Process Safety and Environmental Protection 139 (2020) 133–146

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Refined study on lithium ion battery combustion in open space and a

combustion chamber
Binbin Mao a , Haodong Chen b , Lin Jiang a , Chunpeng Zhao a , Jinhua Sun a ,
Qingsong Wang a,∗
a
State Key Laboratory of Fire Science, University of Science and Technology of China, JinZhai Road 96, Hefei, Anhui, 230026, China
b
School of Engineering, University of Warwick, Coventry, CV4 7AL, UK

a r t i c l e i n f o a b s t r a c t

Article history: More refined combustion tests on 18,650-type lithium ion batteries (LIBs) are conducted both in open
Received 10 January 2020 space (OS test) and a combustion chamber (CC test). High-speed camera is used to capture the fast rupture
Received in revised form 11 March 2020 and ignition of LIB. In OS tests, jet-flame height increases with the state of charge (SOC), ranging from
Accepted 29 March 2020
0.095 to 0.217 m for 70–100% SOC cell. The ejecting velocity of fragments reaches 30 m s−1 . In CC tests, the
Available online 11 April 2020
electrolyte solvent and flammable gas products are ignited by the ignition rods leading to deflagration
and more complete combustion than that in open space. The predicted mass loss ratio of LIB is 14.36%
Keywords:
agreeing with experiments. As SOC increases, more lithium metal is available in anode to react with
Lithium ion battery safety
Jet flame
electrolyte to generate more flammable gases. Higher SOC leads to higher specific combustion heat of
Flame height the mixed gas products, thus increases the severity of thermal runaway and combustion. The total heat
Combustion chamber release of a LIB fire can be predicted by adding the contribution of all organics’ combustion heats based
Heat release rate on thermodynamic data.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Nomenclature
Lithium ion batteries (LIBs) have been widely used for their
high capacity, long cycle life and friendly to environment. Mean- A Specific oxygen consumption
while, the fire accidents caused by thermal runaway (TR) of LIB are D Diameter of nozzle (mm)
reported frequently (Lisbona and Snee, 2011; Wang et al., 2012). Estored Electric energy stored in the cell (J)
An LIB contains four main components: cathode, anode, separa- HRR Heat release rate (kW)
tor and electrolyte. The conventional cathodes are the oxides of HRsvo Heat release at the safety valve open (kJ)
transition metals, and the anode is often the natural graphite. The L Flame height (m)
electrolyte is the solution of lithium salts dissolved in carbonates- mloss Mass loss (g)
based solvent. These materials are active to react with each other QF Specific heat generation (MJ kg−1 )
exothermically under high temperature (Wang et al., 2012). There THR Total heat release (kJ)
have been many researches about the thermal property of these THRwhole Total heat release of the whole test process (kJ)
components using thermal analysis tools such as differential scan- YOX,∞ Mass fraction of oxygen in ambient air
ning calorimetry (Röder et al., 2014), C80 micro calorimeter (Wang
Subscripts
et al., 2009) and accelerating rate calorimeter (Mao et al., 2020; Wu
jf Jet flame
et al., 2018).
sf Stable combustion flame
In addition to thermal analysis, combustion tests (Huang et al.,
2016, 2015; Ping et al., 2018; Ribière et al., 2012) on the commercial

LIBs were also conducted in order to show their TR process and

∗ Corresponding author.
E-mail addresses: icemao@mail.ustc.edu.cn (B. Mao), linghao@ustc.edu.cn
(H. Chen), jianglin@ustc.edu.cn (L. Jiang), ustczcp@mail.ustc.edu.cn (C. Zhao),
sunjh@ustc.edu.cn (J. Sun), pinew@ustc.edu.cn (Q. Wang).
damage power. When the LIB is exposed to external heating, the
cell case swells firstly due to the vaporization of electrolyte and gas
generation from chemical reactions. For pouch cells, the swell can
be observed, while the swell of the cell with hard case may not be

https://doi.org/10.1016/j.psep.2020.03.037
0957-5820/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
134 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
visible. Then the safety valve, if the cell has one, is opened to release
solvent vapors accompanied with gas products and aerosols. For
some other types of LIBs without safety valve, such as pouch cells,
the shell will be cracked for the high inner pressure. If temperature
continues increasing, the oxygen produced by the decomposition
of cathode (Liu et al., 2018) or lithium salts (Chen et al., 2016) can
react with electrolyte solvent and anode. Finally, the LIB falls into
TR with temperature skyrocketing and aggressive material ejection
(Finegan et al., 2015). The ejected materials may combust in the air
leading to fire accidents. Koch (Koch et al., 2018) reported that the
solid mass loss accounts for a major fraction of the total mass loss
for LIB.
The previous studies mainly focused on the influence of state
of charge (SOC) (Chen et al., 2015; Fu et al., 2015; Huang et al.,
2015; Ping et al., 2015; Ribière et al., 2012; Said et al., 2019a),
cathode materials (Chen et al., 2019, 2015; Liu et al., 2016; Said
et al., 2020) and environmental pressure (Chen et al., 2019) on
LIB’s fire features. As SOC increases, the fire risk and severity of
LIB also increase. Stoliarov’s group designed Copper Slug Battery
Calorimetry (CSBC) combined with oxygen consumption calorime-
try to investigate the heat generation inside the battery and of the
flaming combustion simultaneously (Liu et al., 2015, 2016; Said
et al., 2019a), and this technique was also promoted to investi-
gate the cascading failure of LIB arrays (Said et al., 2020, 2019b).
Heat release rate (HRR), voltage, temperature variation and gas
products are the normal output data. Fire risks of the flammable
electrolyte solvent released at safety valve open may be ignored
in previous studies (Chen et al., 2015; Fu et al., 2015; Wang et al.,
2019b) for the lack of ignition device. Liu (Liu et al., 2015, 2016)
and Said (Said et al., 2019a) utilized heating wire to ignite the
gases released at safety valve open, and found that the combus-
tion heat at safety venting was comparable or higher than that
released at TR (Liu et al., 2015). Liao et al. (Liao et al., 2020) inves-
tigate the gas products of NCM LIB during TR with the aid of sealed
pyrolysis autoclave and gas chromatography-mass spectrometer.
The flammable gases were mainly carbon oxides, hydrocar-
bons, C2 H4 O2 and C2 H6 O, and the types of the gases increased
with SOC.
Besides, the trigger of TR is too fast to be caught by naked eyes
or digital video, and the time scale of the rupture process is in mil-
liseconds. Finegan et al. (Finegan, 2016; Finegan et al., 2017, 2018;
Finegan et al., 2015) utilized the high-speed tomography to inves-
tigate the thermal runaway process of LIB, and their study showed
the collapse process of the electrode rolls inside the LIB. Spinner
et al. (Spinner et al., 2015) used high-speed camera to investigate
the lithium ion battery cell-to-cell failure events inside custom fire
chamber. Some batteries experienced sustained flame while oth-
ers only had sparks (Spinner et al., 2015). Avdeev et al. (Avdeev and
Gilaki, 2014) used the high-speed camera to capture the nonlinear
mechanical deformation of the LIB when exposed to lateral impact.
In this study, we will focus on the trigger stage and ignition process
of LIB fire. It’s meaningful to reveal the phenomenon of ignition
stage that can help us understand the TR mechanism of LIB and
make proper precautions. Therefore, observing the trigger stage of
TR is truly one of the goals of this paper with the aid of high-speed
camera.
As stated above, a large portion of the cell materials are ejected
out during TR including solids and gases, and the former accounts
for the majority according to Koch’s study (Koch et al., 2018). In
this study, a combustion chamber with ignition rods is designed
in the more refined study on LIB’s combustion characteristics. The
chamber collects the solid ejections that are also considered as a
part of the burning residue. The mass difference between the intact
cell before test and the burning residue is mainly caused by the gas
exhausting. Scorching ignition rods can ignite the solvent vapors,
flammable gas products and aerosols immediately leading to more
Table 1
Basic parameters of the cell sample.
Description Value Unit
Mass 44.0 ± 0.3 g
Cut-off voltage (charge/discharge) 4.2/2.75 V
Surface area 0.0042 m2
Stored electric energy (Estored ) 2903.4 ± 715.5 (0% SOC, pseudo) J
14765.4 ± 738.6 (50% SOC)
20,210.0 ± 434.6 (70% SOC)
23,810.5 ± 841.4 (80% SOC)
24,988.1 ± 609.9 (90% SOC)
28,207.4 ± 511.9 (100% SOC)
complete combustion and help us know the burning feature of LIB
more deeply.
In this paper, two series of refined combustion tests on the
18,650-type Li(Ni0.5 Co0.2 Mn0.3 )O2 /graphite based LIBs with differ-
ent SOCs were conducted, one in open space and the other involving
a confinement chamber. The combustion behaviors of LIB under
these two different conditions are investigated comprehensively
from the aspect of fire behavior, mass loss, fuels and heat release. In
open space tests (OS tests), a high-speed camera was used to record
the fast trigger process of TR. The flame type was determined and
the flame height was quantified. In the combustion chamber tests
(CC tests), a cylindrical combustion chamber was applied to col-
lect the solid ejections, and the mass difference between the intact
cell before test and the burning residue is mainly caused by the
gas exhausting. The aerosols and gases were ignited immediately
by scorching rods at the rupture of the safety valve and TR, lead-
ing to more complete combustion. X-ray diffractometry (XRD) was
used to show the phase change of cathode after TR. The influence
mechanism of SOC on combustion behavior is revealed form the
aspects of fuel and internal reactions. A non-destructive method is
proposed to estimate the combustion heat of LIB.
2. Experimental setup
2.1. Test samples
The test samples were commercial 18,650-type cylindrical bat-
teries (98% Li(Ni0.5 Co0.2 Mn0.3 )O2 +2% LiMn2 O4 /graphite, nominal
capacity: 2.0 Ah), which were 18 mm in diameter and 65 mm in
length. The organic solvent of electrolyte was the mixture of ethy-
lene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl
carbonate (EMC) with specific combustion heat of 12.38, 18.41 and
14.56 MJ kg−1 , respectively (Eshetu et al., 2013). The lithium salt is
LiPF6 , and the separator is ceramic coated on both sides (Mao et al.,
2018). In order to know the mass distribution of the components,
the fully discharged cell was disassembled in glove box with the
tube cutter and nipper plier. The mass of the electrolyte solvent was
obtained after drying the jelly roll. The separator was weighed after
washed by DMC and dry. The electrode materials were scraped off
the current collector with the aid of N-Methylpyrrolidone. The mass
ratios of the ingredients in electrolyte or electrodes were assessed
after consulting with manufacture and referring to the industrial
data base (Ping et al., 2015; Ribière et al., 2012). Fig. 1 shows the
mass distribution of the test sample.
The cell was first fully charged, and then discharged to the
desired SOCs by setting the ratio of discharged capacity to the cell’s
nominal capacity. The electric energy stored in the cell at the cut-off
voltage of discharge, 2.75 V, is regarded as the zero point of electric
energy. The basic parameters of the cell are listed in Table 1, and
the electric energy is read from battery cycler.
The experiment contains two parts: 1. OS test, i.e. the cells
combusted in open space; 2. CC test, i.e. the cells combusted in
 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Fig. 1. Mass fraction of the cell’s components (total mass is 44.0 ± 0.3 g).
Fig. 2. Photos of the battery samples.
a combustion chamber. The battery sample, electric heater and
heating power of these two tests are the same.
2.2. Apparatus and experimental procedures
2.2.1. OS test
In OS test, batteries were charged to high SOCs: 70%, 80%, 90%
and 100% in order to observe jet flame. The photos of the battery
samples are shown in Fig. 2, and the cells’ external plastic packages
are striped. When the LIB falls into TR, the positive cap can block the
vertical ejection, and the gases will eject from the five holes with
lotus-like flame (Zhong et al., 2018), so the flame height can’t be
measured. In order to observe the vertical jet flame and measure the
flame height, the gases should eject vertically, thus the positive cap
of the battery was removed prior to tests. Fig. 2(b) shows the cutting
method of the cap. As shown in subgraph (a), the positive cap is
similar to the tab of a pouch cell, and its remove does not influence
the chemical property or cycle performance of the battery.
Fig. 3 shows the experimental setup of OS test. The battery was
housed in a self-made cylindrical hollow heater with a power of
150 W. The height of the heater was 80 mm, and the outer diameter
was 61 mm. The battery container was made of copper and stainless
steel whose thickness were both 7.5 mm as shown in Fig. 3. The cop-
per with high thermal conductivity could enhance heat conduction
and heat the cell uniformly. The stainless steel guaranteed safety
in case of explosion of the cell. A heating element with 5.5 mm
135
in thickness wrapped around the stainless steel tightly and uni-
formly. In some tests, a thermocouple with 1 mm in diameter was
pasted on the battery surface. Therefore, the space of the thermo-
couple and paste tape should be considered, and sometimes, the
cell might swell after TR. So the inner diameter of the hollow heater
was 20 mm that was a little wider than the cell’s diameter (18 mm)
for the convenience of insertion and pulling out of the specimen.
As shown in Fig. 3, the red region represents a battery. The heater
was placed in the ambient air. Due to the narrow space inside the
internal cavity and the high thermal conductivity of the copper,
this self-made heater can heat the cell to TR effectively. Using this
heater, the time to TR and trigger temperature of TR showed good
repeatability according to our previous study (Zhong et al., 2018),
which proved that our self-made heater was reliable.
A high-speed camera (Phantom, v710, 7000 frames per second
(fps)) was used to capture the fast trigger process of TR. Meanwhile,
the phenomenon was monitored by a digital video (DV) camera
(Sony, HDR-CX900E, 50 fps), and the flame height was measured
based on video (Orloff, 1981; Tao et al., 2016). The flame tempera-
ture was recorded by four K-type thermocouples with diameter of
0.5 mm. The distance between each thermocouple was 3 cm, and
the distance between #4 thermocouple and battery top surface
was 1.5 cm as shown in Fig. 3. The temperature variation of the
same battery sample with same heating method was exhibited in
our previous study (Zhong et al., 2018). The combustion features,
including flame shape, mass loss and heat release, are the focus of
this study. Repeatability is important for battery combustion tests,
in order to ensure reliable experimental results, every test under
the same SOC was repeated as high as 12 times.
2.2.2. CC test
Combustion chamber technique was initially presented in Ref.
(Said et al., 2019a) to study the combustion of battery materi-
als ejected from prismatic cells. Subsequently, this technique was
modified to fit cells of 18,650 form factor to investigate the cascad-
ing failure of lithium ion cell arrays (Said et al., 2019b). In our study,
six different SOCs (0, 50, 70, 80, 90 and 100%) of the battery sam-
ples were burned inside the combustion chamber. The combustion
heat measured by experiments is compared with the theoretical
calculation, and the differences between the combustion behavior
in open space and in chamber will be revealed.
As shown in Fig. 4, both the heater and battery sample were
placed inside the combustion chamber that was made by a stain-
less steel tube with 10 cm in inner diameter and 18 cm in height
and used to collect the flammable gases and material ejections. In
order to homogenize the flow of ejected battery materials before
they reached the ignition rods, an iron wire mesh was placed at
the outlet of the chamber. The line diameter of the wire mesh
was 0.33 mm, and the distance between two neighboring lines was
2.72 mm. Five stainless-steel ignition rods (each was about 200 W)
were fixed on the wire mesh to ignite the released aerosols and
gases. The diameter and length of the ignition rods were 1 and
14 cm, respectively. The ignition rods were evenly distributed at
the outlet of the chamber and the spacing between the central lines
of the neighboring rods was 2 cm. The temperature of ignition rods
was as high as 700 ◦ C, and the temperature between two rods was
higher than 350 ◦ C. The detailed temperature data of ignition rods
are shown in supplemental materials S1 (Fig. S1). All these appara-
tuses were under the hood of a standard cone calorimeter (FTT) as
shown in Fig. 4. The dimension of the exhaust hood made of stain-
less steel was 41 cm × 41 cm. The exhaust gases were all collected
by the hood and transferred to the gas analyzer (SERVOPRO 4100) to
measure HRR based on oxygen consumption method (Babrauskas,
1984). The fan flow rate was 24 L s−1 . Every test under each SOC
was repeated 6 times.
136 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146

Fig. 3. Schematic of the experimental setup of OS test. Not drawn to scale.

Fig. 4. Schematic of the experimental setup of CC test (not drawn to scale), referred to Ref. (Said et al., 2019a).

After the experiments, the batteries were disassembled in air,
and the residual cathode materials were collected to do XRD anal-
ysis to reveal the phase changes as a result of combustion and the
reactions happening in cathode.
3. Results and discussion
3.1. OS test
3.1.1. Combustion phenomenon of LIB in open space
When the battery gets into TR, violent jet flame may occur. The
representative video of the 100% SOC cell’s combustion in OS test
is shown in supplemental video 1. Sometimes, the flame may be
blown off by the high-speed ejection in OS test, and the combus-
tion process would be shorter. However, in most cases, the gases
are ignited and the flame is not blown off, thus the combustion will
last longer and have similar process. The representative combus-
tion process of OS test is shown in Fig. 5 and the supplemental video
1. As exhibited in Fig. 5, the combustion process can be summarized
into the following stages: ejection of solid and gaseous mixture,
solid phase combustion in the form of sparks, intermittent fire balls
and jet flames, stable gaseous flame, abatement and extinguish-
ment. When the battery was over heated, the flammable gases and
electrolyte vapors flowed upwards after the open of safety valve,
and their amount increased dramatically just before TR as shown
in Fig. 5(a). When sparks ejected, the flammable gases could be
 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Fig. 5. Whole combustion process recorded by DV camera.
ignited forming aggressive fire balls. Three successional fire balls
are observed by DV camera, whose interesting details are recorded
by the high-speed camera as shown in Fig. 6. After fire balls, a short
extinguishment appeared and followed by jet flames immediately,
and the jet flame ejected upwards during TR. The shape of the
jet flame was ellipsoid, accompanied by a large quantity of black
smoke as shown in Fig. 5(h–k). After jet flame, combustion became
stable and the flame was jumping. Finally, flame weakened and
extinguished.
The high-speed camera (7000 fps) can record the fast trigger
process of TR, especially the rotation and split of fire balls. Driven by
the high pressure gases, the first fire ball rotated rapidly as shown
in Fig. 6(c–d). Divided by the symmetry axis of battery, the left fire
ball rotated in anti-clockwise direction while the right one did so
in clockwise direction (Fig. 6(d)). With the formation of vortices,
more fresh air was entrained leading to more complete and intense
combustion, so the luminance of fire ball increased with the spin-
ning of the gas swirl as shown in Fig. 6(c–d). As for the third fire
ball, the original big fire ball was split into three separated ones as
shown in Fig. 6(f–h). The three white arrows indicate their moving
directions. The luminance of three fire balls increased as they were
moving to the edge. The last two pictures show the stable jet flame
combustion.
In order to analyze the ejecting speed and destructive power
of LIB TR, two electrode fragments, P1 and P2, are selected in
Fig. 6(g–h). Taking the battery nozzle as the origin of coordinates,
the motion paths of P1 and P2 are shown in Fig. 7(a). The fragments
eject in the nearly vertical direction, and their heights vs. time are
137
shown in Fig. 7(b). The ejecting velocities of P1 and P2 are calculated
to be 25.71 and 29.91 m s−1 , respectively.
The battery flame temperature is estimated to be 1000 ◦ C
according to the thermocouple data as shown in supplemental
materials Fig. S3. At different stages, the flame types are also differ-
ent. The jet flame is found to be turbulent and driven by momentum,
while the flames during stable combustion and abatement stages
are laminar and driven by buoyancy (Delichatsios, 1993; Hu et al.,
2013). The detailed determination process of flame type is shown
in supplemental materials (Section S2).
3.1.2. Flame height in open space
The flame height here employs the time-average flame height
rather than the mean flame height at which the intermittency is 0.5
defined by Zukuski (Zukoski et al., 1985). Each frame of the video
was cut into single picture, then transformed into binary figures by
Matlab software (Huang et al., 2015). The detailed image processing
method is shown in supplemental material S3. The binary figure is
saved as a matrix in Matlab, and each pixel is an element in the
matrix. The value of the element in the flame region is 1 while the
value of the background region is 0. The flame height on each frame
is calculated based on the matrix and image scale. The time-mean
height of the jet flame (Ljf ) and the stable combustion flame (Lsf )
are shown in Table 2. D is the diameter of the nozzle measured
by the vernier caliper after TR, and the value was 6.98 mm. The
pictures of the nozzles are shown in the supplemental materials
(Fig. S2). Ljf is generally larger than Lsf , and both increase with SOC.
It should be noted that the values of Ljf /D for common gas fuels
138 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146

Fig. 6. Images of the LIB combustion recorded by high-speed camera.

Table 2 the burner (Delichatsios, 1993; Glassman et al., 2014). In addition to

Flame height and specific combustion heat of the mixed gas products by LIB TR.
the nozzle diameter, Fu et al. (Fu et al., 1989 (in Chinese)) derived
SOC (%) Ljf (m) Ljf /D Lsf (m) QF (MJ kg−1 ) that the height of the turbulent jet flame was also proportional
70 0.095 ± 0.050 13.604 ± 7.140 0.076 ± 0.027 5.185 ± 2.721 to the specific oxygen consumption of the fuel (A) and the mass
80 0.166 ± 0.060 23.798 ± 8.563 0.096 ± 0.051 9.071 ± 3.264 fraction of oxygen in ambient air (YOX,∞ ) as shown in Eq. (2)
90 0.185 ± 0.042 26.523 ± 5.950 0.112 ± 0.020 10.109 ± 2.268   
100 0.217 ± 0.076 31.140 ± 10.818 0.123 ± 0.037 11.869 ± 4.123
3
Ljf = AD/ 8 cYOX , ∞ (2)
2
(230 for methane; 350 for propane; 175 for hydrogen; and 50 for
CO) (Heskestad, 1999) are larger than that of LIB in this study. CO2 where c is a constant equal to 0.0128 for cylindrical free jet flame;
(non-combustible) accounts for a large portion of the gas released YOX,∞ is 23.3%. Based on the measurement results of Ljf , A can be
from LIB. Golubkov (Golubkov et al., 2014) and Said investigated the calculated according to Eq. (2). The specific heat generation of the
composition of the gas released from NCM LIB during TR, and found mixed gas products, QF , is proportional to A (QF = 13.1 MJ kg−1 ×A
that fractions of CO2 (mol%) were 41.2% (Golubkov et al., 2014) and kg) according to oxygen consumption theory (Babrauskas, 1984),
24.3% (Said et al., 2020), respectively. As reported in literature (Kim and the calculation results are shown in Table 2.
et al., 2011), the normalized flame length of the diluted hydrogen Golubkov et al. (Golubkov et al., 2014) measured the com-
jet decreases dramatically (about 33% decrease) with the addition ponents of the gas products (mol%) generated by 100% SOC
of inert gases (N2 and CO2 , volume fraction = 20%) to the fuel, due to Li(Nix Coy Mnz )O2 (NCM) cell after TR, and the combustion heat
the reducing of the local reaction rate and lower burning velocity. of these gas products is calculated to be 11.66 MJ kg−1 accord-
So it is also understandable that the Ljf /D of LIB’s TR gas products is ing to the gas components, which agrees well with our result,
lower compared to pure fuels because of CO2 emerging. 11.869 ± 4.123 MJ kg-1 , as shown in Table 2. QF is close to the
As stated in supplemental material S2, the jet flame in this study heat value of some common gas fuels, such as CO (10.071 MJ kg−1 )
is turbulent non-premixed free jet flame. The overall combustion (Glassman et al., 2014) and water gas (bituminous, 11.354 MJ kg−1 ).
reaction can be assumed as The increase of A and QF with SOC indicates that higher SOC does
not only increase the electrical energy stored in the battery, but
(1kg)F + (Akg)OX → [(1 + A)kg]P+Q F (1)
also leads to higher specific combustion heat of the released gas
where F, OX and P represent the fuel (i.e. the mixed gas products products, thus increases the risk and severity of fire. It helps us to
released by TR battery), oxidant and combustion product, respec- understand the influence mechanism of SOC on the fire risk and TR
tively. QF is the specific heat generation of F. Here the oxidant is severity of LIB from the aspect of the specific combustion heat of
oxygen. The height of turbulent diffusion flame is proportional to the released gas products, and the detailed mechanism is analyzed
the nozzle diameter, D, while irrespective of the fuel velocity from in Section 3.2.5.
 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Fig. 7. Movement of the two fragments (P1 and P2) in Fig. 6(g–h).
3.2. CC test
3.2.1. Burning behavior of LIB in CC test
The combustion in CC test has two visible burning processes
(except 0% SOC batteries): 1. combustion of electrolyte solvent and
other gas products at the safety valve open; 2. deflagration at TR.
The upper 3 rows of Fig. 8 shows the fire behavior of 0, 50 and 100%
SOC batteries with combustion chamber and ignition rods, and the
last row shows the phenomena of safety valve open and TR of 0 and
50% SOC batteries in open space. The detailed videos of the battery
combustion in CC tests are shown in supplemental videos 2–5.
A flame bursts at the rupture of safety valve because the ejected
aerosols and gases are ignited immediately by the ignition rods as
shown in Fig. 8(a), (e) and (i), while the flame does not occur in (m)
and (o) without chamber or ignition rods although many gases and
aerosols are also released. When the battery goes into TR, the 50%
SOC battery without combustion chamber only ejects sparks and
gases but does not combust, while a deflagration flame is observed
in Fig. 8(g). It shows that combustion chamber and ignition rods can
lead to more complete and violent combustion. As SOC increases
(50%→100% SOC), the flame of TR and deflagration becomes more
violent and dazzling as shown in Fig. 8(g) and (k).
It is interesting that although there are many aerosols and gases
released by 0% SOC battery at TR in Fig. 8(n), no deflagration is
observed in Fig. 8(c) even with the combustion chamber and igni-
tion rods. It indicates that most gases released by 0% SOC battery
at TR are not combustible. The mechanism of this interesting phe-
nomenon will be discussed in Section 3.2.5.
3.2.2. Mass loss
The combustion chamber collected the ejected solid materials
that are also considered as a part of the burning residue. The intact
cell was weighed before test, then the mass of combustion residues
was measured after test, and the mass loss (mloss ) was their differ-
ence value. So gas exhausting was the main inducements of mass
loss in CC test. The mass loss ratio to the battery’s initial mass is
shown in Fig. 9(a). An exponential relationship between mloss and
Estored is found (lg(mloss ) = 0.021Estored +0.514, R2 = 0.948) as shown
in Fig. 9(b), indicating that the mass loss increases with Estored and
its increasing speed has an ascending trend with Estored .
According to the decomposition path of LiPF6 (Larsson et al.,
2017), LiF is remained in the burning residue as well as the Al2 O3
coating on separator (Al2 O3 coating accounts for 65 wt. % of our
separator). Thanks to the mass distribution of the cell that was mea-
sured previously (Fig. 1), we could predict the contribution of the
139
mass loss ratio for organics namely the binder (3.66%), electrolyte
solvent (7.58%), PE in separator (2.17%) and PF5 in LiPF6 (0.95%), as
shown in the first column of Fig. 9(a). It should be noted that this
prediction does not include the mass loss of Li(Ni0.5 Co0.2 Mn0.3 )O2
caused by its disproportionation and oxygen release. The predicted
total mass loss ratio is 14.36% close to the experimental results of
0 and 50% SOC batteries as shown in Fig. 9(a). The deflagration was
more violent at higher SOC, so smoke and exhausted gases also took
away more solid powders. On the other hand, as SOC increases, the
amount of the high valence state Ni and Co ions increases, so cath-
ode material can produce more oxygen and lead to higher mass
loss. Thus the mass loss increases with SOC and may exceed the
total mass of organic materials at 70–100% SOC.
3.2.3. Generation of COx and conservative analysis on gas toxicity
Another important feature of LIB fire is the toxic gas release
from liquid evaporation, thermal decomposition, chemical reac-
tion between cell components and incomplete combustion. The gas
compositions are complicated including HF, PF5 , POF3 , NOx , COx and
SO2 (Larsson et al., 2014; Lecocq et al., 2016; Ribière et al., 2012).
In this study, the gas we focus on is COx (CO2 and CO). The gas gen-
eration rate of COx during combustion is shown in supplemental
material S4: Fig. S8. The gas generation rates reached peak values
when TR occurred. The total COx generation is determined by the
integration of the generation rates from the onset of safety venting
to the end of TR as shown in Table 3 as well as the normalized value.
As SOC increases, the generations of CO and CO2 have an increase
trend. In Said’s combustion test on the fully charged NCM LIB array
(Said et al., 2020), the normalized production of CO is 0.035 ± 0.007
per initial mass of failed cells in N2 atmosphere, which is higher
than our results (0.019 ± 0.003). The difference indicates that the
CO produced by the cell is a fuel and burned in the flaming com-
bustion. Therefore, the CO detected during combustion may be the
rest of the original CO that is not burned or the products of the
incomplete combustion of other carbonous substances.
Carbon monoxide is a tasteless, odorless, non-irritating but
highly toxic gas, and any exposure to ambient air with CO lev-
els higher than 100 ppm (vol%) would be dangerous to human
health (Prockop and Chichkova, 2007). Acute CO toxicity can occur
when ambient air with CO levels reaching 1000 ppm (vol%), i.e.
unconsciousness, respiratory failure, and death after 1 h of expo-
sure (Omaye, 2002). From experiments, the maximum generation
of CO is 1.141 g, i.e. 0.146 g Wh−1 . Irreversible Effects Threshold
(IET) and First Lethal Effects Threshold (FLET) (INERIS, 2009; Ribière
et al., 2012) are two toxicity limit values defined in the French
140 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146

Fig. 8. Fire behavior of different SOC cells with (a–l) and without (m–p) combustion chamber.

regulatory context to perform toxic hazard studies in industrial energies of our test batteries required for reaching the individual
environment. We consider the maximum quantity of CO release, toxicity limit IET and FLET at 60 min exposure time are 319 Wh
and the gas is evenly distributed in a room of 50 m3 . According (equivalent to 41 LIB samples in our study) and 1257 Wh (equiva-
to the basic extrapolation in Ref. (Ribière et al., 2012), the electric lent to 160 LIB samples in our study), respectively. Generally, one
 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Fig. 9. Mass loss data. (a) is the comparison between the predicted and experimental mass loss ratio; (b) is semi-log plot of mloss vs. electric energy stored in cell.
Table 3
Generation of CO and CO2 for different SOC batteries in CC tests.
Gas generation (g) Normalized gas generation (mg/g)a
SOC
CO CO2 CO
70% 0.65 ± 0.15 7.64 ± 1.05 14.86 ± 3.51
80% 0.68 ± 0.10 8.01 ± 0.93 15.45 ± 2.33
90% 0.63 ± 0.13 8.85 ± 1.02 14.41 ± 3.06
100% 0.85 ± 0.13 8.81 ± 1.06 19.22 ± 3.02
a
Normalized by dividing cell’s initial mass.
Tesla electric car contains over seven thousand 18,650-type cells,
and the energy storage system is about 85 kW h exceeding the crit-
ical electric energy 319 and 1257 Wh greatly. It should be noted
that the above section is a conservative analysis on the gas toxic-
ity without considering other toxic gases such as HF, PF5 , and Nox .
This conservative analysis still warns us that emerging e-mobility
application would actually deserve dedicated studies focusing on
the toxicity impacts in the case of EV fire. For storage fires and elec-
tric car fires, the volume may be less than 50 m3 due to confinement.
If fire propagated to neighboring cars, the toxicity would be worse
and more fatal.
3.2.4. Peak HRR and the influence of the oxygen released from
cathode
HRR is a common indicator of fire hazard reflecting heat release
rate. The typical HRR curves are shown in Fig. 10(a)-(b) and supple-
mental materials (Fig. S9). Except 0% SOC battery, the HRR curves
of 50–100% SOC present two distinct peaks attributed to the com-
bustion after safety valve open and deflagration at TR, respectively.
As for the 0% SOC battery, flame only occurred after the open of
safety valve but deflagration was not observed at TR. The peak HRR
is normalized by the battery surface area (0.0042 m2 ) as shown
in Fig. 10(c), and it shows an increase trend with the ascending
of SOC. The normalized HRRs of batteries with 100% and 90% SOC
are slightly higher than that of fuel oil and that of PE, respectively.
For 80% SOC battery, this is equivalent to that of PPMA while the
0% SOC battery presents the lowest value. The 100% SOC battery
has an extremely high reaction rate when going into TR, and the
combustion heat is released in a short time. The high reaction rate
not only lies in the higher combustion rate, but also in the faster
exothermic redox processes at the electrolyte/electrodes interface
141
and in the faster heat release at internal short-circuit (Ribière et al.,
2012).
The layered NCM cathode materials release oxygen during phase
change when exposed to high temperature (Bak et al., 2013, 2014;
CO2
Röder et al., 2014), and the phase change of different SOC cathodes
173.57 ± 23.91
after TR will be shown in Fig. 12. For the clean cathode materi-
182.15 ± 21.20
201.11 ± 23.12 als without electrolyte, mass spectroscopy detected oxygen and
200.17 ± 24.12 CO2 release when exposed to high temperature (Bak et al., 2013).
However, oxygen is not detected in the thermal analysis tests on
the components’ mixtures (Kong et al., 2005; Liu et al., 2018) or in
the TR gas products from commercial cells (Fernandes et al., 2018;
Golubkov et al., 2014; Larsson et al., 2018; Wu et al., 2013). Sto-
liarov’s group (Liu et al., 2015) measured the gases released from
a NCM 18,650-type battery during TR with a chamber purged with
nitrogen, and found that the oxygen production is too small to
influence the HRR measurement by cone calorimeter. They also
conducted TR propagation tests on the 18,650-type NCM battery
pack in N2 atmosphere, and found that the amount of O2 was rel-
atively small and only accounted for 0.1% of the total gas products
(mol%) (Said et al., 2020). The chemical crosstalk (Liu et al., 2018),
i.e. the cathode-produced oxygen is consumed by anode with great
heat generation, is another mechanism of LIB TR. In other words,
the majority of the oxygen released by cathode should be con-
sumed inside the commercial cell, and the amount of the oxygen
ejected out was too small to influence the HRR measurement by
cone calorimeter. So in this paper, the total heat release (THR) of
the battery combustion is the integration of the HRR curves without
considering the effect of the oxygen released by cathode.
3.2.5. THR and fuel analysis
THR of the whole test process (THRwhole ) is calculated by inte-
grating HRR curve from the open of safety valve to the end of TR. As
shown in Fig. 10(c) and (d), the peak HRR shows an increasing trend
with SOC, and THRwhole does so when SOC increases from 0% to 70%
but approximately keeps a constant value when SOC is 70–100%.
The deflagration reaction becomes more violent as SOC increases
which is shown in the supplemental videos 2–5. The combustion
heats normalized by the cell’s initial mass are shown in Table 4.
The combustion heats of the highly charged NCM cells (70–100%
SOC cells) in CC tests are similar with Said’s results that the heat
of flaming combustion of individual NCM cell is 2.3 ± 0.3 kJ g−1 in
CSBC experiments (Said et al., 2020).
142 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146

Fig. 10. HRR and total heat release (THR) for different SOC cells: (a)-(b) is the typical HRR curves of 0% and 90% SOC cells, respectively, the HRR variations of 50%, 70%, 80%
and 100% SOC cells are shown in supplemental materials (Fig. S9); (c) is the normalized peak HRR (MW m−2 ) by battery surface area; (d) is HRsvo , THRwhole , their ratio and
the predicted THR.

Table 4 lated in anode is a critical ingredient to generate flammable gases

Normalized combustion heat per initial cell mass of CC tests.
SOC Combustion heat (kJ g−1 )
0% 0.7 ± 0.1
50% 1.2 ± 0.1
70% 2.3 ± 0.2
80% 2.0 ± 0.2
90% 2.3 ± 0.3
100% 2.2 ± 0.2
The heat release at the safety valve open (HRsvo ) is the integra-
tion of HRR curve after safety valve open excluding the later heat
release at TR and deflagration. The time gap between safety valve
open and TR is about 2 min, and electrolyte solvent vapors are the
main flammable gases (Fernandes et al., 2018; Larsson et al., 2018).
For 0% SOC cells, the combustion heat (30 kJ) are mainly related to
the combustion of solvent at the safety valve open because there
was no deflagration at TR as stated in Section 3.2.1 and Fig. 10(a).
Thus HRsvo /THRwhole of 0% SOC could be regarded as 100%. How-
ever, this parameter has a decrease trend from 45% to 37.5% as
SOC increases from 50% to 100%, indicating that the importance of
the solvent released at the safety valve open is decreasing as SOC
increases, and the flammable gas products released at TR become
the dominant fuel of LIB fire.
During the later TR and deflagration, the flammable gases
produced by inner chemical reactions include H2 , CO and hydrocar-
bons. The detailed reactions contributed to these gas generations
are shown in supplemental materials S6, and the lithium interca-
(Golubkov et al., 2014; Jiang et al., 2018; Wang et al., 2019a). There-
fore, no deflagration was observed for 0% SOC cell as shown in
Fig. 8(c) due to the lack of lithium in anode. As SOC increases, more
intercalated lithium is available to generate flammable gases. This
is another important mechanism by which the SOC influences the
TR risk and severity of LIB.
In addition to flammable gas products, separator is also an
important fuel in LIB fire, and its combustion heat is calculated
in next paragraph. However, the security threat of separator is its
melting to cause a large area of internal short circuit rather than
burning to release heat. On the other hand, electrolyte solvent can
eject, flow out, and react with lithium to release flammable gases,
so the solvent has higher fire threat than separator.
The mass ratio of EC, EMC and DMC is regarded as 1:1:1 in elec-
trolyte solvent. The separator is Al2 O3 -coated on both sides, and the
inner polymer PE only accounts for 35% (Mao et al., 2018). The spe-
cific combustion heats of PE and binder are found in Ref. (Tewarson
et al., 1994; Walters et al., 2000). Thanks to the mass distribution
of the battery that was previously estimated as shown in Fig. 1,
we could predict the contribution of the combustion heat for elec-
trolyte solvent, PE and binder from thermodynamic data as shown
in the first column of Fig. 10(d). The measured THRwhole of 70–100%
SOC cell is approximately equal to and a little lower than the pre-
dicted THR. In addition to ejecting out and combustion, the organic
components are also consumed inside the cell to generate internal
heat, so the measured combustion heat is lower than the prediction,
because the later assumes that all organic materials are combusted
 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146 143

Fig. 11. Combustion ashes.

outside. After all, as for highly charged batteries (70–100% SOC),

their combustion heat can still be estimated through simple addi-
tion of the combustion heat of all organics based on thermodynamic
data without destructive tests. In the future, a generalized evaluat-
ing method on the LIB’s combustion heat may be established: firstly,
know the battery type (hard-case or pouch type) and weigh the
battery; then estimate the mass distribution of the battery based
on its type, industrial data base and early literatures; finally, pre-
dict the combustion heat of the LIB based on the thermodynamic
data of organic parts. However, there are various kinds of com-
mercial cells with different chemistry systems, shapes, dimensions
or packages. For example, the mass ratio and specific combustion
heat of the case in the hard-case and pouch cells are different.
Therefore, this generalized evaluating method requires lots of com-
bustion data on various kinds of LIBs and needs our persistent
efforts.

3.2.6. Combustion ashes and cathode XRD analysis

Fig. 8 shows that 0% SOC cells have no deflagration, and
Fig. 11(a)-(c) further validate that the 0% SOC electrodes still stay
integrity. The current collectors and separator don’t melt. The Al
foil is melted to beans in 50% SOC cells as shown in Fig. 11(d).
The cathode materials become powders for 50%–100% SOC cells as
shown in Fig. 11(e). However, the anode copper current collectors
remain the roll shape as shown in Fig. 11(f). When the battery is
half or higher charged, the maximum inner temperature is higher
than aluminum’s melting point of 660.4 ◦ C, but lower than copper’s,
1083.4 ◦ C.
According to XRD patterns (Fig. 12), the cathode of 0% SOC cell
does not have any change compared to the intact NCM material (the
bottom pattern in Fig. 12). The amount of Ni4+ cation in NCM is the
most important unstable factor to decrease the thermal stability of
cathode (Bak et al., 2014), and the reduction of Ni4+ into Ni2+ at high
temperature releases oxygen to cause severe exothermic redox
reactions (Bak et al., 2014). During the charging process (lithium
extraction from cathode), Ni2+ and Co3+ are oxidized to Ni3+ or Ni4+
and Co4+ , respectively. As for the 0% SOC battery, the amounts of
the high-valence Ni3+ , Ni4+ or Co4+ are small, so its crystal structure
is stable enough to stay intact even heated to 312.3 ◦ C (Zhong et al.,
Fig. 12. XRD patterns of intact NCM and the cathodes from different SOC cells after
combustion.
2018) as shown in Fig. 12. The XRD patterns of 70–100% SOC cath-
odes are similar and all include MnO and Ni, indicating the similar
phase change path (Huang et al., 2016; Röder et al., 2014):
T ,solv.
NCM(R3m) −→ (Mn, Ni)O(Fm3m)+CoO+Ni+O2 (3)
where T means heating, and solv. means coexistence with solvent.
The Li(Ni0.5 Co0.2 Mn0.3 )O2 cathode with electrolyte first converts
from a layered structure (space group R3m) to disordered LiM2 O4 -
type spinel and M3 O4 -type spinel phase (space group Fd3m) as
temperature increases, then the spinel is converted to MO-type
rock salt phase (Fm3m), and metallic phase are presented after
heated to 600 ◦ C (Cho et al., 2013). In Fig. 12, the carbon may come
from anode, and LiF is the decomposition product of LiPF6 . The
50% SOC NCM is more stable than that of 100% SOC due to the
lower extents of Li+ extraction and less high valence state metal
ions, and (Mn, Ni)O (Fm3m) is not detected in the 50% SOC cathode
residue. CoO exists in 50% SOC cells, but CoO is not stable, and it may
144 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Fig. 13. THR/mloss in CC tests and comparison with QF in OS test.
a
results of CC test; b calculated based on jet flame model in Section 3.1.2.
decompose further or react with others as temperature ascends, so
it disappeared in 70–100% SOC batteries. High SOC cathode contains
a larger amount of high valence state metallic ions, so it suffers sev-
erer damage and releases more oxygen during TR. This is another
important mechanism by which the SOC influences the thermal
reactivity of LIB.
3.3. Comparison of OS and CC test
In OS test, the battery combusts in open space, and the swirl
and split of fire balls and jet flame can be observed, but sometimes,
the flame may be blown off due to the high-speed jet and the com-
bustion process is shorter in this case. The flammable aerosols and
gases released at the safety valve open don’t burn in open space.
In CC test, the movement of the released aerosols and flammable
gases are confined by the combustion chamber, and the piloted
ignition leads to earlier onset of combustion. The solid ejection is
collected by the combustion chamber, and the mass loss is mainly
caused by gas exhausting. Taking 100% SOC cell as an example, in
our previous study (Zhong et al., 2018), the same battery sample
combusted in open space; the specific mass loss was 2.23 ± 0.29 g
Wh−1 , and the combustion heat release was 6.74 ± 1.12 kJ Wh-1 . In
the CC test of this study, the mass loss and combustion heat change
to be 1.72 ± 0.11 g Wh-1 and 12.17 ± 1.29 kJ Wh-1 , respectively. As
the data indicated, the combustion chamber contributes to more
complete combustion and improves the repeatability of LIB com-
bustion test. Therefore, the combustion-chamber method can be
generalized in the field of LIB fire investigation coping with the
high randomness of TR.
Fig. 13 shows the THR versus mass loss of different SOC cells
in CC tests, and the slope of the dotted line represents THR/mloss
as listed in the embedded table. QF is the specific heat generation
of the mixed gas products calculated based on the flame height as
shown in Table 2. Higher SOC means more lithium intercalated in
the anode leading to more kinds of flammable gas products (Liao
et al., 2020). However, THR/mloss measured in CC test is the com-
bustion property of the whole battery and influenced by mass loss.
Less solid powder is flowing out with the exhausted gases thus mloss
is small for 70% SOC cell. The deflagration of 100% SOC cell is violent
and the mass loss is large. So THR/mloss of 70% SOC cell is large while
the value of 100% SOC cell is small. Interestingly, the calculated QF s
of 80% and 90% SOC in OS tests agree well with the experimental
THR/mloss in CC tests.
4. Conclusions
A series of refined combustion tests on 18,650-type LIBs
with different SOCs were conducted both in open space and
within the combustion chamber. In OS tests, a high-speed cam-
era was used to capture the fast trigger stage of TR. In CC
test, combustion chamber and ignition rods led to more com-
plete combustion and helped us reveal the burning feature of
LIB more deeply. The influence mechanisms of SOC on LIB fire
risk are revealed from these two perspectives: the specific com-
bustion heat of the mixed gas products and the amount of
high-valence metal ions in cathode. The major conclusions are
as follows:
In OS test, the combustion process of LIB can be divided into
the following stages: ejection of solid and gaseous mixture, solid
phase combustion in the form of sparks, intermittent fire balls
and jet flames, stable gaseous flame, abatement and extinguish-
ment. The fire balls are rotating and split. At the trigger stage
of TR, the ejecting velocity of the electrode fragment is approx-
imately equal to 30 m s−1 . The time-mean heights of jet flame
(9.5∼21.7 cm) and stable combustion flame (7.6∼12.3 cm) increase
with SOC (70∼100%). The specific combustion heat of the mixed gas
products (QF ) is calculated to be 5.185–11.869 MJ kg−1 (70–100%
SOC) according to free jet flame model. Higher SOC implies more
intercalated lithium is available in anode to react with electrolyte
and generate more flammable gases, thus increases the fire risk
of LIB.
In CC test, electrolyte vapors at the safety valve open are ignited
by the ignition rods, and deflagration at TR is observed. The major-
ity of the aerosols and gas products released by 0% SOC cell at TR are
non-flammable. The predicted mass loss ratio of the cell is 14.36%
agreeing with the experimental results of 0% and 50% SOC cells.
High-valence metal ions are the key factors decreasing the thermal
stability of Li(Nix Coy Mnz )O2 thus the high SOC cathode suffers sev-
erer phase change according to XRD analysis. For highly charged
batteries (70–100% SOC batteries), their THRs can be estimated by
adding the combustion heats of all organics based on the thermo-
dynamic data. Thus, such calculation method can be an alternative
option to destructive tests when evaluating the combustion heat of
a LIB.
 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
This work is supported by the National Natural Science Foun-
dation of China (No. 51674228 & 51976209), and the Fundamental
Research Funds for the Central Universities (No. WK2320000038).
Dr. Q.S. Wang is supported by Youth Innovation Promotion Asso-
ciation CAS (No. Y201768) and Dr H.D. Chen is supported by
the European Union’s Horizon 2020 research and innovation pro-
gramme under the Marie Sklodowska-Curie grant agreement No
749512. We sincerely appreciate Dr. Stanislav I. Stoliarov’s sugges-
tion on this work.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.psep.2020.03.
037.
References
Avdeev, I., Gilaki, M., 2014. Structural analysis and experimental characterization of
cylindrical lithium-ion battery cells subject to lateral impact. J. Power Sources
271, 382–391, http://dx.doi.org/10.1016/j.jpowsour.2014.08.014.
Babrauskas, V., 1984. Development of the cone calorimeter - a bench-scale heat
release rate apparatus based on oxygen-consumption. Fire Mater. 8, 81–95,
http://dx.doi.org/10.1002/fam.810080206.
Bak, S.-M., Nam, K.-W., Chang, W., Yu, X., Hu, E., Hwang, S., Stach, E.A., Kim, K.-B.,
Chung, K.Y., Yang, X.-Q., 2013. Correlating structural changes and gas evolu-
tion during the thermal decomposition of charged Lix Ni0.8 Co0.15 Al0.05 O2 cathode
materials. Chem. Mater. 25, 337–351, http://dx.doi.org/10.1021/cm303096e.
Bak, S.M., Hu, E., Zhou, Y., Yu, X., Senanayake, S.D., Cho, S.J., Kim, K.B., Chung, K.Y.,
Yang, X.Q., Nam, K.W., 2014. Structural changes and thermal stability of charged
LiNix Mny Coz O2 cathode materials studied by combined in situ time-resolved
XRD and mass spectroscopy. ACS Appl. Mater. Interfaces 6, 22594–22601, http://
dx.doi.org/10.1021/am506712c.
Chen, M., He, Y., De Zhou, C., Richard, Y., Wang, J., 2016. Experimental study on the
combustion characteristics of primary Lithium batteries fire. Fire Technol. 52,
365–385, http://dx.doi.org/10.1007/s10694-014-0450-1.
Chen, M., Ouyang, D., Weng, J., Liu, J., Wang, J., 2019. Environmental pressure effects
on thermal runaway and fire behaviors of lithium-ion battery with different
cathodes and state of charge. Process. Saf. Environ. Prot. 130, 250–256, http://
dx.doi.org/10.1016/j.psep.2019.08.023.
Chen, M., Zhou, D., Chen, X., Zhang, W., Liu, J., Yuen, R., Wang, J., 2015. Investigation on
the thermal hazards of 18650 lithium ion batteries by fire calorimeter. J. Therm.
Anal. Calorim. 122, 755–763, http://dx.doi.org/10.1007/s10973-015-4751-5.
Cho, Y.-H., Jang, D., Yoon, J., Kim, H., Ahn, T.K., Nam, K.-W., Sung, Y.-E., Kim,
W.-S., Lee, Y.-S., Yang, X.-Q., Yoon, W.-S., 2013. Thermal stability of charged
LiNi0.5 Co0.2 Mn0.3 O2 cathode for Li-ion batteries investigated by synchrotron
based in situ X-ray diffraction. J. Alloys Compd. 562, 219–223, http://dx.doi.org/
10.1016/j.jallcom.2013.02.060.
Delichatsios, M., 1993. Transition from momentum to buoyancy-controlled turbu-
lent jet diffusion flames and flame height relationships. Combust. Flame 92,
349–364, http://dx.doi.org/10.1016/0010-2180(93)90148-V.
Eshetu, G.G., Grugeon, S., Laruelle, S., Boyanov, S., Lecocq, A., Bertrand, J.-P., Marlair,
G., 2013. In-depth safety-focused analysis of solvents used in electrolytes for
large scale lithium ion batteries. PCCP 15, 9145–9155, http://dx.doi.org/10.1039/
C3CP51315G.
Fernandes, Y., Bry, A., de Persis, S., 2018. Identification and quantification of gases
emitted during abuse tests by overcharge of a commercial Li-ion battery. J. Power
Sources 389, 106–119, http://dx.doi.org/10.1016/j.jpowsour.2018.03.034.
Finegan, D.P., 2016. X-ray Imaging of Failure and Degradation Mechanisms of
Lithium-ion Batteries. UCL (University College London).
Finegan, D.P., Darcy, E., Keyser, M., Tjaden, B., Heenan, T.M.M., Jervis, R., Bailey, J.J.,
Malik, R., Vo, N.T., Magdysyuk, O.V., Atwood, R., Drakopoulos, M., DiMichiel, M.,
Rack, A., Hinds, G., Brett, D.J.L., Shearing, P.R., 2017. Characterising thermal run-
away within lithium-ion cells by inducing and monitoring internal short circuits.
Energy Environ. Sci. 10, 1377–1388, http://dx.doi.org/10.1039/c7ee00385d.
Finegan, D.P., Darcy, E., Keyser, M., Tjaden, B., Heenan, T.M.M., Jervis, R., Bailey, J.J., Vo,
N.T., Magdysyuk, O.V., Drakopoulos, M., Michiel, M.D., Rack, A., Hinds, G., Brett,
D.J.L., Shearing, P.R., 2018. Identifying the cause of rupture of Li-ion batteries
during thermal runaway. Adv. Sci. 5, 1700369, http://dx.doi.org/10.1002/advs.
201700369.
145
Finegan, D.P., Scheel, M., Robinson, J.B., Tjaden, B., Hunt, I., Mason, T.J., Millichamp, J.,
Di Michiel, M., Offer, G.J., Hinds, G., Brett, D.J., Shearing, P.R., 2015. In-operando
high-speed tomography of lithium-ion batteries during thermal runaway. Nat.
Commun. 6, 6924, http://dx.doi.org/10.1038/ncomms7924.
Fu, W., Zhang, Y., Wang, Q., (in Chinese) 1989. Combustion Science. Higher Education
Press, Beijing.
Fu, Y., Lu, S., Li, K., Liu, C., Cheng, X., Zhang, H., 2015. An experimental study on burn-
ing behaviors of 18650 lithium ion batteries using a cone calorimeter. J. Power
Sources 273, 216–222, http://dx.doi.org/10.1016/j.jpowsour.2014.09.039.
Glassman, I., Yetter, R.A., Glumac, N.G., 2014. Combustion. Academic Press.
Golubkov, A.W., Fuchs, D., Wagner, J., Wiltsche, H., Stangl, C., Fauler, G., Voitic, G.,
Thaler, A., Hacker, V., 2014. Thermal-runaway experiments on consumer Li-ion
batteries with metal-oxide and olivin-type cathodes. RSC Adv. 4, 3633–3642,
http://dx.doi.org/10.1039/C3RA45748F.
Heskestad, G., 1999. Turbulent jet diffusion flames: consolidation of flame
height data. Combust. Flame 118, 51–60, http://dx.doi.org/10.1016/S0010-
2180(98)00161-8.
Hu, L., Wang, Q., Delichatsios, M., Tang, F., Zhang, X., Lu, S., 2013. Flame height and lift-
off of turbulent buoyant jet diffusion flames in a reduced pressure atmosphere.
Fuel 109, 234–240, http://dx.doi.org/10.1016/j.fuel.2012.12.050.
Huang, P., Ping, P., Li, K., Chen, H., Wang, Q., Wen, J., Sun, J., 2016. Experimental and
modeling analysis of thermal runaway propagation over the large format energy
storage battery module with Li4 Ti5 O12 anode. Appl. Energy 183, 659–673, http://
dx.doi.org/10.1016/j.apenergy.2016.08.160.
Huang, P., Wang, Q., Li, K., Ping, P., Sun, J., 2015. The combustion behavior of
large scale lithium titanate battery. Sci. Rep. 5, 1–12, http://dx.doi.org/10.1038/
srep07788.
INERIS, 2009. Portail Substances Chimiques (Accessed 18 November 2019) https://
substances.ineris.fr/fr//page/23/.
Jiang, F., Liu, K., Wang, Z., Tong, X., Guo, L., 2018. Theoretical analysis of lithium-ion
battery failure characteristics under different states of charge. Fire Mater. 42,
680–686, http://dx.doi.org/10.1002/fam.2522.
Kim, M., Oh, J., Yoon, Y., 2011. Flame length scaling in a non-premixed turbulent
diluted hydrogen jet with coaxial air. Fuel 90, 2624–2629, http://dx.doi.org/10.
1016/j.fuel.2011.03.036.
Koch, S., Fill, A., Birke, K.P., 2018. Comprehensive gas analysis on large scale auto-
motive lithium-ion cells in thermal runaway. J. Power Sources 398, 106–112,
http://dx.doi.org/10.1016/j.jpowsour.2018.07.051.
Kong, W., Li, H., Huang, X., Chen, L., 2005. Gas evolution behaviors for several cathode
materials in lithium-ion batteries. J. Power Sources 142, 285–291, http://dx.doi.
org/10.1016/j.jpowsour.2004.10.008.
Larsson, F., Andersson, P., Blomqvist, P., Loren, A., Mellander, B.E., 2014. Character-
istics of lithium-ion batteries during fire tests. J. Power Sources 271, 414–420,
http://dx.doi.org/10.1016/j.jpowsour.2014.08.027.
Larsson, F., Andersson, P., Blomqvist, P., Mellander, B.E., 2017. Toxic fluoride gas
emissions from lithium-ion battery fires. Sci. Rep. 7, 10018, http://dx.doi.org/
10.1038/s41598-017-09784-z.
Larsson, F., Bertilsson, S., Furlani, M., Albinsson, I., Mellander, B.-E., 2018. Gas explo-
sions and thermal runaways during external heating abuse of commercial
lithium-ion graphite-LiCoO2 cells at different levels of ageing. J. Power Sources
373, 220–231, http://dx.doi.org/10.1016/j.jpowsour.2017.10.085.
Lecocq, A., Eshetu, G.G., Grugeon, S., Martin, N., Laruelle, S., Marlair, G., 2016.
Scenario-based prediction of Li-ion batteries fire-induced toxicity. J. Power
Sources 316, 197–206, http://dx.doi.org/10.1016/j.jpowsour.2016.02.090.
Liao, Z., Zhang, S., Li, K., Zhao, M., Qiu, Z., Han, D., Zhang, G., Habetler, T.G., 2020.
Hazard analysis of thermally abused lithium-ion batteries at different state of
charges. J. Energy Storage 27, http://dx.doi.org/10.1016/j.est.2019.101065.
Lisbona, D., Snee, T., 2011. A review of hazards associated with primary lithium and
lithium-ion batteries. Process. Saf. Environ. Prot. 89, 434–442, http://dx.doi.org/
10.1016/j.psep.2011.06.022.
Liu, X., Ren, D., Hsu, H., Feng, X., Xu, G.-L., Zhuang, M., Gao, H., Lu, L., Han, X., Chu,
Z., Li, J., He, X., Amine, K., Ouyang, M., 2018. Thermal runaway of lithium-ion
batteries without internal short circuit. Joule 2, 2047–2064, http://dx.doi.org/
10.1016/j.joule.2018.06.015.
Liu, X., Stoliarov, S.I., Denlinger, M., Masias, A., Snyder, K., 2015. Com-
prehensive calorimetry of the thermally-induced failure of a lithium
ion battery. J. Power Sources 280, 516–525, http://dx.doi.org/10.1016/j.
jpowsour.2015.01.125.
Liu, X., Wu, Z., Stoliarov, S.I., Denlinger, M., Masias, A., Snyder, K., 2016. Heat release
during thermally-induced failure of a lithium ion battery: impact of cathode
composition. Fire Saf. J. 85, 10–22, http://dx.doi.org/10.1016/j.firesaf.2016.08.
001.
Mao, B., Chen, H., Cui, Z., Wu, T., Wang, Q., 2018. Failure mechanism of the lithium
ion battery during nail penetration. Int. J. Heat Mass Transf. 122, 1103–1115,
http://dx.doi.org/10.1016/j.ijheatmasstransfer.2018.02.036.
Mao, B., Huang, P., Chen, H., Wang, Q., Sun, J., 2020. Self-heating reaction and thermal
runaway criticality of the lithium ion battery. Int. J. Heat Mass Transf. 149, http://
dx.doi.org/10.1016/j.ijheatmasstransfer.2019.119178.
Omaye, S.T., 2002. Metabolic modulation of carbon monoxide toxicity. Toxicology
180, 139–150, http://dx.doi.org/10.1016/S0300-483X(02)00387-6.
Orloff, L., 1981. Simplified radiation modeling of pool fires. Symp. (Int.) Combust. 18,
549–561, http://dx.doi.org/10.1016/S0082-0784(81)80060-4.
Ping, P., Kong, D., Zhang, J., Wen, R., Wen, J., 2018. Characterization of
behaviour and hazards of fire and deflagration for high-energy Li-ion cells
by over-heating. J. Power Sources 398, 55–66, http://dx.doi.org/10.1016/j.
jpowsour.2018.07.044.
146 B. Mao et al. / Process Safety and Environmental Protection 139 (2020) 133–146
Ping, P., Wang, Q., Huang, P., Li, K., Sun, J., Kong, D., Chen, C., 2015. Study of the
fire behavior of high-energy lithium-ion batteries with full-scale burning test. J.
Power Sources 285, 80–89, http://dx.doi.org/10.1016/j.jpowsour.2015.03.035.
Prockop, L.D., Chichkova, R.I., 2007. Carbon monoxide intoxication: an updated
review. J. Neurol. Sci. 262, 122–130, http://dx.doi.org/10.1016/j.jns.2007.06.037.
Ribière, P., Grugeon, S., Morcrette, M., Boyanov, S., Laruelle, S., Marlair, G., 2012.
Investigation on the fire-induced hazards of Li-ion battery cells by fire calorime-
try. Energy Environ. Sci. 5, 5271–5280, http://dx.doi.org/10.1039/c1ee02218k.
Röder, P., Baba, N., Wiemhöfer, H.D., 2014. A detailed thermal study of a
Li[Ni0.33 Co0.33 Mn0.33 ]O2 /LiMn2 O4 -based lithium ion cell by accelerating rate and
differential scanning calorimetry. J. Power Sources 248, 978–987, http://dx.doi.
org/10.1016/j.jpowsour.2013.09.146.
Said, A.O., Lee, C., Liu, X., Wu, Z., Stoliarov, S.I., 2019a. Simultaneous measurement
of multiple thermal hazards associated with a failure of prismatic lithium ion
battery. Proc. Combust. Inst. 37, 4173–4180, http://dx.doi.org/10.1016/j.proci.
2018.05.066.
Said, A.O., Lee, C., Stoliarov, S.I., 2020. Experimental investigation of cascading failure
in 18650 lithium ion cell arrays: impact of cathode chemistry. J. Power Sources
446, 227347, http://dx.doi.org/10.1016/j.jpowsour.2019.227347.
Said, A.O., Lee, C., Stoliarov, S.I., Marshall, A.W., 2019b. Comprehensive analysis of
dynamics and hazards associated with cascading failure in 18650 lithium ion cell
arrays. Appl. Energy 248, 415–428, http://dx.doi.org/10.1016/j.apenergy.2019.
04.141.
Spinner, N.S., Field, C.R., Hammond, M.H., Williams, B.A., Myers, K.M., Lubrano, A.L.,
Rose-Pehrsson, S.L., Tuttle, S.G., 2015. Physical and chemical analysis of lithium-
ion battery cell-to-cell failure events inside custom fire chamber. J. Power
Sources 279, 713–721, http://dx.doi.org/10.1016/j.jpowsour.2015.01.068.
Tao, C., Shen, Y., Zong, R., 2016. Experimental determination of flame length of
buoyancy-controlled turbulent jet diffusion flames from inclined nozzles. Appl.
Therm. Eng. 93, 884–887, http://dx.doi.org/10.1016/j.applthermaleng.2015.09.
049.
Tewarson, A., Chu, F., Jiang, F., 1994. Combustion of halogenated polymers. Fire Saf.
Sci. 4, 563–574, http://dx.doi.org/10.3801/IAFSS.FSS.4-563.
Walters, R.N., Hackett, S.M., Lyon, R.E., 2000. Heats of combustion of high tem-
perature polymers. Fire Mater. 24, 245–252, http://dx.doi.org/10.1002/1099-
1018(200009/10)24:5<245::AID-FAM744>3.0.CO;2-7.
Wang, Q., Mao, B., Stoliarov, S.I., Sun, J., 2019a. A review of lithium ion battery fail-
ure mechanisms and fire prevention strategies. Prog. Energy Combust. Sci. 73,
95–131, http://dx.doi.org/10.1016/j.pecs.2019.03.002.
Wang, Q., Ping, P., Zhao, X., Chu, G., Sun, J., Chen, C., 2012. Thermal runaway caused
fire and explosion of lithium ion battery. J. Power Sources 208, 210–224, http://
dx.doi.org/10.1016/j.jpowsour.2012.02.038.
Wang, Q., Sun, J., Chen, C., 2009. Effects of solvents and salt on the thermal stability of
lithiated graphite used in lithium ion battery. J. Hazard. Mater. 167, 1209–1214,
http://dx.doi.org/10.1016/j.jhazmat.2009.01.125.
Wang, Z., Yang, H., Li, Y., Wang, G., Wang, J., 2019b. Thermal runaway and fire behav-
iors of large-scale lithium ion batteries with different heating methods. J. Hazard.
Mater. 379, 120730, http://dx.doi.org/10.1016/j.jhazmat.2019.06.007.
Wu, K., Yang, J., Liu, Y., Zhang, Y., Wang, C., Xu, J., Ning, F., Wang, D., 2013.
Investigation on gas generation of Li4 Ti5 O12 /LiNi1/3 Co1/3 Mn1/3 O2 cells at ele-
vated temperature. J. Power Sources 237, 285–290, http://dx.doi.org/10.1016/j.
jpowsour.2013.03.057.
Wu, T., Chen, H., Wang, Q., Sun, J., 2018. Comparison analysis on the thermal runaway
of lithium-ion battery under two heating modes. J. Hazard. Mater. 344, 733–741,
http://dx.doi.org/10.1016/j.jhazmat.2017.11.022.
Zhong, G., Mao, B., Wang, C., Jiang, L., Xu, K., Sun, J., Wang, Q., 2018. Thermal run-
away and fire behavior investigation of lithium ion batteries using modified
cone calorimeter. J. Therm. Anal. Calorim. 135, 2879–2889, http://dx.doi.org/10.
1007/s10973-018-7599-7.
Zukoski, E., Cetegen, B., Kubota, T., 1985. Visible structure of buoyant diffusion
flames. Symp. (Int.) Combust. 20, 361–366, http://dx.doi.org/10.1016/S0082-
0784(85)80522-1.