 300300, China
b
College of Science, Civil Aviation University of China, Tianjin 300300, China

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

Keywords: The gas emission of lithium-ion battery thermal runaway (LIB-TR) is of great significance for the early warning
Lithium-ion battery and safety assessment of TR. A Raman spectroscopy methodology for in-situ real-time measurement of LIB-TR gas
Thermal runaway composition and explosion risk was proposed in this paper. The TR gas released by commercial 18,650 LIBs
Raman spectroscopy
during external heating abuse was used to study its compositions at different states of charge (SOC) and at­
Vent gas
Explosion limit
mosphere. The lower explosive limit (LEL), upper explosive limit (UEL) and explosive limit range (ELR) were
calculated based on the gas composition detection results of Raman spectrum. The results show that Raman
spectroscopy can detect organic solvent vapor (OSV) immediately when the safety valve is opened. When the TR
occurs, the proportion of CO, CO2, H2, CH4, C2H4, and C3H6 increases rapidly. SOC and atmosphere directly
affect the explosion characteristics of TR gas. In air atmosphere, LEL, UEL and ELR increase with the increase of
SOC, and the explosion risk of TR gas in nitrogen atmosphere is lower than that in air atmosphere. The results
reveal that Raman spectroscopy presents a promising tool for the early detection of LIB-TR and the explosion risk
assessment of TR gas.

1. Introduction
At present, one of the main bottlenecks limiting the applications of
lithium-ion batteries (LIBs) is the potential danger of thermal runaway
(TR) [1]. In recent years, the accidents caused by LIB-TR rose sharply
with the increasing applications of LIBs, posing a serious threat to the
safety of users’ lives and property [2]. Therefore, it is necessary to make
a fundamental study of the TR risk, and then develop appropriate
methods to realize the early warning of TR.
LIBs under abusive conditions can lead to an unexpected rise in
temperature. If the temperature is not effectively controlled, the reac­
tion between the materials inside the battery will intensify, producing a
large amount of gas and releasing heat, resulting in TR [3–6]. It is
noteworthy that most of the gases generated by the reactions are
combustible. When the gases exhausted from the battery accumulate to
a certain degree, there will be a potential explosion risk [7–9]. In
addition, the research shows that before the actual TR occurs, the gas
sensor can detect the fault signal earlier than the voltage sensor and
temperature sensor, and detecting the fault signal in advance can
improve the safety of LIB application [10]. In this regard, the research on
the exhaust behavior of LIBs and the explosion characteristics of exhaust
gases is of great significance to the selection of characteristic gases for
early detection and evaluating the explosion risk of gases.
In the conventional gas detection technology, gas chromatogra­
phy–mass spectrometry (GC–MS) is widely used in TR gas detection
because of its high detection sensitivity and good repeatability. Fourier-
transform infrared spectroscopy (FTIR) analyzes the gas composition
and concentration information through the position and intensity of the
absorption peak in the spectrogram, which has the advantages of fast
detection speed and low detection cost. Furthermore, acidic gases such
as HF can be absorbed with saturated aqueous sodium hydroxide solu­
tion and measured by Ion Chromatography (IC). Table 1 lists a few ex­
amples of experimental research on gas detection of LIBs or LIB internal
materials. According to Table 1, thermal abuse triggered TR is widely
used in LIB safety research. The main gases of TR include CO2, CO, H2,
hydrocarbons and organic solvents, and most TR gas components are
flammable.
In addition, some researchers have studied the explosion limit of
mixed gases according to the analysis results of battery TR process

* Corresponding authors.
E-mail addresses: 2019071042@cauc.edu.cn (T. Liu), chenda@cauc.edu.cn (D. Chen).

https://doi.org/10.1016/j.est.2022.105905
Received 25 March 2022; Received in revised form 6 August 2022; Accepted 17 October 2022
Available online 21 October 2022
2352-152X/© 2022 Elsevier Ltd. All rights reserved.
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

Nomenclature FTIR Fourier-transform infrared spectroscopy

GC Gas Chromatography
CH4 Methane H2 Hydrogen
CO Carbon monoxide IC Ion Chromatography
CO2 Carbon dioxide LEL Lower Explosion Limit
C2H2 Ethyne LMO LiMn2O4
C2H4 Ethylene LPF LixFePO4
C2H4O Ethylene oxide LTO Li4Ti5O12
C2H6 Ethane MS Mass Spectrometry
C3H6 Propylene n Molar amount
C3H8 Propane n0 Initial amount of gas in the chamber
C4H6 1,3-butadiene N2 Nitrogen
C4H8 2-methyl propene NCA LixNiyCozAl1-y-zO2
C4H10 n-butane NMC LixNiyMnzCo1-y-zO2
C5H8 1-Pentyne O2 Oxygen
C5H10 1-pentene OSV Organic solvent vapor
C5H12 n-pentane P Internal pressure of the chamber
C3H6O3 Dimethyl carbonate PVDF Polyvinylidene fluoride
C4H8O2 Ethyl acetate R Gas constant
C6H6 Benzene SEI Solid electrolyte interphase
C6H12 2-methyl-1-pentene SOC State of Charge
C7H14 n-heptene SVO Safety valve opened
C8H8 Styrene TR Thermal runaway
DMC Dimethyl carbonate T1 Battery surface temperature
EA Ethyl acetate T2 Gas temperature
EC Ethylene carbonate UEL Upper Explosion Limit
ELR Explosion limit range V The chamber volume

[24–27]. Li et al. [28] studied the combustion limit and flammability
range of exhaust gases from LixNiyCozAl1-y-zO2 (NCA) and LixFePO4
(LPF) batteries, and found that the exhaust combustion risk of LPF
battery under the same SOC is lower than that of NCA battery. Chen
et al. [29] calculated the gas explosion limit of the battery TR under
different SOCs, ambient temperature and external heating temperature
using the theoretical formula, and then compared the calculated results
with the FRTA explosion limit instrument.
The current researches mainly focus on the gas components and
explosion limit after LIB-TR. Nonetheless, the exhaust of LIB-TR is a
continuous process, and the gas components varied with time quickly.
Presently, researchers customarily used GC–MS, FTIR and gas sensors to
analyze the gas components, promoting the fundamental understanding
of the LIB-TR mechanism. However, some disadvantages limits the
further applications of these tools in evaluating the LIB-TR. GC–MS is
not capable of continuously monitoring the gas components emitted by
LIB-TR [30], while FTIR is not capable of detecting diatomic synuclear
gases such as H2, N2 and O2 [31]. As for the gas sensors, the sensitivity
and selectivity combined to limit their applications in LIB-TR, which
may result in a significant measurement error. Moreover, the explosive
limits of LIB-TR varies with the exhaust gases from sample to sample,
thus requiring an in-situ real time tool to detect the gases generated from
each LIB-TR process accurately and simultaneously.
In the present work, Raman spectroscopy strategy was developed for
in-situ analysis of mixed gases generated from each LIB-TR process, in
which the Raman system was custom designed to fit TR experiments on
batteries with different SOC states by external heating in both of air
environment and nitrogen environment. With the combination of
multivariate calibration methods, Raman spectroscopy is capable of
detecting six main gas components produced by TR in real time,
providing a unique advantage to evaluate the explosion limit accurately.
Meanwhile, the gas components generated by the LIB-TR were also
analyzed by GC–MS for reference. Based on the gas analysis results of
each LIB-TR process, the parameters of lower explosion limit (LEL),
upper explosion limit (UEL) and explosion limit range (ELR) were
calculated with Le Chatelier formula accurately. These results provide
sufficient information to evaluate the effects of environment and SOC on
the explosive characteristics of each TR in individual battery, making
the Raman spectroscopy capable of the early detection of LIB-TR as well
as evaluation of the explosion risk of exhaust gases.
2. Experimental
2.1. Samples
18,650 commercial LIBs were used as the experimental sample in this
study. The specific parameters of the battery are shown in Table 2. The
batteries were charged and discharged through the CT3001d battery
charge and discharge test device (Lanhe CT3001d, Wuhan Land Elec­
tronic Co. Ltd., China). The batteries were discharged to the cut-off
voltage of 2.75 V at the discharge rate of 0.2C (520 mA), the batteries
with 25 %, 50 % and 75 % SOC are charged at the charge rate of 0.2C
(520 mA), the batteries with 100 % SOC were charged to 4.2 V at the
charge rate of 0.2C (520 mA), and then were charged at constant voltage
until the current were reduced to 0.02C (52 mA). In order to maintain
the stability of the batteries, place it in a 25 ◦ C incubator for 24 h after
charging and discharging. Subsequently, the LIB was placed at an
incubator with a temperature of 25 ◦ C for 24 h to maintain their stability
after charging.
2.2. Experimental apparatus
Fig. 1 shows the principle of the LIB gas analysis apparatus. The
volume of the TR chamber is 5 L, which is sealed by bolts and gaskets.
The battery was heated by an unclosed circular heating ring with an
inner diameter of 18 mm and a height of 65 mm, which could provide
40 W heating power. After the battery was sleeved into the heating ring,
a width of 5 mm would be reserved. The K-type armored thermocouple
was placed on the part of the battery surface not covered by the heating
ring to measure the battery surface temperature (marked as T1), and

2
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

Table 1 suction port and close the exhaust port, and use the vacuum pump
Summary of research on gas production of LIBs or LIB internal materials. The (Model 2XZ Sliding Vane Rotary Vacuum Pump, Nanjing Hansu Motor
abbreviation of cathode material represents the Lib using the cathode material as Co. Ltd., China) to pump the pressure in the experimental chamber and
the experimental object. the gas circulation pipeline to 0.02 MPa (absolute) through the suction
Reference Test object Abuse test Atmosphere Gas detected port. Then close the suction port and connect it to the nitrogen cylinder
Yuan [11] LPF Thermal Air H2,CO,CO2,CH4, (99.99 % N2). Open the suction port and the valve of nitrogen cylinder,
NMC abuse C2H2,C2H4,C2H6 and then open the exhaust port for 5 min of purging. Repeat the above
LTO operation three times to ensure that there is nitrogen atmosphere in the
Larsson LCO Thermal Air CO,HF, organic experimental chamber and gas circulation pipeline.
[12] abuse carbonates
Zhang [13] NMC Thermal Nitrogen H2,CO,CO2,CH4,
When the battery was heated, the gas sampling pump was turned on
abuse C2H2,C2H4,C2H6, to circulate the gas in the TR chamber occurred. The constant pressure
C3H4 valve was used to control the pressure stability of the gas pool during the
C3H6,C3H8,C4H6, TR experiment. The autosampler was connected with the gas circulation
C4H8,C4H10,C5H10,
pipeline and GC–MS to record the TR process occurred. The flowmeter
C6H6
C6H12,C9H18,C3H6O3, was used to keep the flow rate of the gas circulation pipeline stable
C4H8O2,C5H10O3 during the experiment, and the check valve was used to place the gas
Sun [14] LCO Thermal Air CO, CO2, HF, toxic backflow when TR occurred began. Meanwhile, the whole gas circu­
LMO abuse organic products lating pipeline was heated to 100 ◦ C with a heating belt to prevent the
NMC
OSV from condensing.
LFP
Fernandes LPF Overcharge Air H2,CO,CO2,CH4,
[15] C2H4,C2H6,C3H6
C2H6O,C2H5F, 2.3. Gas analysis
C2H4O2,C2H6O,
CH4O,HF The schematic diagram of Raman gas analysis system is shown in
Hoelle [16] NMC Puncture Argon H2,CO,CO2,CH4, Fig. 2. In this study, A 532 nm laser was used as the excitation light
C2H4
source. The maximum output power of the laser was 300 mW and it was
Essl [17] NMC/ Thermal Nitrogen H2,CO,CO2,CH4,
LMO abuse C2H2,C2H4,C2H6, powered by 24 V DC power supply. The laser was transmitted to the
Organic carbonates, Raman probe through the excitation fiber with core diameter of 105 μm
C3H8,C4H10,C6H14, and numerical aperture of 0.22, and irradiated the gas sample in the gas
HF
pool. The Raman backscattering signals were collected through the
Sturk [18] LPF Thermal Nitrogen CO2,CO, Organic
NMC/ abuse carbonates, receiving fiber with core diameter of 600 μm and numerical aperture of
LMO Fluorinated 0.39. In order to enhance the Raman signals of the gases, the constant
hydrocarbons,HF, pressure valve was controlled to stabilize the internal pressure of the gas
POF3 pool at 120 kPa. As a result, the gases in the pressurized pool reflected
lammer NCA Thermal Air H2,CO,CO2,CH4,
the gas variations in the battery during the LIB-TR experiment.
[19] abuse C2H2,C2H4,C2H6
Abraham NCA Thermal Air H2,CO,CO2,CH4, As a reference for Raman spectral analysis, Agilent gas chromatog­
[20] abuse C2H4,C2H6 raphy–mass spectrometry (GC6890P-MS5975C) was used to analyze the
Koch [21] NMC Thermal Air H2,CO,CO2,CH4, gas composition after LIB-TR. HP-PLOT/Q chromatographic column of
abuse C2H4,C2H6,C3H6
Agilent J & W technologies was selected for chromatographic separa­
Kriston Electrolyte Thermal Air CO2,HF,PF5,
[22] abuse
tion, where helium was selected as GC carrier gas, and a constant flow
Bertilsson Electrolyte Thermal Air HF,POF3 rate of 1.3 mL/min was maintained. When TR occurred, the automatic
[23] abuse injector was opened with 100 μL injection volume. After sample injec­
tion, GC–MS began analysis.
The oven of GC was maintained from the initial temperature of 50 ◦ C
Table 2 for 10 min, then increased to 250 ◦ C at 5 ◦ C/min, and then maintained
Specification of the 18650 LIB. for 10 min. The single analysis time of GC–MS was 60 min, so as to
Parameter Value Parameter Component
achieve the best separation effect. The molecular formula and corre­
sponding structural formula of each gas component are identified by
Nominal capacity 2600 mAh Cathode material Lithium cobalt oxide
using National Institute of standards and Technology (NIST) spectro­
Charging voltage 4.2 ± 0.05 V Anode material Graphite
Nominal voltage 3.63 V Separators PP,PE gram standard database in combination with the fragment ion peak of
Cell weight 45.0 ± 0.6 g Electrolyte solvents DMC,EA,EC the substance.
Max charge current 2600 mA Salt LiPF6
Cut-off voltage 2.75 V Binder PVDF
2.4. Gas explosion hazard analysis

another K-type thermocouple was placed 30 mm above the battery The Le Chatelier formula is suitable for calculating the explosion
safety valve to measure the temperature of the battery exhaust gas limit of multi-component gas mixtures. It is widely used in engineering
(marked as T2). The pressure sensor was used to record the pressure applications due to the small error between calculation results and ex­
change inside the TR chamber. The pressure sensor was then directly periments. TR can produce a variety of flammable gases, so the explo­
connected with the data recorder, and the thermocouple signal line and sion limit can be calculated using Le Chatelier formula [32]. When the
heating ring power line inside the chamber were connected with the type and concentration of battery gas are known, the LEL and UEL are
data recorder through the aviation plug to ensure the air tightness of the calculated by Eqs. (1) and (2):
chamber.
In view of the fact that most of the internal materials of the battery LELmix = ∑
1
(1)
n
were combustible, in order to exclude the effect of oxygen in the air on Xi
LELi
the production of gases during the process of LIB-TR, this study carried 1

out a controlled experiment in nitrogen atmosphere. First, open the

3
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

Fig. 1. Schematic of gas analysis system for lithium ion battery.

where LELmix′ and UELmix′ are the revised lower and upper explosive
limits for gas mixtures (%), and B is the volume fraction of carbon di­
oxide in the gas mixture.
In order to analyze the explosion risk of thermally runaway gas of LIB
comprehensively, the amount of thermally runaway gas discharged from
LIB was calculated through Eq. (6):
PV
n= − n0 (6)
RT

where n is the amount of gas released by the battery (mol), P is the

pressure value after the internal pressure of the chamber stabilizes after
TR (Pa), V is the volume of the experimental chamber that is 0.005 m3, R
is the gas constant that equals to 8.31 J/(mol⋅K), T is the gas temperature
inside the chamber (K), n0 is the initial amount of gas in the reactor at
the beginning of the experiment (mol).
Fig. 2. Schematic of Raman gas analysis system.

3. Results and discussion

1
UELmix = ∑
n (2)
Xi 3.1. Temperature and mass loss
UELi
1

In this study, the TR process of the battery under different experi­

where LELmix and UELmix are the lower explosion limit and upper ex­
mental conditions could be divided into three stages: (I) The battery
plosion limit of mixed gas respectively (%), and Xi is the volume fraction
surface temperature rose steadily under the constant power heating of
of a component in the gas mixture (%), LELi and UELi are the lower and
the heating ring; (II) Battery safety valve opened (SVO), the material
upper explosion limits of a specific component in the gas mixture (%).
inside the battery was ejected at a high speed cooling the battery to a
The TR of the battery would often generate the inert gas CO2 [33]. In
certain extent, and then the temperature rose rate increased; (III) TR
the process of heat transmission, the inert gas not only does not
occurred, the surface temperature increased sharply, reach a maximum
participate in the reaction, but also acts as a medium to absorb the re­
temperature within a few seconds, and then began to decrease.
action energy, so that the combustion explosion reaction cannot produce
The characteristic temperatures of the TR process of LIBs under
enough energy to maintain the reaction [34]. Consequently, the influ­
various experimental conditions are shown in Table 3. In air or nitrogen
ence of inert gas on the explosion limit of mixed gas should be consid­
environment, the SVO temperature and TR onset temperature of LIB
ered. The explosion limit of gas can be estimated by the following
decreased with the increased of SOC. With the increase of SOC, the
improved empirical Eqs. (3) and (4) [29], ELR is obtained by subtracting
number of lithium ions embedded in the negative electrode increases,
LEL from UEL:
resulting in the instability of intercalated carbon and the decrease of
1 + 1−BB reaction activation energy [35]. In addition, during the charging process
(3)
′
LELmix = LELmix ×
100 + LELmix × 1−BB
% of the battery, Ni2+ and Co3+ of the positive electrode are oxidized to
Ni3+ or Ni4+ and Co4+ respectively. The higher the SOC is, the more high
1 + 1−BB valence metal cations in the positive electrode, resulting in a worse
(4)
′
UELmix = UELmix ×
100 + UELmix × 1−BB
% thermal stability of the positive electrode and the more prone the battery
to TR [36].
′
ELR = UELmix − LELmix
′
(5) Under the same SOC, the SVO temperature was less affected by the
atmosphere, because the decisive factor of SVO was the pressure dif­
ference between the inside of the safety valve and the environment.

4
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

Table 3
Experimental data of lithium ion battery under various experimental conditions.
Environment SOC(%) T1-SVO(◦ C) T2-SVO(◦ C) T1-TR(◦ C) T2-TR(◦ C) T1max(◦ C)

Air 25 187.3 36.2 306.9 48.3 357.1

Air 50 184.4 37.3 291.9 79.2 523.6
Air 75 184.1 35.5 264.1 135.6 701.8
Air 100 162.6 38.3 228.3 353.1 585.6
Nitrogen 25 187.7 38.1 312.7 50.2 339.5
Nitrogen 50 185.4 40.0 293.5 81.3 510.9
Nitrogen 75 184.1 35.3 269.1 124.2 632.7
Nitrogen 100 166.4 39.2 237.6 188.2 559.2

After SVO, the internal materials of the battery in the air environment
contacted with oxygen in the air to generate oxidation reaction, which
speeded up the process of TR, thus resulting in a higher TR onset tem­
perature. When TR occurred, the internal material ejected at a high
speed, and there was no oxygen in the nitrogen environment. The in­
ternal material could not react with the oxygen in the environment,
resulting in the decreased maximum temperature of TR.
As shown in Table 3, SOC and gas environment have little impact on
T2-svo. The reason is that before SVO, the internal reaction of the battery
was carried out in a closed system, and the reaction was only related to
the internal material characteristics of the battery. T2-TR of 25 % and 50
%SOC batteries in nitrogen environment is slightly higher than that in
air environment. The reason may be that the onset temperature of TR in
nitrogen environment is higher and the internal reaction is more suffi­
cient. In the air environment, the gases discharged by 75 % and 100 %
SOC TR were mixed with oxygen to cause combustion and explosion,
resulting in T2-TR significantly higher than that of the battery in nitrogen
environment. The data in Table 3 shows that the nitrogen environment
has a certain inhibitory effect on the thermal runaway hazard of LIB.
The mass loss of LIBs after TR under different experimental condi­
tions is shown in Table 4. The main components of battery mass loss
were due to the emission of gases in the battery, together with the in­
ternal substances of the battery sprayed from the safety valve during TR
process. The battery mass loss increases with the increase of SOC, and
the mass loss of 25 %, 50 % and 75 % SOC increases linearly. The mass
loss of 100 % SOC battery was significantly higher than that of 75 % SOC
battery, a large number of internal substances were sprayed violently
from the 100 % SOC battery without complete reaction, resulting in the
maximum temperature of the battery was lower than that of 75 % SOC.
At the same SOC, the mass loss of the battery in the nitrogen envi­
ronment was higher than that in the air environment. The reason is that
the onset temperature of TR in the nitrogen environment is higher, and
the consumption of material reaction in the battery increases, thus
resulting in the increase of the mass loss of the battery.
3.2. Gas composition analysis
According to previous studies, the main gases generated in the TR of
LIB are CO2, CO, H2, CH4, C2H4 and C3H6 [19–21,37]. The Raman
characteristic peaks of different gases were determined by using stan­
dard gases, as shown in Fig. 3. In order to determine the relationship
between the height of characteristic peak and gas concentration, 31
concentrations were configured for each gas using N2 as equilibrium gas.
Taking CO as an example, the relationship between characteristic peak
and gas concentration is shown in Fig. 4. In order to show the
Table 4
Battery mass loss after TR.
SOC (%) Mass loss-air (g) Mass loss-nitrogen (g)
25 3.788 4.7
50 5.666 5.826
75 7.887 8.514
100 17.055 17.55
O2+N2
C3H6+N2
C2H4+N2
CH4+N2
CO2+N2
CO+N2
H2+N2
Fig. 3. Raman characteristic peak spectrum of standard gas.
relationship between Raman characteristic peak height and gas con­
centration clearly, the Raman characteristic peaks corresponding to the
15 concentrations are shown in Fig. 4, with a concentration difference of
approximately 3 %.For the hydrocarbon gas with overlapping peaks, the
Raman spectrum database of target gas with different concentrations
was established, the optimal variables related to the target gas concen­
tration were selected by using the classical partial least square (PLS),
and a quantitative model was established for prediction. The minimum
R2 of the training set is not less than 0.91.
In the air environment, the Raman spectra of the battery with 100 %
SOC in three stages are shown in Fig. 5. Before SVO, the internal gases
were not discharged from the battery, and there were only N2 and O2 in
the gas pool. After SVO, the OSV in the battery was discharged, resulting
in the reduction of N2 and O2 content. When LIB-TR occurred, other
gases except the OSV were detected.
As mentioned above, the variations of gases in the process of TR
under different SOCs in air environment are shown in Fig. 6. It should be
noted that the original Raman spectrum collected by the spectrometer
includes various noise signals in addition to the ideal signals. These
noise signals will interfere with the characteristic signals of the gas.
Therefore, the change of gas concentration is not a smooth curve. In
practice, these fluctuations are slight and have little impact on the
measurement accuracy. Before SVO, the gases generated by the reaction
of internal materials accumulated in the battery. When the pressure
difference between the internal pressure of the battery and the external
atmospheric pressure reached the design threshold of the safety valve,
the safety valve opened, the internal gases were released through the
safety valve. In the very beginning, the gases mainly consisted of the
gasified electrolytic liquid. Since there was no gas exchange with the
outside during the TR experiment, the OSV content increased gradually,
making the proportion of N2 and O2 decreased gradually.
With the increase of SOC, the thermal stability of the battery de­
creases, and the time interval between the battery SVO and LIB-TR de­
creases. Therefore, the proportion of OSV before LIB-TR decreases with
the increase of SOC. After LIB-TR, CO2, CO and some hydrocarbon gases
were detected, and the proportion of OSV decreased. With the increase
of SOC, the types of gases detected increase. CH4, C3H6, H2 and CO2 were

5
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

16000

(a) 14000
(b) 0.55%
40 3.09%
5.70%
8.35%
12000

Raman intensity (a.u)

11.06%
30 13.53%
10000 16.12%
CO2 (vol.%)

18.65%
21.13%
8000 23.80%
20 26.44%
31.61%
6000 34.15%
36.86%
10 4000 40.00%
y = 0.0029 x - 0.1374
R2 = 0.998 2000
0
0
0 2000 4000 6000 8000 10000 12000 14000 1320 1340 1360 1380 1400 1420 1440 1460
Peak high (a.u) Wavenumber (cm-1)

Fig. 4. (a) Quantitative regression curve of CO2 characteristic peak height and concentrations, (b) Raman characteristic peaks of different CO2 concentrations.

reflect the gas generation of the battery. Similar to the experimental

4x104
Before SVO (256s) results in air environment, once the safety valve was opened, the heated
3x104 After SVO (527s)
After TR (711s) 1556 (O2) 2328 (N2)
and vaporized organic solvent inside the battery was discharged from
2x104 the safety valve. The amount of OSV was inversely proportional to SOCs,
1x104 which was reflected in the Raman spectra straightforwardly.
0 Compared with air environment, the battery with 25 % SOC in ni­
Raman intensity (a.u)

4x104 trogen environment did not generate C3H6 after LIB-TR, indicating that
3x104 921 O2 played an important role in the process of TR. Table 5 shows the final
2x104 (organic solvent) 2967 (organic solvent) proportion of various gases under different test conditions. With the
1x104 increase of SOCs, the proportion of various gases showed an upward
0
trend. The generation of hydrocarbon gas was least affected by the gas
4x104 environment. In the air environment, the combustible gases generated in
3x104 the battery during TR react completely and incompletely with oxygen in
1344 (C2H4)
1390 (CO2)
1282 (CO2)

the air to generate CO2. Due to the internal materials of the battery were
2140 (CO)

2x104
593(H2)

1x104
0
500 1000 1500 2000
Wavenumber (cm-1)
Fig. 5. Raman spectrum of gas samples at different stages.
detected after TR for batteries with 25 % and 50 % SOC. For batteries
with 75 % and 100 % SOC, CO and C2H4 were also detected after TR.
During the LIB-TR, the internal reaction of the battery is intense and
the gas release rate is fast. A large amount of gases is generated in a short
time, resulting in a rapid increase in the content of various gases. The
proportion of various gases generated later shows a slow upward trend,
indicating that the residual substances in the battery are still reacting
slowly after TR. With the increase of SOC, the concentrations of CO2, CO,
CH4, C3H6, C2H4 and H2 increase. It reveals that the intensity of battery
TR is correlated with SOCs. The higher the SOC, the more intense the
reaction, the more kinds of gases and the greater the amount of gases
generated. The variation of O2 proportion of batteries with 25 % and 50
% SOC after TR was similar to that of N2. Since N2 did not participate in
the reaction in the whole process of the experiment, it indicated that
batteries with 25 % and 50 % SOC consumed less O2 during LIB-TR. The
decline rate of O2 proportion of batteries with 75 % SOC after LIB-TR
was significantly higher than that of N2, which indicated that more O2
participated in the reaction during TR. The battery with 100 % SOC
consumed almost all the oxygen in the container during TR, indicating
that severe combustion occurred during LIB-TR.
Similarly, the gas variations in the process of LIB-TR under different
SOCs in nitrogen environment are shown in Fig. 7. In the nitrogen
environment, there is no reaction between oxygen and internal sub­
stances in the battery during the experiment. The analysis results truly
CH4+C3H6 C2H4+C3H6
more fully oxidized in LIB-TR under air conditions, the nCO/nCO2 under
nitrogen conditions at 75 % and 100 % SOC was higher than those of air
2500 3000 3500 conditions. As shown in Figs. 6 and 7, the sharp rise of battery tem­
perature, the decrease of OSV concentration and the rapid rise of various
gases almost occur at the same time, indicating that the gas reaction rate
of internal substances is rapid when LIB-TR occurs. The results reveal
that the combustible gases were generated instantaneously rather than
slow accumulation.
Under all experimental conditions, the Raman spectrometer can
detect OSV immediately after SVO. OSV is not an inherent substance in
the atmospheric environment and can only be generated when the
battery is in a dangerous state, so it can be used as a characteristic gas for
early detection. In the actual battery application scenario, the Raman
spectrum system can be connected with the battery management system
(BMS). The Raman spectrum system collects the gas components in the
environment where the battery is located in real-time and feeds them
back to the BMS. Once a characteristic gas such as OSV is detected, the
BMS can send an alarm to realize the early detection of TR. Therefore,
Raman spectroscopy presents a promising tool for early warning of LIB-
TR.
After the Raman spectrum of TR gases tended to be stable, in order to
conduct a more comprehensive analysis of the gas generated after TR,
the TR gases were analyzed by GC–MS. The analysis results are shown in
Table 6. H2 mainly comes from the reaction between the binder poly­
vinylidene fluoride (PVDF) and the anode lithium embedded metal [38].
CO and CO2 come from the oxidation reaction of organic solvents and
the reaction of organic solvents with lithium [39,40]. Hydrocarbon
gases come from the decomposition of SEI and the reaction of organic
solvents with lithium [39,41]. C3H6O3(DMC) and C4H8O2(EA) are
organic solvents in the electrolyte. Due to the boiling points of these two
organic solvents are low and the gas circulation pipeline is heated in the

6
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

(a) 80 400 80 600

78 (b) 78
76 76 550
74 74
72 TMAX=357.1 350 72 TMAX=523.6
70 70 500
21 300 21 450
20 battery temperature 20 battery temperature
Percentage/%

Percentage/%
CH4 19 CH4 400
19 18 thermal runaway

Temperature/

Temperature/
18 H2 250 17 H2 T=291.9 350
CO2 CO2
6 C3H6 200 6 C3H6 300
N2 N2
5 O2 5 O2 250
4 OSV 150 OSV
4 200
3 thermal runaway 100 3 150
2 safety valve open T=306.9
2 100
T=187.3 safety valve open
1 50 1 T=184.4
50
0 0
0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000
Time/s Time/s
25%SOC 50%SOC
80
(c) TMAX=701.8
(d) 80
76 70
safety valve open 700 safety valve open 700
72 T=184.1 60 T=162.6
68 600 50 TMAX=585.6 600
64
Percentage/%

Percentage/%
20 battery temperature
500 500

Temperature/
Temperature/
20 battery temperature H2
18 H2 TR onset
CH4
TR onset
CH4 T=264.1 400 T=228.3 400
15 C2H4
16 C2H4 C3H6
14 C3H6 CO
CO 300 300
6 10 CO2
CO2 N2
5 N2 200 O2 200
4 O2 OSV
3 OSV 5
2 100 100
1
0 0 0 0
0 200 400 600 800 0 200 400 600 800
Time/s Time/s
75%SOC 100%SOC

Fig. 6. Variation curves of temperature and main gas percentages with time under air environment.

experiment, the vaporized organic solvent will not liquefy rapidly,
resulting in the detection of DMC and EA by GC–MS. The formation of
C2H4O(ethylene oxide) comes from the secondary one-electron reduc­
tion of radical anion molecules [42]. The amount of gases produced by
LIB-TR is positively correlated with SOCs. In addition, the types of hy­
drocarbon gases with high carbon number after TR of 100 % SOC battery
under air conditions were less than those of nitrogen conditions, and the
reason is that these gases may be consumed in the combustion process
[13]. In addition, the decomposition product of lithium salt in the
electrolyte at high temperature will react with water to generate highly
toxic gas HF [43]. When TR occurs, the lithium salt released from the
battery will also react with water in the environment to generate HF
[12].
According to the gas analysis results, most of the gases generated by
the LIB-TR during the experiment are combustible (CO, H2, hydrocar­
bons), and some gases are toxic to human body (CO, C2H4O, C6H6). The
generation source of these gases is mainly the reaction between the
lithium embedded in the negative electrode and the organic solvents in
the electrolyte. According to the working principle of the LIB, The higher
the SOC, the more lithium ions embedded in the negative electrode, and
the greater the amount of gases generated by the reaction.
3.3. Gas explosion characteristics
In order to analyze the explosion risk in the whole process of gas
emission from LIB-TR, Raman spectroscopy is used to determine the
explosion limit with gas analysis results. The explosion limit of
combustible gas involved in this study is shown in Table 7. According to
the measurement results of GC–MS, the main components of the organic
solvents in the electrolyte measured in the experiment are the mixture of
DMC and EA, and the ratio between the two organic solvents is 65:35.
Combined with the data in Table 7, Eqs. (1) and (2), the LEL and UEL of
mixture are 3.19 % and 11.19 %, respectively. Since there was no
combustible gases discharged from the battery before SVO, and only
OSV was generated from the SVO procedure to the LIB-TR. As a result,
the explosion limit of battery exhaust gases from SVO to LIB-TR was
determined by the mixture of two OSVs. Therefore, this study focuses on
the variation of the explosion limit of the mixed gases emitted by the
LIB-TR. With the combination of the gas detection results and Eqs. (1) ~
(4), the curve of the explosion limit of the gases emitted by the LIB-TR is
obtained, as shown in Fig. 8. Due to the explosion limit of combustible
gases is much higher than that of OSV, resulting in the rapid rise of
explosion limit when TR occurs.
The internal organic solvents of 100 % SOC battery was almost
consumed due to violent reaction. Therefore, except for 100 % SOC
battery, the organic solvents inside the battery continued to evaporate
after TR, resulting in the gradual increase of OSV concentration. The
concentration of OSV has a significant impact on the explosion limit of
mixed gas. The explosion limit of battery with 100 % SOC shows a slow
and stable increase trend after a sharp rise, and the explosion limit in
other cases shows a downward trend with the slow rise of OSV
concentration.
In the air environment, the rising rates of LEL and UEL released by
LIB-TR increase with the increase of SOCs. The reason is that the CO2
released by the LIB-TR increases with the increase of SOCs, and the
battery with 100 % SOC produces a large amount of CO2 due to violent

7
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

(a) 400 (b) 100

100.0 TMAX=510.9℃
500
TMAX=339.5℃
97.5 battery temperature
battery temperature 95
H2 H2
95.0 CH4
300 CH4 400

Temperature/℃
Temperature/℃

Percentage/%
Percentage/%

CO2 90 C3H6 TR onset

92.5 N2 CO2 T=293.5℃
OSV TR onset N2
T=312.7℃ OSV 300
90.0 200 85
safety valve open
6 6 T=185.4℃
200
4 4
100
safety valve open
2 T=187.7℃
100
2

0 0
0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000
Time/s Time/s
25%SOC 50%SOC
100 700 (d) 100 600
(c) TMAX=632.7℃
battery temperature
battery temperature
95
H2 H2
600 90
CH4 CH4 500
90
C2H4 C2H4
TMAX=559.2℃
85 C3H6 500 80 C3H6
TR onset
Temperature/℃

Temperature/℃
CO
Percentage/%

Percentage/%
CO T=269.1℃ 400
80 CO2 70 CO2
N2
400 N2
OSV OSV
5 60 TR onset 300
safety valve open 300 14 T=237.2℃
4 T=184.1℃ safety valve open
12
T=166.4℃
3
200 10 200
8
2 100 6
100
1 4
0 2
0
0 0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600
Time/s Time/s
75%SOC 100%SOC

Fig. 7. Variation curve of temperature and main gas percentage with time under nitrogen environment.

Table 5 Table 6
Final proportion of gas emissions in Raman experiment. Gas analysis results under different experimental conditions.
SOC CO CO2 H2 Hydrocarbons OSV nCO/ Gases Air Nitrogen
(%) (%) (%) (%) (%) nCO2
25 % 50 % 75 % 100 % 25 % 50 % 75 % 100 %
25 %A / 2.14 1.56 0.42 5.65 /
H2 ● ● ● ● ● ● ● ●
50 %A / 3.61 3.39 0.68 5.66 /
CH4 ● ● ● ● ● ● ● ●
75 %A 2.77 5.38 5.20 2.24 6.21 0.52
CO ● ● ● ● ● ● ● ●
100 18.34 14.15 9.94 4.20 0.91 1.28
CO2 ● ● ● ● ● ● ● ●
%A
C2H2 ⋄ ⋄ ● ● ⋄ ⋄ ⋄ ⋄
25 %N / 2.70 1.69 0.20 4.69 /
C2H4 ● ● ● ● ● ● ● ●
50 %N 2.13 3.47 0.69 6.91 /
C2H4O ● ● ● ● ● ● ● ●
75 %N 4.86 4.51 5.49 2.87 5.15 1.08
C2H6 ⋄ ⋄ ● ● ⋄ ⋄ ● ●
100 14.13 4.97 8.11 4.41 0.80 2.84
C3H6 ● ● ● ● ● ● ● ●
%N
C3H8 ⋄ ● ● ● ⋄ ● ● ●
A C4H6
Experiments in air environment. ⋄ ● ● ● ⋄ ● ● ●
N
Experiment in nitrogen environment. C4H8 ⋄ ● ● ● ⋄ ● ● ●
C4H10 ⋄ ● ● ● ⋄ ⋄ ⋄ ●
C5H8 ⋄ ● ● ● ⋄ ● ● ●
combustion, thus resulting in the maximum rise rate of explosion limit. C5H10 ⋄ ● ● ● ⋄ ⋄ ⋄ ●
In the nitrogen environment, the explosion limit of the gases released by C5H12 ⋄ ⋄ ● ● ⋄ ⋄ ⋄ ●
the LIB-TR with 25 % SOC is higher than that of the LIB-TR with 50 % C3H6O3 ⋄ ● ● ● ● ● ● ●
C4H8O2
SOC. As shown in Fig. 7, the proportion of CO2 released by the LIB-TR
⋄ ● ● ● ● ● ● ●
C6H6 ⋄ ● ● ● ● ● ● ●
with 25 % SOC in the nitrogen environment is higher, resulting in the C6H12 ⋄ ⋄ ● ● ⋄ ● ● ●
battery with the explosion limit higher than 50 % SOC. C7H14 ⋄ ⋄ ⋄ ⋄ ⋄ ● ● ●
The explosion characteristics after the gas composition is stable are C8H8 ⋄ ⋄ ⋄ ⋄ ⋄ ⋄ ⋄ ●
shown in the Table 8.The explosion limit of the LIB-TR gases under air ●Indicates the gas is detected.
conditions is higher than that of nitrogen conditions except for batteries ⋄Indicates the gas is not detected.
with 25 % SOC. The reason is that some combustible gases react with O2
under air conditions, resulting in increased CO2 generation. It is worth
noting that the LEL of the gases released from the LIB-TR with low SOC is

8
Q. Zhang et al. Journal of Energy Storage 56 (2022) 105905

Table 7
Explosion limits of different gases [12,44].
DMC EA H2 CO CH4 C2H4 C3H6

LEL (%) 4.22 2.2 4 12.5 5 2.7 2.4

UEL(%) 12.87 9 75 74 15 36 11

Table 8
low and easy to reach the critical concentration of explosion. However, Gas explosion characteristics: explosion limits and ERL (vol% in air).
the ELR of the gases released from the LIB-TR with the high SOC is SOC(%) Aira Nitrogena
larger, and the risk of explosion is greater. For example, the gases
LEL(%) UEL(%) ELR(%) LEL(%) UEL(%) ELR(%)
generated by the LIB-TR with 100 % SOC are significantly more than
that of other batteries, which has a high risk of explosion. 25 3.88 15.64 11.76 4.49 19.16 14.67
50 4.22 20.36 16.14 3.78 17.11 13.33
The results of calculating the gas emission of LIB-TR under different 75 5.00 25.92 20.83 4.9 24.13 19.23
experimental conditions according to Eq. (6) are shown in Table 9. As 100 8.25 59.17 50.92 6.42 42.39 35.97
shown in Table 9, the higher the SOC, the more unstable the chemical a
“Air” or “Nitrogen” here specify the nature of the gas atmosphere outside the
properties of the internal materials of the battery. It is easier to generate
tested cell in our experimental conditions, not the oxidant species used to
gases at high temperature, resulting in the increase of the amount of determine explosion limits of the combustible gas mix measured, which in both
gases released by the LIB-TR with the increase of SOCs. With the same case was air.
SOC, the amount of gases generated by the LIB-TR in the nitrogen
environment is less than that of the air environment. In the nitrogen
environment, the combustible gases generated by the reaction of ma­ Table 9
terials in the battery can not undergo oxidation reaction with O2, and the Volume of gas emitted under different experimental conditions.
chain reaction of free radicals is inhibited, thus resulting in the reduction SOC (%) Gas volume-air (mmol) Gas volume-nitrogen (mmol)
of gas generation [45,46].
25 21.56 14.41
Combined with Table 8, the amount of gases generated by the LIB-TR 50 55.79 48.93
with low SOC is slight. While the amount of gases generated from the 75 84.61 72.47
LIB-TR with 100 % SOC is the largest, and its ELR is the largest. 100 126.65 115.48

(a) 10 (b) 8
LEL-25%-Air LEL-25%-N2
LEL-50%-Air LEL-50%-N2
9 LEL-75%-Air LEL-75%-N2
LEL-100%-Air 7 LEL-100%-N2
8

6
LEL (%)
LEL (%)

6 5

5
4
4

3
3

0 25 50 75 100 125 150 0 25 50 75 100 125 150

Time (s) Time (s)

(c) 70 (d) 60
UEL-25%-Air
UEL-50%-Air UEL-25%-N2
UEL-75%-Air UEL-50%-N2
60 UEL-100%-Air UEL-75%-N2
50 UEL-100%-N2

50
UEL (%)

UEL (%)

40

40

30
30

20
20

10 10
0 25 50 75 100 125 150 0 25 50 75 100 125 150
Time (s) Time (s)

Fig. 8. LEL and UEL curves after TR under various experimental conditions.

9
Q. Zhang et al.
Therefore, in the confined space, even if the battery has already un­
dergone TR, it is still necessary to pay much attention to the secondary
hazards that may be caused by the remaining combustible gas during the
rescue process.
4. Conclusion
In this paper, Raman spectroscopy was used to detect the main
exhaust components of batteries with different SOC in the whole process
of TR, and combined with GC–MS to analyze the trace gas produced by
TR. At the same time, the gas explosion risk was studied based on the
results of in-situ gas analysis. This study draws the following
conclusions:
(1): The severity of battery TR increased with the increase of SOC, and
the mass loss after battery TR was positively correlated with SOC.
Under the same environment, the onset temperature of battery
TR and the opening temperature of safety valve decreased with
the increase of SOC. Compared with batteries in air environment,
in nitrogen environment, the onset temperature of battery TR
with the same SOC increased and the maximum temperature of
battery TR decreased. Inert gas environment has a certain
inhibitory effect on the thermal hazard of battery TR.
(2): According to the analysis results of Raman spectrum, the main
exhaust gas of the battery after SVO was organic solvent vapor,
and the concentration of organic solvent vapor increases with
time before TR occurs. When TR occurred, a large amount of gas
was rapidly discharged from the battery. The main components of
the mixed gas were CO2, CO, H2, C2H4 and C3H6. In the air
environment, the batteries with 25 % and 50 % SOC consumed
less O2 during TR, while the batteries with 100 % SOC almost
completely consumed the O2 inside the container when TR
occurred.
(3): According to the analysis results of GC–MS, the higher the SOC of
the battery, the more side reactions will occur in the internal
materials, the more kinds of gases will be generated after TR, and
toxic gases such as CO, C2H4O and C6H6 will be generated.
Because the inert gas environment inhibits the oxidation reaction
of combustible gases, when the SOC is the same, there are more
kinds of gases released by the battery TR in nitrogen
environment.
(4): Except for LIBs with 100 %SOC, TR gas LELs of other LIBs are
lower than that of CH4,and TR gas UELs of all SOC LIBs are higher
than that of CH4, indicating that TR gas explosion risk is higher
than CH4. The ELR of the gas released by the battery TR with 100
% SOC can still reach 50.92 % after combustion.
This study proves the feasibility of applying Raman spectroscopy
technology to TR gas detection, and calculates the LEL, UEL and ELR of
gas according to the experimental results, which provides technical
support and theoretical basis for evaluating the explosion risk of TR gas
and TR early warning. Since the theoretical formula calculation results
will inevitably deviate from the actual results, the next step will be to
measure the TR gas explosion limit through experiments. At the same
time, the detection accuracy of Raman spectrum is improved to achieve
faster fault signal detection.
CRediT authorship contribution statement
Qingsong Zhang: Conceptualization, Methodology, Funding
acquisition.
Tiantian Liu: Conceptualization, Methodology, Writing- Original
draft preparation.
Chaolong Hao: Methodology, perform part of experiments.
Yirun Qu: Perform part of experiments.
Jianghao Niu: Perform part of experiments.
10
Journal of Energy Storage 56 (2022) 105905
Qiong Wang: Supervision, Funding acquisition.
Da Chen: Conceptualization, Supervision, Funding acquisition.
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.
Data availability
No data was used for the research described in the article.
Acknowledgement
This work is supported by the Key Program of the Joint Fund for Civil
Aviation Research with National Natural Science Foundation of China
(no. U2033204). The scientific research project of Tianjin municipal
education commission (2021KJ061) and Tianjin graduate scientific
research innovation project (2021YJSO2B10).
References
[1] Q. Wang, P. Ping, X. Zhao, G. Chu, J. Sun, C. Chen, Thermal runaway caused fire
and explosion of lithium ion battery, J. Power Sources 208 (2012) 210–224.
[2] W.-T. Luo, S.-B. Zhu, J.-H. Gong, Z. Zhou, Research and development of fire
extinguishing technology for power lithium batteries, Procedia Eng. 211 (2018)
531–537.
[3] Z. Liao, S. Zhang, K. Li, G. Zhang, T.G. Habetler, A survey of methods for
monitoring and detecting thermal runaway of lithium-ion batteries, J. Power
Sources 436 (2019), 226879.
[4] X. Feng, M. Ouyang, X. Liu, L. Lu, Y. Xia, X. He, Thermal runaway mechanism of
lithium ion battery for electric vehicles: a review, Energy Storage Mater. 10 (2018)
246–267.
[5] X. Feng, D. Ren, X. He, M. Ouyang, Mitigating thermal runaway of lithium-ion
batteries, Joule 4 (2020) 743–770.
[6] F. Diaz, Y. Wang, R. Weyhe, B. Friedrich, Gas generation measurement and
evaluation during mechanical processing and thermal treatment of spent li-ion
batteries, Waste Manag. 84 (2019) 102–111.
[7] H. Li, Q. Duan, C. Zhao, Z. Huang, Q. Wang, Experimental investigation on the
thermal runaway and its propagation in the large format battery module with Li
(Ni1/3Co1/3Mn1/3)O2 as cathode, J. Hazard. Mater. 375 (2019) 241–254.
[8] H. Li, W. Peng, X. Yang, H. Chen, J. Sun, Q. Wang, Full-scale experimental study on
the combustion behavior of lithium ion battery pack used for electric vehicle, Fire.
Technol 56 (2020) 2545–2564.
[9] Y.-L. Zhu, C.-J. Wang, F. Gao, M.-X. Shan, P.-L. Zhao, Q.-F. Meng, Q.-B. Wu,
Rupture and combustion characteristics of lithium-ion battery under overcharge,
J. Energy Storage 38 (2021), 102571.
[10] S. Koch, K.P. Birke, R. Kuhn, Fast thermal runaway detection for lithium-ion cells
in large scale traction batteries, Batteries 4 (2018).
[11] L. Yuan, T. Dubaniewicz, I. Zlochower, R. Thomas, N. Rayyan, Experimental study
on thermal runaway and vented gases of lithium-ion cells, Process Saf. Environ.
Prot. 144 (2020) 186–192.
[12] F. Larsson, S. Bertilsson, M. Furlani, I. Albinsson, B.-E. Mellander, Gas explosions
and thermal runaways during external heating abuse of commercial lithium-ion
graphite-LiCoO2 cells at different levels of ageing, J. Power Sources 373 (2018)
220–231.
[13] Y. Zhang, H. Wang, W. Li, C. Li, Quantitative identification of emissions from
abused prismatic Ni-rich lithium-ion batteries, eTransportation 2 (2019), 100031.
[14] J. Sun, J. Li, T. Zhou, K. Yang, S. Wei, N. Tang, N. Dang, H. Li, X. Qiu, L. Chen,
Toxicity, a serious concern of thermal runaway from commercial li-ion battery,
Nano Energy 27 (2016) 313–319.
[15] Y. Fernandes, A. Bry, S. de Persis, Identification and quantification of gases emitted
during abuse tests by overcharge of a commercial li-ion battery, J. Power Sources
389 (2018) 106–119.
[16] S. Hoelle, S. Scharner, S. Asanin, O. Hinrichsen, Analysis on thermal runaway
behavior of prismatic lithium-ion batteries with autoclave calorimetry,
J. Electrochem. Soc. 168 (2021), 120515.
[17] C. Essl, A.W. Golubkov, E. Gasser, M. Nachtnebel, A. Zankel, E. Ewert, A. Fuchs,
Comprehensive Hazard analysis of failing automotive lithium-ion batteries in
overtemperature experiments, Batteries 6 (2020).
[18] D. Sturk, L. Rosell, P. Blomqvist, A. Ahlberg Tidblad, Analysis of li-ion battery gases
vented in an inert atmosphere thermal test chamber, Batteries 5 (2019).
[19] M. Lammer, A. Königseder, V. Hacker, Holistic methodology for characterisation of
the thermally induced failure of commercially available 18650 lithium ion cells,
RSC Adv. 7 (2017) 24425–24429.
[20] D.P. Abraham, E.P. Roth, R. Kostecki, K. McCarthy, S. MacLaren, D.H. Doughty,
Diagnostic examination of thermally abused high-power lithium-ion cells, J. Power
Sources 161 (2006) 648–657.
Q. Zhang et al.
[21] S. Koch, A. Fill, K.P. Birke, Comprehensive gas analysis on large scale automotive
lithium-ion cells in thermal runaway, J. Power Sources 398 (2018) 106–112.
[22] A. Kriston, I. Adanouj, V. Ruiz, A. Pfrang, Quantification and simulation of thermal
decomposition reactions of li-ion battery materials by simultaneous thermal
analysis coupled with gas analysis, J. Power Sources 435 (2019), 226774.
[23] S. Bertilsson, F. Larsson, M. Furlani, I. Albinsson, B.-E. Mellander, Lithium-ion
battery electrolyte emissions analyzed by coupled thermogravimetric/Fourier-
transform infrared spectroscopy, J. Power Sources 365 (2017) 446–455.
[24] Q. Zhang, J. Niu, Z. Zhao, Q. Wang, Research on the effect of thermal runaway gas
components and explosion limits of lithium-ion batteries under different charge
states, J. Energy Storage 45 (2022), 103759.
[25] M. Henriksen, K. Vaagsaether, J. Lundberg, S. Forseth, D. Bjerketvedt, Laminar
burning velocity of gases vented from failed li-ion batteries, J. Power Sources 506
(2021), 230141.
[26] W. Li, S. Rao, Y. Xiao, Z. Gao, Y. Chen, H. Wang, M. Ouyang, Fire boundaries of
lithium-ion cell eruption gases caused by thermal runaway, iScience 24 (2021),
102401.
[27] S. Ogunfuye, H. Sezer, A.O. Said, A. Simeoni, V.Y. Akkerman, An analysis of gas-
induced explosions in vented enclosures in lithium-ion batteries, J. Energy Storage
51 (2022), 104438.
[28] W. Li, H. Wang, Y. Zhang, M. Ouyang, Flammability characteristics of the battery
vent gas: a case of NCA and LFP lithium-ion batteries during external heating
abuse, J. Energy Storage 24 (2019), 100775.
[29] S. Chen, Z. Wang, J. Wang, X. Tong, W. Yan, Lower explosion limit of the vented
gases from li-ion batteries thermal runaway in high temperature condition, J. Loss
Prev. Process Ind. 63 (2020), 103992.
[30] B. Gerelt-Od, J. Kim, E. Shin, H. Kang, N. Kim, C. Jo, H. Son, S. Yoon, In situ raman
investigation of resting thermal effects on gas emission in charged commercial
18650 lithium ion batteries, J. Ind. Eng. Chem. 96 (2021) 339–344.
[31] P. Wang, W. Chen, J. Wang, J. Tang, Y. Shi, F. Wan, Multigas analysis by cavity-
enhanced raman spectroscopy for power transformer diagnosis, Anal. Chem. 92
(2020) 5969–5977.
[32] A.R. Baird, E.J. Archibald, K.C. Marr, O.A. Ezekoye, Explosion hazards from
lithium-ion battery vent gas, J. Power Sources 446 (2020), 227257.
[33] A.W. Golubkov, S. Scheikl, R. Planteu, G. Voitic, H. Wiltsche, C. Stangl, G. Fauler,
A. Thaler, V. Hacker, Thermal runaway of commercial 18650 li-ion batteries with
LFP and NCA cathodes – impact of state of charge and overcharge, RSC Adv. 5
(2015) 57171–57186.
[34] Y. Liu, X. Liu, X. Li, Numerical investigation of hydrogen detonation suppression
with inert particle in pipelines, Int. J. Hydrog. Energy 41 (2016) 21548–21563.
11
Journal of Energy Storage 56 (2022) 105905
[35] Y. Peng, L. Yang, X. Ju, B. Liao, K. Ye, L. Li, B. Cao, Y. Ni, A comprehensive
investigation on the thermal and toxic hazards of large format lithium-ion batteries
with LiFePO4 cathode, J. Hazard. Mater. 381 (2020), 120916.
[36] S.-M. Bak, E. Hu, Y. Zhou, X. Yu, S.D. Senanayake, S.-J. Cho, K.-B. Kim, K.Y. Chung,
X.-Q. Yang, K.-W. Nam, Structural changes and thermal stability of charged
LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD
and mass spectroscopy, ACS Appl. Mater. Interfaces 6 (2014) 22594–22601.
[37] A.W. Golubkov, D. Fuchs, J. Wagner, H. Wiltsche, C. Stangl, G. Fauler, G. Voitic,
A. Thaler, V. Hacker, Thermal-runaway experiments on consumer li-ion batteries
with metal-oxide and olivin-type cathodes, RSC Adv. 4 (2014) 3633–3642.
[38] A.D. Pasquier, F. Disma, T. Bowmer, A.S. Gozdz, G. Amatucci, J.M. Tarascon,
Differential scanning calorimetry study of the reactivity of carbon anodes in plastic
li-ion batteries, J. Electrochem. Soc. 145 (1998) 472–477.
[39] J.-S. Shin, C.-H. Han, U.-H. Jung, S.-I. Lee, H.-J. Kim, K. Kim, Effect of Li2CO3
additive on gas generation in lithium-ion batteries, J. Power Sources 109 (2002)
47–52.
[40] Y. Fu, S. Lu, K. Li, C. Liu, X. Cheng, H. Zhang, An experimental study on burning
behaviors of 18650 lithium ion batteries using a cone calorimeter, J. Power Sources
273 (2015) 216–222.
[41] D. Aurbach, A. Zaban, Y. Ein-Eli, I. Weissman, O. Chusid, B. Markovsky, M. Levi,
E. Levi, A. Schechter, E. Granot, Recent studies on the correlation between surface
chemistry, morphology, three-dimensional structures and performance of li and li-
C intercalation anodes in several important electrolyte systems, J. Power Sources
68 (1997) 91–98.
[42] G. Gachot, S. Grugeon, G.G. Eshetu, D. Mathiron, P. Ribière, M. Armand,
S. Laruelle, Thermal behaviour of the lithiated-graphite/electrolyte interface
through GC/MS analysis, Electrochim. Acta 83 (2012) 402–409.
[43] H. Yang, G.V. Zhuang, P.N. Ross, Thermal stability of LiPF6 salt and li-ion battery
electrolytes containing LiPF6, J. Power Sources 161 (2006) 573–579.
[44] M.G. Zabetakis, in: Flammability Characteristics of Combustible Gases and Vapors
Bureau of Mines, Pittsburgh, PA (United States), 1964, pp. 114–116.
[45] X. Cao, Y. Lu, J. Jiang, Z. Wang, H. Wei, Y. Li, Y. Li, C. Lin, Experimental study on
explosion inhibition by heptafluoropropane and its synergy with inert gas, J. Loss
Prev. Process Ind. 71 (2021), 104440.
[46] B. Zhou, S. Yang, W. Yang, X. Jiang, W. Song, J. Cai, Q. Xu, Z. Tang, Variation
characteristics of active groups and macroscopic gas products during low-
temperature oxidation of coal under the action of inert gases N2 and CO2, Fuel 307
(2022), 121893.