ArticlePDF Available

Abstract and Figures

Lithium-ion batteries (LiBs) are a proven technology for energy storage systems, mobile electronics, power tools, aerospace, automotive and maritime applications. LiBs have attracted interest from academia and industry due to their high power and energy densities compared to other battery technologies. Despite the extensive usage of LiBs, there is a substantial fire risk associated with their use which is a concern, especially when utilised in electric vehicles, aeroplanes, and submarines. This review presents LiB hazards, techniques for mitigating risks, the suppression of LiB fires and identification of shortcomings for future improvement. Water is identified as an efficient cooling and suppressing agent and water mist is considered the most promising technique to extinguish LiB fires. In the initial stages, the present review covers some relevant information regarding the material constitution and configuration of the cell assemblies, and phenomenological evolution of the thermal runaway reactions, which in turn can potentially lead to flaming combustion of cells and battery assemblies. This is followed by short descriptions of various active fire control agents to suppress fires involving LiBs in general, and water as a superior extinguishing medium in particular. In the latter parts of the review, the phenomena associated with water mist suppression of LiB fires are comprehensively reviewed.
Content may be subject to copyright.
Energies 2020, 13, 5117; doi:10.3390/en13195117 www.mdpi.com/journal/energies
Review
A Review of Lithium-Ion Battery Fire Suppression
Mohammadmahdi Ghiji 1,*, Vasily Novozhilov 1, Khalid Moinuddin 1, Paul Joseph 1, Ian Burch 2,
Brigitta Suendermann 2 and Grant Gamble 2
1 Institute of Sustainable Industries and Liveable Cities, Victoria University,
Melbourne, VIC 3030, Australia; Vasily.Novozhilov@vu.edu.au (V.N.); Khalid.Moinuddin@vu.edu.au
(K.M.); Paul.Joseph@vu.edu.au (P.J.)
2 Maritime Division, Defence Science & Technology Group, Melbourne, VIC 3207, Australia;
Ian.Burch@dst.defence.gov.au (I.B.); Brigitta.Suendermann@dst.defence.gov.au (B.S.);
Grant.Gamble@dst.defence.gov.au (G.G.)
* Correspondence: Mohammadmahdi.ghiji@vu.edu.au
Received: 5 August 2020; Accepted: 28 September 2020; Published: 1 October 2020
Abstract: Lithium-ion batteries (LiBs) are a proven technology for energy storage systems, mobile
electronics, power tools, aerospace, automotive and maritime applications. LiBs have attracted
interest from academia and industry due to their high power and energy densities compared to
other battery technologies. Despite the extensive usage of LiBs, there is a substantial fire risk
associated with their use which is a concern, especially when utilised in electric vehicles, aeroplanes,
and submarines. This review presents LiB hazards, techniques for mitigating risks, the suppression
of LiB fires and identification of shortcomings for future improvement. Water is identified as an
efficient cooling and suppressing agent and water mist is considered the most promising technique
to extinguish LiB fires. In the initial stages, the present review covers some relevant information
regarding the material constitution and configuration of the cell assemblies, and phenomenological
evolution of the thermal runaway reactions, which in turn can potentially lead to flaming
combustion of cells and battery assemblies. This is followed by short descriptions of various active
fire control agents to suppress fires involving LiBs in general, and water as a superior extinguishing
medium in particular. In the latter parts of the review, the phenomena associated with water mist
suppression of LiB fires are comprehensively reviewed.
Keywords: lithium-ion battery; thermal runaway; fire suppression; water mist
1. Introduction
The first lithium-ion battery (LiB) was proposed by Yoshino in 1985, based on earlier research
by Whittingham [1] in the 1970s, and Goodenough et al. [2,3] during the 1970s1980s. LiBs became
commercially available in 1991 [4] and have become the battery chemistry of choice for electronic
devices, transportation and energy storage [5]. LiBs offer great energy and power density, light
weight and a long lifespan [6,7] when compared to older battery chemistries, as listed in Table 1. It
can be seen that LiB technology has a high energy density and is ideal for cyclic applications. It is
smaller and lighter compared to conventional lead-acid or Nickel Cadmium batteries. These
advantages are encouraging for the replacement of conventional battery technologies with lithium-
ion [8]. However, if the internal temperature of a LiB increases beyond its operating range, by external
or internal means, components of the battery may become unstable and tend to generate additional
heat. If this heat does not dissipate, the battery temperature will elevate further, thereby accelerating
the process of heat release. This process is called thermal runaway. LiB chemistry differs from battery
technologies such as lead-acid, nickel-cadmium, zinc bromide and alkaline by using a flammable
organic electrolyte, presenting a fire risk during thermal runaway process that needs to be addressed
Energies 2020, 13, 5117 2 of 30
to ensure a safe operating environment. Although fire can be extinguished by many methods, the
effects of thermal runaway are more difficult to manage and continued cooling is required.
Table 1. Characteristics of different battery technologies [9]. Response time is the time to deliver
maximum power output over a specific time, with h = hours; min = minutes; ms = milliseconds; s =
seconds; NA = not applicable.
Lifetime
Years
(Cycles)
Power
Densit
y
Wkg1
(kWm
3)
Energy
Density
Whkg1
(kWhm
3)
Dischar
ge Time
Rechar
ge
Time
Operating
Temperatu
re (°C)
Self-
Discharge
(%/day)
Critical
Voltage/
Cell (V)
Lithium-
ion
battery
815 (500
6000)
230
340
(1300
10000)
100250
(250
620)
minh
minh
10 to 50
0.10.3
3
Lead-
acid
battery
315 (2000)
75300
(90
700)
3050
(75)
minh
816 h
10 to 40
0.10.3
1.75
Advance
d lead-
acid
battery
315 (3000)
75300
(90
700)
3050
(75)
minh
816 h
10 to 40
0.10.3
2
Nickel-
cadmiu
m
battery
1520
(2500)
150
300
(75
700)
4580
(<200)
sh
1 h
40 to 45
0.20.6
1
Zinc
bromide
flow
battery
510 (300
1500)
50150
(125)
6080
(2035)
s10 h
4 h
10 to 45
01
0.170.3
Vanadiu
m redox
flow
battery
1020 (13
103)
NA
(0.52)
75 (20
35)
s10h
min
0 to 40
010
0.70.8
This paper reviews the processes associated with LiB thermal runaway and fire suppression.
Extinguishing agents are examined and the mechanisms associated with fire suppression are
presented.
2. Lithium-Ion Battery Components
A lithium-ion cell consists of a cathode, an anode, separator, and electrolyte. The anode and
cathode materials are deposited onto copper and aluminium foil current collectors, respectively. The
electrolyte enables the movement of lithium ions between the electrodes, while the separator fits
between the anode and cathode preventing shorting between the two electrodes but permitting ion
transfer. During the discharge reaction, lithium ions move from the anode and insert into the voids
between layers of cathode crystals (the process named intercalation). Upon charging, lithium ions
move from the cathode on the positive side of the battery and insert into the anode. The LiB
components and processes are illustrated in Figure 1. During the initial charge, intercalated lithium
ions react immediately with the solvent of the electrolyte and form a passivation layer on the anode,
the Solid-Electrolyte Interphase (SEI), which is permeable to lithium ions but not to the electrolyte
[7]. The stability of the SEI is a determining factor of LiBs’ safety and life.
The details of each battery component are provided in the following sections.
Energies 2020, 13, 5117 3 of 30
Figure 1. The principle of the lithium-ion battery (LiB) showing the intercalation of lithium-ions
(yellow spheres) into the anode and cathode matrices upon charge and discharge, respectively [10].
2.1. Cathode
The cathode composition gives the name to the type of LiB. Lithium metal oxides such as
Lithium Cobalt Oxide (LCO), Nickel Cobalt Aluminium Oxide (NCA), Lithium Cobalt Phosphate
(LCP), Nickel Cobalt Manganese Oxide (NCM), Lithium Manganese Oxide (LMO), Lithium Iron
Phosphate (LFP), Lithium Iron Fluorosulphate (LFSF) and Lithium Titanium Sulphide (LTS) have
been used as cathode materials owing to their high capacity for lithium intercalation and compatible
chemical and physical properties (e.g., for the reversibility of the intercalation reactions) necessary
for lithium ion transport. Figure 2 presents cell specific capacity and average discharge potential of a
series of cathode materials [11]. LCO, NCA and NCM all have a layered structure with high energy
density at the cost of lower thermal stability, and contain expensive cobalt. LMO has a spinel-like
structure, great thermal stability and high voltage but relatively low capacity. LFP has a stable olivine
structure and has attracted significant interest [1215] due to low cost as it does not contain cobalt,
has high average voltage and a low susceptibility to thermal runaway compared to NCM and LCO,
providing a good balance between performance and safety [1618]. To date, cathode materials with
high capacity and voltage such as nickel- [1924], manganese- [25] and lithium-rich [19,2531]
materials, carbon-coated LFP nanospheres [32] and vanadium pentoxide [33] have been recognized.
Higher contents of nickel and lithium increase the specific capacity of the cathode material but
decrease thermal stability. The thermal instability of LiBs have been systematically characterised
using synchrotron-based X-ray techniques [34,35]. The outcomes of these investigations provided
fundamental understanding and guidance which is vital to develop safer batteries with a high energy
density.
Energies 2020, 13, 5117 4 of 30
Figure 2. Average discharge potentials and specific capacity of common cathodes [11].
2.2. Anode
The most common material used for LiB anodes is graphite due to its high negative potential.
Other materials such as lithium titanate and silicone operate at lower negative voltages reducing the
energy and power density, making them less practical except for fast charging devices [36] and fixed
energy storage where the importance of energy density is less significant [37]. Lithium titanate and
silicone enable lithium ions to travel more readily which decreases the internal resistance and reduces
battery heating compared to the graphite anode [38]. Studies to identify new materials for anodes
with higher capacity and voltage have been undertaken. Materials such as silicon [39,40], tin [41],
antimony [42], germanium [43,44], silicon oxide [45], transition metal oxide: MO (where M is cobalt,
nickel, copper or iron) [44,46], ultra-thin graphene nanosheets [47], and layered boron-nitrogen-
carbon-oxygen material with adjustable composition [48] have been tested. In the development of
new anode materials, properties including capacity retention, conductivity, volume expansion,
dendrite formation, and stability of the SEI layer should be considered before commercialisation [49].
2.3. Separator
In LiBs, the cathode and anode are separated by a porous membrane called the separator [50].
The separator is a crucial component in a lithium-ion cell, it prevents electrical short circuits between
the two electrodes but allows transport of lithium ions between the electrodes [51]. The most popular
separator materials for LiBs with organic electrolytes are made of microporous polyolefin films such
as polyethylene (PE), polypropylene (PP), or laminates of polyethylene and polypropylene offering
outstanding chemical stability, mechanical properties, and acceptable cost [51]. The low melting point
of polyolefins (135 °C for PE and 165 °C for PP) qualifies their utilisation as a thermal fuse to shut
down the cell by losing porosity and permeability if an over-temperature condition occurs [51]. New
separator designs such as ceramic composite (frequently alumina and silica) [5255] and multilayered
ceramic composite (with a shutdown feature through different phase change layers) [5658] have
been established with improved mechanical strength and thermal stability. Other separator materials
and designs include polyester fibre non-woven membranes [56], silica/polyvinylidene fluoride
porous composite matrix [59], porous-layer-coated polyimide nanofiber [60] and
polyformaldehyde/cellulose nanofibre blends [61].
2.4. Electrolyte
The electrolyte infills the space between the separator and electrodes. The electrolyte
formulation in LiBs is dependent on the electrode materials and operating conditions [36]. The typical
electrolyte for LiBs is made of a flammable carbonate-based organic solvent such as ethylene
Energies 2020, 13, 5117 5 of 30
carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate
(EMC), and/or propylene carbonate (PC) [62], with additives including lithium hexafluorophosphate
(LiFP6), lithium hexafluoroarsenate monohydrate (LiAsF6), lithium perchlorate (LiClO4), and lithium
tetrafluoroborate (LiBF4) to improve cycling [63]. New electrolytes aim to mitigate the fire risk
associated with conventional electrolytes using more stable lithium salts [64,65], additives [6674],
ionic liquid [7577], non-flammable solvents [78,79], synthesized aqueous electrolytes [80,81],
polymer electrolytes [8284] and/or solid-state electrolytes [66,8587].
The performance, cost and safety of LiBs depend on their electrochemistry. For example, a
lithium-ion cell with a LCO positive and a graphite negative electrode delivers high voltage and
energy density but presents a higher thermal runaway risk which may lead to cell rupture, venting,
ignition of the electrolyte and fire [88].
3. Lithium-Ion Battery Systems
Lithium-ion cells are commercially available in button, cylindrical, pouch and prismatic designs
as illustrated in Figure 3.
Figure 3. Lithium-ion cell designs and structures [7]. (ad) show cylindrical, button, prismatic, and
pouch cells, respectively.
To supply the desired power and energy from a battery system (an energy storage system), the
cells are connected in parallel to increase the capacity or in series to raise the voltage.
A battery system usually consists of a number of battery packs, which are made of multiple
battery modules, each containing a number of cells with series and/or parallel configuration as
depicted in Figure 4.
Energies 2020, 13, 5117 6 of 30
Figure 4. Packaging of typical battery systems. Image is adopted from [89].
4. Thermal Runaway and Fire
Despite the extensive usage of LiBs in energy storage applications, they are susceptible to
thermal runaway and fire [90] which is the primary safety concern when used in hybrid electric
vehicles (HEVs) [91,92], electric vehicles (EVs) [91,9396], aeroplanes and submarines [97,98]. The LiB
systems used in these applications consist of multi-cell packs and modules where thermal runaway
in a single cell can initiate thermal runaway in adjacent cells and consequently compromise the
integrity of the entire battery system [99,100].
The conditions which may lead to thermal runaway and fire in LiBs fall into four categories
[101]:
Electrical abuse (over-charging/discharging) [36,102106]: Over-charging or discharging to
voltages beyond the manufacturers specified charge window can cause lithium plating, or
dendrite formation, on the anode. Over time, this may pierce the separator causing a short circuit
between electrodes and lead to thermal runaway.
Thermal abuse (over-temperature) [88,90,107109]: Internal temperature in the 90120 °C range
will cause the SEI layer within a LiB to decompose exothermically. At temperatures above 200
°C, the hydrocarbon electrolyte can decompose and release heat.
Mechanical abuse (penetration, pinch, and bend) [93,110]: Mechanical abuse, usually caused by
external mishap to the LiB such as car crash or during installation, can result in electrical shorting
between the electrodes, via the electrolyte, producing localised heating.
Internal short circuit (ISC) [94]: An ISC occurs due to the failure of the separator, allowing contact
between the cathode and anode via the electrolyte. This can happen due to any of the above
abuse conditions, or as a result of a manufacturing fault.
Any of these abuse conditions may result in an increase in the internal temperature of the cell,
which in turn can initiate exothermic reactions such as SEI decomposition. This can lead to a loss of
protection to the anode such that the fluorinated binder within the anode can react exothermically
with lithiated carbon, exothermic reactions between the intercalated lithium and electrolyte, or
cathode decomposition giving off oxygen enabling combustion with the electrolyte [88]. The heat
released increases the temperature of the cell and initiates additional reactions, which generate extra
heat, creating a heattemperature reaction loop. This loop results in high internal temperatures and
pressures which can lead to cell swelling, cell rupture, gas venting (sometimes violent) and possibly
fire [94].
At temperature above the normal operating range, electrochemical reaction processes, many of
which occur simultaneously are very complex. To exemplify, Figure 5 overviews the thermal
runaway processes of LCO/graphite. At temperature above 69 °C, the SEI start to decompose
followed by exothermic reactions between anode and electrolyte, and anode materials and the binder,
separator meltdown, electrolyte decomposition, and reactions between the cathode material and
electrolyte [111].
Energies 2020, 13, 5117 7 of 30
Figure 5. A schematic of thermal runaway processes in lithium cobalt oxide (LCO)/graphite cell [66].
During thermal runaway in a LiB, the electrolyte and separator may significantly contribute to
the heat released in the presence of oxygen through their ignition and burn properties. The electrolyte
and separator have low mass in a LiB but high effective heat of combustion, and account for
approximately 80% of the heat release in a LiB fire [112,113]. As shown in Figure 6, the effective heat
of combustion for a commercial LMO pouch cell has been measured as 4.03 ± 0.34 MJ kg1 with the
electrolyte and separator contributing up to 1.92, and 1.34 MJ kg1, respectively [112].
Figure 6. (a) The total heat of combustion measured through the experimentations. (b) heat of
combustion of battery components determined by thermodynamic calculations. Adopted from [112].
The thermal runaway process poses serious fire safety implications [114], especially for confined
spaces such as in passenger vehicles, aeroplanes and submarines [97]. The likelihood and severity of
fire risks associated with LiBs were presented over the past two decades where more than 300 fires
or fire-related incidents with 40 fatalities reported [97]. Table 2 lists some of the LiB thermal runaway
and fire incidents reported over the last two decades [94,111]. The LiB fire incidents are widespread,
Energies 2020, 13, 5117 8 of 30
from small consumer electronics such as mobile phones to large EVs and airplanes. Potential causes
of the LiB accidents and mechanisms leading to the separator tearing, piercing and collapsing,
subsequently internal short circuit, and possibly thermal runaway are presented in Figure 7. The
numerous accidents have demonstrated that LiB technology is a serious safety concern, which has
obliged governments to enforce new regulations and fire protection technologies for transport and
storage of these devices [93,115].
Table 2. Selected LiBs fire and explosion accidents [94,111].
No.
Date
Location
Incident Description
Possible Cause
1
March 2019
Brabant,
Netherlands
A HEV (BMW i8 plug-in hybrid) started to smoke
in a showroom
Unknown.
2
January
2019
Adelaide,
Australia
Electric road bike exploded and caught fire
Internal short circuit
3
January
2019
Florida, USA
An EV (Tesla Model S) caught fire
Crash.
4
June 2018
Vancouver,
Canada
e-cigarette caused fire in the baggage
compartment of a WestJet flight, making an
emergency landing
Unknown.
5
August 2017
California,
USA
An EV (Tesla Model X) caught fire after crashing
into a garage
Crash deformed the battery modules initiating short circuit,
outgassing and fire.
6
September
2016
Worldwide
Samsung recalled more than 2.5 million Galaxy
Note 7 phones after 35 fire cases
Manufacturing defect in Samsungs batteries causing shorts
between internal positive and negative poles.
7
August 2016
Paris, France
An EV (Tesla Model S) car caught fire during a
promotional tour
Unknown.
8
July 2106
Rome, Italy
An EV police car caught fire.
Unknown.
9
July 2106
Nanjing, China
The battery pack of an EV (bus) caught fire after
heavy rain.
Water immersion causing short circuit.
10
June 2106
Beijing, China
An iEV5 caught fire.
Overheating by loose wire connection.
11
June 2106
Shenzhen,
China
An EV (Wuzhou Dragon) bus caught fire.
A short circuit created by wire deterioration.
12
January
2016
Gjerstad,
Norway
An EV (Tesla Model S) car caught fire during fast
charging at a fastcharger Station.
Short circuit while charging.
13
September
2015
Hangzhou,
China
The battery pack of an HEV bus caught fire.
Unknown.
14
April 2015
Shenzhen,
China
An EV (Wuzhou Dragon) bus caught fire while
charging in a carpark.
The Battery Monitoring System failed to stop charging, the
battery pack was overcharged.
15
October
2013
Tennessee,
USA
An EV (Tesla Model S) car collided with metal
objects at highway and caught fire.
Short circuit induced by piercing and deformation of the
battery pack after colliding with the metal objects.
18
January
2013
Takamatsu,
Japan
The battery pack caught fire in a Boeing 787
traveling from Yamaguchi-Ube to Tokyo.
Internal short circuit.
19
January
2013
Boston, USA
The battery pack caught fire and spread the
smoke in the entire cabin of a Boeing 787.
Internal short circuit.
20
May 2012
Shenzhen,
China
An EV (BYD E6 taxi) car caught fire after a rear-
end collision and hitting a tree.
High-speed accident damaged the high voltage circuit. Shorts
occurred in the broken circuit.
21
July 2011
Shanghai,
China
An EV bus caught fire
Overheated LiFePO4 batteries
22
May 2011
Burlington,
USA
An EV (Chevy Volt) car caught fire three weeks
after a side-pole impact test and damaged the
neighbouring cars.
The pole impact broke the cooling system and the battery
module. Coolant conducted an external short circuit and
ignited combustible venting gas.
23
April 2011
Hangzhou,
China
An EV (taxi) car caught fire.
Faulty battery.
24
September
2010
Dubai, UAE
A Boeing B747-400F cargo plane caught fire
Overheated batteries.
25
January
2010
Urumqi, China
Two EVs (buses) caught fire.
Overheated LiFePO4 batteries.
26
July 2009
Shenzhen,
China
Cargo plane caught fire before flying to the USA.
Spontaneous combustion of LiBs.
27
June 2008
Tokyo, Japan
A HEV (Honda) caught fire.
Overheated LiFePO4 batteries.
28
June 2008
Columbia, USA
The battery pack of an adjusted HEV (Prius) car
caught fire during driving.
Loose connection causing battery to overheat.
29
2006now
Worldwide
Thousands of mobile phone fires and/or
explosions
Internal shorts, manufacturer’s defect, overheating, etc.
Energies 2020, 13, 5117 9 of 30
Figure 7. Various abuse conditions resulting in separator malfunction, subsequently internal short
circuit, and possibly thermal runaway and fire [94].
5. Fire Protection Techniques
Fire protection measures are considered at the cell, battery, module, pack, system and enclosure
levels. The fire protection plan must take into account hazards from outside the battery system and
compartment producing more complications to the design of systems. Figure 8 depicts various levels
of fire protection from cell components to system and compartment designs.
Figure 8. Levels of fire protection. Adapted from [116].
5.1. Safety at Cell Level
Within the cell, safety measures to reduce or prevent thermal runaway can be added through
the modification of materials or structure, design, and utilisation of safety devices [117]. Significant
works have been done to improve the safety of LiBs by modifying cathode and anode materials, and
electrolyte chemistry.
Energies 2020, 13, 5117 10 of 30
The choice of cathode material primarily determines the thermal stability and energy delivery.
As an example, SEI decomposition begins around 130 °C for LCO, at 240 °C for NMC, at 270 °C for
LMO and at 310 °C for LFP cathodes [118]. The cathode material can be modified to improve thermal
stability by coating with materials [19,27] such as TiO2 [119], LiNi0.5Co0.5O2 [120], Al2O3, MgO [120],
LixCoO2 [120]; substitution of certain metals (e.g., nickel and aluminium partially replacing cobalt
[121,122]); and doping with materials such as zirconium [123127].
The anode surface can be modified for capacity retention at an elevated temperature of 50 °C by
deposition of Al2O3 [128], SrO, Mn4N, K2SO4, CaCl2, CaF2, SrF2, Ag, Mg or Zn onto graphite [129]. The
anode modification can be extended by smoothing the SEI surface and covering active edge structures
by adding substances to the electrolyte such as phosphamide additives (N,N-diallyic-diethyoxyl
phosphamide) [130132], and substitution of conventional graphite anode with silicon [133], silicon
nanowires [134] and spinel lithium titanate oxide, Li1.33Ti1.67O4 (LTO) [38]. It has been demonstrated
through calorimetric analyses [135] and thermal runaway tests [38,136] that LTO is a safer anode
material compared to graphite.
The carbonated solvents of electrolyte are the main contributor to fire induced by LiB thermal
runaway [67]. Reducing solvent and increasing lithium salt (e.g., LiPF6) content can decrease the
electrolyte outgassing at temperatures above 100 °C [137], but changing the balance of lithium salt to
solvent affects the thermal stability of the cathode and intercalated graphite [138140]. The safety of
electrolyte has been enhanced using additives [6774,121], for example: phosphonate electrolyte [67],
tris(2,2,2-trifluoroethyl) phosphate [68,109], phosphates, phosphites [141], fluorinated propylene
carbonates [142], nanodiamonds and nanoparticles [72], boron nitride aerogels and boron nitride
nanotubes [73], fluorinated cyclotriphosphazene [69], hexamethoxy cyclotriphosphazene [143,144],
vinylene carbonate [145], polymerizable monomer, 1,1-(methylenedi-4,1-phenylene) bismaleimide
[146], trimethyl phosphite and trimethyl phosphate [144], phosphazene-based flame retardants
[147]). Substitution of electrolyte with ionic liquids [7577] (e.g., 1-ethyl-3-methylimidazolium
bis(fluorosulfonyl)imide [50], and solid polymer electrolyte [8587] is another method to improve the
safety of the electrolyte. Further information on each approach can be found in [118].
At the cell level, internal devices such as pressure relief vents, current interrupts, Positive
Temperature Coefficient (PTC) devices and shutdown separators can prevent or limit the impact of
internal malfunction [148]. Pressure relief vents release at elevated internal cell pressures directing
the hot gas evacuation away from the cell and avoiding cell rupture [149151]. The opening of the
pressure relief vent is also associated with positive circuit cut-off preventing current flow. PTC
devices, consisting of a conductive polymer which is a closed circuit in normal conditions, activate at
abnormal high currents and high temperatures by melting the polymer [152] and breaking the circuit
[148,153]. Shutdown separators consist of layered films with different phase transition temperatures
which can close the separator pores and halt lithium ion transport [56,57].
5.2. Safety at Module and Pack Level
The Battery Management System (BMS) is the primary safety device at the module and pack
level [90]. The BMS controls and prevents over-charge, over-discharge, and operates the battery pack
for best application performance and long lifespan, generally achieved by balancing the state of
charge of each cell [154]. BMS has attracted a lot of research interest over the past years to estimate
accurately state of charge to avoid over-charging [155157], and develop models for health prognosis
[158,159], fault diagnostic [160163], and charge control [164]. Figure 9 illustrates the response of the
different safety devices to various abusive conditions.
Energies 2020, 13, 5117 11 of 30
Figure 9. Results of various abuse conditions on a LiB with safety devices enabled [152]. BMSbattery
management system, PTCpositive temperature coefficient device, CIDcurrent interrupt device.
Together with the BMS, the Thermal Management System (TMS) provides safety protection to
large battery packs. The TMS maintains an optimum operating temperature (20 °C to 40 °C [165,166])
for each cell and reduces temperature changes within and between modules. External heating devices
are required to raise the temperature of battery packs if the temperature is below the desired range
[167]. At temperatures above the desired set point, cooling technologies are needed to provide heat
removal and prevent heat transfer between cells. The cooling techniques include one or a
combination of spacing [168170], air cooling (forced airflow) [171173], liquid cooling [174,175],
phase change material (PCM) cooling [116,165,176,177], or heat pipe cooling systems [178180].
5.3. Safety at Compartment Level
Despite the safety measures at cell and module level, malfunctions in the safety system,
accidental abuse or spontaneous internal short circuits may induce battery fire [118]. The fire safety
measures developed at the cell level may not yet be available in cells selected for energy storage
projects due to commercial (cost, schedule, availability) or cell performance reasons. Fire safety at the
compartment level is then important to halt fire growth and prevent fire spread from the
compartment. The battery compartment should be constructed to survive structurally and halt the
spread of a fire to adjacent spaces. To prevent pressure build-up within the battery compartment
during a thermal runaway event, incorporating an opening as a pressure relief exhaust is
recommended, enabling systems within the compartment to withstand the pressure increases [116].
Lastly, an appropriate fire suppression system should be integrated into the design of the battery
compartment.
6. Lithium-Ion Battery Fire Detection and Suppression
It has been shown that LiB fires can be detected using conventional heat detectors (reportedly
the slowest method therefore not recommended), smoke detectors and combined smoke-heat
detectors (reportedly the fastest method therefore recommended) [118].
Fire initiates when a fuel and an oxidiser are exposed to a source of heat, raising the temperature
above the flash point of the fuel-oxidiser mixture. Interrupting any one of the four elements of fire
isolating the fuel from the ignition source, isolating the oxygen from the fuel, cooling the fuel below
the ignition temperature, or interrupting the combustion reactionscan halt combustion. When the
pressure build-up ruptures a lithium-ion cell, the flammable electrolyte is released, the thermal
runaway process can supply adequate heat to initiate a fire.
Energies 2020, 13, 5117 12 of 30
There are six classes of fire and there are extinguishants to match the classes [115,181183], each
class is described below:
Class Afires involving solid materials such as textiles, wood or paper.
Class Bfires involving flammable liquids such as oils, petrol, or diesel.
Class Cfires involving combustible gases.
Class Dfires involving metals.
Class Efires involving energised electrical devices.
Class Ffires involving combustible cooking oils such as in deep-fat fryers.
The fire class of a LiB fire is contentious due to the various components which make up the
battery; separator material, construction material and electrodes (Class A), flammable liquid
electrolyte (Class B) and energised electrical apparatus (Class E) [184]. The fire suppression method
should suppress any LiB fire and control any rise in battery temperature. If not sufficiently cooled,
thermal runaway reactions may continue and the battery re-ignite; this is a major challenge for LiB
fire suppression systems. Adjacent cells may also undergo thermal runaway if heat propagation from
the initial cell is not controlled. It is more important to cool the cells in a large battery pack, to prevent
heat propagation, than to extinguish fires from a single cell. LiB firefighting strategies should be
based on not only extinguishing the burning cell, but include cooling the burning cell as well as its
adjacent cells.
The best practice fire extinguishing medium for LiBs is yet to be established [5,116]. Wilkens et
al. [116] have listed, from a selection of LiB manufacturers, the recommended fire-extinguishing
media for their batteries, obtained from their Material Safety Data Sheet (MSDS). This list is
reproduced as Table 3.
Table 3. List of fire extinguishing media suggested by various lithium-ion battery manufacturers for
their products as suggested in randomly selected MSDS [116].
Company
Country
Date
Battery
Chemistry
Water
CO2
Foam
Chemical/Dry
Powder
Nitrogen
Sand
Halon*
Whatever
Suitable
Yuka
energy
China
2011
Pack
LCO
×
×
×
×
Makita
USA
2013
Pack
NCO
×
×
×
Enertech
Korea
2017
Pack
NMC
×
×
×
Samsung
Korea
2011
Cell
NMC
×
×
Samsung
Korea
2016
Cell
NMO
×
×
×
×
×
Saft
France
2009
Pack
LCO
×
×
×
×
Bipower
USA
2017
Pack
LCO
×
×
×
LG Chem
Korea
2013
Cell
NMC
×
Motorola
USA
2017
Pack
LCO
×
×
×
×
Ideal
USA
2010
Cell
LCO
×
×
×
SDPT
China
2016
LCO
×
×
Bren-
Tronics
USA
2013
Pack
LCO
×
×
×
×
Advance
Energy
USA
2011
LCO
×
Leo Energy
Singapore
2014
NMC
×
×
IDX
Japan
2016
Pack
LMO
×
×
×
×
×
Panasonic
USA
2015
NMC
×
×
×
×
Total
12
10
9
12
2
2
1
2
* Note that Halon-based products deplete the ozone layer and are prohibited.
It can be seen in Table 3 that the extinguishants most commonly recommended by
manufacturers are water and chemical/dry powder, closely followed by CO2 and foam [185]. Details
of commonly used extinguishants are provided in the next section. Some extinguishants may
extinguish LiB electrolyte fires but may not control thermal runaway and the involvement of adjacent
cells.
Energies 2020, 13, 5117 13 of 30
6.1. Types of ExtinguishantsThe Basics
6.1.1. Water Extinguishants
Water-based extinguishants provide the most cost-effective method to fight fires [185,186].
Water is an excellent cooling medium due to its high heat capacity and latent heat of vaporisation
and may be able to mitigate or halt the propagation of thermal runaway to surrounding batteries. It
should be noted that water can react with LiPF6 and form toxic and harmful hydrogen fluoride (HF)
[187], which may be chemically reduced by lithium and produce combustible hydrogen [188],
conduct current and cause external short circuits in a cell which may result in LiB thermal runaway
[118].
There are four types of water-based suppressants:
Water jet: Water jet suppressants apply a stream of water directly to burning materials,
providing cooling and inhibiting re-ignition. Water jets should not be employed on live electrical
equipment due to electric shock concerns.
Water spray or sprinkler: Water spray or sprinkler suppressants use a spray of fine water
droplets, each droplet is surrounded by air, which is non-conductive. The spray has enough
momentum for droplets to penetrate the fire plume and cool surfaces, as well as expanding some
energy through vaporisation to cool the air.
Water with added surfactants: Adding surfactants to the water can improve the efficacy of
water extinguishment. Surfactants decrease the water’s surface tension so that it coats the burning
materials and cools more efficiently.
Water mist: Water mist comprises a range of droplet sizes under 1000 μm, droplets that are
much smaller than those from a sprinkler. Finer droplets have a larger surface area to volume ratio
compared to larger droplets resulting in a greater absorption of heat energy from the hot air for the
same volume of water, while the larger drops within the drop size distribution can penetrate the fire
plume and cool the burning material.
6.1.2. Foam Extinguishants
Foam fire extinguishants can be used on Class A and Class B fires, therefore they can be
employed to extinguish LiB fires [185]. The foam cools and seals the surface of a liquid or solid,
putting a barrier between flammable vapour and the hot surface/fuel and starving the fire of air. To
be effective the foam must fully encapsulate the cell which is a challenging task as LiBs are considered
to have multi-stage jet fires, presenting high-velocity flammable gas venting.
6.1.3. Powder/Dry Powder Extinguishants
Powder extinguishants work by chemically interrupting the fire reactions. However, they do not
provide cooling and re-ignition may occur. Powders may create breathing problems, especially inside
enclosures [189].
6.1.4. Carbon Dioxide (CO2)
Carbon dioxide extinguishes by smothering the fire, replacing the oxygen in the combustion
zone with CO2. CO2 can be used on Class A and B fires and is safe to use on electrical fires (Class E).
CO2 extinguishants do not leave any residue; however, their use can result in breathing issues,
especially if used in enclosures. CO2 is not an ideal extinguishing agent for LiB fires due its low
cooling capacity [188].
6.1.5. Halon-Based Extinguishants
Halon suppresses fire by chemically disrupting the combustion reactions. Halon 1211 (a liquid
streaming extinguishant) and Halon 1301 (a gaseous flooding extinguishant) do not leave any residue
and are rated for Class B and E fires, but are effective on Class A fires. Halons are global warming
Energies 2020, 13, 5117 14 of 30
agents and deplete the ozone layer resulting in a cessation in production in 1994 under the Clean Air
Act [190,191], yet they remain an integral part of fire safety in many naval ships, aircraft, tanks, and
submarines [192]. Halon-based extinguishants do not provide cooling.
6.2. Lithium-Ion Battery Fire Suppression Studies
Numerous researchers have studied LiB fires in order to find an effective suppressant. It has
been reported by the National Technical Information Service [193,194] that Halon-based products can
extinguish a LiB fire [195], but cannot mitigate the internal temperature increase and stop re-ignition
after the extinguishment of a fire [193]. In studies performed by Rao et al. [196], heptafluoropropane
(HFC-227ea or FM200), a halogenated extinguishant which does not result in ozone depletion,
showed superior behaviour in suppressing LiB fires when compared to carbon dioxide and powder
extinguishants. The effectiveness of heptafluoropropane in suppressing LiB fires was also reported
by Wang et al. [197], while Liu et al. [198] found Novec 1230 to be effective.
LiB fire suppression can also be achieved by applying large amounts of water to a battery or by
submerging the battery in water [199]. Both of these methods can extinguish a LiB fire and cool the
battery, inhibiting exothermic reactions and preventing re-ignition. This technique is impractical for
large battery modules, although water sprinklers may be viable. Det Norske Veritas - Germanischer
Lloyd (DNV-GL) [199] investigated the effectiveness of extinguishants such as F500 and FireIce
(water surfactants), PyroCool (foam), Stat-X (aerosol) and water sprinklers in suppressing a LiB fire
and cooling a battery undergoing thermal runaway. All systems extinguished the fires, but the water-
based systems had better continued cooling ability. Egelhaaf et al. [200] demonstrated that water can
suppress a LiB fire, and the addition of surfactant and gelling agents can decrease the volume of
water required for firefighting. Tests performed by the Federal Aviation Administration (FAA) [201]
concluded that water-based extinguishants (water, Hartindo AF-31, Aqueous A-B-D (Class A, B and
D) are effective suppressant and coolant mediums compared to the non-aqueous extinguishants
[199].
An alternative water extinguishing system is water mist [187,202205]. Water mist may be an
appropriate suppressant for large battery modules due to its low volumetric requirement and cooling
capability. Testing conducted by the National Fire Protection Research Foundation, US, showed that
water mist can effectively suppress a fire involving an electric vehicle battery [206]. It has also been
demonstrated that the extinguishing effect of water mist can be improved by adding 5% F500 solution
and 5% anionic non-ionic surfactant to pure water [207]. The effectiveness of adding 3% aqueous film
forming foam to water mist on re-ignition of a 18650-type LiCoO2 lithium ion battery pack (10 Ah ×
4) fire has been analysed by Li et al. [208]. It was reported that water mist with 3% aqueous film-
forming foam was more effective in delaying the re-ignition compared to ABC dry powder
extinguishers, and carbon dioxide.
Considering the potential effectiveness of water mist in suppressing LiB fires and cooling the
battery to control thermal runaway, further details about the parametric water mist fire suppression
systems (WMFSS) are presented next.
6.3. Water Mist Characterisation
To fully comprehend water mist spray dynamic, performance, and behaviour, the following
parameters should be characterised [209]:
Droplet size distribution (DSD);
Spray cone angle;
Spray velocity;
Mass flow rate;
Spray momentum.
The water mist characteristics will also be influenced by the existence of a fire but are first
described in a non-fire environment.
Energies 2020, 13, 5117 15 of 30
6.3.1. Droplet Size Distribution (DSD)
Water mist contains droplets of different sizes, which alters with time and location as the spray
droplets collide, vaporise, or impinge on surfaces and drop out. The Droplet Size Distribution (DSD)
refers to the range of droplet sizes presented in a mist spray. It influences the vaporisation rate, the
spray dynamics, the entrainment of gases, and spray momentum relative to the buoyancy of the fire
plume. Generally, the size of drops in a spray is defined by a single droplet size parameter, such as a
mass mean diameter (MMD) or volumetric median diameter (VMD) [210]. The VMD, expressed as
VMD (DV 0.5), denotes the midpoint droplet size, where 50% of the volume of spray contains smaller
particles, and the other 50% of the volume, larger particles than the mean. The most common measure
of droplet size is the sauter mean diameter (SMD) which is the mean diameter with the same ratio of
volume to surface area as the entire domain. It should be mentioned that a single parameter cannot
fully determine a drop size distribution as two sprays with the same VMD or SMD are not necessarily
alike. To demonstrate, NFPA 750 [211] employed the curve of cumulative volume percentage versus
diameter to indicate the distribution of mass, volume and drop sizes in a water mist.
It has been reported [212,213] that water mists with SMDs smaller than 300 μm can significantly
cool and extinguish diffusion flames. The efficacy of the WMFSS depends on the range of particle
sizes produced. Smaller droplets create larger surface areas and improve vaporisation rate and
cooling effect, which increases the efficiency of the WMFSS by decreasing the amount of water
required for fire suppression [210]. In contrast, droplets of a larger size have higher momentum
enabling them to have a greater capability of entering a fire plume and smoke layer, and consequently
wet and cool burning materials and hot gases. Thus, a spray with larger droplets may be more
effective to finer droplets in extinguishing an unobstructed fire, whereas a spray with finer droplets
may be more effective over the larger droplets in extinguishing an obstructed fire [210].
6.3.2. Spray Cone Angle
Solid cone nozzles are usually utilised in WMFSSs, producing either 90° or 120° spray cones
(surrounding the central, straight-through axis) [210]. Other cone angles are possible but not
commercially available for fire extinguishment systems.
A solid cone nozzle forms a full-cone spray that is more diluted downstream of the nozzle by
the entrainment of gases. Most of the water mass is located near the spray central axis, while the outer
spray regions contain less liquid mass and more water vapour. Droplet velocities are also much
higher in the region closer to the spray axis and decrease in the radial direction due to interaction
with entrained gases. Smaller spray cone angles lead to a denser spray with a higher probability of
droplet collisions. These collisions can result in a change of droplet velocity and size which can affect
the vaporisation and cooling rates. Droplets can either disintegrate into smaller drops or combine to
form larger drops (droplet coalescence) [214].
6.3.3. Spray Velocity
The magnitude of spray velocity determines the atomisation regime, while the direction of the
penetrating jet defines the shape of the spray cone. The velocity of each individual droplet is
transferred to the surrounding air through the drag effects which enhances the air entrainment and
increases the mass flux of the spray cone. Spray mass flux and velocity (velocity of water droplets
plus the air entrained in the flow) determines the spray momentum dictating the total effect of the
spray on a fire plume [210].
6.3.4. Mass Flow Rate
The mass flow (discharge) rate of the spray is dependent on the injection pressure and the total
area of the nozzle orifice. To design a nozzle, its required mass flow rate can be estimated using the
spray heat absorption ratio (SHAR) or required extinguishing medium portion (REMP) values,
discussed by Mawhinney et al. [210].
Energies 2020, 13, 5117 16 of 30
6.3.5. Spray Momentum
Spray momentum is calculated as the summation of mass of water droplets and the mass of
entrained air, multiplied by the velocity of the droplets and entrained air. For a constant mass
discharge rate, an increase in spray velocity also increases the air entrainment rate, which
subsequently increases the spray momentum. The direction of the spray momentum plays a
significant role in fire suppression as an injection above the fire plume may lead to the water mist
penetration and vaporisation where the water vapour can reach the seat of the fire [210]. An injection
under the fire plume with co-directional flows may not generate the turbulent flame mist mixing
required to improve vaporisation and cooling, and the water vapour produced will be moved away
from the burning surface instead of driven down to it. To assess the benefits of utilising high- or low-
velocity water mist nozzles, the directional component of the momentum in addition to the
magnitude of spray velocities should be taken into account.
6.4. Water Mist Nozzle Characteristics
Structure of spray is mainly determined by the type and operating conditions of the nozzle such
as the injection pressure. Nozzles basically can be divided into two categories: single- and multiple-
hole nozzles. Considering the spray pattern, nozzles can be categorised into full cone, hollow cone,
or flat spray. In water mist systems, various types of nozzles are used including single and multiple
orifice nozzles which can produce different pattern based on the application. Figure 10 shows
different types of nozzles and their spray patterns.
Figure 10. Nozzle types and their spray patterns.
6.5. Mechanisms of Fire Extinguishment using Water Mist
There are five mechanisms associated with a WMFSS in a closed compartment [215]:
Gas-phase cooling;
Oxygen depletion and flammable vapour dilution;
Wetting and cooling of the fuel surface;
Radiation attenuation;
Kinetic effects, enclosure effects, turbulent mixing and cycling.
Generally, all mechanisms take place to some extent during fire suppression of LiB fires in
enclosures.
Energies 2020, 13, 5117 17 of 30
6.5.1. Gas-Phase Cooling
Water mist consists of very fine droplets: generating fine droplets increases the surface area to
volume ratio of the droplets enhancing the rate of vaporisation by absorption of heat from the flames,
hot combustion gases, smoke layer and hot surfaces [216].
In the gas-phase cooling process, the heat in the combustion zone is absorbed by the vaporisation
of water droplets which leads to a decrease in the temperature of the flames. The flames will be
extinguished if the temperature falls below the critical temperature required to maintain combustion.
The cooling process also diminishes the flame radiation to the fuel surface, decreasing the fuel
pyrolysis rate.
6.5.2. Oxygen Depletion and Flammable Vapour Dilution
With a WMFSS, the water droplets are vapourised and the total volume occupied by the water
vapour increases by more than three orders of magnitude [210]. The water volume expansion results
in disruption of air entrainment into the flame and dilution of both oxygen and flammable vapour
concentration around the flame. The decrease in the oxygen concentration in an enclosure due to the
introduction of water mist is dependent on the fire size and the length of the pre-suppression period,
the enclosure volume and ventilation conditions in the enclosure [216].
A fire can be extinguished if the oxygen concentration falls below that necessary to maintain
combustion, the limiting oxygen concentration [50]. The concentration of oxygen can be reduced by
a combination of (a) depletion due to consumption by fire, (b) dilution due to displacement by the
water vapour, and (c) dilution by combustion products [217]. The oxygen depletion, displacement,
and flammable vapour dilution in a fire environment are depicted in Figure 11.
Figure 11. Schematic of oxygen displacement, depletion and flammable vapour dilution induced by
the water mist vaporisation in the fire environment.
6.5.3. Wetting and Cooling of the Fuel Surface
The main extinguishment mechanism for many solid and liquid fuels is wetting and cooling of
the fuel surface. Much like a sprinkler, the larger drop sizes have sufficient momentum to penetrate
the fire plume to reach the seat of the fire. This process is associated with a reduction in the pyrolysis
rate of the fuel.
6.5.4. Radiation Attenuation
Radiation attenuation occurs due to the presence of water vapour between the fuel and the
flame. The water vapour absorbs radiant energy, re-radiating at a lower intensity to the fuel surface
[50].
Water droplets convecting within a compartment also absorb heat and reduce radiation to and
from walls, as reported in a study by Mawhinney et al. [215] where the radiant heat flux to the walls
Energies 2020, 13, 5117 18 of 30
in an enclosure could be decreased by 70% using a WMFSS. It has been found that finer droplets can
attenuate the thermal radiation at a lower concentration of water when compared to larger spray
droplets [218]. The mechanism of radiation attenuation generated by a water-mist spray is shown in
Figure 12.
Figure 12. Schematic of attenuation of thermal radiation by a water-mist spray [216].
6.5.5. Kinetic Effects, Enclosure Effects, Turbulent Mixing and Cycling
Kinetics refers to the effects that the environmental variables have on the chemical reaction rates
and formation of intermediate reaction compounds.
Water mist can vary the kinetics which can intensify or extinguish the flame [215]. The flame
may be intensified on first contact with the water mist due to vaporisation at the flame surface
increasing turbulence and entrainment [210]. This can increase the fuel/air mixing, causing an
increase in combustion rate and a flare-up of the fire [210]. Alternatively, kinetic effects may lead to
fire suppression due to gas-phase cooling and oxygen depletion/dilution. The water mist and
entrained and vitiated gases dilute the combustible gases and when combined with flame cooling,
varies the combustion rate from its stoichiometric condition that may extinguish the flame.
Enclosure effects have been investigated by Mawhinney et al. [215] and Liu et al. [219]. In
enclosures, the influences of oxygen depletion and dilution are intensified. When water mist is
initiated, the hot gases trapped in the upper layer of a closed compartment are cooled quickly. The
momentum of the expanding water vapour carries the mixture of water vapour and gases toward the
fire, leading to localised oxygen depletion. Depending on the temperature and depth of the hot layer,
the cooling of the hot gases can lead to a volume contraction, producing a negative pressure [210]. If
flashover occurs before mist activation, it is difficult to determine whether the expansion due to mist
vaporisation or contraction due to cooling will dominate. To halt the creation of a negative pressure
pulse, water mist can be injected in multiple steps. This process has been used by Liu et al. [219] to
demonstrate an improvement in suppressing fires in enclosures.
6.6. Water Mist Fire Suppression System Characteristics
The performance of the WMFSS is primarily determined by the characteristics of sprays
generated by nozzles [220]. Different types of nozzles, e.g., single- and multi-hole, can significantly
vary the mass distribution of sprays. The single-hole nozzle produces relatively larger droplets,
longer penetration length with a higher concentration in the region beneath the nozzle in comparison
with the multi-hole nozzle [216].
Typically, WMFSS consist of multiple nozzles where the spacing between nozzles and distance
from the floor/target (here the LiB) are determined by the distribution of the flux density of individual
nozzles and the size of compartment and potential fire. The position of the nozzle can affect the
performance of the suppression system. If a nozzle is located directly above a fire, the water droplets
of the spray will travel the least distance to reach the fire and may show better performance in
suppressing the fire. In contrast, while installation of multiple nozzles will involve a higher cost for
Energies 2020, 13, 5117 19 of 30
the system, multiple nozzles may show better performance in suppressing the fire by distributing
mists more uniformly and enhancing the oxygen depletion process. However, activation of two
nozzles may render a drop in the pressure of the water supply and reduce the performance of the
spray [216].
The design of WMFSS is considered as “project specific”, where each particular hazard or
occupancy requires its own specific design for the optimum efficiency. It is therefore not possible to
design a mist system simply by reference to one of the standards available such as NFPA 750 [211],
BS 8489 [221], or CEN TS 14972 [222]. For example, while BS 8489 sets out the design criteria for a
water mist system, its suitability for a particular fire risk should be examined according acceptable
test protocols. For a lithium-ion battery compartment, a suitable WMFSS (with or without
complementary suppressing agents such as surfactants, foam or gas) might include a zonal approach,
based on each module, where the fire suppression system automatically activates on detection of a
local temperature increase (beyond the thermal and battery management systems), thus enabling
early intervention, and possibly avoiding heat transfer to adjoining cells, major battery damage and
other fire damage.
7. Summary and Outlook
LiBs attract interest due to their high voltage capability, superior energy density, lightweight,
low self-discharge and long lifespan for electrical energy storage. Any abuse condition (thermal,
electrical, and mechanical) that is beyond the safe operating window can affect the performance of
the battery and cause safety concerns such as thermal runaway, electrolyte gas venting, fire and
explosion. The hazards and safety concerns associated with the use of LiBs are an important
consideration in battery selection. Numerous LiB fires and explosion incidents have been reported;
therefore, measures should be taken at different levels (design of batteries, chemistry, safety
components and firefighting) to alleviate fire concerns. Techniques to improve the safety of LiBs at
the cell, module, pack and compartment levels to mitigate the fire risk have been reviewed. Currently,
limited lithium-ion cells are constructed with safe cell chemistry and internal components, and these
safety features may not be available in cells selected for energy storage projects due to commercial
(cost, schedule, availability) or performance reasons. Battery management systems that maintain a
safe operating environment for modules and packs, are well established, with constant advances
being applied. However, fire incidents do still occur.
Although fires involving LiBs can be extinguished by many methods, the effects of thermal
runaway are more difficult to manage and continued cooling is required. The associated problems
also often become exacerbated as LiB assemblies tend to be in a tightly packed configuration, and are
kept in enclosures with minimum leeway and free spaces. Therefore, battery compartment
construction and design should maintain an intact boundary to a fire or explosion, but should also
include passive thermal management utilising a combination of space separation, cooling, and zonal
fire suppression within a module, and insulation between battery modules to limit thermal runaway
to adjacent modules. Given that many of the halon-based firefighting agents are banned owing to
their environmental implications and that inert gases, such as nitrogen or argon, are less effective in
their own right, the main impetus in finding alternative ways of fighting LiB fires mainly hinges on
enhancing the effectiveness of, and perhaps finding smarter ways of deploying, water as the most
efficient medium for continuous extinguishing and cooling. In this context, the extinguishment may
be enhanced by using environmentally friendly additives, or, better yet, in combination with an inert
gas stream such as nitrogen, and the cooling improved through better design and implementation of
spray systems. In both counts, water is the ideal medium for obvious reasons. Water mist is now well
established as a fire suppression technique, but limited information is available for suppressing LiB
fires. Water mist with additives and surfactants, or in conjunction with a gaseous extinguishing
medium, is considered the most promising extinguishing and cooling method for LiBs. Further
investigations on the thermal behaviour of LiBs during firefighting using water mist and different
mediums are necessary to establish appropriate guidelines to extinguish LiB fires.
Energies 2020, 13, 5117 20 of 30
Author Contributions: Conceptualization, Writing-original draft, Visualization, M.G.; Project administration,
Resources, Supervision, V.N.; Conceptualization, Funding acquisition, Resources, Supervision, K.M.; Writing-
Review & Editing, Resources, Supervision, P.J.; Writing-review & editing, Resources, Data Curation, I.B.;
Writing-review & editing, Conceptualization, Data Curation, B.G.; Writing-Review & Editing, Resources,
Funding acquisition, Project administration, G.G. All authors have read and agreed to the published version of
the manuscript.
Funding: This work was supported by Victoria University and the Defence Science and Technology of Australia.
Acknowledgments: One of us, M.G., is grateful to Victoria University and the Defence Science and Technology
of Australia for the provision of a post-doctoral research fellowship.
Conflicts of Interest: The authors declare no conflict of interest
Nomenclature:
BMS
Battery Monitoring System
CID
Current Interrupt Device
DEC
Diethyl Carbonate
DMC
Dimethyl Carbonate
DNV-GL
Det Norske Veritas and Germanischer Lloyd
DSD
Droplet Size Distribution
EC
Ethylene Carbonate
EMC
Ethyl Methyl Carbonate
EV
Electric Vehicle
FAA
Federal Aviation Administration
FDS
Fire Dynamics Simulator
HEV
Hybrid Electric Vehicle
HF
Hydrogen Fluoride
HRR
Heat Release Rate
ISC
Internal Short Circuit
LCO
Lithium Cobalt Oxide
LCP
Lithium Cobalt Phosphate
LFP
Lithium Iron Phosphate
LFSF
Lithium Iron Fluorosulphate
LiB
Lithium-ion Battery
LMO
Lithium Manganese Oxide
LTO
Lithium Titanate Oxide
LTS
Lithium Titanium Sulphide
MMD
Mass Mean Diameter
MSDS
Material Safety Data Sheet
NCA
Nickel Cobalt Aluminium Oxide
NCM
Nickel Cobalt Manganese Oxide
NFPA
National Fire Protection Association
PC
Propylene Carbonate
PCM
Phase Change Material
PE
Polyethylene
PP
Polypropylene
PTC
Positive Temperature Coefficient
REMP
Required Extinguishing Medium Portion
SEI
Solid-Electrolyte Interface
SFPE
Society of Fire Protection Engineers
SHAR
Spray Heat Absorption Ratio
SMD
Sauter Mean Diameter
TMS
Thermal Management System
VMD
Volumetric Median Diameter
WMFSS
Water Mist Fire Suppression System
Energies 2020, 13, 5117 21 of 30
References
1. Whittingham, M.S. Chalcogenide Battery. U.S. Patent No. 4,009,052, 22 February 1977.
2. Mizushima, K.; Jones, P.C.; Wiseman, P.J.; Goodenough, J.B. LixCoO2 (0< x<-1): A new cathode material
for batteries of high energy density. Mater. Res. Bull. 1980, 15, 783789.
3. Thackeray, M.; David, W.; Bruce, P.; Goodenough, J.B. Lithium insertion into manganese spinels. Mater.
Res. Bull. 1983, 18, 461472.
4. Yamahira, T.; Kato, H.; Anzai, M. Nonaqueous Electrolyte Secondary Battery. U.S. Patent No. 5,053,297, 1
October 1991.
5. Blum, A.F.; Long, R.T., Jr. Fire Hazard Assessment of Lithium Ion Battery Energy Storage Systems; Springer:
New York, NY, USA, 2016.
6. Whittingham, M.S. Electrical energy storage and intercalation chemistry. Science 1976, 192, 11261127.
7. Tarascon, J.-M.; Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 2001, 414,
359367.
8. Pacala, S.; Socolow, R. Stabilization wedges: solving the climate problem for the next 50 years with current
technologies. Science 2004, 305, 968972.
9. Cavanagh, K.; Ward, J.; Behrens, S.; Bhatt, A.; Ratnam, E.; Oliver, E.; Hayward, J. Electrical Energy Storage:
Technology Overview and Applications; CSIRO: Canberra, Australia, 2015; EP154168.
10. Roy, P.; Srivastava, S.K. Nanostructured anode materials for lithium ion batteries. J. Mater. Chem. A 2015,
3, 24542484.
11. Nitta, N.; Wu, F.; Lee, J.T.; Yushin, G. Li-ion battery materials: present and future. Mater. Today 2015, 18,
252264.
12. Li, J.; Suzuki, T.; Naga, K.; Ohzawa, Y.; Nakajima, T. Electrochemical performance of LiFePO 4 modified
by pressure-pulsed chemical vapor infiltration in lithium-ion batteries. Mater. Sci. Eng. B 2007, 142, 8692.
13. Takahashi, M.; Ohtsuka, H.; Akuto, K.; Sakurai, Y. Confirmation of long-term cyclability and high thermal
stability of LiFePO4 in prismatic lithium-ion cells. J. Electrochem. Soc. 2005, 152, A899A904.
14. Zaghib, K.; Shim, J.; Guerfi, A.; Charest, P.; Striebel, K.A. Effect of carbon source as additives in LiFePO4
as positive electrode for lithium-ion batteries. Electrochem. Solid-State Lett. 2005, 8, A207A210.
15. Jiang, J.; Dahn, J.R. ARC studies of the thermal stability of three different cathode materials: LiCoO2;
Li[Ni0.1Co0.8Mn0.1]O2; and LiFePO4, in LiPF6 and LiBoB EC/DEC electrolytes. Electrochem. Commun.
2004, 6, 3943.
16. Dong, Y.Z.; Zhao, Y.M.; Chen, Y.H.; He, Z.F.; Kuang, Q. Optimized carbon-coated LiFePO4 cathode
material for lithium-ion batteries. Mater. Chem. Phys. 2009, 115, 245250.
17. Armand, M.; Tarascon, J.-M. Building better batteries. Nature 2008, 451, 652657.
18. Martha, S.K.; Haik, O.; Zinigrad, E.; Exnar, I.; Drezen, T.; Miners, J.H.; Aurbach, D. On the thermal stability
of olivine cathode materials for lithium-ion batteries. J. Electrochem. Soc. 2011, 158, A1115A1122.
19. Shi, J.L.; Xiao, D.D.; Ge, M.; Yu, X.; Chu, Y.; Huang, X.; Zhang, X.D.; Yin, Y.X.; Yang, X.Q.; Guo, Y.G. High
Capacity Cathode Material with High Voltage for LiIon Batteries. Adv. Mater. 2018, 30, 1705575.
20. Xia, Y.; Zheng, J.; Wang, C.; Gu, M. Designing principle for Ni-rich cathode materials with high energy
density for practical applications. Nano Energy 2018, 49, 434452.
21. Sun, Y.-Y.; Liu, S.; Hou, Y.-K.; Li, G.-R.; Gao, X.-P. In-situ surface modification to stabilize Ni-rich layered
oxide cathode with functional electrolyte. J. Power Sources 2019, 410, 115123.
22. Li, Y.; Li, X.; Wang, Z.; Guo, H.; Li, T.; Meng, K.; Wang, J. A novel layered Ni-rich cathode hierarchical
architecture of densely integrating hydroxide nanoflakes onto oxide microspheres with superior lithium
storage property. Mater. Chem. Front. 2018, 2, 18221828.
23. Chen, R.; Zhang, H.; Xie, J.; Lin, Y.; Yu, J.; Chen, L. Preparation, Lithium Storage Performance and Thermal
Stability of NickelRich Layered LiNi0. 815Co0. 15Al0. 035O2/RGO Composites. ChemElectroChem 2018, 5,
31763182.
24. Jang, S.H.; Jung, K.; Yim, T. Silyl-group functionalized organic additive for high voltage Ni-rich cathode
material. Curr. Appl. Phys. 2018, 18, 13451351.
25. Nayak, P.K.; Erickson, E.M.; Schipper, F.; Penki, T.R.; Munichandraiah, N.; Adelhelm, P.; Sclar, H.; Amalraj,
F.; Markovsky, B.; Aurbach, D. Review on challenges and recent advances in the electrochemical
performance of high capacity Liand Mnrich cathode materials for Liion batteries. Adv. Energy Mater. 2018,
8, 1702397.
Energies 2020, 13, 5117 22 of 30
26. Hou, X.; Wang, Y.; Song, J.; Gu, H.; Guo, R.; Liu, W.; Mao, Y.; Xie, J. Electrochemical behavior of Mn-based
Li-rich cathode material Li1. 15Ni0. 17Co0. 11Mn0. 57O2 fluorinated by Nh4f. Solid State Ion. 2018, 325, 1
6.
27. Liu, Y.; Fan, X.; Zhang, Z.; Wu, H.-H.; Liu, D.; Dou, A.; Su, M.; Zhang, Q.; Chu, D. Enhanced electrochemical
performance of Li-rich layered cathode materials by combined Cr doping and LiAlO2 coating. Acs Sustain.
Chem. Eng. 2018, 7, 22252235.
28. Zhou, H.; Yang, Z.; Yin, C.; Yang, S.; Li, J. Fabrication of nanoplate Li-rich cathode material via surfactant-
assisted hydrothermal method for lithium-ion batteries. Ceram. Int. 2018, 44, 2051420523.
29. Ding, X.; Xiao, L.-N.; Li, Y.-X.; Tang, Z.-F.; Wan, J.-W.; Wen, Z.-Y.; Chen, C.-H. Improving the
electrochemical performance of Li-rich Li1. 2Ni0. 2Mn0. 6O2 by using Ni-Mn oxide surface modification.
J. Power Sources 2018, 390, 1319.
30. Li, X.; Zhang, K.; Mitlin, D.; Paek, E.; Wang, M.; Jiang, F.; Huang, Y.; Yang, Z.; Gong, Y.; Gu, L. LiRich Li
[Li1/6Fe1/6Ni1/6Mn1/2] O2 (LFNMO) Cathodes: Atomic Scale Insight on the Mechanisms of Cycling Decay
and of the Improvement due to Cobalt Phosphate Surface Modification. Small 2018, 14, 1802570.
31. Li, X.; Qiao, Y.; Guo, S.; Jiang, K.; Ishida, M.; Zhou, H. A New Type of LiRich RockSalt Oxide
Li2Ni1/3Ru2/3O3 with Reversible Anionic Redox Chemistry. Adv. Mater. 2019, 31, 1807825.
32. Wang, X.; Feng, Z.; Huang, J.; Deng, W.; Li, X.; Zhang, H.; Wen, Z. Graphene-decorated carbon-coated
LiFePO4 nanospheres as a high-performance cathode material for lithium-ion batteries. Carbon 2018, 127,
149157.
33. Yao, J.; Li, Y.; Massé, R.C.; Uchaker, E.; Cao, G. Revitalized interest in vanadium pentoxide as cathode
material for lithium-ion batteries and beyond. Energy Storage Mater. 2018, 11, 205259.
34. Bak, S.-M.; Shadike, Z.; Lin, R.; Yu, X.; Yang, X.-Q. In situ/operando synchrotron-based X-ray techniques
for lithium-ion battery research. NPG Asia Mater. 2018, 10, 563580.
35. Nam, K.W.; Bak, S.M.; Hu, E.; Yu, X.; Zhou, Y.; Wang, X.; Wu, L.; Zhu, Y.; Chung, K.Y.; Yang, X.Q.
Combining in situ synchrotron X‐ray diffraction and absorption techniques with transmission electron
microscopy to study the origin of thermal instability in overcharged cathode materials for lithiumion
batteries. Adv. Funct. Mater. 2013, 23, 10471063.
36. McDowall, J. Understanding lithium-ion technology. In Proceedings of the Battcon, Marco Island, FL, USA,
May 2008.
37. Huang, P.; Ping, P.; Li, K.; Chen, H.; Wang, Q.; Wen, J.; Sun, J. Experimental and modeling analysis of
thermal runaway propagation over the large format energy storage battery module with Li4Ti5O12 anode.
Appl. Energy 2016, 183, 659673.
38. Yao, X.; Xie, S.; Chen, C.; Wang, Q.; Sun, J.; Li, Y.; Lu, S. Comparisons of graphite and spinel Li1. 33Ti1.
67O4 as anode materials for rechargeable lithium-ion batteries. Electrochim. Acta 2005, 50, 40764081.
39. Kim, H.; Han, B.; Choo, J.; Cho, J. Threedimensional porous silicon particles for use in highperformance
lithium secondary batteries. Angew. Chem. Int. Ed. 2008, 47, 1015110154.
40. Liu, J.; Kopold, P.; van Aken, P.A.; Maier, J.; Yu, Y. Energy storage materials from nature through
nanotechnology: A sustainable route from reed plants to a silicon anode for lithiumion batteries. Angew.
Chem. Int. Ed. 2015, 54, 96329636.
41. Zhang, W.M.; Hu, J.S.; Guo, Y.G.; Zheng, S.F.; Zhong, L.S.; Song, W.G.; Wan, L.J. Tinnanoparticles
encapsulated in elastic hollow carbon spheres for highperformance anode material in lithiumIon
batteries. Adv. Mater. 2008, 20, 11601165.
42. Prikhodchenko, P.V.; Gun, J.; Sladkevich, S.; Mikhaylov, A.A.; Lev, O.; Tay, Y.Y.; Batabyal, S.K.; Yu, D.Y.
Conversion of hydroperoxoantimonate coated graphenes to Sb2S3@ graphene for a superior lithium
battery anode. Chem. Mater. 2012, 24, 47504757.
43. Choi, S.; Cho, Y.G.; Kim, J.; Choi, S.N.; Song, H.K.; Wang, G.; Park, S. Mesoporous Germanium Anode
Materials for LithiumIon Battery with Exceptional Cycling Stability in Wide Temperature Range. Small
2017, 13, 1603045.
44. Chan, C.K.; Zhang, X.F.; Cui, Y. High capacity Li ion battery anodes using Ge nanowires. Nano Lett. 2008,
8, 307309.
45. Liu, Z.; Yu, Q.; Zhao, Y.; He, R.; Xu, M.; Feng, S.; Li, S.; Zhou, L.; Mai, L. Silicon oxides: a promising family
of anode materials for lithium-ion batteries. Chem. Soc. Rev. 2019, 48, 285309.
46. Reddy, M.; Rao, G.S.; Chowdari, B. Metal oxides and oxysalts as anode materials for Li ion batteries. Chem.
Rev. 2013, 113, 53645457.
Energies 2020, 13, 5117 23 of 30
47. Shang, H.; Zuo, Z.; Li, L.; Wang, F.; Liu, H.; Li, Y.; Li, Y. Ultrathin graphdiyne nanosheets grown in situ on
copper nanowires and their performance as lithiumion battery anodes. Angew. Chem. Int. Ed. 2018, 57, 774
778.
48. Tzadikov, J.; Auinat, M.; Barrio, J.; Volokh, M.; Peng, G.; Gervais, C.; Ein‐Eli, Y.; Shalom, M. Layered Boron
NitrogenCarbonOxygen Materials with Tunable Composition as LithiumIon Battery Anodes.
ChemSusChem 2018, 11, 29122920.
49. Wang, A.; Kadam, S.; Li, H.; Shi, S.; Qi, Y. Review on modeling of the anode solid electrolyte interphase
(SEI) for lithium-ion batteries. npj Comput. Mater. 2018, 4, 126.
50. Julien, C.; Mauger, A.; Vijh, A.; Zaghib, K. Lithium batteries. In Lithium Batteries; Springer: Cham,
Switzerland, 2016; pp. 2968.
51. Arora, P.; Zhang, Z. Battery separators. Chem. Rev. 2004, 104, 44194462.
52. Herle, S.P.; Gordon, J.G. Ceramic Coating on Battery Separators. U.S. Patent No. 10,193,116 B2, 29 January
2019.
53. Shi, C.; Zhang, P.; Chen, L.; Yang, P.; Zhao, J. Effect of a thin ceramic-coating layer on thermal and
electrochemical properties of polyethylene separator for lithium-ion batteries. J. Power Sources 2014, 270,
547553.
54. Shin, W.-K.; Kim, D.-W. High performance ceramic-coated separators prepared with lithium ion-
containing SiO2 particles for lithium-ion batteries. J. Power Sources 2013, 226, 5460.
55. Kim, C.-S.; Yoo, J.-S.; Jeong, K.-M.; Kim, K.; Yi, C.-W. Investigation on internal short circuits of lithium
polymer batteries with a ceramic-coated separator during nail penetration. J. Power Sources 2015, 289, 41
49.
56. Orendorff, C.J. The role of separators in lithium-ion cell safety. Electrochem. Soc. Interface 2012, 21, 61.
57. Zhang, S.S. A review on the separators of liquid electrolyte Li-ion batteries. J. Power Sources 2007, 164, 351
364.
58. Li, Z.; Xiong, Y.; Sun, S.; Zhang, L.; Li, S.; Liu, X.; Xu, Z.; Xu, S. Tri-layer nonwoven membrane with
shutdown property and high robustness as a high-safety lithium ion battery separator. J. Membr. Sci. 2018,
565, 5060.
59. Costa, C.M.; Kundu, M.; Cardoso, V.F.; Machado, A.V.; Silva, M.M.; Lanceros-Méndez, S.
Silica/poly(vinylidene fluoride) porous composite membranes for lithium-ion battery separators. J. Membr.
Sci. 2018, 564, 842851.
60. Sun, G.; Dong, G.; Kong, L.; Yan, X.; Tian, G.; Qi, S.; Wu, D. Robust polyimide nanofibrous membrane with
porous-layer-coated morphology by in situ self-bonding and micro-crosslinking for lithium-ion battery
separator. Nanoscale 2018, 10, 2243922447.
61. Liu, J.; Yang, K.; Mo, Y.; Wang, S.; Han, D.; Xiao, M.; Meng, Y. Highly safe lithium-ion batteries: High
strength separator from polyformaldehyde/cellulose nanofibers blend. J. Power Sources 2018, 400, 502510.
62. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 2004, 104, 4303
4418.
63. Wang, Q.; Sun, J.; Chen, C. Thermal stability of LiPF6/EC + DMC + EMC electrolyte for lithium ion batteries.
Rare Metals 2006, 25 (Suppl. 1), 9499.
64. Dahbi, M.; Ghamouss, F.; Tran-Van, F.; Lemordant, D.; Anouti, M. Comparative study of EC/DMC LiTFSI
and LiPF6 electrolytes for electrochemical storage. J. Power Sources 2011, 196, 97439750.
65. Li, F.; Gong, Y.; Jia, G.; Wang, Q.; Peng, Z.; Fan, W.; Bai, B. A novel dual-salts of LiTFSI and LiODFB in
LiFePO4-based batteries for suppressing aluminum corrosion and improving cycling stability. J. Power
Sources 2015, 295, 4754.
66. Wang, Q.; Jiang, L.; Yu, Y.; Sun, J. Progress of enhancing the safety of lithium ion battery from the electrolyte
aspect. Nano Energy 2019, 55, 93114.
67. Zeng, Z.; Wu, B.; Xiao, L.; Jiang, X.; Chen, Y.; Ai, X.; Yang, H.; Cao, Y. Safer lithium ion batteries based on
nonflammable electrolyte. J. Power Sources 2015, 279, 612.
68. Xu, K.; Zhang, S.; Allen, J.L.; Jow, T.R. Nonflammable electrolytes for Li-ion batteries based on a fluorinated
phosphate. J. Electrochem. Soc. 2002, 149, A1079A1082.
69. Zhang, Q.; Noguchi, H.; Wang, H.; Yoshio, M.; Otsuki, M.; Ogino, T. Improved thermal stability of LiCoO2
by cyclotriphosphazene additives in lithium-ion batteries. Chem. Lett. 2005, 34, 10121013.
70. Jiang, L.; Wang, Q.; Sun, J. Electrochemical performance and thermal stability analysis of LiNixCoyMnzO2
cathode based on a composite safety electrolyte. J. Hazard. Mater. 2018, 351, 260269.
Energies 2020, 13, 5117 24 of 30
71. Jiang, L.; Wang, Q.; Li, K.; Ping, P.; Jiang, L.; Sun, J. A self-cooling and flame-retardant electrolyte for safer
lithium ion batteries. Sustain. Energy Fuels 2018, 2, 13231331.
72. Gogotsi, Y.; Zhao, M.-Q.; Cheng, X.-B. Additives for Suppressing Dendritic Growth in Batteries. U.S. Patent
Application No. 16/050,987, 7 February 2019, .
73. Ergen, O.; Zettl, A.K. High Temperature Li-Ion Battery Cells Utilizing Boron Nitride Aerogels And Boron
Nitride Nanotubes. U.S. Patent Application No. 15/822,563, 16 June 2020.
74. Schmitz, R.; Garsuch, A.; Chesneau, F.F.; Schmidt, M.; Yamamoto, T.; Semrau, G. Overcharge Protection
Electrolyte Additive for Lithium Ion Batteries. U.S. Patent No. 10,153,516, 11 December 2018.
75. Lewandowski, A.; Świderska-Mocek, A. Ionic liquids as electrolytes for Li-ion batteriesAn overview of
electrochemical studies. J. Power Sources 2009, 194, 601609.
76. Francis, C.; Louey, R.; Sammut, K.; Best, A.S. Thermal stability of pyrrolidinium-FSI ionic liquid electrolyte
and lithium-ion electrodes at elevated temperatures. J. Electrochem. Soc. 2018, 165, A1204.
77. Moganty, S.; Wu, Y.; Abbate, L.; Brown, K.; Sinicropi, J.; Torres, G. Modified Ionic Liquids Containing
Triazine. U.S. Patent Application No. 16/037,902, 17 January 2019.
78. Feng, J.; Ai, X.; Cao, Y.; Yang, H. Possible use of non-flammable phosphonate ethers as pure electrolyte
solvent for lithium batteries. J. Power Sources 2008, 177, 194198.
79. Feng, J.; Sun, X.; Ai, X.; Cao, Y.; Yang, H. Dimethyl methyl phosphate: A new nonflammable electrolyte
solvent for lithium-ion batteries. J. Power Sources 2008, 184, 570573.
80. Takechi, K.; Yang, R. Aqueous Electrolyte with Ethers and Batteries Using the Electrolyte. U.S. Patent No.
10,193,188, 29 January 2019.
81. Takechi, K.; Yang, R. Aqueous Electrolytes with Protonic Ionic Liquid and Batteries Using the Electrolyte.
No. 15/663,262, 31 January 2019.
82. Zhu, Y.; Wang, X.; Hou, Y.; Gao, X.; Liu, L.; Wu, Y.; Shimizu, M. A new single-ion polymer electrolyte based
on polyvinyl alcohol for lithium ion batteries. Electrochim. Acta 2013, 87, 113118.
83. Du, Z.; Su, Y.; Qu, Y.; Zhao, L.; Jia, X.; Mo, Y.; Yu, F.; Du, J.; Chen, Y. A mechanically robust, biodegradable
and high performance cellulose gel membrane as gel polymer electrolyte of lithium-ion battery. Electrochim.
Acta 2019, 299, 1926.
84. Zhao, L.; Fu, J.; Du, Z.; Jia, X.; Qu, Y.; Yu, F.; Du, J.; Chen, Y. High-strength and flexible cellulose/PEG based
gel polymer electrolyte with high performance for lithium ion batteries. J. Membr. Sci. 2020, 593, 117428.
85. Wakihara, M.; Kadoma, Y.; Kumagai, N.; Mita, H.; Araki, R.; Ozawa, K.; Ozawa, Y. Development of
nonflammable lithium ion battery using a new all-solid polymer electrolyte. J. Solid State Electrochem. 2012,
16, 847855.
86. Youcef, H.B.; Armand, M.; Orayech, B.; Saurel, D.; Shanmukaraj, D. Solid Polymer Electrolyte Based on
Modified Cellulose and Its Use in Lithium or Sodium Secondary Batteries. U.S. Patent Application No.
15/663,262, 3 January 2019.
87. Yushin, G.; Turcheniuk, K.; Yiran, X.; Song, A.-Y.; Borodin, O.; Nitta, N. Solid Electrolyte Technology with
Rearrangeable Bonds for Metal And Metal-Ion Batteries. U.S. Patent Application No. 16/022,572, 3 January
2019.
88. Spotnitz, R.; Franklin, J. Abuse behavior of high-power, lithium-ion cells. J. Power Sources 2003, 113, 81100.
89. Otto, A.; Rzepka, S.; Mager, T.; Michel, B.; Lanciotti, C.; Günther, T.; Kanoun, O. Battery Management
Network for Fully Electrical Vehicles Featuring Smart Systems at Cell and Pack Level. In Advanced
Microsystems for Automotive Applications; Springer: Berlin/Heidelberg, Germany, 2012; pp. 314.
90. Joachin, H.; Kaun, T.D.; Zaghib, K.; Prakash, J. Electrochemical and Thermal studies of LiFePO4 cathode in
lithium-ion cells. ECS Trans. 2008, 6, 1116.
91. Yang, H.; Amiruddin, S.; Bang, H.J.; Sun, Y.-K.; Prakash, J. A review of Li-ion cell chemistries and their
potential use in hybrid electric vehicles. J. Ind. Eng. Chem. 2006, 12, 1238.
92. Al-Hallaj, S.; Selman, J.R. Thermal modeling of secondary lithium batteries for electric vehicle/hybrid
electric vehicle applications. J. Power Sources 2002, 110, 341348.
93. Ruiz, V.; Pfrang, A.; Kriston, A.; Omar, N.; van den Bossche, P.; Boon-Brett, L. A review of international
abuse testing standards and regulations for lithium ion batteries in electric and hybrid electric vehicles.
Renew. Sustain. Energy Rev. 2018, 81 Pt 1, 14271452.
94. Feng, X.; Ouyang, M.; Liu, X.; Lu, L.; Xia, Y.; He, X. Thermal runaway mechanism of lithium ion battery for
electric vehicles: A review. Energy Storage Mater. 2018, 10 (Suppl. C), 246-267.
Energies 2020, 13, 5117 25 of 30
95. Larsson, F.; Andersson, P.; Mellander, B.-E. Lithium-ion battery aspects on fires in electrified vehicles on
the basis of experimental abuse tests. Batteries 2016, 2, 9.
96. Lecocq, A.; Bertana, M.; Truchot, B.; Marlair, G. Comparison of the fire consequences of an electric vehicle
and an internal combustion engine vehicle. In Proceedings of the International Conference on Fires In
Vehicles-FIVE 2012, Chicago, IL, USA, 2728 September 2012; SP Technical Research Institute of Sweden:
Boras, Sweden, 2012.
97. Depetro, A. Future Submarine Fire Safety Study. MSc. Thesis, Victoria University, Melbourne, Australia,
2016.
98. Buckingham, J.; Hodge, C.; Hardy, T. Submarine power and propulsion-application of technology to
deliver customer benefit. In Proceedings of the UDT Europe, Glasgow, UK, Scotland, 2628 June 2008.
99. Spinner, N.S.; Field, C.R.; Hammond, M.H.; Williams, B.A.; Myers, K.M.; Lubrano, A.L.; Rose-Pehrsson,
S.L.; Tuttle, S.G. Physical and chemical analysis of lithium-ion battery cell-to-cell failure events inside
custom fire chamber. J. Power Sources 2015, 279 (Suppl. C), 713721.
100. Lamb, J.; Corendorff, J.; Steele, L.A.M.; Spangler, S.W. Failure propagation in multi-cell lithium ion
batteries. J. Power Sources 2015, 283 (Suppl. C), 517523.
101. McDowall, J. A guide to lithium-ion battery safety. Battcon 2014, 1, 123.
102. Ye, J.; Chen, H.; Wang, Q.; Huang, P.; Sun, J.; Lo, S. Thermal behavior and failure mechanism of lithium
ion cells during overcharge under adiabatic conditions. Appl. Energy 2016, 182 (Suppl. C), 464474.
103. Yuan, Q.; Zhao, F.; Wang, W.; Zhao, Y.; Liang, Z.; Yan, D. Overcharge failure investigation of lithium-ion
batteries. Electrochim. Acta 2015, 178 (Suppl. C), 682688.
104. Yamamoto, Y.; Kato, K.; Lin, L.; Fukui, M. A thermal management system for lithium-ion battery in mobile
systems. In Proceedings of the European Conference on Circuit Theory and Design (ECCTD), Dresden,
Germany, 812 September 2013; IEEE: Piscataway, NJ, USA, 2013; pp. 14.
105. Li, Z.; Huang, J.; Liaw, B.Y.; Metzler, V.; Zhang, J. A review of lithium deposition in lithium-ion and lithium
metal secondary batteries. J. Power Sources 2014, 254 (Suppl. C), 168182.
106. Lisbona, D.; Snee, T. A review of hazards associated with primary lithium and lithium-ion batteries. Process
Saf. Environ. Prot. 2011, 89, 434442.
107. Guo, L.S.; Wang, Z.R.; Wang, J.H.; Luo, Q.K.; Liu, J.J. Effects of the environmental temperature and heat
dissipation condition on the thermal runaway of lithium ion batteries during the charge-discharge process.
J. Loss Prev. Process Ind. 2017, 49 Pt B, 953960.
108. Yang, H.; Bang, H.; Amine, K.; Prakash, J. Investigations of the exothermic reactions of natural graphite
anode for Li-ion batteries during thermal runaway. J. Electrochem. Soc. 2005, 152, A73A79.
109. Lee, C.W.; Venkatachalapathy, R.; Prakash, J. A Novel FlameRetardant Additive for Lithium Batteries.
Electrochem. Solid-State Lett. 2000, 3, 6365.
110. Lamb, J.; Orendorff, C.J. Evaluation of mechanical abuse techniques in lithium ion batteries. J. Power Sources
2014, 247 (Suppl. C), 189196.
111. Wang, Q.; Ping, P.; Zhao, X.; Chu, G.; Sun, J.; Chen, C. Thermal runaway caused fire and explosion of
lithium ion battery. J. Power Sources 2012, 208 (Suppl. C), 210224.
112. Ribière, P.; Grugeon, S.; Morcrette, M.; Boyanov, S.; Laruelle, S.; Marlair, G. Investigation on the fire-
induced hazards of Li-ion battery cells by fire calorimetry. Energy Environ. Sci. 2012, 5, 52715280.
113. Ping, P.; Wang, Q.; Huang, P.; Li, K.; Sun, J.; Kong, D.; Chen, C. Study of the fire behavior of high-energy
lithium-ion batteries with full-scale burning test. J. Power Sources 2015, 285 (Suppl. C), 8089.
114. MacNeil, D.; Lu, Z.; Chen, Z.; Dahn, J.R. A comparison of the electrode/electrolyte reaction at elevated
temperatures for various Li-ion battery cathodes. J. Power Sources 2002, 108, 814.
115. Zheng, W. GB/T 31485 Translated English of Chinese Standard, Safety Requirements and Test Methods for Traction
Battery of Electric Vehicle; 2015; ICS, p. 17.
116. Wilkens, K.; Johnsen, B.; Bhargava, A.; Dragsted, A. Assessment of Existing Fire Protection Strategies and
Recommendation for Future Work, in Project BLUE BATTERY, Part II; Danish Institute of Fire and security
Technology, Hvidovre, Denmark, 2017.
117. Liu, K.; Liu, Y.; Lin, D.; Pei, A.; Cui, Y. Materials for lithium-ion battery safety. Sci. Adv. 2018, 4, eaas9820.
118. Wang, Q.; Mao, B.; Stoliarov, S.I.; Sun, J. A review of lithium ion battery failure mechanisms and fire
prevention strategies. Prog. Energy Combust. Sci. 2019, 73, 95131.
119. Li, J.; Zhang, Q.; Liu, C.; He, X. ZrO 2 coating of LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials for Li-ion
batteries. Ionics 2009, 15, 493496.
Energies 2020, 13, 5117 26 of 30
120. Kannan, A.M.; Manthiram, A. Surface/chemically modified limn2 o 4 cathodes for lithium-ion batteries.
Electrochem. Solid-State Lett. 2002, 5, A167A169.
121. Love, C.T.; Johannes, M.D.; Swider-Lyons, K. Thermal Stability of Delithiated Al-substituted Li
(Ni1/3Co1/3Mn1/3) O2 Cathodes. ECS Trans. 2010, 25, 231.
122. Zhou, F.; Zhao, X.; Jiang, J.; Dahn, J. Advantages of Simultaneous Substitution of Co in Li [Ni1 3Mn1 3Co1
3] O2 by Ni and Al. Electrochem. Solid-State Lett. 2009, 12, A81A83.
123. Liu, S.; Dang, Z.; Liu, D.; Zhang, C.; Huang, T.; Yu, A. Comparative studies of zirconium doping and
coating on LiNi0. 6Co0. 2Mn0. 2O2 cathode material at elevated temperatures. J. Power Sources 2018, 396,
288296.
124. Yang, L.; Ren, F.; Feng, Q.; Xu, G.; Li, X.; Li, Y.; Zhao, E.; Ma, J.; Fan, S. Effect of Cu doping on the structural
and electrochemical performance of LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials. J. Electron. Mater. 2018,
47, 39964002.
125. Liu, H. Lithium Ion Battery and Positive Active Material Thereof. U.S. Patent Application No. 16/045,723,
31 January 2019.
126. Chaoyi, Z.; Zhu'an, Y.; Wang, L.; Daixiang, Y.; Peng, P.; Xiang, Q.; Mei, M.; Li, L. Spherical or Spherical-
Like Cathode Material for Lithium-Ion Battery and Lithium-Ion Battery. U.S. Patent Application No.
16/022,757, 17 January 2019.
127. Chaoyi, Z.; Wang, L.; Zhu'an, Y.; Daixiang, Y.; Xiang, Q.; Mei, M.; Peng, P. Spherical or Spherical-Like
Cathode Material for a Lithium Battery, a Battery and Preparation Method and Application Thereof. U.S.
Patent Application No. 16/751,337, 21 May 2020.
128. Jung, Y.S.; Cavanagh, A.S.; Riley, L.A.; Kang, S.H.; Dillon, A.C.; Groner, M.D.; George, S.M.; Lee, S.H.
Ultrathin direct atomic layer deposition on composite electrodes for highly durable and safe Liion
batteries. Adv. Mater. 2010, 22, 21722176.
129. Drews, A.R.; Anandan, V. Electrode design to improve li-ion battery safety. U.S. Patent Application No.
15/668,876, 7 February 2019.
130. Xu, W.; Wang, J.; Ding, F.; Chen, X.; Nasybulin, E.; Zhang, Y.; Zhang, J.-G. Lithium metal anodes for
rechargeable batteries. Energy Environ. Sci. 2014, 7, 513537.
131. Lin, D.; Liu, Y.; Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 2017,
12, 194.
132. Cao, X.; Li, Y.; Li, X.; Zheng, J.; Gao, J.; Gao, Y.; Wu, X.; Zhao, Y.; Yang, Y. Novel phosphamide additive to
improve thermal stability of solid electrolyte interphase on graphite anode in lithium-ion batteries. ACS
Appl. Mater. Interfaces 2013, 5, 1149411497.
133. Boukamp, B.; Lesh, G.; Huggins, R. Allsolid lithium electrodes with mixedconductor matrix. J.
Electrochem. Soc. 1981, 128, 725.
134. Chan, C.K.; Peng, H.; Liu, G.; McIlwrath, K.; Zhang, X.F.; Huggins, R.A.; Cui, Y. High-performance lithium
battery anodes using silicon nanowires. Nat. Nanotechnol. 2008, 3, 31.
135. Belharouak, I.; Koenig, G.M., Jr.; Amine, K. Electrochemistry and safety of Li4Ti5O12 and graphite anodes
paired with LiMn2O4 for hybrid electric vehicle Li-ion battery applications. J. Power Sources 2011, 196,
1034410350.
136. Feng, X.; Sun, J.; Ouyang, M.; Wang, F.; He, X.; Lu, L.; Peng, H. Characterization of penetration induced
thermal runaway propagation process within a large format lithium ion battery module. J. Power Sources
2015, 275, 261273.
137. Park, C.-K. Nonaqueous Electrolyte for Lithium Battery Safety. U.S. Patent No. 10,038,220, 31 July 2018.
138. Wang, Q.; Sun, J.; Chen, C. Effects of solvents and salt on the thermal stability of lithiated graphite used in
lithium ion battery. J. Hazard. Mater. 2009, 167, 12091214.
139. Wang, Q.; Sun, J.; Chen, X.; Chu, G.; Chen, C. Effects of solvents and salt on the thermal stability of charged
LiCoO2. Mater. Res. Bull. 2009, 44, 543548.
140. Jiang, J.; Dahn, J. Effects of solvents and salts on the thermal stability of LiC6. Electrochim. Acta 2004, 49,
45994604.
141. Xu, W.; Deng, Z.; Bolomey, P. Stabilized Nonaqueous Electrolytes for Rechargeable Batteries. U.S. Patent
No. 7,638,243, 29 December 2009.
142. Guerfi, A.; Duchesne, S.; Kobayashi, Y.; Vijh, A.; Zaghib, K. LiFePO4 and graphite electrodes with ionic
liquids based on bis (fluorosulfonyl) imide (FSI)− for Li-ion batteries. J. Power Sources 2008, 175, 866873.
Energies 2020, 13, 5117 27 of 30
143. Prakash, J.; Lee, C.W.; Amine, K. Flame-retardant additive for Li-ion batteries. U.S. Patent No. 6,455,200, 24
September 2002.
144. Yao, X.; Xie, S.; Chen, C.; Wang, Q.; Sun, J.; Li, Y.; Lu, S. Comparative study of trimethyl phosphite and
trimethyl phosphate as electrolyte additives in lithium ion batteries. J. Power Sources 2005, 144, 170175.
145. Lee, H.-H.; Wang, Y.-Y.; Wan, C.-C.; Yang, M.-H.; Wu, H.-C.; Shieh, D.-T. The function of vinylene
carbonate as a thermal additive to electrolyte in lithium batteries. J. Appl. Electrochem. 2005, 35, 615623.
146. Xia, L.; Wang, D.; Yang, H.; Cao, Y.; Ai, X. An electrolyte additive for thermal shutdown protection of Li-
ion batteries. Electrochem. Commun. 2012, 25, 98100.
147. Tsujikawa, T.; Yabuta, K.; Matsushita, T.; Matsushima, T.; Hayashi, K.; Arakawa, M. Characteristics of
lithium-ion battery with non-flammable electrolyte. J. Power Sources 2009, 189, 429434.
148. Balakrishnan, P.; Ramesh, R.; Kumar, T.P. Safety mechanisms in lithium-ion batteries. J. Power Sources 2006,
155, 401414.
149. Yeh, S.-F. Actuating Structure of Battery Safety Valve. U.S. Patent No. 10,103,371. 16 October 2018.
150. Cherng, J.-Y.; Pin-Shiuan, L.; Cheng, T.-T. Lithium Battery with Exhaust Structure. U.S. Patent No.
10,121,998, 6 November 2018.
151. Coman, P.T.; Rayman, S.; White, R.E. A lumped model of venting during thermal runaway in a cylindrical
Lithium Cobalt Oxide lithium-ion cell. J. Power Sources 2016, 307, 5662.
152. Finegan, D.P. X-Ray Imaging of Failure and Degradation Mechanisms of Lithium-Ion Batteries. Ph.D.
Thesis, UCL (University College London), London, UK, 2016.
153. Doughty, D.H.; Roth, E.P. A general discussion of Li ion battery safety. Electrochem. Soc. Interface 2012, 21,
3744.
154. Lu, L.; Han, X.; Li, J.; Hua, J.; Ouyang, M. A review on the key issues for lithium-ion battery management
in electric vehicles. J. Power Sources 2013, 226, 272288.
155. Wei, Z.; Meng, S.; Xiong, B.; Ji, D.; Tseng, K.J. Enhanced online model identification and state of charge
estimation for lithium-ion battery with a FBCRLS based observer. Appl. Energy 2016, 181, 332341.
156. Wei, Z.; Zhao, J.; Ji, D.; Tseng, K.J. A multi-timescale estimator for battery state of charge and capacity dual
estimation based on an online identified model. Appl. Energy 2017, 204, 12641274.
157. Xiong, B.; Zhao, J.; Su, Y.; Wei, Z.; Skyllas-Kazacos, M. State of charge estimation of vanadium redox flow
battery based on sliding mode observer and dynamic model including capacity fading factor. IEEE Trans.
Sustain. Energy 2017, 8, 16581667.
158. Dong, G.; Yang, F.; Wei, Z.; Wei, J.; Tsui, K.-L. Data-driven battery health prognosis using adaptive
Brownian motion model. IEEE Trans. Ind. Inform. 2019, 16, 47364746.
159. Liu, K.; Hu, X.; Wei, Z.; Li, Y.; Jiang, Y. Modified Gaussian process regression models for cyclic capacity
prediction of lithium-ion batteries. IEEE Trans. Transp. Electrif. 2019, 5, 12251236.
160. Kim, T.; Adhikaree, A.; Pandey, R.; Kang, D.; Kim, M.; Oh, C.-Y.; Back, J. Outlier mining-based fault
diagnosis for multiceli lithium-ion batteries using a low-priced microcontroller. In Proceedings of the 2018
IEEE Applied Power Electronics Conference and Exposition (APEC), San Antonio, TX, USA, 48 March
2018; IEEE: Piscataway, NJ, USA, 2018; pp. 33653369.
161. Feng, X.; Weng, C.; Ouyang, M.; Sun, J. Online internal short circuit detection for a large format lithium ion
battery. Appl. Energy 2016, 161, 168180.
162. Wei, Z.; Dong, G.; Zhang, X.; Pou, J.; Quan, Z.; He, H. Noise-immune model identification and state of
charge estimation for lithium-ion battery using bilinear parameterization. IEEE Trans. Ind. Electron. 2020, 1,
1-19.
163. Wei, Z.; Zhao, D.; He, H.; Cao, W.; Dong, G. A noise-tolerant model parameterization method for lithium-
ion battery management system. Appl. Energy 2020, 268, 114932,
164. Zou, C.; Klintberg, A.; Wei, Z.; Fridholm, B.; Wik, T.; Egardt, B. Power capability prediction for lithium-ion
batteries using economic nonlinear model predictive control. J. Power Sources 2018, 396, 580589.
165. Yan, J.; Wang, Q.; Li, K.; Sun, J. Numerical study on the thermal performance of a composite board in
battery thermal management system. Appl. Therm. Eng. 2016, 106, 131140.
166. Ye, Y.; Saw, L.H.; Shi, Y.; Tay, A.A. Numerical analyses on optimizing a heat pipe thermal management
system for lithium-ion batteries during fast charging. Appl. Therm. Eng. 2015, 86, 281291.
167. Zhai, H.; Cui, X. Thermal Management System. U.S. Patent Application No. 16/044,708, 31 January 2019.
168. Coleman, B.; Ostanek, J.; Heinzel, J. Reducing cell-to-cell spacing for large-format lithium ion battery
modules with aluminum or PCM heat sinks under failure conditions. Appl. Energy 2016, 180, 1426.
Energies 2020, 13, 5117 28 of 30
169. Fan, L.; Khodadadi, J.; Pesaran, A. A parametric study on thermal management of an air-cooled lithium-
ion battery module for plug-in hybrid electric vehicles. J. Power Sources 2013, 238, 301312.
170. Chen, K.; Wang, S.; Song, M.; Chen, L. Structure optimization of parallel air-cooled battery thermal
management system. Int. J. Heat Mass Transf. 2017, 111, 943952.
171. Mahamud, R.; Park, C. Reciprocating air flow for Li-ion battery thermal management to improve
temperature uniformity. J. Power Sources 2011, 196, 56855696.
172. Yu, K.; Yang, X.; Cheng, Y.; Li, C. Thermal analysis and two-directional air flow thermal management for
lithium-ion battery pack. J. Power Sources 2014, 270, 193200.
173. Yang, N.; Zhang, X.; Li, G.; Hua, D. Assessment of the forced air-cooling performance for cylindrical
lithium-ion battery packs: A comparative analysis between aligned and staggered cell arrangements. Appl.
Therm. Eng. 2015, 80, 5565.
174. Zhao, J.; Rao, Z.; Li, Y. Thermal performance of mini-channel liquid cooled cylinder based battery thermal
management for cylindrical lithium-ion power battery. Energy Convers. Manag. 2015, 103, 157165.
175. Karimi, G.; Dehghan, A. Thermal analysis of highpower lithiumion battery packs using flow network
approach. Int. J. Energy Res. 2014, 38, 17931811.
176. Kizilel, R.; Sabbah, R.; Selman, J.R.; Al-Hallaj, S. An alternative cooling system to enhance the safety of Li-
ion battery packs. J. Power Sources 2009, 194, 11051112.
177. Al Hallaj, S.; Selman, J. A novel thermal management system for electric vehicle batteries using phase
change material. J. Electrochem. Soc. 2000, 147, 32313236.
178. Bustamante, J.G.; Sole, J.D. Internal Battery Cell Cooling with Heat Pipe. U.S. Patent Application No.
15/132,668, 29 January 2019.
179. Weng, Y.-C.; Cho, H.-P.; Chang, C.-C.; Chen, S.-L. Heat pipe with PCM for electronic cooling. Appl. Energy
2011, 88, 18251833.
180. Yu, M.G.; Wang, S.H.; Hu, X.F. Heat transfer capacity of composite cooling system for automobile lithium-
ion battery with heat pipe and phase change materials. Adv. Mater. Res. 2014, 941944, 24692473.
181. National Fire Protection Association. NFPA 13, Standard for the Installation of Sprinkler Systems; National Fire
Protection Association: Quincy, MS, USA, 2002.
182. Liu, Z.; Kim, A.K.; Carpenter, D. A study of portable water mist fire extinguishers used for extinguishment
of multiple fire types. Fire Saf. J. 2007, 42, 2542.
183. Watanabe, N.; Sugawa, O.; Suwa, T.; Ogawa, Y.; Hiramatsu, M.; Hino, T.; Miyamoto, H.; Okamoto, K.;
Honma, M. Comparison of fire behaviors of an electric-battery-powered vehicle and gasoline-powered
vehicle in a real-scale fire test. In Proceedings of the 2nd International Conference on Fires in Vehicles-
FIVE, Chicago, IL, USA, 2728 September 2012.
184. Ouyang, D.; Chen, M.; Huang, Q.; Weng, J.; Wang, Z.; Wang, J. A Review on the Thermal Hazards of the
Lithium-Ion Battery and the Corresponding Countermeasures. Appl. Sci. 2019, 9, 2483.
185. Reif, R.H.; Liffers, M.; Forrester, N.; Peal, K. Lithium Battery Safety. Prof. Safety 2010, 55, 32.
186. Farrington, M.D. Safety of lithium batteries in transportation. J. Power Sources 2001, 96, 260265.
187. Larsson, F. Lithium-Ion Battery Safety-Assessment by Abuse Testing, Fluoride Gas Emissions And Fire
Propagation. Ph.D. Thesis, Chalmers University of Technology,Göteborg, Sweden, 2017.
188. Wang, Q.; Li, K.; Wang, Y.; Chen, H.; Duan, Q.; Sun, J. The efficiency of dodecafluoro-2-methylpentan-3-
one on suppressing the lithium ion battery fire. J. Electrochem. Energy Convers. Storage 2018, 15(4), 41-51.
189. Beitland, S.; Stokland, O.; Skaug, V.; Skogstad, A.; Klingenberg, O. Inhalation of fire extinguisher powder.
Eur. J. Trauma 2006, 32, 286291.
190. Jiang, Z.; Chow, W.; Li, S. Review on additives for new clean fire suppressants. Environ. Eng. Sci. 2007, 24,
663674.
191. Gann, R.G.; Burgess, S.R.; Whisner, K.C.; Reneke, P.A. Preface to the Cumulative Proceedings of the First 14
Halon Options Technical Working Conferences, NIST Pubs, Gaithersburg, Maryland, USA, May 2017.
192. Benson, C.; Fernando-Cerezo, G.; Holborn, P.; Mba, D. Fire suppression systems in aircraft: Their past,
present & future. Fire Investig. 2016, 1, 3441.
193. Summer, S.M. Flammability Assessment of Lithium-Ion and Lithium-Ion Polymer Battery Cells Designed for
Aircraft Power Usage; US Department of Transportation, Federal Aviation Administration: Washington, DC,
USA, 2010.
194. Ditch, B.; de Vries, J. Flammability characterization of lithium-ion batteries in bulk storage FM Global:
Johnston, Norwood, Massachusetts, USA, March 2013.
Energies 2020, 13, 5117 29 of 30
195. Webster, H. Flammability Assessment of Bulk-Packed, Rechargeable Lithium-Ion Cells in Transport Category
Aircraft; Office of Aviation Research, Federal Aviation Administration: Washington, DC, USA, 2006.
196. Rao, H.; Huang, Z.; Zhang, H.; Xiao, S. Study of fire tests and fire safety measures on lithiumion battery
used on ships. In Proceedings of the 2015 International Conference on Transportation Information and
Safety (ICTIS), Wuhan, China, 2528 June 2015; IEEE: Piscataway, NJ, USA, 2015; pp. 865870.
197. Wang, Q.; Shao, G.; Duan, Q.; Chen, M.; Li, Y.; Wu, K.; Liu, B.; Peng, P.; Sun, J. The efficiency of
heptafluoropropane fire extinguishing agent on suppressing the lithium titanate battery fire. Fire Technol.
2016, 52, 387396.
198. Liu, Y.; Duan, Q.; Xu, J.; Chen, H.; Lu, W.; Wang, Q. Experimental study on the efficiency of dodecafluoro-
2-methylpentan-3-one on suppressing lithium-ion battery fires. Rsc Adv. 2018, 8, 4222342232.
199. Hill, D. Considerations for Energy Storage Systems (ESS) Fire Safety; DET NORSKE VERITAS (U.S.A.), INC.
(DNV GL), Dublin, OH, USAUnited States, 2017.
200. Egelhaaf, M.; Kress, D.; Wolpert, D.; Lange, T.; Justen, R.; Wilstermann, H. Fire Fighting of Li-Ion Traction
Batteries. Sae Int. J. Altern. Powertrains 2013, 2, 3748.
201. Maloney, T. Extinguishment of Lithium-Ion and Lithium-Metal Battery Fires; US Federal Aviation
Administration: Washington, DC, USA, 2014; pp. 46-51.
202. Larsson, F.; Andersson, P.; Blomqvist, P.; Lorén, A.; Mellander, B.-E. Characteristics of lithium-ion batteries
during fire tests. J. Power Sources 2014, 271, 414420.
203. Andersson, P.; Arvidson, M.; Evegren, F.; Jandali, M.; Larsson, F.; Rosengren, M. Lion Fire: Extinguishment
and mitigation of fires in Li-ion batteries at sea. DiVA, 2018, 49, p. 49 .
204. Zhu, M.-X.; Zhu, S.-B.; Gong, J.-H.; Zhou, Z. Experimental Study on Fire and Explosion Characteristics of
Power Lithium Batteries with Surfactant Water Mist. Procedia Eng. 2018, 211, 10831090.
205. Zhang, Q.; Cao, W.; Bai, W. Experimental study on inhibition effect of water mist on thermal runaway of
lithium ion batteries. Fire Saf. Sci. 2017, 4, 8.
206. Long, R.T.; Blum, A.F.; Bress, T.J.; Cotts, B.R. Best Practices for Emergency Response to Incidents Involving
Electric Vehicles Battery Hazards: A Report on Full-Scale Testing Results; National Fire Protection Research
Foundation: Quincy, MA, USA, 2013.
207. Luo, W.-T.; Zhu, S.-B.; Gong, J.-H.; Zhou, Z. Research and development of fire extinguishing technology
for power lithium batteries. Procedia Eng. 2018, 211, 531537.
208. Li, Y.; Yu, D.; Zhang, S.; Hu, Q.; Liu, X.; Wang, J. On the fire extinguishing tests of typical lithium ion
battery. J. Saf. Environ. 2015, 15, 120125.
209. Lefebvre, A.H.; McDonell, V.G. Atomization and Sprays; CRC Press: Boca Raton, FL, USA, 2017.
210. Mawhinney, J.R.; Back, G.G., III. Water mist fire suppression systems. In SFPE Handbook of Fire Protection
Engineering; Springer: New York, NY, USA, 2016; pp. 15871645.
211. National Fire Protection Association. NFPA 750 Standard for Water Mist Fire Suppression Systems; NFPA:
Quincy, MA, USA, 2010.
212. Braidech, M.; Neale, J.; Matson, A.; Dufour, R. The Mechanism of Extinguishment of Fire By Finely Divided
Water; Underwriters Laboratories Inc. for the National Board of Fire Underwriters; National Board of Fire
Underwriters: New York, NY, USA, 1955; p. 73.
213. Rasbash, D.; Rogowski, Z.; Stark, G. Mechanisms of extinction of liquid fires with water sprays. Combust.
Flame 1960, 4, 223234.
214. Baumgarten, C. Mixture Formation in Internal Combustion Engines; Springer Science & Business Media:
Berlin, Germany, 2006.
215. Mawhinney, J.; Dlugogorski, B.; Kim, A. A closer look at the fire extinguishing properties of water mist.
Fire Saf. Sci. 1994, 4, 4760.
216. Mahmud, H. Simulation of the Suppression of Fires Using Water Mists. Ph.D. Thesis, Victoria University,
Melbourne, Australia, 2016.
217. Back, G.G., III; Beyler, C.L.; Hansen, R. A quasi-steady-state model for predicting fire suppression in spaces
protected by water mist systems. Fire Saf. J. 2000, 35, 327362.
218. Dembele, S.; Wen, J.; Sacadura, J.-F. Experimental study of water sprays for the attenuation of fire thermal
radiation. J. Heat Transf. 2001, 123, 534543.
219. Liu, Z.; Kim, A.; Su, J. Improvement of efficacy of water mist in fire suppression by cycling discharges.
Second International Conference on Fire Research and Engineering, Gaithersburg, Maryland, USA, August 1997,
275281.
Energies 2020, 13, 5117 30 of 30
220. Liu, Z.; Kim, A.K. A review of water mist fire suppression systemsfundamental studies. J. Fire Prot. Eng.
1999, 10, 3250.
221. British Standards Institution. BS 8489 Fixed Fire Protection Systems. Industrial and Commercial Watermist
Systems. Code of Practice for Design and Installation; British Standards Institution: London, UK, 2016.
222. National Standards Authority of Ireland. SR CEN/TS 14972Fixed Firefighting SystemsWatermist Systems
Design and Installation. National Standards Authority of Ireland, Dublin, Ireland, 2011.
© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).
... Nevertheless, some drawbacks are related to costs and health-monitoring concerns. A cell in a Li-ion battery is composed of the following basic elements: the anode and cathode electrodes, a separator and an electrolyte [12]. The anode is a copper foil, coated with a material characterised by high negative potential (e.g., graphite, lithium, titanate, silicone) [13], while the cathode is an aluminium foil, coated with a material of high specific electrical capacity, which gives the name to the battery type. ...
... The anode is a copper foil, coated with a material characterised by high negative potential (e.g., graphite, lithium, titanate, silicone) [13], while the cathode is an aluminium foil, coated with a material of high specific electrical capacity, which gives the name to the battery type. Since high content of nickel and lithium increases the electrical capacity, the most used materials for cathode coatings are lithium metal oxides (LMO), lithium cobalt oxide (LCO), nickel cobalt aluminium oxide (NCAO), nickel cobalt manganese oxide (NCMO), lithium ferrite phosphate (LFP), lithium ferrite fluor-sulphate (LFSF) and lithium titanium sulphide (LTS) [12,14,15]. The interaction between the anode and the cathode is realised by means of the electrolyte, which enables the transfer of lithium ions between the electrodes, while the separator prevents short circuits. ...
... The safety issues are essentially related to the electrolyte employed for the ionic conductivity. Indeed, to achieve high performance, Li-ion batteries employ electrolytes based on organic solvents, loaded with Li salt, creating a risk of environmental contamination due to leakage and potential flammability [12]. To solve leakage problems, batteries with solid polymer electrolytes have been developed (e.g., Li-Po batteries) and are typically preferred for aerospace applications [16]. ...
Article
Full-text available
Lithium batteries employed in lightweight fixed-wing UAVs are required to operate with large temperature variations and, especially for the emerging applications in hybrid propulsion systems, with relevant transient loads. The detailed dynamic modelling of battery packs is thus of paramount importance to verify the feasibility of innovative hybrid systems, as well as to support the design of battery management systems for safety/reliability enhancement. This paper deals with the development of a generalised approach for the dynamic modelling of battery packs via Thevenin circuits with modular hysteretic elements (open circuit voltage, internal resistance, RC grids). The model takes into account the parameters’ dependency on the state of charge, temperature, and both the amplitude and sign of the current load. As a relevant case study, the modelling approach is here applied to the Li-Po battery pack (1850 mAh, 6 cells, 22.2 V) employed in the lightweight fixed-wing UAV Rapier X-25 developed by Sky Eye Systems (Cascina, Italy). The procedure for parameter identification with experimental measurements, obtained at different temperatures and current loads, is firstly presented, and then the battery model is verified by simulating an entire Hybrid Pulse Power Characterisation test campaign. Finally, the model is used to evaluate the battery performance within the altitude (i.e., temperature) envelope of the reference UAV. The experiments demonstrate the relevant hysteretic behaviour of the characteristic relaxation times, and this phenomenon is here modelled by inserting Bouc–Wen hysteresis models on RC grid capacitances. The maximum relative error in the terminal output voltage of the battery is smaller than 1% for any value of state of charge greater than 10%.
... However, the risk of an arc due to a direct current fault is very high, as experimentally confirmed [4]. In addition, the necessity for a fire detection and prevention system to ensure the safe use of next-generation power sources is emerging, as cases of fire in solar power systems and ESSs have been reported [5][6][7][8]. ...
Article
Full-text available
Every year, diverse types of safety accidents cause major damage to human life and property. In particular, failure to suppress safety accidents caused by fires during the early stages can lead to large-scale accidents, which in turn can cause more serious damage than other types of accident. Therefore, this paper presents an analysis of the prevailing research trends and future directions for research on preventing safety accidents due to fire. Since fire outbreaks can occur in many types of places, the study was conducted by selecting the places and causes involved in frequent fires, using fire data from Korea. As half of these fires were found to occur in buildings, this paper presents an analysis of the causes of building fires, and then focuses on three themes: fire prevention based on fire and gas detection; fire prevention in electrical appliances; and fire prevention for next-generation electricity. In the gas detection of the first theme, the gas referred to does not denote a specific gas, but rather to the gas used in each place. After an analysis of research trends for each issue related to fire prevention, future research directions are suggested on the basis of the findings. It is necessary to evaluate the risk, select a detection system, and improve its reliability in order to thoroughly prevent fires in the future. In addition, an active emergency response system should be developed by operating a fire prevention control system, and safety training should be developed after classifying the targets of the training targets appropriately.
... One of the central challenges in battery fire research is that there is no data evaluation for full-scale battery power systems . To help accelerate research, currently there are more than 20 Li-ion battery fire databases globally (Finegan et al. 2017;Ghiji et al. 2020;Sun et al. 2021). ...
Article
This paper describes the phenomenon of increasing use of Li-ion batteries in both EV and ES applications and the need to investigate battery fire issue especially to the building structures. We suggest the adoption of translational forensics to help accelerate our understanding of battery fires from different stackholders.
... The fire test simulates a vehicle under fire conditions to verify whether the battery system will explode [20,108,109]. SAND2005-3123 [75] requires that the test sample at 100% SOC be placed in a cylindrical fixture heated by radiation for 10 min, where the temperature of the heater is 890 °C. In UL 2580-2020 [77], the external fire is conducted on the bottom surface of the test object and the fire source is located in the middle of the test object. ...
Article
Full-text available
The frequent safety accidents involving lithium-ion batteries (LIBs) have aroused widespread concern around the world. The safety standards of LIBs are of great significance in promoting usage safety, but they need to be constantly upgraded with the advancements in battery technology and the extension of the application scenarios. This study comprehensively reviews the global safety standards and regulations of LIBs, including the status, characteristics, and application scope of each standard. A standardized test for thermal runaway triggering is also introduced. The recent fire accidents in electric vehicles and energy storage power stations are discussed in relation to the upgrading of the rational test standards. Finally, the following four suggestions for improving battery safety are proposed to optimize the safety standards: (1) early warning and cloud alarms for the battery’s thermal runaway; (2) an innovative structural design for a no-fire battery pack; (3) the design of a fire water injection interface for the battery pack; (4) the design of an immersive energy storage power station. This study provides insights for promoting the effectiveness of relevant safety standards for LIBs, thereby reducing the failure hazards.
... In recent years, many incidents caused by lithium-ion batteries have been reported, such as batteries in mobile phones catching fire and the fire incident concerning the lithium battery of the Boeing 787 Dreamliner. Moreover, most of the electric vehicle fire incidents seem to be caused by batteries [1][2][3]. Many lithium-ion battery safety incidents are considered as material or usage issues. ...
Article
Full-text available
A lithium-ion battery is a type of rechargeable battery which is widely used in many applications, such as electronic products and electric vehicles. Practical applications use many lithium-ion batteries which are connected in series and in parallel. Many incidents have occurred due to battery safety issues in recent years. The connection of lithium-ion batteries has safety problems if the batteries are not well controlled in packing and assembling. In this regard, the use of enabling technologies is essential to the proper operation of the batteries’ assembly manufacturing. This paper investigates the manufacturing of lithium-ion batteries smartly controlled by the industrial internet of things (IIoT)-based configuration for a real case. The paper further describes the implementation and its evaluation using various sensor nodes and subsystems. An event data model and a solution present the ability to enable data sharing and interoperability among various components in our work. The solution has highlighted a number of key capabilities and aspects of novelty in lithium-ion battery manufacturing and the IIoT.
Chapter
Conventional power plants generate electricity using fossil fuels (oil, coal, and gas). These power plants are far away from the load area, and transmission and distribution systems are required to manage the load from the conventional power plant. In conventional power plants, most of the issues with grid ancillary services are solved by the large generators themselves. With the advancements and innovations in renewable energy sources and their harnessing techniques, distributed generation has become a novel concept, and the energy storage system (ESS) is an essential component of the hybrid energy system and the smart grid. The ESS helps in mitigating the intermittency of renewable energy sources; it also helps in bridging the gap between energy production and energy demand. With the intermittent and unpredictable nature of renewable energy sources like solar and wind, grid ancillary services are not easy to obtain. The ESS is the best solution to incorporate these services. The ancillary services include grid stabilization, renewable energy integration, power quality, frequency regulation, load following, peak shaving, spinning reserve, time-shifting, and transient stability. Energy is stored in mechanical, chemical, and electrical forms. In mechanical form, energy storing technologies are pumped hydro ESSs, compressed air ESSs, and flywheel ESSs. In chemical form, energy is stored in batteries, flow batteries, and regenerative fuel cells. In electromagnetic form, energy is saved in capacitors, supercapacitors, and superconductors.
Article
Full-text available
All over the world, different countries protect themselves, and their citizens from the effects of fires and accidents with the help of their fire and disaster management services. While executing firefighting or technical rescue and disaster relief tasks, these services use several methods and technical solutions during intervention. The aim is to find the best practices and solutions in the field of technical equipment, organisation and method. The applied methods are the analysis of international publications, papers from the previous years and the author’s own domestic and international experiences. The good solutions found in this research that raise the effectiveness and the safety of the fire services (especially in Hungary) are demonstrated in this paper.
Article
Nowadays, the global trend of reducing exhaust emissions and the increasing the demand for clean energy sources have initiated the development of electric vehicles by many vehicle manufacturers. We are starting to encounter electric vehicles, whose mass production is relatively new, on the roads more and more every day. Fire response methods, which are one of the most common emergencies encountered in electric vehicles, which are widely used, differently in the extinguishing agent and extinguishing methods of fires compared to gasoline or diesel engine vehicles. In this study, the causes of the thermal leak formation mechanism in batteries, which are the most basic place of fires encountered in electric vehicles, will be examined, and information on the methods of intervention to the fire that may occur will be examined. By means of the results obtained from here, the possibilities of application in electric and semi-electric (hybrid) vehicles will be discussed.
Article
A rapid transition in the energy infrastructure is crucial when irreversible damages are happening quickly in the next decade due to global climate change. It is believed that a practical strategy for decarbonization would be 8 h of lithium‐ion battery (LIB) electrical energy storage paired with wind/solar energy generation, and using existing fossil fuels facilities as backup. To reach the hundred terawatt‐hour scale LIB storage, it is argued that the key challenges are fire safety and recycling, instead of capital cost, battery cycle life, or mining/manufacturing challenges. A short overview of the ongoing innovations in these two directions is provided. A practical strategy for energy decarbonization would be eight hours of lithium‐ion battery electrical energy storage, paired with wind/solar energy generation, and using existing fossil fuels facilities as backup. To reach the hundred terawatt‐hour scale battery storage, this work argues that the key challenges are fire safety and recycling, instead of capital cost, battery cycle life, or mining/manufacturing challenges.
Article
Full-text available
Accurate estimation of state of charge (SOC) is critical to the safe and efficient utilization of battery system. Model-based SOC observers have been widely used due to their high accuracy and robustness, but they rely on a well parameterized battery model. This paper scrutinizes the effect of measurement noises on model parameter identification and SOC estimation. A novel parameterization method combining instrumental variable (IV) estimation and bilinear principle is proposed to compensate for the noise-induced biases of model identification. Specifically, the IV estimator is used to reformulate an overdetermined system so as to allow co-estimating the model parameters and noise variances. The co-estimation problem is then decoupled into two linear sub-problems which are solved efficiently by a two-stage least squares algorithm in a recursive manner. The parameterization method is further combined with a Luenberger observer to estimate the SOC in real time. Simulations and experiments are performed to validate the proposed method. Results reveal that the proposed method is superior to existing method in terms of the immunity to noise corruption.
Article
Full-text available
As one of the most promising new energy sources, the lithium-ion battery (LIB) and its associated safety concerns have attracted great research interest. Herein, a comprehensive review on the thermal hazards of LIBs and the corresponding countermeasures is provided. In general, the thermal hazards of the LIB can be caused or aggravated by several factors including physical, electrical and thermal factors, manufacturing defect and even battery aging. Due to the activity and combustibility of traditional battery components, they usually possess a relatively high thermal hazard and a series of side reactions between electrodes and electrolytes may occur under abusive conditions, which would further lead to the thermal failure of LIBs. Besides, the thermal hazards generally manifest as the thermal runaway behaviors such as high-temperature, ejection, combustion, explosion and toxic gases for a single battery, and it can even evolve to thermal failure propagation within a battery pack. To decrease these hazards, some countermeasures are reviewed including the application of safety devices, fire-retardant additives, battery management systems, hazard warnings and firefighting should a hazard occur.
Patent
Use of a secondary anode active material with a redox potential between 0 volts (Li/Li+) and the potential of the primary anode active material. The secondary active material is provide to store Li in situations where the charge rate exceeds the charge acceptance of the primary anode active material, thus forming a reservoir to capture Li and prevent Li plating. The secondary active material may be reversible or irreversible.
Article
Lithium ion batteries (LIBs) are booming due to their high energy density, low maintenance, low self-discharge, quick charging and longevity advantages. However, the thermal stability of LIBs is relatively poor and their failure may cause fire and, under certain circumstances, explosion. The fire risk hinders the large scale application of LIBs in electric vehicles and energy storage systems. This manuscript provides a comprehensive review of the thermal runaway phenomenon and related fire dynamics in singe LIB cells as well as in multi-cell battery packs. Potential fire prevention measures are also discussed. Mitigating the hazards associated with a growing number of LIB applications represents a significant new challenge for the fire safety engineering community. Some perspectives and outlooks on the future of LIB fire safety research and safety engineering are given.