Journal of Power Sources 282 (2015) 299e322

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Review

A review of lithium and non-lithium based solid state batteries

Joo Gon Kim a, 1, Byungrak Son a, **, 1, Santanu Mukherjee b, 1, Nicholas Schuppert b,
Alex Bates b, Osung Kwon c, Moon Jong Choi a, Hyun Yeol Chung d, Sam Park b, *
a
Wellness Convergence Research Center, DGIST, 333 Techno Jungang-daero, Hyeongpung-Myeon, Dalseong-Gun, Daegu 711-873, Republic of Korea
b
Department of Mechanical Engineering, University of Louisville, KY 40292, USA
c
College of Liberal Education, Keimyung University, Daegu 704-701, Republic of Korea
d
Department of Information and Communication Engineering, Yeungnam University, Gyeongbuk 712-749, Republic of Korea

h i g h l i g h t s

A comprehensive review of all aspects of solid state batteries: design, materials.

Tabular representations to underscore the characteristics of solid state batteries.

Solid state electrolytes to overcome the safety issues of liquid electrolytes.

a r t i c l e i n f o a b s t r a c t

Article history: Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment
Received 13 October 2014 such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks,
Received in revised form including expensive sealing agents and inherent hazards of re and leakages. All solid state batteries
17 January 2015
utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid
Accepted 9 February 2015
Available online 16 February 2015
state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This
paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used,
and a detailed literature review of various important advances made in research. The paper exhaustively
Keywords:
Solid state batteries
studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium
Solid electrolytes based systems. Non-lithium based solid state batteries are attaining widespread commercial applica-
Lithium based batteries tions, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic
Lithiation/delithiation diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity
Solid electrodes to occupy a niche in the alternative energy sector.
2015 Elsevier B.V. All rights reserved.

1. Introduction and background
The advent of solid state batteries must be understood in the
context of the challenges faced by modern storage systems, espe-
cially Li-ion batteries. Existing Li-ion batteries, apart from the
storage and active components, contain considerable quantities of
auxiliary materials and cooling equipment [1]. Loss of battery
quality due to continuous charging and discharging cycles, am-
mability, dissolution of the electrolyte, and from vehicle to grid
utilization has been another important concern. Solid state
* Corresponding author.
** Corresponding author.
E-mail addresses: brson@dgist.ac.kr (B. Son), Sam.Park@louisville.edu (S. Park).
1
These authors contributed equally to this work.
batteries are being extensively studied and researched with a view
to solving these problems [1,2]. Conventional batteries, e.g., the Li-
ion battery, usually consist of a liquid electrolyte, which helps
transport Li ions to and from the cathode and anode [3e5]. How-
ever, this increases the chance of leakage of the electrolyte if any
holes are present; this is one of the main drawbacks of the con-
ventional Li-ion battery. Another problem inherent in the liquid
electrolyte battery is the formation of dendrites of Li, which make it
prone to explosion [5,6]. In order to surmount these problems, a
solid electrolyte can be positioned between the electrodes. This is
the principle underlying the solid state battery [3,4]. The advantage
of this type of battery is a reduction in the net weight and volume of
the battery, greater energy output, and easy transfer of Li ions,
which affords better efciency [3,5]. Solid state batteries also
exhibit some advantages over the other commonly known energy

http://dx.doi.org/10.1016/j.jpowsour.2015.02.054
0378-7753/ 2015 Elsevier B.V. All rights reserved.
300 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
storage devices, capacitors [7,8]. The advantages lie in the very
small self-discharge of the solid state batteries, minimal wear and
tear, and yield of a more uniform output voltage [7,8]. In recent
decades, solid state batteries, especially solid state lithium ion
batteries, have been widely used [9e13]. Ideally, a solid state
electrolyte should have high cation conductivity, with good me-
chanical properties and good chemical stability that cannot be
easily reduced by the metal itself [9,14]. Moreover, owing to rapidly
growing microelectronics and integrated optoelectronics circuits,
there is an increasing demand for new, lightweight batteries with
high-cycle life and high energy density. In a commercial lithium ion
battery, the liquid electrolyte carries the risk of explosion and re;
moreover, the separators and packaging limit the size of the bat-
teries. All these factors have contributed to the development of all-
solid state batteries [14e16]. However, solid state batteries also
present challenges, such as their relatively lower power density,
high ionic resistance at room temperatures, and manufacturing
cost [3,15]. The atomic layer deposition (ALD) technique is an
important method applied in the manufacture of solid state thin
lm electrolytes [17e20], but it is rather costly and indeed forms
the bulk of the cost of the battery [3,21].
2. Solid state batteries
A solid state battery is similar to a liquid electrolyte battery
except in that it primarily employs a solid electrolyte. The parts of
the solid state Li ion battery include the anode, cathode and the
solid electrolyte [22,23]. The anode is attached to copper foil, which
helps improve the electrical conductivity of the battery. [22]. Dur-
ing the charging cycle, there is movement of the Li ions of the
LiCoO2 crystal toward the electrolyte interface [22,24]. As a result,
the Li ions cross over to the carbon layers in the anode through the
electrolyte. During the discharging cycle, the reverse process takes
place, and the Li ions travel via the electrolyte toward the LiCoO2
particles [22,23,25]. Solid state batteries can overcome some of the
inherent problems of liquid electrolyte batteries, being less haz-
ardous and having a less ammable electrolyte-electrode system
and better storage capacity. In the eld of power supply for cardiac
pacemakers with low-power requirements, all solid state batteries
are well established because of safety, lifetime, and achievable
energy density [26,27]. As mentioned in a book, all solid state
battery is one of new type of batteries with excellent safety and
high energy density [28]. Substitution of liquid electrolyte by a solid
allows simplication of the cell structure, and many restrictions in
terms of architecture and safety are eliminated [29,30]. Solid state
electrolytes are being intensively researched as the key which
present safety advantages over present liquid Li-ion technology
[31e33]. The non-ammability of their solid electrolytes offers a
fundamental solution to safety concerns and remarkable environ-
mental compatibility [34e38].
Also the solid state electrolytes tend to last longer, as they un-
dergo less wear and tear during operation, are more proof against
shocks and vibrations, and can operate within a larger temperature
range, up to about 200  C. However, they have several disadvan-
tages as well [6]. Solid state electrolytes, and consequently batte-
ries, are not suitable for use in low and ambient temperature
conditions, and the power and current output is generally less
[39,40]. This is because of the large resistance of the solid oxide at
room temperature to ionic conductivity, whereas this does not
occur at elevated temperatures. In addition, at ambient or room
temperature, the stress created at the electrode-electrolyte inter-
face due to continuous contact with the solid electrolyte tends to
reduce the longevity of the battery [6,41]. Fig. 1 is a schematic di-
agram of a lithium based solid state battery. The curved arrows
indicate the movement of the Li ions during the charging and the
discharging process, respectively. The electrons produced due to
the reaction are used to drive a load in the external circuit. The set
of cathode and anode materials and their corresponding suitable
electrolytes are also given in Fig. 1, marked with matching colors (in
the web version).
2.1. Structure of solid state batteries
2.1.1. Cathode
The cathode in the solid state battery is important, as it supplies
the battery with the necessary ions during the charging process and
vice versa during the discharging process. The cathode must be
structurally stable during this process. It is important that the ionic
conductivity of the cathode be good, as the charging and dis-
charging process involves the transference of ions across it
[6,24,42]. Commonly used cathode materials for lithium based solid
state batteries are lithium metal oxides, as they exhibit most of the
above necessary properties. Lithium cobalt oxide (LCO), which has
the stoichiometric structure LiCoO2, is a widely used lithium metal
based oxide. LCO exhibits a layered structure that is suitable for the
lithiation/delithiation process, and it has a relatively high specic
energy of about 150 mAh g1, which makes it a preferred cathode
material [6,24,43]. LCO exhibits an octahedral arrangement with a
layer of lithium atoms between oxygen and cobalt [44,45]. How-
ever, it is relatively costly to manufacture, especially with the use of
cobalt [45]. Lithium manganese oxide (LiMn2O4) is another mate-
rial used in the cathode of solid state batteries [46,47]. This com-
pound produces very little resistance to the passage of lithium ions
during the lithiation and delithiation process, thanks to its spinel
based structure, which makes it suitable for use [6]. LiMn2O4 has its
drawbacks too, notably phase change during the ion transfer pro-
cess, which hinders stability, and a lower capacity than LCO.
LiFePO4, another lithium based phosphate, has the advantage of
being less hazardous and less expensive to produce than the other
lithium based oxide materials [6,48]. Moreover, LiFePO4 has an
olivine based structure (a one-dimensional chain of lithium ions),
which greatly assists the transfer of ions and provides less resis-
tance to the path of ion transfer [6,24]. On the other hand, phos-
phorus has a high self-discharge rate, which reduces the longevity
of this material.
Apart from these lithium based oxides, vanadium based oxides
have also been tested, as they exhibit similar layered structures that
help during the lithiation/delithiation process. However, they
produce low output voltages and sometimes they lack longevity,
which has limited their use as cathode materials in solid state
batteries [6,49,50]. In fact, the overall performance of a solid state
battery is still limited by the performance of cathode materials, as
its specic capacity is generally lower [14]. The application of
nanoparticles to the typical cathode, such as LiCoO2, can produce
better properties, but they will react more strongly with the elec-
trolyte at high temperature and lead to more safety issues than
using such materials in the micrometer range [14,51]. Coating the
nanoparticles with a stabilizing layer can reduce this problem, but
it also reduces the lithiation/delithiation rate of the cathode.
2.1.2. Anode
Materials that can store Li/Li to great capacity are usually
potentially good anode materials. This is because the anode is
where the lithiation takes place during the charging process. Pure
lithium metal has been tried as an anode material. Unemoto et al.
have used lithium anodes in lithium sulfur battery systems with
room temperature ionic lithium (RTIL) liquid fused with silica
nanoparticle solid state electrolyte and they were able to achieve a
discharge capacity of 690 mAh g1 after 45 cycles of operation [52].
Cai et al. have used lithium metal anode with a LiMn2O4 cathode
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Fig. 1. A schematic representation of a representative lithium based solid state battery, showing the direction of ion movement and some of the possible anode, electrolyte, and
cathode combinations.
system and have obtained a 91.39% capacity retention after 1000
cycles of use at room temperature conditions [53]. Taib et al. have
incorporated lithium anodes in solid state cells having biopolymer
(chitosan) based solid state electrolyte and have obtained a stable
discharge capacity of 160 mAh g1 up to 50 cycles of operation [54].
However pure lithium metal anodes have their drawbacks. An
important problem associated with lithium anodes is their inability
to be used in high temperature operations, because of the lithium
metal's very high sensitivity to elevated temperature conditions
[55,56]. Accelerating rate calorimeter (ARC) results have shown
that, as the number of cell cycles of operation rises, there is a
considerable increase in the self-heating of the Li anodes because of
the increase in the surface area of the anodes due to the lithiation
process [56]. According to Sacken et al., the primary reason for this
failure is that the structural integrity and morphology of Li cannot
be manipulated properly [56]. Therefore, several safety issues need
to be kept in mind when using Li anodes. Another drawback of the
dendrite formation effect is the development of non-uniform cur-
rent density across the cell, which in turn leads to local temperature
gradients throughout the cell surface [57]. This makes it difcult to
integrate the cell, especially in miniature devices, as the tempera-
ture gradient becomes hazardous [57]. Also, this dendrite forma-
tion steadily depletes the amount of lithium necessary for the cell
cycling process and may even result in the short circuit of the cell
[57].
Apart from uncombined metallic lithium, lithium based metal
oxides such as lithium titanate (LTO) have also been used. The
stoichiometry of lithium titanate is Li4T5O12. The main advantage of
LTO is its octahedral structure, which can easily integrate lithium
ions within it during the lithiation process [58e60]. Also, LTO does
not undergo much structural change during the lithiation/deli-
thiation process and is relatively stable, which makes it suitable for
use. However, LTO has a rather low specic energy of 175 mAh g1,
which sometimes limits its usage to areas where low power output
is required [41,59]. Carbon and carbon based materials are
commonly used anode materials in solid state batteries [61,62].
Graphite too is quite widely used as an anode material in solid state
batteries, yielding several advantages, such as having a layered
structure that can incorporate the lithium ions during the
301
lithiation/delithiation process, its ability to withstand large
numbers of charging and discharging cycles, and relative ease of
manufacture [62,63]. Graphite can also easily be doped with other
materials to improve its capacity. The major problem with graphite
is its rather low capacity.
Soft carbon is another material used. It benets from having a
disordered structure that is favorable toward incorporating Li ions
[58,63]. Therefore, at present, graphitic carbons are commonly used
for the anode of the commercial lithium battery because they have
a higher specic charge and more negative redox potential than
most metal oxides or polymers; further, they demonstrate better
cycling performance than lithium alloy, thanks to high structural
stability and less volumetric expansion in the lithiation reaction
[14]. Fig. 2 is a schematic representation of the different solid state
battery systems with their applications and respective capacities.
Metallic alloy-based anodic systems have also been studied,
notably Sn, Pb, Sb, Al, and Zn along with their alloy systems [4]. The
principle behind their use is the ability of the alloy atoms to store
multiple lithium atoms in the host crystal lattice. One of the best-
known tin-based anodes is Li4.4Sn, which is the nal phase after
lithiation. A theoretical maximum gravimetric capacity of
959.5 mAh g1 has been calculated for this system [5]. However, the
primary problem with these tin-based anodes is that they suffer
from large volume changes (and consequently large stresses) dur-
ing the lithiation process, fracture takes place quickly, and hence
their longevity is rather short [5]. Silicon- and carbon-based com-
posite anodes have been tested. Carbon is used to reduce the large
volume expansion experienced by the Si anode during lithiation
[5]. Wang et al. reported a gravimetric capacity of 794 mAh g1 of
Si/C composite anode systems after about 20 cycles of operation
[5,64]. Anodes in solid state battery systems tend to be subjected to
large quantities of stress, which take its toll on their longevity.
Several groups have studied the development of stress and its
distribution in solid state battery anodes during operation.
Mukhopadhyay and Sheldon have shown that stress in the Li-based
anode due to the lithiation/delithiation process arises mainly from
a change in lattice dimensions [65]. Unalloyed metallic Li being
relatively soft, these problems are magnied compared to anodic
alloys. Some of the processes that lead to disintegration are plastic
302 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322

Fig. 2. The capacities of different types of batteries and their respective applications [41,159]. The diagram shows that thin lm Li ion based solid state batteries provide some of the
best properties in terms of both energy density and capacity.

deformation, fragmentation, and fracturing [62,65]. Another factor
is that the lithiation/delithiation results in a reduction in elastic
modulus along the basal planes and there is a consequent increase
in elastic modulus perpendicular to the basal planes. These unequal
expansions and reductions of the Li-based anodes further make
their integration difcult [66]. As a result of the stresses and me-
chanical changes, the energy necessary for the phase trans-
formation is reduced, as is the ability of the Li anode to operate at
elevated temperatures [65]. This leads to a number of losses during
the running of the cell, especially hysteresis losses during the
lithiation/delithiation process, which serve to decrease the overall
output of the cell [65,67]. Huang et al. have developed a compre-
hensive mechanics model for understanding the stress generated
during lithiation in solid state lithium ion battery anodes [68]. They
determined that the important factors are plastic deformation of
the electrode and also stress due to Li rich and poor phases formed
during the lithiation process [68]. During the delithiation process,
however, tensile hoop stress is created, which results in contraction
of the sample. Fig. 3 illustrates the stress induced in a Si nano-
particle and its consequent cracking due to the lithiation process
taking place. Silicon nanowires have been developed as lithium ion
battery anodes, as they tend to contain less stress due to the
lithiation/delithiation process [69]. Sethuraman et al. have studied
the development of stress in silicon anodes in-situ due to the
electric potential in the cell during its performance [67]. They re-
ported that the Si anodes undergo cyclically varying tensile and
compressive stresses of magnitudes sometimes as high as 1.5 GPa
[67]. Based on the thermodynamic considerations obtained from
the Larche-Cahn chemical potential theory, the authors demon-
strated the existence of electrical potential-based stress in the
anodic silicon and found the ratio of potential change to stress to be
62 mV GPa1 [67].
2.1.3. Conguration of electrodes
Various electrode and electrolytic congurations have been
tested for solid state battery systems. For example, one of the rst
new designs from the usual coin cell strategy was plastic-based
LiPON electrolyte or PLiON, which provided a great deal of exi-
bility and ease of use [70]. Some other congurations that have
been tried are the cylindrical, prismatic, and at. These have been
considered to be the most versatile congurations, leading to op-
timum surface area contact between the anode/electrolyte and the
cathode/electrolyte [70]. Another important factor is the dendrite
formation in the Li anodes, owing to its close proximity to the

Fig. 3. Part (a) shows a TEM image of lithiation and consequent cracking of the Si nanoparticle. As can be seen from the image, the crystalline Si nanoparticle (c-Si) shares a common
interface with the tungsten electrode on side and a Li counter electrode. During the lithiation process, as seen in part (b) the Si particle has cracked and the Li envelopes it quickly
and even enters the particle forming a core shell of pure Si with an external amorphous LixSi. Thus it can be understood how lithiation causes cracks due to induced stress [355,356].
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
electrolyte and the consequent electrical reaction. Scrosati et al.
were able to solve this problem by doping the Li anodes with other
metals (Co, Ta); this conguration was called the rocking-chair
technology [71]. Short circuiting due to dendrite formation is a
practical problem which has been described by Nishi [72]. Ac-
cording to him, dendrite formation causes the problem of short
circuiting by penetrating into the electrodes and causing poor cycle
performance [72]. According to Song et al., the presence of long
interconnect and channels allow paths for the dendrites to grow
and proceed [73]. These, consequently lead to the reduction of cell
efciency and ultimately internal short circuiting. Therefore they
have recommended the application of non-porous polymer mem-
branes to prevent the growth of these dendrites [73]. The choice of
the electrode/electrolyte conguration is, therefore, very important
to the proper functioning of the cell, and its optimization is abso-
lutely essential. Further, thick lm technology has been studied
by several groups. This basically involves the deposition of layers of
composite materials from their precursor solvents; these compos-
ite materials are further ground and compacted with a polymeric
binder to produce the necessary electrode. Kim et al. have used
thick lm technology to develop electrodes for microbatteries,
which were deposited on metallic current collectors [74]. A poly-
meric gel electrolyte consisting of PVDF-LiPF6-propylene carbonate
(PC)-ethylene carbonate (EC) was used to complete the cell [74].
Vapor deposition technology to deposit thin lm electrodes has
been studied by Fleischauer et al. [75]. They were able to deposit
porous silicon thin lms having a very high aspect ratio, which
were approximately 500 nm in height. This resulted in a form of 3D
microstructure for the thin lm batteries [75]. Teixidor et al. have
demonstrated the formation of carbon pillars as microelectrodes
for thin lm lithium ion batteries [76]. For this purpose, litho-
graphic patterning coupled with thermal decomposition of cross-
linked photoresists was used. The photoresist acted as the solvent
and the curing of the dispersion was done by UV light [76]. Inter-
digitated conguration cells were studied and modeled by Zadine
et al. [77]. They used nite element analysis (FEA) for modeling and
were able to study the rate constraints of the electrochemical
processes, especially those due to collector resistance with this
technique [77].
Composite ceramic electrodes, an important class of solid state
electrodes, have been developed and studied by a number of
groups. Mizuno et al. have prepared composite ceramic electrodes
by thorough grinding of the precursor materials LiCoO2 and
Li2S.P2S5. [78]. The nal step in the design of the composite ceramic
electrode involved the pressing together of the Li based positive
electrode, the In foil negative electrode and the electrolyte which
were then held together by stainless steel current collectors. The
authors have reported a discharge capacity of 75 mAh g1 at a cut
off voltage of 1.5 V [78]. Wei and coworkers have developed a metal
oxide electrode for application in all solid state sodium recharge-
able batteries [79]. A 22 mm thick P2Na2/3[Fe1/2Mn1/2]O2 cathode
and 52 mm thick Na2Ti3O7$La0.8Sr0.2MnO3 composite anode pre-
pared by solid state reactions was used, yielding a capacity of
152 mAh g1 at 350  C [79].
Delaizir et al. have studied the process of spark plasma sintering
to develop ceramic electrodes for all solid state batteries [80]. They
have developed monoclinic Li3V2(PO4)3 as both the anode and the
cathode. Non uniform sized precursor materials were used to
perform the sintering so as to achieve the highest degree of
compactness. The authors have mentioned that the compactness of
the electrolyte is important in controlling the electrical conduc-
tivity; an optimal ionic conductivity of 2.8 * 104 S cm1 was ob-
tained [80]. They have demonstrated rather promising surface
capacity of 2.2 mAh cm2 for a cut off potential of 2.45 V [80].
Electrode architecture is another important factor while
303
designing the solid state battery. To have a better interface between
electrodes and solid electrolyte, Soo et al. have developed rubbery
block copolymer type electrode systems [81]. They have used these
electrodes in Li based solid state battery systems and good cycling
properties have been noticed under room temperature conditions
[81]. Zhang et al. have developed columnar nanostructured tin
oxide electrodes for Li ion rechargeable batteries [82]. These tin
oxides are essentially columnar grains with a coating of nano-
particles, 20 nm in diameter [82]. A reversible capacity of
460 mAh g1 is obtained under ambient conditions at a current
density of 0.3 mA cm2 [82]. Li et al. have studied mesoporous
anode systems which were made of Co3O4 [83]. These mesoporous
systems demonstrated a capacity of 700 mAh g1 after 20 cycles of
operation which has been considered to be a reasonable result [83].
To facilitate electrochemical reactions, several approaches have
been researched to have a good solidesolid contacts between
electrode and electrolyte [35,36,84e90]. The achievement of close
contacts and the increase contact areas are important aspects to
have an effective chargeetransfer reaction as explained by Tasu-
misago et al. [84]. Using nanocomposites by a ball milling process,
the surface coating of active material particles with thin lms
associated with a pulsed laser deposition (PLD) techniques, and
using supercooled liquid of glass electrolyte have been established
to have a favorable contact at the interface between electrode and
electrolyte which leads to a good performance of all solid state
batteries [36,84,85,89e92].
2.1.4. Electrolyte
As the performance of a solid state battery depends on the
diffusion of ions within the electrolyte, solid electrolytes are
required to have high ionic conductivity and very low electronic
conductivity and should exhibit a high degree of chemical stability
[14,93]. Crystalline materials such as lithium halides, lithium
nitride, oxy-salts, and suldes have been found to be good as solid
electrolytes. The most favorable features of the solid electrolyte are
that there is no corrosive or explosive leakage and the chance of
internal short circuit is less, and hence it is safer [14,94]. Solid
electrolytes should have a sufcient number of mobile ions to
enable conduction to proceed smoothly. Solid state electrolytes
should therefore have enough vacancies in their crystal lattice to
permit the ions to move, and the overall activation energy must be
low [94,95].
Different types of solid state electrolytes have been employed,
based on their congurations and electrode/electrolyte materials
setups. Therefore, solid state electrolytes are broadly classied into
two types, bulk solid state electrolytes and thin lm solid state
electrolytes. The primary distinction is on the degree of thickness of
the electrolyte; thickness of bulk solid state electrolytes are usually
in the range of several hundred micrometers, whereas that of thin
lm solid state electrolytes are in the range of hundreds of nano-
meters to several microns. Another primary area of difference be-
tween the two is the way they are fabricated: bulk solid state
electrolytes are usually prepared by techniques such as mechanical
milling, sintering and compaction, annealing and heat treatment
whereas thin lm solid state electrolytes are fabricated by pulsed
laser deposition, spark plasma sintering, CVD etc.
a) Bulk solid state electrolytes (electrolytes at the macroscale)
Among the most commonly used solid state electrolytes are the
solid polymeric electrolytes (SPE) [96]. The main aim while devel-
oping SPEs is to obtain ionic conductivities as high as those of liquid
electrolytes [96]. If the polymer is obtained by complexing it with
an inorganic salt, then it has a low lattice energy, which makes the
resultant SPE more stable [96]. Frequently used polymereinorganic
304 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
salt electrolyte complexes include PEOeLiCF3SO3 and PEO-LiBF4
[96e98]. One of the important types of inorganic solid state elec-
trolytes is the NASICON type electrolyte having the general formula
LiM2(PO4)3, where M is usually Ti, Ge, or Hf [99]. However, an
important drawback of this type of electrolyte is its steady degra-
dation due to grain boundary effects that creep in Refs. [99,100].
Polymer gel electrolytes have also been tried by several groups
[101]. The primary advantage of this type of electrolyte is that the
host of the polymer compound forms a relatively strong and stable
bond with considerable amounts of organic liquid. This consider-
ably enhances the cell performance [101]. Composite polymers are
another class of polymeric systems that have been utilized [102].
They consist of a distribution of nanosized granular materials as
llers in a larger SPE host. However some problems still do exist
with polymeric systems like ammability and sometimes a lack of
signicant room temperature conductivity. Current research looks
at overcoming these problems [102,103].
Solid state electrolytes with the garnet structure (general for-
mula A3B2C3O12) are also used frequently [100]. They include
Li5La3B0 2O12, where B0 is usually Bi, Sb, Na, or Ta. These garnet type
solid state electrolytes have shown ionic conductivities around 4 *
104 S cm1 [100]. LiPON-based electrolytes show the greatest
promise because of their inherent safety, ability to transport
charges quickly, and thermal stability.
Vanadium-based electrolytes have also been studied
[6,104e106]. These xerogel vanadium pentoxides contain sheets of
two vanadium oxide layers, with all the vanadyl bonds on the
outside, leading to a distorted octahedral coordination around the
lithium instead of the square pyramidal coordination found in
crystalline V2O5 [6,106]. MnO6 crystals are connected to one
another in three dimensions by sharing of the edges. LiO4 tetra-
hedral shares each of its four corners with another MnO6 unit but is
actually structurally unique [107]. This leads to the formation of a
three-dimensional network of octahedral and tetrahedral sites,
whereby the Li ions can travel through the pores of the electrolyte.
The different types of building units are responsible for the wide
variety of properties in MDOs [108,109]. MDOs exhibit excellent
electrochemical properties of several manganese-oxide phases and
are attracting much attention as positive electrodes in lithium
batteries.
Apart from the above mentioned inorganic solid state electro-
lytes, organic solid state electrolytes have also been studied. Kim
et al. have developed polymer solid state electrolytes based on
Polyethylene glycol (PEG) coupled with organic hybrids and plas-
ticizers [110]. The authors have reported ionic conductivities of 4.5
* 105 S cm1 at room temperature conditions [110]. Xuan and
coworkers have developed a polymer electrolyte from ionic liquid
(IL) and PEO and have reported a reversible cycle capacity of
140 mAh g1 for their solid state systems [111]. Sulfur-based
lithium solid state electrolytes have been tried as well. The most
prominent is Li3.25Ge 0.25P0.75S 4, which demonstrated considerable
electrochemical stability and very good ionic conductivity of 2.2 *
103 S cm1 at room temperature [119,120]. Suldes materials with
extremely high lithium ionic conductivity of 12 mS cm1 at room
temperature was reported by Kamaya et al. [112]. Y. Seion et al.
reported that a heat-treated Li2SeP2S5 has an extremely high ionic
conductivity of 1.7 *102 S cm1 and the lowest conduction acti-
vation energy of 17 kJ mol1 at room temperature [113]. The proper
functioning of the solid state battery depends not only on its
chemistry but also on its proper integration in the cell and its
stability with respect to the cathode/electrolyte and anode/elec-
trolyte interface.
b) Thin lm solid state electrolytes (electrolytes at the nanoscale)
The most commonly used thin lm solid state electrolyte is the
LiPON (lithiumephosphorus-oxy-nitride) electrolyte [114e116]. It
is usually a glassy electrolyte and is obtained by the RF magnetron
sputtering process [114]. The N versus O ratio is the most important
factor in the fabrication of this electrolyte and, with optimum N/O
ratios, ionic conductivities as high as 1e2 mS cm1 have been ach-
ieved [114]. Current studies have also shown that polyethylene
oxide (PEO) coupled with LiXF6, where X is P, As, or Sb (PEO:LiXF6),
is a good ionic conductor [117,118]. Conductivity and mechanical
strength were improved further by the addition of inorganic llers
such as Al2O3 or TiO2 [119]. The LIPON thin lms were obtained by
RF magnetron sputtering of the Li3PO4 target, using nitrogen gas
[120]. The exact composition of the electrolyte obtained was
Li3.3PO3.8N0.22, along with optimum conductivities of 104 S cm1
[120].
2.2. Charge transfer mechanism for a solid state battery
The charge transfer mechanism of solid state electrolytes is
distinct from that of liquid electrolyte-based cells and batteries.
Solid state electrolytes depend on diffusion of ions as the driving
force behind the charge transfer mechanism. In a Li-based solid
state electrolyte, the diffusion process results in Li ions from the
electrolyte entering the cathode and anode by the lithiation pro-
cess, as rst reported by Whittingham and Yazami [121,122].
Similarly, delithiation is the loss of Li ions from the particular
compound (electrode, in this case). The charging involves deli-
thiation from the cathode and lithiation in the anode via diffusion
through the electrolyte. Likewise, during the discharging process,
the opposite reaction takes place, involving the diffusion of the ions
via the solid state electrolyte [122,123]. This lithiation process de-
mands that the host species be able to accommodate the Li ions
rather easily, and the cathode and anode should thus be selected
accordingly. The higher the number of Li ions owing into the
electrodes, the greater the current that is produced, and the cell
voltage is proportional to the Fermi potential difference between
the anode and cathode [3,9,121]. This potential difference decreases
with the working of the cell [9]. Conductivity of ions across the solid
electrolyte takes place usually by migration of mobile ions across
vacancies or interstitials in the electrolyte [124]. The presence of
defects in the solid electrolyte crystal lattice (Frenkel defects)
further facilitates the ion hopping mechanism across the solid state
electrolyte [124]. Other prevalent mechanisms include the inter-
stitialcy or the knock-on mechanism, in which a metal cation
does not move unless it is able to move its neighboring ions and
thereby create a path for itself [124]. A theory that has been pro-
posed is the random walk, in which there is occasional ion hop-
ping that is totally random [124]. The Li ion travels into an
interstitial point in the host (the electrode, in this case) lattice and
moves from one interstitial to another by the same mechanisms as
explained above [125,126]. Li ions usually diffuse via this mecha-
nism because of their small size and the relatively less energy
needed to move from point to point [3]. There must be holes or
vacancies in the host (electrode) lattice for diffusion of Li ions to
take place through them. A schematic representation of the diffu-
sion process for the Li ions across the grain boundary is shown in
Fig. 4. This demonstrates that a concentration gradient is created at
the grain boundary, which helps in the grain boundary diffusion
process. This method of lithiation, however, requires much larger
activation energy than other mechanisms of diffusion [126,127].
Charge transfer at the interface of the solid state electrolyte and
electrode is also another important phenomena that needs to be
considered. An important way in which the interface can be
distinguished is by the equilibrium of the charged species across
the interface [128]. Interfaces across which the charged species
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Fig. 4. A formation of the concentration gradient of Li ions at the grain boundary with time as the cell undergoes its charging and discharging cycles. This concentration gradient
acts as the driving force for the diffusion of Li ions at the grain boundary interface [127,357]. The initial concentration gradient is denoted by C0 and the thickness of the grain by d. A
2D structure is shown here with x and y directions as marked.
tend to equilibriate and these are called non-blocking interfaces
and those across which the charged species do not equilibriate are
blocking interfaces [128]. An example of the former is the Ag/
Ag4RbI5 interface, whereas C/Ag4RbI5 constitutes a blocking inter-
face. In a non-blocking interface subject to an applied potential
difference, the rate of cation transfer from electrode to electrolyte is
equal to the rate of metal deposition on the electrode In the
blocking interfaces, this equilibrium rate is not reached [128]. The
ow of charge across the interface is a function of the difference
between the thermodynamic potentials at the electrolyte and the
electrode surfaces respectively. The movement of the charged
species may occur by convection or diffusion as the case may be
[128,129]. When other external impulses, such as applied potential
does not exist, the charge transfer takes place simply by a chemical
potential gradient [129]. An important parameter to consider here
is the Debye length (rd).The spread or distribution of the charged
species across the interface is determined by the size of rd and a
uniform spread of the charge occurs only when rd is greater than
the ionic radii [128].
Solid electrolyte interfaces are an important aspect of the charge
transfer process. They usually start to form on the surface of the
electrode due to the gradual decomposition of the electrolyte. The
SEI layer acts as a passivating agent preventing any further degra-
dation of the electrolyte and the electrode. The SEI also helps in
improving the cyclic performance of the electrodes. Andersson
et al. have shown the formation of lithium based SEIs having the
general formula LixPFyOz and Hu and coworkers have shown the
formation of SEIs in Cr2O3 based systems [130,131].
2.3. Design considerations in selection of a solid state electrolyte
The electrolyte is one of the most important parts of the solid
state battery. Solid state electrolytes are known mainly for their fast
and efcient ion transport properties. It has also recently been
shown by Gadjourava et al. that solid state electrolytes should
usually have a crystalline structure for a high ionic conduction rate
[132,133]. The following are some of the important general pa-
rameters that must be considered in selection of the electrolyte.
(i) Chemical and thermal stability:
305
The solid state electrolyte is usually held between the anode and
the cathode, and unwanted reactions must be avoided at the in-
terfaces of the electrodes with the electrolyte [96]. Also, the elec-
trolytes must be able to work perfectly in an electrochemical
regime from 0 V to about 4e5 V [96,134]. Therefore, chemical and
electrochemical stability is an essential property in a solid state
electrolyte. Versatility of the solid state battery dictates that it must
be able to work in a broad temperature range. Usually, lithium
based rechargeable batteries used for military purposes are sub-
jected to a temperature range of 50  C to 80  C, and the electrolyte
must be able to function perfectly in this temperature range
without showing any thermal degradation [96]. Thermal stability is
thus another important factor that must be considered when
choosing the electrolyte.
(ii) Ion transference number:
The ion transference or transport number indicates the contri-
bution of the different ions toward the total electric current carried
by the electrolyte [96,135]. The ion transference number of the solid
state electrolyte should be close to unity or even, ideally, exactly
unity [96,136]. This is because the main purpose of the electrolyte is
to allow the ow of the ions (cations) and prevent any electrons
from traveling. However, in reality, the ion transference number is
usually about 0.5, indicating only half of the necessary ionic species
moving through the electrolyte [96,137,138]. Therefore, the elec-
trolyte selected should have an ion transference number as close to
unity as possible, leading to efcient transport of the cations,
reduction in the concentration of polarization, and consequently
higher power density [96].
A general comparison can be made here, for example, a solid
polymer-based lithium salt such as (PEO)20LiClO4 has a lithium
transference number of 0.31, whereas that for PEO-based LiAsF6
exhibits an ion transference number of 0.44 [139]. However, suit-
ably prepared gel polymer lms have shown ion transference
numbers greater than 0.95, as demonstrated by Zainol et al. [140].
Ghosh and coworkers have prepared a solid lithium-based polymer
electrolyte with the high ion transference number of 0.9 at room
temperature [141]. Ion transport numbers of liquid electrolytes are
slightly higher, that of molten sodium chloride being
306 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
approximately 0.5 [142].
(iii) Mechanical strength and stability:
The solid state electrolyte will have to withstand clamping
forces when it is xed between the anode and the cathode. It will
also have to bear the wear and tear of regular usage. It must work
not only in a smaller laboratory setup but must also be able to
reproduce its functionality when scaled up for industrial usage
[96,143]. It must therefore have high mechanical strength and
stability.
2.4. Processing routes for solid state electrolytes
Engineering the microstructure of the solid state electrolyte is
vital, as this gives optimum properties and also helps in main-
taining the properties of the electrode/electrolyte interface without
steady degradation or corrosion.
a) Processing routes for bulk solid state electrolytes:
Garnet type solid state electrolytes such as Li7La3Zr2O12 have
been fabricated at extremely high temperatures (1500 K) by Mur-
ugan et al. [144]. However, this very high temperature fabrication is
a practical drawback. Solegel synthesis techniques have been tried
with varying degrees of effectiveness [144]. Laser annealing is
another important fabrication technique, which has been found to
have the advantageous ability to be localized and thoroughly
manipulated [145]. Inorganic solid state electrolytes such as LLZO
have been prepared by the laser annealing technique. Precursors
used are Li2CO3, La2O3, and Zr(NO3)2.6H2O immersed in HNO3 to
form a solution [146]. Consequent ltration followed by subjecting
to intense laser pulses results in the formation of the required LLZO
solid state electrolyte powder [146]. The spark plasma sintering
technique has been used by Chang et al. to develop Al substituted
LiHf2(PO4)3-based solid state electrolytes [147]. The precursors
used were Li2CO3, HfO2, NH4H2PO4, and Al(NO3)2.9H2O. XRD pat-
terns have indicated a crystalline structure similar to NASICON, and
the SEM microstructure shows a predominantly porous micro-
structure [147]. Electrical tests have shown that spark plasma sin-
tered samples have an optimum conductivity of 2.6 * 105 S cm1,
as against 6.5 * 106 S cm1 for conventionally sintered samples,
which proves the advantage of the process [147]. Polymeric solid
state electrolytes have also been studied in detail and various
mechanisms have been employed to prepare them. Sequira and
Hooper have prepared lithium-based polymeric electrolytes having
the empirical formula (PEO)x-LiCF3SO3, using a solegel technique,
and they have studied its properties in the range of 100  Ce170  C
[148]. Plasticized polymers based on PEOeLiN(CF3SO2)2 have been
prepared by condensation with tetraglyme and the resultant
polymeric solid state electrolyte has conductivity of 4.74 * 104 S/
cm at room temperature conditions [149].
Cold compaction method to prepare the solid state electrolyte is
another important technique that has been tried by several groups.
Feng et al. developed a Li1.5Al0.5Ge1.5(PO4)3 (LAGP) solid state
electrolyte by the method of mechanical milling, calcination and
cold compaction [150]. LiPF6 was used as the electrolyte along with
Li metal as the counter and reference electrodes. The researchers
have shown electrical conductivity of the as prepared LAGP sample
up to 3.5 * 106 S cm1 and stability up to 7 V [150]. Jak et al. have
developed a ceramic based solid state lithium electrolyte using
static as well as dynamic compaction [151]. The authors have noted
a difference in Li ion conductivity; the dynamically compacted
system gave a higher conductivity of up to three orders of magni-
tude. Overall, an optimal ionic conductivity 2 * 104 S cm1 was
obtained under ambient conditions [151].
A lithium based solid state electrolyte created by the process of
hot press sintering at 1230  C and having the composition
Li7La3Zr2O12 (LLZ) has been developed and studied by Kotobuki and
coworkers [152]. The structure of the resulting solid state electro-
lyte resembles a garnet. The researchers have reported an optimal
electrical conductivity of 1.8 * 104 S cm1 at room temperature
conditions [152].
Sulde and oxide glass electrolytes have been used by rapid
melt quenching and mechanochemical techniques [153e156]. A.
Hayashi et al. showed the successful preparation from a mixture of
crystalline Li2S and P2S5, using a mechanical milling technique, and
also compared with melt quenching in 2001 [154]. An oxide glass-
ceramic electrolyte of Li2.9B0.9S0.1O3.1 with high Li ion conductivity
and low melting property was developed by mechanical milling
and subsequent heat treatment at 290  C by M. Tatsumisago et al.
[153].
b) Processing routes for thin lm solid state electrolytes:
The pulsed laser deposition (PLD) technique has been tested by
Nakagawa et al. to develop a solid state electrolyte, especially thin
lm lithium-based solid electrolytes [157]. An ArF excimer laser
was used for the purpose and thin lms were obtained, which gave
optimal electrical conductivities of approximately 4.1 * 107 S cm1
at room temperatures [157]. Kim et al. have investigated the use of
magnetron sputtering to fabricate thin lm solid state LieBeOeN
electrolyte systems [158]. Glassy amorphous thin lms were ob-
tained and characterization results showed that the amount of N in
the lms decreased with the addition of more Li in the composition
[158].
As can be seen from the above review, different fabrication
processes are possible for varying types of solid state electrolytes,
and they will discussed in more detail in the subsequent sections.
3. Thin lm solid state batteries
Nanomaterials and thin lms are capable of suitable utilization,
thanks to their enhanced properties. Nanoscale electrolytes pre-
pared in the form of thin lms offer high energy density (research
on active electrode and electrolytic materials currently puts the
theoretical energy densities at about 200 Wh kg1), a longer life-
time, exibility, and extreme lightness, which tends to reduce the
overall weight of the system [159]. Thin lm battery systems,
especially Li based systems, are already in applications in zero
emission vehicles, in the aerospace sector, in military facilities, and
in medical instrumentation [159,160].
3.1. Background
One of the earliest thin lm solid state batteries to have been
studied was that based on the Li electrolyte, produced by Hitachi
Co., Japan [161]. The battery was called the all-solid state thin lm
battery and incorporated a TiS2 cathode, a metallic lithium anode,
and a Li3.6Si0.6P0.4O4 thin lm electrolyte prepared by the RF
sputtering technique [161]. However, it was not immediately
deployed commercially, as it was not sufcient for the larger elec-
tronic devices prevalent at that time [161]. NTT Co., Japan, achieved
further advances in thin lm solid state batteries by developing a
Li3.4V0.6Si0.4O4 glassy electrolyte based solid state battery by the RF
sputtering technique [162,163]. Eveready Battery Co. and Bellcore
Co. have developed solid state batteries using sulde glasses
(Li4P2S7 and Li3PO4eP2S5) as electrolytes [164]. More recently, Baba
et al. developed the rocking chair type solid state battery using
LiPON electrolyte, LixV2O5 anode, and LiMn2O4 cathode, by RF
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
sputtering [165]. They have also developed solid state batteries
without using a Li anode (for example by using a V2O5 anode) and
have been able to obtain capacities of approximately 10 mAh cm2
[165,166].
3.2. Thin lm solid state battery electrodes
Electrodes of thin lm batteries play an important role in the
proper performance of the battery; hence, it is essential to choose
the right electrode materials for solid state batteries [159]. The
most important factors to be kept in mind when selecting the
materials are their capacity for energy storage, a considerable
contact surface area with the electrolyte for the electrochemical
reactions to take place effectively, and the ability to support lith-
iation/delithiation, especially if the battery to be designed will be Li
based [159]. For anodes, materials that have good Li storage prop-
erties tend to be favored. Alloys of Al, Sn, and Si are suitable choices,
as they provide good specic capacity (a LieSi alloy, Li4.4Si, provides
a theoretical specic capacity of 4200 mAh g1, versus
3600 mAh g1 for Li metal) and have reversible electrochemical
reactions with lithium [167e170]. Initially, thin lm Li based solid
state battery systems used transition metal oxides or chalcogenides
as anodes, but these materials usually had reduced redox potential
values. These materials included WO2, TiS2, and MoO2 [71,171,172].
Since then, several other materials have been tested to develop
suitable anodes for solid state batteries. Amorphous carbon has
been used, as its processing temperature is lower and it provides
better storage capacity than graphite [173,174]. It has also been
hypothesized that the addition of aluminum and gallium to
graphite will improve capacity, as they form solid solutions.
Alloying of carbonaceous anodes with transition elements such as
vanadium and nickel are also being studied for the purpose
[175,176].
A good cathode material is expected to have light weight, su-
perior energy density, very limited self-discharge, and good cyclical
capacity [159]. Commonly used cathode materials include LiCoO2,
LiMnO2, olivines such as LiFePO4 and metal chalcogenides such as
TiS2 and V2O5 [177,178]. Transition metal dioxides of the general
empirical formula LiMO2 (where M V, Cr, Fe, Co, and Ni) are very
common. Structurally, they resemble NaCl; however, the structure
appears a bit distorted and the parent structure is the a-NaFeO2
type [179e184]. The lithium and the transition metal atoms are
positioned at the octahedral and the interstitial sites, resulting in an
overall layered structure. It is this structure that provides thermo-
dynamic stability and good electrical capacity, making these suit-
able as cathode materials. Doping of LiCO2 has also been tried with
elements such as Mg, Al, Cu, Ni, or Sn to improve its reversibility
and lower the processing cost, with good results [185,186]. Li based
phosphor olivines (e.g., LiFePO4) have been used as cathodes in
solid state thin lm battery systems. The advantages of LiFePO4 are
its high energy density, thermal stability, relatively cheap pro-
cessing cost, and high theoretical capacity (170 mAh g1) [187,188].
However, it has relatively low electrical conductivity (~109 e
~1010 S cm1), and efforts are therefore underway to improve its
properties by further processing and alloying techniques [188]. The
effect of external/manufacturing pressures also play an important
role in the fabrication of thin lm batteries. As stated by Patil et al.,
lower manufacturing pressures result in a good electrode porosity,
however, it causes rather poor connection between the particles
[159]. On the other hand, high pressures provide for low porosity
and better contacts between the particles. It has been noted that
thin lm electrolytes demonstrating low porosity show greater
stresses due to Li ion insertion/deinsertion [159]. Therefore the
application of an optimum working pressure is necessary to for the
best cell working [189]. Sometimes, mathematical and analytical
307
models have been utilized to optimize the external pressure for the
best cell output [189]. A schematic representation of a cross-section
across a thin lm solid state battery is given in Fig. 5, which shows
the arrangement of the cathode, anode, and the respective current
collector layers and how they are aligned with respect to the
substrate.
3.3. Thin lm systems
Lithiumeoxygen and nitrogen based polymer thin lm elec-
trolytes have been widely studied for their use in solid state bat-
teries [158,190,191]. Notable in this regard is the work on Li ion
conducting thin lm solid state polymeric electrolytes by Kim et al.
[158]. The solid state electrolyte obtained was a glassy LieBeOeN
thin lm. The sputtering target was made by sintering and had
compositions of Li2OeB2O3 (1LBO), 3Li2OeB2O3 (3LBO), and
5Li2OeB2O3 (5LBO). The sputtering was done on Al substrates in
nitrogen atmospheres [158]. Electrochemical studies have shown
that the 3LBO based lm has maximum ionic conductivity of 2.3 *
106 S cm1 at room temperature [158]. A SieV anode based thin
lm solid state battery was fabricated by Lee et al. [192]. It had the
conguration Si0.7V0.3/LIPON/LiCoO2 and has demonstrated a ca-
pacity of 50 mAh/cm within a range of 2 V and 3.9 V [192]. Wu et al.
developed Li based thin lm electrolyte for solid state battery ap-
plications [193]. The target consisted of a LieTieSiePeO lm,
which was fabricated by cold pressing. The precursors of the target
were Li2CO3, SiO2, TiO2, and NH4H2PO4 in the molar ratios of
1.3:0.6:4:5.4 [193]. RF magnetron sputtering was used for the
fabrication process of the thin lm solid state electrolyte [193].
Characterization has shown that the thin lm had a smooth,
awless surface and a thickness of 2.6 mm [193]. EDX analysis gave
the approximate formula of the thin lm as LixTi2Si0.32P3.6O7.16N2.52.
XRD data showed the mostly amorphous nature of the electrolyte.
A room temperature conductivity of 9.2 * 106 S cm1 was obtained
[193].
Among the non-Li based solid state thin lm batteries, Aber-
ouette et al. studied the performance of Ag deposited on Ag-doped
germanium chalcogenide thin lm solid state electrolyte system
[194]. Si was used as the substrate and Si3N4 was deposited on it
using CVD to a thickness of 1800 A. After this, the surface was
thoroughly cleaned and a further 300 A thickness of chalcogenide
glass and 150 A thickness of silver were deposited on the substrate.
The chalcogenide obtained had different compositions: Ge20Se80,
Ge30Se70, Ge33Se67, and Ge40Se60 [194]. The entire system was
irradiated by a light of intensity 4.5 mW cm2 to photo-dissolve the
Ag in the chalcogenide lm [194]. Structural characterization re-
sults showed the presence of Ag deposits on the lm surface and
uniform dendritic morphology. Also, electrical tests indicated a
signicant difference in the local resistivity in the Ag rich and the
Ag poor regions. The authors suggested this to be a simple method
of developing thin lm solid electrolytes for solid state battery
applications [194]. Barium cerate/zirconate perovskite (BCZY)
based solid state thin lm cells have been studied by various
groups. A primary reason for the increased interest in this class of
materials as solid state electrolytes is their relative electrochemical
stability and considerable ionic conductivity [195,196]. Co-pressing
and co-ring methods and spray methods to develop the cells have
been extensively researched and are in common use [197e199].
Barison et al. studied the performance and analysis of doped
barium cerate thin lms having the formula BaCe0.65Zr0.2Y0.15O3-
d (BCZY) as solid state electrolytes [200]. The sputtering was done
on a commercially obtained BCZY target in an argon and/or oxygen
atmosphere with working pressure between 0.5 * 102 mbar and 2
* 102 mbar. Deposition rates of 0.7 mm h1 were obtained, and the
thin lms obtained had a thickness of between 2 mm and 10 mm
308 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Fig. 5. Cross-section of a thin lm solid state battery showing the different components. The substrate acts as a support on which the thin lm is usually deposited [159].
[200]. The substrate was chosen to be Ni-BCZY and NiO-BCZY. SEM
studies have shown that thin lms deposited at higher pressures
(2.1 * 102 mbar) tend to show more crystallinity than those
deposited at lower pressures (5 * 103 mbar). XRD studies also
indicate the crystallinity of the sputter deposited lms, although
higher temperature deposited lms (400  C) tend to show a greater
degree of crystallinity, as seen from the sharpness of the XRD peaks,
which can be attributed to better phase formation at higher tem-
peratures [200]. The authors successfully demonstrated sputter
deposition of BCZY solid state electrolytes on porous substrates,
which can have solid state battery applications [200]. Zhou et al.
reported progress in research on nanostructured thin lm elec-
trodes for lithium batteries. The thickness of a typical nano-
structured thin lm is less than 200 nm [201]. Thin lm electrodes
do not require additives to enhance conductivity or structure. The
resistance of the lm is signicantly reduced by the reduction in
thickness [201]. The dense structure of a thin lm contributes to its
durability. Thin lm electrodes can be produced by magnetron
sputtering, pulsed laser deposition (PLD), electron beam evapora-
tion, chemical-vapor deposition, electrostatic-spray evaporation,
chemical-vapor deposition, electrostatic-spray deposition (ESD), or
solegel fabrication [201]. Chiu et al. used the sputtering technique
to develop solid state batteries having LiNiO2 and LiNi0.8Co0.2O2
polycrystalline electrolytes [202,203]. Nickel as a component in the
thin lm electrolytes was also tested by Xia et al., who developed
LiNi0.5Mn0.5O2 electrolytes by the PLD technique [204]. Similar
work on micron sized solid state batteries has also been done by
Kushida et al. [205], showing that a number of micron sized bat-
teries placed on a Si substrate have a uniform output capacity of
approximately 9.2 mAh cm2 for 100 cycles at 3.6 V [205]. A lithium
silicate based solid state battery was developed by Nakagawa et al.,
who employed the pulsed laser deposition (PLD) technique to
fabricate the thin lm solid state electrolyte. They reported an ionic
conductivity of 2.5 * 108 S cm1 at room temperature for the
Li2SiO3 thin lm [157]. The electrolyte was characterized as amor-
phous in nature. A Li anode and LiCoO2 cathode were used for the
study [157].
Other techniques used to fabricate the electrolytes for thin lm
solid state batteries include the electrostatic-spray deposition
technique and the DSM-Soulll process [206]. The electrostatic-
spray deposition process has been employed to prepare nano-
crystalline ceramic powders. The Soulll process involves the
integration of ceramic in a very high molecular weight polymer
[206]. This matrix is then extruded to produce the thin lm. The
process has been used to produce BPO4$yLi2O thin lm solid state
electrolytes [206]. The latest improvement in the thin lm battery
solid state battery technique was achieved by Kuwata et al. This
battery involved having a LiCoO2 cathode, Li6.1V0.61Si0.39O5.36 solid
state glassy electrolyte, and SnO based anode [207]. The entire
fabrication was done simply by the sequential PLD technique
[207,208].
A novel technique is the use of MoO3 nanobelts to enhance the
performance of lithium based solid state batteries [209]. The
rationale for the choice of MoO3 is its high structural anisotropy
[209], which helps the lithiation process. The authors showed a
capacity retention as high as 92% after 15 cycles of operation, vis-


a-vis the 60% retention in non-MoO3 lithiated solid state batteries
[209]. LiMnPO4 nanoplates were grown on the cathodes to enhance
the performance of Li based solid state batteries [210]. The high
theoretical energy density of LiMnPO4 (701 Wh kg1) was the
motivation for this study [210]. The LiMnPO4 was grown via a solid
state reaction using oleic acid surfactant, yielding a uniform po-
tential of 4.1 V and a specic capacity of 168 mAh g1 [210]. The
feasibility of Cu in solid state battery systems has been studied by
several groups. An important piece of work in this regard was
conducted by Dahm and coworkers [211]. They used a complex
sulfonium iodide coupled with cuprous iodide as the solid state
electrolyte. Maximum conductivity of 1.3 S cm1 was obtained for
the electrolyte having the formula 4-methyl-1,4-oxathianium io-
dide [211]. Another improvement in the area of solid state batteries
involving copper components, especially at the nanoscale, is the
development of CuSbS2 nanobricks by Zhang et al. [212]. The
nanobrick electrolyte was prepared by the hot injection method
using an oleylamine surfactant [212]. Discharging and charging
capacities of 1090 mAh g1 and 761.6 mAh g1 were obtained,
respectively, but they then deteriorated with the lifecycle of the
battery, and the capacity after 50 cycles of operation was only about
85.7 mAh g1 [212]. Sodium based thin lm solid state batteries
have also been studied. Early work in this regard was done by West
et al. and Munshi et al., who developed sodium based anodes such
as NaxCr3O8 [213,214]. However, even though these cells performed
their operations, the output voltages obtained were not satisfac-
tory. More recently, cells utilizing P(EO)8NaCF3SO3 as solid state
polymer electrolytes and Na15Pb4 as anodes have achieved some
success [215,216]. However, issues remain, such as the rapid drop in
capacity after relatively few cycles and the irreversible phase
change of the electrodes. These still need to be overcome [217].
3.4. Challenges and current status
A lot of research and developmental work is still going on in the
eld of Li ion batteries to improve its performance. A cyclical per-
formance of 10,000 cycles without much drop in cell output and
potential has been noted, indicating good performance [218,219]. It
has also been proposed that using stacks of cells instead of single
cell can help improve the capacity of the cells. However thin lm
systems present certain drawbacks related to the electrolyte
thickness and integration which prevent them from achieving their
full potential.
One important drawback of the thin lm battery system is that
its performance may be constrained by the nature of its geometry
[159]. The current that can be drawn from the thin lm battery is
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Table 1
The properties of Li based solid state battery systems, along with their open circuit voltages and electrical outputs.
Anode Cathode
Li alloy Li4Ti5O12-carbon ber composite
Indium foil Composite consisting of LiCoO2, acetylene
powder and electrolyte powder
Li metal LiCoO2
Li metal Li metal
Anode: Li metal Solid state composite air cathode
Molten Li Cu0.1V2O5 painted on the electrolyte surface
Indium LiCoO2
Li metal Li foil
highly dependent on the geometry and interfacial contact at the
electrolyte/cathode and the electrolyte/anode interface [159,220].
A thin lm electrolyte presents a rather at surface to both the
anode as well as the cathode side, which constitutes an apparent
drawback compared to conventional bulk electrodes, where the
surface roughness of the solid electrolytes enhances the net surface
area available, thereby increasing output current [159]. Another
important factor that affects the output and integration of thin lm
systems is the lack of thickness of the electrolyte and the interfacial
resistance that occurs at the electrode/electrolyte interface [221].
Tarascon and Armand have stated that too thin electrolytes tend to
have large amount of volumetric expansion which has a negative
effect on the working of the battery [70]. Also minor mistakes in the
correct positioning of the electrodes and electrolytes result in a
large drop in cell potential and contaminations of both the elec-
trodes and the electrolyte [222]. An interlayer has been developed
to help prevent this from occurring [221,223]. Understanding the
type of secondary reaction taking place at the interface, which is
most common at high temperatures (thereby limiting cell perfor-
mance), is another priority, as this may detract from the cell's
functionality at high temperatures [159]. One of the major inte-
gration problems encountered by thin lm solid state batteries is
the loss of charge retention capacity. This is because, after the rst
charging/discharging cycle, the solid electrolyte interface is formed,
which reduces the charge retention capacity [159]. To overcome
this problem, a proportional mixture of cathodic and anodic ma-
terial is required. Another problem during manufacturing and
integration is low pressure during manufacturing, as high pressures
cannot be applied, owing to the inherent thin nature of the solid
state electrolytes [159]. This results in weak contacts between the
various components of the cell, even though the electrode porosity
is reasonably good. However, this problem can be ameliorated by
selecting a proper pressure during the fabrication process [159].
Other challenges of thin lm solid state batteries are a consid-
erable volumetric change in the electrodes takes place during the
charging-discharging process, leading to loss of material. If this can
be avoided by changing the cell chemistry or better engineering
design, then the output of the solid state cells can be improved
further. Solid state thin lm battery fabrication relies to a large
extent on sputtering techniques, which are costly and hard to scale
up during production times [224]. Also, it has been difcult to apply
everything that has been obtained during the R&D stage to actual
industrial outputs [224]. However, further progress is expected in
this eld soon. A target has been set of achieving 200 Wh kg1 as
capacity and 500 Wh l1 or more within the next few years [225]. It
is expected that solid state cells, especially lithium based cells, will
have several advanced applications such as biometric scanners and
smart cards [159,225].
4. Lithium based solid state batteries
Much research has concentrated on the study of lithium and
309
Electrolyte OCV Electrical output Ref.
70Li2Se29P2S5eP2S3 glasses 1.8 V 140 mAh g1 [240]
Li2SeP2S5 2V 90 mAh g1 [39]
Li5La3Ta2O12 3.5 V 83 mAh g1 [247]
Lithium borosilicate glass 3V N/A [248]
Lithium based glass ceramic 2.6e3.6 V 11.34 mAh [249]
Al doped Li7La3Zr2O12 2e3.5 V 176 mAh g1 [255]
(100-x) (0.6Li2S. 0.4SiS2). xLi4SiO4 3.1 V 90 mAh g1 [257]
Polyethylene oxide based lithium (LiFePO4) 3.45 V 140 mAh g1 [312]
lithium ion based solid state batteries, mostly devoted to the study
of different lithium ion based electrolyte systems and how the solid
state batteries perform with these systems. Lithium based solid
state electrolytic systems fall into the following categories. Table 1
presents a summary of the types of anode, cathode, and electrolytes
used in solid state batteries and their respective open circuit
voltage and electrical outputs.
4.1. Glassy electrolyte systems
4.1.1. Background
Glassy electrolyte systems have received a lot of interest in
recent years, starting with the chance discovery by Kunze of the
AgIeAg2SeO4 glassy solid state electrolyte system [226]. Conduc-
tivities of approximately 102 S cm1 were obtained at room
temperature conditions [226]. Further development in this area
was accomplished by Malugani et al., who developed solid state
glassy electrolyte systems of the type Li2SeP2S5 doped with LiI, and
obtained ionic conductivities in the range of 103 S cm1 under
room temperature conditions [227]. However, the solid state elec-
trolyte was very hygroscopic in nature, and this affected the proper
functioning of the cell [227]. Subsequently, Akridge and Vourlis
succeeded in introducing thiosilicate glasses into their solid state
systems [228,229]. Levasseur achieved another important advance
by developing thin lm lithium borate based glassy electrolytes
with amorphous titanium oxysulde as the cathode [230].
Considerable further developments have occurred in this area,
especially by utilizing Radio Frequency (RF) sputtering to develop
oxynitride electrolytes [231]. On similar lines, Jones and Akridge
have more recently developed solid state oxo-thio glassy solid state
systems, which have provided ionic conductivities of approxi-
mately 2 * 105 S cm1 [232].
4.1.2. Phenomenon of ion transport
Anderson and Stuart proposed the theory of ion transport in
their seminal work in 1954 [233]. Further interpretation and study
of this model has been undertaken by several researchers, notably
Martin and Angell [234], who suggested that the ionic transport
mechanism consists of a simple ion hopping from one site to
another based on the energy gradient [234,235]. The two most
important energy terms involved in this equation are the electro-
static binding energy (Eb) and the electrostatic strain energy (Es)
[235]. The AndersoneStuart model has been highly successful in
explaining ion transport in glassy solid state electrolytes by taking
into account some very important parameters, viz. the elastic
modulus (G) of the system, the Madelung constant (b), which is a
measure of the separation between the ions, and the covalency
parameter (Y), which is a measure of the charge neutralization
between the solid state ions and their immediately adjacent
neighbors [235]. The most notable application of the Andersone-
Stuart model has been the successful explanation of ion transport in
glassy Li based iodides such as LiI [235].
310 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
However, some signicant drawbacks remain. The model does
not explain the presence of vacant cationic sites in the electrolytes.
Neither does it fully explain the preference of the ions to occupy
particular sites in the glass lattice [235]. These anomalies have been
resolved by the model proposed by Bunde et al., which is known as
the dynamic structure model [236]. This model proposes that cat-
ions have their own particular pathways and thereby make their
own sites in the glassy lattice. Relaxation of the lattice structure
results in modication of the position of the empty sites, so that
they can be taken up by the next batch of moving cations [236]. This
dynamic structure model has proven its usefulness by helping
explain the ion exchange in silicate and alumino-silicate glasses
[236].
Further advances in this area have been achieved by Funke et al.,
who proposed the unied site relaxation model [237,238]. This
takes into account the entire spectrum of ion hopping from dc to
infrared frequencies [238,239]. Sulfur and phosphorus based glassy
solid state electrolytes have been tested for applications in lithium
based solid state batteries [240e242]. Tatsumisago and Hayashi
studied the performance of lithium, phosphorus and sulfur based
glassy electrolytes in solid state batteries [240], and were able to
obtain glassy electrolytes with increased ionic concentrations by
mechanical milling and twin roller rapid quenching methods.
Another technique adopted by researchers to improve ionic
conductivity has been to add small quantities of lithium ortho-
oxosalts (LixMOy) [240]. Conductivity values of 5 * 103 S cm1
have been obtained for these glass based electrolytes at room
temperatures under open circuit conditions, equating to about half
the room temperature conductivity of liquid electrolytes [240].
Also, during the solid state battery operation (i.e., at a constant
current density of 12.7 mA cm2 and 100  C), these electrolytes
have been able to show energy densities of 140 mAh g1 and an
ability to work for 700 cycles without suffering any reduction in
output [240]. Citing some of the advantages of the glass based
electrolytes, the authors pointed out that these batteries hold great
promise for future use as solid state batteries in several applications
[240]. Work on similar lines was performed by Trevey and co-
workers [241], who used differing compositions of a
Li2SeLi2OeP2S5 solid electrolyte in their research. The electrolytes
were prepared by mechanical milling techniques using planetary
ball mills for the purpose [241]. The researchers prepared three
different systems: the -20P2S5, -25P2S5, and -30P2S5 systems [241].
Results indicated that conductivity decreased steadily with an in-
crease in the amount of P2S5 in the system, from 3 * 104 S cm1 to
approximately 1.6 * 104 S cm1 [241]. Overall, the samples
exhibited a general amorphous nature, even though sharp peaks
were observed at 26.8 and 34 . Crystalline Li3PS4 and Li4P2S6
phases are seen from the Raman data [241]. Electrical studies
indicated that the best performance was exhibited by the electro-
lyte with the -20P2S5 composition, which had an electrical output
of 90 mAh g1, whereas the -30P2S5 had the poorest performance
[241]. The authors indicated that the performance dropped steeply
after about 25 cycles and therefore these electrolytes do not yet
present a viable commercial alternative [241]. Nagao, Hayashi, and
Tatsumisago studied lithium and sulde based solid electrolytes for
solid state battery applications [242]. The main active component
of the electrolyte was the Li2SeP2S5 part, and the composition that
was chosen primarily was the 80Li2Se20P2S5. The solid state
electrolyte was fabricated properly using planetary ball mills, along
with a small quantity of lithium titanate [242]. Electrical results
have shown the charge and discharge voltages to be around 2 V and
1.1 V, respectively, and a discharge capacity of 120 mAh g1 [242]. A
sudden change in the potential toward the end of the charging
process was attributed to internal short-circuiting in the lithium
batteries [242]. A reversible capacity of 1350 mAh g1 was observed
for the cells, at a current density of 0.013 mA cm2. Results showed
that, even though the output capacity was high, further studies are
still required before they can put the ndings to practical use [242].
Work on Li2SeP2S5 systems has also been performed by other
groups, who have tried adding different compounds to stabilize the
electrolyte system, but capacity fading of these sulde based elec-
trolyte systems has remained the major issue [243e246]. Similarly,
considerable research has been done in the study of glassy phos-
phorus based lithium ion solid state batteries [39,247e249]. Inte-
grated solid state batteries were studied by Goncalves et al. [250].
The study was based on lithium phosphorus oxy-nitride (LiPON)
lm electrolytes. Annealing of the cathode material LiCoO2 lms
exhibited a polycrystalline structure with orientation in the (104)
planes and fewer at (003) and (101) planes [250]. The LiPON 1 mm
lms were deposited on top of Al disc plates, with the surface
already covered with 100 nm of Pt to avoid an unwanted reaction
between the LiPON and the Al plate. The LiPON lm was covered
with a 100 nm layer of Pt and 500 nm of Al coatings for protection
[250]. Results indicated that, when LiPON was coupled with LiCoO2
as the cathode material, there was a net improvement in the
charging and discharging ability of the cell, and the electrochemical
efciency simply increases [250]. These factors further serve to
establish the superiority of LiPON lms in solid state battery utili-
zation. Table 2 lists the solid state electrolytes commonly used
commercially and their room temperature conductivities, as well as
their crystalline nature.
4.2. Ceramic based electrolyte systems
Ohta et al. coated the surface of the LiCoO2 with Li4Ti5O12by
spray-coating [251]. They used seven different samples with vary-
ing thicknesses. Characterization was done by electrochemical
impedance spectroscopy (EIS), which showed the reduction of the
interfacial resistance by the interposition of Li4Ti5O12 [251]. The
spectrum consisted of high as well as low frequency regions and
looked similar to Warburg impedance. High frequency limits were
almost constant, which the authors attributed to a change in the
resistance of the electrolytic layers. Different thicknesses gave
different interfacial resistances [251]. Glass ceramic based electro-
lytes tended to improve the efciency of the cell, thanks to better
charge distribution characteristics [251]. Kotobuki and Kanamura
worked on lithium, lanthanum, and tantalum based ceramic elec-
trolytes for lithium based solid state batteries [247]. The electrolyte
was prepared by the sintering method and the resultant crystal
structure of the electrolyte was like that of a garnet. The anode
consisted of Li metal, whereas the cathode was LiCoO2, both of
which were in contact with the Li5La3Ta2O12 (LLTa) electrolyte
[247]. Very clear redox couple of the LiCoO2 was obtained, even
after prolonged storage of the battery for about a year. XRD results
proved its garnet like structure, whereas cyclic voltammetry and
other electrochemical testing showed that this solid state battery
had oxidation peaks at 3.75 V and 3.95 V, which corresponded to
the oxidation peaks of LiCoO2 [247]. Discharge capacity obtained
was about 83 mAh g1, approximately half the theoretical capacity
[247]. The authors have suggested that a three-dimensional design
of the battery will be able to enhance its functional capability [247].
Jak et al. developed an all-solid state lithium battery to operate at
room temperature up to 150  C [252]. The ceramic electrolyte is
made from Li-doped BPO4, a crystalline material with a primary
particle size of about 50 nm. At room temperature, the SE con-
ductivity was 2  106 S/cm. Conductivity increased to 2 *
104 S cm1 for explosively compacted samples. An alternative
electrolyte is Li1.3Al0.3Ti1.7(PO4)3 (LATP), with a bulk conductivity of
2 * 103 S cm1 at room temperature [252]. Thin foils are used to
reduce internal resistance and increase ionic conductivity. The
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Table 2
Li based solid state electrolytes, their stoichiometries, crystal structure, and repeat units; and optimum conductivity values.
Electrolyte Crystal
nature
Lithium lanthanum titanate (LLTO) Crystalline
Lithium based superionic conductor (LISICON) Crystalline
Sulfur doped lithium based superionic conductor (thio- Crystalline
LISICON)
Lithium lanthanum barium tantalum oxide Crystalline
Li ion conducting mesoporous oxide Composite
Sulde glass Amorphous
LiPON Amorphous
cathode material is LiMn2O4 (LMO) and the anode material is
Li4Ti5O12 (LTO). In a liquid electrolyte, the liquid penetrates the
electrodes, giving rise to high ionic conductivity. In an all-solid state
battery, this interaction is absent. To increase the ionic conductivity
of the SE, an amount of electrolyte material is mixed with electrode
material and carbon black [252].
A second method to increase ionic conductivity in the SE is to
use a Li-ion conducting polymer in place of the polymeric binder.
Softening the electrode-electrolyte interface by adding an inert
liquid, ethylene carbonate (EC), has been shown to increase ionic
conductivity. Magnetic pulse compaction was used, after all com-
ponents were assembled, to improve densities and interfacial
contacts. A capacity of 160 mAh g1 was reported [252].
Birke et al. developed a monolithic, fully inorganic solid state
lithium battery [253]. The goals were to use a ceramic lithium
electrolyte with high ionic conductivity and a large stability win-
dow, and to use a second ion conductor for a sintering additive to
prevent high preparation temperatures. The sintering agent used
was 0.44LiBO2$0.56LiF with an ionic conductivity of 106 S cm1
[253]. The negative electrode was Li4Ti5O12, the solid electrolyte
was Li1..3Al0.3Ti1.7(PO4)3, and the positive electrode was LiMn2O4.
The solid electrolyte had a lithium rich stability limit of 2.4 V vs.
lithium and presented a total conductivity of 3 * 104 S cm1 [253].
Kobayashi et al. developed a lithium all-solid state battery using
spark-plasma sintering (SPS) [254]. The electrolyte at the positive
electrode was made from a lithium lanthanum titanate (Li,La)TiO3
[Li0.41La0.47TiO2.91] with an ionic conductivity of 103 S cm1 at
22  C and an activation energy of 30.1 kJ mol1 [254]. Using elec-
trostatic spray deposition (ESD), LiMn2O4, a positive electrode, was
deposited on the electrolyte pellets. The electrolyte on the negative
side was a solid polymer electrolyte (SPE), ethylene oxide co-2-(2-
methoxyethoxy) ethyl ether, and the negative electrode was Li
metal. The resulting total conductivity was 2  105 S cm1 [254].
Meikhail et al. studied the usage of lithium borosilicate glass elec-
trolyte in lithium based solid state batteries. An important advan-
tage of using glass is that glass is isotropic and has no grain
boundaries, which can enhance conductivity [248]. The lithium
based borosilicate was prepared by melt quenching in a mold at a
temperature of about 1273e1450 K from H3BO3, Li2Co3, and LiCl
precursors [248]. The researchers showed that the activation en-
ergy of lithium borate based glass is linearly dependent, while that
of corresponding glasses that have halides in them follow a poly-
nomial pattern. The authors attributed this to the presence of
halide ions, which cause this type of variation [248]. Also, lithium
borosilicate has shown better conductivity than lithium chloride
because of the presence of lithium oxide instead of lithium chloride
[248]. Kumar et al. studied the working of a solid state rechargeable
lithium ion battery having an oxygen/air component [249]. Struc-
turally, their cell was made up of a lithium anode, lithium ion
conducting glass ceramic (GC) as the cathode, and a high surface
area air cathode made up of carbon and conducting to lithium ions.
They were able to demonstrate very good thermal stability and
311
Stoichiometry Ionic conductivity at room temperature Ref.
(S cm1)
Li3xLa2/3  xTiO3 103 [1,14,339,340]
Li14ZnGe4O16 106 [14,96,318,339,341]
Li3.4Si0.4P0.6S0.4 6.4 * 104 [14,260,339,341]
Li6La2BaTa2O12 4 * 105 [14,165,339,342]
LiIeAl2O3 2.6 * 104 [14,200,339,343]
Li2S LiI GeS2 Ga2S3 103 [14,278,339]
Li2.88PO3.73N0.14 3.3 * 106 [14,160,210,339]
performance of the cell in the temperature range of 30e105  C at a
current density of 0.05e0.25 mA cm2 [249]. The OCV obtained was
in the range of 2.6e3.6 V, depending on the temperature and other
operating conditions. Charging and discharging capacities of 4.87
and 5 mAh, respectively, were obtained [249]. An energy density of
about 750 Wh kg1 was reported for this cell. The results, at these
particular temperature conditions, indicate that the cell can be used
for different purposes that require high energy and power densities
[249]. Jin and McGinn's research focused on an Al doped lithium
based solid state battery. The electrolyte composition used in their
work was Li7La3Zr2O12 [255]. The anode and cathode were Li metal
and Cu0.1V2O5 based slurry painted on the electrolyte, respectively.
An output of 53 mAh g1 was obtained at a constant current density
of 5 mA cm2 [255]. The best performance of the battery was ob-
tained at a temperature of around 50  C, at which the output was
176 mAh g1 when a current density of 10 mA cm2 was applied
[255]. Impedance spectroscopy has shown that the interfacial
resistance of both the anode and the cathode drops down steeply at
about 50  C; hence the better performance of the cell around this
temperature [255].
Emery, Brousse, and coworkers tested a lithium-based solid
state electrolyte system by the principle of sintering [256]. The
precursor materials were Li3N and elemental Mn, and they were
subject to thorough mechanical milling followed by sintering under
a nitrogen stream at 750  C for 7 h. XRD patterns have shown that
two phases, Li7Mn4 and Li6.2Mn4, tend to coexist [256]. Having an
empirical formula of Li7  xMn4, it is seen that there is a gradual loss
in crystallinity with increasing x [256].
4.3. Amorphous electrolyte based systems
Amorphous electrolytes have been studied by various groups for
use in solid state batteries [86,257]. Sakurai et al. worked on
amorphous lithium based lms [86]. Liquid electrolytes carry the
inherent dangers of leakage and ammability, to counter which the
researchers proposed a solid amorphous electrolyte [86]. Komiya
and colleagues used amorphous lithium based electrolytes in their
research [257]. The composition for their electrolyte was (100  x)
(0.6Li2S. 0.4SiS2). xLi4SiO4. LiCoO2 was used as the cathode and
indium as the anode. XRD was employed to study the crystallinity
of the electrolyte prepared. It was observed that the XRD responded
to various crystalline peaks in the sample, namely those corre-
sponding to Li2S, SiS2, and Li4SiO4 [257]. Charge and discharge
characteristics showed that the cells with x 5 and 20 gave output
voltages of approximately 3.1 V and 2.7 V, respectively [257]. The
small drop in this discharge voltage is because of the smaller con-
tact area between the LiCoO2 and the electrolyte surface. The
electrical capacity of the cells is high, but they go on decreasing
with the number of cycles they operate, starting from 90 mAh g1
in the rst cycle to about 70 mAh g1 after ten cycles. The output
becomes a constant at approximately 60 mAh g1 [257]. The
coulombic efciencies approach 100% in the initial cycles but
312 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322

Table 3
The various lithium based solid state battery systems (anode, cathode, and electrolyte systems), along with their fabrication techniques and optimum conductivity values
under working conditions.

Anode Electrolyte Cathode Electrolyte fabrication technique Conductivity Ref.

LiMn2O4 Cobalt oxide doped polyethylene LiMn2O4/electrolyte Metathesis polymerization N/A [309]
oxide (PEO) electrolyte reaction
Graphite based Polystyrene doped with varying LiCoO2 Solegel reaction of polystyrene, 5.83 * 105 S cm1 for [316]
quantities of Al2O3 n-butyl acetate, LiCF3SO3, and 10 wt% Al2O3
Al2O3 precursors
Potassium Polyethylene oxide (PEO)/KBrO3 Carbon paper doped Hot pressing of PEO and KBrO3 7.74 * 108 S cm1 at [317]
with iodine powders. 303 K a composition of
70PEO: 30KBrO3
Li foil Li doped polyacrylonitrile (PAN) Carbon composite electrode Prepared from heat treated and N/A [318]
electrolyte ltered solutions of PAN, EC, PC,
and LiPF6 precursors
Li foil Polyurethane acrylate (PUA) based Li0.33MnO2/PEG/LiTFSI/carbon Solvent free casting with 5.5*104 S cm1 [319]
electrolyte with SiO2 content black 2-hydroxyethyl acrylate,
Li0.33MnO2/PEG/LiTFSI/carbon black urethane acrylate, and
isophorone di-isocyanate
precursors
Mg Mg(CH3COO)2 doped PVA-PEG (I2 (I2 C electrolyte) Solution casting from 50: 3.23*105 S cm1 for 30 [320]
C electrolyte) 50 wt% of PEA and PVG wt% Mg(CH3COO) 2 at 100  C
followed by addition of
Mg(CH3COO)2 with constant
stirring
Li Tri-ethyl sulfonium bisimide, lithium Li Formation of an ionic liquid 10 mS cm1 at 45  C [321]
TFSI, polyethylene oxide and (IL) with S2TFSI, TFSI. and PEO
tetrahydrofuran and solution casting with
tetrahydrofuran
Au Poly(epichlorohydrin-co ethylene Au Prepared by solegel technique about 4.2 * 105 S [322]
oxide-co allyl glycidyl ether) [p(EEO-AGE)] from the cm1 at 55  C
coupled with lithium perchlorate and P(EEO-AGE) precursor
lithium bis(triuoromethanesulfonyl)imide
Mg ribbons PVA(1-x) (MgBr2)x/2(PWA)x/2 70:30 TiO2:graphite Prepared by solution casting of the 105 S cm1 at 20  C [326]
x 0.0, 0.1, 0.2, 0.3, 0.4 & 0.5 gm. precursors, coupled with continuous for 10 wt% SN
stirring
Graphite xLi2S.(100  x)P2S5 LiCoO2 Prepared by hot and cold pressing of 3.1 * 104 S cm1 for [328]
where x 50e80 Li2SeP2S5 precursors the 75Li2S:25P2S5
composition

decrease continuously thereafter [257]. The authors concluded that
the cell shows good electrical stability and characteristics for
practical use, although its output decreases; further work is
necessary in that direction [257]. Table 3 presents a summary of the
types of anode, cathode, and electrolytes used in solid state batte-
ries and their respective open circuit voltage and electrical outputs.
5. Non-lithium based solid state batteries
Non-lithium based solid state electrolytes have been used
extensively to study the functioning and performance of solid state
batteries. Ceramics are some of the most common non-Li based
solid state electrolytes [258]. These solid electrolytes usually
conduct ions by the translation of point defects, and energy is
required in the process. This makes them good conductors at higher
temperatures, as the high temperature provides the necessary en-
ergy for the process [99,258]. Phosphates such as NASICON are
considered to be good sodium ion conductors. Similarly, sulde
based solid state electrolytes are used in many solid state applica-
tions [99]. Non-Li based solid state electrolytes are described in this
section in greater detail. Table 4 presents, in greater detail, the
different non-Li based solid state battery systems and their fabri-
cation methods.

Table 4
The various non Li based solid state electrolyte systems used, their fabrication techniques and their optimum conductivity values under working conditions.

Anode Electrolyte Cathode Electrolyte fabrication Conductivity Ref.

technique

Glass and silver powder in AgI doped borate glasses Carbon and Iodine in Solid state reaction 6.73 * 104 U1 cm1 [259]
weight ratio 67: 33 having the composition weight ratio 30: 70 involving silver iodide,
xAgI-(1 e x)[0.67Ag2O e 0.33B2O3] silver oxide and boron
oxide as the precursors.
Silver Ag4P2O7 doped with varying Iodine coupled with Melt quenching 4.1 * 104 S cm1 at 60 mol% SbI3 [264]
concentrations of SbI3. carbon ber
2 1
Silver (Ag2OeP2O5eLiCl) containing Graphite coupled with Melt quenching of 2.88 * 10 S cm for 25 wt% Al2O3 [266]
silver components iodine LiCl, NH4H2PO4, AgNO3
and alumina powders.
Gold paste mixed with Dy2O3eWO3eBi2O3 Gold paste mixed with Mechanical milling of 1.4 * 104 S cm1 at 200  C [280]
isopropanol isopropanol Bi2O3, Dy2O3 and WO3
followed by calcination
at 800  C for 16 h
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
5.1. Silver based systems
Masoud et al. studied the potential applicability of borate
glasses having silver constituents in solid state battery systems
[259]. Borate glasses, especially AgI doped borate glasses, are pre-
sumed to have fast ionic conductivity. The borates used for exper-
iment had the formula xAgI-(1  x)[0.67Ag2O  0.33B2O3], where x
was chosen to be 0.4, 0.5, 0.6, 0.7, and 0.8 [259]. The cathode con-
sisted of carbon and iodine in the weight ratio 30: 70, whereas the
anode was composed of glass and silver powder in the weight ratio
of 67: 33 [259]. The chargeedischarge characteristics indicated the
highest performance when x 0.6 in the formula of the silver
based borate glass. It presented a DC conductivity of 6.73 *
104 U1 cm1 at ambient temperature conditions [259]. The au-
thors found that silver doped borate glasses, especially with x 0.6
in the formula composition, can be a suitable candidate for solid
state batteries [259]. The presence of AgI improved conductivity, as
it supplied mobile Ag ions and produced a weak ionic bond with
easy availability of Ag ions [259]. Silver based glassy electrolytes
were also studied by Agrawal et al. The stoichiometry of the solid
state electrolyte in this case was x[0.75AgI: 0.25AgCl]: (1  x)
[Ag2O: WO3] [260]. Silver metal was used as the anode and Carbon
along with iodine (C I2) as the cathode. The electrolyte was
prepared by the technique of melt quenching from its salt pre-
cursors. Room temperature conductivity of 4 * 103 S cm1 was
obtained for the stoichiometry 0.7[0.75AgI: 0.25AgCl]: 0.3[Ag2O:
WO3]. Characterization results have proven the existence of the
glassy electrolyte, which the authors claim produces satisfactory
results under working conditions [260]. In addition, there was a
steady increase in the room temperature conductivity of the sil-
veretungsten glass system with increasing x up to x 0.7, after
which there was a noticeable decrease [260]. The authors attrib-
uted the increase to be the optimum concentration and to have the
largest number of mobile ions. This is shown graphically in Fig. 6.
Das et al. studied the working of solid state batteries using
different zinc cadmium halide doped silver phosphate glass elec-
trolytes [261]. The halide doped glass electrolytes were prepared by
the melt quenching technique of zinc or cadmium doped silver
nitrate and ammonium dihydrogen phosphate in equimolar ratio in
a platinum dish. Along with this electrolyte, silver metal was used
Fig. 6. A graphical representation of dependence of conductivity at room temperature
versus different stoichiometries of the silveretungsten glass system [260].
313
as the anode and graphite combined with iodine was the cathode.
Characterization showed that the glasses so prepared were usually
amorphous and crystallinity was almost absent [261]. Electro-
chemical characterization results indicated a high ionic transfer
number in the range of 98.5% for the cadmium chloride doped
glasses, with a conductivity of approximately 4.64 * 105 S cm1
[261]. Solid state electrolyte based on silver thiocyanate complexed
with polyethylene oxide (PEO-AgSCN) was studied by Sekhon et al.
[262]. The electrolyte was prepared by solidication from the
precursor solutions and thorough drying. The results show that
complexing between the polymer and the silver salt takes place in
the amorphous stage, because no new peaks are noticed in the XRD
data, and this is conrmed by the FTIR spectra. A maximum con-
ductivity of 1.3 * 106 S cm1 is obtained for electrolyte samples
that have an O: Ag ratio of 8.8: 1 [262]. Progressive increase in Ag
ion concentration tends to lower conductivity. Conductivity is also
seen to increase at the melting point of the polymer, owing to a
phase change from the quasi-crystalline phase to an amorphous
phase [262]. It has also been observed that, on the exposure of
these electrolytes to light, white spots are formed on their surface;
this has been attributed to the photolysis of the silver salt. The
authors suggested that solid state electrolytes of this type are
mainly anionic conductors and can be used for solid state battery
applications [262]. AgI doped silver borate based superionic glasses
as solid electrolytes were also studied by Bhattacharya and Ghosh
[263]. AgI doped borate based glasses of the composition
xAgI  (1  x) (Ag2Oe2B2O3) were prepared by the melt quenching
technique, the anode being silver metal foil and graphite along with
iodine being the cathode. The amount of AgI can be manipulated
from x 0 to x 0.5. Asymmetric BeO bonds in the borate ion were
observed from the strong bands at 1350 cm1 and 1000 cm1 in the
FTIR spectra [263]. Results showed that, with the increase of AgI up
to x 0.5 in the formula composition, there was a change in the
borate structure as it expanded to accommodate more Ag ions. The
authors explained that, with the increased doping of the borate
glass with AgI, more Ag ions took part in the ion transport, which
greatly increased the ionic conductivity of the electrolyte system
[263]. Suthanthiraraj and Sarumathi studied silver phosphate
(Ag4P2O7) based solid electrolytes having varying concentrations of
antimony iodide (SbI3) [264]. The electrolyte was prepared by the
melt quenching technique. XRD was used to conrm the formation
of the silver pyrophosphate phase. The anode and cathode were
composed respectively of silver and iodine coupled with carbon
ber and phenothiazine. Impedance spectroscopic analysis was
done in the range of 20 Hz to 1 MHz and a maximum ionic con-
ductivity of 4.1 * 104 S cm1 was obtained at a concentration of
60 mol% SbI3 [264]. Addition of SbI3 of more than 60 mol % resulted
in a decrease in conductivity, owing to the formation of cross links
in the pyrophosphate network and hindrance to the movement of
silver ions [264]. Also, the authors noticed nano-sized AgI particles
in the electrolyte from FESEM analysis, formed from an endo-
thermic reaction at 420 K; this improved ionic conductivity. They
reported the unique nature of these multiphase superionic solids,
which assist ionic conductivity [264]. Fast ion conducting silver
based solid state electrolytes having a tellurite component were
studied by Lefterova et al. [265]. The base composition of the solid
state electrolyte was AgIeAg2SO4eTeO2, and the electrolyte was
prepared by melt quenching from its precursors. Observations of
the performance of the electrolyte showed that the best ionic
conductivity of 2.3 * 102 S cm1 at room temperature was ob-
tained for the electrolyte having composition 60 AgI e 24 Ag2SO4 e
16 TeO2 [265]. However, the authors noted that AgI had to be added
to obtain this conductivity [265]. They concluded that the addition
of tellurites and halide systems to a glassy silver based electrolyte
greatly improved its ionic conductivity [265].
314 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Phosphate glasses and phosphate based solid state electrolytes
(Ag2OeP2O5eLiCl) containing silver components were tested for
applications in batteries by Das and coworkers [266]. The silver
phosphate glass samples were prepared by forming a mortar and
then melting and quenching [266,267]. The anode was silver metal
and the cathode consisted of graphite combined with iodine. The
maximum conductivity reported was approximately 8.91 *
105 S cm1 under ambient conditions and 4.16 * 103 S cm1 at
200  C for 15 wt% LiCl. With the addition of varying quantities of
Al2O3, a maximum conductivity of 3.32 * 104 Scm1 under
ambient conditions and 2.88 * 102 Scm1 was obtained for 25 wt%
Al2O3. Conductivity increased with an increase in temperature, and
similarly with Al2O3 concentration. Analysis of the char-
geedischarge characteristics showed that undoped Ag2OeP2O5
glasses (OCV of 0.298 V) do not fare as well as those with LiCl
doping (OCV of 0.668 V) [266]. Further, the electrolyte when doped
with Al2O3 (up to 25%) was found to perform better than an elec-
trolyte with no Al2O3 doping. and therefore has potential use in
solid state batteries [266]. Venkateswarlu and Satyanarayana
developed and tested a silver based all-solid state primary battery
[268]. The electrolyte was a glassy compound with the composition
AgIeAg2O-(SeO2 V2O5); silver selenovanadate (SSV). The solid
electrolyte had a conductivity of 2.63  102 S cm1 at 30  C and
activation energy of 0.22 eV [268]. Performance was tested with
several cathode materials. Silver based solid electrolytes have a
high ionic conductivity and stability under temperature variations.
The anode was Ag/SE and the cathode was [(I C) SE] TAAI,
where Ag 3 was silver powder, SE the SSV solid electrolyte, I iodide,
C graphite, and TAAI tetra-alkyl ammonium iodide (A methyl,
ethyl, and butyl). SE was added to the anode to improve interfacial
contacts. The cathode was varied by changing the weight ratios of
the individual components. The anode mixture was pressed at
5000 kg cm2, producing a 10 mm diameter and 1.5e2.0 mm thick
pellet [268]. The cathode pellet was 1 mm thick. The outer battery
jacket was made of an ebonite material and sealed with epoxy
resin. The OCV reached thermodynamically calculated values of
687 mV. An energy density of 3.21 Wh kg1 was reported [268].
Delaizir et al. developed an all-solid state silver battery assembled
in one step using spark plasma sintering (SPS) [269]. At room
temperature, silver and copper ion conductors tended to exhibit
high ionic conductivity; 0.05 S cm1 for glassy Ag6I4WO4 and
0.34 S cm1 for crystalline Rb4Cu16I7Cu14. They used composite
electrodes for their battery system, obtained by mechanical milling
of Ag0.7V2O5 and Ag6I4WO4 (1:1 weight ratio) for approximately
2 h. The ionic conductivity of the glass-ceramic Li2SeP2S5 was
104 S cm1 [269]. The cell studied by Delaizir et al. was a sym-
metric silver cell: Ag0.7V2O5//Ag6I4WO4//Ag0.7V2O5. It is a glass-
ceramic and stable in open air [269].
5.2. Perovskite based systems
ABO3 type crystals that exhibit the perovskite structure are
commonly used as ionic conductors [270]. Lanthanum gallate has
very good ionic conductivity and is used in solid state batteries and
electrochemical cells in the medium temperature range of
approximately 700e1000 K [271]. Lanthanum gallate based solid
electrolytes exhibit comparably low thermal expansions, like zir-
conia based solid state electrolytes. They can also be made to
conduct oxygen and oxide ions by doping them with alkaline earth
metals. However, these electrolytes also have certain disadvan-
tages, which include the volatility of gallium oxide, the cost of
procuring gallium, and high reactivity of the perovskites under
oxidizing and reducing conditions [272]. Ceria based solid state
electrolytes have also been considered by a number of researchers.
These include electrolytes of the family of Ce1  xMxO2  d (M Gd
or Sm and x 0.1 or 0.2) [273,274]. Ceria based electrolytes
demonstrate better ionic conductivities than comparable ZrO2
electrolytes, especially at low temperatures. However, ceria based
electrolytes suffer from the drawback that Ce4 ions are partially
reduced to Ce3 ions, which hinders oxygen ion transport
[275,276]. Bi2O3 have been considered for solid state electrolytes by
several researchers.
A comprehensive study of the FCC Bi2O3 (d-Bi2O3) was under-
taken by Takahashi et al. [277]. They reported that d-Bi2O3 has the
highest oxide ion conductivity when doped with aliovalent metal
ions. It has been shown that d-Bi2O3 exhibits oxide ion conductivity
approximately 1e2 orders of magnitude greater than zirconia for
the same temperatures [277]. The best conductivities are shown by
the d phase with a uorite defect; however, this is a high temper-
ature phase and exists at 1000e1100 K. Bismuth based mixed
conductors and bismuth molybdates such as Bi2MoO6 and Bi2MoO9
have also been studied [278,279]. Jiang et al. conducted a detailed
study of a bismuth based solid electrolyte for application in solid
state battery systems [280]. They based their choice of electrolyte
material on the superior ionic conductivity demonstrated by the d-
Bi2O3 system. The electrolyte was made by the solid state reaction
mechanism. The authors mechanically milled the stock powder
precursors (Bi2O3, Dy2O3, and WO3) and then calcined at high
temperatures (800  C for 16 h), followed by sintering [280]. Elec-
trical conductivity values were found to have the best values for
dopant compositions of about 11e13 %, and the highest conduc-
tivity value obtained was 1.4 * 104 S cm1 at 200  C [280]. This is
considerably higher than that of erbia, which is known to have the
highest conductivity (2.8 * 105 S cm1 at 200  C) among materials
exhibiting a similar structure. However, higher dopant concentra-
tions greater than 17% were found to reduce conductivity [280].
This was because the high amount of doping disturbs the stability
of the structure, which is best maintained at 11e13 % doping. The
authors showed the working of an electrolyte with better erbia
based electrolytes, which is suitable for solid state applications
[280]. Barium cerate based perovskites were studied by Iwahara
and colleagues [277]. Barium doped ceria usually exhibits very good
oxide ion conductivity, as well as n-type semiconductor properties.
These perovskites normally show a cubic or octahedral structure
[281]. Zuo et al. worked on developing a new solid electrolyte that
is barium based [282], fabricating a new composition, namely
Ba(Zr0.1Ce0.7Y0.2)O3  d or BZCY7 [282]. The sample was prepared by
solid state reaction techniques, and Ba(Ce0.8Y0.2)O3 or BCY20 was
used as a control to compare the properties [282]. A comparative
study of the ionic conductivities showed that BZCY7 had higher
ionic conductivities than the usual solid electrolytes such as YSZ
and LSGM. The solid state system used Ni-BZCY7 as the anode and
Ba(Ce0.4Pr0.4Y0.2)O3 (BCPY4) as the cathode. The BZCY7 electrolyte
demonstrated an ionic conductivity of 9 * 103 S cm1 at 500  C,
whereas those for YSZ and LSGM at the same temperatures were 5 *
104 S cm1 and 5 * 103 S cm1, respectively [282]. Open circuit
voltages obtained at 500  C and 600  C were 1.05 V and 1.01 V,
respectively. A maximum power density of 270 mW cm2 was
obtained at 700  C. Moreover, polarization studies indicated that at
500  C the polarization resistance of the electrodes and the elec-
trolytes was 3.2 Ucm2 and 2 Ucm2, respectively [282]. The authors
succeeded in demonstrating that a barium based electrolyte has
better electrical properties than standard solid state electrolytes
such as YSZ or LSGM. However, the major challenges are the
development of suitable cathodes for this electrolyte and obtaining
good conductivity values above 550  C [282].
5.3. Sodium based systems
Sodium and sulfur based solid state electrolytic systems were
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
studied by Hayashi et al. [283], who fabricated a sulde based glass
ceramic electrolyte obtained from the high temperature Na3PS4
cubic phase. NaeSn alloy was used as the counter and reference
electrode, and TiS2 was the working electrode [283]. During elec-
trochemical measurements, room temperature conductivity of
approximately 104 S cm1 was obtained, along with an output
voltage of 1.6 V [283]. The authors pointed out that this was the rst
time that high temperature stabilized cubic Na3PS4 had been used
as a solid state electrolyte system [283]. In addition, a variety of
other sodium based solid state electrolyte and battery systems have
been tested. The most common are the sodium ion conducting solid
state electrolyte system having the general formula Na1xZr2SixP3-
xO12, commonly referred to as NASICON based systems [284]. These
electrolytes usually have a three-dimensional structure and a
network of channels and pores through which the Na ions move.
The most common NASICON structures usually contain two SiO4
tetrahedra for every PO4 tetrahedra present [285e290]. Further
improvements to NASICON based systems have been achieved by
the replacement of zirconium with titanium [291]. Similarly,
replacement of zirconium with hafnium has also yielded improved
conductivity [292]. However, other elements such as indium,
scandium, germanium, magnesium, gallium, and uorine have also
been tested doped with the NASICON electrolyte, producing lower
conductivities [286,287,293e299].
A sintering process has been used by Fuentes et al. to prepare
NASICON-based solid state electrolytes from the precursor mate-
rials SiO2, Na3PO4.12H2O, and ZrO2 [300]. They were thoroughly
pulverized in a mechanical mill with intermittent heating. Sintering
was done at a temperature of 1200  C for 10 h exposed to the at-
mosphere. Further ring of the pellets took place in vacuum before
a nal sintering in air at approximately 1300  C for 16 h [300].
Subsequently, different NASICON samples were prepared at
increasing or decreasing sintering temperatures. XRD character-
ization data have shown that the NASICON is formed only if calci-
nation has taken place at 1100  C or higher and the precursors
remain uncombined at lower temperatures [300]. Electrical studies
have shown that the activation energy of the NASICON pellets
ranges from 0.36 eV to 0.39 eV for those sintered at high temper-
atures and 0.31 eVe0.32 eV for those sintered at higher tempera-
tures [300].
Another sodium based electrolyte that has been the subject of
research is beta alumina having the formula Na2O.Al2O3. It basically
has a layered structure that consists of very dense areas of
aluminum oxide interspersed with less dense layers of sodium
oxide [301]. This results in a structure that has a densely packed
arrangement of oxygen atoms with some aluminum atoms at the
octahedral and tetrahedral sites [302]. The conduction mechanism
has been attributed to the movement of the sodium ions among the
lattice and the interstitial sites in the crystal structure [303,304].
The potential drawbacks of the Li based solid state systems have
prompted research into sodium based solid state electrolyte sys-
tems. Sodium based systems exhibit good conductivity and can act
as replacements for Li based systems, especially when incorporated
with polymer gel electrolytes [305].
Therefore, non-Li based solid state batteries have been found to
possess good ionic conductivity, resistance to leakage, and absence
of side reactions. Extensive research has been done in this eld and
many newer solid state electrolytes are still being fabricated.
However, some challenges remain, such as the cost of the raw
materials (especially transition metals), miniaturization, scalability,
and efcient performance at lower temperatures. A detailed ow-
chart of the general process of the steps involved in the fabrication
of a solid state battery (anode/electrolyte/cathode) system is shown
in Fig. 7, with the help of images to further elucidate the steps
involved in the process.
315
6. Polymer electrolyte based solid state batteries
Several researchers have conducted studies of polymer elec-
trolyte based solid state batteries. The history of polymer based
electrolytes starts with the reporting of conductivities of poly-
ethylene oxide (PEO) alkali metal salt complexes by Wright et al.
[306]. PEO based polymers have been widely used since then as
solid state electrolytes [307]. The most commonly used solid state
electrolyte system is PEO and polypropylene oxide complexed with
Li salts. The prevalence of PEO based systems has been attributed to
the ability of the ethylene group to form complexes easily with
lithium based salts and also the ease with which the polymer side
chains dissolve Li in them [307,308]. Polymer based electrolytes
possess several advantages, such as enhanced safety and stability
against easy discharge [309e311]. A general schematic of ion con-
duction through polymer electrolytes is shown in Fig. 8. A
comprehensive list of different polymers, their repeating units, and
the temperatures at which they give optimum conductivity is
presented in Table 5.
6.1. Inorganic polymer composite based electrolyte systems
a) PEO based inorganic electrolyte systems:
Appetecchi et al. studied the performance of hot-pressed
nanocomposites containing Li based solid state electrolytes. Poly-
ethyleneoxide (PEO) based lithium electrolytes have the advantage
of good ionic conductivity, which can be utilized in solid state
batteries [312]. The electrolytes were prepared by ball milling fol-
lowed by hot pressing at a temperature of 80e100  C. Character-
ization of the electrolyte was done by differential scanning
calorimetry (DSC) and thermogravimetric analysis (TGA). The
thermal data revealed a sharp peak at 64.8  C and 66  C, which
indicates the melting of PEO. Electrical measurements were carried
out within a decreasing temperature range of 100  Ce76  C [312].
Open circuit voltages of around 3.45 V were obtained. The most
striking result shown by the cell was that it exhibited almost no
change in voltage during the whole discharge process. An increase
in the ohmic losses of the cell was observed when the transition
was made from charging to discharging. A maximum electrical
capacity of about 140 mAh g1 was obtained, corresponding to a
temperature of 100  C, and the effective output dropped to
120 mAh g1 at 83  C [312]. The results indicate that these elec-
trolytes can be used in Li/LiFePO4 based solid state batteries. Some
amount of reduction in capacity is noticed, owing to a reduction in
the conductivity of the electrolyte [312]. Bullock and Konas syn-
thesized a cobalt oxide based polymer system, by a metathesis
polymerization reaction mechanism, to act as the electrolyte in an
all solid state battery [309]. The solid state battery had a LiMn2O4
anode and cathode, the electrolyte being unsaturated polyethylene
oxide (PEO) containing cobalt oxide nanoparticles. These nano-
particles can be used to store Li ions during the electrochemical
reaction, and the unsaturated PEO improves ionic conductivity
[309]. NMR spectra and gel permeation chromatography (GPC)
have conclusively shown the formation of the polymer. The re-
searchers theorized that this novel type of polymeric electrolyte
system will prevent leakages and help in the development of solid
state batteries with enhanced ionic conductivity and electrical
output [309]. Similar research based on the PEO based electrolyte
was conducted by Hassoun et al. [313], who prepared the electro-
lyte by the hot-pressing technique; energy density of 2250 Wh g1
was obtained for an output voltage of 2.5 V [313]. The output
voltage remained fairly stable; this therefore represents an
achievable solid state battery that can be used for future applica-
tions [313]. Shin et al. studied the application of a PEO based
316 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322

Fig. 7. A schematic representation of the fabrication process of a solid state battery system. (a) The fabrication of the cathode is done by mixing it with binder (PTFE & C). (b)
Fabrication of the cathode on the stainless steel substrate which acts as support. (c) Thoroughly purging the cathode as well as the electrolyte in vacuum at elevated temperature to
remove any traces of water vapor or impurities. (d) Keeping it in a furnace to obtain remove any trace of alcohol. (e) Pasting the cathode with the electrolyte. (e) Testing of the SSB.

producing a favorable outcome [314]. Jeon et al. similarly studied a

Fig. 8. Ion conduction through a polymer electrolyte. The reactions that take place at
the interface are clearly shown. Lithium ions move into and out of the electrodes via
the intercalation process, and the electrolyte allows the ow of the ions.
LiCF3SO3 solid state electrolyte doped with titania [314], and were
able to show that the addition of titania resulted in a decrease of
overall crystallinity of the electrolyte and also reduced the contact
resistance between the electrode and electrolyte, thereby
PEO based solid state electrolyte matrix interspersed with LiClO4
dissolved in it [315]. However, in this case the working capacity of
the cell decreased with the number of cycles because of non-
uniform sulfur positioning along the electrolyte [315]. Lim et al.
developed an Al2O3 based solid polymer based electrolyte by the
solegel reaction mechanism for a lithium based solid state battery
[316]. The precursors for the polymer were Al2O3, LiCF3SO3, n-butyl
acetate, and polystyrene. Characterization of the electrolyte after
preparation was done by an impedance analyzer and SEM [316].
The cathode consisted of LiCoO2 and the anode was graphite based.
Electrochemical results showed that ionic conductivity tended to
increase with Al2O3 concentration in the electrolyte and then
decrease. The highest ionic conductivity obtained was 5.83 *
105 S cm1 for 10 wt% Al2O3 [316]. SEM images showed well
dispersed Al2O3 llers and no clumping formation up to 10 wt%
Al2O3 concentration. The authors attributed this to greater con-
centrations of Al2O3 forming larger aggregates and thereby hin-
dering the ion transfer process.
Solid inorganic polymer electrolytes were studied by Chandra
et al., who fabricated a polyethylene oxide (PEO)/potassium
bromate (KBrO3) based electrolyte by the hot press technique [317].
The anode consisted of potassium, whereas the cathode had a layer
of carbon lm doped with iodine. An increase in ionic conductivity
of about 100 times was noticed with the progressive addition of the

Table 5
Li based polymer solid state electrolytes used in various solid state systems and their repeating units, along with the output room temperature conductivities obtained.

Polymer system Repeating unit Electrolyte used Room temp. conductivity (S cm1) Ref.
9
Polyvinyl alcohol [PVAc] (C2H4O)n (PVAc)-LiCF3SO3 10 [96,344]
Polymethyl-methacrylate [PMMA] e[CH2C(eCH3) (eCOOCH3)]ne PMMA-LiClO4 4 * 103 [96,211,345,346]
Polyethylene oxide [PEO] e[CH2CH2O]ne PEO-LiBF4 106 [96]
Polyethylene oxide [PEO] e[CH2CH2O]ne PEO8-LiClO4 108 [307,347]
Polyoxymethylene [POM] e[CH2O]ne POM-LiClO4 108 [114,307,348,349]
Polypropylene oxide [PPO] e[CH3CH2CH2O]ne PPO8eLiClO4 108 [307]
Polysiloxane/poly-dimethyl-siloxane [DMS] e[(CH3)2SiO]ne DMS-LiClO4 105 [307,350]
PEO linked polysiloxane [PGPS] PEO-H(OSiH2)nOH PGPS-LiClO4 104 [307,351]
Polypropylene oxide [PPO] e[CH3CH2CH2O]ne PPO-LiCl4-LiBr-AlCl3 2*102 [307,352e354]
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
KBrO3 up to 50 wt% salt concentration, and the optimum conduc-
tivity shown by the electrolyte was 7.74 * 108 S cm1 at room
temperatures at a composition of 70PEO: 30KBrO3 [317]. Higher salt
concentration introduced brittleness into the electrolyte lm,
which hindered its further performance. SEM studies too showed a
gradual reduction in crystallinity with the addition of further po-
tassium salt. The OCV obtained was 2.58 V [317]. This new elec-
trolyte has performed satisfactorily under low current conditions
and relatively large potassium salt conditions (~50% salt concen-
tration) [317]. The graphical representation of the increase in ionic
conductivity with increasing temperature is shown in Fig. 9. Here it
may also be noticed that there is a major jump in ionic conductivity
values at 65  C for all compositions, which the authors attributed to
a semicrystalline phase transition process taking place in the
polymeric PEO system.
b) Non PEO based inorganic electrolyte systems:
A Li/polyacrylonitrile (PAN) based solid electrolyte was devel-
oped by Abraham and Jiang for lithium based solid state batteries,
by the solegel technique [318]. The anode consisted of solegel thin
Li metal foil (50 mm thickness), and the cathode was a thin layer of
carbon composite ber. The entire setup was kept in a heat sealed,
closed plastic bag, in which pores were made to allow oxygen to
reach the cathode. An OCV of 3.05 V was obtained for atmospheric
air and 2.85 V for pure dry oxygen [318]. The OCV was found to
remain almost constant during the discharging process from 2.85 V
to 2.75 V [318]. A strong absorption peak at 795 cm1 and elec-
trochemical calculation showed that the main product formed
during the discharging process was Li2O2. The cell output obtained
was 800 mAh g1 and 600 mAh g1 at 1 mA cm2 and 2 mA cm2,
respectively [318]. It has been suggested that having the cell in the
form of strips or stacks improves battery output [318]. Jiang et al.
developed a new solid polyurethane acrylate (PUA) based ceramic
polymer for applications in lithium based solid state batteries [319].
The fabrication of this electrolyte was done by a solvent free casting
method, and the cathode and anode materials were Li0.33MnO2/PEG
(polyethylene glycol) and lithium foil, respectively [319]. During the
charging/discharging cycles, the cell demonstrated an initial
discharge capacity of 180 mAh g1 and a reversible capacity of
140 mAh g1 after 100 cycles of running [319]. There was a small
Fig. 9. A graphical representation of the relationship between conductivity and tem-
perature of the polymer electrolyte lms having the stoichiometry (1  x)PEO:xKBrO3.
A linear increase in conductivity was observed up to 65  C, at which there is a major
spike in conductivity for the different compositions [317].
317
decrease in the capacitance with an increasing number of cycles,
attributed to increased interfacial resistance between the electro-
lyte and cathode with the number of cycles [319]. The cell
demonstrated stable voltages of 3.5 V at the start, before dropping
to 3.25 V after approximately ve days. A self-discharge rate of
0.05% per day at 60  C was noted, which is better than comparable
liquid electrolyte Li-ion batteries [319]. Polu et al. have fabricated a
polyvinyl alcohol (PVA)/polytethylene glycol (PEG) coupled with
magnesium acetate solid electrolyte by a solution cast technique for
use in solid state batteries [320]. The solid state battery consisted of
a magnesium based anode and a cathode having carbon bers
doped with iodine. They found maximum conductivity to be 3.23 *
105 S cm1 at 30 wt% of Mg(CH3COO)2 at 100  C operating tem-
perature [320]. The authors observed that conductivity increased
with increasing salt concentration and then decreased [320]. This
was attributed to an increase in the number of active charge car-
riers with increasing salt concentration up to the maximum and
then formation of ion pairs and ion triplets, which hinder further
conductivity [320]. Fisher et al. studied sulfur based hybrid solid
polymer electrolytes [321]. The hybrid electrolyte consisted of tri-
ethyl sulfonium bis(triuorosulfonyl)imide (S2TFSI), lithium TFSI,
and polyethylene oxide (PEO), and was fabricated by the solution
casting method. Lithium based electrodes were used to complete
the circuit [321]. The experiment was performed by applying a
current density of 0.1 mA cm2 and reversing the current direction
hourly. Ionic conductivities of 0.117 mS cm1 and 1.20 mS cm1
were observed at 0  C and 25  C, respectively [321]. When the
temperature was increased to 45  C, the authors noticed an even
greater increase in the conductivity value, to 10 mS cm1. The au-
thors succeeded in demonstrating the high stability of this elec-
trolyte, even at greater than 4.5 V at the Li/Li cathodic interface
[321]. Rodrigues et al. studied the properties of polymer based solid
state electrolytes [322]. The basic monomer of the polymer elec-
trolyte was the terpolymer: poly(epichlorohydrin-co ethylene
oxide-co allyl glycidyl ether) [322]. The nal polymer was obtained
by adding other precursors such as lithium perchlorate and lithium
bis(triuoromethanesulfonyl)imide by the solegel technique. Ion
blocking gold electrodes of 10 mm diameter were used as both
anode and cathode. The experiments were performed in the tem-
perature regime of 25  Ce100  C, and readings were taken at 7-
degree intervals [322]. A maximum of 4.2 * 105 Scm1 was ob-
tained at a temperature of 55  C for this electrolyte [322]. The glass
transition temperature Tg of the electrolyte was obtained at 48  C
[322]. The authors claimed that the presence of oxygen ions in the
terpolymer was benecial for ion transport, and they exhibited
good thermal stability at high temperatures [322].
Guobao and coworkers investigated polymer based secondary
lithium batteries [323]. The X-ray diffraction peaks corresponding
to PTFE became weak when the carbon electrode accommodated
more lithium. The peak disappeared when the lithium consumed
exceeded a critical value of about 1200 mAh per gram of PTFE under
these experimental conditions [323]. The small discrepancy be-
tween the experimental value (1200 mAh g1) and the theoretical
value (1070 mAh g1) indicated that the decomposition of the
electrolyte on the surface of the carbon electrode also contributed,
to a small extent, to capacity loss [323]. Hence, the PTFE indeed
reacted with electrochemically formed lithium on the surface of the
carbon electrode during the discharge process of the Li/C cell [323].
Electronically conducting polymers such as phosphor-olivines were
studied by Chung and coworkers [324]. Electrical conductivity
measurements were made on samples sectioned from pellets
densied at 700e850  C. All doped compositions Li1  xMxFePO4
(M Mg, Al, Ti, Nb or W) showed room-temperature conductivities
in excess of 103 S cm1. The temperature dependence of conduc-
tivity in the doped samples varied somewhat with ring
318 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
temperature. Samples red at 700  C were not dense enough for us
to rule out a signicant contribution to the DC resistivity from the
grain boundaries, and samples red at 850  C contained a signi-
cant fraction of Fe2P phase [324]. It has been assumed that the
conductivity is predominantly electronic at these high values.
Samples containing 1 atom% each of Mg2, Zr4, and Nb5 have
conductivities within a factor of three of one another, and show
similar activation energies in the range 60e80 meV. The identically
processed undoped sample has a much higher activation energy,
close to 500 meV [324]. The activation energies may include terms
for both defect formation and migration (for example for a polar-
onic mechanism) [324].
6.2. Polymer based thin lm electrolyte systems
a) PEO based thin lm electrolyte systems
A study on polyethylene oxide (PEO) thin lm solid electrolytes
was reported by Ibrahim and Johan [325]. The study involved
varying the composition of the electrolyte with compounds such as
lithium hexauoride (LiF6), ethylene carbonate (EC), and amor-
phous carbon nanotubes (aCNT) [325]. The electrolyte was fabri-
cated by the solution casting method, and thermal
characterizations were done by differential scanning calorimetry.
The maximum electrical conductivity obtained was 103 S cm1 at
5 wt % aCNT [325]. The authors showed that the electrical con-
ductivity improved with the addition of aCNTs, as the nanotubes
prevented the recrystallization of the PEO based electrolyte and
established routes for the easier transport of Li ions [325]. The
work of Abdel-Samiea et al. concentrated on developing and
studying solid polymer electrolytes interspersed with small crystals
to be used for magnesium based rechargeable cells [326]. The
electrolyte was fabricated from polyvinyl alcohol (PVA), hydroqui-
none, magnesium bromide, phosphotungstic acid (PWA), and
varying amounts of succinonitrile (SN) precursors, by the solution
cast technique [326]. The cathode and anode were made of 70:30
TiO2:graphite and Mg pellets, respectively. The initial conductivity
values were low, in the region of about 107 S cm1, but then
increased to about 106 S cm1 when SN was slowly added. The
highest conductivity of the electrolyte obtained was about
105 S cm1 at 20  C for 10 wt% SN [326]. The authors' explanation
for this increase was that SN reduces the crystallinity of the elec-
trolyte and the increased polarity of SN itself [326]. A maximum
capacity of 17.5 mAh g1 has been reported for this cell [326].
b) Non PEO based thin lm systems:
Rhodes and coworkers made a detailed study of solid polymer
electrolytes of nanoscale dimensions [327]. The electrolytes were
obtained by electro-deposition of phenol on acetonitrile and using
indiumetin oxide substrates [327]. AFM was used to characterize
the thickness of the lm, which was found to be approximately
50 nm [327]. The optimum conductivity obtained was about 7 4 *
1010 S cm1. This provides a route to the application of nanoscale
thin lms for miniaturized solid state devices [327]. Sakuda et al.
developed a sulde based solid electrolyte for applications in Li
based solid state batteries [328]. They used glassy suldes such as
Li2SeP2S5 as the main constituents in their solid state sulde based
electrolytes [328], which were prepared by both hot and cold
pressing from their initial powder stage. Ionic conductivity was
found to have greatly increased when the amount of molding
pressure was increased. A maximum ionic conductivity of
104 S cm1 was obtained for a molding pressure of 70 MPa, and a
further increase of the pressure resulted in decreasing conductivity
[328]. When used in a battery with a LiCoO2 cathode and graphite
anode, it gave a discharge capacity of 133 mAh g1 and reasonable
stability under a number of cycles [328]. The authors believed that
these glassy solid state electrolytes would be useful, as they have
considerable microstructural free volume, which enables easy ion
diffusion [328]. Polysiloxane polymer based solid state electrolytes
were developed and studied by Hooper et al. [329]. The electrolyte
they used for this purpose was poly (bis[2-(2-methoxy-ethoxy)
ethoxy]propylsiloxane. These solid state polymer electrolytes were
produced by hydrosilation reaction from their respective precursor
allyl ethers, followed by hydrogenation with hexane [329]. The
researchers also doped these polymers with varying quantities of Li
to study changes in electrical and conducting properties [329]. They
reported the best conductivity values as 3.9 * 104 S cm1 at room
temperature for oxygen to Li ratios approximately 40:1 [329]. Li
doping has the advantage of improving room temperature con-
ductivity values and providing more stability [329]. Many other
groups have conducted research on solid polymer electrolytes for
use in solid state batteries. Bannister et al. obtained optimum ionic
conductivities of about 105 S cm1 from an acrylate based polymer
electrolyte [330]. The conductivity measurement was done at
100  C [330]. Sanchez et al. studied the properties of polyelectrolyte
lithium salt having a peruorosulfonated side chain [331]. How-
ever, they obtained low conductivities of about 105 S cm1 at
30  C, which they attributed to the lithium ion's strong interaction
with the sulfonyl group [331]. Ito and colleagues studied lithium
salt based polyelectrolytes having PEO oligomers and sulfonated
side chains [332]. They obtained room temperature conductivity of
4.45 * 106 S cm1 and a Li transference number of 0.75 [332].
Angel et al. studied a novel polymer in salt based system, in which
the electrolyte was a AlCl3 e LiBr e LiClO4 e PPO based system
[333], and were able to obtain room temperature conductivities as
high as 0.02 S cm1 [333]. Polymers obtained from organic matter
have been used to prepare solid state batteries too. The advantage
of using organic and natural polymers is their abundance, afford-
ability, and biodegradability [334]. Yulianti and coworkers used
chitosan (a naturally occurring polymer) with different doping
agents such as Cu and Ag to develop a polymer based solid state
battery system [334]. A schematic for the fabrication process and
testing of a similar polymer based system is presented in Fig. 10.
The dopings were done by the ion implantation method. The au-
thors concluded that this could provide a new way of developing
more environmentally friendly solid state batteries [334]. Nystrom
et al. developed an ultrafast all-polymer based solid state battery
[335]. The electrolyte was fabricated from cellulosic bers obtained
from algae, and a coating of polypyrrole was provided, approxi-
mately 50 nm thick [335]. The battery exhibited only 6% loss in
capacity over about 100 cycles of operation and showed good
promise for commercial applications [335]. Recently, increasing
ionic conductivity, two approaches have been investigated, (i)
suppressing crystal generation in the polymer by adding ller and
(ii) creating a comb-shaped polymer framework [336,337]. The
ionic conduction in poly (ethylene carbonate) (PEC) based rubbery
electrolyte including lithium salts was reported by Tominaga et al.
[338]. The Li transfer number of PEC e LiBF4 (44.4 wt%) electrolyte
was measured and the value was estimated to be ~0.5 at 100  C
which [338]. Okumura and Nishimura reported that the lithium ion
transfer number of a PEC based polymer electrolyte is 0.4 and the
highest ionic conductivity is 0.47 mS cm1 at 20  C [336]. PEC based
polymer electrolytes have a moderate conductivity with a high
lithium ion transfer number.
7. Conclusion
There has been a tremendous recent increase in the amount of
research and understanding of solid state batteries, especially in the
 J.G. Kim et al. / Journal of Power Sources 282 (2015) 299e322
Fig. 10. A owchart showing the fabrication and development technique of a Li
polymer based solid state electrolyte and graphite anode. LIPON is known to remain
stable throughout long cycles of performance [334].
last two decades. Most of the work has focused on developing solid
state battery systems with enhanced energy and power densities.
Cathodes and anodes with good microstructural properties are
being developed to provide good electrochemical and ionic con-
duction pathways. However, some fundamental challenges remain.
A primary challenge is the high cost of production, particularly of
the lithium which makes it difcult to use in large-scale applica-
tions. Currently, most of the lithium based solid state batteries have
been used for mobile and small-scale applications. Secondly, the
output power densities and longeterm cycle life are still not
satisfactory. One of the major reasons for this is the fast degradation
of the lithium based cathodes owing to microstructural change or
dendrite formation. Proper understanding of the electrode-
electrolyte interface and tailoring the microstructure of the cath-
ode accordingly can help mitigate this problem. In-situ testing
probes can help us understand some of the reaction mechanisms
going on at the interface. At present also, the weight of the active
material is about 60% of the total battery, which is also a hindrance
to optimum performance, and research is going on to develop
319
thinner cells. Electrolytes of about 10 mm thickness have recently
been developed, which have been able to produce power densities
comparable with those of existing electrolytes. An increase in the
application of polymer based solid state electrolytes has been very
benecial, greatly improving the exibility of the electrolyte sys-
tems and at the same time giving good ionic conductivity values.
Considerable work needs to be done in this area before solid state
batteries, especially lithium based systems, become ubiquitous.
Elucidating the lithiation/delithiation mechanism, developing a
sound model, acquiring a thorough understanding of the chemis-
tries and reactions going on at the electrode-electrolyte interface,
and preventing capacity from fading by engineering the electrode
microstructure are among the important aspects to which attention
should be paid. Solid state batteries have shown very good promise
and potential during the time they have been under research, and
the current focus should be on slowly bringing them to a state
where they can be deployed in medium- and then large-scale
operations.
Acknowledgment
This work was supported by the DGIST R&D Program of the
Ministry of Education, Science, and Technology of Korea (15-BD-
01).
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