Recent Progress in Lithium Ion Battery Technology

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Recent Progress in Lithium Ion Battery Technology
Author’s Details:
Ramalan, A. M*1., Yusuf A. S2., Umar M., Buba, A. D. A
1Department of Physics, University of Abuja 2Department of Physics, Federal university of technology
minna
Abstract
this paper is aimed at giving a detailed review on the recent advancements in lithium ion battery technology
focusing on the underlying principle; design and configuration; materials; fabrication techniques;
application; and challenges of lithium ion batteries (LIBs). The first rechargeable Li-ion batteries with
cathode of layered TiS2 and anode of metallic Li was reported by Whittingham while working at Exxon in
1976 but this invention was not successful due to the problems of Li dendrite formation and short circuit
upon extensive cycling and safety concern. However, there was a turnaround when Goodenough offered a
theoretical framework for possible materials for effective intercalation/deintercalation and Yohsino carried
out the first safety test on Li-ion batteries to demonstrate their enhanced safety features. LIBs consist of two
electrodes, anode and cathode, immersed in an electrolyte and separated by a polymer membrane; and
works by converting chemical energy into electrical energy and vice versa through charging and
discharging processes. Most of the LIB models are derived from the porous electrode and concentrated
solution theories which mathematically describe charge/discharge and species transport in the solid and
electrolyte phases across a simplified 1D spatial cell structure. The cathode materials can be categorized
based on voltage, typically 2-Volt, 3-Volt, 4-Volt and 5-Volt and currently LiCoO2 and LiFePO4 are most
widely used in commercial Li-ion batteries because of their good cycle life (>500 cycles). Carbon is a
dominant anode material although there are other materials available such as Nexelion; the choice of anode
materials significantly influences the electrochemical performances, including cyclability, charging rate,
and energy density of Li-ion batteries. A typical liquid electrolyte is a solution of lithium salts in organic
solvents which must be carefully chosen to withstand the redox environment at both cathode and anode sides
and the voltage range involved without decomposition or degradation. Separators are essential components
of Li-ion batteries and plays a critical role to avoid direct physical contact between the cathode and anode,
and prevents short circuit to occur. A number of benefits are offered by this technology such as lightweight,
high energy density power sources for a variety of devices. However, cost is one of the major challenges in
the development of LIBs, another issue that is yet to be resolved is that the battery capacity tends to fade
upon electrochemical cycling. Hence, if the opportunities embedded in the LIB technology is properly
harnessed, there will create an economically viable environment.
1.1 Introduction
The rapidly growing energy demands has given rise to a large increase in demand for more efficient,
sustainable and renewable energy resources. Recent statistics shows that our society relies on fossil fuels for
most of its energy needs and the combustion of these fossil fuels leads to the emission of greenhouse gases
into the atmosphere. Global warming is a direct consequence of the accumulation of greenhouse gases.
Internal combustion engines are a major source of CO2 emission and hence alternative energy sources for
automotive propulsion applications is one of the prime focuses of research throughout the world
(Deshpande, 2011).
The renewable sources such as solar energy and wind energy are “green” sources of energy but these are
intermittent sources. Energy may be available in amounts and at times and places that are different from
those when and where one is in need of it; but for a continuous use, storage of energy is necessary. Thus,
methods to store and transport energy from place to place can be of great importance, storage in chemical
form is often a useful intermediate stage; this may involve the use of electrochemical systems and devices
that act as transducers to convert between electrical and chemical quantities – energies, potentials, and
fluxes (Huggins, 2009). Such electrochemical transduction systems are often called galvanic cells or

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batteries with which one can store energy in the form of chemical potential difference and use it whenever
and wherever it is needed (Huggins, 2009; Deshpande, 2011).
A major advantage of electrochemical transduction methods is that they can operate isothermally and thus
avoid the so-called Carnot limitation (Huggins, 2009). This makes it possible to achieve much greater
efficiencies than are available by the use of thermal conversion processes. In many cases, electrochemical
cells can also be operated in the reverse direction. Thus, it is possible to devise reversible electrochemical
systems in which electrical energy is converted to chemical energy (the chemical system is charged), and the
process can later be reversed to give electrical energy again (the chemical system is discharged) (Huggins,
2009).
The application of batteries in different market segments has been growing at a very high rate and their
requirements have been putting ever-increasing incentives on the development of better, and lower cost,
energy storage devices and systems. This has led to a lot of research and development activity, and there
have been a number of important technological changes in recent years. A number of these have not been
just incremental improvements in already-known areas, but involve the use of new concepts, new materials,
and new approaches. An important reason for this progress has been the fact that such things as the
discovery of fast ionic conduction in solids and the possibility of solid electrolytes, the concept of the use of
materials with insertion reactions as high-capacity electrodes, and the discovery of materials that can
produce lithium-based batteries with unusually high voltages have caused a number of people with
backgrounds in other areas of science and technology to be drawn into this area. The result has been the
infusion of new materials, concepts, and techniques into battery research and development (Huggins, 2009).
Furthermore, among the various presently available battery technologies such as lead-acetate battery, metal-
hydride battery, nickel-cadmium battery, lithium ion battery, among others, lithium based batteries are
known to have the highest gravimetric and volumetric energy storage capacity (Deshpande, 2011; Obrovac
et al., 2007).
1.2 Li-Ion Batteries (LIBs)
Li-ion batteries are currently the dominant mobile power sources for portable electronic devices, exclusively
used in cell phones and laptop computers (Deng et al., 2009). Li-ion batteries are considered the powerhouse
for the personal digital electronic revolution starting from about two decades ago, roughly at the same time
when Li-ion batteries were commercialized (Deng, 2015). As one may has already noticed from his/her
daily life, the increasing functionality of mobile electronics always demand for better Li-ion batteries. For
example, to charge the cell phone with increasing functionalities less frequently as the current phone will
improve quality of one’s life. Another important expanding market for Li-ion batteries is electric and hybrid
vehicles, which require next-generation Li-ion batteries with not only high power, high capacity, high
charging rate, long life, but also dramatically improved safety performance and low cost (Deng, 2015).
The demand for Li-ion batteries increases rapidly, especially with the demand from electric-powered
vehicles. It is expected that nearly 100 GW hours of Li-ion batteries are required to meet the needs from
consumer use and electric-powered vehicles with the later takes about 50% of Li-ion battery sale by 2018
(Yoshino, 2012). Furthermore, Li-ion batteries will also be employed to buffer the intermittent and
fluctuating green energy supply from renewable resources, such as solar and wind, to smooth the difference
between energy supply and demand. For example, extra solar energy generated during the daytime can be
stored in Li-ion batteries that will supply energy at night when sun light is not available. Large-scale Li-ion
batteries for grid application will require next-generation batteries to be produced at low cost.
2.0 LITERATURE REVIEW
This chapter briefly reviews the history on the development of Li-ion batteries. It presents a basic concept,
design and configuration, principle of operation. Recent experimental advances in Li-ion batteries are
equally discussed.

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2.1 Historical Overview: Invention and development of Li-ion batteries
Batteries are so ubiquitous today that they are almost invisible to us, yet they are a remarkable invention
with a long and storied history, and an equally exciting future. Batteries have been with us for a long time.
American scientist and inventor Benjamin Franklin first used the term “battery” in 1749 when he was doing
experiments with electricity using a set of linked capacitors (Alarco and Talbot, 2015). The first true battery
was invented by the Italian physicist Alessandro Volta in 1800. The chronological development of the
battery technology is summarised in Table 2.1.
The first rechargeable Li-ion batteries with cathode of layered TiS2 and anode of metallic Li was reported by
Whittingham while working at Exxon in 1976 (Whittingham, 1976). Exxon subsequently tried to
commercialize the Li-ion batteries, but was not successful due to the problems of Li dendrite formation and
short circuit upon extensive cycling and safety concern (Levine, 2010). Also in 1976, Besenhard proposed to
reversibly intercalate Li+ ions into graphite and oxides as anodes and cathodes, respectively. In 1981,
Goodenough first proposed to use layered LiCoO2 as high energy and high voltage cathode materials.
Interestingly, layered LiCoO2 did not attract much attention initially (Mizushima et al., 1981; Deng, 2015).
Table 2.1 Chronological development of battery technology (Dunning, 2016; LaVine, 2017;
Richard, 2017)
Year
Inventor/National
Type of Invention
1791
Galvani (Italy)
Animal Electricity
1800
Alessandro Volta (Italy)
Invention of Voltaic Cell (Cu/brine/Zn)
1833
Michael Faraday (UK)
Faraday’s Law of Electrolysis
1836
John Daniel (UK)
Daniel Cell (Cu/CuSO4//ZnSO4/Zn)
1868
Georges Leclanche (France)
Zn(s) + 2 MnO2(s) + 2 NH4Cl(aq) → ZnCl2+ Mn2O3(s) + 2
NH3(aq) + H2O
1899
Waldemar Jugner (Sweden)
Cd+2NiO(OH)+2H2O=Cd(OH)2+2Ni(OH)2
1901
Thomas Edison (USA)
Fe + 2NiO(OH)+2H2O=Fe(OH)2+2Ni(OH)2
Mid 1960s
Union Carbide (USA)
Zn (s) +2MnO2(s) → ZnO (s) +Mn2O3(s)
1970s
Various
Valve Regulated Lead Acid Cells
1981
1990
Various
MH+NiO(OH) = M+Ni(OH)2
1980s/90s
John Goodenough (USA)/Yoshino
Akira (Japan)
Lithium Ion Batteries
2017
Helena Braga (Portuga)/John
Goodenough (USA)
Glass Lithium Ion Batteries (Controversial)
In 1983, Goodenough also identified manganese spinel as a low-cost cathode material. However, the lack of
safe anode materials limited the application of layered oxide cathode of LiMO2(M = Ni, Co) in Li-ion
batteries. It was discovered that graphite, also with layered structure, could be a good candidate to reversibly
store Li by intercalation/deintercalation in late 1970s and early 1980s (Deng, 2015). In 1987, Yohsino et al.
filed a patent and built a prototype cell using carbonaceous anode and discharged LiCoO2 as cathode (Deng,
2015). Both carbon anode and LiCoO2 cathode are stable in air which is highly beneficial from the
engineering and manufacturing perspectives. This battery design enabled the large-scale manufacturing of
Li-ion batteries in the early1990s (Deng, 2015).
Yohsino carried out the first safety test on Li-ion batteries to demonstrate their enhanced safety features
without ignition by dropping iron lump on the battery cells, in contrast to that of metallic lithium batteries
which caused fire (Yoshino, 2012). Yohsino’s success is widely considered the beginning of modern
commercial Li-ion batteries. Eventually Sony, dominant maker of personal electronic devices such as
Walkman at that time, commercialised Li-ion batteries in 1991. It was a tremendous success and supported
the revolution of personal mobile electronics. To acknowledge their pioneering contribution to the
development of Li-ion battery, Goodenough, Yazami, and Yoshino were awarded the 2012 IEEE Medal for
Environmental and Safety Technologies (Deng, 2015). Japan is still leading the share of global Li-ion
battery market dominating 57% global market in 2010 (Deng, 2015). In the past two decades, there is some
notable progress in development of Li-ion batteries, particularly the introduction of low-cost cathode of
LiFePO4 by Goodenough in 1996 and high capacity anode of C–Sn–Co by Sony in 2005 (Deng, 2015). The

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recent development of high capacity anode based on nanostructured silicon (theoretical-specific capacity of
4200 mAh/g) is also worthy to be highlighted (Deng, 2015). In 1990s, Dahn and colleagues pioneered the
exploration of composites of C/Si obtained from pyrolysis of silicon-containing polymers as promising
candidate as anode materials for Li-ion batteries (Deng, 2015).
In 2017, a team of researcher at The University of Texas at Austin led by Goodenough announced the
development of a glass Lithium ion battery which could achieve up to a 10-fold improvement in energy
density—the amount of energy stored—in one case, and a three-fold improvement in another (LaVine,
2017). In one experiment, Goodenough estimates a 30-fold improvement on the best density in a lithium-ion
battery today—8,500 watt-hours per kilogram. Moreover, this was accomplished not using exotic materials,
but cheap sodium and sulfur. That means, unlike many other reported battery breakthroughs, this one could
actually be used in mainstream-priced cars (LaVine, 2017). This discovery has since generated a lot of
controversies among scientists on the law guiding the operation of the newly discovered invention. (LaVine,
2017).
2.2 Mechanism of Operation: Design and Configuration of the Li-Ion Batteries
2.3 Theoretical Framework
Most of the current rigorous Li-ion battery models are derived from the porous electrode and concentrated
solution theories proposed by Newman and Tiedemann (1975) and Doyle et al. (1993) which
mathematically describe charge/discharge and species transport in the solid and electrolyte phases across a
simplified 1D spatial cell structure. This 1D model of a Li-ion battery considers dynamics along only one
axis (the horizontal x-axis) and neglects the dynamics along the remaining two axes (y-axis and z-axis)
(Dao, Vyasarayani, & McPhee, 2012). This approximation is applicable to most cell structures as the length
scale of a typical Li-ion cell along the x-axis is on the order of 100 µm, whereas the length scale for the
remaining two axes is on the order of 100,000 µm or more (Chaturvedi, Klein, Christensen, Ahmed, &
Kojic, 2012).
Mathematical models could play a crucial role in guiding the development of new intercalation materials,
electrode microstructures, and battery architectures, in order to meet the competing demands in power
density and energy density for different envisioned applications, such as electric vehicles or renewable (e.g.
solar, wind) energy storage. Porous electrode theory (PET), pioneered by J. Newman and collaborators,
provides the standard modelling framework for battery simulations today (Ferguson, 2014).
In porous electrode theory for Li-ion batteries, transport is modelled via volume averaged conservation
equations (DeVidts & White, 1997). The solid active particles are modelled as spheres, where intercalated
lithium undergoes isotropic linear diffusion. For phase separating materials, such as LixFePO4 (LFP), each
particle is assumed to have aspherical phase boundary that moves as a ‘shrinking core’, as one phase
displaces the other (Ferguson, 2014). In these models, the local Nernst equilibrium potential is fitted to the
global open circuit voltage of the cell, but this neglects non-uniform composition, which makes the voltage
plateau an emergent property of the porous electrode (Ferguson, 2014). For thermodynamic consistency, all
of these phenomena should derive from common thermodynamic principles and cannot be independently
fitted to experimental data. The open circuit voltage reflects the activity of intercalated ions, which in turn
affects ion transport in the solid phase and Faradaic reactions involving ions in the electrolyte phase (Bazant,
2013).
2.4 Experimental Framework
Current rechargeable batteries based on ion insertion/extraction in electrodes, including Li-, Na-, Mg-, and
Al-ion batteries, have been increasingly studied in both the academia and industry (Liu et al., 2016).
However, sodium, magnesium, and aluminum have a lesser reducing effect than lithium (- 2.71, - 2.37, and -
1.66 V vs. S.H.E. (Standard hydrogen electrode), respectively, compared with - 3.04 V for Li) as well as low
gravimetric capacities (1165, 2046, and 2978 mAh/g, respectively; compared with lithium, 3850 mAh g-1)
(Liu et al., 2016). Thus, devices based on metallic sodium, magnesium, or aluminum anodes have lower

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energy densities and operating voltages than those with lithium metal anodes (Huie, Bock, Takeuchi,
Marschilok, & Takeuchi, 2015; Liu, Neale, & Cao, 2016).
To date, only Li-ion rechargeable batteries have been successfully commercialized and become an
irreplaceable power source. In Li-ion rechargeable batteries, the cathodes that store lithium ions via
electrochemical intercalation must contain suitable lattice sites or spaces to store and release working ions
reversibly. Robust crystal structures with sufficient storing sites are required to produce a material with
stable cyclability and high specific capacity (Liu et al., 2016). In addition, a cathode with high
electrochemical intercalation potential can be used to develop a high energy density battery with a given
anode. This is because the energy density of the device equals the product of the specific capacity of the
electrode materials and the working voltage that is determined by the differential electrochemical potentials
between the cathode and anode (Liu et al., 2016).
The energy density and power density of a battery are two parameters essential to evaluating its practical
performance, and they are commonly presented in Ragone plots (Dubal, Ayyad, V. Ruiz, & Gómez-Romero,
2015). Although batteries offer a much higher energy density than electric double-layer capacitors (EDLCs),
also often referred to as supercapacitors or ultracapacitors, and electrochemical pseudocapacitors, they
possess relatively lower power density and shorter cyclic life (Liu, Neale, & Cao, 2016). A significant
number of studies have been conducted on the synthesis and characterization of various nanostructured
cathode and anode materials with large specific surface area and short solid-state transport distance, offering
an enhanced power density as well as a better cyclic stability (Liu, Neale, & Cao, 2016). The energy storage
performance has been enhanced by conformably applying a thin (typically a couple of nanometres) and
porous carbon film (with a pore size of a few nanometers or less) on nanostructured cathode or anode
materials (Liu, Neale, & Cao, 2016). Other carbon materials including carbon nanotubes, graphene, and
graphene oxide have been introduced into electrodes as electrically conductive additives, structural
stabilizers, reactive precursors, or catalysts/promoters, leading to a significant enhancement in the electrical
energy storage performance of electrodes and batteries (Liu, Neale, & Cao, 2016). A high power density can
also be obtained by fabricating hybrid supercapacitor batteries. However, enhancement of the energy density
in a battery is limited by the lithium-ion storage capacity and the cell potential. The storage capacity is
determined by the amount of lithium ions that can be reversibly inserted and extracted through a reversible
first-order phase transition in intercalation reactions under the operating conditions of the battery (Liu,
Neale, & Cao, 2016).
The electrochemical potential varies with the materials in question, showing a direct correlation with their
electronic configuration. Considerable research efforts have been devoted to achieving large specific
capacity, good cyclic stability, and high rate capability in electrode materials (Liu, Neale, & Cao, 2016).
However, experimental studies on controlling and tuning the electrochemical potentials of electrode
materials are limited, although some notable theoretical studies have calculated and analysed
electrochemical potentials based on the electronic structure and atomistic potentials (Islam & Fisher, 2013).
The cell voltage and electrochemical potentials of electrode materials can provide insight for designing and
developing suitable materials for batteries with high energy density in the future.
The choice of electrodes depends upon their electrochemical potential values (
A

for anode and
C

for
cathode) as well as their positions to the highest occupied molecular orbital – lowest unoccupied molecular
orbital (HOMO-LUMO) energy gap (
Eg
) of electrolyte (Roy & Srivastava, 2015). For a stable cell,
A

must be lower in energy than the LUMO of electrolyte, otherwise the electrolyte will be reduced and on the
other hand
C

position should be in higher energy than HOMO of electrolyte to inhibit the oxidation of
electrolyte as shown in Figure 2.2 (Goodenough, 2013). The high-energy storage density can be achieved in
a cell with maximum electrochemical potential difference of anode and cathode as well as their high lithium
intercalation ability though at the same time the stability of electrolyte should not be overlooked (Roy &
Srivastava, 2015).

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Figure 2.1 Relative energies of the electrolyte window, Eg, and the relationship between electrochemical
potentials of electrodes and the HOMO or LUMO of the electrolyte (Liu, Neale, & Cao, 2016)
2.4.1 Voltage of a Battery
Cell voltage is determined by the compatibility of the whole system, including the anode, cathode, and
electrolyte. In particular, the difference in chemical potential between the anode (mA) and the cathode (mC)
is termed as the working voltage, also known as the open circuit voltage, VOC (Obrovac and Chevrier, 2014):
 
C
A
OC
Ve



(2.)
where e is the magnitude of the electronic charge. This working voltage is also limited by the
electrochemical window of the electrolyte, which, as illustrated in Figure 2, is determined by the energy gap
from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO).
The anode and cathode must be selected such that the mA of the anode lies below the LUMO and the mC of
the cathode is located above the HOMO; otherwise, the electrolyte will be reduced on the anode or oxidised
on the cathode to form a passivating solid electrolyte interphase (SEI) film (Pistoia & Nazri, 2003). It is
worth noting that this SEI film permits the diffusion of Li ions through the film under a uniform electric
field and reduces the over potential and concentration polarization (Park, 2012). The SEI can also prevent
the aggregation of electrochemically active particles and maintain a uniform chemical composition at the
electrodes.
2.4.2 Potential Hysteresis
Hysteresis is always observed between the charge and discharge curves in all charge/discharge
measurements of electrode materials, which can be explained in two ways. First, Goodenough (2013)
consider the charge potential to be greater than the discharge potential (Figure 4a) due to the polarization
arising from the internal resistance of the electrode materials (Goodenough and Park, 2013).

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Figure 2.2 (a) Potential hysteresis in the charge/discharge procedure of an ideal insertion electrode
material. (b) The potential drop in the interval between charge and discharge.
This polarization decreases the discharge potential below the open circuit voltage, and it increases the charge
potential to reverse the chemical reaction on the electrode. In addition, the internal resistance drop (IR drop)
also leads to a drop in potential (drop in IR) between the end of charge and the beginning of discharge
(Figure 4b). Second, over potential is the driving force behind electrochemical phase transitions in insertion
electrodes (Tang, Carter, & Chiang, 2010).
The plateau on the potential–capacity curve indicates the two-phase coexistence region of the phase
transition, and the span of the plateau represents the width of the miscibility gap. In general, phase
transitions during the charge step are accompanied by the extraction of Li ions from the host lattice and the
dragging of electrons from the d orbitals of transition metal ions. Likewise, Li ions and electrons are inserted
into the relative lattice positions and electronic orbitals during discharge. It is worth noting that the
corresponding energy changes are different in this reversible phase transition. During the discharge step, Li
ions enter the interstitial space of the host lattice and electrons are accepted into the transition metal d
orbital, followed by an energy decrease and phase stabilization. However, in reverse, more energy is
consumed as ions and electrons must be promoted from the lower energy states. In particular, the energy
spent during charge is slightly higher than that delivered during discharge. This energy difference is the
source of the potential gap between the charge and discharge curves. Thus, a higher over potential results in
a phase transition at the electrode during the charge procedure. The IR drop originates from the change of
internal resistance, including the resistance of the electrolyte, electrode materials, and other connectors or

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auxiliaries. The drawback of the IR drop includes energy consumption, leading to a decrease in the
efficiency of the battery and the safety issues from the released heat. These resistances can be decreased or
eliminated to overcome the side effects efficiently. Effective approaches used in laboratories or factories
include a conductive coating on the surface of active materials (Su, Jing, & Zhou, 2011), which enhances the
performance of the connecting components and makes use of the highly conductive auxiliaries.
3.0 MATERIALS AND FABRICATION TECHNIQUES
A basic Li-ion cell consists of a cathode (positive electrode) and an anode (negative electrode) which are
contacted by an electrolyte containing lithium ions. The electrodes are isolated from each other by a
separator, typically microporous polymer membrane, which allows the exchange of lithium ions between the
two electrodes but not electrons. This chapter highlights the materials for the fabrication of Li-ion batteries
(LIBs). An overview of the recent advances in fabrication techniques of Li-ion batteries (LIBs) is given.
Various sections including electrode (anode and cathode), electrolytes, separators and electrode-electrolyte
interface and also different types of these materials are discussed. The selection criteria of electrode
materials for lithium-ion batteries are discussed, including societal, economical, and technical
considerations. These include their natural abundance; lack of competition with other industrial applications;
eco-friendly nature for processing, usage and recycle; and low cost.
3.1 Electrode Materials
The electrode (cathode and anode) and electrolyte are the most important active materials that determine the
performance of a Li-ion battery. As anode materials offer a higher Li-ion storage capacity than cathodes do,
the cathode material is the limiting factor in the performance of Li-ion batteries (Liu, Neale, & Cao, 2016).
The energy density of a Li-ion battery is often determined collectively by the Li-ion storage capacity and the
discharge potential of the cell. The factors determining the Li-ion storage capacity through intercalation are
as follows: (1) the capability of the host, or the electrode, to change the valence states; (2) the available
space to accommodate the Li ions; and (3) the reversibility of the intercalation reactions. The discharge
potential of a cathode is directly proportional to the reduction of Gibbs free energy when Li ions are inserted
into the electrode (Liu, Neale, & Cao, 2016).
3.1.1 Cathode Materials
There are a number of candidates that have been explored as cathode materials for Li-ion batteries. The
cathode materials can be categorized based on voltage versus lithium. Typically: 2-Voltcathode materials are
TiS2 and MoS2 with 2-D layered structure; 3-Volt cathode materials are MnO2 and V2O5; 4-Volt cathode
materials are LiCoO2, LiNiO2 with 2-D layered structure and 3-D spinel LiMn2O4 and olivine LiFePO4; 5-
Volt cathode materials are olivine LiMnPO4, LiCoPO4, and Li2MxMn4−xO8 (M = Fe, Co) spinel 3-D
structure. Generally, high cathode voltage is desirable as energy stored is proportional to the cell operating
voltage. However, electrolyte stability has to be taken into consideration in selecting high voltage cathode
materials (Deng, 2015).
Currently LiCoO2 and LiFePO4 are most widely used in commercial Li-ion batteries because of their good
cycle life (>500 cycles). LiCoO2 can be easily manufactured in large scale and is stable in air. Its practical
capacity is ~140 mAh/g and the theoretical capacity is 274 mAh/g upon full charge (Deng, 2015). In
addition to its low practical capacity, other noticeable disadvantages of the LiCoO2 are their high material
cost and the toxicity of cobalt. On the other hand, LiFePO4-based cathode materials are attracting much
attention in the past decade due to its low cost and low environmental impact. Compared to LiCoO2,
LiFePO4 also offers a number of advantages, such as stability, excellent cycle life, and temperature tolerance
(−20 to 70°C). However, LiFePO4 has a problem of poor electronic and ionic conductivity at 10−10 S/cm
and 10−8 cm2/sec, respectively, as well as relatively low capacity (Chung & Chiang, 2002). The other issue
is one-dimensional channels for lithium ion diffusion which can easily be blocked by defects and impurities.

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3.1.2 Anode Materials
Anode materials are extensively investigated and there is a bigger pool of candidates and materials. The
electrochemical performances, including cyclability, charging rate, and energy density of Li-ion batteries are
significantly affected by anode materials selected. Since the first commercialization of carbonaceous anodes,
carbon is still dominant in commercial Li-ion batteries today (Deng, 2015). Graphitic carbon with layered
structure can facilitate the movement of lithium ions in and out of its lattice space with minimum
irreversibly, resulting in an excellent cyclability (Megahed & Scrosati, 1994). However, the carbon anodes
are soon approaching their theoretical maximum capacity of 372 mAh/g over the past two decades of
development. Carbon alternatives with high-energy density and enhanced safety are required to meet the
demands for increases in energy and power densities, especially to meet the demands from electric vehicles
(Deng and Lee, 2013). Fuji Film introduced tin composite oxide (TCO) as a carbon alternative in 1997 but
was not very successful due to the poor cycling performance (Idota et al., 1997). Sony Cooperation
announced new-generation Li-ion batteries with the trade name of Nexelion in 2005. The anode of Nexelion
is based on a carbon–tin–transition-metal composite (e.g., Sn–Co–C), and the compound is mainly
amorphous or microcrystalline aggregates. Those efforts have rekindled another wave of interest in anode
materials for Li-ion batteries (Deng, 2015).
Besides Sn, many other elements that are known to alloy with lithium, including silicon, are good candidates
to replace carbon for lithium storage. These elements could alloy and de-alloy with lithium
electrochemically at room temperature. However, the alloying/dealloying process during
charging/discharging is accompanied by substantial variations in the specific volume of the material. The
induced huge mechanical stress could lead to the destruction of the crystal structures and disintegrate the
active materials and current collectors within a few cycles, or the so-called “pulverization” issue (Deng,
2015). The resulting poor cyclability has significantly limited their usability in practical situations. The
engineering approach to solve the poor cyclability problem is to introduce composites. In such a composite
material, one component (usually carbon) functions as a stress absorber whereas the other (such as silicon or
tin) provides the boost in capacity. Through this approach a composite with capacity higher than carbon and
cyclability better than Sn or Si can be achieved. A number of combinations involving carbon have been
explored, among them Si/C (Dimov, Xia, & Yoshio, 2007) and SnO2/C (Winter & Besenhard, 1999) have
attracted much interest.
Other carbon-based materials that have been extensively studied are buckminsterfullerene, carbon
nanotubes, and graphene. Carbon nanotubes, in particular, can be a good lithium host on grounds of their
excellent electronic conductivity and other properties associated with their linear dimensionality
(Baughman, Zakhidov, & deHeer, 2002; Che, Lakshmi, Fisher, & Martin, 1998). However, current interest
is focused on CNT-and graphene-based composites instead of pristine CNTs or graphene to achieve much
higher capacity than that of pristine carbon (Wang, Zeng, & Lee, 2006; Kumar, Ramesh, Lin, & Fey, 2004).
Another family of anode materials with high capacity is metal oxides, although metal oxides are generally
poor in conductivity, properly tailored metal oxides at nanoscale have demonstrated promising
characteristics (Deng, 2015).
3.2 Electrolytes
Electrolyte must be carefully chosen to withstand the redox environment at both cathode and anode sides
and the voltage range involved without decomposition or degradation. Additionally, electrolyte should be
inert and stable in an acceptable temperature range. In commercial Li-ion batteries, typically a liquid
electrolyte is a solution of lithium salts in organic solvents. However, the existing organic liquid electrolyte
can potentially catch fires under conditions of thermal runaway or short circuit due to volatile and
flammable nature of the solvents which are highly toxic. Ideally, the electrolyte should also be
environmentally benign and can be produced at low cost in the future (Deng, 2015). Polar aprotic organic
solvents, such as carbonate solvents with high dialectic constant, are selected to solvate lithium salts at a
high concentration (1 M typically). On the other hand, solvents with low viscosity and low melting point are
required to meet the requirement for high ionic mobility in the operating temperature range. Various organic
solvents have been explored, including dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate,

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propylene carbonate, ethylene carbonate, diethoxyethane, dioxolane, γ-butyrolactone, and tetrahydrofuran.
Heteroatom-containing organic solvents have also been explored. Various lithium salts have been explored,
including LiPF6, LiBF4, LiAsF6, LiClO4, and LiCF3SO3 (Deng, 2015). It should be noticed that anions are
selected to avoid being oxidized on the charged surface of cathodes, which rules out those simple anions of
Cl−, Br−, and I−. LiPF6 is a particular outstanding lithium salt from the perspective of safety, conductivity
and the balance between ionic mobility and dissociation constant. However, LiPF6 can react with water to
form highly corrosive HF. Therefore, moisture must be minimized in handling of LiPF6 electrolyte. In fact,
the success of first commercial Li-ion batteries could be ascribed to the industrial scale availability of high-
purityLiPF6 with minimal amount of water (Deng, 2015).
The solvents are typically formulated and mixed to address the requirements on viscosity, conductivity and
stability and to match with the lithium salts selected. For example, high dielectric solvents with high
viscosity are typically mixed and balanced with solvents with low viscosity to achieve a liquid state
electrolyte within a required temperature window (Deng, 2015). The commonly used electrolyte is 1M
LiPF6 in a 50:50 w/w mixture of ethylene carbonate (EC, melting point of 34°C and boiling point of
260.7°C) and diethyl carbonate (DEC, melting point of 2–4°C and boiling point of 90°C) or dimethyl
carbonate (DMC, melting point of 2°C and boiling point of 90°C). Generally, the EC can bind Li+ ions more
strongly than DEC or DMC (Zhu, Ng, & Deng, 2014). The formulated electrolyte offers reasonably good
stability over a wide potential range. Additives to further enhance the electrolyte stability and improve the
formation of good solid-electrolyte interphase (SEI) are also added in many cases. The various formulated
additives in terms of chemical compositions and percentages used by different companies in making Li-ion
batteries could be considered business secrets (Deng, 2015).
Other types of electrolyte have also been developed and proposed for Li-ion batteries, such as polymer, gel
and ceramic electrolyte. Polymer electrolytes are solvent-free using high molecular weight-based polymers
with dissolved lithium salts (Croce, Appetecchi, Persi, & Scrosati, 1998). One should be aware that polymer
electrolyte is not considered polyelectrolyte. The obvious advantages of polymer electrolyte over liquid
electrolyte are (1) improved safety properties due to low volatility, (2) design flexibility, and (3) potential to
eliminate separators. Arguably, polymer electrolyte could be more conveniently processed as compared to
that of liquid electrolyte. Simplified processes could reduce the cost significantly. Similar to other
electrolyte, polymer electrolyte must be stable under the operating conditions of Li-ion batteries from
electrochemical, thermal and mechanical perspectives (Deng, 2015). One of the widely studied polymer is
poly (ethylene oxide) which has been coupled with various lithium salts, such as LiCF3SO3 and LiClO4. The
ion conduction in poly(ethylene oxide) mainly occurs at amorphous phases. The ions can be transported by
the semi random motion of short polymer segments. In order to maintain a good mechanical stability, ionic
conductivity will be sacrificed. The conductivity is typically about 10-8 S/cm, which is significantly less
than that of liquid electrolyte. Li-ion batteries based on polymer electrolyte are design flexible and can be
fabricated as cylindrical, coin, prismatic, flat cells and other configurations (Deng, 2015).
Another type of electrolyte is based gels in which both lithium salts and polar solvents are dissolved and
added into inactive networks of high-molecular-weight polymers. LiPF6 and carbonate solvents are typically
used similar to those in liquid electrolyte discussed above. The liquid phases are fully absorbed within the
polymers which can avoid the leakage issue in contrast to that of pristine liquid electrolyte (Deng, 2015).
Meanwhile, the ionic conductivity of gel electrolyte could be dramatically increased as compared to that of
polymer electrolyte. There are a number of polymers explored as the hosts, including polyacrylonitrile,
polyvinyl chloride, polyvinylidene fluoride and Poly(methylmethacrylate). In the preparation of gel
electrolyte, one can simply increase the viscosity of liquid electrolyte by adding soluble polymers.
Alternatively, one can soak the microporous polymer matrix into the electrolyte (Deng, 2015).
Recently, ceramic electrolyte is also re-attracting much attention. Ceramic electrolyte has long been
explored for fuel cells, and their application in Li-ion batteries is attracting increasing interest. The obvious
advantage to use ceramic electrolyte is safety, for example, no more flammable organic solvents needed.
Those batteries with ceramic electrolyte can find applications in high-temperature environment, including
handheld orthopaedic tools and other batteries powered medical devices that need to be sterilized in

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autoclaves under high temperature and high pressure conditions. The batteries autoclaved should be able to
withstand for at least 130°C and are impermeable up to 30 psi in heated water, and importantly, deterioration
in performance should be minimum after sterilization. Another interesting advantage to use ceramic
electrolyte for high-temperature applications is that the ionic conductivity of ceramic electrolyte increases
with increasing temperature. This is because the creation and movement of ionic point defects, which
determines the ionic conductivity, requires energy. One area of intensive research is to achieve ceramic
electrolyte with reasonably high conductivity at room temperature. Various sulfides, oxides and phosphates
have been explored. The author would anticipate that ceramic electrolyte will eventually be used in next-
generation Li-ion batteries in electric vehicles, mainly for its excellent safety performance which can
enhance the customer confidence and acceptance (Deng, 2015).
3.3 Separators
Separators are essential components of Li-ion batteries. In fact, separators are commonly used in most
electrochemical systems with liquid electrolyte, including fuel cells, capacitors and various kinds of batteries
based on different chemistry. The separator in a Li-ion battery plays the critical roles to avoid direct physical
contact between the cathode and anode, and prevents short circuit to occur. At the same time, the separator
allows lithium ions in the electrolyte to pass through it. The separators must be chemically stable and inert in
contact with both electrolyte and electrodes. At the same time, it is required to be mechanically robust to
withstand the tension and puncture by electrode materials and the pore size should be less than 1 μm.
Although various separators, including microporous polymer membranes, nonwoven fabric mats and
inorganic membranes have been explored, the microporous polyolefin materials based polymer membranes
are dominantly used in commercial Li-ion batteries with liquid electrolyte.
The microporous polymer membranes could be made very thin (typically about ~25 μm) and highly porous
(typically 40%) to reduce the resistance and enhance ionic conductivity (Deng, 2015). At the same time, the
polymer membranes could still be mechanically robust. Other parameters that have to be considered in the
selection of microporous polymer membranes are low yield or shrinkage, permeability, wettability and cost.
Another interesting advantage to use microporous polymer membrane as the separator is that, with properly
designed multilayer composites, the separator can shut the battery in the case of short circuit or thermal
runaway, functioning similar to a thermal fuse (Deng, 2015). It is required to have at least two functional
parts in the separator: one part that will melt to close the pores and the other part provides mechanical
strength to keep isolating the anode and cathode. One typical example is the Celgard® (North Carolina,
USA) microporous separator made of both polyethylene (PE) and polypropylene (PP), in the form of trilayer
of PP-PE-PP. The melting points of PE and PP are 135 and 165°C, respectively (Deng, 2015). In the case of
over-temperature approaching that of melting point of PE, the porosity of the membrane could be closed by
PE, preventing further reactions. So for commercial Li-ion batteries, the shutdown temperature is about
130°C (Deng, 2015).
For the development of future Li-ion batteries for high-temperature applications, inorganic membranes as
separators are highly attractive. The all-solid Li-ion batteries should also be further investigated to meet
those niche markets of high-temperature applications. Another parameter that determines the commercial
success of a separator is cost. The cost of the existing polymer separator in a Li-ion battery could be as high
as one-fifth of the total cost of the battery (Deng, 2015). Therefore, intensified research on the development
of highly improved separators at reasonably low price for Li-ion batteries is required (Deng, 2015).
3.4 Electrode/Electrolyte Interface
The cell capacity is referred by the total charge transferred in the electrode-electrolyte interface, which
depends on the current passed through the external circuit during charging discharging process. At high
current, during rapid charging the rate of ion transfer across electrode-electrolyte interfaces occurs in a
diffusion-controlled mechanism (Marcicki, Conlisk, & Rizzoni, 2014). It is predicted that Li may
accumulate on the negative electrode and electrolyte interface when the Li-ion flux during the charge
transfer reaction becomes higher than the Li-ion diffusion flux into the negative electrode (Li, Huang, Liaw,
Metzler, & Zhang, 2014; Purushothaman & Landau, 2006). The massive dendritic growth of Li can be

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observed when the lithium ion concentration exceeds a certain saturation level (0.077 mol cm-3). Such
deposition leads to the deformation of underneath electrode surface, and causes internal short and thermal
runway of battery (Li, Huang, Liaw, Metzler, & Zhang, 2014). Moreover, the dead Li deposited on the
electrode surface creates internal resistance in cell and the changes at the electrode surfaces alters the rate
due to slow diffusion of Li+–ion at the interface resulting irreversible capacity fading. The electrochemical
decomposition of electrolyte at the electrode-electrolyte interface is also responsible for capacity fading
forming the solid-electrolyte interphase (SEI) layer on the active material. Though the SEI layer leads to
irreversible capacity fading in a cell, it also acts as a protective layer against further decomposition of
electrolyte at the electrode-electrolyte interface (Roy and Srivastava, 2015). The characteristic Columbic
efficiency associated with capacity fading can be calculated as the fraction of the electrical charge stored
during charging that is recoverable during discharge after each cycles,
100 disch
ch
Q
Q

(Roy and Srivastava,
2015).
The most common and fundamental source of capacity fade in successful Li-ion batteries (which manage to
resist degradation over hundreds of cycles) is the loss of lithium to the solid-electrolyte interphase (SEI),
which typically forms at the negative electrode during recharging. Initially, SEI formation protects the
electrode against solvent decomposition at large negative voltage, but over time it leads to a gradual capacity
fade as the SEI layer thickens. A solid theoretical understanding of this phenomenon will assist the design of
batteries, for example by enabling the quantitative interpretation of accelerated aging tests, where a battery
is cycled at a high temperature to hasten the progress of capacity fade (Thomas, Bloom, Christophersen, &
Battaglia, 2008).
The selection of materials intimately depends on their crystal structure, physical properties (specific
capacity, electrical conductivity, mechanical stability etc.), chemical properties (intercalation, reversibility)
and many other factors. Other than the structure and properties of materials, size and shape of materials
matter effectively on the performance of LIB. The first generation anode materials were basically
micrometre sized particles where the Li intercalation/de-intercalation reactions occur. The rate of
intercalation-deintercalation of lithium ion strongly depends upon the diffusivity of lithium ion (Bruce,
Scrosati, & Tarascon, 2008). The Li ion diffusion in a host material is associated with Li-ion diffusion
coefficient and diffusion length in the material. In an indirect way diffusivity or diffusion length is
represented as:
2
ion
Li
LD


(3.1)
where
ion
L
is diffusion length and
Li
D
is the diffusion coefficient. While
Li
D
depends upon the nature of
material,
ion
L
depends upon the size of material. Thereby the strategy to achieve high energy and high power
or fast Li intercalation-deintercalation up to certain extends depends on controlling the size of materials
(Roy and Srivastava, 2015). For example, rutile TiO2 having low diffusion coefficient of 10-15 cm2/s are
believed to accommodate a negligible amount of Li ions at room temperature. However, significant changes
can be observed for 5-15nm sized rutile TiO2 nanoparticles showing a full loading of lithium (x > 1 in
LixTiO2) and about 0.7 Li per rutile TiO2 insertion-removal in subsequent cycles (Roy & Srivastava, 2015).
Miniaturization of electrode materials also allows a large surface area in contact with the electrolyte
resulting higher charge/discharge rates (Goriparti, et al., 2014). However, reduction of material size has not
found to be always beneficial for the purpose. The very fast Li+ intercalation-deintercalation often leads to
undesirable side reactions and damage the battery life (Roy and Srivastava, 2015). Consequently, in last few
years, nanomaterials in different morphology have been investigated for application as anodes in LIB.

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4.0 BENEFITS AND CHALLENGES OF Li-ION BATTERIES
4.1 Benefits/Applications
Li-ion batteries are highly advanced as compared to other commercial rechargeable batteries, in terms of
gravimetric and volumetric energy. Figure 4.1 compares the energy densities of different commercial
rechargeable batteries, which clearly shows the superiority of the Li-ion batteries as compared to other
batteries (Tarascon & Armand, 2001). Although lithium metal batteries have even higher theoretical energy
densities than that of Li-ion batteries, their poor recharge ability and susceptibility to misuses leading to fire
even explosion are known disadvantages (Deng, 2015).
Figure 4.1 Comparison of energy densities and specific energy of different rechargeable batteries (Deng,
2015).
Li-ion batteries provide lightweight, high energy density power sources for a variety of devices. To power
larger devices, such as electric cars, connecting many small batteries in a parallel circuit is more effective
and more efficient than connecting a single large battery (Andrea, 2010). Such devices include portable
devices: mobile phones and smartphones, laptops and tablets, digital cameras and camcorders, electronic
cigarettes, handheld game consoles and torches (flashlights); power tools: Li-ion batteries are used in tools
such as cordless drills, sanders, saws and a variety of garden equipment including whipper-snippers and
hedge trimmers; and electric vehicles: including electric cars, hybrid vehicles, electric bicycles, personal
transporters and advanced electric wheelchairs. Also radio-controlled models, model aircraft, aircraft, and
the Mars Curiosity rover (Miller, 2015).
Li-ion batteries are used in telecommunications applications. Secondary non-aqueous lithium batteries
provide reliable backup power to load equipment located in a network environment of a typical
telecommunications service provider. Li-ion batteries compliant with specific technical criteria are
recommended for deployment in the Outside Plant (OSP) at locations such as Controlled Environmental
Vaults (CEVs), Electronic Equipment Enclosures (EEEs), and huts, and in uncontrolled structures such as
cabinets. In such applications, li-ion battery users require detailed, battery-specific hazardous material
information, plus appropriate fire-fighting procedures, to meet regulatory requirements and to protect
employees and surrounding equipment (Wikipedia, 2017b).

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4.2 Challenges
The increasing demand for energy storage requires further improvements in the existing Li-ion batteries and
the development of next-generation Li-ion batteries, in particularly, to reduce the cost of Li-ion batteries. It
is still colossally challenging to develop new battery chemistry to replace the existing Li-ion battery
technology. One of the critical challenges in advancing lithium ion battery technologies is that the battery
capacity tends to fade upon electrochemical cycling. Fracture and decrepitation of the electrodes is observed
as a result of lithium diffusion during the charging and discharging operations. During the battery operation,
when lithium is inserted into (or extracted from) the active materials of both positive and negative
electrodes, volume expansion (and contraction) occurs (Deshpande, 2011).
In order to increase energy density Li-ion batteries, it is desirable to find electrode couples with both high-
specific capacities and high operating cell voltage. As discussed previous, there are a large number of anode
candidates that could dramatically increase the specific capacities, in particularly, with highly attractive Si-
and Sn-based anodes. It is still challenging to prepare Si nanomaterials on a large scale with low cost. Sn-
based anodes suffer from the issue of poor cycling performance due to pulverization. Therefore, one of the
possible future anodes could be Si-Sn-based composites (Wang, Wen, Liu, & Wu, 2009). In contrast to that
of anode candidates, the cell capacity is mainly limited by the low capacity of cathode candidates. The
existing cathode material of LiCoO2 is expensive and highly toxic. The increasingly popular LiFePO4 has a
low capacity. The facilely prepared Ni-Co-Mn-based cathodes developed by Argonne National Laboratory
are highly attractive, especially from industrial prospective (Deng, 2015). However, the specific capacity is
still considered moderate, and both Co and Ni are expensive and toxic. Future cathode materials should try
to avoid the use of either Co or Ni, or other toxic elements, from environmental perspectives. Additionally,
the ideal cathode should be able to reversibly insert/extract multiple electrons per 3d metal. The future low-
cost cathode materials could be Mn-and/or Fe-based. The issue of intrinsically low conductivity should be
creatively addressed, most likely by nanotechnology and nanocomposites. There is relatively no much room
to increase the operating cell voltages with the current known cathode candidates under exploration.
Composite cathodes with two or three 3d metals and polyanions are highly promising (Deng, 2015).
The safety concern is another challenge that needs to be properly addressed. The recent news on fires of Li-
ion batteries, involving the Boeing 787 passenger aircrafts, Tesla Model S cars, highlights the importance of
battery safety. To ensure the wide acceptance of electric vehicles and expanded the market of Li-ion battery
powered vehicles, automakers should invest significantly on the battery management systems to enhance
safety of the huge battery packs in vehicles (Deng, 2015). Alternatively, nonflammable Li-ion batteries
should be developed, including those Li-ion batteries based on aqueous electrolyte or ceramic electrolyte,
and all-solid-state batteries. Next-generation Li-ion batteries, most likely, will be using high voltage (5 V)
cathodes and high capacity anodes (such as Si-or Sn-based). Therefore, intensive research is required to gain
better understanding about those electrode materials in terms of stability and interaction with electrolyte.
Instead of intensively pursuing of high-energy density, there should be increasing emphasis on battery safety
as well. Standardized battery safety testing procedures should be widely employed (Deng, 2015).
It is still challenging to develop electrode materials with low carbon footprint, or the so-called “green
batteries”. Ideally, future Li-ion batteries should use biologically derived organic or inorganic electrodes,
using aqueous electrolyte. Carbon and silicon can be derived from biomasses. The recent attempts to explore
virus-assisted synthesis of electrode materials for Li-ion batteries attracted much enthusiasm (Lee, et al.,
2009). It will be interesting to explore large-scale synthesis at room temperature using biological templates,
including genetically modified virus. Organic electrodes that will not be easily dissolved by electrolyte can
be further developed for sustainable Li-ion batteries (Chen, et al., 2008). Therefore, one area of future
research could be focusing on “sustainable” and “green” Li-ion batteries.
5.1 Conclusion
A review on the recent progress in lithium ion battery technology with the systematic appraisal of the
historical background; theoretical and experimental concepts; applications and challenges of the energy
storage device was carried out in this study. The history and theory of LIB, the experimental concept and

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recent advances in the energy storage technology were discussed. The basic working principle and processes
were also discussed. An overview of the materials involved in the fabrication of the LIB including cathode,
anode, electrolytes and separators is given as well as their benefits and their limitation.
The solid-electrolyte interphase (SEI) which defines the cell capacity during charging discharging process
was discussed. A range of practical benefits and applications in different areas were highlighted and the
current challenges faced by the technology with the probable solutions were discussed.
5.2 Recommendations
The appraisal of the recent progress in lithium ion battery technology has revealed the enormous advantages
of this technology. Based on these benefits, this study recommends that:
i. research effort should focus on the replacement of LiCoO2 commonly used cathode material
which is expensive and highly toxic.
ii. finding electrode couples with both high-specific capacities and high operating cell voltage
should be of research interest.
iii. government at all levels should invest in the development of this technology economically viable.
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