ArticlePDF Available

Reality and Future of Rechargeable Lithium Batteries


Abstract and Figures

Compared to other types of rechargeable batteries, the rechargeable lithium battery has many advantages, such as: higher energy density, lower self-discharge rate, higher voltages and longer cycle life. This article provides an overview of the cathode, anode, electrolyte and separator materials used in rechargeable lithium batteries. The advantages and challenges of various materials used in rechargeable lithium batteries will be discussed, followed by a highlight of developing trends in lithium battery research.
Content may be subject to copyright.
204 The Open Materials Science Journal, 2011, 5, (Suppl 1: M2) 204-214
1874-088X/11 2011 Bentham Open
Open Access
Reality and Future of Rechargeable Lithium Batteries
Haisheng Tao, Zhizhong Feng, Hao Liu, Xianwen Kan and P. Chen*
Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L
3G1, Canada
Abstract: Compared to other types of rechargeable batteries, the rechargeable lithium battery has many advantages, such
as: higher energy density, lower self-discharge rate, higher voltages and longer cycle life. This article provides an
overview of the cathode, anode, electrolyte and separator materials used in rechargeable lithium batteries. The advantages
and challenges of various materials used in rechargeable lithium batteries will be discussed, followed by a highlight of
developing trends in lithium battery research.
Keywords: Rechargeable lithium battery, cathode, anode, electrolyte, separator, review.
Energy and environment are the two most challenging
issues faced by our society. With the production of oil
predicted to decline and the number of vehicles and their
pollution impact to increase globally, a safe, low-cost, high-
efficiency and environmentally friendly alternative power
sources have become a most urgent need. Solar energy, H2
energy, fuel cells and batteries are attracting considerable
interest as alternative power sources. Specifically, batteries
are portable and easily replaced, commonly used in
household and industrial applications such as energy storage
and management [1]. Among various existing batteries (Fig.
1), lithium batteries have raised the most interest and have a
high priority on the development of energy projects in many
countries because of their high energy density, long cycle
life, cost-effective, long lasting, and abuse-tolerant
properties [2].
Fig. (1). The energy density of different batteries.
*Address correspondence to this author at the Department of Chemical
Engineering, University of Waterloo, 200 University Avenue West,
Waterloo, Ontario, N2L 3G1, Canada; Tel: (519) 888-4567x35586; Fax:
(519) 746-4979; E-mail:
Rechargeable lith ium battery is of present interest. There
are many kinds of rechargeable lithium batteries. They have
different classifications according to the forms of lithium
(e.g. lithium metal as anode directly, we call it lithium
battery. For lithium trans-metal salt as anode, we call it
lithium ion battery. Usually, we simp ly call them lithium
battery). Based on the types of electrolytes (such as lithium-
aqueous battery, lithium-organic battery), and the kinds of
cathodes (such as lithium cobalt oxide battery, lithium nickel
oxide battery, lithium manganese oxide battery, lithium iron
phosphate battery, sulfur battery), we have several other
classifications as well.
However, each battery composes of one or several cells,
and each cell has its own characteristic cell potential (V),
capacity (Ah kg1 or Ah L1), and energy density (Wh kg1 or
Wh L1). These characteristics are determined by the
chemical properties of each component of the cell. To
provide the required voltage and capacity, the cells can be
connected in series or parallel configuration. Three primary
functional components of an individual cell are the anode
(negative electrode), the cathode (positive electrode), and the
electrolyte. The transfer of Li ions between the two
electrodes is facilitated by the dissociated lithium salts in the
electrolyte. To fabricate a complete cell, however, requires
additional components, such as a separator, current collector,
tab and cell can.
In the case of discharge, the transfer of energy and
current of a rechargeable lithium battery occurs when the
electrodes are connected externally to a load (Fig. 2). Li ions
are liberated from the anode, pass through the separator, and
are “inserted” into the cathode. At the same time, the anode
releases electrons, which pass through the external circuit
and then arrive at the cathode. In the case of charge, the
process is reversed. The cycling of a battery depends not
only on the property of individual components: cathode,
anode, electrolyte and separator, but also on the
compatibility among different components. During the
development of rechargeable lithium batteries, the first
breakthrough was the discovery of Li ion intercalation
compounds that enable reversible Li ion
intercalation/deintercalation, which opened the concept of
Reality and F uture of Rechargeable Lithium Batteries The Open Materials Science Journal, 2011, Volume 5 205
rechargeability. A second breakthrough was the application
of nanostructured materials, which continuously improve the
performance of rechargeable lithium batteries [3].
Nanostructured materials can increase the specific surface
area as well as reduce diffusion length for electronic and Li
ion transport, leading to a high charge/discharge rate.
Fig. (2). Schematic illustration of a lithium battery (in the case of
As one of the great successes of modern
electrochemistry, the lithium battery has played a key role in
the consumer electronic market. Thanks to the improvement
of the electrodes and electrolytes, the lithium battery is
moving to dominate not only portable battery industry (MP3
player, laptop, cell phone and camera etc.), but also
electronic automotive transpor tation (electric vehicles, full
hybrid electric and plug-in electric vehicles). But the reality
is complex: although scientists have produced numerous
potential battery chemistries, problems of various natures
still prevent the large scale application of lithium batteries
for the electronic automotive transportation. None of them
perform well on all the crucial factors of cost, safety,
durability, power and capacity [4]. To further advance in the
science and technology of lithium batteries, new strategies
must be implemented. This includes modifications of the
electrode and electrolyte components and further
improvements in their safety, environmental sustainability
and energy content.
The following sections provide a review of rechargeable
lithium batteries in terms of cathode, anode, electrolyte and
separator. Significant changes to the properties and
performance of these battery components brought by the
development of intercalation and nanostructured materials
are demonstrated. The challenges and potentials of
rechargeable lithium batteries are also discussed.
The material for an ideal cathode of a rechargeable
lithium battery should have following properties: First, the
material may be capable of reversibly
intercalating/deintercalating Li ions at a large capacity and
high potential. Second, the material should undergo minimal
structural change during Li ion intercalation/ deintercalation,
as required for good cycle performance. Third, the material
should suffer minimal redox potential change during Li ion
intercalation/deintercalation, as required for smooth
charge/discharge curves. Fourth, the material should have
high electronic conductivity, high Li ion diffusion rate and
conductivity, as required for high charge/discharge rate.
Lastly, the material should be chemically stable with the
electrolyte under operating potentials.
The intensively studied cathode materials mainly include
lithium cobalt oxide, lithium nickel ox ide, lithium
manganese oxide, and olivine phases, in particular, lithium
iron phosphate (LiFeO4). Additionally, sulfur based cathode
materials have attracted significant attention recently,
because of their high specific capacity (1670 Ah Kg1). For
lithium cobalt oxide and lithium nickel oxide, both of them
contained layered structure which could offer highly
accessible ion diffusion pathways. The benefit in using
lithium iron phosphate is that, in addition to being naturally
abundant and inexpensive, they are less toxic than cobalt,
manganese, and nickel compounds. There are many merits
making sulfur as a very suitable cathode material, such as the
low equivalent weight, low cost, high capacity, and
environmental friendliness. The advantages and
disadvantages of different cathode materials are discussed
2.1. Lithium Cobalt Oxide and Lithium Nickel Oxide
Lithium cobalt oxide (LiCoO2) is an intercalation
material allowing reversible intercalation/deintercalation of
Li ion. LiCoO2 has a large tap density (2.83.0 g cm3),
large gravimetric capacity (~140 Ah Kg1), excellent
cyclability (500~800 cycles), and high operating voltage (3.6
V). These desirable qualities make LiCoO2 a widely used
cathode material in commercial batteries. However, when the
cell is over-charged or over-discharged, the instability of
LiCoO2 structure could lead to severe material degradation
and even explosion of the cells. This raises serious operation
concerns for commercial operation, but even more so for
personal batter ies. Additionally, cobalt is a relatively rare
and expensive metal, which limits the widespread
implementation of LiCoO2 in power batteries for electric
Besides LiCoO2, there are several other well-known Li
ion intercalation compounds. Lithium nickel oxide (LiNiO2)
is considered a preferred cathode material for its larger
gravimetric capacity (275 Ah Kg1), higher natural
abundance and lower toxicity as compared with LiCoO2. But,
the structure of LiNiO2 is not as stable as that of LiCoO2
8]. To mitigate the structural instability, partial substitution
of Ni with Al, Ga, Mg or Ti is consid ered. For example,
LiNi0.75Al0.25O2 has shown higher thermal stability and safer
operation during over-charge. Moreover, a novel layered
material of LiNi0.32Mn0.33Co0.33Al0.01O2 with -NaFeO2
structure synthesized by sol-gel method has been used as a
cathode in lithium batteries. The capacity retention of
LiNi0.32Mn0.33Co0.33Al0.01O2 has been improved to 97% [9].
Another problem with LiNiO2 is the capacity fading [10],
which may be solved by partially substituting Ni with Ti and
Mg. A typical example is LiNi1-xTix/2Mgx/2O2, which has
been used as a cathode material at a high capacity of 180 Ah
Kg-1 and good thermal stability [11].
206 The Open Materials Science Journal, 2011, Volume 5 Tao et al.
The high capacity of Ni-rich Li[Ni1-xMx]O2 (M=Co, Mn)
is very attractive, if the structural instability and thermal
properties are improved. Yang-Kook Sun et al. synthesized a
spherical core-shell structure with a high capacity (from the
Li[Ni0.8Co0.1Mn0.1]O2 core) and a good thermal stability
(from the Li[Ni0.5Mn0.5]O2 shell) [12]. This core-shell
structured Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2/carbon cell
has a superior cyclability and thermal stability relative to the
Li[Ni0.8Co0.1Mn0.1]O2 at the 1 C rate for 500 cycles.
Expanding on this idea, a concentration-gradient cathode
material for rechargeable lithium batteries based on a layered
lithium nickel cobalt manganese oxide was developed [13].
This novel high-capacity and safe cathode material with an
average composition of Li[Ni0.68Co0.18Mn0.18]O2, in which
each particle consists of bulk material Li[Ni0.8Co0.1Mn0.1]O2
coated by a concentration-gradient outer layer which the
reactive nickel ions are gradually substituted by manganese
ions. As expected, this concentration-gradient cathode
material achieved a high capacity of 209 Ah Kg1 and also
showed superior thermal stability.
2.2. Lithium Manganese Oxides
Lithium manganese oxides yield a high operating voltage
(3.7 V) and are favored over LiCoO2 and LiNiO2 in electric
vehicles because they are safe, cheap and non-toxic. There
are two well known "lithium-rich" manganese oxides, the
spinel LiMn2O4 [14-17] and orthorhombic LiMnO2
Unfortunately, the capacity of these materials decreases
rapidly during cycling at normal operating temperatures due
to structural instability, but this problem can be solved
through cationic substitution with Cr, Al, Mg, and Fe [15,
19-23]. It was reported that Al-doped LiAl0.1Mn1.9O4
materials using a room-temperature solid-state grinding
reaction followed by calcination showed the obviously
improved cyclability compared with the pristine LiMn2O4
[24]. Another problem is its limited cycling and storage
performance at elevated temperatures (>40 oC), which can be
improved by changing the structure (such as using
synthesizing bi-substituted LiMn2-xAlxO4-zFz) [25, 26], or
modifying the surface (such as acetylacetone, boron oxide
and alkali-hydroxydes solution treatment) [27, 28].
2.3. Lithium Iron Phosphate
In 1996, lithium iron phosphate (LiFePO4) was
discovered and used as a cathode material for rechargeable
lithium batteries [29, 30]. It gained vehicle market
acceptance because of its low cost, low toxicity, excellent
thermal stability, and high gravimetric capacity (170 Ah
Kg1). However, the main application barrier of LiFePO4 was
its intrinsically low electrical conductivity [31]. This may be
overcome by synthesizing LiFePO4 in nanoparticles.
Alternatively, the same improvement in electrical
conductivity can be achieved by carbon coating of LiFePO4
[32-34] or doping LiFePO4 with various metal elements [35-
37]. It was reported that stoichiometric Cu-doped lithium ion
phosphate LiFe1-xCuxPO4/C (x = 0, 0.01, 0.015, 0.02, 0.025)
cathode materials had been synthesized by a solid state high
temperature reaction in an inert atmosphere using Cu(Ac)2 as
a dopant and FePO4 as a precursor. The charge/discharge test
showed that the cathode materials possessed the excellent
charge/discharge capacities, about 150 Ah Kg1 and 297 Ah
L1 at a rate of 0.1 C and more than 127 Ah Kg1 and 252 Ah
L1 at a rate of 2 C [38]. These approaches do not increase
the lattice electronic conductivity or chemical diffusion
coefficient of lithium within the crystal.
The power density (i.e., the charge/discharge rate) of
LiFePO4 is limited by the rate of Li ion and electron
migration through the electrolyte into the electrode [39].
Strategies to increase the charge/discharge rate of LiFePO4
have focused on improving electron transport overall [35] or
simply at the cathode surface [31, 40], along with reducing
the diffusion distance by using nano-sized materials [41, 42].
Moreover, LiFePO4 nanoparticals coated with a lithium
phosphate layer demonstrated an extremely high
charge/discharge rate [43] due to the lithium phosphate outer
layer providing an ultrafast charging and discharging Li ion
tunnel. Another promising cathode material is LiFeSO4F
[44]. By introducing fluorine and by replacing phosphate
group with more electron-withdrawing sulphate groups, this
material does not need nanostructuring or carbon coating.
2.4. Sulfur-Based Materials
The specific capacity of sulfur (S) cathodes is high (1670
Ah Kg1) compared to that of most other materials, e.g.,
LiCoO2, LiNiO2, LiMn2O4, LiMnO2 and LiFePO4. In
addition, S has a low cost and readily available, having a
wide operation temperature range and possibility of long
cycling. However, it has not been widely commercialized
because of the poor electrical conductivity of elemental S
and polysulfide shuttling that occurs during charge/discharge
cycles [45]. To solve these problems as well as large volume
change of S, a nanostructured S-carbon [46] and a
hierarchically structured S-carbon nanocomposite [47] were
developed for cathodes.
Lithium sulfide (Li2S) is also a possible cathode material.
Similar to S, the poor electronic conductivity of Li2S restricts
its practical application, despite a high theoretical capacity of
1166 Ah Kg1 [48, 49]. Metal additives (such as Cu, Co, and
Fe) have been employed to enhance the conductivity of Li2S-
based cathodes [48-50]. But the metal additives result in a
lower output voltage [49, 50]. A nanostructured Li2S-carbon
[47] has been employed as a cathode material to solve the
insulation and solubility of polysulphide anions during
charge/discharge [51].
Both S-carbon and Li2S-carbon nanostructured materials
use electrical conductive micro/mesoporous carbon for
loading S or Li2S. These materials have a high specific
surface area in contact with electrolytes as well as a reduced
diffusion length for electronic and Li ion transport. These
properties lead to a high charge/discharge rate. Furthermore,
the spatial confinement of micro/mesoporous carbon
represses the solubility of polysulphide anions.
There are a number of commercial cathode materials
available. However few of them can meet all the necessary
requirements. Considering of these, ternary materials [Such
as LiCoxMnyNi1-x-yO2 (0<x<0.5, 0<y<0.5)] and sulfur are the
possible cathodes to be commercialized. Table 1 summarizes
the properties of commonly used materials in rechargeable
lithium batteries.
Reality and F uture of Rechargeable Lithium Batteries The Open Materials Science Journal, 2011, Volume 5 207
The materials for the ideal anode of rechargeable lithium
batteries should have following properties: First, the anode
materials may have the ability to reversibly
intercalate/deintercalate Li ion, at a large capacity and low
potential. Similar to cathode materials, the anode materials
should suffer minimal structural and redox potential change
during the Li ion intercalation/deintercalation. These two
requirements are important for good cycle performance and a
smooth charge/discharge curve. Second, the anode materials
should have high electronic conductivity, high Li ion
diffusion rate and conductivity. Lastly, the anode materials
should form a good solid-electrolyte interface with
electrolytes at the first circle, and remain chemically stable
with the electrolyte in the subsequent cycles.
Carbon-based materials are generally used in commercial
Li ion batteries as the anode. However, based on the
limitation of the theoretical gravimetric capacities of these
materials (372 Ah Kg1, LiC6), many efforts have been
carried out to develop higher capacity anode materials, such
as Li-based materials, Tin-based materials, Transition-metal
oxides and silicon. The advantages and disadvantages of
different types of anode materials are discussed below.
3.1. Li-Based Materials
Lithium is a most electropositive (3.04 V versus
standard hydrogen electrode) as well as the lightest metal in
the elemental table [3]. As an anode material, it has a
theoretical capacity of 3860 Ah Kg1. However, lithium can
react with organic electrolytes, resulting in an insulating
layer or gas evolution, thus increasing the internal pressure
in the cell. Meanwhile, lithium dendrites form on the lithium
electrode surface during charge/discharge, bringing in two
serious results: a gradual fading of capacity due to the
fracture of dendrites, and internal short circuiting of cells due
to the penetration of dendrites through the separator. Ionic
conductors, lithium phosphorus oxynitride, lithium nitride,
lithium superionic conductors (LISICON) and different
electrolytes have been used to restrain the formation of
lithium dendrites [52-60].
In order to improve the safety of lithium batteries, Li3-
xCoxN (x=0.1~0.6) was used as a new material to substitute
the existing lithium anode. Despite the large and reversible
capacity (760 Ah Kg1 or 1500 Ah L1), moisture sensitivity
can restrict the practical use of this material [61].
3.2. Carbon-Based Materials
In commercial Li ion batteries, soft carbon (such as
nature graphite) and hard carbon (such as pyrolytic carbon
from polymer) are widely used as the anode, because of
theirs low and smooth charge/discharge potential, and good
cycle performance. It has some shortcomings, however, such
as low capacity (372 Ah Kg1 or 830 Ah L1), bad
performance under high charge/discharge rates (lithium can
deposit on the surface of graphite), and cointercalation of
organic solvent into graphite [62, 63]. Many current research
efforts are focused on searching for new materials to
substitute graphite anodes.
Graphene is a two-dimensional aromatic monolayer of
carbon atoms. It has been proposed that Li ion could be
adsorbed on both sides of graphene sheets, which leads to
two layers of lithium for each graphene sheet, with a
theoretical capacity of 744 Ah Kg1 through the formation of
[64, 65]. It was reported that the electrochemical
performances were supposed to be greatly enhanced if
combined with Fe3O4 nanoparticles and graphene [66]. The
Fe3O4 nanoparticles were dispersed on graphene sheets via
microwave irradiation synthesis. As anode materials for Li
ion batteries, they showed high reversible capacities, as well
as significantly enhanced cycling performances (about 650
Ah Kg1 after 50 cycles) and high rate capabilities (350 Ah
Kg1 at 5 C), which might be attributed to graphene sheets
not only acted as electron conductors, but also buffers which
accommodated the strains of Li ion insertion/extraction and
relieved the strain associated with the volume variations
during cycles.
Table 1. Comparison of Typical Cathode Materials
LiCoO2 LiMn2O4 LiFePO4
Theoretical Capacity (Ah Kg1) 145 148 170
Commercial Capacity (Ah Kg1) 135~ 140 100~ 110 140~160
Tap Density (Kg L1) 2.6~3.0 1.8~2.4 0.8~1.4
Discharge Plateau (V) 3.6 3.7 3.3
Cycle Life (Cycles) 500-800 1000-1500 > 3000
Working Temperature (oC) 20~55 20~50 20~60
1. Simple process
2. High volumetric capacity
1. Cheap
2. Simple process
1. Cheap
2. Eco-friendly
3. Safe
1. Expensive
2. Toxic
1. Capacity fades
at elevated
1. Low conductivity
2. Complex process
3. Low volumetric
Applied Areas Portable Devices Electric Vehicles Electric Vehicles
208 The Open Materials Science Journal, 2011, Volume 5 Tao et al.
3.3. Tin-Based Materials
Lithium will form alloys with some metals under certain
conditions, in which Li ion can reversibly
intercalate/deintercalate. Metals and alloys have been
investigated for anode application since 1970, and have a
much larger capacity than that of graphite. A commercial
battery based on a low-melting alloy (an alloy of Bi, Pb, Sn
and Cd) for anodes was introduced in the 1980s [67, 68].
Li22Sn5 has a high theoretical capacity of 990 Ah Kg1 or
7200 Ah L1. However, the volume and composition of this
kind of alloy change during the electrochemical reaction,
leading to fragmentation of the alloy [69, 70].
Intermetallic compounds MM´ (M is an “active” element,
can form an alloy with lithium, and M´ is an “inactive”
element, cannot form an alloy with lithium) have been used
as anode materials, and the cycling performance of these
compounds can be improved significantly if the active alloy
element is finely dispersed completely in an inactive matrix
[71]. Therefore, it is believed that the inactive species
provides structural stability and combats the expansion of the
alloy composite. The reversible reactivity of intermetallic
compound SnFe with Li ion has been explored for an anode
material [72-74]. The benefit arises from the alloy formation
between Li ion and Sn atoms at the grain boundaries of
SnFe3 particles [75]. However, the cycling performance was
improved at the expense of the capacity. Another approach
to improve the cycling performance was that Li ion could be
intercalated into the intermetallic compound Cu6Sn5 to yield
the product Li13Cu6Sn5 with the volumetric capacity of 2964
Ah L1. In addition, Li ion does not alloy or react with the
“inactive” component (i.e., Cu), which further increases the
stability of the anode. Note that Cu6Sn5 has relatively small
irreversible capacities compared to tin oxides [76].
Tin-based amorphous oxides, SnMxOy (M is B, P or Al,
x1), have a high volumetric specific capacity of more than
2200 Ah L1. In these compounds, Sn forms the
electrochemically active center for Li ion intercalation, and
the other metal group provides an electrochemical inactive
network of -(M-O)- bonding, to confer high reversibility in
Li ion storage and release [77, 78]. This type of the material
has not been commercialized because of poor long-term
cyclability and the fact that a large amount of the capacity is
irreversibly lost during the first cycle (because many Li ion s
have reacted to form Li2O and solid-electrolyte interface
Tin-transition metal-carbon (Sn-TM-C) alloys have been
used to replace graphite as the anode for Li ion batteries [79].
The Sony Corporation launched in 2005 a Li ion battery that
uses a “tin-based amorphous anode” comprising tin, cobalt
and carbon as the anode [80]. The Sn-Co-C system has been
proposed to be the best choice among Sn-TM-C (TM=
transition metal) for anodes in Li ion batteries since a
nanostructure consisting of amorphous CoSn grains in a
carbon matrix is formed during sputtering or during
mechanical milling [81-83]. It was reported that Sn30Co30C40
had good capacity retention for at least 100 cycles at around
425 Ah Kg1, and Sn30Co15TM15C40 also showed good
capacity retention for at least 100 cycles ranging from 270
Ah Kg1 for samples with TM=Ni to 500 Ah Kg1 for
samples w ith TM=Ti, which might be attributed to the
desired nanostructured-type XRD pattern [84].
3.4. Transition-Metal Oxides
Transition-metal oxides (MO) were proposed as anode
materials for their large capacity at low potentials [85, 86].
The reaction mechanism between MO (M is Co, Ni, Cu or
Fe) and Li ion differs from the classical Li ion
intercalation/deintercalation or Li-alloying processes [87]. It
involves the composition and decomposition of Li2O,
accompanied with the reduction and oxidation of the
transition metal, respectively. The capacities of these
transition-metals are all greater than 700 Ah Kg1, with high
capacity retention and high recharging rate. These systems
hold much promise for future development.
Among MO materials, the capacities of Ti-based oxides
are less than half that of graphite (175 Ah Kg1 for
Li4Ti5O12). However, these materials have many advantages,
such as outstanding stability, rapid charge rate, and wide
operating temperature (range from 50 °C to 75 °C). The
combination of these advantages results in ultra long
durability (around 20 years) and cycle life (9000 cycles). In
addition, these batteries do not explode or result in thermal
runaway under harsh conditions [88, 89].
3.5. Silicon
Among all the compounds proposed to replace the
graphite anode, silicon is very promising because it has a
theoretical specific capacity of 4200 Ah Kg1 (for Li22Si5)
[90, 91]. Moreover, silicon is the second most abundant
element on earth and already has a mature industrial
infrastructure in existence. It is an attractive material when
considering commercial applications. But the biggest
holdback preventing the commercial application of silicon is
the large inherent change in specific volume (up to about
410%) during the intercalation/deintercalation of Li ion. This
causes crumbling, and a loss of electrical contact between
the active material and the current collector [69, 92-95].
Recently, Si nanowires were developed as the anode material
to accommodate the large volume change and to avoid
capacity loss during cycling [96-102]. In addition, nanowires
form direct chemical bonds with the current collector for
good adhesion and electron transport, which makes the
binding polymer and conducting graphite unnecessary. The
observed specific capacity was about 2800 Ah Kg1 [84].
Yushin et al. conducted a large-scale hierarchical bottom-up
assembly route for the formation of Si on the nanoscale-
containing rigid and robust spheres with irregular channels
for rapid access of Li ions into the particle bulk. Reversible
capacities of the C-Si nanocomposite reached up to 1,950 Ah
Kg1, which is over five times higher than that of the
theoretical capacity of graphite [103, 104].
The capacity of different anode materials is shown in Fig.
(3). Despite many candidates for anode materials, graphite is
the only widely used commercial anode material. Other
anode materials, such as Li4Ti5O12 and Li22Sn5, are currently
on a small scale application. Looking into the future, the
trend of anode materials may shift to high capacity lithium or
silicon materials.
Reality and F uture of Rechargeable Lithium Batteries The Open Materials Science Journal, 2011, Volume 5 209
Fig. (3). The capacity of different anode materials.
Electrolyte is one of the key components of a battery,
which is commonly referred to as a solution comprising
solvents and salts (such as LiPF6, which is well known for its
rapid dissolution in carbonate solvents, lower cost and good
conductivity [105, 106]). The choice of electrolytes is very
crucial, and depends on the choice of the anode and the
cathode. For instance, graphite anodes operate in a highly
reducing voltage range (<1.2 V vs lithium), at which point
most electrolytes are thermodynamically reduced. To ensure
reversible behavior, the deposition of an efficient passivating
layer at the graphite surface is necessary during the first
cycle. The electrolyte was probably oxidized when the
lithium oxide cathode materials were charged up to more
than 4 V vs lith ium [7, 107]. Electrolyte oxidation leads to
irreversible loss of capacity, because of the generation of
new chemical species, which deposit on the electrode surface
as an insulating layer or evolve as a gas, thus increasing the
internal pressure in the cell. Electrolyte oxidation is believed
to be the main failure mechanism for rocking-chair
technology [108]. Thus, minimizing electrolyte oxidation is
a major requirement in enhancing the cycle life and
improving the performance of lithium batteries at elevated
temperatures. Fortunately, the electrolyte oxidation reaction
is limited. Most of the electrolytes can be used beyond the
voltage range of their thermodynamic stability [108].
4.1. Traditional Organic Liquids
There are numerous liquid compounds available to be
selected as electrolytes. Viscosity, dielectric constants and
ionic conductivity of an organic liquid should be considered
first to determine a suitable electrolyte. Most liquid
electrolytes are composed of ethylene carbonate (EC) and
dimethyl carbonate (DMC). EC is present in almost all
commercial compositions, because of its low cost, good
electrochemical stability, and high dielectric constant which
permits better ionic dissociation of the salt and improves the
ionic conductivity. Furthermore, it can provide a protective
layer on the surface of graphite that prevents further reaction
[109]. However, a pure EC-based electrolyte was not used
because of its high freezing point (35-38 oC), which is not
compatible with practical application. DMC, commonly
known as a thinning solvent, is used with EC to reduce the
viscosity. Note that a pure DMC-based electrolyte is not
compatible with graphite anodes, since no passivation layer
can build up during cycling [108]. In general, the traditional
liquid electrolytes have several disadvantages, such as
flammability and a narrow range of operating temperatures
[110]. These problems could be solved by novel electrolytes
such as ionic liquids, organic solid electrolytes or inorganic
solid electrolytes.
4.2. Ionic Liquids
Ionic liquids as electrolytes for lithium batteries have
been studied in recent years [111-113]. The ionic liquids are
nonflammable as they contain no volatile compound. In
addition, they show a broad electrochemical stability
window (generally>4 V). Early attempts to cycle Li ion
batteries using electrolytes on the basis of ionic liquids failed
because of electrolyte reduction occurring at the low
potential [114]. One type of good ionic liquid utilized as an
electrolyte is an aluminum chloride (AlCl3) based solution.
However, AlCl3 is toxic and difficult to process [115-117].
(trifluoromethylsulfonyl) imide [111] and n-
hexyltrimethylammonium-bis (trifluoromethylsulfonyl)
imide [118] (AlCl3-free ionic liquids) were successfully
developed and have been used as electrolytes. Highly
reversible and stable cycling have also been obtained using
1-ethyl-3-methylimidazolium-bis (trifluoromethylsulfonyl)
imide as the electro lyte [119]. A solvent-free, ternary
polymer electrolytes based on a novel poly
(diallyldimethylammonium) bis (trifluoromethanesulfonyl)
imide polymeric ionic liquid (PIL) as polymer host and
incorporating PYR14TFSI ionic liquid and LiTFSI salt are
reported (Ternary polymer electrolytes containing
pyrrolidinium-based polymeric ionic liquids for lithium
batteries) [120]. The PIL-based polymer electrolytes
exhibited room temperature ionic conductivity above 104 S
cm1, and the Li/PIL-LiTFSI-PYR14TFSI /LiFePO4 solid-
state batteries are capable to deliver above 140 Ah Kg1 at 40
oC. Over all, still only a few ionic liquid electrolytes have
been found suitable for lithium batteries because of their
high viscosity issues [121].
4.3. Organic Solid Electrolytes
Many efforts have been dedicated to develop all-solid-
state Li ion batteries [2]. Organic polymers (rubbery
electrolytes) are the promising candidates. Polymer
electrolytes are commonly composed of a lithium salt (LiX)
and a high-molecular-weight polymer such as polyethylene
oxide (PEO). However, PEO crystallization below 60 oC is a
challenge for electrolyte application at lower temperature. As
a result, PEO-LiX electrolytes work only at temperatures
above 60 oC. The most common approach for lowering the
operational temperature is adding liquid plasticizers (such as
propylene carbonate or polyethylene glycol ethers) or gels
(contain 60-95% liquid) [122]. But this method promotes the
deterioration of the electrolyte’s mechanical properties and
increases its reactivity towards the lithium anode. A series of
“polymer-in-salt” materials were developed as electrolytes,
in which lithium salts were mixed with small quantities of
the polymers, e.g., polypropylene oxide and polyethylene
oxide. The glass transition temperature of these materials is
low enough to remain rubbery at room temperature with
good Li ion conductivity and high electrochemical stability
210 The Open Materials Science Journal, 2011, Volume 5 Tao et al.
[123]. When using TiO2 or Al2O3 nanoparticles as solid
plasticizers in PEO, a solid-state polymer electrolyte has
been developed [124]. The conductivity of these electrolytes
increased and the crystallization was well prevented. Li ion
doped plastic crystalline matrixes are stable over a potential
of 5 V and very attractive for battery applications in
combination of possible structural variations of plastic
crystal matrixes and conductivities [125]. Huang et al. have
prepared a novel solid-state composite polymer electrolyte
based on poly (ethylene oxide) (PEO) by using LiClO4 as
doping salts and inorganic-organic hybrid poly
(cyclotriphosphazene-co-4, 40-sulfonyldiphenol) (PZS)
microspheres as fillers [126]. Compared with traditional
ceramic fillers such as SiO2, PZSMS in PEO-based polymer
electrolytes leads to higher enhancement in ionic
4.4. Inorganic Solid Electrolytes
Other promising candidates for solid electrolytes are
inorganic materials (brittle superionic glass electrolytes). For
inorganic solid electrolytes, lithium superionic conductors
(LISICON) are very importance with respect to achieving an
all solid-state lithium battery. This technology may solve the
safety problems of the rechargeable Li ion batteries using
nonaqueous liquid electrolytes. In 1978, Li14Zn(GeO4)4, a
type of LISICON was found [127], which attracted attention
for its potential application as a solid electrolyte [128].
A new solid system based on lithium germanium sulfide
and lithium silicon sulfide was found [129, 130], named
“thio-LISICON”. This is the first example of crystalline
ionic conductor with a high ionic conductivity and high
decomposition potential at room temperature. Sulfide-based
electrolytes generally have a higher Li ion conductivity, by
several orders of magnitude, compared with oxide-based
electrolytes. For example, the Li ion conductivity of thio-
LISICON is around 10-3 S cm1 for Li3.25Ge0.25P0.75S4, four
orders of magnitude higher than Li14Zn(GeO4)4, a typical
oxide LISICON.
The thio-LISICO N has high electrochemical stability,
which is important for all solid-state lithium batteries. Many
studies focused on the binary Li2S-P2S5 system [131].
70Li2S-30P2S5 (mol%) glass was prepared by a quenching
melt techniques [132]. The obtained glass-ceramic showed
high Li ion conductivity of 2.1103 S cm1 at room
temperature. Glass-ceramic Li2S-P2S5 electrolytes were
prepared by a single step ball milling process at 55 oC [133].
The produced crystalline glass-ceramic materials exhibit
high Li ion conductivity over 10-3 S/cm at room temperature
with a wide electrochemical stability window of 5 V.
Ideally, liquid electrolytes will be replaced by solid state
electrolytes that can perform similarly without excessive
safety issues [134]. The current barriers with solid state
electrolytes include inferior charge/discharge rate, ionic
conductivity, interfacial stability and mechanical strength
[135, 136]. Efforts have been carried out to find a solid state
electrolyte that can outperform liqu id electrolytes.
A separator is an important component of a battery cell,
as it prevents short circuit by separating the anode from the
cathode, as well as providing passages for Li ion [137]. In a
Li ion battery, the separator is required to be capable of
battery shutdown at the temperature below that at which
thermal runaway occurs, and the shutdown should not result
in loss of mechanical integrity. Otherwise, the electrodes
could come into direct contact and the resulting chemical
reactions cause thermal runaway [111]. Shutdown is an
important trait of a good separator for the safety of lithium
batteries. The promising separators are those with high
electrolyte permeability and mechanical strength, as well as
good thermal, chemical, and electrochemical stability.
5.1. Organic Separators
In commercially available lithium batteries, microporous
membranes fabricated from polyethylene (PE) and
polypropylene (PP) are used as separators [138-140]. These
polyolefin separators are suitable for batteries, since they can
be used for hundreds of cycles without any chemical or
physical degradation. The collapse of the pores occurs when
the temperature approaches the melting point of the material,
which forms a nonporous insulated film and results in a
sharp increase in impedance. Since the impedance of a PP
separator increases less than that of a PE separator, the
impedance of the PP separator may not be large enough for
complete shutdown, and thermal runaway could still happen.
Therefore, PE is the preferred separator material for most Li
ion batteries [141, 142]. Robust mechanical properties of the
separator are expected even above the shutdown temperature
because the battery temperature may increase continuously
after shutdown. When the separator undergoes a meltdown,
the mechanical properties of the separator could deteriorate
greatly and the cell may experience an internal short circuit,
resulting in a hazard. The shutdown temperature of a
separator should be lower than its meltdown temperature. A
sandwiched separator containing one porous PE layer
between two porous PP layers (PP-PE-PP trilayer) has been
made to maintain the robust mechanical properties. The PE
layer offers a lower shutdown temperature; whereas the PP
provides mechanical stability above the shutdown
temperature (such as Celgard® [143]). The shutdown
temperature and meltdown temperature were increased to
142 °C and 155 °C respectively, when the separator was
coated with diethylene glycol dimethacrylate [144]. When
silica nanoparticles were added to the separator, the
meltdown temperature increased to 170 °C [145]. Polyolefin
membrane separators, however, have several drawbacks,
such as large thermal shrinkage near its melting/softening
temperature, low porosity and low wettability in electrolyte
solutions. Silica-composite nonwovens using polyolefin fiber
and nanosize silica powder showed not only better
wettability than the polyolefin-based membrane and
nonwoven, but also thermal shrinkage of ~3% at 160 °C
under air atmosphere and thermally stable at 150 °C in the
liquid electrolyte [146].
5.2. Inorganic Separators
Separators can also be made of inorganic sub-micron
sized particles and a small amount of polymer binder, which
have dimensional stability at a high temperature as well as
wettability [147]. This type of separator is highly desirable
for the developmen t of large-size lithium batteries, especially
those installed in electric vehicles and power tools.
Nonwoven support materials can improve the mechanical
Reality and F uture of Rechargeable Lithium Batteries The Open Materials Science Journal, 2011, Volume 5 211
strength of inorganic separators [146]. Recently, nonwoven
supported inorganic separators prepared via a sol-gel coating
method were commercialized for Li ion batteries [148, 149].
Kim et al. prepared an inorganic separator by coating
inorganic submicrometer sized Al2O3 particles on a
nonwoven matrix Aramid fiber followed by an E-beam
irradiation treatment [150]. The mechanical and thermal
properties of the separator were greatly enhanced by the
simple curing under E-beam irradiation. Remarkable
improvements of the separators with respect to the battery
safety have been demonstrated by a series of abuse tests.
However, the practical application of the inorganic particle
coated nonwoven separators using polymeric binders has not
been realized, because of insufficient mechanical strength to
withstand the roll-to-roll manufacturing process [150].
The performance of rechargeable lithium batteries
depends on the properties of cathodes, anodes, electrolytes
and separators. The discovery of intercalation materials has
played a significant role in increased performance. Th e
intercalation materials, such as the graphite anode and the
LiCoO2 cathode, impact the large scale commercialization of
rechargeable lithium batteries. Besides intercalation
materials, the application of nanostructured materials results
in substantial improvemen ts of r echargeable lithium
batteries. Currently, lithium cobalt oxide, lithium manganese
oxide and lithium iron phosphate are the most used cathode
materials. Other promising cathode materials, such as sulfur
and lithium sulfide, are under development. In the area of
anode materials, graphite is the most widely used. However,
the tin-based anode material technology is maturing, and the
lithium or silicon-based materials are also becoming next
generation anode materials. In the past, lithium was chosen
as the anode material of lithium batteries due to its largest
theoretical energy density. However, the market for lithium
anodes has dropped due to safety concerns and battery
stability . As shown in Fig. (1), the highest energy density of
existing Li ion batteries is only about 150 Wh Kg1 or 300
Wh L1, and the maximum energy density of the ideal Li ion
batteries is about 580 Wh kg1 or 1810 Wh L1. The ideal
lithium-sulfur (Li-S) battery has a much higher energy
density of 2500 Wh kg1 or 2800 Wh L1. In this regard, the
Li-S battery may be the rechargeable lithium battery of the
From potable electronics to electric vehicles or hybrid
electric vehicles, power sources that have a high
charge/discharge rate, high power density, long cycle life,
and safe operation are in constant demand. The successful
design of new assembly technology, discovery of new
materials, and development of new theories will promote the
development of next generation rechargeable lithium
[1] Howell D. Progress Report for Energy Storage Research and
Development. U. S. Department of Energy 2009.
[2] Tarascon J-M, Armand M. Issues and challenges facing
rechargeable lithium batteries. Nature 2001; 414: 359-67.
[3] Arico AS, Bruce P, Scrosati B, Tarascon JM, Van Schalkwijk W.
Nanostructured materials for advanced energy conversion and
storage devices. Nat Mater 2005; 4 (5): 366-77.
[4] Tollefson J. Charging up the future. Nature 2008; 456: 436-40.
[5] Thomas M, David WIF, Goodenough JB, Groves P. Synthesis and
structural characterization of the normal spinel LiNi2O4. Mater Res
Bull 1985; 20 (10): 1137-46.
[6] Dahn JR, Vonsacken U, Michal CA. Structure and electrochemistry
of Li1±yNiO2 and a new Li2NiO2 phase with the Ni(OH)2 structure.
Solid State Ionics 1990; 44 (1-2), 87-9.
[7] Dahn JR, Vonsacken U, Juzkow MW, Aljanaby H. Rechargeable
LiNiO2 carbon cells. J Electrochem Soc 1991; 138 (8): 2207-11.
[8] Plichta E, Salomon M, Slane S, et al. A rechargeable Li/LixCoO2
cell. J Power Sources 1987; 21: 25-31.
[9] Wang F, Yang J, NuLi YN, Wang JL. Highly promoted
electrochemical performance of 5 V LiCoPO4 cathode material by
addition of vanadium. J Power Sources 2010; 195 (19): 6884-7.
[10] Ohzuku T, Yanagawa T, Kouguchi M, Ueda A. Innovative
insertion material of LiAl1/4Ni3/4O2 (R
m) for lithium-ion
(shuttlecock) batteries. J Power Sources 1997; 68 (1): 131-4.
[11] Gao Y, Yakovleva MV, Ebner WB. Novel LiNi1-xTix/2Mgx/2O2
compounds as cathode materials for safer lithium-ion batteries.
Electrochem Solid State Lett 1998; 1: 117-9.
[12] Sun YK, Myung ST, Kim MH, Prakash J. Amine K, Synthesis and
characterization of Li [(Ni0.8Co0.1Mn0.1)0.8 (Ni0.5Mn0.5) 0.2] O2 with
the microscale core-shell structure as the positive electrode material
for lithium batteries. J Am Chem Soc 2005; 127 (38): 13411-8.
[13] Sun YK, Myung ST, Park BC, Prakash J, Belharouak I, Amine K.
High-energy cathode material for long-life and safe lithium
batteries. Nat Mater 2009; 8: 320-4.
[14] Guyomard D, Tarascon JM. Rechargeable Li1+xMn2O4/carbon cells
with a new electrolyte- composition-potentiostatic studies and
application to practical cells. J Electrochem Soc 1993; 140 (11):
[15] Tarascon JM, Wang E, Shokoohi FK, McKinnon WR, Colson S.
The spinel phase of LiMn2O4 as a cathode in secondary lithium
cells. J Electrochem Soc 1991; 138 (10): 2859-64.
[16] Tarascon JM, Guyomard D. Li metal-free rechargeable batteries
based on Li1+XMn2O4 cathodes (0x1) and carbon anodes. J
Electrochem Soc 1991; 138 (10): 2864-8.
[17] Gummow RJ, Liles DC, Thackeray MM. Lithium extraction from
orthorhombic lithium manganese oxide and the phase
transformation to spinel. Mat Res Bull 1993; 28: 1249-56.
[18] Armstrong AR, Bruce PG. Synthesis of layered LiMnO2 as an
electrode for rechargeable lithium batteries. Nature 1996; 381
(6582): 499-500.
[19] Cho J, Park B. Li2+xMn0.91 Cr1.09O4 cathode materials for Li-ion
cells. Electrochem Solid State Lett 2000; 3 (8): 355-8.
[20] Davidson IJ, McMillan RS, Slegr H, et al. Electrochemistry and
structure of Li2-xCryMn2-yO4 phases. J Power Sources 1999; 81:
[21] Dahn JR, Zheng T, Thomas CL. Structure and electrochemistry of
Li2CrxMn2-xO4 for 1.0x1.5. J Electrochem Soc 1998; 145 (3):
[22] Jang YI, Huang BY, Chiang YM, Sadowa DR. Stabilization of
LiMnO2 in the -NaFeO2 structure type by LiAlO2 addition.
Electrochem Solid State Lett 1998; 1:13-6.
[23] Thackeray MM. Manganese oxides for lithium batteries. Prog Solid
State Chem 1997; 25 (1-2): 1-71.
[24] Yuan AB, Tian L, Xu WM, Wang YQ. Al-doped spinel
LiAl0.1Mn1.9O4 with improved high-rate cyclability in aqueous
electrolyte. J Power Sources 2010; 195 (15): 5032-8.
[25] Amatucci G, Du Pasquier A, Blyr A, Zheng T, Tarascon JM. The
elevated temperature performance of the LiMn2O4/C system:
Failure and solutions. Electrochim Acta 1999; 45 (1-2): 255-71.
[26] Amatucci GG, Pereira N, Zheng T, Tarascon JM. Failure
mechanism and improvement of the elevated temperature cycling
of LiMn2O4 compounds through the use of the LiAlxMn2-xO4-zFz
solid solution. J Electrochem Soc 2001; 148 (2): A171-82.
[27] Amatucci GG, Blyr A, Sigala C, Alfonse P, Tarascon JM. Surface
treatments of Li1+xMn2-xO4 spinels for improved elevated
temperature performance. Solid State Ionics 1997; 104 (1-2): 13-
[28] Wang EI, Mass M. Methode of Treating Lithium Manganese Oxide
Spinel. US5783328, July 21, 1998.
[29] Padhi AK, Nanjundaswamy KS, Goodenough JB. Phospho-olivines
as positive-electrode materials for rechargeable lithium batteries. J
Electrochem Soc 1997; 144 (4): 1188-94.
212 The Open Materials Science Journal, 2011, Volume 5 Tao et al.
[30] Goodenough JB, Padhi AK, Nanjundaswamy KS, Masquelier C.
Cathode materials for secondary (rechargeable) lithium batteries.
US5910382, June 8, 1999.
[31] Herle PS, Ellis B, Coombs N, Nazar LF. Nano-network electronic
conduction in iron and nickel olivine phosphates. Nat Mater 2004;
3 (3): 147-52.
[32] Wang YG, Wang YR, Hosono E, Wang KX, Zhou HS. The design
of a LiFePO4/Carbon nanocomposite with a core-shell structure
and its synthesis by an in situ polymerization restriction method.
Angew Chem Int Ed 2008; 47: 7461-5.
[33] Ravet N, Abouimrane A, Armand M. From our readers. Nat Mater
2003; 2: 702.
[34] Sun YK, Oh SM, Myung ST, Amine K, Scrosati B. 15th
International Meeting on Lithium Batteries; July 2010; Montréal,
Québec, Canada; 1010.
[35] Chung SY, Bloking JT, Chiang YM. Electronically conductive
phospho-olivines as lithium storage electrodes. Nat Mater 2002; 1
(2): 123-8.
[36] Guo YG, Hu JS, Wan LJ. Nanostructured materials for
electrochemical energy conversion and storage devices. Adv Mater
2008; 20 (15): 2878-87.
[37] Wu SH, Chen MS. 15th International Meeting on Lithium
Batteries; July 2010; Montréal, Québec, Canada; 1010.
[38] Chang ZR, Lv HJ, Tang H, Yuan XZ, Wang HJ. Synthesis and
performance of high tap density LiFePO4/C cathode materials
doped with copper ions. J Alloys Compd 2010; 501 (1): 14-7.
[39] Nishimura S, Kobayashi G, Ohoyama K, Kanno R, Yashima M,
Yamada A. Experimental visualization of lithium diffusion in
LixFePO4. Nat Mater 2008; 7 (9): 707-11.
[40] Ravet N, Chouinard Y, Magnan JF, Besner S, Gauthier M, Armand
M. Electroactivity of natural and synthetic triphylite. J Power
Sources 2001; 97-8: 503-7.
[41] Delacourt C, Poizot P, Levasseur S, Masquelier C. Size effects on
carbon-free LiFePO4 powders. Electrochem Solid State Lett 2006;
9 (7): A352-5.
[42] Kim DH, Kim J. Synthesis of LiFePO4 nanoparticles in polyol
medium and their electrochemical properties. Electrochem Solid
State Lett 2006; 9 (9): A439-42.
[43] Kang B, Ceder G. Battery materials for ultrafast charging and
discharging. Nature 2009; 458: 190-3.
[44] Recham N, Chotard JN, Dupont L, et al. A 3.6 V lithium-based
fluorosulphate insertion positive electrode for lithium-ion batteries.
Nat Mater 2010; 9 (1): 68-74.
[45] Kolosnitsyn VS, Kuzmina EV, Karaseva EV. 15th International
Meeting on Lithium Batteries; July 2010; Montréal, Québec,
Canada; 1010.
[46] Ji XL, Lee KT, Nazar LF. A highly ordered nanostructured carbon-
sulphur cathode for lithium- sulphur batteries. Nat Mater 2009; 8:
[47] Liang CD, Dudney NJ, Howe JY. Hierarchically structured
sulfur/Carbon nanocomposite material for high-energy lithium
battery. Chem Mater 2009; 21: 4724-30.
[48] Hayashi A, Ohtsubo R, Ohtomo T, Mizuno F, Tatsumisago M. All-
solid-state rechargeable lithium batteries with Li2S as a positive
electrode material. J Power Sources 2008; 183 (1): 422-6.
[49] Zhou YN, Wu CL, Zhang H, Wu XJ, Fu ZW. Electrochemical
reactivity of Co-Li2S nanocomposite for lithium-ion batteries.
Electrochim Acta 2007; 52 (9): 3130-6.
[50] Obrovac MN, Dahn JR. Electrochemically active lithia/metal and
lithium sulfide/metal composites. Electrochem Solid State Lett
2002; 5 (4): A70-3.
[51] Yang Y, McDowell MT, Jackson A, Cha JJ, Hong SS, Cui Y. New
nanostructured Li2S/silicon rechargeable battery with high specific
energy. Nano Lett 2010;10: 1486-91.
[52] Chu MY. Rechargeable Positive Electrodes. US5686201,
November 11, 1997.
[53] Visco SJ, Katz BD, Nimon YS, Jonghe LCD. Protected active
metal electrode and battery cell structures with non-aqueous
interplayer architecture. US2008/0038641A1, February 14, 2008.
[54] Skotheim TA, Sheehan CJ, Mikhaylik YV, Affinito J. Lithium
anodes for electrochemical cells. US7247408B2, June 24, 2007.
[55] Visco SJ, Nimon YS, Katz BD. Ionically conductive composites
for protection of active metal anode. US2008/0057387A1, March
6, 2008.
[56] Bates JB, Protective lithium ion conducting ceramic coating for
lithium metal anodes and associate method. US5314765, May 24,
[57] Visco SJ, Katz BD, Nimon YS, Jonghe LCD. Protected active
metal electrode and battery cell structures with non-aqueous
interplayer architecture. US2008/0038641A1, February 14, 2008.
[58] Visco SJ, Katz BD, Nimon YS, Jones PC. Protected active metal
electrode and battery cell structures with non-aqueous interplayer
architecture. US7282295B2, October 16, 2007.
[59] Visco SJ, Nimon YS, Li/air non-aqueous batteries.
US2007/0117007A1, May 24, 2007.
[60] Yurity VM, Chariclea SK, Igor K, Cathie B. Separation of
electrolytes. US2010/0129699A1, May 27, 2010.
[61] Shodai T, Okada S, Tobishima S, Yamabi I. Study of Li3-xMxN
(M=Co, Ni or Cu) system for use as anode in lithium rechargeable
cells. Solid State Ionics 1996; 86-88: 785-9.
[62] Besenhard JO, Yang J, Winter M. Will advanced lithium-alloy
anodes have a chance in lithium-ion batteries? J Power Sources
1997; 68 (1): 87-90.
[63] Winter M, Besenhard JO, Spahr ME, Novak P. Insertion electrode
materials for rechargeable lithium batteries. Adv Mater 1998; 10
(10): 725-63.
[64] Dahn JR, Zheng T, Liu YH, Xue JS . Mechanisms for lithium
insertion in carbonaceous materials. Science 1995; 270 (5236):
[65] Liu YH, Xue JS, Zheng T, Dahn JR. Mechanism of lithium
insertion in hard carbons prepared by pyrolysis of epoxy resins.
Carbon 1996; 34 (2): 193-200.
[66] Zhang M, Lei DN, Yin XM, et al. Magnetite/graphene composites:
Microwave irradiation synthesis and enhanced cycling and rate
performances for lithium ion batteries. J Mater Chem 2010; 20
[67] Winter M, Besenhard JO. Electrochemical lithiation of tin and tin-
based intermetallics and composites. Electrochem Acta 1999; 45:
[68] Anani A, Crouch-Baker S, Huggins RA. Kinetic and
thermodynamic parameters of several binary lithium alloy negative
electrode materials at ambient temperature. J Electrochem Soc
1987; 134: 3098- 102.
[69] Boukamp BA, Lesh GC, Huggins RA. All-solid lithium electrodes
with mixed-conductor matrix. J Electrochem Soc 1981; 128 (4):
[70] Wang JQ, Raistrick ID, Huggins RA. Behavior of some binary
lithium alloys as negative electrodes in organic solvent-based
electrolytes. J Electrochem Soc 1986; 133 (3): 457-60.
[71] Zhang SC, Fang Y, Xing YL, Jiang T, Sun MM. 15th International
Meeting on Lithium Batteries; July 2010; Montréal, Québec,
Canada; 1010.
[72] Mao O, Dunlap RA, Dahn JR. Mechanically alloyed Sn-Fe(-C)
powders as anode materials for Li- ion batteries-I. The Sn2Fe-C
system. J Electrochem Soc 1999, 146 (2), 405-13.
[73] Mao O, Dahn JR. Mechanically alloyed Sn-Fe(-C) powders as
anode materials for Li-ion batteries-II. The SnFe system. J
Electrochem Soc 1999; 146 (2): 414-22.
[74] Mao O, Dahn JR. Mechanically alloyed Sn-Fe(-C) powders as
anode materials for Li-ion batteries-III. Sn2Fe: SnFe3C
active/inactive composites. J Electrochem Soc 1999; 146 (2): 423-
[75] Beaulieu LY, Larcher D, Dunlap RA, Dahn JR. Reaction of Li with
grain-boundary atoms in nanostructured compounds. J Electrochem
Soc 2000; 147 (9): 3206-12.
[76] Kepler KD, Vaughey JT, Thackeray MM. LixCu6Sn5 (0<x<13): An
intermetallic insertion electrode for rechargeable lithium batteries.
Electrochem Solid State Lett 1999; 2 (7): 307-9.
[77] Idota Y, Kubota T, Matsufuji A, Maekawa Y, Miyasaka T. Tin-
based amorphous oxide: A high-capacity lithium-ion-storage
material. Science 1997; 276 (5317): 1395-7.
[78] Courtney IA, Dahn JR. Electrochemical and in situ x-ray
diffraction studies of the reaction of lithium with tin oxide
composites. J Electrochem Soc 1997; 144 (6): 2045-52.
[79] Park MS, Kim JH, Kang YM. 15th International Meeting on
Lithium Batteries; July 2010; Montréal, Québec, Canada; 1010.
[81] Todd ADW, Mar RE, Dahn JR. Tin-transition metal-carbon
systems for lithium-ion battery negative electrodes. J Electrochem
Soc 2007; 154 (6): A597-604.
Reality and F uture of Rechargeable Lithium Batteries The Open Materials Science Journal, 2011, Volume 5 213
[82] Ferguson PP, Todd ADW, Dahn JR. Comparison of mechanically
alloyed and sputtered tin-cobalt- carbon as an anode material for
lithium-ion batteries. Electrochem Commun 2008; 10 (1): 25-31.
[83] Ferguson PP, Dahn JR. Effect of annealing on Sn30Co30C40
prepared by mechanical attriting. Electrochem Solid State Lett
2008; 11 (11): A187-9.
[84] Ferguson PP, Martine ML, George AE, Dahn JR. Studies of tin-
transition metal-carbon and tin- cobalt-transition metal-carbon
negative electrode materials prepared by mechanical attrition. J
Power Sources 2009; 194 (2): 794-800.
[85] Lazzari M, Scrosati B. Rechargeable lithium batteries with non-
metal electrodes. US4464447, August 7, 1984.
[86] Idota Y. Nonaqueous Secondary battery. US5478671, December
26, 1995.
[87] Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM. Nano-
sized transition-metaloxides as negative-electrode materials for
lithium-ion batteries. Nature 2000; 407 (6803): 496-9.
[88] Kavan L, Gratzel M. Facile synthesis of nanocrystalline Li4Ti5O12
(spinel) exhibiting fast Li insertion. Electrochem Solid State Lett
2002; 5 (2): A39-42.
[89] Ohzuku T, Ueda A, Yamamoto N. Zero-strain insertion material of
Li[Li1/3Ti5/3]O4 for rechargeable lithium cells. J Electrochem Soc
1995; 142 (5): 1431-5.
[90] Wen CJ, Huggins RA. Chemical diffusion in intermediate phases in
the lithium-silicon system. J Solid State Chem 1981; 37 (3): 271-8.
[91] Loveridge M, Lain M, Liu FM, Coowar F, Macklin B, Green M.
15th International Meeting on Lithium Batteries; July 2010;
Montréal, Québec, Canada; 1010.
[92] Green M, Fielder E, Scrosati B, Wachtler M, Moreno JS.
Structured silicon anodes for lithium battery applications.
Electrochem Solid State Lett 2003; 6 (5): A75-9.
[93] Li H, Huang XJ, Chen LQ, Wu ZG, Liang Y. A high capacity
nano-Si composite anode material for lithium rechargeable
batteries. Electrochem Solid State Lett 1999; 2 (11): 547-9.
[94] Graetz J, Ahn CC, Yazami R, Fultz B. Highly reversible lithium
storage in nanostructured silicon. Electrochem Solid State Lett
2003; 6 (9): A194-7.
[95] Kasavajjula U, Wang CS, Appleby AJ. Nano- and bulk-silicon-
based insertion anodes for lithium-ion secondary cells. J Power
Sources 2007; 163 (2): 1003-39.
[96] Park MH, Kim MG, Joo J, et al. Silicon nanotube battery anodes.
Nano Lett 2009; 9 (11): 3844-7.
[97] Cui LF, Yang Y, Hsu CM, Cui Y . Carbon-silicon core-shell
nanowires as high capacity electrode for lithium ion batteries. Nano
Lett 2009; 9 (9): 3370-4.
[98] Chan CK, Ruffo R, Hong SS, Huggins RA, Cui Y. Structural and
electrochemical study of the reaction of lithium with silicon
nanowires. J Power Sources 2009; 189 (1): 34-9.
[99] Chan CK, Ruffo R, Hong SS, Cui Y. Surface chemistry and
morphology of the solid electrolyte interphase on silicon nanowire
lithium-ion battery anodes. J Power Sources 2009; 189 (2): 1132-
[100] Cui LF, Ruffo R, Chan CK, Peng HL, Cui Y. Crystalline-
amorphous core-shell silicon nanowires for high capacity and high
current battery electrodes. Nano Lett 2009; 9 (1): 491-5.
[101] Chan CK, Peng HL, Liu G, et al. High-performance lithium battery
anodes using silicon nanowires. Nat Nanotechnol 2008; 3 (1): 31-5.
[102] Ruffo R, Hong SS, Chan CK, Huggins RA, Cui Y. Impedance
analysis of silicon nanowire lithium ion battery anodes. J Phys
Chem C 2009; 113 (26): 11390-8.
[103] Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J, Yushin G.
High-performance lithium-ion anodes using a hierarchical bottom-
up approach. Nat Mater 2010; 9 (4): 353-8.
[104] Magasinski A, Hertzberg B, Dixon P, Yushin G. 15th International
Meeting on Lithium Batteries; July 2010; Montréal, Québec,
Canada; 1010.
[105] Tarascon JM, Guyomard D. New electrolyte compositions stable
over the 0-V to 5-V voltage range and compatible with the
Li1+xMn2O4 Carbon Li-ion cells. Solid State Ionics 1994; 69 (3-4):
[106] Ding MS, Xu K, Zhang SS, Amine K, Henriksen GL, Jow TR.
Change of conductivity with salt content, solvent composition, and
temperature for electrolytes of LiPF6 in ethylene carbonate-ethyl
methyl carbonate. J Electrochem Soc 2001; 148 (10): A1196-204.
[107] Guyomard D, Tarascon JM. Li matal-free rechargeable
LiMn2O4/Carbon cells-Their understanding and optimization. J
Electrochem Soc 1992; 139 (4): 937-48.
[108] Guyomard D, Tarascon JM. High-voltage stable liquid electrolytes
for Li1+XMn2O4 /Carbon rocking- chair lithium batteries. J Power
Sources 1995; 54 (1): 92-8.
[109] Oh B, Rempel J, Ofer D, Sriramulu S, Barnett B. 15th International
Meeting on Lithium Batteries; July 2010; Montréal, Québec,
Canada; 1010.
[110] Liu ZQ, Huang FQ, Yang JH, Wang BF, Sun JK. New lithium ion
conductor, thio-LISICON lithium zirconium sulfide system. Solid
State Ionics 2008; 179: 1714-6.
[111] Sakaebe H, Matsumoto H. N-methyl-N-propylpiperidinium bis
(trifluoromethanesulfonyl) imide (PP13-TFSI)-novel electrolyte
base for Li battery. Electrochem Commun 2003; 5: 594-8.
[112] Nakagawa H, Izuchi S, Kuwana K, Nukuda T, Aihara Y. Liquid
and polymer gel electrolytes for lithium batteries composed of
room-temperature molten salt doped by lithium salt. J Electrochem
Soc 2003; 150: A695-700.
[113] Ishikawa M, Yamagata M. 15th International Meeting on Lithium
Batteries; July 2010; Montréal, Québec, Canada 1010.
[114] Holzapfel M, Jost C, Nova´k P. Stable cycling of graphite in an
ionic liquid based electrolyte. Chem Comm 2004; (18): 2098-9.
[115] Carlin RT, Fuller J, Hedenskoog M. Reversible lithium-graphite
anodes in room-temperature chloroaluminate melts. J Electrochem
Soc 1994; 141: L21-2.
[116] Fuller J, Osteryoung RA, Carlin RT. Rechargeable lithium and
sodium anodes in chloroaluminate molten-salts containing thionyl
chloride. J Electrochem Soc 1995; 142: 3632-6.
[117] Fuller J, Carlin RT, Osteryoung RA. The room temperaturei liquid
1-ethyl-3-methylimidazolium tetrafluoroborate: Electrochemical
couples and physical properties. J Electrochem Soc 1997; 144:
[118] Katayama Y, Yukumoto M, Miura T. Electrochemical intercalation
of lithium into graphite in room- temperature molten salt
containing ethylene carbonate. Electrochem Solid-State Lett 2003;
6: A96-7.
[119] Holzapfel M, Jostb C, Novak P. Stable cycling of graphite in an
ionic liquid based electrolyte. Chem Commun 2004; 2098-9.
[120] Appetecchi GB, Kim GT, Montanina M, et al. Ternary polymer
electrolytes containing pyrrolidinium-based polymeric ionic liquids
for lithium batteries. J Power Sources 2010; 195 (11): 3668-75.
[121] Lewandowski A, Swiderska-Mocek A. Ionic liquids as electrolytes
for Li-ion batteries-An overview of electrochemical studies. J
Power Sources 2009; 194 (2): 601-9.
[122] Stallworth PE, Fontanella JJ, Wintersgill MC, et al. NMR, DSC
and high pressure electrical conductivity studies of liquid and
hybrid electrolytes. J Power Sources 1999; 81: 739-47.
[123] Angell CA, Liu C, Sanchez E. Rubbery solid electrolytes with
dominant cationic transport and high ambient conductivity. Nature
1993; 362 (6416): 137-9.
[124] Croce F, Appetecchi GB, Persi L, Scrosati B. Nanocomposite
polymer electrolytes for lithium batteries. Nature 1998; 394 (6692):
[125] MacFarlane DR, Huang JH, Forsyth M. Lithium-doped plastic
crystal electrolytes exhibiting fast ion conduction for secondary
batteries. Nature 1999; 402 (6763): 792-4.
[126] Zhang JW, Huang XB, Wei H, Fu JW, Huang YW, Tang XZ.
Novel PEO-based solid composite polymer electrolytes with
inorganic-organic hybrid polyphosphazene microspheres as fillers.
J Appl Electrochem 2010; 40 (8): 1475-81.
[127] Alpen UV, Bell MF, Wichelhaus W. Ionic conductivity of
Li14Zn(GeO4)4 (LISICON). Electrochim Acta 1978; 23: 1395-7.
[128] Hong HYP. Crystal structure and ionic conductivity of
Li14Zn(GeO4)4 and other new Li+ superionic conductors. Mat Res
Bull 1978; 13: 117-24.
[129] Murayama M, Sonoyama N, Yamada A, Kanno R. Material design
of new lithium ionic conductor, thio-LISICON, in the Li2S-P2S5
system. Solid State Ionics 2004; 170 (3-4): 173-80.
[130] Kanno R, Hata T, Kawamoto Y, Irie M. Synthesis of a new lithium
ionic conductor, thio-LISICON- lithium germanium sulfide system.
Solid State Ionics 2000; 130 (1-2): 97-104.
[131] Hayashi A, Kitaura H, Ohtomo T, Hama S. Tatsumisago M, 15th
International Meeting on Lithium Batteries; July 2010; Montréal,
Québec, Canada; 1010.
214 The Open Materials Science Journal, 2011, Volume 5 Tao et al.
[132] Minami K, Mizuno F, Hayashi A, Tatsumisago M. Lithium ion
conductivity of the Li2S-P2S5 glass- based electrolytes prepared by
the melt quenching method. Solid State Ionics 2007; 178 (11-12):
[133] Trevey J, Jang JS, Jung YS, Stoldt CR, Lee SH. Glass-ceramic
Li2S-P2S5 electrolytes prepared by a single step ball billing process
and their application for all-solid-state lithium-ion batteries.
Electrochem Commun 2009; 11 (9): 1830-3.
[134] Mizuno F, Hama S, Hayashi A, Tadanaga K, Minami T,
Tatsumisago M. All solid-state lithium secondary batteries using
high lithium ion conducting Li2S-P2S5 glass-ceramics. Chem Lett
2002; (12): 1244-5.
[135] Hashimoto Y, Machida N, Shigematsu T. Preparation of
Li4.4GexSi1-x alloys by mechanical milling process and their
properties as anode materials in all-solid-state lithium batteries.
Solid State Ionics 2004; 175 (1-4): 177-80.
[136] Takada K, Inada T, Kajiyama A, et al. Solid state batteries with
sulfide-based solid electrolytes. Solid State Ionics 2004; 172 (1-4):
[137] Zhang SS. A review on the separators of liquid electrolyte Li-ion
batteries. J Power Sources 2007; 164 (1): 351-64.
[138] Kim SS, Lim GBA, Alwattari AA, Wang YF, Lloyd DR.
Microporous membrane formation via thermally-induced phase-
separation. 5. Effect of diluent mobility and crystallization on the
structure of isotactic polypropylene membranes. J Membr Sci
1991; 64 (1-2): 41-53.
[139] Vadalia HC, Lee HK, Myerson AS, Levon K. Thermally-induced
phase-separation in ternary crystallizable polymer-solutions. J
Membr Sci 1994; 89 (1-2): 37-50.
[140] Matsuyama H, Yuasa M, Kitamura Y, Teramoto M, Lloyd DR.
Structure control of anisotropic and asymmetric polypropylene
membrane prepared by thermally induced phase separation. J
Membr Sci 2000; 179 (1-2): 91-100.
[141] Venugopal G, Moore J, Howard J, Pendalwar S. Characterization
of microporous separators for lithium-ion batteries. J Power
Sources 1999; 77 (1): 34-41.
[142] Arora P, Zhang ZM. Battery separators. Chem Rev 2004; 104 (10):
[144] Chung YS, Yoo SH, Kim CK. Enhancement of meltdown
temperature of the polyethylene lithium- ion battery separator via
surface coating with polymers having high thermal resistance. Ind
Eng Chem Res 2009; 48 (9): 4346-51.
[145] Yoo SH, Kim CK. Enhancement of the meltdown temperature of a
lithium ion battery separator via a nanocomposite coating. Ind Eng
Chem Res 2009; 48 (22): 9936-41.
[146] Cho TH, Tanaka M, Onishi H, et al. Silica-composite nonwoven
separators for lithium-ion battery: Development and
characterization. J Electrochem Soc 2008; 155 (9): A699-703.
[147] Prosini PP, Villano P, Carewska M. A novel intrinsically porous
separator for self-standing lithium- ion batteries. Electrochim Acta
2002; 48 (3): 227-33.
[148] Augustin S, Hennige V, Horpel G, Hying C. Ceramic but flexible:
new ceramic membrane foils for fuel cells and batteries.
Desalination 2002; 146 (1-3): 23-8.
[149] Hennige V, Hying C, Hörpel G. Pyrogenic oxidic powder,
production thereof and use thereof in a separator for
electrochemical cell. US7759009B2, July 20, 2010.
[150] Kim M, Shon JY, Nho YC, Lee TW, Park JH. Positive effects of e-
beam irradiation in inorganic particle based separators for lithium-
ion battery. J Electrochem Soc 2010; 157 (1): A31-4.
Received: January 18, 2011 Revised: May 17, 2011 Accepted: June 23, 2011
© Tao et al.; Licensee Bentham Open.
This is an open access article licensed under the terms of the Creative Commons Attribution Non-Commercial License (
which permits unrestricted, non-commercial use, distribution and reproduction in any medium, provided the work is properly cited.
... This charge transfer occurs due to segmental relaxation, where the charge is transferred from one segment to another in the polymer matrix. Charge transfer is more effective when the polymer matrix is amorphous [2]. In the amorphous phase of polymer matrix, there is more free spaces which allow more ions movement when compared to the crystalline phase of polymer matrix. ...
... Assuming two or more compounds are mixed, the spectra peaks will shift due to physical interactions and chemical reactions [4]. The absorption band at wave number 1402 cm -1 corresponded to -CF2 stretching on PVDF-HFP [2]. The peak at 1171 cm -1 is assigned to the symmetrical stretching mode CF2 of PVDF-HFP, which had shifted due to adding salt. ...
Full-text available
SPE (Solid Polymer Electrolyte) is an alternative to substitute conventional liquid electrolytes as it has a better safety level and has been produced using the solution casting method. An effort to increase the SPE conductivity of the PVDF-HFP/TiO2/ LiTFSI system has been carried out by adding LiBOB as an additive. LiBOB (lithium bis(oxalate) borate) is a salt compound that can interfere with the crystallization process of polymer chains, so it is expected to increase ion conductivity. However, the results showed a decrease in the conductivity from 3.643 x 10-5 S/cm to 8.658 x 10-6 S/cm. These results were proven by the XRD, FTIR, SEM, and TGA characterization. Based on XRD (X-ray Diffraction) analysis, the addition of LiBOB increased the crystallinity phase. The results of the SEM (Scanning Electron Microscope) analysis showed that the pore size was partially reduced, the distance between the pores became longer, and the pore closure occurred due to agglomeration. The FTIR (Fourier Transform Infrared spectroscopy) analysis showed the interaction of LiBOB salts in the PVDF-HFP/LiTFSI/TiO2 system, and based on TGA (Thermogravimetric Analysis) analysis, the addition of LiBOB affected the heat stability of the SPE. The CV (Cyclic Voltammetry) analysis showed that the addition of LiBOB in the SPE system could reduce the reversibility and magnitude of the current.
... In that regard, graphite and lithium metal are both excellent anodes, indicated by reduction potentials against Li/Li + of less than −0.5 V [49,50]. However, lithium boasts a specific capacity of 3860 mA·h·g −1 , nearly ten times higher than graphite's 372 mA·h·g −1 [50,51]. ...
Full-text available
Biopolymers are an emerging class of novel materials with diverse applications and properties such as superior sustainability and tunability. Here, applications of biopolymers are described in the context of energy storage devices, namely lithium-based batteries, zinc-based batteries, and capacitors. Current demand for energy storage technologies calls for improved energy density, preserved performance overtime, and more sustainable end-of-life behavior. Lithium-based and zinc-based batteries often face anode corrosion from processes such as dendrite formation. Capacitors typically struggle with achieving functional energy density caused by an inability to efficiently charge and discharge. Both classes of energy storage need to be packaged with sustainable materials due to their potential leakages of toxic metals. In this review paper, recent progress in energy applications is described for biocompatible polymers such as silk, keratin, collagen, chitosan, cellulose, and agarose. Fabrication techniques are described for various components of the battery/capacitors including the electrode, electrolyte, and separators with biopolymers. Of these methods, incorporating the porosity found within various biopolymers is commonly used to maximize ion transport in the electrolyte and prevent dendrite formations in lithium-based, zinc-based batteries, and capacitors. Overall, integrating biopolymers in energy storage solutions poses a promising alternative that can theoretically match traditional energy sources while eliminating harmful consequences to the environment.
Sodium–sulfur (Na‐S) battery technology is one of the most developed types of high‐temperature battery, due to its considerable potential for energy storage and load leveling in power systems. These systems are eligible for use in large‐scale energy storage system applications due to their outstanding energy density, high efficiency of charge/discharge, low materials cost, and long life cycle of up to 15 years. However, several challenges must be overcome to ensure the safe operation of Na‐S batteries – mostly related to the reduction of the high operation temperatures. For this purpose, it is critical to develop new solid electrolytes with high ionic conductivity at room temperature. Taking this into account, ceramic/polymer composites are good candidates to achieve this goal. However, it is important to note an increase of capacity and cyclability is also desirable for Na‐S technology, and one of the strategies used to address this issue is the use of nanostructured carbon to host sulfur or to bind it to a polymer. Since the inception of Na‐S technology in the mid‐1970s, several patents have been developed. Analysis of these patents indicate that, on the one hand they aim to integrate these systems into the electrical grid to compensate the fluctuations of power demand and supply, especially of renewable energies, while on the other hand they show battery component improvements to achieve lower operating temperatures.
Recent lithium consumption is doubled in a decade due to the Li-ion battery (LIB) demand for electric vehicles, the energy storage system, etc. The LIBs market capacity is expected to be in strong demand due to the political drive by many nations. Wasted black powders (WBP) are generated from the manufacturing of the cathode active material and spent LIBs. The recycling market capacity is also expected to expand rapidly. This study is to propose a thermal reduction technique for recovering Li selectively. The WBP, containing 7.4 % Li, 62.1 % Ni, 4.5 % Co, and 0.3 % Al, was reduced in a vertical tube furnace using a 10 % H2 gas as a reducing agent at 750 ºC for 1 h, and 94.3 % of Li was recovered from a water leaching, while other metal values, including Ni and Co remained in the residue. A leach solution was treated in a series of crystallisations, filtering, and washing. An intermediate product was produced and re-dissolved in hot water at 80 ºC for 0.5 h to minimise Li2CO3 content into a solution. A final solution was crystallised repeatedly to produce the final product. A 99.5 % of LiOH·H2O was characterised and passed the impurity specification by the manufacturer as a marketable product. The proposed process is relatively simple to utilise to scale up for bulk production, and it can also be contributed to the battery recycling industry as the spent LIBs are expected to overabundance within the near future. A brief cost evaluation confirms the process feasibility, particularly, for the company that produces cathode active material (CAM) and generates WBP in their own supply chain.
Cost-effective, simple, and easily reproducible synthesis methods of polymers are of profound significance when it comes to extracting high battery performance metrics from polymeric redox-active materials. This work reports a procedure for the solvothermal synthesis of a poly(hydroquinonyl-benzoquinonyl sulfide) (PHBQS) polymer and the development of its nanostructured composites with multiwalled carbon nanotubes (MWCNTs). Polymers are tested as high-performance cathode materials for Li⁺ and Mg²⁺ batteries. In configurations, compared to neat PHBQS, the [email protected]%MWCNT cathode exhibits superior electrochemical performance with high active material utilization owing to improved ion/electron transport pathways. Galvanostatic characterization of the [email protected]%MWCNT cathode in lithium batteries exhibited peak capacity up to 358 mAh g–1 at a current density of 50 mA g–1 (C/8) and excellent rate performance with a discharge capacity of 236 mAh g–1 maintained even at high current density of 10C. The galvanostatic characterization in Mg batteries reveals more sluggish kinetics with a stable capacity of 200 mAh g–1 at 50 mA g–1.
Full-text available
Graphene-based materials are widely applied due to their interesting physical and chemical properties, but their hydrophobic surface and toxicity to living creatures limit their application in some fields. Biopolymers are incorporated with graphene-based materials to overcome these issues and improve their biodegradability, biocompatibility, and ecological friendliness, and the synergetic effect enhances other properties as well. These properties make graphene-based materials a novel subject of interest in science and industry. In this study, the various applications of developed biopolymer/graphene-based composites are broadly addressed, and recent progress in the field is emphasized. Modification, stability, and compatibility are among the key merits for developing highly advanced composites with desirable properties. The major challenges and some recommendations in various applications based on reviewed studies are covered. However, the development of environmentally friendly, low-cost, high-quality, and large-scale biopolymer/graphene-based composites for specified applications is challenging. Studies based on application and trend are conducted. Opportunities and limitations can guide researchers in the field to solve challenges, provide directions for future studies, and optimize sustainable biopolymer/graphene-based composites for specified industrial applications.
Owing to its high energy density, simple device design, and flexibility; Lithium-ion batteries (LIBs) have attracted much consideration as the most promising energy storage devices for their wide application in mobile phones, laptops, and also in electric vehicles. One of the critical parts of commercial LIBs which significantly affects its performance is the anode materials. The archetypal anode material applied for LIB is carbon-based nanostructures due to its stable solid electrolyte interface and remarkable conductivity. However, the low specific conductivity of these carbonaceous materials paves researchers to develop new potential alternatives. In this regard, different transition metal-based anode materials and their composites with carbon have demonstrated much high theoretical capacitance. Among these, CoO and Co3O4 with porous carbon nanofiber composites showed an incredible capacity of 952 mAh g⁻¹ after 100 cycles and equally exceptional rate performance at high current densities. Such free-standing nanofibers (NFs) of cobalt-based composites can be prepared via the electrospinning technique by applying the electric field between the nozzle and collector while introducing the polymeric solution. This low-cost, one-step fabrication process devoid of using any hazardous chemical is found to be sustainable and successfully scaled up for massive production of ready to use binder-free anodes for industrial applications. Additionally, the facile tuning of the surface area, porosity, and composition added the broad applicability of electrospun NFs as battery electrodes. Therefore, this chapter summarizes the current achievements, the challenges, and opportunities for future research on electrospun cobalt-based nanocomposites as anodes for LIBs.
There are lots of scientific innovations taking place in lithium-ion battery technology and the introduction of lithium metal oxide as cathode material is one of them. Among them, LiCoO2 is considered as a potential candidate for advanced applications due to its higher electrochemical performance. But it suffers some problems related to storage efficiency, safety, and cost. To improve the properties of LiCoO2, there is a lot of research carried out in this field and mainly focuses on its structural modification. Implementing new synthetic approaches, such as electrospinning is found to be more attractive in recent years for developing nanomaterial with improved physical and chemical properties. Electrospinning is a low-cost and simple procedure for the fabrication of 1D nanostructure. Electrospun LiCoO2 nanostructures exhibit high specific surface area, short ionic and electronic diffusion pathways, and mechanical stability, which can enhance the specific capacity and thus the battery performance and safety. This chapter reviews different morphologies of electrospun LiCoO2 nanostructures, structural modification by coating, and different electrospun LiCoO2 composites.
Full-text available
The internet of things (IoT) is a distributed heterogeneous network of lightweight nodes with very minimal power and storage. The IoT energy system for smart applications such as smart grid, smart building, and smart transportations depends on the IoT architecture, determining the high or low‐energy consumption levels. Most of the IoT objects are power‐driven by batteries with short life spans that require replacement. The replacement phase is tedious; hence this paper comprehensively discussed the IoT energy system, energy resources, and energy storage as these three elements are crucial to enable energy efficiency for the IoT applications. In comparison to the battery‐powered solutions, the scavenging of infinite quantities of energy makes the IoT systems robust. Therefore, this paper further elaborates on understanding the current situation in terms of renewable energy harvesting for these low‐energy systems. The IoT energy storage highlighted in this paper includes fuel cell, lithium battery, and supercapacitor technology. This paper also provides the findings for IoT energy system challenges and open issues in management and storage in terms of bidirectional, continuity, autonomy, fluctuation, conversion, consumption, integration, multifunction, and stability. This paper will assist researchers in more quality yet practical energy usage and savings, better IoT system architecture, and smart application sustainability.
Full-text available
In this research, we present the results on the effect of the partial doping of divalent Mg2 + in the place of monovalent Li + in LTO (lithium titanate, Li4Ti5O12) material. For the mother compound as well as Mg doped with the formula Li4-xMgxTi5O12 (x = 0 and 0.05), the partial influence of magnesium on structural, impedance and conductivity properties have been investigated. A systematic presentation of the results of the structural and electrical properties of the anode materials are studied through TG/DTG, XRD, FESEM with EDS and LCR. The observed diffraction peaks are in full agreement with the ordered LTO spinel structure belonging to the Fd-3 m space group. The doped material is quite large with grain size upto above 1.1 μm in diameter and also has a wide distribution range. The impedance properties of the Li4-xMgxTi5O12 (X = 0, 0.05) anode materials are studied in the temperature ranging from room temperature to 120 °C and frequency ranging from 20 Hz to 1 MHz by employing complex impedance spectroscopy (CIS). The conductivity studies reveal that the Mg doped material Li3.95 Mg0.05Ti5O12 exhibits highest electrical conductivity of 3.03 × 10–5 S/cm.
Full-text available
Microporous membranes were prepared by the thermally induced phase separation (TIPS) process of a ternary solution of HDPE, ditrydecylphthalate and hexadecane. The equilibrium phase diagram calculations were carried out in terms of a pseudo-binary system, considering the solvent mixture to be one component, to show the effect of the interaction parameter on the phase diagram. The experimental results showed that by varying the composition of the solvent pair, i.e., by varying the interaction parameter systematically, the phase diagrams can be controlled successfully. Liquid—liquid phase separation was obtained also below the melting point by controlling the composition of the solvent mixture. It is also shown that the membrane morphology can be controlled with different solvent compositions when the cooling conditions are kept constant.
A new series of cathode materials Li2+xMn0.91Cr1.09O4 (x = 0.7, 0.9, 1.1, and 1.3) was prepared from the reaction of Mn0.91Cr1.09O4 and LiOH . H2O by heat-treatment at 700 degrees C for 3, 6, and 12 h. The length of the heat-treatment significantly influenced the capacity, with longer heat-treatment times resulting in smaller capacities. Li3.1Mn0.91Cr1.09O4 phases heat-treated for 3 h showed the highest discharge capacity of 220 mAh/g at the 0.1 C rate (18 mA/g) cycled between 4.5 and 2 V. Tests of Li2+xMn0.91Cr1.09O4 in Li-ion cells (C/Li3.1Mn0.91Cr1.09O4) showed an initial capacity of 220 mAh/g at the 0.1 C rate, and relatively good rate capability from the 0.2 C to the 2 C rate between 4.5 and 2 V.
One of the greatest challenges for our society is providing powerful electrochemical energy conversion and storage devices. Rechargeable lithium-ion batteries and fuel cells are amongst the most promising candidates in terms of energy densities and power densities. Nanostructured materials are currently of interest for such devices because of their high surface area, novel size effects, significantly enhanced kinetics, and so on. This Progress Report describes some recent developments in nanostructured anode and cathode materials for lithium-ion batteries, addressing the benefits of nanometer-size effects, the disadvantages of 'nano ', and strategies to solve these issues such as nano/micro hierarchical structures and surface coatings, as well as developments in the discovery of nanostructured Pt-based electrocatalysts for direct methanol fuel cells (DMPCs). Approaches to lowering the cost of Pt catalysts include the use of i) novel nanostructures of Pt, ii) new cost-effective synthesis routes, iii) binary or multiple catalysts, and iv) new catalyst supports.
To improve the high temperature performance of Li1+xMn2 O4/carbon rocking-chair secondary batteries we searched for and identified a new electrolyte composition whose range of stability extends up to 4.9 V vs. Li at room temperature and 4.8 V vs. Li at 55°C for the LixMn2O4 material.
Li[Li1/3Ti5/3]O4 having a defect spinel-framework structure Fd3̄m; a = 8.46 angstrom) was prepared and examined in non-aqueous lithium cells. Li[Li1/3Ti5/3]O4 (white in color) was reduced to Li2[Li1/3Ti5/3]O4 (dark blue) at a voltage of 1.55 V and the reaction was highly reversible. X-ray diffraction measurements indicated that the lattice dimension did not change during the reaction. Li[Li1/3Ti5/3]O4 + Li+ + e- ⇔ Li2[1/3Ti5/3]]O4 8(a) 16(d) 32(e) 16(c) 16(d) 32(e) Since the reaction consists of lithium ion and electron insertion into/extraction from the solid matrix without a noticeable change in lattice dimension, called a zero-strain insertion reaction, capacity failure due to the damage to the solid matrix was not observed over after 100 cycles. Feasibility of zero-strain insertion materials for advanced batteries is discussed based on the experimental results.
Intermetallic compounds react with Li to produce high capacity negative electrodes for lithium-ion batteries. Because of the violent reactions occurring during the alloying process between lithium atoms and the active alloy, the cycle life of these materials is generally poor. In this paper we show that nanostructured SnMn3C, which has a low affinity for lithium, behaves differently from any intermetallic system reported to date. Using in situ X-ray diffraction, in situ Sn-119 Mossbauer spectroscopy, and electrochemical experiments on mechanically alloyed samples of nanostructured SnMn3C, we show that the grain boundaries apparently act as channels to allow Li to enter the particles. The lithium atoms then reversibly react with Sn atoms at and within the grain boundaries to deliver a working capacity of approximately 150 mAh/g with no capacity loss with cycle number.
LiMnO2 of the α-NaFeO2 structure type has previously been obtained only by the ion-exchange of lithium salts with α-NaMnO2. In this paper, we show that LiAlxMnl-xO2 solid solutions can be crystallized in this structure under conditions where neither pure end-member does. The compounds were synthesized by firing homogeneous hydroxide precursors in a reducing atmosphere to control the manganese valence state. A composition LiAl0.25Mn0.75qO2 shows a first-charging voltage of ∼4 V against a lithium electrode, but develops 4 and 3 V plateaus upon cycling, indicating transformation to spinel-like cation ordering within the oxide. Unlike previously reported lithium manganese spinels, the compound of this study shows excellent reversible capacity (148 mAh/g at C/5 rate; 182 mAh/g at C/15 rate) when cycled over both the 4 and 3 V plateaus, and an energy density (545 Wh/kg) surpassing that of the spinels.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Several properties including porosity, pore-size distribution, thickness value, electrochemical stability and mechanical properties have to be optimized before a membrane can qualify as a separator for a lithium-ion battery. In this paper we present results of characterization studies carried out on some commercially available lithium-ion battery separators. The relevance of these results to battery performance and safety are also discussed. Porosity values were measured using a simple liquid absorption test and gas permeabilities were measured using a novel pressure drop technique that is similar in principle to the Gurley test. For separators from one particular manufacturer, the trend observed in the pressure drop times was found to be in agreement with the Gurley numbers reported by the separator manufacturer. Shutdown characteristics of the separators were studied by measuring the impedance of batteries containing the separators as a function of temperature. Overcharge tests were also performed to confirm that separator shutdown is indeed a useful mechanism for preventing thermal runaway situations. Polyethylene containing separators, in particular trilayer laminates of polypropylene, polyethylene and polypropylene, appear to have the most attractive properties for preventing thermal runaway in lithium ion cells.