PGB Li Safety JPS 155 (2006) 401-414

Journal of Power Sources 155 (2006) 401–414
Review
Safety mechanisms in lithium-ion batteries

P.G. Balakrishnan, R. Ramesh, T. Prem Kumar ∗
Electrochemical Power Systems Division, Central Electrochemical Research Institute, Karaikudi 630006, Tamil Nadu, India
Received 18 October 2005; received in revised form 1 December 2005; accepted 2 December 2005
Available online 28 February 2006
Abstract
With increasing use of lithium-ion power packs, reports of occasional incidents of severely debilitating and sometimes fatal tragedies appear in
the news. This review analyzes possible scenarios that trigger such hazards before proceeding to discuss safety mechanisms such as pressure release
valves, one-shot fuses, reversible and irreversible positive temperature coefficient elements, shutdown separators, chemical shuttles, non-flammable
electrolytes and coatings.
© 2006 Published by Elsevier B.V.
Keywords: Lithium-ion batteries; Safety; Battery hazard; Non-flammable electrolytes; Thermal runaway
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
2. Lithium-ion battery hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
3. Conventional safety devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
3.1. Safety vents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
3.2. Thermal fuses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
3.3. Other circuit breakers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
4. Self-resetting devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
4.1. Ceramic PTC materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
4.2. Conductive-polymer PTC devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
5. Shutdown separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
6. Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
6.1. Non-flammable electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
6.2. Redox shuttles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
6.2.1. Halide shuttles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
6.2.2. Metallocene shuttles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
6.2.3. Aromatic redox shuttles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
6.3. Shutdown additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
6.4. Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
6.5. Electrolyte salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
6.5.1. LiPF3 (C2 F5 )3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
6.5.2. LiN(SO2 CF3 )2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
6.5.3. LiBC4 O8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
7. Active materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
7.1. Carbon anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
7.2. LiCoO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
∗ Corresponding author. Tel.: +91 4565 227888/227550–9; fax: +91 4565 227779.
E-mail addresses: premlibatt@yahoo.com, prem@cecri.res.in (T. Prem Kumar).
0378-7753/$ – see front matter © 2006 Published by Elsevier B.V.

doi:10.1016/j.jpowsour.2005.12.002
402 P.G. Balakrishnan et al. / Journal of Power Sources 155 (2006) 401–414
7.3. LiNiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410

7.4. LiMn2 O4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
7.5. LiFePO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
8. Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
1. Introduction They can suffer premature failure if subjected to conditions for

which they are never designed. Any abuse, including dispos-
Perhaps the word lithium itself has questions of safety tagged ing in fire, overcharging, external short circuiting or crushing,
to it. In fact, safety is a recurring theme even with lithium-ion can trigger spontaneous heat-evolving reactions, which can lead
cells where metallic lithium is replaced with lithium-insertion to fire and explosion. Lithium-ion batteries must pass a num-
active materials. Ridden with a poor understanding of the ber of safety tests before they can be certified for use by a
fledgling lithium-ion battery technologies, what manufactur- consumer. The tests include electrical tests such as external
ers and consumers fear are accidents during use or inadvertent short circuit, mechanical tests such as nail penetration, crush-
abuse. For example, in an incident that occurred at Apple in ing, dropping to the ground, and environmental tests such as
1995, lithium-ion batteries got overcharged during an in-house heating in a microwave oven, throwing into a hot liquid, and
testing of a newly manufactured PowerBook 5300 portable com- leak tests in a vacuum. Several techniques have been devised to
puter [1]. Apple then removed all lithium-ion power packs from improve safety. They include use of safety vents, positive tem-
their product lines [2]. Hereabouts, Ericsson announced that perature coefficient (PTC) elements, shutdown separators, more
its mobile phones and other portable electronic applications oxidation-tolerant or less flammable electrolyte constituents and
would wean away from lithium-ion batteries [3]. In fact, several redox shuttle mechanisms. In this paper we review safety mech-
other OEM manufacturers have also been proactive in recalling anisms adopted in commercial lithium-ion batteries.
their products. In 2000, in cooperation with the U.S. Consumer
Product Safety Commission, Dell voluntarily recalled 27,000 2. Lithium-ion battery hazards
lithium-ion batteries, manufactured by Sanyo Electric Co. Ltd.,
and sold in notebook computers. Compaq also recalled 55,000 Apart from the fact that lithium batteries have highly oxidiz-
notebook lithium-ion batteries manufactured by Sony Corpora- ing and reducing materials, their safety is compounded by the
tion because of a defect in the circuit board that controls the fact that the design of these non-aqueous cells has an inherent
recharge and discharge processes. One of the recent lithium-ion drawback of poor heat dissipation. Compared to lithium metal-
battery recalls with the USPSC was in 2002 when, upon receiv- anode batteries, lithium-ion cells are considered to be safer.
ing five reports of batteries overheating (in three of the instances The redox potentials of metallic lithium and lithiated carbons
they caught fire), EV Global Motors Company announced the (Lix C6 ), for example, are similar. The reactive surface area of
recall of 2000 batteries in their electric bicycles. the carbonaceous anode with a typical particle size of about
Withdrawal of products, loss of market and even a ban on 10 ␮m is large. Although the specific surface area of the lithi-
lithium-ion batteries were part of a backlash prompted by these ated carbon electrode has been demonstrated to increase by a
incidents. Thus arose the need for safety in commercial lithium- factor of five upon cycling [8], the reactivity of anode is kineti-
ion battery applications. Today, lithium-ion batteries are the cally limited by the slow transport of lithium from the galleries to
state-of-the-art power sources for a variety of portable electronic the surface of the graphitic electrode [9–11]. Another important
devices. They combine high energy density and excellent cycle factor that contributes to enhanced safety of lithium-ion batteries
life, and have no memory effect. That no lithium battery-related vis-à-vis lithium metal anode batteries is the much higher melt-
accident has been reported in the recent past is testimony to ing point of Lix C6 as compared to that of lithium metal. The
improved safety characteristics of present-day lithium battery low melting point of lithium (180 ◦ C) poses an additional risk of
products. The excellent safety record has been brought about fire hazard from molten lithium generated by inadvertent over-
by regulations governing the safety of the cells [4]. Continual heating. However, exothermic reactions between Lix C6 and the
improvements in safety are being made especially with large electrolyte can be triggered by the application of heat [12,13].
battery packs as for electric traction and load leveling [5]. The The potential ranges experienced in common 4-V lithium-
gravity of the situation becomes evident considering the market ion cells are beyond the thermodynamic stability windows of
share for lithium batteries. Of the US$ 37 billion battery market the electrolytes. Electrolytes, therefore, decompose upon con-
in 2000, about US$ 2.9 billion was shared by lithium batteries, tact with the charged active materials, both anodes [14–19] and
the share for primary and secondary lithium batteries being US$ cathodes [20–24]. The interface between the cathode and the
1.1 and 1.8 billion, respectively [6]. According to a prediction electrolyte is further complicated by partial dissolution of the
rechargeable lithium battery market should grow to more than positive active materials [25–27]. This is particularly a problem
US$ 2.1 billion by 2009 [7]. at the end of charging and at elevated temperatures, conditions
Lithium-ion batteries combine highly energetic materials in under which electrolyte oxidation can proceed at accelerated
contact with a flammable electrolyte based on organic solvents. rates [28–34].
P.G. Balakrishnan et al. / Journal of Power Sources 155 (2006) 401–414 403
The temperature of a cell is determined by the heat balance leakage or venting of corrosive or toxic materials in the bat-
between the amount of heat generated and that dissipated by the tery; both chemical and physical hazards can cause equipment
cell. When a cell gets heated above a certain temperature (usu- damage due to breakage or corrosion of electrical/electronic
ally above 130–150 ◦ C), exothermic chemical reactions between components; environmental hazards arise from the reactive and
the electrodes and electrolyte set in, raising its internal temper- flammable nature of lithium and/or leakage of toxic materials
ature. If the cell can dissipate this heat, its temperature will from batteries that are improperly disposed.
not rise abnormally. However, if the heat generated is more than An area that has often been overlooked is the possible embrit-
what can be dissipated, the exothermic processes would proceed tlement of container metal with lithium (similar to hydrogen
under adiabatic-like conditions and the cell’s temperature will embrittlement). This can happen if the metal in question is
increase rapidly. The rise in temperature will further accelerate capable of alloying with lithium. In such a case, a spontaneous
the chemical reactions, rather than the desired galvanic reactions, transfer of lithium to the alloying metal casing can occur [42].
causing even more heat to be produced, eventually resulting in This can lead to a structural destruction of the container mate-
thermal runaway [9,35,36], whose onset temperature determines rial, resulting in leakage paths. Lithium embrittlement at highly
the safety limit of the device. Any pressure generated in these stressed regions of battery containers can accelerate crack prop-
processes can cause mechanical failures within cells, triggering agation. Although lithium battery leakages have been observed,
short circuits, premature death of the cell by irreversible inter- no conclusive evidence is available to merit extensive research
ruptions in the current path, distortion, swelling and rupture of in this direction.
cell casing.
It is clear that the thermal stability of batteries depends on its 3. Conventional safety devices
ability to dissipate the heat. The ability of an object to absorb
heat is defined by its thermal capacity. Obviously, for a given A predominant mechanism by which lithium batteries are
amount of heat, bigger and heavier objects would suffer less rendered safe involves limiting the current passing through them.
temperature rise than would a similar object that is smaller and Current-limiting devices such as positive thermal coefficient
lighter. Thus, for lithium-ion batteries, which are designed for devices are designed to respond to high temperatures. Several
applications where size and weight are a premium, a decrease in factors play a role in the operation of these devices: the ambient
the thermal capacity is an unavoidable penalty. Thus, heat dissi- temperature, thermal insulating properties of the container, heat
pation in lithium-ion batteries turns out to be a major engineering generated in the equipment, cumulative heat in the battery pack,
challenge, especially for those designed for high power appli- and rate and duration of discharge. Thus, it becomes necessary to
cations. Designs for effective heat dissipation must be adopted consult the manufacturer or conduct tests in order to determine
both at the cell and battery pack levels. Heat dissipation can the suitability of a battery pack for a particular application.
occur by convection and radiation at the surface of the cell. Heat Apart from preventing flow of excessive currents that can
dissipation by convection depends, among other things, on the potentially damage cells, current-limiting protection devices
external surface area and geometry of the cell. However, heat must withstand continuous flow of the load’s design current
dissipated by radiation depends on the nature of the surface and tolerate normal surges and transients. Furthermore, safety
of the cell and makes up nearly 50% of the dissipation [37]. devices must also fit into very small spaces and must be rela-
Radiation dissipation can be improved by use of cell cases that tively cheap. For acceptance in commerce, the current-limiting
have high thermal conductivity and labels that have high emis- device must be fail-proof, which also means that it should not
sivity. Thermal performance is rarely a cause for cell failure be prone to false tripping, factors that can decide customer dis-
in low-power cells that have simple designs. However, thermal satisfaction. It must be pointed out that batteries regulated with
design of high-power cells is not that simple. Poor designs can external electronic devices such as PTC elements and integrated
result in localized hotspots within the cell, which can lead to cell circuits would not only have higher manufacturing costs but also
failure. lower energy density.
Possible exothermic reactions that trigger thermal runaway
include [36,38]: (i) thermal decomposition of the electrolyte; 3.1. Safety vents
(ii) reduction of the electrolyte by the anode; (iii) oxidation of
the electrolyte by the cathode; (iv) thermal decomposition of the Conventional safety mechanisms include such devices as
anode and cathode; and (v) melting of the separator and the con- vents and current-limiting devices like fuses and circuit break-
sequent internal short. Moreover, high-voltage metal cathodes ers. Safety vents open in response to a sudden increase in cell
are known to release oxygen at elevated temperatures [39,40]. pressure, allowing gases to escape. If the pressure inside a cell
Thermal runaway is often caused under abuse conditions, which builds up, a plastic laminate membrane is punctured by a spike
can be thermal (overheating), electrical (overcharge, high pulse incorporated in the vent in the cell top. A safe release of internal
power) or mechanical (crushing, internal or external short cir- pressure precludes dangerous rupture of the cell casing. Safety
cuit) [36,41]. vents can be designed to operate at pre-set internal cell tempera-
It must be noted that the release of materials from batteries can tures. Today, vents are a back-up safety device. During instances
be benign, mild or violent. Battery hazards are classified accord- of electrical abuse, other devices such as a positive temperature
ing to the damage they cause [35]. Physical hazards involve a coefficient device (described below) override the vent. If bat-
simple rupture of battery case; chemical hazards result from teries are subjected to severe mechanical abuse conditions, the
safety vent provides a means of releasing internal pressure and Thermistors sense the internal temperature of the battery,
prevents the cell from reaching excessively high temperatures. and provide information to an external control through a cali-
Kato et al. [43] developed a safety mechanical link by which brated resistance. Thermistor controls may be located in a battery
a concave aluminum disk welded to the cathode would break charger. The thermistor is attractive as the control can be set to
the circuit upon release of gas. In this design, lithium carbonate meet specific conditions of charge and to regulate input current
deliberately added to the LiCoO2 cathode mix would decompose to the battery. This device can also be used to control the bat-
to yield CO2 when the cell is overcharged to greater than 4.8 V. tery through T/t control, where T and t are the temperature
The built-up pressure would push the aluminum disk, discon- and time, respectively. PTC thermistors have a positive temper-
necting the cathode lead from the circuit. This simple mechanism ature coefficient, as will be described below. Similarly, thermis-
prevents the cell from the thermal runaway caused by an exces- tors whose resistances decrease with increasing temperature are
sive overcharge. Choi et al. [44] have shown that in addition to called negative temperature coefficient (NTC) thermistors. Both
providing safety, the added lithium carbonate can suppress the are used for monitoring and protection of control circuits.
initial irreversibility of the carbon anode. The thermostat or temperature cut-off (TCO) devices oper-
Since the safety vent opens up the cell, spewing out a signif- ate at a fixed temperature, and can be used to terminate charge
icant quantity of volatile organics, it is used as a back-up safety (or discharge) when a pre-set internal battery temperature is
device. In fact, other safety devices such as PTC elements over- reached. TCOs are usually resettable. They are connected in
ride the safety vent during abuse. Under severe mechanical and series with the cell stack.
electrical abuse conditions, the vent provides a safe means of Electronic safety circuits, commonly referred to as protection
releasing internal pressure before the cell reaches excessively circuit module (PCM), are usually attached to battery packs as
high temperatures. separate modules. In the event of a wrongful condition, such
as short circuit, the PCM opens the battery circuit and prevents
3.2. Thermal fuses damage to the pack. Some groups believe that the cell chemistry
in lithium-ion cells can be modified and safety levels raised,
The oldest and most common current limiter is the one-shot rendering PCMs redundant [45].
fuse, which is a wire of a fusible alloy with resistance and ther- Unlike aqueous electrolyte cells, which have an inher-
mal characteristics that allow it to melt when a pre-set current ent balance-adjusting mechanism such as gas recombination,
flows through it. Some fuses require several seconds to trip, but lithium-ion cells require an external overcharge/overdischarge
they are inherently fast-acting. The advantages of the fuse as a protection system, particularly those for use in specialized appli-
safety device lie in its simple construction, low cost and avail- cations as in electric traction and spacecraft. This can be pro-
ability in a wide range of currents and voltages ranges. Fuses act vided through an electronic control circuit. However, the cost
by destroying themselves, thereby positively and permanently component of the circuits is kept small as compared to the
opening the circuits they protect. Thus, they must be replaced cost of the batteries themselves. The basic circuitry consists
once blown, which is another advantage (as it draws the atten- of a bypass circuit controlled by a microchip based on MOS-
tion of the user to take action for resuming service) although FET. The bypass circuit gets activated when a cell in a pack
the mechanical action involves labor. However, fuses can pre- reaches a given state-of-charge/discharge earlier than other cells.
maturely blow under other conditions such as pulse discharges Thus, the charge/discharge process is terminated until balance is
(or repeated pulse discharges that can degrade the alloy), which regained. Open-circuit voltage of lithium-ion cells can be used
are normal operational modes of batteries. Moreover, there is the as indicators of their state-of-charge, electronic controllers can
possibility of inadvertent replacement with fuses with higher or be designed to sense voltages and, thereby, switch on or off
lower current ratings, which can result in improper use of equip- the charging/discharging circuit. This ensures charge balance
ment. Fuses are wired in series with the cell stack and will open among cells in a pack and damage by overcharge/overdischarge
when a pre-set cell temperature is reached. Thermal fuses are of individual cells. In specialized applications, battery packs
employed as protection against thermal runaway and are usually come with protection circuits that monitor cell temperature and
set to open at 30–50 ◦ C above the maximum operating temper- activate cooling gadgets such as fans.
ature of the battery. Fuses are cheap and are ideal for low-cost,
throwaway products with limited warranties. 4. Self-resetting devices
3.3. Other circuit breakers Factors such as inconvenience of replacement and prema-
ture failure of fuses (which call for time-consuming technical
Other circuit breakers such as magnetic switches, bimetallic services), unsuitability of integrating devices such as mag-
thermostats and electronic protection circuit modules can be netic/thermal switches onboard, size restrictions and cost led
used to protect power packs and to monitor their temperature. to a search for a self-resetting, fuse-like device. Thus, emerged
They must also tolerate continuous design current as that of safety devices called positive temperature coefficient devices
the load as well as occasional current surges, without tripping. based on materials whose resistance increases dramatically with
However, their size and cost often rule out the application of the a rise in temperature. For example, if a large current flows across
first two in many onboard circuits, especially where space is at the PTC element, as during external short circuiting, its temper-
a premium. ature rises up abruptly up due to Joule heat evolution within the
PTC element. A concomitant and abnormally high resistance of ders their reaction time to moderate over-currents longer than
the PTC element prevents current flow. Thus, upon activation, those of the components in the gadget. The sluggish response
the resistance of the PTC element shoots up, leading to a precip- can damage costly equipment.
itous fall in the current, which limits heat generation in the cell.
Once the cause for alarm is removed, the cell and PTC element 4.2. Conductive-polymer PTC devices
cool and the resistance of the latter drops, allowing resumption
of charge/discharge. PTC elements are generally installed inside Conductive-polymer PTC devices are non-linear PTC ther-
cells. The temperature above which the resistance of the PTC mistors based on a composite of polymers and conductive par-
element jumps to an infinite value is called the “trip tempera- ticles. It is known that above their glass transition temperatures
ture,” whose value is generally set at about 100 ◦ C. (Tg ) polymers transform into an amorphous state and return to
Although the primary purpose of PTC devices is to protect their crystalline state upon cooling to temperatures below their
batteries against external short circuits, they also provide pro- Tg . At normal operating temperatures, the conductive particles
tection under certain other electrical abuse conditions. This is embedded in a crystalline polymer matrix provide a low resis-
accomplished by limiting current flow when the cell temperature tance path for current flow. At elevated temperatures (typically
reaches the designed activating temperature of the PTC device. ∼125 ◦ C), the polymer’s structure changes to an amorphous
For extended equipment life, the PTC must work reversibly. state. The accompanying expansion of the matrix breaks the
Although PTC devices can operate in this way several times, it conductive pathway between the embedded particles, rapidly
will not reset indefinitely. Fortunately, when they cease to reset, increasing the device’s resistance by several orders (Fig. 1). This
they remain in their high-resistance condition, rendering the cell reduces the current to a relatively low and safe level. An advan-
unusable. PTC devices usually come as surface-mountable units tage of PTC devices is that this trickle current maintains the
and are compatible with pick-and-place equipment. Thus, they internal temperature of the cell high, prevents the conductive
carry little assembly-costs. But because they are costlier than chains from returning to their original state. In other words,
fuses, they become economically attractive only when used in the trickle current “latches” the PTC device in its tripped state.
equipment that are costly or demand long-term warranties. Upon opening the circuit the device cools, allowing the polymer
matrix to return to its normal state and returns the resistance of
4.1. Ceramic PTC materials the device to its normal low value. Fig. 2 shows the variation of
the resistance of a PTC device as a function of temperature.
Ceramic materials with fuse-like action were the materials Conductive-polymer PTC devices are made from a blend
of choice for early PTC elements. Ceramic PTC devices can of plastics and conductive materials. The temperature of the
operate under high voltages and can return to their normal resis- conducting-polymer PTC device is determined by the ambient
tance mode with great accuracy. Thus, they are attractive for temperature and heat generated by internal I2 R losses. Under
application in several high-voltage circuits although their rela- normal operating conditions, the I2 R losses are too low to gen-
tively large sizes preclude their use in miniature high-component erate enough heat to transform the polymer into its amorphous
density gadgets. It must be noted that their applicability in low- state. However, under abuse conditions when large currents flow
voltage circuits is undermined by their high inherent resistance, through the device, the I2 R losses become sufficiently high,
the high voltage drop across which can cause problems with increasing the temperature and hence the resistance of the PTC
the operation of the gadget. Another intrinsic disadvantage with element. The reduction in the current in turn reduces the I2 R
ceramic PTC materials is their high thermal mass, which ren- losses. Upon regaining thermal equilibrium, the PTC device
Fig. 1. Principle of a conductive-polymer PTC device. Distribution of ceramic particles at: (a) normal operating temperature and (b) trip temperature.
permeability, these microporous separators display a protective

property during cell abuse. For example, if the cell temperature
rises abnormally because of an excessive overcharge, for exam-
ple, the heat generated softens PE and closes the micropores
in the film. This is called separator “shutdown” [50,51]. Once
shutdown occurs, ionic transport between the electrodes is effec-
tively stopped and current ceases to flow [51]. If the separator
can retain mechanical integrity above its shutdown temperature,
it can provide a margin of safety to the device; otherwise, the
electrodes can come into direct contact, react chemically, leading
to thermal runaway. However, it is possible that due to thermal
inertia the temperature can continue to rise even after shutdown.
Under such conditions the separator would melt and short the
electrodes, leading to violent reactions and heat generation. This
Fig. 2. Representation of the variation in the resistance of a PTC device as a phenomenon is called “meltdown” or “breakdown” of the sep-
function of temperature. arator [48]. Therefore, in order to ensure safety of the cell, the
difference between the “shutdown” and “meltdown” tempera-
allows a circuit current insufficient to cause damage but enough tures should be as large as possible.
to maintain the device’s trip temperature. The safety device thus Separators made entirely of high-density polyethylene melt
gets latched in its tripped state. It must be pointed out that at 135 ◦ C and lose mechanical integrity above this temperature.
conductive-polymer PTC devices allow a small residual leakage However, separators made by laminating layers of polypropy-
current through the circuit after its tripped state. The resulting lene and polyethylene maintain mechanical integrity at least up
voltage drop across the device can be a concern in certain gad- to 165 ◦ C, the melting point of polypropylene. It is interesting
gets, especially those that demand precise power requirements. to note that although ultrahigh molecular weight polyethylene
Conductive-polymer PTC current-limiters still have some melts at 135 ◦ C, separators made from this material retain their
inherent problems. Although they can trip in a few millisec- mechanical integrity up to at least 180 ◦ C as the viscosity of the
onds’ time, their response times are still inferior to those of material is such that it maintains physical integrity. Shutdown
fuses. However, they are suitable for applications where a slow- separators are reliable and lithium-ion battery manufacturers are
blow fuse-like characteristic is tolerated. They are also costlier increasingly opting for their incorporation in their products.
than common fuses. Moreover, the maximum current and volt- The most common shutdown separators have high molecu-
age they can tolerate are also limited. However, as compared lar weight polypropylene blended with super-high molecular
to their ceramic counterparts, conductive-polymer PTC current weight polyethylene [45]. Here, the unique shutdown property
limiters have low normal resistances, which means that they of polyethylene is combined favorably with the high mechanical
do not influence the normal operation of the battery. Moreover, integrity of polypropylene at elevated temperatures. Because the
because of their low thermal mass, polymeric PTC devices react shutdown is irreversible, once actuated, these separators leave
quickly to over-current conditions. Additionally, small surface- the cells permanently damaged.
mount polymeric PTC devices can be constructed.
As noted above, an important concern with external safety 6. Electrolytes
mechanisms such as PTC devices is their ability to respond when
hazardous reactions occur at high rates [46]. In order to obviate The key to a safe high-performance lithium-ion cell lies in
this problem, Feng et al. [47] developed an internal self-actuating the identification of a suitable electrolyte. Lithium is intrinsi-
thermal cut-off mechanism. Here, the electrodes themselves cally unstable with any commonly known electrolyte. More-
would have a PTC effect, an effect that is achieved by coating over, lithium battery electrolytes based on alkyl carbonate
the current collector with a suitable PTC material. According to solvents are known to react vigorously at elevated temper-
Feng et al. [47], this would be much more responsive to inter- atures with lithiated graphite and delithiated cathodes (e.g.,
nal heat changes than external PTC devices, providing cut-off at Lix CoO2 (x < 0.5)) [19,52–54]. At elevated temperatures, the
a pre-set activation temperature. Moreover, these internal PTC SEI on the graphite anode gets destroyed, allowing rapid and
devices are reversible, which ensures reusability of the batteries direct reaction with the lithiated graphite underneath the pas-
once the reason for heat build-up is removed. sivating layer. In their delithiated forms, cathodes are highly
oxidizing and enter into exothermic reactions with alkyl car-
5. Shutdown separators bonates, especially at elevated temperatures. Careful calori-
metric studies have thus become mandatory to determine
Separators for lithium-ion batteries are polyolefin microp- the safety of electrode–electrolyte combinations. According
orous films and are generally uniaxially drawn polyethylene to Aurbach et al. [55], commonly used electrolytes such as
(PE) and polypropylene (PP), biaxially drawn PE or multi- LiPF6 in EC–DEC–DMC are only a compromise. They are
axially drawn PP/PE/PP [48,49]. In addition to conventional flammable and their electrochemical windows are limited to
characteristics such as good mechanical strength, electrolyte about 4.5 V. Alternatives to such alkyl carbonate solvents are
not on the horizon although alternative salts such as lithium

bis(oxalato)borate, LiBC4 O8 (LiBOB) [56], and lithium flu-
oroalkylphosphates (e.g., Li[PF3 (C2 F5 )3 ]) [57–59] are being
considered in place of LiPF6 . Aurbach et al. [55] suggest that
under the circumstances, it is only prudent that additives that
can protect electrode-active materials even at high temperatures
by forming highly protective films on the electrodes be investi-
gated. In fact, new formulations of solvents and salts are unveiled
continually with an eye on safety and performance. A number
of additives are also being investigated to make up for problems
due to protective films at the positive and negative electrodes.
Additives have also been sought to lower electrolyte flammabil-
ity under cell venting. Redox couples that shuttle back and forth
Fig. 3. A schematic showing the working of a redox shuttle. Compound R gets
as additives to limit overcharge and additives that produce gas for oxidized at the positive electrode to O, which diffuses to the negative electrode
activating current interrupter devices have also attracted interest. and gets reduced to the original molecule.
6.1. Non-ﬂammable electrolytes

positive electrode at potentials slightly higher than the typi-
Solvents used in lithium-ion batteries are typically low- cal charging plateau. The oxidized forms of these molecules
boiling and have flash points around 30 ◦ C. Thus, a major danger diffuse to the negative electrode, where they get reduced with-
from a cell that vents or explodes arises from the flammabil- out side-reactions back to the starting neutral molecules, which
ity of the hot electrolyte vapors that are spewed out. Although then shuttle back to the positive electrode (Fig. 3). Thus, redox
identification of a solvent–salt combination that not only pos- shuttles shunt the excess charge injected into the cell during
sesses desirable properties for use in batteries but also has the overcharge. In this way, redox shuttles can indefinitely ‘lock’ the
ability to resist combustion under heat or in the presence of an cathode potential at the oxidation potential of neutral molecules
external flame may only be a dream, it is possible to develop elec- until termination of the charge. In principle, all the Faradaic cur-
trolytes that are not easily flammable [60–67]. Thus, the aim is rent goes for the reversible reactions, which means that the redox
to look for “low flammability” or “flame retarding” electrolytes couple acts as a controlled internal short. A necessary condition
that do not support continued combustion when the source of is that both the oxidized and reduced forms of the molecules be
heat, spark or flame is withdrawn. An important consideration mobile in the electrolyte.
here is that the heat of reaction of the electrolyte with the charged It is possible to visualize scenarios under which the over-
electrode materials should also be low so that a self-sustaining charge current becomes too high for the redox couple to carry,
combustion reaction does not occur under accidental heating. letting the excess current to delithiate the cathode and causing
Present-day electrolyte formulations are a trade-off between irreversible decompositions. To avoid consequent safety hazards
the electrolyte’s flammability and performance in the cell. The arising under this condition, the current limit that can be shunted
reduced battery performance is due either to electrochemical should be maximized by employing large concentrations of the
instability (which leads to capacity fading) or increased viscos- shuttling molecules [70]. The identification of such a redox
ity of the additive (which affects capacity utilization and power). species is fraught with several conditionalities: (i) both the
Since performance cannot be sacrificed, studies mostly focus on oxidized and reduced forms of the redox molecule must not
flame-retardants as the additives or co-solvents in known elec- only be inert towards cell constituents, but also have sufficient
trolytes [60–64]. Fluorinated compounds [61] and organophos- thermal stability; (ii) the solubility and diffusion coefficient of
phorus compounds [61,62,68] are among the most investigated the shuttling molecules in the non-aqueous battery electrolyte
as co-solvents to decrease flammability. For example, trimethyl should be high; (iii) the oxidation potential of the redox
phosphate, a popular flame retardant, has been studied for its couple must be lower than the decomposition potential of the
electrochemical stability on the positive and negative electrodes electrolyte solvents but slightly higher than the overcharge
of lithium-ion cells [60–63]. However, it is important to note that cut-off voltage; (iv) the shuttle must be electrochemically
since electrolytes react with the active materials in lithium-ion reversible and must not enter into side-reactions; and (v) the
batteries, the surface chemistry at the anode and cathode is a reversibility of the couple should last for the entire lifetime
key factor that decides cell performance. Therefore, the design of the cell. A number of soluble redox couples have been
of new electrolytes must also consider the properties of the SEI suggested as shuttles for overcharge protection, but they work
formed with the electrolyte. only at high charging voltages, which means they actually do
not respond to heat generation in batteries.
6.2. Redox shuttles
6.2.1. Halide shuttles
Redox shuttles are among the most promising mechanisms The earliest shuttles, employed for 3-V lithium metal
for overcharge protection [69]. The working of redox shuttles, batteries, were based on halides [71,72]. For example, the
added to electrolytes, involves electrochemical oxidation at the iodine/iodide couple can be oxidized at the cathode at 3.20 V
and reduced at the lithium anode. Halide shuttles were, how- son they are called “shutdown additives” in the battery indus-
ever, abandoned as the volatility and reactivity of the oxidized try [81,83]. There are two classes of shutdown additives: one
forms (free halogens) rendered such cells impracticable. releases gases, which in turn activate a current interrupter device,
while the other undergoes polymerization, thereby blocking ion
6.2.2. Metallocene shuttles transport in the electrolyte. Gas-releasing shutdown additives
Metallocenes, which form redox pairs, MC/MC+ , are among include biphenyl [81,84], cyclohexylbenzene [81], pyrocarbon-
the earliest chemical shuttles investigated, and were tested in ates [81] and phenyl-tert-butyl carbonate [85]. Biphenyl and
3-V lithium cells [73–76]. The redox potentials of these couples other substituted aromatic compounds constitute the polymer-
can be tuned by varying the substituent groups at the cyclopen- izable class of shutdown additives [86–88]. It can be deduced
tadienyl rings [77]. In fact, the potential can be tailored by as that both the gassing and polymerizable additives are sure-shots
much as 450 mV by varying the number and electron-donating against overcharging. Thus, an approach to a reliable line of
or electron-withdrawing nature of the substituents. Ferrocene defense against catastrophic failure due to overcharging would
shuttles have withstood over a hundred “turnovers” in lithium be to incorporate a redox shuttle and a shutdown additive in
cells. However, ferrocenes can block ionic paths on the sur- the cell such that the activation potential of the latter is higher.
face of the cathode, which can reduce the power capabilities of Nevertheless, given the paramount importance of safety, espe-
the cell. Moreover, their adsorption on the cathode can result cially in consumer gadgets and children’s toys, redox chemical
in capacity loss [74]. The situation is more complex in the shuttles, which can only provide limited overcharge protection
case of lithium-ion cells, for application in which the poten- [79,89] and cannot prevent catastrophic failure as obtained dur-
tial of the redox couple must be higher than the end-of-charge ing severe overcharging, shutdown protection mechanisms such
electrode potential (say, 4.3 V versus Li+ /Li). Additionally, the as polymerizable additives must be incorporated even at the cost
SEI-covered graphite electrode in lithium-ion cells does not sup- of termination of useful life of the battery. Some studies have
port the reduction of MC+ , rendering the soluble redox couple extended the polymerization reaction into the separator, immo-
inoperable. bilizing the electrolyte [90].
6.2.3. Aromatic redox shuttles 6.4. Ionic liquids

Redox shuttles based on aromatic compounds have also been
investigated. They include 3-V cell shuttles such as tetracya- Several room temperature ionic liquids (molten salts) present
noethylene and tetramethylphenylenediamine [78]. The selec- themselves as possible electrolytes in lithium-ion batteries
tion of 4-V cell shuttles for lithium-ion cells based on LiMn2 O4 , [91–95]. Not only are they not prone to forming SEI on
LiCoO2 and LiNiO2 , however, presents more challenges as only the electrodes, they have inherent safety characteristics by
a handful of substances are amenable to reversible turnover at virtue of their thermal stability, non-flammability, non-volatililty
potentials around 4.0 V versus Li+ /Li. These include complexes and low heat of reaction with active materials. The non-
of cerium, iridium, iron or ruthenium with phenanthroline or flammability is effective in preventing batteries from catching
bipyridine. Again, their redox potentials can be tuned by varying fire, while non-volatility prevents batteries from bursting. Fur-
the number, nature and position of the substituents on the aro- thermore, they have favorable electrochemical stability win-
matic rings [79]. However, their shunting currents are low due dows for application in lithium-ion cells. One of the central
partly to their limited solubilities in non-aqueous electrolytes issues is identification of ionic liquids with sufficient lithium-
and partly to the low diffusion coefficients resulting from their ions to allow high flux of lithium-ion through the electrolyte
large sizes and molecular weights. [96].
According to Adachi et al. [79] anisole-based compounds, Ionic liquids based on the (1-ethyl-3-methylimidazolium)
which have high solubility in lithium battery electrolytes, should cation are particularly interesting because of their low viscosi-
make for a better class of redox shuttles. Anisole compounds ties [97–99], but are not sufficiently stabile towards reduc-
with two methoxy groups at 1,2-(ortho-) and 1,4-(para-) position in the lithium-ion cell environment [95]. An other-
tions display reversibility at the 4-V region [79]. The authors wise potential electrolyte, the imidazolium salt, 1-ethyl-3-
suggest an empirical structure–property relationship for anisole- methylimidazolium tetrafluoroborate (EMI-BF4 ), has a reduc-
type shuttles, which can help in the design and selection of tion potential of about 1 V versus Li+ /Li, which is too high
more efficient redox shuttles [80]. Adachi et al. [79] conclude for lithium battery electrolytes [93,99–102]. However, with the
that 4-bromo-1,2-dimethoxybenzene provides the best shunt- hope that the reduction potential of the EMI+ cation can be
ing performance among 4-V shuttles. Furthermore, anisole-type tailored by incorporation of organic functional groups [100],
shuttles are stable against reduction at carbonaceous anodes. Hayashi et al. [103] developed alkylated EMI-BF4 molten
Other 4-V shuttles reported in the literature include bipyridyl salts, 1-ethyl-2,3,4,5-tetramethylimidazolium tetrafluoroborate
and biphenyl carbonates as well as difluoroanisoles [81,82]. and 1,2-diethyl-3,4(5)-dimethylimidazolium tetrafluoroborate.
Both salts exhibited very little decomposition at 0 V versus
6.3. Shutdown additives Li+ /Li and a wide electrochemical window (up to 5 V ver-
sus Li+ /Li). Additionally, the latter electrolyte had a relatively
Some less known additives, also intended for overcharge low melting point of about 20 ◦ C and a good specific con-
protection, terminate cell operation permanently. For this rea- ductivity of 1.44 mS cm−1 at 20 ◦ C. Quaternary ammonium
cations are another class of compounds that can withstand reduc- 6.5.2. LiN(SO2 CF3 )2
tion at the anode. Sakaebe and Matsumoto [104] have shown Commonly known as LiTFSI, lithium bis(trifluoromethyl-
higher coulombic efficiency and larger utilization of the pos- sulfonyl)imide [121] has an electronic structure that delocalizes
itive electrode as well as improved safety with a N-methyl- its negative charge, thereby reducing ion pairing [122]. LiTFSI
N-propylpiperidinium–bis(trifuoromethanesulfonyl)imide elec- also has good thermal and hydrolytic stability. Although good
trolyte. It is hoped that with sustained research an ionic liquid cycling efficiencies with lithium have been reported [123] with
electrolyte with desirable safety and electrochemical character- LiTFSI, it tends to corrode the aluminum current collector in
istics will emerge. cells with LiCoO2 electrodes [124] for which the nominal rated
voltage is 4.1 V. Wang et al. [125] demonstrated superior rate
6.5. Electrolyte salts capability of Li4 Ti5 O12 /LiCoO2 cells in which solutions of
the salt in 3-methoxypropionitrile or 3-ethoxypropionitrile were
State-of-the-art lithium-ion cells use LiPF6 as electrolyte salt. used as the electrolyte.
However, LiPF6 is thermally unstable and decomposes to LiF
and PF5 [105,106], a reaction that gets accelerated in the pres- 6.5.3. LiBC4 O8
ence of organic solvents. PF5 hydrolyzes to form HF and PF3 O, Chelating boronate salts with six- and seven-membered rings
which react with both the anode and cathode, deteriorating cell [126] as well as those with five-membered rings [119,127] on the
performance [107]. However, LiPF6 possesses some properties boron atoms are presently being considered. The unsubstituted
desirable for lithium-ion battery environment that replacing the five-member ring salt, lithium bis(oxalato)borate, commonly
salt will entail certain trade-offs. But today it is the best com- called LiBOB, has been found to have good high-temperature
promise, for alternatives to LiPF6 pose too many problems [55]: stability [57]. LiBOB has many unique properties [56,112,128]:
LiClO4 is potentially explosive in contact with organics, LiBF4 has a thermal stability up to 300 ◦ C (much above the 80 ◦ C
interferes with the SEI at the anode (but it has better thermal sta- for LiPF6 ) [57]; stabilizes aluminum (the current collector in
bility and lower sensitivity towards moisture [108,109]), LiAsF6 the cathode) up to >5.0 V versus Li+ /Li [116] in a manner
is toxic, solutions of LiSO3 CF3 have too low conductivities, and similar to LiPF6 ; forms a stable solid electrolyte interface
LiN(SO2 CF3 )2 and LiC(SO2 CF3 )3 do not effectively passivate graphite anode even in propylene carbonate-containing elec-
the aluminum current collector at the positive electrode, leading trolytes [57,128,129]; forms solutions of high conductivity; has
to its corrosion [110]. Salts such as LiBF4 , LiPF6 , LiAsF6 , etc., low cost; and its disposal in water does not release toxic mate-
form a layer of LiF on the graphite anode surface [111,112]. rials. Most importantly, it has superior safety characteristics
Larger the amount of LiF in the SEI, the lower is the onset tem- [130,131]. LiBOB-based electrolytes have also been shown to
perature for thermally activated reactions in the SEI [113–115]. be stable for electrochemical cycling up to 4.3 V with LiNiO2
Below we discuss new salts being considered for lithium battery [132] and up to 4.5 V with LiCoO2 [133]. One attraction with
use: LiPF3 (C2 F5 )3 (LiFAP) [57,59], LiN(SO2 CF3 )2 (LiTFSI) LiBOB is that it does not form LiF on graphite during cell cycling
[55,116] and LiBC4 O8 (LiBOB) [56,117–119]. [112].
Despite its projection as a potential electrolyte salt, it must be
6.5.1. LiPF3 (C2 F5 )3 noted that several properties of LiBOB remain unknown. Addi-
In order to overcome the easy hydrolyzability of LiPF6 , a new tionally, several other things need to be factored into before
class of compounds known as lithium fluoroalkylphosphates LiBOB can be accepted as an electrolyte salt. This includes its
was introduced [57–59]. The premise for their development was low solubility in solvents with low dielectric constant, lower
that the substitution of one or more fluorine atoms in LiPF6 conductivity of their solutions in typical carbonate mixtures as
with electron-withdrawing perfluorinated alkyl groups should compared to LiPF6 , easy hydrolyzability (although the mono-
stabilize the P F bond, rendering it stable against hydrolysis. hydrate of LiBOB is stable [57]) and difficulty in large-scale
In fact, lithium fluoroalkylphosphates exhibit good resistance synthesis of high-purity LiBOB [134,135]. Safety features of
against hydrolysis. The hydrophobic perfluorinated alkyl groups LiBOB-bearing cells are being evaluated [132,133,136,137].
sterically shield the phosphorus against hydrolysis. The new Although enhanced safety can be realized with fully lithiated
compounds also have conductivity comparable to that of LiPF6 graphite, safety concerns remain in the case of cathodes where
[57]. The stabilization of the P F bond results in an improved a higher self-heating rate is observed, which suggest reactions
thermal stability of the salt [57,58]. Oesten et al. [58] showed that between LiBOB and oxide cathodes.
LiPF3 (C2 F5 )3 (LiFAP) exhibits a far superior stability towards
hydrolysis and that electrolytes containing LiFAP exhibited 7. Active materials
reduced flammability. The authors suggest that LiFAP has a
combination of flame-retardant moieties, fluorinated derivatives Commercial lithium-ion batteries are thermally stable up
and phosphoric acid esters [58]. Gnanaraj et al. [120], who inves- to ∼60 ◦ C [138], above which their performance declines.
tigated the thermal stability of solutions of LiPF6 and LiFAP in Anode/electrolyte reactions occur first [139], while cath-
EC–DEC–DMC mixtures using accelerating rate calorimetry ode/electrolyte reactions dominate the heat-evolution processes
(ARC), showed that the onset temperature for thermal reactions at elevated temperatures [19]. The latter if allowed to progress
of LiFAP solutions were higher than 200 ◦ C (LiPF6 solutions: can be hazardous. Violent reactions are known to occur in the
<200 ◦ C) although their self-heating rate was very high. charged state of lithium-ion batteries. In fact, although lithiated
carbon anodes are considered safer than metallic lithium anodes reaction [31]
[9], at large values of x in Lix C6 (x ∼ 1 for graphite) they can
Li0.5 CoO2 → 0.5LiCoO2 + 16 Co3 O4 + 16 O2 .
react with the electrolyte under abusive conditions, releasing
heat. Similarly, at small values of x in Lix CoO2 , Lix NiO2 and The released oxygen can then react with organic solvents to
Lix Mn2 O4 , the cathodes can adversely influence their thermal generate heat. By ARC, Jiang and Dahn [156] showed that
stability [31,140]. Therefore, thermal studies on negative elec- organic solvents can reduce Li0.5 CoO2 (the normally fully
trodes are performed in their lithiated state and positive elec- charged composition) to Co3 O4 and CoO, eventually even to
trodes in the delithiated state. Because cell temperatures during Co metal and that the reactivity of Lix CoO2 in electrolyte can
abuse reactions can melt the aluminum current collector but not be affected by particle size, surface area, electrolyte compo-
the copper current collector, Biensan et al. [141] conclude that sition, etc. [156,157]. MacNeil et al. [158] reported that the
cell temperatures should reach between 659 ◦ C (mp of Al) and first thermal processes between Lix CoO2 and electrolyte can
1083 ◦ C (mp of Cu). be described by an auto-catalytic reaction. In fact, the reaction
of Li0.5 CoO2 with EC–DEC begins at 130 ◦ C, which is much
lower than the decomposition temperature of Li0.5 CoO2 itself
7.1. Carbon anode
[152]. Baba et al. [154], who evaluated the thermal stability of
chemically delithiated LiCoO2 (Li0.49 CoO2 ) by DSC, the active
The composition of the SEI on graphite depends on the
cathode decomposed the electrolyte at 190 ◦ C, the mechanism
electrolyte composition and strongly affects the onset temper-
of which may be written as follows for EC [152]:
ature for thermal reactions at the graphite anode [142–144].
While the composition of the SEI is dictated more by the salt Li0.5 CoO2 + 0.1C3 H4 O3 (EC)
in the case of electrolytes with LiBF4 and LiPF6 , the solvent
takes a prominent role with electrolytes containing salts such → 0.5LiCoO2 + 0.5CoO + 0.3CO2 + 0.2H2 O.
as LiCF3 SO3 and LiN(SO2 CF3 )2 [114]. Thermal reactions at A DSC peak at 230 ◦ C is ascribed to the oxidation of the elec-
salt-based SEIs proceed via surface salt decomposition, yield- trolyte caused by oxygen released from Li0.49 CoO2 [154]. Jiang
ing mainly LiF [113]. On the other hand, thermal reactions in and Dahn [156] showed that the reactivity of Li0.5 CoO2 was
predominantly solvent-based SEIs proceed via decomposition higher in LiBOB–EC–DEC than in LiPF6 –EC–DEC. The lower
of lithium-alkyl carbonates to Li2 CO3 [114]. For this reason, stability of the LiBOB-based electrolyte must be seen in the
the latter type of SEIs is thermally more stable. Thermal stabil- backdrop of the fact that the LiBOB can effectively stabilize the
ity of salt-based SEIs can be improved by controlling reactions SEI of LiC6 . This means that graphite/LiCoO2 cells cannot be
involving salts complexing their anions with anion acceptors rendered safer by replacing LiPF6 with LiBOB in the electrolyte.
[145–148]. Besides, anion acceptors increase lithium-ion diffu-
sion and transport number by suppressing ion-pair formation. In 7.3. LiNiO2
fact, Herstedt et al. [115] showed that the addition of tris(penta-
fluorophenyl)borane (TPFPB) to LiBF4 –EC–DEC improves the In its delithiated state, LiNiO2 has a poor thermal stability
cyclability and raises the thermal stability of graphite anodes by due to the presence of the unstable Ni4+ ion [159]. Lix NiO2
as much as 60 ◦ C. (x = 0.3) releases oxygen at a lower temperature than Lix CoO2
DSC and ARC studies have shown that carbon anodes cycled (x = 0.4). The lower stability of Lix NiO2 is attributed to easier
in carbonate-based electrolytes undergo exothermic reactions reduction of Ni3+ as compared to Co3+ [160]. Hence, a cell
between 60 and 200 ◦ C [19,149–151]. Components of the SEI with LiNiO2 may be less tolerant under abusive conditions [31].
on MCMB cycled in LiPF6 –EC–DMC have been shown to be Ohzuku et al. [161] have reported that Li0.15 NiO2 undergoes an
the source of an exothermic reaction below 100 ◦ C [149], while exothermic reaction at about 200 ◦ C. Arai et al. [160] suggest
above 100 ◦ C intercalated lithium is believed to participate in that at 200 ◦ C, Lix NiO2 transforms into a rocksalt structure due
the thermal reactions. According to Menachem et al. [151] a to cation mixing. The decomposition of LiNiO2 in the absence
chemically bonded SEI formed by mild oxidation of graphite of air may be described by [162]
suppresses exothermic reactions and has a lesser tendency to
‘peel off’ from the anode during heating. In an exciting discov- 2LiNiO2 → Li2 O + 2NiO + 21 O2 .
ery, Jiang and Dahn [130] found that the addition of LiBOB to
At x values less than 0.25, Lix NiO2 undergoes highly exothermic
EC–DEC significantly improved the thermal stability of LiC6 .
reactions with common electrolytes with an onset temperature
LiBOB is believed to form a robust SEI on lithiated carbon
around 200 ◦ C.
surface, preventing any exothermic process until 170 ◦ C as com-
pared to an onset temperature of 80 ◦ C with LiPF6 –EC–DEC
7.4. LiMn2 O4
[130].
The better thermal tolerance of LiMn2 O4 as compared to
7.2. LiCoO2 LiCoO2 was demonstrated by studies on LiMn2 O4 electrodes
[140] and 18650-type cells with LiMn2 O4 [163]. ARC stud-
Lix CoO2 is thermally unstable and can decompose, releas- ies showed that cells with LiCoO2 exhibited thermal runaway
ing oxygen at elevated temperature [152–155] according to the beyond 155 ◦ C, while those with LiMn2 O4 were stable up to
180 ◦ C [164]. MacNeil et al. [164] demonstrated that the reac- Recently, several studies have concentrated on enhancing the
tion heat generated by LiMn2 O4 in LiPF6 –EC–DEC increased cyclability of cathodes by coating cathode particles with oxides,
with increasing amount of electrolyte. Improved cycling per- glasses, etc. [173–182]. An attendant benefit is an increase in the
formance of LiMn2 O4 at 55 ◦ C with the addition of TPFPB in thermal stability of the coated materials in contact with the elec-
an EC–DMC-based electrolyte has been reported [147]. In fact, trolyte. Cho et al. [183] demonstrated that LiCoO2 coated with
the additive improves the thermal stability of LiPF6 –EC–DMC nanoparticle-AlPO4 blocked the thermal runaway of lithium-ion
electrolytes [148]. cells in addition to significantly reducing electrolyte oxidation
and cobalt dissolution into the electrolyte. Cho et al. [184] also
7.5. LiFePO4 demonstrated the 12 V overcharge behavior of the AlPO4 -coated
LiCoO2 and LiNi0.8 Co0.1 Mn0.1 O2 in terms of their exothermic
Probably the most exciting alternative to LiCoO2 for large- behavior. Cho [185] showed that a thickness of 20 nm for the
size lithium-ion cells is LiFePO4 . It is thermally stable for AlPO4 coating was optimal. Although increased thickness of
its reactivity with electrolytes is very low [131,139,165] the coating drastically reduced the exothermic reaction between
and no heat evolution is observed below 200 ◦ C. Edstrom Lix CoO2 and increased the onset temperature of oxygen evo-
et al. [166], who characterized the SEI formed on carbon- lution, the reduced lithium-ion diffusivity was detrimental to
coated LiFePO4 in LiPF6 –EC–DEC by photoelectron spec- cycling performance.
troscopy with synchrotron radiation, detected no solvent reac- Fey et al. [186] showed that LiCoO2 coated with cobalt oxides
tion or decomposition products on the cathode surface, which displayed increased resistance to decomposition reactions with
suggests that the phosphate group does not react with the the electrolyte. Not only was the temperature of the reaction
solvents. raised by 11 ◦ C, but the coating also reduced the exothermicity
of the reaction. With the objective of improving the elevated-
8. Coatings temperature performance of LiMn2 O4 , Vidu and Stroeve [187]
investigated the electrochemical characteristics of LiMn2 O4
Thermal stability of the electrolyte in contact with active coated with poly(diallyldimethylammonium chloride) (PDDA).
materials is of great concern in lithium-ion batteries [167]. In By in situ electrochemical atomic force microscopic analysis
order to mitigate this problem, electrolyte additives that prevent under potential and temperature control, Vidu and Stroeve [187]
direct reaction of the electrolyte with the active material have showed that the PDDA layer blocks surface reactions that cause
been tested. For example, additives such as ␥-butyrolactone have degradation of the cathode and led to improved thermal stability
been shown to reduce direct reaction of nickel-based cathodes in in an organic electrolyte under charge and discharge.
their charged states with electrolytes. The additive was reported
to decompose, encapsulating the cathode with decomposition 9. Conclusions
products [168]. Although lithium-ion cells with this additive
did not explode during nail penetration tests at 4.35 V and over- If abused by the user or not carefully designed by the man-
charge tests up to 12 V, concerns about its compatibility with the ufacturer, batteries can be potentially dangerous. Conscious of
anode and cathode remain. the consequences, battery manufacturers incorporate a variety
Improvement of thermal stability by encapsulation of active of safety measures in the design of their cells. While the man-
material particles has been applied to anode active materials ufacturer does what is best to render their products foolproof,
also. Kuribayashi et al. [169] synthesized the first prototype an equal responsibility lies with the user, who must adhere to
of core-shell-structured carbon composites. Yoshio et al. [170] Instructions For Use that the manufacturer supplies with the
showed that coating carbon on graphite can effectively suppress power pack in order to avoid mishaps in their handling. Con-
the decomposition of propylene carbonate on the anode as well sumer education is also important. Consumers must specifically
as subsequent exfoliation of graphite. They also showed that the refrain from abuses such as short circuiting or drawing more
coating arrested the decomposition of ethylene carbonate-based current than the battery is designed for, use of undersized bat-
solvents and thus the formation of solid electrolyte interface teries, operation or storage at too high or too low temperatures,
on the anode. Moreover, the coating improved the coulombic use of chargers designed for other battery chemistries, over-
efficiency and decreased the irreversible capacity. Similarly, Yu charging (both at too high a voltage and for too long a period),
et al. [171] showed that microencapsulation of graphite with overdischarging, use in environments with excessive vibration
nanosized nickel-composite particles blocked some of the edge and improper disposal.
surfaces exposed to the electrolyte, diminishing solvent co-
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PGB Li Safety JPS 155 (2006) 401-414

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Journal of Power Sources 155 (2006) 401–414

Safety mechanisms in lithium-ion batteries

0378-7753/$ – see front matter © 2006 Published by Elsevier B.V.

7.3. LiNiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410

1. Introduction They can suffer premature failure if subjected to conditions for

permeability, these microporous separators display a protective

not on the horizon although alternative salts such as lithium

6.1. Non-ﬂammable electrolytes

6.2.3. Aromatic redox shuttles 6.4. Ionic liquids

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