energies
Review
Large-Scale Li-Ion Battery Research and Application in
Mining Industry
Lingyu Meng 1,2 , Guofa Wang 1,2 , Khay Wai See 3, *, Yunpeng Wang 3 , Yong Zhang 4 , Caiyun Zang 5 ,
Rulin Zhou 2 and Bin Xie 3
Citation: Meng, L.; Wang, G.; See,
K.W.; Wang, Y.; Zhang, Y.; Zang, C.;
Zhou, R.; Xie, B. Large-Scale Li-Ion
Battery Research and Application in
Mining Industry. Energies 2022, 15,
3884. https://doi.org/10.3390/
en15113884
Academic Editor: Anup Barai
Received: 19 April 2022
Accepted: 17 May 2022
Published: 25 May 2022
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Energies 2022, 15, 3884. https://doi.org/10.3390/en15113884
1 School of Mechanical Electronic & Information Engineering, China University of Mining &
Technology-Beijing, Beijing 100083, China; mly929996@outlook.com (L.M.); wanggf@tdmarco.com (G.W.)
2 Beijing Tianma Intelligent Control Technology Co., Ltd., Beijing 101399, China; zhourl@tdmarco.com
3 Azure Mining Technology, CCTEG, Level 19, 821 Pacific Highway, Chatswood, NSW 2067, Australia;
ypwang@cctegamt.com (Y.W.); 13816691338@163.com (B.X.)
4 China Mining Products Safety Approval and Certification Center, Beijing 100013, China;
zhangyong509@126.com
5 China Coal Technology and Industry Group Shanghai Co., Ltd., Shanghai 200030, China; shaq2014@163.com
* Correspondence: kwsee@cctegamt.com
Abstract: The lithium-ion battery (LIB) has the advantages of high energy density, low self-discharge
rate, long cycle life, fast charging rate and low maintenance costs. It is one of the most widely used
chemical energy storage devices at present. However, the safety of LIB is the main factor that restricts
its commercial scalable application, specifically in hazardous environments such as underground
coal mines. When a LIB is operating under mechanical and electrical abuse such as extrusion, impact,
overcharge and overheating, it will trigger thermal runaway and subsequently cause fire or even an
explosion. According to the relevant requirements in IEC60079, the explosion-proof protection of LIB
can be adapted to the working environment of high dust and explosive gas environments such as in
the mining face of coal production. This paper presents an overview of the LIB-relevant technology,
thermal runaway, safety and applications in the general mining industry with implications to establish
a theoretical and technical basis for the application of high-capacity LIBs in the industry. These then
promote intelligent, safe and efficient production not only for the coal mine industry but also for
non-coal applications.
Keywords: lithium-ion battery; thermal runaway; battery safety; large-scale energy storage;
explosion-proof electric vehicles; mining industry
1. Introduction
The lithium metal battery was first proposed by Gilbert n. Lewis in 1912. In 1970,
M.S. Whittingham proposed and began to study LIBs and patented the Li//TiS2 batteries
in 1974. In 1991, the first commercial LIB came out [1]. After more than 100 years of
development, the LIB has gradually become one of the most widely used chemical energy
storage methods because of its high energy density, low self-discharge rate, long cycle life,
fast charging rate and low maintenance costs [2].
LIBs are mainly used in 3C products, electric vehicles (EVs), communication base
stations, energy storage renewable integration and other fields, especially in the field of
heavy traction. Many countries around the world regard the development of EVs as an
important strategic measure to deal with climate change and optimize the energy structure.
The scale of the EV market increases year by year, exceeding 1 million in 2017 and 2 million
in 2018. In 2020, as the global automobile market was shrinking, the EV market grew
against the trend, with sales increasing by 41.6% year-on-year to 3.07 million vehicles,
and a penetration rate reaching 4%. In the mining industry, 30–50% of the total mining
energy usage is related to diesel used by the major mining vehicles that have a number of
https://www.mdpi.com/journal/energies
Energies 2022, 15, 3884 2 of 31

undesirable characteristics, which will likely disappear from the domestic market within
the next few decades. EVs injected new energy into the world’s economic growth. EV
power batteries are mainly composed of ternary lithium battery (NCM) and lithium iron
phosphate (LFP), accounting for 62.5% and 39.2%, respectively [3], and the proportion
of LFP batteries is growing rapidly, mainly because LFP batteries have a large thermal
stability range and stable discharge rate, which can ensure no explosion in malignant
traffic accidents. Based on the technical requirements for the safety of LIBs for mining
(Trial) issued and implemented by the Chinese National Center for safety standards in
2012, it is required that only LFP batteries are allowed to be used for all underground LIB
power supplies in coal mines, and the battery enclosure needs to be an explosion-proof
design [4,5].
In recent years, with the wide use of EVs, although mining explosion-proof EVs
have also been preliminarily applied, the traditional explosion-proof diesel vehicles still
dominate the market. The diesel-powered vehicles, among other disadvantages such as
high exhaust emission, high noise, high failure rate, high operation cost and low efficiency,
also cause considerable detrimental health effects to the mining workers, particularly in
confined areas such as an underground coal mine that has limited ventilation [6,7]. The
mining explosion-proof EVs can effectively avoid the shortcomings of explosion-proof
diesel trucks, improve the underground working environment and realize the efficient
utilization of mining vehicles [8,9].
Further applying and popularizing explosion-proof EVs requires the following chal-
lenges to be solved urgently: First, the restrictions by industry standards. At present,
only LFP batteries are allowed to be used, and the maximum permissible capacity of a
single battery is 100 Ah, resulting in a short mileage range of mining explosion-proof
EVs with an average travel distance of only 80 km for a typical machine, which cannot
meet the needs of multiple coal seams, multiple panels and the long travel distance of
large production mines. Second, the long charging time, with an average of up to 4 h for
every machine, and the strict national mine safety regulations for charging requirements
underground have considerably restricted the mass adoption of mining EVs. Third, the
low temperature in certain coal mines presents various challenges and complications in
operating the lithium-battery-powered machine and subsequently reduces the likeliness of
adopting the technology. Last but not least, the risk and consequences of thermal runaway
of LIBs working in underground coal mines, especially in a concentrated gas environment,
are not fully investigated. At present, to the best of the authors’ knowledge, there are no
effective countermeasures and solutions.
This paper presents an overview of LIB technology and its safety implications for the
application in the mining industry. In particular, the contents deeply focused on the analysis
of the LIB thermal runaway mechanism and prevention methods for the anticipation of
establishing a theoretical and technical basis for the application of high-capacity LIBs and
subsequently promote the intelligent, safe and efficient production in the coal mine industry.

2. LIB Cathode Material

In the last decade, the LIB has been rapidly adopted in most of the 3C products
and EV market due to its high energy density, long cycle life, fast charging rate, wide
operation temperature range, no memory effect and lack of pollution to the environment.
The chemistries are mainly divided into four types.

2.1. Lithium Cobalt Oxide (LCO)

The chemical formula of the LCO battery is LiCoO2 , and it is a layered inorganic
compound. Compared with other types of LIBs, LCO has the highest theoretical energy
density and volume specific energy [10]. In addition, the LCO battery also has the advan-
tages of simple fabrication processes, a stable working voltage, good cycle stability and
high compaction density [11]. As the market demand has grown, the research on the LCO
battery has been continuously improved with working voltage increases from 4.2 V to
 2.1. Lithium Cobalt Oxide (LCO)
The chemical formula of the LCO battery is LiCoO2, and it is a layered inorganic com-
pound. Compared with other types of LIBs, LCO has the highest theoretical energy den-
Energies 2022, 15, 3884 3 of 31
sity and volume specific energy [10]. In addition, the LCO battery also has the advantages
of simple fabrication processes, a stable working voltage, good cycle stability and high
compaction density [11]. As the market demand has grown, the research on the LCO bat-
4.45
teryV.has
Thebeen
specific capacity of
continuously LCO in production
improved with workinghas voltage
reached increases
185 mAh/g,fromand4.2isVrapidly
to 4.45
moving towardscapacity
V. The specific its theoretically specific
of LCO in capacity
production hasofreached
274 mAh/g [12]. The
185 mAh/g, main
and application
is rapidly mov-
field of LCO is 3C electronic products.
ing towards its theoretically specific capacity of 274 mAh/g [12]. The main application
fieldThe reactions
of LCO is 3Cof LCO electrodes
electronic are as follows:
products.
During
The reactions of LCO electrodes areisasdetached:
the charging process, Li-ion follows:
During the charging process, Li-ion is detached: +
LiCoO2 → Li1− x CoO2 + xLi + xe−
LiCoO → Li CoO + 𝑥Li + 𝑥e
During the discharging process: Li-ion is embedded:
During the discharging process: Li-ion is embedded:
+ −
Li1−Li
x CoO 2 + xLi
CoO + 𝑥e →→LiCoO
+ 𝑥Li+ xe LiCoO2
LCOhas
LCO hasaaspinel
spinelstructure
structureand andaalayered
layeredstructure.
structure.The
Thelayered
layeredstructure
structurehas
hasthe
thebest
best
chemical
chemicalproperties.
properties.Li Liions
ionsbetween
betweenCoOCoO22 layers
layers are
arecontinuously
continuously detached
detached andand embed-
embed-
ded
dedduring
duringthethecharge-and-discharge
charge-and-dischargeprocess, process,and andLCOLCOcan cankeep
keepthe
thelayered
layeredstructure
structure
stable
stablewithout
withoutcollapse,
collapse,as asshown
shownin inFigure
Figure11[13,14].
[13,14].However,
However,the thecapacity
capacityofofthe
theLCO
LCO
battery
batterywill
willgradually
graduallydecrease
decreaseduring
duringthethecharge-and-discharge
charge-and-dischargecycle, cycle,mainly
mainlydue
duetotothe
the
continuous
continuousexpansion
expansionand andcontraction
contractionofofthethelithium
lithiumcobaltate
cobaltatecrystal
crystalstructure
structureduring
duringthethe
charge-and-discharge process, resulting in crystal defects [15–17]. The crystal
charge-and-discharge process, resulting in crystal defects [15–17]. The crystal structure structure
will
willalso
alsobe
bechanged,
changed,resulting
resultingininaagrain
grainfracture
fractureandandstructure
structurecollapse
collapse[18].
[18].The
Thecathode
cathode
material
material decreases, the internal resistance increases, and the specific capacity decreases.
decreases, the internal resistance increases, and the specific capacity decreases.
Kazuhiro
KazuhiroKawashima
Kawashima etetal. al.[19]
[19]show
showthatthatthe
thequality
qualityof ofthe
thecathode
cathodethin
thinfilms
films(phase
(phase
purity,
purity,crystallinity,
crystallinity,and
andorientation)
orientation)isisessential
essentialforforthin-film
thin-filmbattery
batteryresearch.
research.

Energies 2022, 15, x FOR PEER REVIEW 4 of

Figure1.1.Crystalline
Figure Crystallinestructure
structureofoflayered
layeredLiCoO
LiCoO2 2[13].
[13].

2.2. Lithium Manganate Oxide (LMO)

The cathode chemical formula of the LMO battery is LiMn2O4, which has a cubic spi-
nel crystal structure, as shown in Figure 2 [13]. One cell contains 56 atoms (8 lithium at-
oms, 16 manganese atoms and 32 oxygen atoms). Lithium ions (green) can be freely de-
tached and embedded in the lattice.

Figure
Figure 2. 2. Crystalline
Crystalline structure
structure of spinel
of spinel LiMn2LiMn 2O4 [13].
O4 [13].

The reactions of LMO electrodes are as follows:

During the charging process, Li-ion is detached:
LiMn O → Li Mn O + (1 − 𝑥)Li + (1 − 𝑥)e
During the discharging process, Li-ion is embedded:
 Energies 2022, 15, 3884 4 of 31

2.2. Lithium Manganate Oxide (LMO)

The cathode chemical formula of the LMO battery is LiMn2 O4 , which has a cubic spinel
crystal structure, as shown in Figure 2 [13]. One cell contains 56 atoms (8 lithium atoms,
16 manganese atoms and 32 oxygen atoms). Lithium ions (green) can be freely detached and
embedded in the lattice.
The reactions of LMO electrodes are as follows:
During the charging process, Li-ion is detached:

LiMn2 O4 → Lix Mn2 O4 + (1 − x )Li+ + (1 − x )e−

During the discharging process, Li-ion is embedded:

Lix Mn2 O4 + (1 − x )Li+ + (1 − x )e− → LiMn2 O4

The electrochemical reaction of LMO occurs between 3.0 and 4.5 v, and its theoret-
ical specific capacity is 148 mAh/g. The LMO battery has the advantages of a benign
environmental effect, abundant reserves and excellent electrochemical performance [20].
However, in practical applications, the LMO battery has fast capacity attenuation, low
specific capacity, low conductivity, low ion diffusion efficiency and large structural changes
after the charge-and-discharge process, resulting in the existing materials not being able to
meet the current requirements of energy storage, traction applications and cycle life [21].
Wujie Dong et al. constructed a similar 2–3 nm artificial solid electrolyte interphase (SEI)
layer, which satisfies the expectations of aqueous lithium-ion batteries toward high energy
density, durability, safety, low cost and fast charge/discharge capability [22].

2.3. Lithium Iron Phosphate (LFP)

The cathode chemical formula of the LFP battery is LiFePO4 , which has a regular
olivine crystal structure [23], as shown in Figure 3. There are four LFP units in each cell. The
oxygen atoms are approximately hexagonally stacked. Lithium ions have two-dimensional
mobility and can be freely detached and embedded during the charge-and-discharge
Energies 2022, 15, x FOR PEER REVIEW
process. The PO4 3− -polymer tetrahedron has high stability. LFP has a long platform of the
5 of 32
charge–discharge curve and is safer at high temperatures, which is also the reason the LFP
battery has the highest safety level among lithium batteries.

Figure
Figure 3. Crystal
3. Crystal structure
structure of LFP
of LFP cathode
cathode [23].[23].

TheThe reactionselectrochemical
theoretical of LFP electrodesspecific
are as follows:
capacity of LFP cathode material is 170
During the charging process, Li-ion is detached:
mAh/g. The potential of the lithium metal electrode is approximately 3.45 V, and the the-
oretical energy density is 550 wh/kg. However, due to the low conductivity of LFP, only
LiFePO4 − xLi+ − xe− → xFePO4 + (1 − x )LiFePO4
0.6 mol lithium ion can be used for the intercalation and deintercalation cycle at room
temperature,
Duringand
thethe actual discharge
discharging process:capacity
Li-ion iscan only reach 113 mAh/g [24]. LFP has
embedded:
good cycle performance. When a lithium ion is deintercalated, the volume is reduced by
6.81% [25], which counteracts
FePO4 + xLi + xe− →
the+volume change of the
xLiFePO 4+ (1 − x )anode
carbon in4 the process of
LiFePO
discharging, and this greatly increases the cycle life of the LFP battery.
LFP is widely used in EV power battery and energy storage systems because of its
high specific energy, stable charging and discharging platform, high safety, long cycle life
and moderate cost [26]. Xiao-Guang Yang et al. demonstrate a thermally modulated LFP
Energies 2022, 15, 3884 5 of 31
Figure 3. Crystal structure of LFP cathode [23].

The theoretical electrochemical specific capacity of LFP cathode material is 170

mAh/g.TheThetheoretical
potential electrochemical
of the lithiumspecific capacity of
metal electrode is LFP cathode material
approximately 3.45 V,isand
170 mAh/g.
the the-
The potential
oretical energyofdensity
the lithium
is 550metal
wh/kg.electrode
However, is approximately
due to the low3.45 V, and theoftheoretical
conductivity LFP, only
energy
0.6 moldensity
lithiumision550canwh/kg. However,
be used for the due to the lowand
intercalation conductivity of LFP,cycle
deintercalation onlyat0.6room
mol
lithium ion can be used for the intercalation and deintercalation cycle
temperature, and the actual discharge capacity can only reach 113 mAh/g [24]. LFP has at room temperature,
and
goodthe actual
cycle discharge When
performance. capacity can only
a lithium ionreach 113 mAh/g the
is deintercalated, [24].volume
LFP has good cycle
is reduced by
performance.
6.81% [25], which counteracts the volume change of the carbon anode in the 6.81%
When a lithium ion is deintercalated, the volume is reduced by [25],
process of
which counteracts
discharging, and this thegreatly
volume change of
increases thethe carbon
cycle anode
life of in the
the LFP process of discharging,
battery.
and this
LFPgreatly increases
is widely used in theEV
cycle
powerlife of the LFP
battery andbattery.
energy storage systems because of its
LFP is widely used in EV power battery
high specific energy, stable charging and discharging and energy storage
platform, highsystems
safety, because
long cycle oflife
its
high specific energy, stable charging and discharging platform, high
and moderate cost [26]. Xiao-Guang Yang et al. demonstrate a thermally modulated LFP safety, long cycle life
and moderate
battery to offercost [26]. Xiao-Guang
an adequate Yangper
cruise range et charge
al. demonstrate a thermally
that is extendable modulated
by 10 min LFP
recharge
battery to offer an adequate cruise range per charge that is extendable by
in all climates [27]. In addition, because of LFP’s excellent safety performance, it is widely10 min recharge
in all in
used climates
auxiliary[27].transportation
In addition, because
vehiclesofinLFP’s excellent coal
underground safety performance, it is widely
mines.
used in auxiliary transportation vehicles in underground coal mines.
2.4. Lithium Nickel Manganese Cobalt Oxides (NCM)
2.4. Lithium Nickel Manganese Cobalt Oxides (NCM)
The cathode material of NCM is generally composed of three chemical elements:
The cathode material of NCM is generally composed of three chemical elements:
Nickel, cobalt and
Nickel, cobalt and manganese.
manganese. The
Thechemical
chemicalformula
formulaisisLiNi
LiNixCo
CoyMn
MnzO O2, which maintains
x y z 2 , which maintains
an α-NaFeO 2 layered structure [28], transition elements and lithium elements in each
an α-NaFeO2 layered structure [28], transition elements and lithium elements in each layer,
layer,
as shownas shown in 4.
in Figure Figure 4. The structure
The crystal crystal structure can be regarded
can be regarded as theof
as the stacking stacking of the
the transition
transition
metal metal layer–oxygen
layer–oxygen layer–lithium
layer–lithium layer–oxygen
layer–oxygen layer [29]. layer [29].

Li

TM Slab

Li Slab

Figure 4. Crystal
Figure 4. Crystal structure
structure of
of NCM
NCM cathode. The gray,
cathode. The gray, blue
blue and
and purple
purple spheres
spheres represent
represent Ni,
Ni, Co
Co
and
and Mn
Mn atoms
atoms in
in the
the transmission metal (TM)
transmission metal (TM) layer,
layer, respectively,
respectively, and
and the
the red
red sphere
sphere represents
represents O
O
atoms [28].

The typical composition ratio of nickel cobalt manganese in NCM material is 111,
523 and 811, and the numbers correspond to the content of nickel, cobalt and manganese,
respectively. With the increase in the proportion of nickel, the specific energy of the
NCM battery increases, accordingly; with the increase in the proportion of cobalt, the
battery performance is more stable; with the increase in the proportion of manganese, the
output voltage of the battery increases accordingly [30–33]. NCM combines the advantages
of nickel, cobalt and manganese, so it has a high comprehensive performance, and the
theoretical capacity can reach 278 mAh/g.
Nickel cobalt aluminum (NCA) is a cathode material developed simultaneously with
NCM. Its structure is similar to the NCM α-NaFeO2 layered structure. Because there
is no manganese element, the working voltage of NCA is slightly lower than that of
NCM. When the ratio of nickel, cobalt and aluminum is 0.8:0.15:0.05, it has the best
electrochemical performance [34]. Compared with NCM, NCA only occupies a small
market share. Changting Chu et al. studied large-sized nickel–cobalt–manganese ternary
Energies 2022, 15, 3884 6 of 31

composite oxide agglomerate microspheres, which reduced the specific surface area of the
material, resulting in fewer undesirable interfacial side reactions [35].
NCM has a high specific energy, a long cycle life, stable discharge and good perfor-
mance at low temperatures, which has accounted for 67.37% of lithium batteries in electric
vehicles. However, due to the higher safety risk as compared with the LFP battery, NCM
could cause a cascading effect after single-battery thermal runaway, resulting in fire and
the explosion of the battery pack. At present, it is not permitted to be used in underground
coal mines.

3. LIB Thermal Runaway

3.1. Thermal Runaway Mechanism
Thermal runaway refers to the phenomenon of overheating caused by an exothermic
reaction in the battery due to internal or external factors. The probability of fire and explo-
sion after battery thermal runaway is very low, at approximately one in ten million to one
in a million. However, the safety of lithium batteries is still a common concern. Therefore,
many battery manufacturers recall lithium batteries with problems in the production pro-
cess [36]. EV power battery accidents are mainly characterized by smoke, combustion and
explosion caused by thermal runaway.
A large number of researchers have conducted extensive and in-depth research on the
thermal runaway mechanism of LIB. The research shows that when the thermal runaway
of LIBs occurs, it can be divided into the following stages according to the temperature
distribution, from low to high: The decomposition of the SEI layer, the reaction between the
anode and electrolyte (SEI film regeneration), separator meltdown, decomposition of the
cathode, decomposition of the electrolyte, the reaction between the anode and binder and
burning of the electrolyte [37–39], as shown in Figure 5. Each stage of the thermal runaway
Energies 2022, 15, x FOR PEER REVIEW 7 of 32
reaction does not occur in order, as shown in the figure. With the increase in temperature
and the intensification of the reaction, some stages may occur simultaneously.

Figure 5. Exothermic reaction in different stages of LIB thermal runaway [39].

Figure 5. Exothermic reaction in different stages of LIB thermal runaway [39].

3.1.1. Decomposition of SEI Layer

The first stage is the decomposition of the anode SEI layer due to overheating or
physical penetration. The SEI layer is mainly composed of stable substances such as LIF,
Li2CO3, etc., and metastable substances such as ROCO2, (CH2OCO2Li)2, ROLi, etc. [40–42].
It is generally believed that the reaction begins at 70 °C [43]. As the temperature rises close
to 90 °C, the decomposition of the SEI layer begins to accelerate, and the heat released by
Energies 2022, 15, 3884 7 of 31

3.1.1. Decomposition of SEI Layer

The first stage is the decomposition of the anode SEI layer due to overheating or
physical penetration. The SEI layer is mainly composed of stable substances such as LIF,
Li2 CO3 , etc., and metastable substances such as ROCO2 , (CH2 OCO2 Li)2 , ROLi, etc., [40–42].
It is generally believed that the reaction begins at 70 ◦ C [43]. As the temperature rises close
to 90 ◦ C, the decomposition of the SEI layer begins to accelerate, and the heat released by
decomposition causes lithium to react with the organic electrolyte and release flammable
hydrocarbon gas. The reactions are as follows:
(CH2 OCO2 Li)2 → Li2 CO3 + C2 H4 + CO2 + 0.5O2
2Li + (CH2 OCO2 Li)2 → 2Li2 CO3 + C2 H4
Taeho Yoon et al. [44] studied the thermal decomposition process of SEI of LIB with
a Thermal Gravimetric Analyzer (TGA) and pointed out that the SEI layer will undergo
a decomposition reaction between 50 ◦ C and 300 ◦ C to produce CO2 and C2 H4 . Najmus
Saqib et al. [45] used infrared thermometry to measure the electrolyte temperature during
the heating of an LCO battery. It was found that SEI and electrolyte decomposition occurred
when the temperature was higher than 70 ◦ C. The working spectrum collected during
the heating process showed that with the occurrence of thermal degradation, the ethy-
lene carbonate (EC) ring was opened, resulting in permanent capacity loss of the battery.
Maleki [46] and Ryou [47] observed the SEI layer decomposition process has an exothermic
peak at 100 ◦ C. Zhang [48] observed that there was an exothermic peak in the SEI layer at
130 ◦ C. It can be seen that the decomposition of the SEI layer can generally be considered
to occur at 60–130 ◦ C, and its accurate decomposition temperature is related to battery
chemistry, SEI thickness and SOC state [39].

3.1.2. Reaction between Anode and Electrolyte (SEI Film Regeneration)

The decomposition of the SEI layer causes the lithium intercalation in the carbon anode
to be exposed to the electrolyte, which promotes the reaction between the electrolyte and the
negative lithium intercalation, so as to regenerate the SEI layer and generate hydrocarbon
and alkane gases. The reactions are as follows [36]:
2Li + C3 H4 O3 (EC) → Li2 CO3 + C2 H4
2Li + C4 H6 O3 (PC) → Li2 CO3 + C3 H6
2Li + C4 H6 O3 (DMC) → Li2 CO3 + C2 H6
These reactions usually occur at 100 ◦ C, and the gas released by the reaction will
increase the internal pressure of the battery. Although the internal high temperature of the
battery reaches the ignition point of the gas, it will not cause gas combustion due to the
lack of oxygen.

3.1.3. Separator Melt Down

The common LIB separators are polyolefin membranes made from polyethylene (PE)
and polypropylene (PP). The main problem of polyolefin membranes is poor thermal
stability [49]. When the temperature of the battery rises during operation, the separator
material must not shrink significantly and must not wrinkle. E. P. Roth et al. [50] suggested
that the melting points of PP and PE are 155 ◦ C and 130 ◦ C, respectively, as shown in
Figure 6. When these temperatures are reached, the separator melts, and the internal short
circuit of the battery takes place and results in thermal runaway degradation.
There are three main methods to reduce the thermal runaway caused by separator
melting. The first method is to close the channel of lithium ion passing through the
separator using a multi-layer structure [51], so as to prevent an external short circuit,
accidental overcharge or other further aggravation of battery temperature rise. However,
at a high current density, this closing mechanism has little protection against a short circuit
or rapid overcharge in the battery. When the internal temperature of the battery rises
sharply, it will lead to the melting of the separator material. The second method is to mix
the polyolefin membrane with inorganic nano materials [52,53]. The additional ceramic
 These reactions usually occur at 100 °C, and the gas released by the reaction will in-
crease the internal pressure of the battery. Although the internal high temperature of the
battery reaches the ignition point of the gas, it will not cause gas combustion due to the
lack of oxygen.
Energies 2022, 15, 3884 8 of 31
3.1.3. Separator Melt Down
The common LIB separators are polyolefin membranes made from polyethylene (PE)
material coating with
and polypropylene an The
(PP). ultra-high meltingof
main problem point and good
polyolefin mechanical
membranes properties
is poor thermalwill
sta-
significantly improve
bility [49]. When the thermalofstability
the temperature and rises
the battery dimensional stability of
during operation, thethe membrane
separator ma-
material. In not
terial must addition,
shrinkthe thermal conductivity
significantly and must notandwrinkle.
electrolyte
E. wettability of the
P. Roth et al. [50]membrane
suggested
layer willmelting
that the also increase,
points ofwhich can PE
PP and significantly
are 155 °Cimprove
and 130 the
°C, safety of the battery.
respectively, as shown Thein
third method is to modify the existing polyolefin separator structure and design
Figure 6. When these temperatures are reached, the separator melts, and the internal short functional
separator material
circuit of the batteryto takes
eliminate
placethe lithium
and resultsdendrites
in thermalgenerated
runawaybydegradation.
overheating [54].

9×104
8×104
5×103 Hz
7×104
6×104
5×104
4×104
3×104
2×104
1×104
0

Energies 2022, 15, x FOR PEER REVIEW 9 of 32

Figure 6.
Figure 6. Melting
Melting temperature
temperature of
of PE/PP
PE/PP separator material [50].

3.1.4. Decomposition
3.1.4.There
Decomposition
are three mainof
of Cathode
Cathode
methods to reduce the thermal runaway caused by separator
AAshort
melting. Thecircuit
short first occurs
method
circuit occursinside
is insidethethe
to close battery afterafter
thebattery
channel the separator
of lithium ionhas
the separator had
has ahad
passing meltdown,
through thewhich
sepa-
a meltdown,
will
ratorgenerate
using a a large amount
multi-layer of heat,
structure resulting
[51], so as in
to an exponential
prevent an increase
external
which will generate a large amount of heat, resulting in an exponential increase in the short in the temperature
circuit, accidental
rise rate of the
overcharge
temperature battery.
orrise
other There
ratefurther
of the are also
aggravation
battery. electrolyte
There of
arebattery decomposition
temperature
also electrolyte andHowever,
rise.
decomposition a binder
and aatreaction
a high
binder
alongside
current the
reactiondensity, decomposition
alongside thisthe
closing of the cathode.
mechanismofhas
decomposition These
thelittle reactions
protection
cathode. are
Theseagainst generally
reactionsa short considered to
circuit or con-
are generally rapid
accelerate
overcharge the material
in the battery.
sidered to accelerate reaction in the
When reaction
the material battery
the internal when
in the the
temperatureinternal
battery when temperature
of the
theinternal of the
battery temperature battery
rises sharply,ofit
is higher ◦ C after the separator melts and will happen simultaneously. The heat
will
the lead than
batterytoisthe155melting
higher thanof155the°Cseparator material. melts
after the separator The second
and will method
happenissimultaneously.
to mix the poly-
generation
The heat
olefin rates ofwith
generation
membrane various
rates ofcathode
various
inorganic materials
nano cathode are shown
materials
materials inThe
are
[52,53]. Figure
shown 7 [55].
in Figure
additional 7 [55]. material
ceramic
coating with an ultra-high melting point and good mechanical properties will signifi-
cantly improve the thermal stability and dimensional stability of the membrane material.
In addition, the thermal conductivity and electrolyte wettability of the membrane layer
will also increase, which can significantly improve the safety of the battery. The third
method is to modify the existing polyolefin separator structure and design functional sep-
arator material to eliminate the lithium dendrites generated by overheating [54].

(a) (b)
Figure 7. Comparison of thermal runaway reaction of different cathode materials [55]: (a) Compar-
Figure 7. Comparison of thermal runaway reaction of different cathode materials [55]: (a) Comparison
ison of reaction degrees; (b) comparison of heat generation rates.
of reaction degrees; (b) comparison of heat generation rates.

Accordingto
According to the
the measured
measured values
values in
in Figure
Figure 7,
7, it
it can
can be
be found
found that
thatthe
thesafety
safetyof
ofLFP
LFP
is better than that of LCO, LMO and NCM in terms of the safety of cathode
is better than that of LCO, LMO and NCM in terms of the safety of cathode materials. materials. The
specific
The distribution
specific is LFP
distribution is >LFP
LMO > >LMO
NCM> >NCMNCA >> LCO.
NCA The decomposition
> LCO. of the cath-
The decomposition of
ode material will release oxygen. After mixing the hydrocarbon and
the cathode material will release oxygen. After mixing the hydrocarbon and alkanealkane gas generated
gas
by the reaction
generated by theofreaction
the anodeof electrolyte, a combustion
the anode electrolyte, reaction willreaction
a combustion occur inwill
the battery,
occur in
resulting in breaking through the battery safety valve to form a jet fire. The reactions of
various cathode materials during decomposition are summarized in Table 1.

Table 1. Decomposition reactions for different cathode materials [42,56–58].

Cathode Decomposition
Energies 2022, 15, 3884 9 of 31

the battery, resulting in breaking through the battery safety valve to form a jet fire. The
reactions of various cathode materials during decomposition are summarized in Table 1.

Table 1. Decomposition reactions for different cathode materials [42,56–58].

Cathode Materials Decomposition Equation DecompositionTemperature

LFP 2Li0 FePO4 → Fe2 P2 O7 + 0.5O2 190–285 ◦ C
Li0.2 Mn2 O4 → 51 LiMn2 O4 + 54 Mn2 O4
3Mn2 O4 → 2Mn3 O4 + 2O2
y
LMO LiMn2 O4 → 2LiMn2 O4−y + 2 O2 150–400 ◦ C
LiMn2 O4 → LiMnO2 + 13 Mn3 O4 + 13 O2
Mn2 O4 → Mn2 O3 + 12 O2
h i
Lix (NiCoMn) 1 O2 → 1+3 x Li 1+x x (NiCoMn) x O4 + 1−32x O2
NCA 3 1+ x 160–200 ◦ C
Lix (NiCoMn) 1 O 4(1+x) → Lix (NiCoMn) 1 O1+ x + 1+6 x O2
3 3 3
y
NCM Li0.35 (NiCoMn) 1 O2 → Li0.35 (NiCoMn) 1 O2−y + 2 O2 175–199 ◦ C
3 3

LCO Lix CoO2 → xLiCoO2 + 1−3 x Co3 O4 + 1−3 x O2 220–500 ◦ C

3.1.5. Decomposition of Electrolyte Solution

The electrolyte is essential in LIB. Its basic function is to act as the transfer medium be-
tween the cathode and anode of LIB. Electrolytes can be solid or liquid [49]. The electrolyte
is usually an organic solution with LiPF6, and the solvent is mainly a combination of linear
and cyclic alkyl carbonate, mainly including Ethylene carbonate (EC), diethyl carbonate
(DEC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) [59]. Although the
carbonate solvent is relatively stable, the addition of the LiPF6 solution will make the
organic electrolyte highly volatile and flammable. When battery thermal runaway occurs,
the electrolyte will react with the active electrode material to release a large amount of gas
and heat. The decomposition reaction of LiPF6 is [60]:

LiPF6 → LiF ↓ +PF5 ↑

PF5 is a strong acid, which can lead to the decomposition of EC cyclic carbonate and
react with the trace amounts of water in the electrolyte to form HF, which will also lead to
further decomposition of the solvent and the generation of gas.
The decomposition of the solvent produces many different kinds of gases, including
CO2 , CH4 , C2 H4 , C2 H5 F and other products, as shown in the following equation [58]:

C2 H5 OCOOC2 H5 + PF5 → C2 H5 OCOOPF4 + HF + C2 H4

C2 H4 + HF → C2 H5 F
C2 H5 OCOOPF4 → PF3 O + CO2 + C2 H2 + HF
C2 H5 OCOOPF4 → PF3 O + CO2 + C2 H5 F
C2 H5 OCOOPF4 + HF → PF4 OH + CO2 + C2 H5 F

A large amount of gas generated by the above reaction rapidly increases the internal
pressure of the battery, and finally opens the battery safety valve. The released gas reacts
with O2 generated by the positive active material, which produces smoke and forms a jet
fire. The decomposition of different solvents with temperature is shown in Table 2 [59].
Energies 2022, 15, 3884 10 of 31

Table 2. Boiling point of electrolyte.

Solution Boiling Point

EC 517 K
DEC 400 K
DMC 364 K
EMC 380 K

3.1.6. The Reaction between Anode and Binder

A. Du Pasquier et al. [61] found through experiments that when the internal tem-
perature of the battery is greater than 260 ◦ C, the anode reacts with the polyvinylidene
fluoride (PVDF) binder and LixC6 . The PVDF binder can enhance the reaction rate of LCO.
When the internal temperature of the battery increases, the formation rate of Co3 O4 and the
dissolution rate of Co ions will accelerate at the interface between the active material and
the binder [58]. E. Markevich et al. [62] also found that the presence of the PVDF binder
increased the reactivity of LCO and believed that hydrogen bonds were formed after PVDF
reaction, so the local concentration of acidic substances near LCO particles increased, which
also accelerated the decomposition of LCO. Biensan P [63] found that the initial reaction
temperature of the anode with the binder was 240 ◦ C and the peak reaction rate was 290 ◦ C,
while Maleki H [46] found that the initial reaction temperature was lower than11200
Energies 2022, 15, x FOR PEER REVIEW of ◦32
C
◦
and the reaction peak was 287 C. The reactions between the anode and PVDF binder are
as follows:
base
−CH−CH 2 −+
− CF CFLi2 →→LiF−CH = CF
+ −CH =−CF+−HF
+0.5H
−CH2 − CF2 + Li → LiF + −CH = CF − +0.5H2

3.1.7.
3.1.7.The
TheBurning
Burningof ofElectrolyte
ElectrolyteandandGas GasRelease
Release
The
The burning of the electrolyte will beaccompanied
burning of the electrolyte will be accompaniedby bythe
therelease
releaseofofaalarge
large amount
amount
of gas. Many researchers have performed many experiments
of gas. Many researchers have performed many experiments to collect the gas to collect the gas released by
released
thermal
by thermalrunaway.
runaway. SEE SEE
K WKetW al.et[64]
al. heated
[64] heatedseven different
seven typestypes
different of prismatic LFP bat-
of prismatic LFP
teries withwith
batteries a constant
a constantpower of 640
power W until
of 640 the surface
W until temperature
the surface of the
temperature ofbattery and and
the battery the
internal pressure
the internal pressureof the container
of the container suddenly
suddenly increased
increased andandthe
thebattery
batteryvoltage
voltagedropped
dropped
sharply.
sharply. Then,
Then,the thegas
gaswas
was collected
collected bybythethe
gasgas collection
collectionbagbag
on the sealing
on the cover
sealing of the
cover of
device, and and
the device, the gas
the composition
gas composition was wasanalyzed
analyzed by abygasa chromatography
gas chromatography device. The The
device. ex-
experimental
perimental equipment
equipment is shown
is shown inin Figure
Figure 8,8,and
andthethereleased
releasedgasgascomponents
componentsare areshown
shown
in Table
in Table 3. Hydrogen accounts
accounts for
for the
thehighest
highestproportion,
proportion,accounting
accountingfor formore
morethan
than50%
50%of
thethe
of released
releasedgas,gas,
followed
followedby CO
by 2CO, accounting
2, accounting for 20%, and and
for 20%, hydrocarbon and alkane
hydrocarbon gases
and alkane
are mainly
gases methane,
are mainly accounting
methane, for 10%.
accounting for 10%.

Figure
Figure8.8.Thermal
Thermalrunaway
runawaycollection
collectiondevice
devicefor
forprismatic
prismaticLFP
LFPbattery
battery [64].
[64].

Table 3. Composition of thermal runaway release gas [64].

Gas M1-72 Ah M1-100 Ah M1-180 Ah M2-90 Ah M2-280 Ah M3-120 Ah M3-202 Ah

Composition V, % V, % V, % V, % V, % V, % V, %
Energies 2022, 15, 3884 11 of 31

Y. Fernandes [65] overcharged the 100% SOC commercial LIB, placed the battery in
a closed container, extracted the internal gas during and at the end of the experiment,
and then analyzed and identified the gas composition by gas chromatography, mass
spectrometry and FTIR spectroscopy. He found that the gas release of thermal runaway
mainly has three stages: The first stage releases DMC, EMC, CH4 , CO and CO2 . At this
stage, less gas is released, mainly filling the internal volume of the battery, so it mainly
leads to an increase in the internal pressure of the battery. In the second stage, the battery
shell is cracked, and the battery surface temperature is higher than 110 ◦ C, and a large
number of new gases such as CH3 OCH3 , CH3 OCHO and C2 H4 are generated. In the third
stage, the battery begins to cool down, the generation of CH3 OCH3 , CH3 OCHO, CH4 , CO
and CO2 decreases and the generation of HF increases. The gas composition of the thermal
runaway is shown in Figure 9.

Table 3. Composition of thermal runaway release gas [64].

Gas M1-72 Ah M1-100 Ah M1-180 Ah M2-90 Ah M2-280 Ah M3-120 Ah M3-202 Ah

Composition V, % V, % V, % V, % V, % V, % V, %
CO2022,
Energies 2 7.52 REVIEW
15, x FOR PEER 7.99 11.95 5.69 14.18 6.69 11.912 of 32
C2 H4 4.19 4.18 5.88 0.85 2.30 1.99 1.8
C2 H2 0.07 0.18 0.19 0.05 0.07 0.05 0.1
C2 H6 0.56 0.9 1.31 0.09 0.65 0.41 0.55
C3 H6 0.92 gas is1.76
released, mainly2.8 filling the internal
0.05 volume0.56of the battery,0.23
so it mainly leads
0.47 to an
C3 H8 N.A 0.21 in the internal
increase 0.37 pressure of N.A 0.20
the battery. In 0.1 the battery
the second stage, 0.16shell is
H2 12.79 17.91and the battery
cracked, 23.39 surface temperature
5.74 33.99 than 110 °C,
is higher 15.46 29.89
and a large number of
O2 1.1 0.45 1.48 11.04 3.36 0.58 0.72
new gases such as CH3OCH3, CH3OCHO and C2H4 are generated. In the third stage, the
N2 67.91 61.64 45.23 75.52 36.79 72.14 48.06
CH4 2.06 battery
2.12begins to cool down, the generation
3.35 0.26 of CH 3OCH3, CH3OCHO, CH4, CO and CO2
2.56 1.02 2.64
CO 2.89 decreases
2.66 and the generation
4.04 of HF increases. The
0.73 gas composition
5.33 1.34 of the thermal
3.7 runa-
way is shown in Figure 9.

Figure9.9.Thermal
Figure Thermalrunaway
runawaygas
gascomposition
compositionof
ofLIB
LIB[65].
[65].

3.2.
3.2.Thermal
ThermalRunaway
RunawayInducements
Inducements
There
There are three mainfactors
are three main factorsleading
leadingtotobattery
batterythermal
thermalrunaway:
runaway:Mechanical
Mechanicalabuse
abuse
(penetration,
(penetration, impact, collision, vibration), electrical abuse (overcharge, shortcircuit)
impact, collision, vibration), electrical abuse (overcharge, short circuit)and
and
thermal abuse (overheating) [66]. Mechanical abuse is caused by the distortion of
thermal abuse (overheating) [66]. Mechanical abuse is caused by the distortion of the bat- the
battery due to collision and squeezing, resulting in the rupture of the internal separator
tery due to collision and squeezing, resulting in the rupture of the internal separator of
of the battery and the internal short circuit, which will generate a large amount of heat
the battery and the internal short circuit, which will generate a large amount of heat and
and trigger thermal runaway. Electric abuse is caused by the external short circuit, the fast
trigger thermal runaway. Electric abuse is caused by the external short circuit, the fast
charging and discharging speed and overcharge of the battery. Eventually, the internal
charging and discharging speed and overcharge of the battery. Eventually, the internal
temperature of the battery rises and the separator melts, resulting in an internal short
temperature of the battery rises and the separator melts, resulting in an internal short cir-
cuit and a large amount of heat releasing. Thermal abuse is caused when the internal tem-
perature rise rate of the battery is higher than the heat dissipation rate, so that heat accu-
mulates in the battery, which leads to the separator melting and an internal short circuit,
so as to release more heat and further aggravate the thermal runaway reaction. It can be
 Energies 2022, 15, 3884 12 of 31

circuit and a large amount of heat releasing. Thermal abuse is caused when the internal
temperature rise rate of the battery is higher than the heat dissipation rate, so that heat
accumulates in the battery, which leads to the separator melting and an internal short
circuit, so as to release more heat and further aggravate the thermal runaway reaction. It
can be seen that the three inducements of thermal runaway are inter-connected with each
Energies 2022, 15, x FOR PEER REVIEW 13
other, and the common factor is the internal short circuit of the battery. Figure 10 shows the
relationship between the three causes of thermal runaway [67].

Figure
Figure Main
10.10. factors
Main and internal
factors relationship
and internal of thermal
relationship ofrunaway
thermalinducements [67].
runaway inducements [67].
3.2.1. Mechanical Abuse
3.2.1. Mechanical Abuse
Mechanical abuse refers to the change of the internal structure of the battery caused
Mechanical
by an external force, abuse refers topenetration,
which includes the change of the
impact, internal
collision, structure
vibration, etc.of the battery ca
Different
from
by anelectrical
external abuse andwhich
force, thermal abuse, thermal
includes runaway
penetration, caused
impact, by mechanical
collision, abuseetc. Diff
vibration,
isfrom
generally a violent reaction that occurs instantaneously. Among
electrical abuse and thermal abuse, thermal runaway caused by mechanical abuthe different forms
of mechanical abuse, the most serious is nail penetration, which directly leads to the
generally a violent reaction that occurs instantaneously. Among the different forms o
penetration of the internal separator of the battery, resulting in an internal short circuit.
chanical abuse,
Researchers theconducted
have most serious is nail
in-depth penetration,
research on the dynamicwhich directly
mechanics leads
of LIB to the penetr
materials.
of the
Wei internal
Jen Lai separator
et al. [68] conductedof the battery,
tensile, resulting
compression andin an internal
impact tests on short
the testcircuit.
piece of
a singleResearchers have conducted
LIB. Elham sahraei in-depth
et al. [69] performed CTresearch
scanningon onthe dynamic
cylindrical LIBsmechanics
and soft- of LIB
packed
terials.LIBs
Wei to Jen
detect
Laithe
ettension
al. [68]ofconducted
electrode separator
tensile,bonding.
compressionElham and
sahraei et al. [70]
impact tests on th
established the micromechanical model and carried out the failure sequence
piece of a single LIB. Elham sahraei et al. [69] performed CT scanning on cylindrical of multi-layer
and multi-material batteries in combination with experiments. The mechanical properties of
and soft-packed LIBs to detect the tension of electrode separator bonding. Elham sa
different LIB separators were studied in the literature [71–73].
et al. [70]on
Based established
the research the
onmicromechanical model of
the mechanical properties and carried
battery out the
materials andfailure
sepa- sequen
multi-layer and multi-material batteries in combination with
rators, Takumi Yamanaka et al. [74] developed a new electro-chemical-thermal coupling experiments. The mec
cal properties
calculation model.ofIndifferent LIB
this model, theseparators
needling speedwereand studied
thermalindecomposition
the literaturereaction
[71–73].
are considered, and the “combustion volume” is defined to evaluate
Based on the research on the mechanical properties of battery materials the burning risk. and se
The results show that when the nail penetration speed is 10 times slower than that under
tors, Takumi Yamanaka et al. [74] developed a new electro-chemical-thermal cou
standard conditions, the risk of battery burning increases. Donal P. Finegan et al. [75]
calculation model. In this model, the needling speed and thermal decomposition rea
found through experiments that the temperature at the needled part of the battery placed
are considered,
vertically and the
is the highest, but “combustion
the temperature volume” is defined
propagation to evaluate
rate is slower than thethebattery
burning risk
results show that when the nail penetration speed is 10 times
under nail penetration placed horizontally. Figure 11 shows the heat conduction time after slower than that u
standard conditions, the risk of battery burning increases. Donal P. Finegan et al
found through experiments that the temperature at the needled part of the battery p
vertically is the highest, but the temperature propagation rate is slower than the ba
under nail penetration placed horizontally. Figure 11 shows the heat conduction time
 Energies 2022, 15, 3884 13 of 31

nail penetration. Shan Huang et al. [76] conducted a slow nail penetration experiment
on the 3 Ah soft pack battery, detected that multiple peak temperatures appeared 100 s
before the thermal runaway and found that these peak temperatures decreased rapidly
after they were higher than the safety limit. They believe that the decrease in the internal
Energies 2022, 15, x FOR PEER REVIEW 14 of 32
short-circuit current is the reason for the decrease in temperature, which is due to the tear
of the separator caused by nail penetration, resulting in the increase in contact resistance.

Figure 11.11.
Figure Thermal
Thermalrunaway
runaway propagation afternail
propagation after nail penetration
penetration for for battery
battery placed
placed horizontally
horizontally and and
vertically [75].
vertically [75].

Hsin
Hsin Wanget
Wang et al.
al. [77]
[77] studied
studiedthe mechanical
the mechanical response of a single
response cell with
of a single cella with
thickness of
a thickness
6.5 cm
of 6.5 cmand
anda athree-cell
three-cell stack under
stack compressive
under load. The
compressive indentation
load. depth of the
The indentation ball of
depth with
the ball
a diameter
with of 1 inch
a diameter of 1isinch
limited to 0.245 to
is limited inches,
0.245which is equivalent
inches, which istoequivalent
90% of the cell thickness.
to 90% of the cell
Through experiments, it is found that the short-circuit probability caused by mechanical
thickness. Through experiments, it is found that the short-circuit probability caused by
indentation increases with the thinning of the separator. Ilya Avdeev et al. [78] carried
mechanical indentation increases with the thinning of the separator. Ilya Avdeev et al. [78]
out mechanical modeling of the cylindrical LIB. The homogenization model accurately
carried out the
captured mechanical
mechanical modeling
response of of the cylindrical
battery collision.LIB.
The The
teamhomogenization model accu-
verified the effectiveness
rately captured the mechanical response of battery collision. The team
of the model through dynamic and static tests and verified the feasibility of single-battery verified the effec-
tiveness of by
collision thefinite
model through
element dynamic
analysis. Wangand static[79]
Wenwei tests and out
carried verified
plane,the feasibility
cylindrical andof sin-
gle-battery collision
spherical punch by finite
loading on theelement analysis.
cylindrical battery,Wang
recordedWenwei [79] carried
the deformation outofplane,
degree the cy-
battery under different SOCs and verified the correlation between the
lindrical and spherical punch loading on the cylindrical battery, recorded the deformation parameters of the
battery-equivalent
degree of the battery mechanical model and
under different SOCsSOC.and verified the correlation between the pa-
rameters of the battery-equivalent
3.2.2. Electrical Abuse mechanical model and SOC.
Electrical abuse is generally caused by overcharge. Excessive lithium intercalation of
3.2.2. Electrical Abuse
the anode leads to the formation of lithium crystal branches between the anode and the
Electrical
separator, abuse
which is generally
pierces caused
the separator, by overcharge.
resulting Excessive
in an internal lithium
short circuit, whileintercalation
excessive of
thelithium
anoderemoval
leads toleads to the collapse
the formation of the positive
of lithium crystalcrystal structure.
branches between An the
external
anodeshort
and the
separator, which pierces the separator, resulting in an internal short circuit, while exces-
sive lithium removal leads to the collapse of the positive crystal structure. An external
short circuit will also cause thermal runaway. When the heat production of the battery is
greater than the heat release and the temperature reaches the separator melting tempera-
Energies 2022, 15, 3884 14 of 31

circuit will also cause thermal runaway. When the heat production of the battery is greater
than the heat release and the temperature reaches the separator melting temperature, it will
lead to a short circuit in the battery.
Mao-sung Wu [80] tested the internal short circuit and external short circuit of 750 mAh
lithium batteries with three different separators. The internal short circuit triggered by the
nail penetration experiment is more violent than the battery thermal runaway measured by
an external short circuit. The maximum temperature of an internal short circuit is 350 ◦ C,
while it is 100 ◦ C for an external short circuit. It can be seen that the external15short
Energies 2022, 15, x FOR PEER REVIEW of 32 circuit is
safer than the internal short circuit. This is because the contact area of the electrode short
circuit during an external short circuit is much larger than that of an internal short circuit,
and
of thethe short circuit
electrode current
short circuit is small.
during an external short circuit is much larger than that of an
Junqiu
internal shortLicircuit,
et al. [81]
and proposed an impedance-based
the short circuit current is small. method to describe the heat released
by theJunqiu Li et
battery al. [81]
under anproposed
overcharge.an impedance-based
It is concluded that method
the to describe
thermal the heatafter
runaway re- battery
leased by the battery under an overcharge. It is concluded that the thermal runaway
overcharge can be divided into three stages: The temperature rises slowly in the first stage, after
battery the
where overcharge can is
rate of rise be0.025
divided intoand
◦ C/s three
thestages:
rate ofThe temperature
voltage rises
and heat slowly
rise in the
is low. The second
first stage, where the rate of rise is 0.025 °C/s and the rate of voltage
stage is the rapid temperature rise stage. The temperature rise rate is between and heat rise is low.0.04 ◦ C/s
The second stage is the rapid temperature rise stage. The temperature rise rate is between
and 0.1 ◦ C/s. The separator begins to decompose, a small amount of gas is released and
0.04 °C/s and 0.1 °C/s. The separator begins to decompose, a small amount of gas is re-
the internal temperature of the battery can reach 150 ◦ C or higher. The third stage is the
leased and the internal temperature of the battery can reach 150 °C or higher. The third
exothermic stage after
stage is the exothermic serious
stage thermal
after serious runaway,
thermal and the
runaway, andbattery bulges.
the battery bulges.Figure
Figure12 shows
the three stages during battery overcharge.
12 shows the three stages during battery overcharge.

Figure 12.
Figure 12. Thermal
Thermalrunaway
runawaystages.
stages.The
Thethree stages
three of of
stages battery surface
battery temperature
surface under
temperature over-
under overcharge
charge thermal runaway: (I) Stage I—normal heat-accumulating stage; (II) stage II—fast heat-accu-
thermal runaway: (I) Stage I—normal heat-accumulating stage; (II) stage II—fast heat-accumulating
mulating stage; (III) stage III—heat dissipation stage after severe thermal runaway [81].
stage; (III) stage III—heat dissipation stage after severe thermal runaway [81].
Zhenpo Wang et al. [82] studied the overcharge thermal runaway behavior of LFP
Zhenpo Wang et al. [82] studied the overcharge thermal runaway behavior of LFP and
and NCM (NCM111, NCM622, NCM811) batteries. It is found that the overcharge re-
NCM (NCM111, NCM622, NCM811) batteries. It is found that the overcharge resistance of
sistance of LFP is worse than NCM batteries, and it is more prone to thermal runaway
LFP is worse than
after overcharge. NCM batteries,
However, and
in the case it is more
of thermal prone to
runaway, thethermal
maximumrunaway after overcharge.
temperature of
However,
the LFP battery is low, and the thermal runaway is mild. All NCM batteries burnLFP
in the case of thermal runaway, the maximum temperature of the andbattery is
low, andafter
explode thethermal
thermalrunaway,
runaway is mild.
while Allbattery
the LFP NCM only
batteries burn
releases gasand explode
and does after thermal
not cause
runaway,
a fire. while the LFP battery only releases gas and does not cause a fire.

3.2.3. ThermalAbuse
3.2.3. Thermal Abuse
The
Thedifference
difference ininbattery
batterygroup characteristics
group will cause
characteristics inconsistent
will cause SOCs during
inconsistent SOCs during
battery charging
battery chargingand and discharging,
discharging,which will result
which in local
will result inoverheating in the battery.
local overheating in the battery.
Although the
Although thesame batch
same of batteries
batch is required
of batteries for the same
is required for battery
the same module in EVs,
battery there in EVs,
module
are still a few batteries that experience short circuits and overheating after a certain
there are still a few batteries that experience short circuits and overheating after a certain num-
ber of charge-and-discharge cycles. If the heat dissipation capacity of the battery pack is
number of charge-and-discharge cycles. If the heat dissipation capacity of the battery pack
insufficient, the heat will further accumulate, resulting in the thermal runaway of the sin-
is insufficient, the heat will further accumulate, resulting in the thermal runaway of the
gle battery and even the thermal runaway of the whole battery pack. Therefore, it is very
single battery and even the thermal runaway of the whole battery pack. Therefore, it is
important to heat the single cell and measure the relationship between its internal tem-
very important
perature and thermal to heat the single
runaway. Whencellthe and measure
battery the relationship
temperature between
exceeds a certain range,its
a internal
temperature
timely early warning mechanism can be established to cut off the battery charge and dis- range,
and thermal runaway. When the battery temperature exceeds a certain
acharge,
timelysoearly warning
as to avoid mechanism
battery can be established to cut off the battery charge and
thermal runaway.
discharge,
Peter J.so as to avoid
Bugryniec [83] battery thermal
studied the thermalrunaway.
runaway of the LFP battery by accelerat-
Peter
ing the rate J. Bugryniec(ARC)
calorimeter [83] studied
and oventhe thermalWhen
exposure. runaway of the
the SOC LFP the
is 100%, battery by accelerating
heat release
of the
the cathode
rate and anode
calorimeter (ARC)decomposition is the mainWhen
and oven exposure. factor causing
the SOCbattery thermal
is 100%, runa-release of
the heat
way. When the SOC is low, the anode decomposition is the dominant factor.
the cathode and anode decomposition is the main factor causing battery thermal runaway. After thermal
runaway
When theinSOC
an oven experiment,
is low, the anodethe decomposition
battery temperature anddominant
is the temperature rise rate
factor. are thermal
After
greater than ARC, indicating that external heating will cause more serious thermal runa-
way. Zheng Liao [84] heated the NCM batteries with different SOCs to the target temper-
ature of 218 °C and analyzed the thermal runaway reaction and gas composition of the
battery. The experimental device and temperature loads are shown in Figure 13. For the
gas components released from thermal runaway under different SOCs, the early warning
Energies 2022, 15, 3884 15 of 31

runaway in an oven experiment, the battery temperature and temperature rise rate are
greater than ARC, indicating that external heating will cause more serious thermal runaway.
Energies 2022, 15, x FOR PEER REVIEW
Zheng Liao [84] heated the NCM batteries with different SOCs to the target temperature of
16 of 32
218 ◦ C and analyzed the thermal runaway reaction and gas composition of the battery. The
experimental device and temperature loads are shown in Figure 13. For the gas components
released from thermal runaway under different SOCs, the early warning mechanism is
mechanism is realized by gas sensing technology. References [85,86] analyzed the thermal
realized by gas sensing technology. References [85,86] analyzed the thermal runaway of an
runaway of an LIB through ARC and ISC, established an electric thermal coupling model
forLIB throughcalculation
simulation ARC and and ISC, gave
established an electric thermal
the corresponding thermal coupling model for simulation
runaway prevention
calculation
mechanism. and gave the corresponding thermal runaway prevention mechanism.

(a)

(b)
Figure 13. Thermal runaway experiment of NCM battery [84]. (a) Test container. (b) Load step.
Figure 13. Thermal runaway experiment of NCM battery [84]. (a) Test container. (b) Load step.
4. LIB Safety
4. LIB Measures
Safety Measures
TheThe standardized test oftest
standardized an LIB is very
of an important
LIB is to batterytosafety.
very important In order
battery safety.to In
reduce
order to reduce
thethe
probability of thermal runaway of the LIB, many countries have
probability of thermal runaway of the LIB, many countries have successivelysuccessively issued issued
corresponding standardized tests, among which the most widely used standard is the LIB
corresponding standardized tests, among which the most widely used standard is the LIB
standard issued by the International Electrotechnical Commission (IEC), which includes
standard issued by the International Electrotechnical Commission (IEC), which includes
IEC 62133-2 Secondary cells and batteries containing alkaline or other non-acid electro-
IEC 62133-2 Secondary cells and batteries containing alkaline or other non-acid electrolytes—
lytes—Safety requirements for portable sealed secondary cells, and for batteries made
Safety
from them,requirements for portable
for use in portable sealed secondary
applications—Part 2: Lithium cells, and for
systems [87],batteries
IEC 62619 made
Sec- from them,
for use in portable applications—Part 2: Lithium systems [87],
ondary cells and batteries containing alkaline or other non-acid electrolytes—Safety re-IEC 62619 Secondary cells
and batteries
quirements containing
for secondary alkaline
lithium or batteries,
cell and other non-acid
for use inelectrolytes—Safety
industrial applications requirements
[88] for
andsecondary
IEC 62281lithium
Safety cell and batteries,
of primary for use inlithium
and secondary industrial
cells applications
and batteries[88] duringand IEC 62281
Safety of
transport primary
[89]. China and secondary
has also issued lithium
a series cells and batteries
of standards duringthe
to regulate transport
lithium-ion[89]. China has
power
alsobattery
issuedmarket,
a seriessuch as GB 31241-2014
of standards Lithium
to regulate theion cells and batteries
lithium-ion used in port-
power battery market, such as
able
GBelectronic
31241-2014 equipment-Safety
Lithium ion cellsrequirements [4] and
and batteries usedGBin38031-2020 Electric vehicles
portable electronic equipment-Safety
traction battery safety
requirements requirements
[4] and GB 38031-2020[5]. These standards
Electric vehicles aretraction
constantly updated
battery with
safety the
requirements [5].
development of LIB technology.
These standards are constantly updated with the development of LIB technology.
The introduction of international and national safety standards for LIBs has pointed
The introduction of international and national safety standards for LIBs has pointed out
out the direction and set the threshold for battery manufacturers in terms of LIB perfor-
the direction and set the threshold for battery manufacturers in terms of LIB performance
Energies 2022, 15, 3884 16 of 31
Energies 2022, 15, x FOR PEER REVIEW 17 of 32

indicators. Scholars have conducted in-depth research on improving the safety performance
mance indicators.
of lithium batteries,Scholars
mainlyhave conducted
including thein-depth research
following on improving
five aspects: the safetyprotection,
Overcharge per-
formance of lithium batteries, mainly including the following five aspects: Overcharge
overheat protection, a battery management system (BMS), a Battery Thermal Management
protection, overheat protection, a battery management system (BMS), a Battery Thermal
System (BTMS), and a safety protection device [90], as shown in Figure 14.
Management System (BTMS), and a safety protection device [90], as shown in Figure 14.

TEMPO
Air cooling
Overcharge
MPT
Liquid cooling protection

DBBB,etc
Refrigerant cooling BTMS

PCM cooling Cathode material improvement

Mixed cooling Anode material improvement

Active safety protection Overheat
technology of LIB protection
Thermal protection separator
Thermal fuse

Positive temperature coefficient Flame retardant

element Safety
protection
CID device SOC estimation

Safety calve BMS SOH estimation

Battery balance management

Figure 14. Active safety protection technology of LIB.

Figure 14. Active safety protection technology of LIB.

4.1.4.1. Overcharge Protection

Overcharge Protection
BMS can externally control the charge and discharge voltage of each battery in the
BMS can externally control the charge and discharge voltage of each battery in the battery
battery pack, but it cannot control the chemical changes inside the battery. Adding redox
pack, but it cannot
additives control
is a method to the chemical
improve changes
battery safetyinside the battery.
by avoiding Adding
excessive redox
internal additives is
voltage.
a method to improve battery safety by avoiding excessive internal voltage. When
When the internal voltage of the battery is higher than the end of charging voltage, redox the internal
voltage of thecan
additives battery
carry is higher
out than the
a reversible end of
redox charging
reaction voltage,
between redox additives
electrodes to provide can carry out
over-
a reversible redox reaction between electrodes to provide overcharge protection.
charge protection.
J. Wen
J. Wenetetal.
al. [66] believethat
[66] believe that high-performance
high-performance redoxredox additives
additives should
should have have the
the fol-
lowing characteristics:
following characteristics: TheThereaction voltage
reaction of the redox
voltage of theagent should
redox be 0.3–0.4
agent shouldVbe higher
0.3–0.4 V
than than
higher the charging cut-offcut-off
the charging voltage; the redox
voltage; theagent
redoxreacts
agent reversibly on the positive
reacts reversibly on theand
positive
negative surfaces of the electrode; additive molecules should have a high
and negative surfaces of the electrode; additive molecules should have a high diffusion diffusion coef-
ficient and
coefficient andsolubility
solubilityandandthethe
redox agent
redox should
agent havehave
should goodgood
chemical stability
chemical and can
stability and can
provide long-term charging protection. TEMPO, MPT and DBBB are redox additives used
provide long-term charging protection. TEMPO, MPT and DBBB are redox additives used
in LFP batteries [91–93].
in LFP batteries [91–93].
4.2. Overheat Protection
4.2. Overheat Protection
The main method to improve the safety of LIB is to improve the characteristics of the
LIBThe main method
electrode, to improvediaphragm
binder, electrolyte, the safetyandof LIB ismaterials.
other to improve the characteristics of the
LIB electrode, binder,
To improve electrolyte,
the safety diaphragm
of cathode materialsand other
through materials.
element substitution, researchers
To improve
have replaced Al thewith
safety
CO,ofNicathode
and Mn,materials through
and increased element substitution,
the proportion researchers
of Mn and reduced
havethereplaced
proportionAl of
withNi CO,
in anNi and battery,
NCM Mn, andwhich
increased the proportion
can increase of Mn
the stability andbattery
of the reduced the
proportion
[94,95]. of Ni in an NCM battery, which can increase the stability of the battery [94,95].
TheThe surfaceofofthe
surface thecathode
cathode material
material can
canbebecoated
coatedwith
witha protective coating,
a protective which
coating, is is a
which
thina layer
thin layer of a lithium-ion
of a lithium-ion conductive
conductive compound,
compound, which
which mainly
mainly protects
protects thethe cathode
cathode surface
fromsurface from
direct direct with
contact contact with
the the electrolyte,
electrolyte, enhances
enhances thethe structuralstability
structural stability and
andpre-
prevents
side reactions. For example, fluoride coating has inert characteristics to reduce reaction
heat generation, and phosphate coating has a strong covalent bond to improve material
stability [90].
The battery separator implements a three-layer structure, such as a PE layer sand-
wiched between two PP layers, or high safety separators. By means of ceramic coating,
the thermal shrinkage of the separator is reduced and the separator collapse temperature
Energies 2022, 15, 3884 17 of 31

is increased. Expensive membranes such as polyethylene terephthalate (PET) [96] and

polyimide (PI) [97] are still under research.
The main characteristics of a flame retardant are the higher flash point than the
organic solvent, the inertness and the lack of effect on battery performance. Solid polymer
electrolytes, ionic liquid and electrolytic salt are mainly used to improve the thermal safety
of electrolytes [98].

4.3. Battery Management System (BMS)

In addition to the improvement of the materials of each component of the battery,
BMS is essential in the safe working process of an LIB. In addition to the basic functions
of monitoring the battery voltage, temperature and current, BMS also provides a charge
equalization scheme to ensure that each battery in the battery pack has the same charge
and discharge rate, so that the SOC of the battery is at the same level. Table 4 shows the
current SOC monitoring technology.

Table 4. SOC estimation techniques.

SoC Estimation Techniques

Direct Measurement
• Open circuit voltage
(OCV)
• Terminal voltage
• Impedance spectroscopy
Book-Keeping Estimation Adaptive System Hybrid Methods
• Coulomb counting and
• Coulomb counting • Neural network
OCV combination
(ampere-hour integral) • Support vector machine
• Coulomb counting and
• Modified Coulomb • Fuzzy neural
Kalman filter
counting • Kalman filter
• Extended Kalman filter

State of health (SOH) describes the aging degree of the battery during operation. When
the battery runs to a certain number of cycles, aging will occur, resulting in the decline of
battery capacity. Therefore, BMS must evaluate SOH to quantify the battery discharge depth
and remaining cycle life. SOH depends on SOC and battery internal resistance, so it is very
challenging to estimate. Table 5 shows the main techniques for estimating battery SOH.

Table 5. SOH estimation techniques.

SoH Estimation Techniques

Experimental Methods Model-Based Methods Machine/Deep Learning Methods
• Impedance measurement • Support vector regression
• Adaptive filtering (KF, EKF, UKF,
• Internal resistance • Neural network
RLS, etc.)
• Capacity level • Fuzzy logic
• Electrochemical model
• Incremental and differential of • Long- or short-term memory
• Sliding mode observers
capacity and voltage network, transformer, etc.

4.4. Battery Thermal Management System (BTMS)

The battery thermal management system adjusts the temperature in the battery pack
under different external environments to keep the battery temperature at a suitable working
temperature, avoid overheating and improve electrochemical performance. Battery pack
thermal management can generally be classified as (i) an air cooling method, (ii) liquid
cooling method, (iii) refrigerant-based cooling, (iv) phase change material (PCM) cooling
and (v) hybrid method [99–102]. Battery cooling is complicated by the thermal resistance
of the electrolyte and plastic components in the battery, which limits the heat transfer to
the battery surface. Air cooling is the simplest form and energy-saving method, but the
efficiency is low. It is generally not recommended for high-power or high-energy battery
packs. Liquid cooling has the highest efficiency and provides good uniformity, taking into
account energy consumption, complexity and weight. More advanced methods include
Energies 2022, 15, 3884 18 of 31

PCM cooling, a thermoelectric module or hybrid cooling, which are easy to integrate,
compact and efficient. However, the implementation cost is high, and in some cases, will
significantly increase the complexity of the maintenance of the whole battery pack system.

4.5. Safety Protection Device

A thermal fuse is a type of overheat protection device, which is made of wires with
a special alloy. When the preset current is exceeded, the wire will fuse. When the battery
has short-circuited, excessive joule heat will be generated. When the set temperature of the
thermal fuse is reached (generally 30–50 ◦ C), the thermal fuse will be broken [67].
The positive temperature coefficient element (PTC) is an element of the protection
circuit whose resistance increases with the increase in temperature. The device mainly
prevents overcurrent and overheating of the LIB due to an external short circuit. PTC is
made of a polymer conductive material, with a heat resistance temperature of 72–90 ◦ C,
and can work at a 6–20 A current and high voltage at room temperature [90].
The main function of the current interrupt device (CID) is to cut off the power supply
and ensure the safety of the battery when the battery is in a bad condition or the charging
device malfunctions. Sometimes gas will be generated in the sealed shell, resulting in a
rise in the internal pressure. If the pressure inside the sealed shell rises to an abnormal
state, it will cut off the power supply to ensure the safety of the battery. This technology
has been applied to a variety of LIBs, including cylindrical 18,650 LCO batteries, which can
effectively inhibit the occurrence of thermal runaway caused by overcharge.
When PTC or CID fails or there is a short circuit inside the battery, it will cause w more
serious electrochemical reaction, resulting in the decomposition of the separator inside the
battery and the reaction between the anode and electrolyte to generate a large amount of
gas. In order to prevent the explosion caused by the high internal pressure of the battery,
the safety valve will be torn, so as to release the internal high pressure and reduce the harm
caused by thermal runaway. However, in some cases, the internal pressure of the battery
rises too fast, resulting in the failure of the safety valve to respond in time, which will lead
to the bulging of the battery. When the internal temperature of the battery is too high, it will
even eject jet fire from the safety valve. Therefore, researchers have studied the opening
size of the safety valve, the setting of the bursting pressure and the design of the auxiliary
safety valve to some extent [103,104].

5. Research and Application Status of Large-Scale LIB in Mining Industry

5.1. Research of Large-Scale LIB in Mining Industry
Table 6 lists the recent progress for large-scale LIB applications in mining industry.

Table 6. Recent progress of large-scale LIB applications in mining industry [8,105–111].

Time Research Group Contribution

1986 Kuchta, J.M. Observed the lowest spontaneous combustion temperature of CH4
2005 MSHA The ignition temperature of coal dust cloud is 440 ◦ C to 640 ◦ C
Studied LIB safety performance requirements, chassis design, body
2017 MPSACC
structure, automatic protection and monitoring system, etc.
2018 MPSACC Conducted short circuit and overcharge experiments on 60 Ah LFP battery
Analysis on explosion—proof techniques and standards for lithium—ion
2020 CCTEG
battery power supply used in underground coal mine
Measured TR pressures of LFP cells as a function of free space within
2020 NIOSH
sealed enclosures and observed an inverse power relationship.
Conducted 300 Ah large-scale LFP batteries under external heating. TR can
2021 Binbin Mao
be divided to 4 stages.
Conducted nail penetration test for 202 Ah large-scale battery under
2022 CCTEG
encapsulation protection.
 2018 MPSACC Conducted short circuit and overcharge experiments on 60 Ah LFP battery
Analysis on explosion－proof techniques and standards for lithium—ion battery
2020 CCTEG
power supply used in underground coal mine
Measured TR pressures of LFP cells as a function of free space within sealed enclo-
2020 NIOSH
sures and observed an inverse power relationship.
Energies 2022, 15, 3884 Conducted 300 Ah large-scale LFP batteries under external heating. TR can be divided19 of 31
2021 Binbin Mao
to 4 stages.
Conducted nail penetration test for 202 Ah large-scale battery under encapsulation
2022 CCTEG
Thomas H. dubaniewicz et al. [108]protection.
studied 18,650 and 26,650 cylindrical LIBs, an-
alyzed the morphology and composition of battery anode, cathode and separator with
a scanning Thomas H. dubaniewicz
electron microscope etand al. [108]
then studied
sealed LFP18,650 and 26,650
units cylindrical
in different free LIBs,
spacesana-
in the
lyzed the morphology and composition of battery anode, cathode
ARC device for steady-state heating until battery thermal runaway occurred. Because and separator with a the
scanning electron microscope and then sealed LFP units in different free spaces in the
safety performance of the LFP battery is better than 18,650 battery and 26,650 batteries, the
ARC device for steady-state heating until battery thermal runaway occurred. Because the
relationship between the free space and maximum pressure during LFP thermal runaway
safety performance of the LFP battery is better than 18,650 battery and 26,650 batteries,
is studied and fittedbetween
the relationship by measuring the maximum
the free space and maximum pressure thatduring
pressure the LFP LFPbattery
thermalcan reach.
run-
It takes
away about 34 times
is studied and the volume
fitted of free the
by measuring space of the LFP
maximum unitthat
pressure to meet thebattery
the LFP thresholds
can of
18,650 and It26,650.
reach. takes about 34 times the volume of free space of the LFP unit to meet the thresh-
Binbin
olds Mao et
of 18,650 al.26,650.
and [110] conducted a series of thermal runaway tests on a 300 Ah large-
scale LFPBinbin
batteryMaounder
et al. external heating.
[110] conducted The of
a series experimental
thermal runawayrig oftests
LIBoncombustion tests is
a 300 Ah large-
shown scale
in LFP
Figurebattery under external
15. Figure heating.
15a presents a The experimental
combustion rig of (1.8
chamber m × 1.8 m tests
LIB combustion × 2 ism) as
shown
well as some in monitoring
Figure 15. Figure 15a presents
apparatuses. a combustion
Figure 15b shows chamber
the gas(1.8 m × 1.8and
analysis m ×exhaust
2 m) as sys-
tem. well
Afterasexternally
some monitoring
heatingapparatuses.
the battery Figure 15b shows
to thermal the gas
runaway, theanalysis and exhaust
safety valve opens,sys-
and an
tem. After externally heating the battery to thermal runaway, the safety
aggressive cylindrical flame is observed. Four stages were divided during battery external valve opens, and
an aggressive cylindrical flame is observed. Four stages were divided during battery ex-
heating processes: (i) Constant heating until the safety valve deformed and swelled; (ii) the
ternal heating processes: (i) Constant heating until the safety valve deformed and swelled;
safety valve cracked and heat is released; (iii) combustion and aggressive thermal runaway;
(ii) the safety valve cracked and heat is released; (iii) combustion and aggressive thermal
(iv) abatement
runaway; (iv) andabatement
extinguishment. However, the
and extinguishment. flamingthe
However, combustion accelerates
flaming combustion the occur-
acceler-
renceates
of TR but has little influence on the peak surface temperature.
the occurrence of TR but has little influence on the peak surface temperature.

−
−

− −

− −
− −

−
−
−
−

(a) (b)
Figure 15. Active safety protection technology of LIB: (a) Thermal runaway experimental test setup
Figure 15. Active safety protection technology of LIB: (a) Thermal runaway experimental test setup
for large-scale LFP battery; (b) stage division of thermal runaway process [110].
for large-scale LFP battery; (b) stage division of thermal runaway process [110].

Kuchta [105] indicated the lowest spontaneous combustion temperature of CH4 is

600 ◦ C in their experiment, and the ignition temperature of methane in air is 1040 ◦ C. Even
if the external heating LFP battery is under thermal runaway, the maximum temperature
reached by the battery is 450 ◦ C, which cannot reach the temperature of CH4 detonation.
The ignition temperature of coal dust measured by Kuchta ranges from 160 ◦ C to 220 ◦ C.
During coal mining or processing, coal dust accumulates into the explosion-proof shell of
the battery. MSHA [106] requires that the outer surface temperature of the explosion-proof
shell shall not exceed 150 ◦ C. The ignition temperature of the coal dust cloud is 440 ◦ C to
640 ◦ C. If the temperature of gas released by LFP is higher than 440 ◦ C, it is possible to
detonate external CH4 , resulting in an explosion.
Lei Wo et al. [107] conducted short-circuit and overcharge experiments on a 60 Ah
LFP battery and studied the influence of the LFP battery after thermal runaway on a CH4
explosion. The experimental results show that under the condition of an external short
circuit, the appearance of the battery is intact, there is no combustion, explosion, leakage
and pressure relief and the battery voltage is reduced to 0 V. The battery was seriously
damaged after overcharge, and the battery underwent a combustion explosion and pressure
relief, but it did not cause a secondary CH4 explosion; however, the internal pressure of
the explosion-proof shell reached 4 MPa, exceeding its design pressure. It is verified that
the LFP battery will not cause a secondary explosion even under the condition of a high
concentration of CH4 after thermal runaway; however, the release of gas could potentially
Energies 2022, 15, 3884 20 of 31

lead to excessive pressure in the explosion-proof shell and further cause catastrophic events.
Hence, it is necessary to design a pressure relief technique for the battery enclosure.
Yong Zhang [8] interpreted the LIB vehicle in terms of vehicle operating conditions,
LIB safety performance requirements, chassis design, body structure, automatic protection,
monitoring system, etc. In terms of battery safety performance, all on-board electrical ap-
pliances are required to meet the requirements of the GB 3836 explosive environment [112]
series standards: (i) The temperature of the battery surface shall not exceed 150 ◦ C; (ii) the
capacity of the LFP battery for mining shall not exceed 100 Ah; (iii) the connection mode of
the single battery shall adopt a low-resistance design to avoid heat accumulation; (iv) the
LIB shall be placed separately in an explosion-proof chamber with a pressure of 1.5 MPa,
and a pressure relief valve shall be installed; (v) the protection grade of the LIB shell shall
not be lower than IP55; (vi) when the LIB is fully charged, the braking regenerative energy
shall be completely consumed and absorbed by the special device without overcharging
the battery pack [113,114].
The authors presented a thorough analysis and experimental results on the effect
of encapsulation on the lithium cell that undergoes nail penetration thermal runaway.
Regarding the nail penetrating the cell, the rising temperature and voltage profile of the
cell’s thermal runaway behavior are shown in Figure 16 [111]. Each battery was installed
with 3 sensors, located in the cell’s left wide face, safety valve, and negative terminal
respectively, total 30 sensors. Sensor 31, 32 and 33, as shown in Figure 16c, were installed
in the upper space enclosure to measure the ambient environment above the encapsulated
cells. Note that the instantaneous drop of the cell’s voltage at the onset of thermal runaway
shows that the cell short-circuited internally through the nail penetration. Temperature
sensors T25, T26 and T27 are recorded for the triggered battery. In Figure 16b, the voltage
dropped to 0 within 3 min. The temperature of the safety valve (T26) increased faster
than T25 and T27 due to the reaction gasses and electrolyte breaking through the safety
valve. The highest temperature of the cell’s wide surface (T25) occurred after 5 min of the
triggering, and reaches up to around 490 K. The heat released from the thermal runaway
battery dissipated quickly through the heat conduction of the encapsulation and blocked
transmission by resin separator. The investigations illustrated that the encapsulated cells
have exceptional advantages in providing the required protection to a large number of
series-connected battery cells, particularly for a high-capacity cell.

Table 7. Relationship between protection type and equipment protection level.

EPL Protection Type Sign Group Standards

Intrinsically safe ‘ia’ I GB 3836.4 & IEC 60079.11
Encapsulation ‘ma’ I GB 3836.9 & IEC 60079.18
‘Ma’
Special ‘s’ I GB 3836.24 & IEC 60079.33
2 independent EPL Mb I GB 3836.23 & IEC 60079.14
Intrinsically safe ‘ib’ I GB 3836.4 & IEC 60079.11
Explosion-proof ‘d’ I GB 3836.2 & IEC 60079.1
Increased safe ‘e’ I GB 3836.3 & IEC 60079.7
‘Mb’ Positive-pressure ‘p’,‘px’ I GB 3836.5 & IEC 60079.2
Encapsulation ‘m’,‘mb’ I GB 3836.9 & IEC 60079.18
Sand filling ‘q’ I GB 3836.7 & IEC 60079.5
Special ‘s’ I GB 3836.24 & IEC 60079.33

The LFP battery has a large thermal stability range and is safer than other types of LIBs
in faulty conditions such as short circuits and fire [109]. However, the thermal runaway
heat generation of the LFP battery will also cause a sharp increase in temperature and may
be accompanied by the release of high-temperature gas. The explosion-proof design must
be adopted, and the internal pressure of the explosion-proof container must meet the static
pressure of 1 MPa. There are three explosion-proof protection technologies for LIB vehicles:
Explosion-proof (Ex’d’), intrinsically safe (‘ia’/’ib’) and encapsulation (Ex ‘ma’/’mb’). At
Energies 2022, 15, 3884 21 of 31

the same time, the increased safety type (Ex ‘e’) or the combination of several protection
technologies
Energies 2022, 15, x FOR PEER REVIEW may also be considered to achieve the required protection level. Table227 of
shows
32
the relationship between the protection type and equipment protection level (EPL).

T19 T27
4
520 T20 T28
T21 T29
T22 T30
Air Enclosure T23 T31
480 3
T24 T32
T25 T33

Temperature (K)
194m T26 Voltage
440

Voltage (V)
2
140mm Encapsulation
400
363mm
Resin Thermal 1
360
Seperator Runaway
battery
610mm 320
0

280
0 500 1000 1500

Time (s)
(a) (b)

(c) (d)
Figure
Figure 16.16. Large-scaleLIB
Large-scale LIBpack
packthermal
thermalrunaway
runawayexperiment:
experiment:(a)(a)Model
Model of
of encapsulated
encapsulated cell
cell pack
pack in
in enclosure; (b) experimental measurement of temperature, voltage vs. time; (c) front view of bat-
enclosure; (b) experimental measurement of temperature, voltage vs. time; (c) front view of battery
tery pack sensor installation position; (d) top view of battery pack sensor installation position.
pack sensor installation position; (d) top view of battery pack sensor installation position.
The LFP battery has a large thermal stability range and is safer than other types of
5.2. Application
LIBs in faulty of Large-Scale
conditions suchLIBasinshort
Mining Industry
circuits and fire [109]. However, the thermal runa-
way The South
heat African of
generation mining
the LFPhealth and will
battery safety bureau
also causedefines
a sharpengineering
increase inmobile machin-
temperature
ery formay
and mining operations asby
be accompanied “any
theself-propelled machine used gas.
release of high-temperature for mining, transportation
The explosion-proof
ordesign
relatedmust
operations underground
be adopted, or on thepressure
and the internal mine surface, including any mobile
of the explosion-proof device
container mustthat
is meet
driven by wheels, slides, rails, machinery or installed on the machine”.
the static pressure of 1 MPa. There are three explosion-proof protection technologiesWith the progress
offor LIB vehicles:
battery Explosion-proof
technology, the trend of(Ex’d’),
replacingintrinsically safe (‘ia’/’ib’)
diesel-driven trackless andvehicles
encapsulation (Ex is
with EVs
‘ma’/’mb’).
becoming moreAt the
andsame
moretime, the increased
prominent. safetyEVs
Although typeare
(Exmore
‘e’) or the combination
expensive of sev- or
than gasoline
eral vehicles
diesel protection technologies
and require fixed may also be equipment,
charging considered to theachieve
working theefficiency
required ofprotection
the motor
is level.
muchTablehigher 7 shows the relationship
than that between
of the traditional the protection
internal combustiontype engine,
and equipment
and theprotec-
braking
tion level
energy can (EPL).
be recovered. When EVs are implemented in mining projects, their operating
costs are much lower than diesel vehicles. Figure 17 compares the operating costs of diesel
Table 7.and
vehicles Relationship between
EVs in detail protection type and equipment protection level.
[115].
In 2019,Protection
EPL the carbonType
emissions of commercial
Sign Group vehicles in Australia accounted for 38% of
Standards
the total emissions. Commercial
Intrinsically safe vehicles
‘ia’ mainly I include light commercial
GB 3836.4 trucks, light and
& IEC 60079.11
medium trucks, waste-disposal
Encapsulation vehicles,
‘ma’ mining I and multipurpose vehicles
GB 3836.9 & IEC 60079.18and customized
and‘Ma’
special vehicles. Furthermore,
Special 84%
‘s’ of freight
I vehicles in Australia are light
GB 3836.24 & IEC 60079.33 commercial
vehicles. 2The transformation
independent EPL Mb of light and medium
I fuel GB 3836.23 & IEC 60079.14 reduce
vehicles can significantly
carbon emissions.Intrinsically safe ‘ib’ I GB 3836.4 & IEC 60079.11
‘Mb’ Explosion-proof ‘d’ I GB 3836.2 & IEC 60079.1
Increased safe ‘e’ I GB 3836.3 & IEC 60079.7
 device that is driven by wheels, slides, rails, machinery or installed on the machine”. With
the progress of battery technology, the trend of replacing diesel-driven trackless vehicles
with EVs is becoming more and more prominent. Although EVs are more expensive than
gasoline or diesel vehicles and require fixed charging equipment, the working efficiency
of the motor is much higher than that of the traditional internal combustion engine, and
the braking energy can be recovered. When EVs are implemented in mining projects, their
Energies 2022, 15, 3884 22 of 31
operating costs are much lower than diesel vehicles. Figure 17 compares the operating
costs of diesel vehicles and EVs in detail [115].

500,000
400,000

CA$ /year
300,000
200,000
100,000
0
Fuel Ventilation Maintenance Total
Diesel Electric

Figure 17. Cost comparison between diesel vehicle and EV.

Figure 17. Cost comparison between diesel vehicle and EV.

Australia’s mining industry is also prone to using EVs. Replacing heavy mining
In 2019, the carbon emissions of commercial vehicles in Australia accounted for 38%
vehicles andof the totalmultipurpose
light vehicles
emissions. Commercial withmainly
vehicles EVs brings
includegreat benefits to
light commercial workers
trucks, light and
operators inandopen-pit mineswaste-disposal
medium trucks, and underground mines.
vehicles, miningAs andwith all electric
multipurpose vehicles,
vehicles electric
and cus-
tomizedprovide
mining vehicles and special vehicles.
quiet Furthermore,
and stable 84%can
driving, of freight
output vehicles
higher in torque
Australiaandare light
generate
less heat. commercial
They have vehicles. The transformation
irreplaceable advantages of light and medium
under the mining fuel vehicles can signifi-
conditions of sharp
cantly reduce carbon emissions.
turns and limited space operation. They are not affected by ventilation and have no
Australia’s mining industry is also prone to using EVs. Replacing heavy mining ve-
quantity restrictions on underground
hicles and light operation.
multipurpose vehicles with EVsIn addition,
brings greatelectric
benefitsvehicles
to workers can
andcarry
op- out
regenerative braking
erators in complex
in open-pit mines andterrain, greatly mines.
underground reducing energy
As with wastevehicles,
all electric [116]. electric
European
mining Sustainable Intelligent
vehicles provide Mining
quiet and stableSystems
driving, for
canthe global
output mining
higher torqueindustry proposes
and generate
the creationless
ofheat. They have
a digital mineirreplaceable advantages
in a three-year under With
plan [115]. the mining conditions
a total investmentof sharp turns US
of nearly
$20 million,andthelimited
project space
aimsoperation. Theyaare
to establish not affected
connected, by ventilation
efficient, safe and andattractive
have no quantity
workplace,
restrictions on underground operation. In addition, electric vehicles can carry out regen-
which has erative
been successfully demonstrated in Germany, Poland, Sweden and Finland. The
braking in complex terrain, greatly reducing energy waste [116].
project includesEuropean
the use of an LIB drilling
Sustainable rig Mining
Intelligent and anSystems
auxiliaryfortransportation
the global mining system
industrytopro-
improve
the underground
poses theair pollution
creation causedmine
of a digital by diesel engines,
in a three-year as [115].
plan shown in Figure
With 18.
a total investment of
The global
nearly mining guidelines
US $20 million, Association
the project (GMG)a and
aims to establish the mining
connected, Innovation
efficient, Council
safe and attrac-
of Canadative workplace,
issued which methods
proposed has been successfully
for EVs in demonstrated
underground in Germany,
miningPoland, Sweden
environments in
and Finland. The project includes the use of an LIB drilling rig and an auxiliary transpor-
2018 [117]. The guide focuses on seven parts, explaining the basic knowledge and applica-
tation system to improve the underground air pollution caused by diesel engines, as
tion of EVs, mine
shown in design,
Figure 18.EV design, energy storage system, charging system, operation
precautions and performance standards, which provided application24guidelines
Energies 2022, 15, x FOR PEER REVIEW of 32 for global
mining companies and equipment manufacturers.

Figure 18. European sustainable intelligent mining system.

Figure 18. European sustainable intelligent mining system.
The global mining guidelines Association (GMG) and the mining Innovation Council
of Canada issued proposed methods for EVs in underground mining environments in
2018 [117]. The guide focuses on seven parts, explaining the basic knowledge and appli-
cation of EVs, mine design, EV design, energy storage system, charging system, operation
precautions and performance standards, which provided application guidelines for global
Energies 2022, 15, 3884
Table 8. Test standards for energy-storage systems.
Recommended Industry Standard
E/ECE/324/Rev.2/Add.99/Rev.2
ST/SG/AC.10/11/Rev.5
J2288_200806
UL 1642
UL 2580
CAN/CSA-E62660-1:15
CAN/CSA-E62660-2:15
IEC 62133–2:2017
IEC 61508:2010
IEC 62061:2005 (plus amendments)
US CFR Parts 100–177
Canada TDG
IMDG 2014,2016
IATA Dangerous Goods Regulations
ISO 14990–1:2016
ISO 6165:2012
The rechargeable LIB in the energy storage system is at the core of the operation of electric
vehicles. The battery capacity and energy density determine the operation range of a single
charge of EVs. Energy-storage materials with small volume, light weight, high efficiency,
23 of 31
Topic Citation
Safety requirements of vehicle electric power
United Nations, 2013
train
Criteria, test methods and procedures for
United Nations, 2019
classifying dangerous goods
Standardized test method to determine the
SAE International, 2008
expected life cycles of BEV battery modules
Requirements to reduce the risk of and injury
from fire or explosion when lithium batteries
UL, 2012b
are used or removed from a product
and discarded
Evaluates the ability of the electrical energy
storage assembly to safely withstand simulated
UL, 2013
abuse conditions and prevents exposure of
persons to hazards as a result of the abuse
Performance and life testing of rechargeable
lithium-ion cells for propulsion of BEVs and CSA Group, 2015a
hybrid electric vehicles
Test procedures to observe the reliability and
abuse behavior of rechargeable lithium-ion
CSA Group, 2105b
cells for propulsion of BEVs and hybrid
electric vehicles
Requirements and tests for safe operation of
International Electrotechnical
portable sealed rechargeable lithium cells and
Commission, 2017
LIBs containing non-acid electrolyte
Aspects to be considered when
International Electrotechnical
electrical/electronic/programmable electronic
Commission, 2010
systems are used to carry out safety functions
Requirements and recommendations for the
design, integration, and validation of
International Electrotechnical
safety-related electronical, electronic and
Commission, 2015
programmable electronic control systems
for machines
United States Code of Federal Regulations on United States Office of the Federal
Transportation Register, 2012
Transportation of dangerous goods regulations Transport Canada, 2016
International Maritime Dangerous Goods
International Maritime
Code. IMDG 2014 in force as of January 2016;
Organization, 2017
IMDG 2016 in force as of January 2018
International Air Transport Association International Air Transport
Dangerous Goods Regulations Association, 2018
General safety requirements for electrical
equipment and components incorporated into International Organization for
earth-moving machines as defined in Standardization, 2016a
1506165:2012
Terms and definitions and an identification
International Organization for
structure for classifying
Standardization, 2012a
earth-moving machinery
Energies 2022, 15, 3884 24 of 31

low price and high energy density promote the development of the battery industry. These
excellent characteristics are more critical in mining, because mining vehicles have a larger
volume and weight and higher energy consumption. However, with the increase in the energy
density of a single battery, the safety of the battery decreases. GMG proposed three main
approaches to battery safety: First, limit the number of active materials to achieve a balance
between energy density and safety. Second, add safety mechanisms inside the battery, such
as CID, a safety valve, etc. Third, add an electronic guaranteed circuit to the battery pack.
The test standards of the energy-storage system have multiple criteria. Table 8 summarizes
international standards related to the energy-storage system [117].
China’s EV industry has developed rapidly in recent years, with nearly 6 million in use,
accounting for more than 50% of the world. The intelligent electrification of vehicles has
penetrated the whole auto industry, and the development of EVs can be divided into three
stages: (i) From 1995–2000, EVs were mainly used for passenger cars; (ii) from 2001–2020,
the number of EV passenger cars, buses and logistics vehicles increased sharply; (iii) after
2020, special EVs will become a new growth engine of the market. Through structural
innovation, BYD, an EV company, invented blade batteries, which are designed by skipping
the module when they are grouped. Compared with the modular battery pack design, the
weight-specific energy density of blade batteries can reach up to 180 Wh/kg. Depending
on the particularity of the shape of the blade battery and the stability of the material,
the densely arranged blade battery can act as a simple structural part, and the space
utilization rate is increased from 40% to 60%. Moreover, the blade battery also improves
the disadvantage of the low-temperature resistance of lithium iron phosphate. Even in a
severe cold environment of minus 20 degrees, the discharge capacity of the blade battery is
at least 90% of that at room temperature. It can still maintain the stability of the battery
performance in the low-temperature environment, thus better improving the problem of
low-temperature endurance attenuation of the lithium iron phosphate battery [118]. The
new battery technology accelerates the development of the EV industry.
In the coming period of time, auxiliary transport vehicles for coal mines will change
from diesel engines to electric engines to a large extent. There are 2403 auxiliary transporta-
tion vehicles in use in the Shendong Coal Group, including 456 LIB vehicles. Zhongtian
Hechuang Energy Co., Ltd. has 218 explosion-proof auxiliary transportation vehicles,
including 36 LIB vehicles. It can be seen that LIB vehicles have been preliminarily applied
in some companies, and there is a great space for their development in the future.

6. Conclusions and Prospects

High-capacity LIBs have been widely used in EVs and electrochemical energy storage,
which reaches 300 Ah, while in underground coal mines, the capacity of the LIB needs to be
less than 100 Ah [119]. With the increase in the capacity of a single battery, its energy density
increases accordingly, which leads to an increase in the severity of the thermal runaway of
a single battery and the probability of thermal runaway of battery packs. Battery safety is
particularly important. This review introduced the cathode materials of LIBs, analyzed the
occurrence conditions of internal chemical reactions after thermal runaway, compared the
severity of decomposition and heat release of different cathode materials when thermal
runaway occurs and came to the conclusion that the temperature rise rate of LFP is slower
than that of LMO, LCO and NCM when thermal runaway occurs. This review performed
a detailed analysis of the causes of battery thermal runaway. Regardless of mechanical
abuse, electrical abuse and thermal abuse, the inducing factors of thermal runaway are
attributed to the fierce chemical exothermic reaction caused by the internal short circuit of
the battery, and the excessive temperature rise in the battery could potentially cause fire
and an explosion. Therefore, in order to ensure the intrinsic safety of the battery pack, one
strategy is to select safer cathodes and anodes, electrolytes and separator materials, and the
other is to take away the heat of the thermal runaway battery in time, so as not to cause
the spread of thermal runaway. For battery safety, this review analyzes five dimensions:
Overcharge protection, overheating protection, BMS, BTMS and battery safety protection
Energies 2022, 15, 3884 25 of 31

device. Finally, this review summarized and analyzed the latest research results on the
application of high-capacity batteries in coal mines and introduced the design requirements
of IEC 60079 and GB 3836 series standards for electrical equipment used in an explosive
environment, and considered that, after encapsulation, even if the internal battery is under
thermal runaway, it is cooled by encapsulation materials and buffered in the internal
space of the explosion-proof chamber. Hence, it will not further cascade to the explosive
environment that will potentially lead to fire or explosion accidents.
To summarize, high-capacity LIBs are qualified for application in underground vehicles
and equipment in coal mines; however, increasing the single battery capacity without conduct-
ing thorough thermal runaway studies may bring new potential safety hazards. Therefore,
various meticulous tests must be carried out to verify that the high-energy-density LIB will
not cause a cascade of effects after thermal runaway. High-energy-density lithium batteries
should be used to make breakthroughs from new materials, such as lithium sulfur batteries
and lithium oxygen batteries, for which the theoretical energy density can reach up to 2600
and 3500 Wh/kg, respectively [120,121]. However, sharp decay, poor cycling stability, low
coulombic efficiency and serious safety hazards impede their practical application [122–125].
The Fe7 S8 /SiOx /nitrogen-doped carbon anode exhibited a superior discharge capacity of
1060.2 mA h g−1 , which demonstrates great potential in electrochemical energy storage [126].
In the composition of a battery pack, new thermal insulation and heat transfer materials
should be applied to prevent the thermal runaway propagation of a single battery. A full
operation life cycle battery management system shall be developed to ensure battery charge
and discharge consistency and overcharge and discharge protection. The application of LIBs
in mining auxiliary transportation vehicles is still in its initial stage and has broad market
prospects. It can gradually replace explosion-proof diesel vehicles in the future, so as to ensure
safe, efficient and sustainable mining operations.

Author Contributions: Conceptualization, L.M., G.W. and K.W.S.; methodology, L.M. and K.W.S.;
software, L.M.; validation, C.Z.; formal analysis, L.M. and Y.W.; investigation, L.M. and R.Z.; re-
sources, Y.W., Y.Z. and B.X.; data curation, C.Z. and Y.Z.; writing—original draft preparation, L.M.;
writing—review and editing, K.W.S. and G.W.; supervision, G.W., Y.W. and R.Z.; project administra-
tion, B.X.; funding acquisition, Y.W. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by Tianma Intelligent Control Technology Co., Ltd., grant number
2022TM019-J1.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We acknowledge the funding support from CCTEG for this research and support
of China University of Mining & Technology-Beijing and Tianma Intelligent Control Technology
Co., Ltd.
Conflicts of Interest: The authors declare no conflict of interest.
Energies 2022, 15, 3884 26 of 31

Abbreviations

3C Computer, communication, and consumer electronics

ARC Accelerating rate calorimeter
BMS Battery management system
BTMS Battery thermal management system
CCTEG China Coal Technology Engineering Group
CID Current interrupt device
DBBB 2,5-Di-tert-butyl-1,4-bis benzene
DEC Diethyl carbonate
DMC Dimethyl carbonate
EC Ethylene carbonate
EKF Extended Kalman filter
EMC Methyl ethyl carbonate
EPL Equipment protection level
EV Electronic vehicle
GMG Global mining guidelines
IEC International electrotechnical commission
ISC Internal short circuit
KF Kalman filter
LCO Lithium cobalt oxide
LFP Lithium iron phosphate
LIB Lithium-ion battery
LMO Lithium manganate oxide
MPSACC Mining products safety and certification center
MPT Methylphenothiazine
MSHA Mine safety and health administration
NCA Nickel cobalt aluminum
NCM Lithium nickel manganese cobalt oxide
NIOSH National institute for occupational safety and health
OCV Open circuit voltage
PCM Phase change material
PE Polyethylene
PET Polyethylene terephthalate
PI Polyimide
PP Polypropylene
PTC Positive temperature coefficient element
PVDF Polyvinylidene fluoride
RLS Recursive least squares filter
SEI Solid electrolyte interphase
SOC State of charge
SOH State of health
TEMPO 2,2,6,6-tetramethylpiperidinyl-oxide
TGA Thermal gravimetric analyzer
TM Transmission metal
TR Thermal runaway
UKF Unscented Kalman filter

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