ISSN 1023-1935, Russian Journal of Electrochemistry, 2016, Vol. 52, No. 12, pp. 1095–1121. © Pleiades Publishing, Ltd.

, 2016.
Published in Russian in Elektrokhimiya, 2016, Vol. 52, No. 12, pp. 1229–1258.

A Brief Review: Past, Present and Future of Lithium Ion Batteries1

Florian Schipper* and Doron Aurbach
Bar-Ilan University, Department of Chemistry, Ramat-Gan, Israel
*e-mail: florian.schipper@gmail.com
Received March 28, 2016

Abstract—The review summarizes the development of lithium ion batteries beginning with the research of the
1970–1980s which lead to modern intercalation type batteries. Following the history of lithium ion batteries,
material developments are outlined with a look at cathode materials, electrolyte solutions and anode materi-
als. Finally, with lithium sulfur and lithium oxygen batteries two post intercalation type lithium batteries are
discussed. The focus of the material discussions lies on basic understanding, problems and opportunities
related to the materials.

Keywords: lithium ion batteries, intercalation electrodes, cathode materials, anode materials, lithium-sulfur
batteries, lithium-oxygen batteries

DOI: 10.1134/S1023193516120120

INTRODUCTION which require a battery of high energy density. The

Electricity is a ubiquitous commodity and life as we
know it is hard to imagine with an absence of conve-
nient power supply. The first battery ever conceived
was invented by Alessandro Volta in 1800 to study the
findings of Luigi Galvani on “animal electricity” [1].
The so called voltaic pile was crucial to early electro-
chemical experiments paving the way to fundamental
understandings in the field and the synthesis of pure
alkali metals was achieved via electrolysis powered by
voltaic piles [2]. The primary Leclanche cell, a prede-
cessor to the zinc carbon cell of today, was used in
telegraphy stations and early telephones making it one
of the first commercial batteries [3]. With the inven-
tion of the electrical generator in the mid-19th century
the need for a rechargeable storage system arose and
was met by the lead acid battery of Gaston Plante [4].
Interestingly, combustion engines and electrical
engines competed for some time as means of propul-
sion in cars around the turn of the 19–20th century
[5, 6]. Unfortunately, with more available petroleum
reserves discovered in the early 20th century and the
development of more comfortable gasoline cars, elec-
tric vehicles were soon outperformed by internal com-
bustion engines and discontinued. Nonetheless, lead
acid batteries are still a crucial part in gasoline pow-
ered cars as starter battery, making them the most suc-
cessful secondary battery of the last century.
New impulses to the battery field came in the late
20th with the development of portable consumer elec-
tronics (cell phones, camcorders, portable computers)
1 The article is published in the original.
lead acid battery was not suitable for such applications
and much attention was given to the nickel cadmium
system which was eventually overtaken by the lithium
ion batteries (LIB) in the early 1990s. LIB, as a part of
our daily life, have been improved constantly over the
last 25 years. They have attracted tremendous research
attention with more than 10.000 papers mentioning
LIB in 2015 alone. Followed by the huge successes of
LIB other battery systems (e.g. magnesium and
sodium) have seen increased research interested as
well making the field ever more fruitful [7, 8]. LIB are
connected to big promises made by industry and sci-
entists to play a vital role in many fields ranging from
the development of electrical vehicles, load levelling to
energy storage of alternative power sources (solar,
wind etc.). With some author even going as far as to
foreshadowing resource wars hinging on the develop-
ment of adequate batteries [9].
The text at hand is meant to be a short overview of
the lithium battery field aimed at new students of the
field or interested readers of neighboring disciplines.
Emphasis is given to the development of LIB with a
short historical breakdown of the exciting work of the
1970s–1980s. The second chapter deals with some of
the more popular cathode intercalation compounds
and will deal with basics, problems and opportunities
of new intercalation materials. Electrolyte solutions
and anode materials will be covered briefly at the end
of the second chapter. The closing chapter is devoted
to technologies beyond LIB and a very brief descrip-
tion of the lithium sulfur and lithium oxygen battery
will be given.

1095
1096 FLORIAN SCHIPPER, DORON AURBACH
(а)
Li OR
Structure of TiS2 and LiTiS2
Fig. 1. (a) Intercalation of lithium into the layered structure of TiS2, reprinted with permission from ref. [14], copyright Elsevier
1975. (b) Discharge voltage profile of LixTiS2 in a solution of lithium aluminum chloride in methyl chloroformate, reprinted with
permission from ref. [15], copyright Science 1976.
THE WAY TO LITHIUM ION BATTERIES
(1970–1991)
Before the discovery of lithium intercalation into
host structures mainly primary lithium batteries were
of research interest. The investigation of high tem-
perature molten secondary lithium batteries (e.g. Li/S
and Li/Cl2) never amounted to any commercial suc-
cess due to cost and problems with the inherent highly
corrosive system [10]. Research into the field of mol-
ten lithium systems was soon discontinued in favor of
the more promising sodium sulfur system [11]. How-
ever, the combination of a low molecular weight
(MLi: 7 g mol–1), low density (ρLi: 0.534 g cm–3) with a
very low standard electrode potential (E0, Li: –3.04 V
vs. standard hydrogen electrode) makes metallic lith-
ium an attractive choice as an anode material in bat-
teries. The low potential also means that electrolyte
solutions will react with metallic lithium and early pri-
mary cells focused on solid electrolytes to overcome
this issue. Unfortunately, solid electrolytes don’t allow
for high currents and all solid state primary lithium
batteries were not successful in a wide range. The solid
state lithium | lithium iodine | iodine (Li | LiI | I2)-sys-
tem has been a success in cardiac pace makers since
the early 1970’s and is still in use today allowing for a
compact design of pace makers [12, 13].
In 1975 Wittingham et al. demonstrated via a wet
chemical route (employing n-butyl lithium) the inter-
calation of lithium into a variety of layered transition
metal dichalcogenides (sulfides and selenides) [14].
Lithium is intercalated between the transition metal
layers at a one mole ratio leading to an expansion of
the c lattice parameter (Fig. 1a). Out of the range of
studied compounds TiS2 was particularly interesting
since it offers the lowest molecular weight, potentially
lowest cost and is an electronic conductor. The elec-
trochemical intercalation of lithium into TiS2 demon-
strates an average intercalation voltage of ca. 2 V vs.
Li+/Li reaching nearly the theoretical capacity of
240 mA h g–1 (Fig. 1b) [15]. The idea of lithium inter-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
3.0 (b)
2.5
Cell emf, V
2.0 10 mA
20 mA
1.5
0 0.2 0.4 0.5 0.8 1.0
x in LixTiS2
calation batteries was picked up by EXXON and
turned into an attempt at secondary lithium batteries
in non-aqueous liquid electrolyte solutions [16]. One
major drawback of TiS2 is the rather elaborate synthe-
sis. The material has to be kept under inert conditions
at all time to avoid the decomposition to titanium
oxide and hydrogen sulfide upon the reaction with
water. Another problem arises from the metallic lith-
ium anode itself.
Early studies into non-aqueous liquid electrolyte
solutions in combination with alkali metals showed
the formation of a surface layer. The so called solid
electrolyte interface (SEI) is conductive for alkali met-
als but is an electrical insulator [17]. In general the SEI
formation is beneficial and will passivate the lithium
surface making metallic lithium stable in water free
organic electrolyte systems. Unfortunately, the SEI is
not stable during prolonged cycling and will crack
open which leads to a continuous consumption of
electrolyte and lithium for the continuous SEI refor-
mation [18]. This leads to rater low Coulomb effi-
ciency for lithium of around 90% and secondary
metallic lithium batteries have to be designed with an
adequate excess of lithium metal [18]. Even worse, the
uneven deposition of lithium onto the cracked SEI
leads to the growth of lithium dendrites. The dendrites
will eventually break off and form nano-sized islands
of highly reactive lithium effectively lowering the ther-
mal stability of the cell [19]. In order to overcome the
issue of metallic lithium anodes attempts at lithium
alloys were made, e.g. Li/Al [20], Li/Mg [21]. Using
lithium alloys may lower the dendritic growth rate but
at the cost of capacity and electrode potential. For
Li/Al the deposition potential of lithium is around
0.4 V vs. Li+/Li. This makes the combination with
TiS2 unappealing due to the resulting low cell voltage
of 1.6 V.
The need for a high voltage lithium intercalation
cathode material was met by the layered compound
LiCoO2 (LCO) which was developed by Goodenough
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES
(а)
Co
Li
Co
LiCoO2
Fig. 2. (a) Rhombohedral structure of lithium cobalt oxide showing the layered nature, reprinted with permission from ref. [22],
copyright 1980 Elsevier. (b) Voltage profile of LCO with LiPF6 in ethylene carbonate / dimethyl carbonate (2 : 1), reprinted with
permission from ref. [23], copyright 1996 the Electrochemical Society.
et al. in 1980 [22]. The LCO structure is represented by
a R ( 3 ) m space group with alternating layers of lithium
oxide and cobalt oxide octahedrons (Fig. 2a). The
large size difference of cobalt and lithium leads to a
perfect layered material with little to no cation mixing
(rLi = 0.76 Å, rCo = 0.545 Å). This aspect makes the
synthesis of stoichiometric and phase pure LCO very
easy under various conditions. Lithium can be safely
and reversibly removed up to 0.5 mol leading to a com-
position of Li0.5CoO2 and an upper cut off voltage of
4.2 V vs. lithium (Fig. 2b) [23–25]. LCO has a poor
thermal stability which worsen upon charging beyond
0.5 mol of lithium. Furthermore, structural distor-
tions and cobalt dissolution are known to appear in the
voltage region above 4.2 V vs. lithium [26, 27].
With the high voltage material LCO the only miss-
ing part was a stable, low voltage anode material which
ideally could intercalate lithium in a similar fashion as
TiS2 does. In 1976 Besenhard et al. studied the electro-
chemical intercalation of Li+ and NR 4+ into graphite
and found intercalation potentials close to the ther-
modynamic potential of metallic lithium [28]. Using
lithiated graphite instead of lithium as anode material
seemed very intriguing at the time and a synthesis
employing molten lithium was developed by Basu
et al. in 1979 [29]. Combining LiC6 and TiS2 in a mol-
ten electrolyte gave rise to a reversible lithium interca-
lation battery which was patented in 1981 by the Bell
labs [30]. The operating temperature was dependent
on the employed salt or eutectic and ranged from 375
to 500°C. Clearly the use of the battery was somewhat
limited due to the high temperature requirements but
thousands of cycles were claimed. First attempts at
cycling graphite versus lithium in non-aqueous liquid
electrolytes were unsuccessful due to solvent co-interca-
lation into the lamellar structure of graphite [31–33].
The intercalation of solvated lithium leads to a substan-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
1097
(b)
5.0
4.5
Potential, V
4.0
3.5
3.0
2.5
0 0.2 0.4 0.6 0.8 1.0
x in LixCoO2
tial swelling and exfoliation of the material and a quick
capacity fading is observed. By using a solid polymer
electrolyte it was possible to demonstrate reversible lith-
ium intercalation into graphite. The reported swelling of
only 10% is the value theoretically expected for non-
solvated lithium intercalation [34].
A decisive discovery into the stability of graphite
anodes in nonaqueous electrolyte solutions was made
in 1990 by Dahn et al. [35]. It was shown that by using
a solvent mixture of propylene carbonate (PC) and
ethylene carbonate (EC) lithium can be reversible
intercalated with little fading over the tested 19 cycles
for graphite. This finding was attributed to the forma-
tion of a stable SEI during the first intercalation cycle
at around 0.8 V vs. Li+/Li facilitated by the presence of
EC. The SEI formation, nature and stability on graph-
ite anodes was subject of extensive research in the
1990’s and is still of great interest today [36–42]. The
SEI should be ideally formed before the actual lithium
intercalation takes place. This makes graphite
(Li+ intercalation at <0.25 V [43]) favorable over
amorphous carbons (Li+ intercalation <1.5 V [44]). A
comprehensive review on studies related to the SEI
was given by Novák et al. [36]. Solvent mixtures of
cyclic ester (e.g. ethylene carbonate (EC), propylene
carbonate (PC)) and linear esters (e.g. dimethyl car-
bonate (DMC), diethyl carbonate (DEC)) with LiPF6
are commonly used in commercial lithium ion batter-
ies of today.
A battery based on a LCO cathode, a petroleum
coke anode and a non-aqueous electrolyte solution
(PC:DEC; 1 M LiPF6) was commercialized by Sony
in 1991 and has been widely successful [45]. Since no
metallic lithium is present in this configuration the
name lithium ion battery (LIB) was chosen as a mar-
keting term. Assembling the cell in a discharged state
was a novel idea and has caught on in the lithium ion
Vol. 52 No. 12 2016
1098 FLORIAN SCHIPPER, DORON AURBACH
0.08
0.04
Current, mA
0 are under serious consideration. The very interesting
–0.04
2.0 2.5 3.0 3.5 4.0 4.5
Potential, V
Fig. 3. Cyclic voltammorgam of LiMnO2 showing the first
5 cycles at 10 μV s–1 from 2.0 to 4.6 V vs. Li+/Li; reprinted
with permission from ref. [66], copyright 1999 the Royal
Society of Chemistry.
battery community and is the standard for all com-
mercial LIB nowadays. The stable SEI formation and
absence of graphite exfoliation in EC containing elec-
trolyte solutions lead to the manufacturing of com-
mercial cells with a graphite anode from 1993 onwards.
LITHIUM ION BATTERIES
FROM COMMERCIALIZATION
TO TODAY 1991–2015
After the introduction of LIB to the consumer mar-
ket the versatility of this new type of battery was soon
adapted to portable devices. The high volumetric
energy density of early LIB was around 200 W h L–1.
Twice as high as competing systems at the time,
namely nickel cadmium and nickel metal hydride bat-
teries [46, 47]. This made LIB an ideal choice for lap-
top computers, digital cameras and cell phones which
rapidly dropped in size and weight in 1990’s which can
be partly attributed to LIB. LIB soon outperformed
the competition and are now the leading battery tech-
nology for portable devices with a multi-billion dollar
market and an overall market share of more than 60%
worldwide [48, 49]. The workhorse amongst the dif-
ferent cathode types still is LCO which, owing to its
high tap density of 2.5 g cm–3, can achieve high vol-
umetric energy densities. The last two decades have
seen an improvement in energy density from
~200 W h L–1 to values >400 W h L–1, which was
mostly achieved by better cell engineering [47]. After
the establishment of LIB in the battery market for por-
table consumer electronics the next big leap will be the
development of adequate LIB for electric vehicles
(EV). Even though LCO outmatches other lithium
intercalation cathodes in terms of volumetric energy
density the low capacity of 135 mA h g–1 leads to a low
gravimetric energy density. High energy densities are
necessary to achieve long driving ranges which are
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
crucial to make full EV’s appealing to the consumer
market.
The time before the first LIB and surely the last
25 years have seen the development of a number of dif-
ferent lithium intercalation cathodes [50]. The current
chapter will deal with a selected number of those cath-
ode materials which have seen commercialization or
work on high capacity lithium anodes (e.g. silicon
[51, 52], tin oxide [53] etc.) and the latest develop-
ment into new electrolyte solutions will be covered
briefly at the end of the chapter. The interested reader
5.0 is referred to the following articles for more detailed
reviews on the subject of high capacity anodes and
electrolyte solutions [54–59].
Layered Lithium Transition Metal Oxides
Lithium Manganese Oxide LiMnO2
In an attempt to switch to a cheaper and environ-
mentally benign material LiMnO2 was perused as an
alternative to LCO. The work on LiMnO2 began in the
mid 1990’s with various failed attempts to synthesis
the stoichiometric compound [60, 61]. Unfortunately,
layered LiMnO2 is unstable at elevated temperatures
and an electrochemically inactive orthorhombic phase
is thermodynamically favored [62]. It was inde-
pendently established by Bruce and Delmas that an
ion exchange of NaMnO2 with lithium salts in organic
solvents and temperatures below 150°C gives the lay-
ered LiMnO2 compound [63, 64]. Another possible
way to synthesis LiMnO2 was realized via a low tem-
perature hydrothermal (160°C, 3.5 days) approach
[65]. LiMnO2 is described by a monoclinic lattice with
the C2/m space group.
Electrochemical investigation of LiMnO2 showed a
large initial charge capacity of about 220 mA h g–1 but
a significant drop to 130 mA h g–1 was observed for
subsequent cycles [66]. The first cycle differs markedly
from the following as was analyzed by cyclic voltam-
metry (Fig. 3). A peak around 3.6 V is observed which
is lost for the following cycles. Furthermore, the peak
at 4 V diminishes from the first to the fifth cycle. Once
lithium is deintercalated to a stoichiometry of
Li0.5MnO2 a simple rearrangement of the lattice will
lead to LiMn2O4 [66, 67]. This is achieved by manga-
nese ions moving to empty octahedral sites in the lith-
ium layer. The rearrangement is quite significant and
a large portion of the active material is already trans-
formed to the LiMn2O4 spinel after only 5 cycles [67].
The high initial capacity loss and the spinel forma-
tion render the otherwise interesting material useless
for commercial application. In order to overcome the
structural instability of LiMnO2 a partial substitution
of Mn3+ with cobalt was pursued by Bruce et al.
[68, 69]. A replacement of 10% of manganese for
cobalt was reported to be enough to prevent the initial
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES 1099

5 (а) 5 (b)

4 4

3 3
E, V

E, V
2 2

1 1

0 50 100 150 200 0 50 100 150 200

Q, mA h g–1 Q, mA h g–1
5 (c) 5 (d)

4 4

3 3
E, V

E, V

2 2

1 1

0 50 100 150 200 0 50 100 150 200

Q, mA h g–1 Q, mA h g–1

Fig. 4. Voltage profiles of LiNiO2 derived under different synthesis conditions; reprinted with permission from ref. [70], copyright
1993 Electrochemical Society: (a) LiNO3 + NiCO3 in O2 (750°C), R( 3 )m, I(003)/I(104) = 1.32; (b) LiNO3 + NiCO3 in Air
(750°C), R( 3 )m, I(003)/I(104) = 1.25; (c) LiNO3 + Ni(OH)2 in O2 (750°C), R( 3 )m, I(003)/I(104) = 1.39; (d) Li2CO3 + NiCO3
in O2 (750°C), mix of R( 3 )m and Fm( 3 )m, I(003)/I(104) < 0.6.

capacity loss. The LiMn0.9Co0.1O2 material which now
possess a R ( 3 ) m space group still demonstrates a spi-
nel formation which can be suppressed if higher cobalt
contents are chosen.
Lithium Nickel Oxide LiNiO2
The nickel analogous to LCO was studied as a
cheaper alternative to LCO. LiNiO2 is isostructural to
LCO with an R ( 3 ) m space group and a theoretical
capacity of 273 mA h g–1. However, LiNiO2 is difficult
to synthesize in a pure state due to the instability of the
trivalent nickel at high temperatures [70]. The non-
stoichiometry results in a displacement of nickel and
lithium. Even small amounts of nickel within the lith-
ium layer are known to reduce the discharge capacity
and cycleability considerably [70, 71].
If the nickel content in the lithium layer reaches
50% a new cubic LiNiO2 phase with the Fm ( 3 ) m
space group is formed which is electrochemically
inactive. A qualitative measure to determine the mag-
nitude of the nickel and lithium mixing is given by the
intensity ratio of the X-ray reflections I(003)/I(104).
The (003) reflection is prominent in R ( 3 ) m but is
absent in the Fm ( 3 ) m modification of LiNiO2 [72].
The synthesis temperature, synthesis gas, precursors
as well as the stoichiometry have to be controlled very
carefully in order to gain electrochemically active
lithium nickel oxide [70, 73] (Fig. 4). The more com-
plicated synthesis and poor thermal stability makes
LiNiO2 less attractive for LIB. Even though full cells
with a carbon anode were investigated they never saw
commercialization [74, 75].

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52 No. 12 2016

1100 FLORIAN SCHIPPER, DORON AURBACH
(а)
Rate LiCoO2 >180 mA h g–1
160–180 mA h g–1
0 1.0 150–160 mA h g–1
<150 mA h g–1
0.2 0.8 LiNi1/3Co1/3Mn1/3O2
0.4 0.6
0.6 0.4
0.8
0.2
Safety Capacity
LiMnO2 1.0 0 N(E)
0 0.2 0.4 0.6 0.8 1.0 LiNiO2
LiNi0.5Mn0.5O2
Fig. 5. (a) Phase diagrams of layered lithium NCM with the end members LiNiO2, LiMnO2 and LiCoO2; reprinted with permis-
sion from ref. [87], copyright 2015 WILEY-VCH. (b) Electronic structure of the individual endmembers of NCM: LiCoO2, LiNiO2
and LiMnO2, reprinted with permission form ref. [88], copyright 2008 the Royal Society of Chemistry.
Partially substitution of nickel with manganese was
studied for LixNi(1 – y)MnyO2 with y up to 0.6 [76].
Since pure lithium manganese oxide is not isostruc-
tural to LiNiO2 higher manganese ratios could not be
realized. Furthermore, the measured capacity
decreased with increasing manganese content which
made the material uninteresting for further research at
first. The material was revisited a decade later with
greater success, it appears that the annealing tempera-
ture has to be above 800°C to yield an electrochemi-
cally active material [77, 78]. The composition
LiNi0.5Mn0.5O2 is of great interest and has sparked a lot
of research. It was discussed to consist either of
Ni3+/Mn3+ or Ni2+/Mn4+. The high capacity
(>200 mA h g–1) suggested the latter which was con-
firmed by in-situ X-ray absorption studies and by first
principle calculations [78, 79]. Problems are arising
from the synthesis and ca. 10% of Ni2+ can be found in
the lithium layer impeding the lithium intercalation
[80, 81]. Materials prepared by ion exchange from
NaNi0.5Mn0.5O2 show less cation mixing and good rate
capabilities were reported suggesting that
LiNi0.5Mn0.5O2 is indeed a worthwhile endeavor [82].
The substitution of nickel with cobalt improves the
cycling behavior tremendously when the cobalt con-
tent is ≥ 0.2 in LixNi(1 – y)CoyO2 [74]. This fact was
attributed to a better structural stability of the cobalt
doped material and stoichiometric compounds are
easily prepared in stark contrast to pure LiNiO2
[83, 84]. With more cobalt a decrease of nickel/lith-
ium mixing was observed which explains the enhanced
electrochemical performance of the material [85].
Lithium Nickel Cobalt Manganese Oxide
Li[Ni1 – x – yCoxMny]O2
The work on doping of the individual endmembers
of LiCoO2, LiNiO2 and LiMnO2 eventually culmi-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
(b)
LiCoO2 LiNiO2 LiMnO2
E E E
Co3+/4+:eg
Mn3+/4+:eg
Ni 3+/4+
:eg
Co3+/4+:t2g
Ni3+/4+
:t2g Mn3+/4+:t2g
2–
Co :2p 2–
Co :2p Co2–:2p
N(E) N(E)
nated in the development of intercalation compounds
based on all three transition metals with the general for-
mula Li[Ni1 – x – yCoxMny]O2 [86]. The notation most
common in literature is the abbreviation NCM or NMC
with numbers indicating the decimals of the transition
metals (e.g. NCM523 = Li[Ni0.5Co0.2Mn0.3]O2 etc.).
The different traits associated with manganese, cobalt
and nickel can be summarized as safety, rate/capacity
retention and capacity, respectively (Fig. 5a).
Manganese is electrochemically inactive in the
NCM material and can therefore stabilize the struc-
ture and acts as environmentally friendly and inexpen-
sive filler (Fig. 5b). Cobalt is necessary to facilitate an
easy synthesis with as little structural and stoichiomet-
ric impurities as possible (e.g. no cation mixing). But
cobalt is also prone to react with the electrolyte if the
Co3+/4+ redox region is reached which is the case for
>0.5 mol of lithium extraction from LiCoO2.
The Ni3+/4+ redox eg band shows only a small overlap
with the O2– 2p band and much more lithium can be
extracted from LiNiO2 in theory. In order to achieve a
viable cathode material the transition metal ratio has
to be controlled under aspects of high capacity (more
nickel) or better cycle stability (more cobalt) and
safety (thermal stability)/cost (manganese).
The symmetrical composition NCM333 was stud-
ied by Ohzuku et al. and was found to be cycle stable
with a capacity of ca. 150 mA h g–1 when cycled
between 2.5 – 4.3 V [89]. Extending the voltage win-
dow up to 4.6 V will increase the capacity to values
above 200 mA h g–1 but at the cost of cycle stability
[90]. NCM333 is simple to synthesis via solid state,
sol–gel or co-precipitation reactions and can be cal-
cined in air at 1000°C without any structural impact
[90–92]. Since NCM333 delivers a higher capacity
than LCO it is used for LIB in some of the current full
and hybrid electric vehicles.
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES
The urge to increase the capacity of the NCM fam-
ily is usually met by increasing the nickel content to
compositions >50% nickel which are referred to as
nickel rich materials. The compositions NCM622 and
NCM811 are under intense scrutiny and capacities of
160 and 190 mA h g–1 have been reported respectively
[93, 94]. One problem with nickel rich NCM interca-
lation materials arises during the synthesis. An ambi-
ent air atmosphere is detrimental to the material
capacity due to the easy formation of Li2CO3 and
LiOH on the materials surface. Hence, the synthesis
has to be conducted under an oxygen atmosphere with
low CO2 and water levels. Even storage of the material is
problematic due to the same reasons. A considerable
increase in electrochemically inactive LiOH and Li2CO3
has been reported to occur after only 7 days of ambient
storage [95]. The extent to which this will occur is
related to the cobalt content with less parasitic reac-
tions with higher cobalt levels. Cobalt is believed to act
as a structural stabilizer in the material. The formation
of lithium hydroxide and lithium carbonate is accom-
panied by an oxygen loss in the material which is com-
pensated by a reduction of Ni3+ to Ni2+. One way to
compensate the surface reactivity is given by surface
coating, e.g. Al2O3 [95]. Other pursuits to overcome
these issues can be found in gradient materials. Since
the side reaction occur on the outer surface of the
material a gradual reduction from a nickel-rich core to
a nickel-poor shell leads to a more stable material
(Fig. 6) [96].
The second drawback found in nickel rich materi-
als is the low thermal stability. The onset temperature
of NCM materials is depending on the cobalt content
and reaches values of ca. 250°C for NCM433 and
NCM523. With Ni > 50% a rapid decrease to 170°C
(NCM622) and ca. 145°C (NCM811) is observed
(all measured in charged state; 4.3 V vs. Li+/Li) [97].
Strategies to mitigate the temperature instability are
ranging from surface coating with AlPO4 [98], AlF3
[99] to gradient materials [100]. It is clear that a high
capacity material is attractive for EV’s but consider-
able focus must be paid to its safety aspects.
Lithium Nickel Cobalt Aluminum Oxide
Li[Ni1 – x – yCoxAly]O2
Pursuits to stabilize the LiNiO2 structure went
beyond the previously discussed manganese and cobalt
doping. Further attempts included inactive Al3+ as
replacement for Ni3+ with the structure Li(Ni1 – xAlx)O2
[102, 103]. The material shows an initial capacity of
150 mA h g–1 which is smaller than the usual
200 mA h g–1 found for LiNiO2. A short cycling test
with 30 cycles renders pure LiNiO2 at ca. 100 mA h g–1
while Li(Ni3/4Al1/4)O2 still delivers ca. 140 mA h g–1
[102]. The lower capacity is not surprising since Al3+
does not partake in the electrochemistry of the mate-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52
1101
Surface Interior
= Mn
= Ni
Fig. 6. SEM images and schematics of gradient nickel rich
NCM materials with a nickel rich core and manganese rich
shell, reprinted with permission from Ref. [101], copyright
2011 the American Chemical Society.
rial and hence limits the lithium removal. Aluminum
acts as a structural stabilizer within the nickel layer and
no phase changes occur during cycling leading to an
enhanced cycle stability and greatly increased thermal
stability [102, 104]. The ion radii for Ni3+ and Al3+ on
octahedral sites are 0.56 and 0.535 Å respectively and it
is not unexpected that Li(Ni1 – xAlx)O2 shows a cation
mixing with Al3+ and Ni3+ in the lithium layer [104].
To get the best of both worlds a well ordered lay-
ered LiNiO2 with little cation mixing via cobalt
doping and a good thermal stability via aluminum
doping, the Li[Ni1 – x – yCoxAly]O2 (NCA) material was
developed [105]. The popular composition
Li[Ni0.8Co0.15Al0.05]O2 was shown to have a better cycle
stability and less impedance growth in a full cell setup
compared to Li[Ni0.8Co0.2]O2 [106]. Quite recently the
Li[Ni0.81Co0.10Al0.09]O2 composition was proposed as a
viable NCA candidate. A good electrochemically per-
formance and improved thermal stability over the
classic Li[Ni0.8Co0.15Al0.05]O2 was demonstrated [107].
Lithium Manganese Spinel LiMn2O4
Manganese based intercalation materials are quite
attractive due to the low cost and low environmental
impact of manganese. LiMn2O4 (LMO) was first pro-
posed by Thackeray in 1983 and subsequently exten-
sively studied by his group [108, 109]. The spinel con-
figuration is very attractive in terms of lithium interca-
lation. LMO shows a Fd3m space group with oxygen
forming a cubic closed package while lithium occupies
1/8 of the tetrahedral (8a) sites and manganese 1/2 of
the octahedral (16d) sites (Fig. 7a) [109]. The empty
octahedral (16a) sites share edges with the 8a site and
form a three dimensional pathway for lithium ion
intercalation and deintercalation (Fig. 7b). LMO
No. 12 2016
1102 FLORIAN SCHIPPER, DORON AURBACH
(а) (b)
LiO4 8a site (Li+)
16c site
MnO6
(vacancy)
(c)
LixMn2O4
0.5 1.0 1.5
4.5
4.0
3.5 (I) (II) (III)
Е, V
3.0
2.5
2.0
~
~ the lower voltage plateau is avoided.
0 50 100 150 200 250
Q, mA h g–1
Fig. 7. (a) Crystal structure of LiMn2O4 spinel with lith-
ium sites in orange and manganese sites in blue adapted
with permission from ref. [113], copyright 2012 the Royal
Society of Chemistry; (b) 3D pathway for lithium ion dif-
fusion by linked octahedral vacancies and lithium sites
adapted with permission from ref. [113], copyright 2012 the
Royal Society of Chemistry; (c) typical discharge profile
for LixMn2O4 from x = 0.3 to x = 1.8 (4.2–2.0 V) reprinted
with permission from ref. [111], copyright 1990 The Elec-
trochemical Society.
demonstrates two voltage regimes with two voltage
plateaus around 4 V and a voltage plateau at ca. 3 V
(Fig. 7c) [110]. The insertion/extraction of lithium
ions in the 8a sites takes place at the 4 V region while
preserving the initial cubic spinel lattice but two
phases can be identified [111]. The 3 V plateau relates
to an insertion of lithium ions into the vacant 16c sites
accompanied by a change to a tetragonal phase driven
by the Jahn–Teller distortion of the Mn3+ in
Li2Mn2O4. [111, 112]. The phase change is accompa-
nied by a 5.6% increase in unit cell volume which is
detrimental to the structural integrity of the material
[111]. In addition, the voltage drop of 1 V is consider-
able and might not be suitable for electronics. Operat-
ing LMO within the 4 V region gives a capacity of ca.
120 mA h g–1 and leads to a composition in the delithi-
ated state of Li0.2Mn2O4. Even if the material is oper-
ated solely in the upper 4 V region a rapid capacity fad-
ing is observed which becomes intolerable at elevated
temperatures [114‒116]. Several mechanisms are used
to describe the poor cycle stability of LMO with man-
ganese dissolution being the most prominent. The dis-
proportionation of Mn3+ leads to the formation of
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
Mn4+ and Mn2+ the latter of which is readily dissolved
into the electrolyte. The manganese dissolution is an
inherent problem with manganese containing active
materials and is more pronounced at elevated tem-
peratures and voltages [114–117]. Especially condi-
tions which favor the electrolyte decomposition to
HF are known to accelerate the manganese dissolu-
tion [118].
Since the dissolution of manganese originates from
the Mn3+ ion efforts to increase the average oxidation
state of manganese above 3.5 were undertaken.
Replacing a portion of manganese with Li+, Mg2+,
Zn2+ will increase the overall oxidation state of man-
ganese and was reported to enhance the cycle stability
[119]. However, this increase in stability comes at the cost
of capacity and stable capacities of ca. 100 mA h g–1 were
achieved. Since the Mn3+/4+ redox couple is the active
species in LMO an increase in oxidation state of man-
ganese must be accompanied by a reduced capacity if
Replacing manganese with Al3+ on the other hand
will not affect the oxidation state and was shown to
enhance the capacity retention even at 45°C
[120, 121]. The replacement of manganese by alumi-
num leads to a lower a parameter in the cubic lattice
due to the smaller size of the Al3+ ions compared to
Mn3+ [120]. The composition of LiMn1.7Al0.3O4 was
found to be optimal in terms of capacity retention with
a capacity of ca. 110 mA h g–1. Increasing the Al con-
tent further will gradually decrease the capacity since
more and more Mn3+ is replaced by electrochemically
inactive Al3+. The better stability was attributed to a
better structural integrity for the aluminum doped
LMO which leads to a more stable unit cell parameter a
over 50 cycles [120].
Another approach to enhance the cycle stability
can be found in various coatings of the active material.
The clear aim here is to minimize the contact area
between the material and the electrolyte with electro-
chemically inert materials (e.g. MgO [122], CeO2
[123] ZnO [124], AlF3 [125], AlPO4 [126], LiAlO2
[127] etc.). Most commonly the coatings are believed
to be a HF scavenger which in turn would lead to sup-
pression in manganese dissolution. One general prob-
lem with wet chemical coatings is the non-uniform
coating of usually nano- and sub micrometer sized
particles onto the active material which leaves a lot of
surface area exposed to the electrolyte. Quite recently
powder atomic layer deposition has become popular in
various research fields and its viability in case of
LiCoO2 was already demonstrated [128]. Revisiting
some coatings for LMO with a powder ALD process
could be an interesting study since a uniform thin layer
might be more adequate in shielding the active mate-
rial form the electrolyte.
Despite its shortcomings LMO is commercially
used in power tools were a high power output is
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES 1103

5.0
Ni4+ Ni3+ Ni2+

Mn4+
Potential, V vs. Li+/Li 4.5
140

Discharge capacity, mA h g–1

Mn3+

100
4.0

60

3.5
20
0
0.01 0.1 1 10 100
Rate, h–1
3.0
0 0.2 0.4 0.6 0.8 1.0
x in LixNi0.4Mn1.6O4

Fig. 8. Voltage profile for LixNi0.4Mn1.6O4 with rate capability test (inset), reprinted with permission from ref. [136], copyright 2009
Elsevier.

required which can be met due to the 3D intercalation showed 3.2% [137]. Nonetheless, even the lower dis-
pathway. The significant reduction in cost makes solution still leads to a capacity fading during cycle and
blended electrodes of LMO and NCM attractive for higher manganese dissolutions are observed in cycled
EV’s Furthermore, better storage capability [129], cells [138, 139]. The high voltage plateau of ca. 4.7 V
enhanced thermal stability [130] and better capacity vs. Li+/Li for LNMO is beyond the stability of current
retention [131] haven been demonstrated for electrolyte solutions Tests monitoring the manganese
LMO/NCM blends. dissolution based on the state of charge (100% SOC
refers to the upper cut off voltage in the delithiated
state) showed an increased Mn dissolution with an
Lithium Nickel Manganese Spinel LiNi0.5Mn1.5O4 increase in SOC and temperature [140]. Furthermore,
An interesting offspring of the work on metal doped the formation of NiF2 and MnF2 on the cathode sur-
LMO material (e.g. Ni, Cr, Co) are high voltage spi- face was shown due to the presence of trace HF in the
nels which were missed in the first instance. Several electrolyte solution.
works into LiMxMn0 – xO4 (M = Ni, Cr, Co) type
materials found an increased cycle stability but at the The synthesis of LNMO is a problematic part and
cost of capacity depending on the amount of dopant the material can be found in two space groups namely
[110, 132]. Later studies showed an additional voltage the ordered spinel P4332 or the disordered Fd ( 3 ) m
region around 5 V which was initially missed and gave [136]. The latter was shown in multiple studies to out-
rise to the name 5 V spinels [133, 134]. The length of perform the ordered phase in terms of rate capability
the 5 V region is dependent on the amount of dopant and cycle life [141–143]. Amatucci et al. argued that
and LiNi0.5Mn1.5O4 (LNMO) arose as a promising the higher performance in the Fd ( 3 ) m phase is due to
material with a theoretical capacity of 147 mA h g–1 its higher lithium diffusivity and similar findings were
(Fig. 8) [135]. made by Sun et al. for titanium substituted LNMO
The average oxidation state of manganese is Mn4+ [142, 144]. Ways to shift the synthesis towards the dis-
in LNMO and is unchanged during cycling with nickel ordered phase are cation substitution of nickel and
being oxidized from Ni2+ to Ni3+ and finally to Ni4+. manganese with different metals (e.g. Fe, Co, Ti)
Since manganese is pinned in the +IV oxidation state [142, 143], the synthesis of oxygen non-stoichiometric
Jahn–Teller distortions of the Mn3+ cation are avoided compounds LiNi0.5Mn1.5O4 – δ by adjusting the calci-
and the manganese dissolution should be negligible. nation temperature [141, 145] or by synthesizing nickel
Indeed, samples stored at 55°C for 7 days showed a deficient (LiNi0.4Mn1.6O4) material [136]. Further-
Mn dissolution of 0.3% for LNMO while LMO more, LixNi1 – xO and NiO impurities are likely to

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52 No. 12 2016

1104 FLORIAN SCHIPPER, DORON AURBACH
(a)
Li
FeO6
PO4
Cell voltage, V
a 2
c
Fig. 9. (a) LiFePO4 structure with 1D lithium channels, reprinted with permission from ref. [156], copyright 2000 Elsevier.
(b) Typical voltage profile for LiFePO4 from 3.9 to 2 V, reprinted with permission from ref. [152], copyright 1997 The Electro-
chemical Society.
form during the synthesis. Close attention has to be
paid to synthesis conditions such as O2 pressure, calci-
nation temperature and nickel content in order to keep
the impurities to a minimum [133, 143, 146].
The stability of LNMO in electrolyte solution
during the high voltage cycling is a problematic aspect.
Ways to shield the material were investigated mainly in
form of surface coatings [147–149]. Liu and Manthi-
ram recently showed some promising results with self-
assembled surface layers of Al2O3, ZnO, Bi2O3 and
AlPO4. They form a shell like coating around the
LNMO particles and enhanced capacity retentions
were reported [150].
Lithium Iron Phosphate LiFePO4
The olivine LiFePO4 (LFP) was identified as an
intercalation compound by Goodenoughs group in
1997 (Figs. 9a, 9b) [151, 152]. Initial research demon-
strated only small capacities of less than 120 mA h g–1
but the material gained considerable research interest
due to the cheap and benign nature of iron compared
to cobalt and nickel. Furthermore, LFP demonstrates
a flat voltage profile with a single plateau at ca. 3.55 V
vs. Li+/Li which makes the material more stable in
non-aqueous electrolyte solutions. Unlike LCO, the
Fe2+/3+ redox couple of LFP does not react with state-
of-the-art electrolyte solutions even in a charged state.
In addition the thermal stability of LFP is excellent
with no exothermic reactions up to 400°C (powder
measurement) [153]. The problems associated with LFP
are the low electrical conductivity of < 10–9 S cm–1 [154]
and the poor lithium diffusivity with a diffusion coef-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
(b)
Capacity, mA h/g
0 20 40 60 80 100 120 140 160
5
0.05 mA/cm2, 2.1 mA/g
3
Charging
1st Cycle
5th Cycle
15th Cycle
25th Cycle
1
0 0.2 0.4 0.6 0.8 1.0
у in Li1–yFePo4
ficient DLi of 1.8 ×10–14 to 2.2 × 10–16 cm2 s–1 (from
LiFePO4 to FePO4) [155].
A heads on approach to overcome the low electrical
conductivity is given by various carbon coating tech-
niques. An intimate contact between LFP and a con-
ductive carbon layer leads to an increased electrical
conductivity. Amongst others resorcinol formalde-
hyde gels [157], ball milling [158] and sol–gel process
[159] have been reported to be viable options to
achieve increased performance of LFP. In 2002 Chi-
ang et al. reported on LFP with an 8 orders of magni-
tude higher electrical conductivity [160]. The authors
used different dopants from Mg, Ti, Zr to Nb with the
highest electrical conductivity for a 1 at % Nb doping
in exchange for lithium in LFP. The tremendous con-
ductivity increase was attributed to a p-type semicon-
ductor behavior in the doped LFP. A later study by
Nazar et al. suggested the effect originates from a per-
colating nano-metallic iron phosphide network [161].
The olivine structure of LFP consist of LiO6 octa-
hedra, FeO6 octahedra and PO4 tetrahedra with only
one dimensional lithium ion channels for intercalation
(Fig. 9a). The limited diffusion pathways explain the
low DLi which in combination with micron size parti-
cles leads to a poor electrochemical performance of
the material. Nano-sized LFP was shown to approach
the theoretical capacity of 170 mA h g–1 at room tem-
perature and a C/10 rate with a decent rate capability
[157, 162, 163]. LFP benefited greatly from material
engineering and nanotechnology which allows to min-
imize the impact of the low diffusion coefficient by
shortening diffusion lengths. One drawback of nano-
sized materials is the lower tap density compared to
their micron sized equivalent, hence nano-LFP
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES 1105

(a) (b)
Potential (Li2MnO3 vs. Li), V 5.0 5 1000°C 900°C 850°C 800°C 600°C 400°C
Charge

Potential, V vs. Li/Li+

4.5
4.0 4
Discharge
3.5
3
3.0
30°С 10 mA/g
2.5 55°С first cycle
2
2.0 1000°C 900°C 850°C 800°C 600°C 400°C
100 200 300 0
–1 0 100 200 300 400
Capacity, mA h g
(charge removed/inserted per gram of Li2MnO3) Capacity, mA h/g

Fig. 10. (a) First charge/discharge cycle of Li2MnO3 at 30 and 55°C; reprinted with permission from ref. [183], copyright 2003
the American Chemical Society; (b) First charge/discharge cycle of nano-Li2MnO3 at 25°C at various synthesis temperatures
with the 600 and 400°C samples having stacking faults, particle size is increasing with synthesis temperature; reprinted with per-
mission from ref. [191], copyright 2009 The Electrochemical Society.

demonstrates a lower volumetric energy density. It is and carbon coating LMP yielding a capacity of ca.
noteworthy that other intercalation cathodes can ben- 100 mA h g–1 with a voltage plateau at ca. 4.1 V [174] and
efit from nanotechnology as well to a certain extent. approaching 150 mA h g–1 at a C/20 rate [175].
Total capacity and rate capability are usually higher in
nano-sized materials but so is their reactive surface Another way to increase the intercalation voltage of
area. This is especially problematic if the material LFP can be found in replacing some of the iron with
tends to react with the electrolyte, like LCO. manganese leading to a solid solution of LFP and
LMP. Even though tests demonstrate a better capacity
Combined approaches with nano-sized and elec- if compared to LMP and a higher average voltage
trical conductive LFP makes the material a viable compared to LFP the voltage profile is split in two
choice for LIB and thousands of cycles were demon- regimes [176, 177]. Lithium intercalation occurs at
strated in lab scale experiments [164, 165]. The lower 4.1 and 3.5 V corresponding to the individual materi-
operating voltage of 3 to 4 V allows for a long cycle life als. It is doubtful that such material will find its way
(no side reactions with the electrolyte) and the only to commercialization due to the high voltage drop of
limiting factor in full cells will be the graphite anode. ca. 600 mV.
Since long cycle life, thermal stability (safety), cost Improvements in high voltage electrolytes could be
and environmental impact are of great interest for very interesting and would allow to study the high volt-
large battery applications, LFP is used in some current age olivines LiCoPO4 and LiNiPO4 adequately.
generation EV’s. Furthermore, combinations with the Reported total capacities and capacity fading for these
high voltage lithium titanate spinel anode (Li4Ti5O12, materials are unsatisfactory and fall short when com-
1.5 V vs. Li+/Li, 175 mA h g–1 [166]) show great prom- pared to LFP. It is unclear if the electrochemical
ise for stationary applications were very long cycle life behavior is intrinsic for the material or just reflects the
is a key aspect and even up to 30.000 cycles have been breakdown of the electrolyte solutions [178, 179]. The
demonstrated at a 10C rate [167–169]. materials might benefit from recent research into
The olivine family has been expanded over the room temperature ionic liquids used as 5 V electrolyte
years by LiMnPO4 [170, 171], LiCoPO4 [172] and solutions with 0.5 M LiTFSI with a LiNi0.5Mn1.5O4
LiNiPO4 [173] which show intercalation voltages of cathode [180].
4.1, 4.8 and 5.1 V respectively. The higher voltages
seem appealing at a first glance to increase the energy Lithium Rich Layered Materials
density but are out of the stability window for current xLi2MnO3 · (1 – x)Li(Ni1 – y – zCoyMnz)O2
electrolytes. So far no useful capacities have been
demonstrated for LiCoPO4 and LiNiPO4. LiMnPO4 The layered Li2MnO3 (space group C2/m
(LMP) seems to be a good candidate to replace LFP [181, 182]) gained considerable research interest in the
and increase the energy density along the way. Unfor- early 2000’s due to its anomalous high charge capacity
tunately, LiMnPO4 shows an electrical conductivity of 320 mA h g–1 when charged to 4.7 V at 55°C
3 orders of magnitude lower than LFP and large polar- (Fig. 10) [183]. The +IV oxidation state of manganese
izations are usually observed [174]. It was shown that the in Li2MnO3 would not allow for any lithium extraction
polarization effect can be greatly reduced by nano-sizing even though some authors claimed the formation of

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52 No. 12 2016

1106 FLORIAN SCHIPPER, DORON AURBACH
5.0
4.5
303 mA h g–1
Voltage, V vs. Li/Li+
4.0
3.5
1
16
3.0 36
232 mA h g–1
2.5
0 50 150 250 350
Capacity, mA h g–1
Fig. 11. Voltage fade of lithium rich NCM over 36 cycles;
reprinted with permission from ref. [200], copyright
2013 Elsevier.
Mn5+. Careful XPS and redox titration studies showed
no indication of Mn5+ in the charged material
[184, 185]. Other authors suggested a mechanism
involving the release of oxygen from the lattice form-
ing Li2O and MnO2 on the material surface for Mn4+
species [186, 187]. A third explanation was given by
Bruce et al. based on the oxidation of the electrolyte
under the high voltage condition according to the sim-
plified reaction: R−H → R0 + H+ + e. Hence, provid-
ing electrons (charge) and protons, the latter of which
are exchange with lithium ions of the active material
(H+ ↔ Li+) [183]. The breakdown of the electrolyte is
a complicated matter in itself and gas evolution
including CO2 and oxygen are known to occur on
overcharge [188, 189]. The Li2MnO3 charge mecha-
nism is still not fully understood and is part of an
ongoing debate in the field. Authors usually favor a
combined explanation involving oxygen release and
proton exchange [190, 191]. Anyhow, L2MnO3 can
deliver a high charge capacity on the first charge at ele-
vated temperatures but fails to retain this capacity
already on the first discharge. Attempts to obtain a
high capacity at room temperature and enhanced cycle
stability were pursuit by nano-sizing the material
(Fig. 10b) [192, 193]. It was claimed that defects are
leading to an increase in capacity. The defect struc-
tures are derived at lower temperatures and the particle
size is considerably lower in the defect structures. It is
unclear if the increase is related to the particle size or
indeed defects [191]. Even though nano-Li2MnO3
shows a much better performance with a first discharge
capacity of 236 mA h g–1 a rather fast fading is observed
with only ca. 190 mA h g–1 after 30 cycles [192].
The work on Li2MnO3 sparked a rush of work on
combination of layered materials with the lithium rich
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
phase of the general formula xLi2MnO3 · (1 – x)LiMO2.
The ternary NCM system is under intensive scrutiny by
a multitude of research groups and companies. Thac-
keray et al. studied the structure of the lithium rich
NCM333 compounds with 5 and 10% of lithium excess
(Li1.05Ni1/3Co1/3Mn1/3O2 and Li1.10Ni1/3Co1/3Mn1/3O2).
It was confirmed by HRTEM convergent beam elec-
tron diffraction that two phases (R ( 3 ) m of NCM and
C2/m of Li2MnO3), integrated on a nanoscopic scale,
are present [194]. The Li2MnO3 phase is inactive if
cycled to a low cutoff voltage of 4.4 V but becomes
active once the voltage is increased to 4.6 V [195].
The capacities reported on lithium rich NCM mate-
rials are ranging from 200 up to 300 mA h g–1. Usually
many factors are different starting with the synthesis
conditions, voltage range used, cycling temperature
and more importantly the values of x, y and z in
xLi2MnO3 · (1 – x)Li(Ni1 – y – zCoyMnz)O2 [196–199].
A popular composition in this field seems to be the
xLi2MnO3 · (1 – x)Li(Ni1/3Co1/3Mn1/3)O2 with x =
0.3, 0.5 and 0.7.
Drawbacks related to lithium rich materials are the
faster capacity fading compared to their lithium neu-
tral layered NCM counterpart and a continuous volt-
age fade with cycle progression (Fig. 11) [200]. The
latter is often ascribed to a layered to spinel transfor-
mation and the former to a transition metal dissolu-
tion [201]. Naturally the first response was to coat the
material with a variety of inactive compounds known
from the LiMn2O4 spinel research field (e.g. TiO2
[202], FePO4 [203], ZrO2 [204], AlF3 [205, 206] etc.).
Another approach is found in rising the average oxida-
tion state of manganese in the lithium rich composi-
tion. This can be achieved by either moving to a cobalt
free composition (e.g. 0.3Li2MnO3 · 0.7LiMn0.5Ni0.5O2
[207]) or by applying a cobalt gradient with a manga-
nese rich shell [208].
The research surrounding lithium rich materials is
very active often aiming at increasing the capacity,
capacity stability and suppressing the voltage fade. But
usually without gaining decisive knowledge as to why
and how all those parameters are linked and might
influence each other. The integrated xLi2MnO3 · (1 –
x)Li(NiCoMn)O2 material is a complicated subject
and fundamental understanding is difficult to achieve
with such a compound having multiple redox centers.
Recently, Tarascon et al. set out to study model mate-
rials of the formula Li2Ru1 – xSnxO3. They, show no
voltage decay but high capacities of ca. 280 mA h g–1 and
have, with ruthenium, only one active redox center
[209, 210]. A mechanism explaining the capacity was
formulated to combine cationic oxidation as well as the
formation of anionic peroxo-superoxo (2O2– ↔ (O2)n–)
species [210]. A following study on Li2Ru0.75Ti0.25O3
with a capacity of ca. 240 mA h g–1, but now with volt-
age fading, concluded the origin to be linked to the
trapping of Ti4+ cations in tetrahedral sites [211]. The
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES 1107

Table 1. Properties of a selected number of common solvents in LIB taken from ref. [58]
η, mPa s ε ρ, g cm–3
Solvent Structure Tm, °C Tb, °C
(25°C) (25°C) (25°C)
O
PC O –48.8 242 2.53 64.93 1.200
O
O
EC O 36.4 248 1.90* 89.78 1.321
O
O
DMC 4.6 91 0.59 3.107 1.063
O O
O
EMC –53 110 0.65 2.958 1.006
O O
DME O –58 8 0.46 7.2 0.86
O
* Measured at 40°C.

above mentioned work on fundamental understand-
ings related to lithium rich materials was recently com-
bined into a review paper and the interested reader is
referred to ref. [212].
Lithium rich NCM materials are definitely an
interesting and hot topic and are believed to be the
successor of traditional NCM cathodes owing to their
much higher capacity. Nonetheless, further research is
necessary and fundamental science seems only now to
catch up with the material development and some
much needed insights into the material are gained.
Understanding the material on a fundamental level
will help to develop smarter compositions of Ni-rich
materials and hopefully aid in their development
towards commercialization.
Electrolyte Solutions for Lithium Ion Batteries
Electrolyte solutions for LIB are complicated sys-
tems consisting of a solvent mixture, a salt and any
number of additives. Even though they are a vital part
of any given battery technology, this topic may be less
attractive for many researchers. Because work on elec-
trolyte solutions and related interfacial problems may
be less conclusive than work on cathode materials.
The latter involves more bulk structural analysis that
can provide more unambiguous results. The electro-
lyte solutions used in LIB of today consist of ethylene
carbonate (EC) and linear carbonates (e.g. ethyl
methyl carbonate (EMC), dimethyl carbonate
(DMC)) as solvents in combination with LiPF6 as a
lithium salt. These solutions provide a reasonably wide
electrochemical window for 4–5 V Li batteries, thanks
to complicated passivation phenomena. Additives
used in commercial electrolyte solutions are usually
not disclosed. EC is a vital part and has to be present
to facilitate the SEI formation to prevent graphite
exfoliation as was described in the first part of this
paper. Before LIB had become a commercial reality,
research on electrolyte solutions was focused on
metallic lithium and finding ways to prevent dendritic
growth. The focus changed drastically with the use of
high voltage intercalation cathode materials and with
better understanding of lithium intercalation into soft
carbons and later graphite. In general, a number of
attributes are necessary for an electrolyte solution to
be useable in LIB:
(1) Wide operating temperature range (low meting
point, high boiling point);
(2) Low viscosity of the solvent mixture; promotes
ionic conductivity;
(3) Decent solubility and dissociation of the used
lithium salt in the solvent mixture (high relative per-
mittivity); promotes ionic conductivity;
(4) Large electrochemical window to operate with
low voltage anodes and high voltage cathodes.
Set aside from the above points, other characteris-
tics such as non-toxicity, environmentally benignity,
thermal stability, and of course, low cost are sought
after as well. Electrolyte solutions make up ca. 45% of
a commercial LIB (by mass) and roughly 1/5-th of the
total price generating a considerable market around
them [213, 214].
Solvents
The most used solvents in LIB are cyclic and acy-
clic carbonates but others have been studied as well
(Table 1). The combination of solvents with lithiated
graphite (LiC6) or metallic lithium prevents the use of
protic solvents. Only polar-aprotic solvents which dis-
solve an adequate amount of lithium salt and form

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52 No. 12 2016

1108 FLORIAN SCHIPPER, DORON AURBACH
Table 2. Properties of different lithium salts used in LIB, taken from ref. [58, 244]
Salt Structure
LiPF6 Li+[PF6]–
LiClO4 + –
Li [ClO4]
LiAsF6 + –
Li [AsF6]
–
O O O O
LiBOB B Li+
O O O O
LiTFSI Li+[N(SO2CF3)2]–
* Measured with 0.7 M in PC or EC/DMC blends with esters [244].
solutions with high ionic conductivity are relevant.
These requirements limit the spectrum of relevant sol-
vents families to esters, ethers, alkyl carbonates,
nitriles and sulfones. The combination of low viscosity
solvents with viscous ones which have a high dielectric
constant is an attractive choice and has become the
common practical approach. Indeed most practical
electrolyte solutions are based on EC and linear car-
bonates of lower viscosity. The high melting point of
EC is a problem, but combinations with EMC or
DMC lead to solvent mixtures with an acceptable liq-
uid range and melting points below –20°C [58, 215].
The combinations of EC with solvents such as
DMC, DEC, EMC and LiPF6 became the standard
solutions in LIB. Their improvement is an ongoing
area of interest. Especially their thermal stability and
questionable high voltage stability are considered as
major problems that have to be addressed. Fluorinated
solvents have been reported to improve on both mat-
ters [216–218]. Fluorinated solvents may also act as
flame retardants in LIB but should be used mostly as
co-solvents due to their higher viscosity compared to
their non-fluorinated counterparts [219]. Even though
the C–F bond is polar and adds to the overall relative
permittivity of these solvent, their higher viscosity
leads to lower ionic conductivity [220]. Fluorinated
solvents have been demonstrated to improve the pas-
sivation properties of surface films formed on graphite
and silicon anodes [217, 221, 222].
Salts
A wide variety of salts was used throughout the
development of LIB until a compromise was found
with LiPF6 (Table 2) [223–225]. Any salt used in LIB
has to be beneficial for passivating surface film forma-
tion, inert towards the current collector and thermally
stable. LiClO4 was shown to have a high solubility in
aprotic solvents (high ionic conductivity) but forms
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
σ, mS cm–1
σ, mS cm–1
Al corrosion 1 M in EC–DMC
1 M in PC (25°C)
(25°C)
No 5.8 10.7
No 5.6 8.4
No 5.7 11.1
No ~5.0* ~11.0*
Yes 5.1 9.0
less stable passivation layers on aluminum and most
important, it may be explosive [226, 227]. LiAsF6 was
also tested intensively. However it is toxic, what rules
out its commercial use but not necessarily its applica-
tion in fundamental research.
LiPF6 has become the standard salt for LIB due to
its good balance of properties such as high solubility
and ionic conductivity, stable SEI formation in com-
bination with EC and reasonable thermal stability
[58]. One major drawback found in LiPF6 is the HF
formation with trace amounts of water according to
[228, 229]:
LiPF6 ↔ LiF + PF5,
PF5 + H2O ↔ POF3 + 2HF.
The as formed HF dissolves transition metal cat-
ions via exchange of protons by transition metal ions in
the cathode structure. Thus, providing detrimental
situations in which transition metal cations migrate to
the anode side and are being deposited on the graphite
surface. Their reaction on the graphite side worsens
the anode passivation, leading to side reactions and
consequently, lowering their capacity and increase
their impedance [230, 231]. Transition metals can also
be deposited as oxides or fluorides directly onto the
surface of the cathode thus also leading to an increase
in impedance and eventually cell death [232]. As with
all chemical reactions, an increase in temperature
enhances the rate of side reactions, thus accelerating
the capacity degradation. LiPF6 is far from being the
perfect salt for LIB but makes for a decent compro-
mise of properties.
LiBOB (Li-Bioxalato-borate) has been under
scrutiny since the late 1990 early 2000 and has
attracted some commercial interest [233, 234]. The
electrochemical window of electrolyte solutions
employing LiBOB was reported to be >4.5 V making it
a potential candidate for high voltage spinel cathodes
or olivines [233]. The solubility is in general lower than
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES
that for LiPF6 leading to a lower ionic conductivity
[235]. Some research demonstrated a better high tem-
perature cycle stability for LiBOB since the salt has a
good stability against trace amounts of water and does
not form detrimental HF [236, 237]. A study by Dahn
et al. focused on the thermal stability of LiBOB con-
taining electrolyte solutions and showed a very good
stability in combination with lithiated graphite.
Unfortunately, the reactivity with Li0.5CoO2 was
higher than that for a standard solution of 1 M LiPF6
in EC/DEC [238].
LiTFSI (Bis(trifluoromethane) sulfonamide;
LiN(SO2CF3)2) has become quite popular as a
replacement salt for LiPF6 but several issues are still
not addressed satisfactory. LiTFSI shows a good ther-
mal stability when compared to LiPF6 under similar
conditions and is not prone to HF formation
[239, 240]. LiTFSI solutions show reasonable ionic
conductivity but are less conductive than LiPF6 solu-
tions [58]. The biggest drawback though is the Al cor-
rosion under charged conditions [241]. Recently, it
was demonstrated that concentrated solutions of
LiTFSI in EC or EC/DEC can suppress the alumi-
num corrosion but the conductivity in such systems is
rather low with 0.1 and 0.5 mS cm–1 respectively [242].
Furthermore, using large amounts of expensive salts
seems counter intuitive from an economical point of
view. Another approach studied to compensate for the
aluminum corrosion was by using small amounts of
LiPF6 in combination with LiTFSI in an EC/DMC
solution. Even 1% of LiPF6 was enough to suppress the
Al corrosion [243].
Additives
Probably the easiest way to influence the properties
of electrolyte solutions can be found by adding small
percentages of additives to the solution. The aimed
improvements are usually related to SEI stability/for-
mation, cathode protection, LiPF6 stabilization and
safety features such as overcharge protection or flame
retardation [245].
Reductive additives which have a higher reduction
potential and react before the actual SEI formation
takes place, can produce a preliminary surface film on
the graphite anode. This layer will serve as a corner-
stone for the SEI formation, limiting side reactions
and effectively lowering the irreversible capacity loss
due to the SEI formation. A popular candidate is the
polymerizable vinylene carbonate which shows
improvement in irreversible capacity loss and cycle
stability with graphite anodes [246, 247]. The additives
do not necessarily have to be polymerizable and other
studied compounds are known to be beneficial as well
(e.g. ethylene sulfite [248]). The idea is that they
decompose to insoluble products at a higher reduction
potential forming a preliminary surface film as well.
Even materials that do not decompose within the
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52
1109
operating potential may assist in the SEI formation by
scavenging radicals and suppressing side reactions or
by reacting with the SEI products to form more stable
compositions. One of such compounds is the LiBOB
salt which is known to form very stable SEI layers and
even as little as 1–5 mol % have been reported to be
sufficient to enhance the cycle stability [249].
LiPF6 stability under elevated temperatures is a
big problem in LIB and successfully suppressing or at
least inhibiting the HF formation can have a tremen-
dous positive impact on long term cycle stability. One
way to shift the equilibrium of the PF5 formation
(LiPF6 ↔ LiF + PF5) can be found by simply adding
LiF to the electrolyte solution in a real fundamental
usage of the law of mass action [250]. Even in the
absence of water, PF5 is known to react directly with
the SEI components thus forming LiF, POF3 and CO2
in the process. The gas evolution and especially the
formation of the very toxic POF3 are problematic and
result in a buildup of pressure in the cell thus leading
to increasingly more dangerous conditions in com-
mercial cells. Lowering the acidity of PF5 is a possi-
ble way to reduce the side reactivity and consequently
the gas evolution in LIB. Weak complexing agents
(e.g. Tris(2,2,2-trifluoroethyl) phosphite TTFP
[251]) can coordinate PF5 leading to a better cycle sta-
bility of LIB even under elevated temperatures. LiPF6
stability is also directly linked to the cathode stability
since deterioration occurs due to the presence of HF.
Scavenging water or HF are possible routes to enhance
cathode stability and a number of components have
been positively tested such as butyl amine [252] or
N,N'-dicyclohexylcarbodiimide [253].
Electrolyte solutions can be modified in many ways
and even changing only one component can have
impacts on many attributes of the whole system lead-
ing to a series of necessary tests to truly validate a new
solvent or salt. Simply showing certain improvements
in one aspect but ignoring the impact on other aspects
makes for poor science but has become an increasingly
common practice. Electrolyte solution research is very
demanding and a broad skill set is required to under-
stand various aspects in details. Especially full cell tests
are time consuming and “short” half-cell tests
(~100 cycles) are usually favored but allow only a
glimpse of the picture [254]. Dahn et al. recently pub-
lished a series of papers employing high precision volt-
age/current/time measurement systems, as an exten-
sion to common battery test units [255–257]. When-
ever the coulombic efficiency (CE) is anything but
exactly 1, it means that the system is subject to side
reactions. Using high precision CE measurements
are an elegant way to predict capacity fading after a
few cycles. It was possible to estimate the capacity at
cycle 750 of LTO/LCO or graphite/LCO cells with
various additives after an initial cycling test (1000 h;
ca. 35 cycles) providing a way to shorten total test
times and circumvent long term cycling to some
No. 12 2016
1110 FLORIAN SCHIPPER, DORON AURBACH

Table 3. Overview of some materials studied as anodes in lithium ion batteries, properties taken from ref. [34, 261–263]
Theoretical capacity, Potential range vs. ρ, g cm–3
Material Volume change
mA h g–1 Li+/Li, V 25°C
Li 3860 0 0.53 100%
LiC6 372 ~0.2–0.01 2.25 ~10%
Li4Ti5O12 175 ~1.5 3.5 ~0.2%
Li4.4Si 4200 0.4–0.01 2.23 320%
Li4.4Sn 993 0.6–0.01 7.29 273%

extend [255]. Considering that commercial LIB can
have any number of added compounds in a wide per-
centage range, the methodology developed by Dahn
et al. might be a good option to carry out combinato-
rial studies.
Advancements in Anode Materials
Research into anode materials is most often aimed
at lithium metal alloys such as Li/Si or Li/Sn
(Table 3). Graphite as a real intercalation anode with
a low intercalation potential close to metallic lithium
was something of a lucky find, as was described earlier
in the paper. Since the capacity of graphite is usually
twice as high as those of most cathode materials, mass
balancing in full cells is easily done. Lithium titanate
Li4Ti5O12 (LTO) is another intercalation material
which can be combined with high voltage materials to
give lithium ion battery full cells with reasonable volt-
ages in the range 2–3.3 V. Graphite is the dominating
anode material in commercial LIB and is currently
used either from a synthetic route (mesocarbon
microbeads, MCMB [258]) or from modified natural
flake graphite [259]. The expected high demand in
graphite for LIB in light of electric vehicle develop-
ment puts natural graphite more and more on the
scope of companies since it has the potential to be
available for roughly half the price than synthetic
graphite [260].
Even though having anode materials such as metal-
lic lithium with > 3000 mA h g–1 sounds very impres-
sive, combing such in a useful manner with cathodes
only providing around 200 mA h g–1 is not so import-
ant, from energy density point of view. High capacity
Li anodes are more suited to be the negative material
in lithium sulfur or lithium oxygen batteries which will
be discussed later. The next part shows some recent
developments in metallic lithium, silicon and tin
anodes.
Lithium Metal Anode
A number of researchers are still working to
improve the performance of metallic lithium anodes
in hope to exploit their high gravimetric and volumet-
ric capacity. Three problems hinder the implementa-
tion of metallic lithium: (1) dendrites formation (lead-
ing to short circuits), (2) poor capacity retention when
practical specific charge (per cm2) is exchange upon
cycling and (3) unavoidable continuous reactions with
the electrolyte solutions in practical cells, which dry
the batteries [264]. Different approaches to achieve
limitation or complete suppression of dendrites
growth have been studied and can be divided into SEI
related approaches (modifying the Li surface chemis-
try) or mechanical blocking of dendrites growth [265].
A very well-studied electrolyte solution based on
LiAsF6 in 1,3-dioxolane with stabilizing tertiary amine
additives is one of very few systems that was actually
proven to be suitable for rechargeable Li batteries
[266]. And practical Li/LiMnO2 cells were commer-
cialized [267]. The improved cycling behavior was
attributed to the unique and complicated surface
chemistry of Li metal in this electrolyte solutions that
forms flexible SEI layer, that can accommodate mor-
phological changes during periodic lithium dissolu-
tion/deposition [37, 268]. Unfortunately, the electro-
chemical stability window is limited to ~3.7 V which
made the electrolyte solution a good choice for 3 V
LiMnO2 cathodes but is unsuitable for most of the
current generation cathodes [266].
Despite the renaissance in the study of Li anodes in
recent years, we are skeptical about their relevance to
rechargeable batteries based on liquid electrolyte solu-
tions [37]. It is possible however to use Li metal anodes
in solid-state batteries, in which the electrolyte sys-
tems are based on polymeric matrices (e.g., based on
derivatives of polyethylene oxide [269, 270]) or of solid
Li ions conductors (e.g., Li3PO4–LiPON [271]). The
fields of solid-state and polymeric electrolytes are
broad, well developed and should be beyond the scope
of this paper [272].
Silicon and Tin Anode
A number of elements (Al, Si, Sn, Sb, Ga, Ge etc.)
are known to form alloys with lithium in electrochem-
ical processes, when polarized to sufficient low poten-
tials vs. lithium [273]. The most important elements in
this respect are silicon and tin, whose alloying behav-
ior with lithium is very similar to each other.

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52 No. 12 2016

 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES
Both silicon and tin can be alloyed with 4.4 moles
of lithium leading to a substantial volume expansion
during lithiation (see Table 3). This poses a multitude
of problems when silicon or tin are used as alloying
anodes. Li–Si or Li–Sn compounds cannot withstand
the volume expansion and contraction without break-
ing apart due to high compression and tensile stress
respectively. This leads to cracks within the composite
anode films and eventually more and more active mass
becomes detached form the conductive matrix result-
ing in an accumulation of dead mass in composite
electrode [274]. Furthermore, the cracks thus formed
continuously expose fresh active Li-alloy surface to
the electrolyte solution leading to ongoing side reac-
tions which consume the electrolyte solution [275]. It
was also shown that lithium extraction is not com-
pletely possible in an electrochemical fashion and
some lithium remains within the alloy anodes [276].
All the above mentioned processes lead to a rapid
capacity fading in alloy anodes and a large irreversible
capacity loss is observed during the first cycle (Fig. 12)
[277].
Since the volume expansion causes the most prob-
lems in alloy anodes, ways to accommodate or allevi-
ate the mechanical stresses are commonly used to
enhance cycle stability. It is know that properties of
nano-sized materials differ from those of micron-
sized particles, which also applies to tensile and com-
pressive strength [278]. Shifting the particle sizes of
alloy anodes from micron-size to submicron particles
increases the cycle stability of the material consider-
ably [279, 280]. Nanoparticles in alloy anodes come
with all their advantages (e.g. short diffusion path-
ways) but also disadvantages (e.g. high surface area,
fabrication costs). Furthermore, nano-silicon was
shown to have a strong tendency to merge to bigger par-
ticles offsetting the initial gain by nano-sizing the mate-
rial [276]. Imbedding nano-particles in an appropriate
host matrices, such as carbonaceous composites, is an
easy way to isolate the particles and ensure intimate
contact with to the conductive backbone [281].
Excellent cycling stability was reported for amor-
phous thin film silicon anodes which are produced via
magnetron sputtering or vapor deposition [282, 283].
The performance of such thin film electrodes is
strongly linked to their thickness and decrease with
increasing thickness. This is likely due to longer lith-
ium diffusion pathways and stronger impact of com-
pression and tensile stress in case of too thick alloy
films [284]. It is not completely understood why
amorphous silicon can withstand the high volume
change in a better way compared to their crystalline
counterpart. Explanations are often given by the one
phase nature found during cycling of amorphous sili-
con. In contrast, crystalline silicon undergoes a phase
change from crystalline to amorphous nature during
repeated lithiation/delithiation [276, 285].
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52
1111
2.0 5 2 1
Discharging (de-alloying)
Voltage, V vs. Li/Li+
1.5
1.0
0.5
Charging (alloying)
0 1
5 2
0 1000 2000 3000 4000
Specific capacity, mA h g–1
Fig. 12. Typical voltage profiles for silicon anodes with
5 cycles shown; reprinted with permission form ref. [277],
copyright 2005 Elsevier.
The main focus in alloy anode research lies in
understanding capacity fading mechanisms and to tai-
lor materials accordingly. The high theoretical capaci-
ties of Si and Sn are very tempting but not necessarily
useful in full cells. Sacrificing capacity in order to gain
cycle stability is definitely an option. A stable silicon
anode delivering 800 mA h g–1 is much easier to bal-
ance in lithium ion batteries than anodes having ini-
tially 3000 mA h g–1, but showing capacity fading upon
cycling. Higher capacities might still prove useful in
lithium sulfur batteries were usually metallic lithium is
used as anode in fundamental research but might not be
applicable in future commercial cells [286]. The above
discussed approaches to achieve better cycle stability are
a selected number of strategies found in the literature,
but are far from providing ultimate solutions [55].
BEYOND LITHIUM ION BATTERIES
This final chapter will summarize recent efforts to
develop very high energy density Li batteries, by giving
up Li ions intercalation cathodes and moving to more
energetic cathode reactions. We cover herein very
briefly the emerging fields: Li-sulfur and Li-oxygen
batteries. Low molecular weight cathode materials are
very attractive in terms of high specific capacity. Sulfur
(M(S): 32 g mol–1) and molecular oxygen (M(O2):
32 g mol–1) are being extensively studied as cathode
materials in combination with metallic lithium
anodes. Both systems have been investigated for
decades with decisive findings in recent years putting
them in the focus of many research groups and com-
panies around the world. The Li–S system is more
advanced and is believed to reach commercialization
within the next 5–10 year while Li–oxygen systems
are often ball-parked in a 20–30 year range.
No. 12 2016
1112 FLORIAN SCHIPPER, DORON AURBACH
3.0
Voltage, V vs. Li/Li+
2.5
Charge
I of sulfur reduction products (LiSn moieties, down to
Discharge
II
2.0 III
S8 Li2S8 Li2S4 Li2S2
Li2S
0% 12.5% 25% 50%
1.5 Depth of discharge
Fig. 13. Typical discharge profile of a lithium sulfur battery
(sulfur is loaded onto CMK-3); reprinted with permission
from ref. [288], copyright 2010 the Royal Society of
Chemistry.
Lithium Sulfur Battery (LSB)
Publications on LSB can be found dating back to
the early 1970’s a time when LIB were still two decades
away from commercialization and research on Li bat-
tery systems begun to flourish [287]. After LIB were
introduced to the market, the work on Li–S became
less attractive and interesting. The efforts to promote
the field of electro-mobility, due to increasing envi-
ronmental constraints related to the use of fossil fuels
renew work on Li–sulfur systems, due to their poten-
tial high energy density. Innovative work on novel sul-
fur cathodes was published in 2009 by Nazar et al.
[288]. LSB have a multitude of problems which made
these systems not very appealing. However, intensive
research efforts on these systems seem to provide some
solutions to old problems, related to Li–S cells [289].
The reaction between lithium and sulfur can be
simplified to: 2Li + S ↔ Li2S which gives a theoretical
capacity of 1675 mA h g–1 based on sulfur. This high
capacity makes Li–S very interesting as a future power
source and practical values of 1000 mA h g–1 (S) have
been reported [290]. It is important to mention that
capacities for LSB are often reported in respect to their
sulfur mass and not to the total mass of the sulfur/car-
bon composites. Also, the sulfur loading in composite
electrodes is often in the range of 30–60 wt % which
can be very misleading in terms of actual capacity. The
working voltage of a LSB is about 2 V which leads to a
theoretical gravimetric energy density of 2300 W h kg–1
(based on a sulfur cathode and lithium anode). Pro-
jections often put packed LSB around 600 W h kg–1 a
value about three times higher than that of state-of-
the-art LIB. Furthermore, sulfur is the 10th most
abundant element on earth and can be easily exploited
in near 99.9% purity via the Frasch process [291]. In
addition sulfur is a side product of the petro chemical
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
industry and huge quantities are produced in excess
every year [292]. LSB do not only have a high possible
energy density but the low price of sulfur put them also
in better economical standings compared to LIB. Sul-
fur is non-toxic and environmentally benign. How-
ever, problems linked to the sulfur cathode are the low
electrical conductivity of sulfur, the volume expansion
Li2S) during charge/discharge and the dissolution of
polysulfides into the electrolyte solution during
cycling. The latter may undergo continuous reduction
processes at the negative electrode, which leads to a
shuttle mechanism that avoids completed re-oxidation
of the Li-sulfide moieties to sulfur. Due to which the
capacity of the sulfur cathode in Li–S cells is limited.
Sulfur shows an electrical conductivity of ca.
5 × 10–30 S cm–1 what makes it a very poor electrode
material [293]. Early work on LSB focused either on
high temperature approaches or using electrolyte solu-
tions containing lithium polysulfides to overcome the
low conductivity of pure sulfur. Thermal lithium sulfur
batteries have to operate at >400°C in order to ensure
solubility of the short chain polysulfides and sufficient
mass transport within the cell. However, such cells are
very sensitive to contamination [294]. Better results
were obtained for sulfur containing compounds as
active material such as FeS2 and FeS [295]. However,
FeSx cathodes require high operating temperatures
and suffer from internal resistance. Hence, their
importance as practical battery materials is limited.
Room temperature cells were tested in the late 1980s
by Peled et al. with polysulfides dissolved in THF
[296]. The cells were plagued by passivation of the lith-
ium anode with insoluble discharge products (e.g.
Li2S2, Li2S) which leads to a poor electrochemical per-
formance.
The discharge process in LSB progresses from the
cyclo-octasuflur (S8) involving polysulfides (Li2Sn;
n = 2–8) to Li2S. The density changes from 2.07 g cm–3
(S8) to 1.64 g cm–3 (Li2S) leading to a volume expan-
sion of ca. 80% and eventually to a pulverization of
Li2S [297, 298]. The contact loss between sulfur and
the current collector leads to an increase in “dead”
sulfur in the cells and eventually capacity fading. The
volume expansion cannot be circumvented and has to
be addressed in case of practical LSB for safety and
durability reasons. Furthermore, the Li–polysulfides
(Li2Sn, n > 4) are known to be readily dissolved in
commonly used electrolyte solutions [296]. A typical
discharge profile for LSB displays a stepwise voltage
behavior which reflects the gradual reduction of sulfur
to long chains polysulfide moieties and then, their
reduction to Li2S (Fig. 13). Dissolved Li–polysulfides
migrate through the cell and react with the lithium
anode directly to insoluble Li2S and Li2S2. This pro-
cess is in fact a shuttle mechanism that avoids a full
charging of Li2S back to sulfur, which considerably
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES
(а)
Specific capacity, mA h g–1
3 nm
6.5 nm
Fig. 14. (a) Schematic representation of sulfur loaded CMK-3; reprinted with permission from ref. [290], copyright 2009 Nature;
(b) Cycling performance of CMK-3/S (red points) and PEG modified CMK-3/S (black points); reprinted with permission from
ref. [290], copyright 2009 Nature.
limits the capacity of Li–sulfur cells. Although it was
shown that the presence of Li2S and Li2S2 in surface
films formed on lithium anodes in Li–S cells may
improve their passivation properties, avoiding contact
between sulfur reduction products and Li anodes in
Li–S cells is very desirable for their successful opera-
tion [299].
An elegant way to alleviate problems arising from
the flow of LiSn species towards the anodes in Li–S cells
is found by encapsulating sulfur in carbonaceous matri-
ces, as was suggested by Nazar et al. [290]. The employed
carbon CMK-3 [300] (pore volume: 2.1 cm3 g–1) was
mixed with sulfur and was heat treated to achieve a
melt infusion of sulfur into the meso-porous network.
Followed by a final heating to 155°C, in order to evap-
orate excess sulfur (Figs. 14a, 14b). The intimate con-
tact between sulfur and the electrically conductive car-
bon framework, compensates for the low conductivity
of sulfur. The high pore volume can account for the
volume expansion during sulfur reduction. Further-
more, the Li–sulfides dissolution is retarded when
cathodes comprising sulfur encapsulated in carbon are
used for Li–S cells.
The pioneering work of Nazar et al. promoted
extensive work on composite sulfur-carbon composite
cathodes. It was shown that dissolution of LiSn species
can be suppressed by using functional carbons (e.g.
nitrogen [301], sulfur [302]) instead of pure carbon.
The pore structure of carbons for sulfur cathodes have
to be tailored to meet the needs as viable host net-
works. Macro-, meso- and micropores are defined to
be > 50 nm, 2–5 nm and < 2 nm respectively. Macro-
porous carbon materials are attractive since they can
hold a decent amount of sulfur leading to high specific
capacity of Li–S cells. Anyway, the performance of all
Li–S cells which use common electrolyte solutions is
poor due to the above described shuttle mechanism.
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
1113
(b)
1400
1000
600
200
0
0 5 10 15 20
Cycle number
Recently, better cycling performances of Li–S cells
have been reported for cathodes based on macropo-
rous carbons, by using a room temperature ionic liq-
uids in which the Li–polysulfides shuttle is suppressed
due to the high viscosity of these electrolyte solutions
[303]. The majority of work on carbon hosts structure
is devoted to mesoporous carbons with high pore vol-
umes with which high sulfur loadings, of up to 70%,
can be achieved [290, 301, 302, 304–306]. The small
channels of these carbons lead to a better contact
between the insulating sulfur and the conductive car-
bon matrices. Nevertheless, there is no way to avoid
the detrimental shuttle mechanism in Li–S cells when
any open structure S–C composites are used.
Several approached to fully mitigate and avoid the
shuttle mechanism in Li–S cells were suggested and
tested in recent years. We mention below several
important ones. Polymer coatings on S-carbons
matrices have been investigated, with some level of
success [307, 308]. Moving from mesoporous carbons
to microporous carbons with very small pores (0.5 nm)
gives an opportunity to confine short chained sulfur
allotropes (S2–S4) into the microporous structure of
the carbon [309].
Nazar’s group promotes development of composite
sulfur electrodes based on ‘sticky’ surfaces that
strongly adsorb to them the LiSn formed upon sulfur
reduction. Several families of suitable substrates were
demonstrated for effective composite sulfur cathodes
by this highly innovative group [310, 311].
Another approach, promoted by Aurbach’s group
is to work with S–C matrices covered by stable surface
films which behave like SEI [312, 313], so sulfur
reduction occurs as quasi-solid-state reactions, in
which the products remain fully trapped in the porous
structure.
Vol. 52 No. 12 2016
1114 FLORIAN SCHIPPER, DORON AURBACH
In conclusion, the LSB field has become very
attractive in recent years. Many prominent research
groups throughout the world are pursuing different
approaches to enhance the cycle stability of LSB. Even
though the work on porous carbon materials seems to
be the most popular, other ideas are also serve as
attractive alternatives including the use of ionic liquids
as viscous electrolyte systems [314, 315], modified sep-
arators with fluorinated reduced graphene oxide [316],
redox mediators to enhance Li2S utilization [317],
enhanced SEI formation [313] and using high salt con-
centration in the electrolyte solutions. LiSn dissolution
is largely avoided in saturated solutions [318]. So far,
there is no ultimate approach to fully solve the above
described problems of LSB, so only combined
approaches might be a way to promote this battery
technology further. In general, LSB have been greatly
improved over the last few years and are on a good
track towards commercialization. In this respect, we
can mention the availability of practical Li–S cells
produced by Sion Power (USA) which provide an
energy density of 350 W h kg–1 [319]. Several other
commercialization ventures of Li–S cells by estab-
lished companies are on the way.
Lithium Oxygen Batteries (LOB)
Metal air batteries such as the commercial primary
systems zinc/air and aluminum/air are very attractive
since they offer high practical energy densities due to
the absences of heavy cathodes. Oxygen gas is used as
the cathode supplied by ambient air and only the
porous electrodes’ substrates and catalysts which are
usually attached to them, contribute to the overall
cathodes’ mass. The lithium oxygen combination is
sometimes referred to as the “holy grail” of battery
research, due to the great promise of high energy den-
sity, but seems to be to some extent elusive. In fact,
when intensive research on Li–oxygen systems began
several years ago, there was an advertisement of many
unsupported promises. The intensive and systematic
work that was carried out by several groups, demon-
strated many intrinsic problems related to instability of
all kind of non-aqueous electrolyte solutions and car-
bons during oxygen reduction and oxygen evolution
reactions (ORR and OER respectively). The main dis-
charge product in non-aqueous LOB is Li2O2 which
gives a stunning theoretical capacity of 1168 mA h g–1,
with an average discharge voltage of 3 V vs. lithium,
what means a theoretical energy density around
3500 W h kg–1. Sometimes, higher specific energy
densities are mentioned, ignoring the Li–peroxide
weight in the discharged cells, in order to emphasize
the chance of propulsion by Li–air batteries to rival
internal combustion engines [320]. Hence, the expec-
tations from LOB technology are very high, while
these systems require intensive basic research, before
they may have a chance to proceed towards commer-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
cial successes. Li–oxygen cells are so far in lab scale
only. They include Li metal anode and porous carbon
cathode, fed usually by CO2 and moisture-free pure
oxygen. Relevant electrolyte solutions may employ
moderately polar polyether solvents (from the glyme
family) or more polar solvents such as di-methyl sulf-
oxide (DMSO) with LiTFSI salt as the most import-
ant components. In polyether solvents, superoxide
and peroxide moieties formed upon oxygen reduction
are very nucleophilic and basic in the presence of Li
ions in solutions. The latter are very electrophilic, thus
promoting the reactivity of the former oxygen reduc-
tion products.
The discharge process is complicated, involving the
formation of lithium superoxide LiO2 according to the
following scheme of reactions [321]:
O2 + e → O 2− ,
O 2− + Li+ → LiO2,
2LiO2 → Li2O2 + O2.
The morphology of the Li2O2 formation depends of
the nature of the electrolyte solution. High donor
number solvents such as DMSO have been reported to
promote granular morphology of Li–peroxide depos-
its, leading to ORR with relatively high specific capac-
ity, while in low donor number solvents Li2O2 is pri-
marily formed on the electrode substrate as a thin,
blocking surface film (leading to a ORR with a rela-
tively low specific capacity) [322]. The key problem of
all Li–oxygen cells is the inevitable reactivity of all
kind of polar-aprotic solvents with superoxide and
peroxide moieties in solution phase, promoted by the
presence of electrophilic Li ions [323, 324]. Even the
relatively less reactive ethereal solvents are attacked by
superoxide and peroxide moieties. However, once
solid Li2O2 deposits are formed, they are much less
reactive with solution species [325]. Regarding Li salts
for Li–oxygen cells, LiPF6 is not compatible with
them. In fact, it seems that LiFSI and LiTFSI are the
most suitable salts.
The charging process in LOB is fairly simple fol-
lowing the oxygen evolution reaction (OER) accord-
ing to the scheme below [326]:
Li2O2 ↔ 2 Li++ 2e + O2.
However, oxidation of solid Li2O2 which electronic
and ionic conductivities are very low, requires very
high over-potentials that can exceed 4 V vs. Li. Such
high OER potential endanger the stability of both the
solvents (all relevant ones) and most types of carbona-
ceous materials. Various OER catalysts have been
investigated with α-MnO2 giving a low charging volt-
age of 3.51 V vs. Li+/Li [327]. Using the same catalyst
during discharge also promotes side reactions of the
electrolyte solutions (especially with ethereal solvents
[328]. It seems that stationary catalysis which involve
redox active moieties embedded in the cathode matrix
Vol. 52 No. 12 2016
 A BRIEF REVIEW: PAST, PRESENT AND FUTURE OF LITHIUM ION BATTERIES
cannot be effective in catalyzing oxidation of Li2O2
deposits that burry them on the electrode’ surface.
More and more it becomes clear that the use of electro-
catalysis for OER in Li–oxygen by red-ox mediators in
solution phase is important and helpful [329].
In summary, the chemistry of LOB is very compli-
cated, because the ORR and OER are accompanied by
many possible side reactions, which seem to be inevi-
table. However, intensive work during recent years
clarifies more and more the picture. LOB are far from
commercialization stages. Problems beyond what we
described above: questions about the stability of bind-
ers, choice of really carbonaceous materials, mitigat-
ing complicated side reactions to the level that they are
minor enough to allow prolonged cycle life and
matching compatible anodes to oxygen cathodes have
to be addressed. Much more systematic work is
required in order to promote these systems to become
a practical reality [325, 330, 331].
CONCLUDING REMARKS
Batteries in general have come a long way in a
rather short time since the first tinkering of Volta in
1800. The technology is omnipresent in our daily life
and continuous to attract more and more devoted and
diligent research groups all around the world. Big news
and promises linked to batteries can be found in many
publications and are eagerly picked up by popular sci-
ence magazines.
Li batteries of all kinds are operative thanks to com-
plicated passivation phenomena. They are only meta-
stable and their functioning and durability depend on
delicate balance among interfacial processes and
transport phenomena. Basic scientific research in
which correlation among morphology, surface chem-
istry, structural changes and electrochemical response
are fully understood is mandatory for successful devel-
opment of advanced battery systems (obviously true
for R&D of LIB, LSB and LOB).
LIB in particular have seen a rapid development
from their first commercial introduction in 1991 and
many new intercalation compounds are currently
under scrutiny. Many companies try to establish them-
selves in the battery market motivated by its impressive
current growth and future growth potential. High
capacity intercalation materials such as nickel rich
NCM, are very attractive and start finding commercial
applications. However, increase in energy density
means also safety concerns. Indeed, sufficient time
has to be devoted to the study of safety aspects (ther-
mal runaway, gas evolution etc.) of advanced cathode
materials, in order to avoid severe failures in large bat-
tery packs.
The lithium intercalation electrochemistry is reach-
ing a limit which might be as high as 300 mA h g–1 for
lithium and manganese rich NCM but is still unsatis-
factory for EV applications. New systems like LSB and
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 52
1115
LOB will set the bar higher but have to be developed
much further to achieve the maturity necessary for a
broad commercial success. Both systems have seen
exiting new discoveries and developments in recent
years making them very attractive research fields hun-
gry for new ideas.
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