Energy Storage Materials 7 (2017) 157180

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Energy Storage Materials

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Low voltage anode materials for lithium-ion batteries MARK

a,b,
Ali Eftekhari
a
The Engineering Research Institute, Ulster University, Newtownabbey BT37 OQB, United Kingdom
b
School of Chemistry and Chemical Engineering, Queen's University Belfast, Stranmillis Road, Belfast BT9 5AG, United Kingdom

A R T I C L E I N F O A BS T RAC T

Keywords: Studies of anode materials due to the rapidly growing demand for lithium-ion batteries (LIBs) are an active area
Anode materials of research. However, the primary focus is on the specic capacity and cyclability. An essential requirement of
Lithium-ion battery electrode materials is the operating voltage, which is dened by the redox potential, but there is a tendency to
High voltage battery sacrice this feature in favor of higher capacities. For the cathode materials, there is a common categorization
Low voltage anode
based on the operating voltage (e.g., high voltage cathode delivering a redox potential between 4.55.0 V vs. Li/
Pseudocapacitive anode materials
Li+), but there is no such categorization for anode materials. The present manuscript aims to provide a general
Supercapacitors
review of the anode material to highlight the importance of the operating voltage for an anode candidate.
Furthermore, it is described that compositing the anode materials with carbon nanomaterials can increase the
specic capacity for the delithiation, but part of this capacity is due to the carbon capacitance or
pseudocapacitance mostly occurring at high potentials, which cannot be gained in the full cell performance.
This class of pseudocapacitive anode materials can be of potential interest for energy storage but not
appropriate candidates for the conventional LIBs. It is also emphasized that the delithiation process is the
main duty of an anode material when a LIB is working.

1. Introduction
The initial challenge of lithium-ion batteries (LIBs) was to nd
suitable cathode materials facilitating the Li intercalation/de-intercala-
tion redox system at a relatively high potential (e.g., 4 V vs. Li/Li+).
The rst interesting feature of LIBs is the negative potential of the Li
anode, which provides a rare opportunity to have a high cell voltage. On
the other hand, the Li/Li+ redox system provides a stable and reliable
electrochemistry, which is also employed as the reference electrode in
the majority of works in the realm of LIBs. As a result, the conventional
three-electrode electrochemical cells have been replaced by the two-
electrode cells in studies of LIBs, in which the anode and reference
electrode are a metallic Li electrode.
However, the safety risk of utilizing metallic Li has made it an
impractical anode material. Hence, the quest for nding suitable anode
materials was also an active area of research for advancing the LIBs.
Two unbeatable features of Li anode are somewhat sacriced when
employing another anode material: the redox potential is more positive
in comparison with Li/Li+, and the specic capacity is obviously lesser
than that of metallic Li. The rst choice to replace the metallic Li anode
was graphite, which has been widely employed in the commercial LIBs.
The theoretical capacity of graphite anode is 372 mA h g1, and its
redox potential is slightly higher than that of the metallic Li anode. As a
result, the operating voltage of the LIBs is shifted to 3 V level instead of
4 V. Having a slightly more positive potential than Li/Li+ for the anode
has some advantages, as reaching the less positive potentials close to 0
vs. Li/Li+ may result in the formation of lithium dendrites and a
blocking solid electrolyte interphase (SEI). A possible approach is to
utilize high-voltage (the so-called 5-V) cathode materials to compen-
sate the anode excess potential [1], though 5-V cathode materials are
somehow unstable due to the presence of transition metals at their high
oxidation valances [2].
Fig. 1 shows that even when an anode material with a well-dened
at plateau at 2.0 V vs. Li/Li+ coupled with a 5 V cathode, the cell
voltage is just less than 3 V. This suggests that an anode material with a
more positive potential is not practical. On the other hand, the absence
of a at plateau can turn the battery into a supercapacitor [3,4].
Since the theoretical capacity of graphite is almost achieved
practically, there is a demanding interest in nding new anode
alternatives. Therefore, the focus is on anode materials with high
specic capacities. However, the importance of the anode negative
potential is somehow neglected. This can be understood by the wide
potential window, which is usually employed for the investigation of
the anode materials. Owing to the rapidly growing demands for the
electrochemical energy storage systems, there are always new possibi-
lities for designing new types of storage devices. Thus, such high-
voltage anode materials can nd superior positions in new electro-
chemical systems. However, it is unlikely to consider an anode material

Correspondence address: The Engineering Research Institute, Ulster University, Newtownabbey BT37 OQB, United Kingdom.

http://dx.doi.org/10.1016/j.ensm.2017.01.009
Received 6 December 2016; Received in revised form 24 January 2017; Accepted 24 January 2017
Available online 26 January 2017
2405-8297/ 2017 Published by Elsevier B.V.
A. Eftekhari
Fig. 1. Galvanostatic charge/discharge cycles representing the EcathodeEanode vs.
capacity of ntTiO2/-Li3PO4/Li2CoPO4F cell. This gure includes the voltage proles of
the cathode (Ecathode vs. capacity) and the anode (Eanode vs. capacity) in the middle and
bottom plots. The capacity of the full cell is calculated using the cathode mass.
Reproduced with permission from Ref. [1]. Copyright 2016, Nature Publishing Group.
with a redox potential higher than 2 V vs. Li/Li+ as a promising
candidate for the anode of current LIBs.
One may argue that reducing the operating voltage in favor of the
energy density is a practical approach, as the overall voltage can be
compensated by using the cells in series. However, when the operating
voltage is below 2 V, the conventional LIB architecture loses its
justication, as alternative aqueous batteries can be more economical
and safer. The importance and requirement of delivering a suciently
low potential for anode materials are somehow diminishing, as some
authors do not even illustrate the galvanostatic proles or voltammetric
data and simply focus on the specic capacity without mentioning the
operating voltage (see for example, [5]).
The present manuscript reviews the current anode materials from a
dierent perspective to highlight the importance of the operating
voltage as well as the specic capacity. Here, it is not aimed to provide
a complete list of all anode materials with potentially low-voltage
performance. Instead, we attempt to provide general examples from
most common classes of the materials. This should clarify the overall
concept.
2. Electrochemical studies of anode materials
The fundamental investigation of anode materials in a half-cell is
sometimes misleading. Anode materials are normally investigated as a
cathode in the standard two-electrode cell in which the metallic Li is
employed as the anode and reference electrode. The rst issue is
connected with the direction of charging and discharging. In a full cell,
158
Energy Storage Materials 7 (2017) 157180
Fig. 2. (a) The electrochemical performance of MoO2-LiCoO2 full cell. The galvanostatic
discharge-charge curves of LiCoO2 cathode, LiCoO2-MoO2 full cell and MoO2 anode at a
current rate of 1 C for initial ve cycles. (b) A schematic illustration of the performance of
the half cells. Reproduced with permission from Ref. [234]. Copyright 2016, Elsevier.
charging process includes the lithiation of the anode and de-lithiation
of the cathode (Fig. 2). As a result, the cell will reach its fully charged
status in which the cell voltage is maximum (i.e., most positive
potential of the cathode and most negative potential of the anode).
During the discharging process, the anode undergoes delithiation in
which its potential increases to more positive values and the cathode
undergoes the lithiation in which its potential decreases to less positive
potentials. When the cell is fully discharged, the operating voltage
reaches its minimum value (i.e., least positive potential of the cathode
and most positive potential fo the anode). Therefore, charging and
discharging of the anode and cathode undergo opposite directions. The
importance of this labeling is when the charge and discharge capacities
or potentials are signicantly dierent.
In both anode and cathode cases, the capacity of interest is the
reversible capacity for the lithiation/de-lithiation. This means that the
capacity of an anode material is not x for the Li storage if we can
intercalate xLi but de-intercalate only x/2. This is the reason that the
irreversible capacity reported during the rst charge/discharge cycle is
not reliable. Instead, the rst cycle, at least in many cases, should be
considered as a part of the electroactive material preparation. Fig. 3
shows typical galvanostatic proles of a series of porous graphene
electrodes. The high lithiation capacity is usually interpreted as the Li
storage capacity, but it is not true. The real capacity of Li storage should
be read from the delithiation prole, as the intercalated Li should be
reversibly deintercalated; otherwise, it is useless. This is the case for
some intercalation lithium metal oxides (including cathode materials)
in which Li can be intercalated but cannot be fully deintercalated.
However, this is not the case for pseudocapacitive materials such as
porous graphene. The electric charge presented by the lithiation prole
is not fully for the lithiation process but also an irreversible process
such as Li electroplating at the reactive sites of the carbon or the
reactions associated with the formation of SEI.
Comparing the rst two cycles displays that the delithiation amount
remains intact while the lithiation capacity is declining. If assuming
that the electric charge recorded is due to the lithiation, the amount of
Li intercalated during the lithiation is three times more than that
deintercalated. Even during the second cycle, an excess Li is inter-
A. Eftekhari
Fig. 3. (a) First lithiation/delithiation curves of a series of graphene-based samples at
50 mA g1. (b) Subsequent galvanostatic proles of a graphene-based electrode (PGF-1).
Reproduced with permission from Ref. [27]. Copyright 2016, Royal Society of Chemistry.
calated. Therefore, it is evident that this excess capacity is associated
with a process other than the lithiation, and it is inappropriate to be
considered as the Li storage capacity. In any case, this extra capacity is
misleading because it cannot be used in the reversible cycling of the full
cell.
Fig. 2 demonstrates a typical cell made of two half-cells of LiCoO2
cathode and MoO2 anode. As can be seen, it is not a matter of labeling,
but the cathode lithiation process should be coupled with the anode
delithiation and vice versa. In other words, it is of practical interest to
increase the dierence of the cathode lithiation and the anode
delithiation, which denes the cell voltage when using a LIB.
Therefore, the anode delithiation is the process of interest in the LIB
performance. To avoid any terminology confusion, lithiation/delithia-
tion is used instead of charge/discharge throughout this manuscript.
Another important issue, which is the main focus of the present
manuscript, is the reasonable potential window for the battery perfor-
mance of anode materials. Cathode investigations are typically con-
ducted in a potential window of 3.04.5 V vs. Li/Li+ because most of
the common cathode materials deliver a charge/discharge plateaus at
about 3.44.1 V vs. Li/Li+. In a similar fashion, the anode investiga-
tions are expected to be conducted in a potential window of 02.0 V vs.
Li/Li+ as the operating voltage should be between 0.51.5 V vs. Li/Li+.
However, many researchers examine the candidate anode materials in
a potential window of 03.0 V vs. Li/Li+. In no practical LIB, the anode
voltage can reach as high as 3.0 V vs. Li/Li+. One may argue that these
potential windows are for fundamental studies, and this is not the
performance in a full cell. Note that cathode materials usually deliver a
at plateau; thus, expanding the potential window does not signi-
cantly aect the nal specic capacity recorded. However, anode
materials, as will be discussed later, usually exhibit pseudocapacitive
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Energy Storage Materials 7 (2017) 157180
Fig. 4. (a) The rst ve CVs of Zn2SnO4/graphene electrode, (b) the charge-discharge
proles of Zn2SnO4/graphene. Reproduced with permission from Ref. [233]. Copyright
2017, Elsevier.
behavior. In this case, the overall specic capacity is proportional to the
width of the potential window over a broad potential window (see for
example, [6,7]). On the other hand, there are cases in which the anode
delivers the main part of its capacity below 1.5 V vs. Li/Li+ (see for
example, [8,9]); thus, continuing the delithiation any further is useless
and possibly harmful to the reversible performance.
Fig. 4 shows the electrochemical performance of a Zn2SnO4 anode.
As the cyclic voltammogram suggests, there is no electrochemical
activity at potential more positive than 2.0 V vs. Li/Li+. The corre-
sponding galvanostatic prole also indicates that no lithiation occurs at
positive potentials, and the potential quickly drops to about 1.0 V vs.
Li/Li+. About 90% capacity for delithiation is achieved within the 0
2.0 V potential window. Correlating the voltammetric and galvanostatic
data suggests that the capacity achieved in the 2.03.0 V potential
window is probably due to a double layer capacitance or similar
processes (as can be judged by the featureless CVs), and not associated
with a reversible lithiation/de-lithiation.
There are also anode materials whose redox potentials are at higher
values. Fig. 5 depicts the electrochemical performance of two nickel
oxide anodes. The galvanostatic proles indicate the delithiation
process occurs at two plateaus corresponding to two redox couples
observed in the CVs. In both galvanostatic and voltammetric experi-
ments, the delithiation process continues up to 3.0 V vs. Li/Li+. Table 1
summarizes the operating voltage, specic capacity, and cyclability of
common anode materials classied according to the potential range in
which the specic capacity is achieved.
A. Eftekhari
Fig. 5. (a) The 2nd cyclic voltammogram of the NiO/N-C and NiO nanosheets arrays
electrodes at a scan rate of 0.1 mV s1. (b) Charge/discharge proles at the rst two
cycles; Reproduced with permission from Ref. [232]. Copyright 2016, Elsevier.
3. Carbon
Following the dominant place of graphite as the anode material
[1022], various carbon nanomaterials have also been examined as
potential candidates. The mechanism of the Li storage by these carbon
nanomaterials is dierent from that of the Li intercalation between the
graphite interlayers. Instead, the Li atoms are somehow adsorbed on a
large surface area provided by the carbon. In a sense, this is similar to
the conventional mechanism of carbon-based supercapacitors. It
should be taken into account that this is a combination of capacitive
and pseudocapacitive behaviors; where the high surface area of the
carbon is responsible for the former, and the pseudocapacitance is
based on the Li redox systems in interaction with the carbon functional
groups or dangling bonds. Therefore, the battery performance of
carbon nanomaterial anodes is mainly pseudocapacitive in the absence
of any plateau delivering a constant potential [23,24].
Natural graphite can conduct reversible lithiation/delithiation with
a theoretical capacity of 372 mA h g1 at potentials below ca. 0.3 V vs.
Li/Li+. Since graphite does not have a high surface area like carbon
nanomaterials, the contribution of capacitance or even pseudocapaci-
tance is minimum, and the delithiation is characterized by a at plateau
in the galvanostatic proles [25]. The performance of synthetic
graphite is slightly weaker but very similar to that of natural graphite
[25]. Manipulating the graphite structure can improve the battery
performance of graphite. For instance, uorination can facilitate the
diusion of Li ions through more spacious interlayers and enhance the
specic capacity. However, this inuence is not like common doping of
carbon nanomaterials which results in a stronger pseudocapacitive
behavior. The delithiation potential remains intact regardless of the
uorine content.
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Energy Storage Materials 7 (2017) 157180
This performance is not only limited to graphite but any carbon
material with a straightforward mechanism for the lithium intercala-
tion/deintercalation (rather than pseudocapacitive adsorption on a
high surface area). Sun et al. fabricated a binder-free anode from
graphene and tested it in combination with a LiNi0.5Mn1.5O4 cathode
[26]. The full battery delivered excellent performance comparable to
that of commercial LIBs having a gradually declining but steady cell
voltage in the range of 4.64.4 V. Nevertheless, most of the carbon
nanomaterials with high surface area such as porous graphene simply
provide huge pseudocapacitance for the delithiation monotonically
over the potential window of 03.0 V vs. Li/Li+ [27]. As illustrated in
Fig. 3, the battery performance of graphene is utterly dierent from
that of graphite, because the lithium storage is not based on the well-
known intercalation process. Instead, the pseudocapacitive adsorption
of Li-ions on the high surface area of graphene is strongly dependent
on the surface structure and the presence of functional groups. This is
the reason that a theoretical capacity cannot be calculated for the
graphene samples (unless considering graphene as an ideally at single
sheet). Considering the highly packed architecture of LIBs, high surface
areas cannot provide their surface-based capacity fully.
The intercalation/deintercalation of graphite is not a straightfor-
ward process since graphite anode materials are not of high crystal-
linity to expect a smooth solid-state reaction through the graphite
interlayers. As a result, various mechanisms are involved in the
lithiation/delithiation of graphite, and they become more complicated
when disordered nanostructures are also added to the material
architecture. At a nutshell, the delithiation starts at the least positive
potentials with the deintercalation of Li ions from within the micro-
pores [2830]. The next step is the deintercalation of Li ions
accommodated between the graphite interlayers [30]. However, in
parallel with this step, a dierent mechanism (sometimes distinguish-
able by a middle plateau [31]) is involved for the desorption of the Li
ions adsorbed at the graphene edges and dangling bonds [32,33].
Fig. 6 shows the electrochemical performance of macro-mesopor-
ous hollow carbon spheres. Although the lithiation process undergoes a
sharp peak before the Li plating potential, there is no redox peak
associated with the delithiation process, and it is mainly conducted
through pseudocapacitance. Of course, the base redox couples can be
distinguished by the strong cathodic peaks during the rst cycles and
very weak anodic peaks during the delithiation. In a similar fashion, the
galvanostatic proles of the delithiation process are characterized by
purely pseudocapacitive diagonal lines (Fig. 6b).
While the electrochemical performance of graphite anode is similar
to that of the cathode materials, i.e., based on an intercalation
mechanism; novel anode materials based on conversion mechanisms
have been considered as promising candidates. Fig. 7 compares the
mechanism of lithiation/delithiation by intercalation or conversion.
The intercalation materials are like a rm cage with a limited
availability for accommodating the Li-ions. This results in two key
dierences: the cyclability of the intercalation materials is much better
because the cage retains its rm structure during the lithiation/
delithiation process while the conversion materials undergo massive
volume changes, but the specic capacity of the conversion materials is
much higher as a higher amount of Li can interact with the host
material.
In fact, the prime challenge of the conversion-based materials is to
suppress the volume change, which is also accompanied by severe
capacity fading. A possible solution is to place the electroactive material
within a solid matrix such as ordered mesoporous carbon (OMC) [34].
In this case, the electroactive material is fairly attached to a backbone
while the mesopores can provide required space for the volume
expansion. However, it is not easy to prepare such OMC-based anode
materials in large scale. Therefore, the focus is on compositing the
electroactive material with various carbon nanomaterials, which will be
reviewed throughout this manuscript.
A. Eftekhari Energy Storage Materials 7 (2017) 157180

Table 1
The potential window is the range in which the majority of the specific capacity is achieved, and should not be mistaken by the experiment potential window. The values of the specific
capacities are not accurate and have been estimated from the galvanostatic profiles reported in the corresponding references.

Reference Category Slope Material Initial capacity Reversible capacity Potential range Rate
(mA h g1) (mA h g1) (number of (V)
cycles)

[235] Low Flat Graphite 320 0.10.2 0.035 A g1

[236] Low Flat Sn/Ni bimetallic 850 650 (50) 0.30.8 0.1 A g1
[49] Low Flat 3D silicon/carbon nanotube 2300 1600 (10) 0.20.6 0.5 A g1
[237] Low Flat SiFe 690 640 (100) 0.20.7 0.1 C
[50] Low Flat Ndoped Ccoated Si 3100 1900 (100) 0.30.6 0.2 A g1
[42] Low Flat Si3N4coated Si 2600 1200 (200) 0.10.6 0.2 C
[238] Low Flat Ge/graphene/CNT 1250 0.30.9 0.1 A g1
[239] Low Flat SiOx 1470 1320 (800) 0.20.6 0.2 A g1
[171] Low Flat CoNi2S4/NiCo2S4 2200 00.3 0.1 A g1
[77] Low Flat Ge@GeO2 1150 720 (50) 0.30.6 0.1 A g1
[240] Low Semiflat Carbon micro/nanostructures 400 360 (10) 0.11.2 0.1 A g1
[96] Low Semiflat SnO2 510 480 (400) 0.21.0 0.28 A g1
[215] Low Semiflat CoFe2O4 1400 1200 (200) 0.21.0 0.5 A g1
[241] Low Semiflat NiSi2/Si 1440 0.20.5 0.1 C
[242] Low Semiflat Si/C 870 700 (50) 00.6 0.1 A g1
[99] Low Semiflat SnS2/carbon cloth 1000 880 (60) 00.7 0.65 A g1
[243] Low Semiflat Carboxyl functionalized carbon 160 130 (15) 0.11.0 0.02 A g1
fibers
[94] Low Semiflat Tin nanodots embedded in 720 600 (500) 0.21.2 0.2 A g1
nitrogendoped mesoporous
carbon
[8] Low Semiflat SiMWCNT@C 1250 0.5 A g1
[125] Low Semiflat CuO nanosheets/carbon 670 590 (100) 0.21.0 0.5 A g1
[244] Low Semiflat Fe2O3@carbon/carbon cloth 2300 1600 (60) 01.0 0.2 A g1
[245] Low Pseudocapacitive Silicon/nitrogendoped Graphene 1350 1450 (150) 01.0 0.1 A g1
[246] Low Pseudocapacitive KFeO2 1200 700 (100) 0.11.0 0.09 mA g1
[247] Low Complex ZnO/graphene/carbon nanotube 890 700 (100) 01.3 0.1 A g1
[121] Low Twostep flat Cu2Sb 460 0.90.95, 1.0 0.2 C
1.1
[248] Low/middle Twoflat SnSb 840 01.1 0.1 mA cm2
[249] Low/middle Semiflat Mn3O4 430 0.31.4 0.2 A g1
[250] Low/middle Pseudocapacitive Nitrogencontaining carbon 930 01.8 0.5 A g1
[203] Low/middle Pseudocapacitive SnFe2O4 800 450 (100) 01.8 0.1 A g1
[251] Low/middle Pseudocapacitive CoMn2O4 780 670 02.0 1 A g1
[252] Low/middle Pseudocapacitive SiO2/C 530 01.5 0.1 A g1
[218] Low/middle Complex redox MnCO3 620 400 (200) 01.6 0.1 A g1
[165] Low+middle Twostep flat Li2ZnTi3O8 165 160 (200) 0.30.5, 1.51.6 1 A g1
[253] Low+middle Flat+Pseudocapacitive WN 310 310 (10) 0.21.2 0.2 A g1
[95] Low+middle Flat+Pseudocapacitive Sn3O4 1100 480 (50) 02 0.06 A g1
[254] Low+middle Pseudocapacitive+semi Cu1.5Mn1.5O4 660 580 (5) 02.0 0.1 A g1
flat
[205] Low+middle Pseudocapacitive+semi ZnMn2O4 990 01.1, 1.11.8 0.5 A g1
flat
[229] Low+middle Pseudocapacitive+two PbLi2Ti6O14 1.55 150 (80) 0.51.3, 1.31.4, 0.1 A g1
step flat 1.451.55
[157] Middle Flat Li4Ti5O12 168 1.55 1C
[163] Middle Flat Li4Ti5O12@C 169 162 (100) 1.55 3C
[162] Middle Flat Codoped Li4Ti5O12 250 1.55 0.1 C
[161] Middle Flat Co0.05/Li3Ti4Co0.95CrO12 150 140 (100) 1.51.6 0.2 C
[6] Middle Flat Zn2Ti3O8 x 210 1.4 0.1 A g1
[255] Middle Flat Phosphorus/reduced graphene 1450 980 (50) 1.11.25 0.1 A g1
oxide
[139] Middle Flat Fe3O4 770 1.41.8 0.1 A g1
[151] Middle Flat TiO2 300 200 (150) 2.02.1 0.2 C
[256] Middle Flat Na2Li2Ti6O14/Ag 130 1.351.4 0.1 A g1
[152] Middle Flat TiO2 230 1.8 0.1 C
[257] Middle Flat NiP@C 920 650 (50) 0.81.1 0.05 A g1
[206] Middle Flat ZnMn2O4 820 0.91.6 0.1 A g1
[258] Middle Flat ZnFe2O4@C/graphene 720 725 (50) 1.41.9 0.23 A g1
[141] Middle Flat Cu0.02Ti0.94Nb2.04O7 320 0.91.8 0.1 C
[259] Middle Flat GeP5 2250 200 (40) 0.91.2 0.2 A g1
[130] Middle Flat MnO 700 500 (150) 1.11.4 0.2 A g1
[232] Middle Semiflat NiO/C 700 1.52.0 0.5 C
[175] Middle Semiflat FeP 610 0.71.1 0.1 C
[167] Middle Semiflat Li3VO4/ C 440 1.01.6 0.2 C
[260] Middle Semiflat CoMoO4@graphene 900 730 (200) 1.02.2 0.1 A g1
[149] Middle Twostep flat MoO2 200 1.41.5, 1.71.8 0.16 A g1
[234] Middle Twostep flat MoO2 220 1.41.45, 1.65 0.1 C
1.75
[9] Middle Diagonal Li4C10H4O8 250 170 (20) 0.71.5 0.1 C
[209] Middle Pseudocapacitive+semi MgFe2O4 920 890 (50) 1.42.0 0.1 A g1
(continued on next page)

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A. Eftekhari Energy Storage Materials 7 (2017) 157180

Table 1 (continued)

Reference Category Slope Material Initial capacity Reversible capacity Potential range Rate
(mA h g1) (mA h g1) (number of (V)
cycles)

flat
[233] Middle Pseudocapacitive Zn2SnO4/graphene 840 850 (50) 02 1 A g1
[261] Middle Pseudocapacitive+semi H0.28MoO3 1120 970 (25) 0.22.0 0.1 A g1
flat
[262] Middle Pseudocapacitive+semi CoMoO4/Fe2O3 coreshell 1270 1320 (50) 0.22.0 0.2 C
flat
[216] Middle/high Pseudocapacitive+semi CoFe2O4 950 740 (100) 1.42.4 0.05 A g1
flat
[263] Middle/high Pseudocapacitive+semi NiFe2O4 800 700 (5) 1.53.0 1C
flat
[200] Middle/high Complex Cu2ZnSnS4/graphene 660 0.62.5 0.05 A g1
pseudocapacitive
[213] Middle/high Complex MnCo2O4 1110 1040 (5) 0.72.2 0.2 A g1
pseudocapacitive
[264] Middle/high Complex redox Silicondoped iron oxyhydroxide 940 1.02.2 0.1 A g1
[145] Middle+high Pseudocapacitive+flat Ni0.9Zn0.1O 810 600 (200) 02.1, 2.12.3 0.4 A g1
[265] Middle+high Pseudocapacitive+flat TiO2@MoS2 750 0.22.4 0.1 A g1
[266] Middle+high Pseudocapacitive+flat Fullerenelike MoS2 1100 1100 (100) 02, 22.3 0.1 A g1
[186] Middle+high Pseudocapacitive+flat MoS2graphene 750 780 (50) 02.1, 2.12.3 0.1 A g1
[199] High Flat Co3O4 1080 1.92.3 0.2 C
[168] High Pseudocapacitive+flat Ni3S2 480 600 (30) 01.95, 1.95 0.1 A g1
2.05
[267] High Pseudocapacitive+flat NiCoO2 810 1.92.2 0.08 A g1
[100] Wide Pseudocapacitive+semi Nitrogendoped carboncoated tin 1400 1700 (120) 03 0.2 A g 1
flat oxide
[212] Wide Pseudocapacitive+semi CoFe2O4/graphene 770 1120 (100) 02.5 0.2 A g1
flat
[268] Wide Pseudocapacitive SnO2/polypyrrole 500 300 (50) 03.0 0.1 A g1
[269] Wide Pseudocapacitive Zn2GeO4 350 310 (50) 03 0.2 A g1
[150] Wide Pseudocapacitive Li2MoO3 810 03.0 0.1 A g1
[23] Wide Pseudocapacitive Macromesomicro porous carbon 880 710 (100) 03.0 0.1 A g1
[270] Wide Pseudocapacitive Defective graphene 600 600 (10) 03.0 0.1 A g1
[271] Wide Pseudocapacitive Graphene paper 710 02.5 0.05 A g1
[272] Wide Pseudocapacitive Co3O4/ZnCo2O4 1180 1090 (50) 03 0.1 C
[273] Wide Pseudocapacitive Carbon aerogel 500 03.0 0.1 C
[274] Wide Pseudocapacitive NiMn2O4/C 980 990 (150) 03.0 1 A g1
[275] Wide Pseudocapacitive Ndoped graphene 880 02.5 0.1 A g1
[276] Wide Pseudocapacitive Sn/SnO2@C 760 500 (50) 03.0 0.1 A g1
[277] Wide Pseudocapacitive ZnO/C 1020 830 (100) 02.0 0.1 A g1
[278] Wide Pseudocapacitive ZnCo2O4 920 880 (100) 03 0.2 A g1
[279] Wide Pseudocapacitive N,Fdoped graphene 1110 03.0 0.1 A g1
[231] Wide Pseudocapacitive Macromesoporous hollow carbon 510 510 (10) 03 0.5 A g1
[280] Wide Complex Co3O4 1150 1000 (50) 03 0.1 C
pseudocapacitive
[170] Wide Complex VS4/graphene 1440 1050 (10) 03.0 0.2 A g1
pseudocapacitive
[281] Wide Complex CoGeO3 1450 750 (50) 03.0 0.2 A g1
pseudocapacitive
[282] Wide Complex B,Ndoped C 1300 900 (50) 03.0 0.2 A g1
pseudocapacitive
[283] Wide Complex Co3V2O8 1100 950 (20) 03 0.05 A g1
pseudocapacitive
[284] Wide Complex ZnO/ZnCo2O4 980 900 (200) 0.23.0 1 A g1
pseudocapacitive
[285] Wide Complex GeO2/graphene 2050 1200 (500) 03.0 0.2 A g1
pseudocapacitive
[286] Wide Complex Fe3O4/graphene 800 1120 (200) 03.0 0.2 A g1
pseudocapacitive
[287] Wide Complex Graphene/Co9S8 930 900 (10) 0.53.0 0.1 C
pseudocapacitive

4. Silicon-based materials
Si is one of the promising anode materials with a theoretical
capacity of 3580 mA h g1 [3546], though the Si lattice does not have
enough space to accommodate the Li ions. Therefore, the lithiation
process is accompanied by a huge volume expansion (as large as
300%). This causes severe structural destruction which is accompanied
by the mechanical instability of both the electroactive material and the
SEI formed on the anode. There are some practical approaches to place
Si electroactive particles within a voluminous porous matrix, which can
provide enough space for the volume expansion. However, the point of
interest is that the Si redox potential is very close to that of Li/Li+. The
delithiation process occurs below 0.5 V vs. Li/Li+ (see table Table 1)
[4749]. A porous silicon can reach its theoretical capacity, though, it
cannot maintain the capacity due to the severe structural changes [50].
Lithiation process undergoes two steps resulting in the formation of
amorphous Li13Si4 alloy [5153], which is transformed to the fully
lithiated Li22Si5 phase [53,54]. Obrovac et al. proposed that the
lithiation cannot go further than Li15Si4, and the latter is the fully
lithiated Si [52].

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A. Eftekhari Energy Storage Materials 7 (2017) 157180

Fig. 6. (a) CV curves of the macro-mesoporous hollow carbon spheres at 0.1 mV s1, and (b) galvanostatic charge/discharge curves at 0.5 A g1. Reproduced with permission from Ref.
[231]. Copyright 2016, Elsevier.

When covering Si with carbon, which is indeed a common
architecture in various carbon-based nanocomposites, the well-dened
electrochemical behavior of Si disappears and is replaced by the
pseudocapacitive behavior of the carbon to perform the delithiation
process over a broad range of potential across 03.0 V vs. Li/Li+
[55,56]. Note that this change is due to the high surface area provided
by the carbon nanomaterial. If uniformly coating the Si particles with a
thin layer of carbon, this layer simply serves as a membrane and does
not contribute a high pseudocapacitance. Thus, the delithiation can be
mostly completed under 0.5 V vs. Li/Li+ [57,58] like the case of
pristine Si anode.
Jouybari and Berkemeier reported that coating the Si electrode with
a thin layer of LiPON can signicantly improve the battery perfor-
mance [59]. While the bare Si electrode loses over 70% of its capacity
during only 40 cycles, the capacity fading is negligible for the Si/LiPON
electrode. This cycling performance is ascribed to the stable SEI formed
on the LiPON layer.
Formation of SiO2 and LixSiyOz phase causes a noticeable deviation
from the ideal electrochemical performance of Si anode, as the full
delithiation of lithium silicon oxides require more positive potentials
over 2 V [60]. Miyazaki et al. showed that the cyclability of the Si anode
improves by increasing the oxygen content, but the initial irreversible
capacity loss dramatically increases [61]. The redox systems are
independent of the oxygen content, but the presence of oxygen weakens
the Li intercalation/deintercalation. In fact, the second cycles of
lithiation/delithiation proles are very similar for various contents of

Fig. 7. Comparison of an intercalation and conversion mechanisms for the lithiation/delithiation of electrode materials. Reproduced with permission from Ref. [230]. Copyright 2007,
Elsevier.

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A. Eftekhari
Fig. 8. Galvanostatic charge-discharge voltage proles of (a) SnSex-MWCNT (1:1) and (c) SnSex electrodes for 1st, 2nd and 10th cycles. Cyclic voltammograms of (b) SnSex and (d)
SnSex MWCNT (1:1) hybrid. Reproduced with permission from Ref. [101]. Copyright 2016, Elsevier.
oxygen, and in all cases, the delithiation process is mainly conducted
below 0.6 V vs. Li/Li+ [62]. Table 1 shows that modication of Si anode
performance with a second component might be accompanied by
signicant changes in addition to the specic capacity and cyclability,
but the modied Si anode still remains in the same category.
5. Germanium-based materials
Ge as an alternative to Si is also a promising anode material with a
theoretical capacity of 1600 mA h g1 for the composition of Li4.4Ge
[6376]. The electrical conductivity of Ge is two orders of magnitude
higher than that of Si and so is its ion mobility. However, the main
issue is still the volume expansion and the electrochemical pulveriza-
tion of the Ge. Although the lithiation/delithiation processes are
conducted through several complicated steps, the anode can deliver
most of its capacity below 1.0 V vs. Li/Li+ [77,78]. However, some Ge
compounds under consideration deliver their capacities at much higher
potentials (Table 1).
Li et al. embedded germanium within carbon nanoboxes. The anode
displayed a at plateau at 0.5 V followed by a capacitive behavior up to
1.5 V vs. Li/Li+ [79]. However, the redox system associated with the
delithiation became more well-dened after the rst cycle. They
proposed that after the formation of a SEI during the rst cycle, the
lithiation undergoes distinguishable steps of Li9Ge4Li7Ge2
Li15Ge4Li22Ge5; while the delithiation process occurs in a single step.
Zn2GeO4 has two distinguishable redox couples for the lithiation/
delithiation. The delithiation process occurs at about 0.3 and 1.3 V vs.
Li/Li+, though they tend to merge into each other in the battery
performance [80]. In any case, the anode delivers its delithiation
capacity under 1.5 V vs. Li/Li+.
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Energy Storage Materials 7 (2017) 157180
6. Tin-based materials
Metallic Sn is somehow similar to Si anode; it has a theoretical
capacity of 993 mA h g1 to reach the fully lithiated compound of
Li4.4Sn, and thus, a broad range of Sn-based materials have been
examined as potential anode materials [8193]. The volume expansion
can be as large as 260%. Studies of Sn nanodots embedded in N-doped
mesoporous carbon indicates that the delithiation process undergoes
smoothly in a potential window of 01.3 V vs. Li/Li+ through a
pseudocapacitive behavior [94]. The structural change upon cycling
noticeably aect the delithiation process to occur in a broader range of
potential, but the lithiation remains almost intact upon cycling.
In addition to metallic Sn, other tin compounds can also be
employed as an anode material. However, the overall reaction is
similar as metallic Sn is formed. For instance, when utilizing tin oxide,
it is rst reduced to Li2O and metallic Sn, which further reacts to form
LixSn (0x4.4) [95].
The family of various tin oxides has shown a promising potential as
an anode material [95]. They can be easily synthesized by hydrother-
mal route while the morphology can be controlled by the synthesis
conditions. Depending on the lattice structure and morphology, the
anode potential can fall in quite dierent levels (Table 1).
The electrochemical performance of SnO2 is composed of a well-
dened redox system at the low potentials of metallic anode but
accompanied by strong pseudocapacitance due to the metal oxide
pseudocapacitive behavior. Therefore, a SnO2 anode can deliver a
signicant capacity at low potentials [96], but overall, this region can
be merged to a long pseudocapacitive behavior over the potential range
of 03.0 V vs. Li/Li+ [97,98].
Tin sulde exists in various forms such as SnS, SnS2, Sn2S3, Sn3S4,
A. Eftekhari
Fig. 9. (a) Representative CV curves of the CuO nanosheets/carbon cloth at a scan rate of 0.1 mV s1 between 0.01 and 3 V vs. Li/Li+. (b) Charge-discharge curves for the 1st, 2nd, 5th,
50th and 100th cycles in the potential range 0.013 V at a current rate of 500 mA g1. Reproduced with permission from Ref. [125]. Copyright 2016, Elsevier.
and Sn4S5, from which SnS2 is the most common material for the LIB
anodes. The performance is similar to that of metallic Sn, as the
delithiation can be mainly completed below 0.8 V vs. Li/Li+ [99].
Like tin oxide and sulde, tin selenide in the form of hexagonal
SnSe2 and orthorhombic SnSe is also a promising anode material.
Delithiation occurs at a fairly low potential below 1.0 V vs. Li/Li+
(Fig. 8). As a common approach, carbon-based nanocomposites are
used to distribute the electroactive material over a high surface area
matrix. This provides sucient spaces to overcome the intrinsic
volume expansion while making the electroactive material more
electrochemically accessible to reduce the slow solid-state diusion,
which is benecial in favor of a better rate capability. However, the
carbon nanomaterial simply contributes a pseudocapacitance to the
overall electrochemical performance; a higher capacity is achieved but
over a wider range of potential, which is not favorable for a battery
performance. In most cases, the carbon (pseudocapacitive) contribu-
tion to the overall capacity is in an unfavorable range. For example,
doping SnO2 with carbon can increase the delithiation capacity by 40%,
but in both cases, a specic capacity of ca. 1000 mA h g1 is obtained
below 1.8 V vs. Li/Li+, and the additional 400 mA h g1 is achieved at
higher potentials (1.8 3.0 V) [100], which is not desirable for an
anode material. Both the CVs and galvanostatic proles in Fig. 8 clearly
show that the carbon compositing component does not aect the SnSex
electrochemical performance. Instead, an addition electrochemical
activity, which is of pseudocapacitive nature, is added at the potential
range of 1.03.0 V vs. Li/Li+. Note that the reduction peak appears at
subsequent cycles in the case of SnSex/carbon composite is not a new
phenomenon, and the SnSex decomposition peaks disappear slower in
the presence of carbon component [101].
7. Antimony-based materials
Sb is a neighbor of Sn, which has been widely considered as a
potential anode material in the elemental form or through its basic
compounds [102110]. Sb can facilitate the lithiation/delithiation at a
relatively low potential, but like similar reactive elements, the major
problem of Sb anode is the volume expansion and structural change. A
common approach for overcoming the volume change is to include an
inactive metal as a conductive matrix [111113]. Among possible
choices, Cu2Sb has shown promising results with good cyclability as the
original structure can be regenerated in the course of lithiation/
delithiation [114]. On the other hand, Cu2Sb can be directly synthe-
sized onto the current collector via electrodeposition [115,116].
Manthiram and his coworkers have demonstrated the applicability of
Cu2Sb in the conventional porous electrode design [117120]. Cu2Sb
shows a series of redox systems characterized by several peaks in the
cyclic voltammetry, but these peaks are very close, and thus, the
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Energy Storage Materials 7 (2017) 157180
delithiation plateaus are along each other in a narrow potential window
of 0.91.1 V [121]. Similar behavior can be observed for the AlSb alloys
[122].
The combination of the elements of interest reviewed above can
gain their advantages while overcoming some disadvantages. A possi-
ble candidate is SnSb, which has been successfully employed as an
anode material [110,123]. As can be expected, the lithiation and
delithiation processes undergo several complicated steps, but all under
1 V vs. Li/Li+. Interestingly, the electrochemical performance is
signicantly dierent for sodiation and desodiation for sodium-ion
batteries, but still, all the processes occur under 1 V vs. Na/Na+ [124].
Walter et al. tested a full cell made of SnSb anode and LiCoO2 cathode,
and the cell performance was somewhat comparable with the com-
mercial LIBs delivering a voltage gradually declining between 3.5
2.7 V [124].
8. Metal oxides
CuO is one of the few metal oxides which deliver a well-dened
redox system at very low potentials. The electrochemical behavior is
associated with a weak redox system at high potentials (ca. 2.4 V vs. Li/
Li+) and a strong lithiation/delithiation redox at ca. 0.2 V vs. Li/Li+
(Fig. 9). There are also tiny peaks in between, which provide a
pseudocapacitive behavior over a broad range of potential. The
galvanostatic proles exhibit a plateau in the range of 0.20.9 V vs.
Li/Li+ with an excellent cyclability [125]. The capacity fading is mainly
associated with the redox system at high potentials or the middle
pseudocapacitive, as the delithiation at low potentials, which covers
80% of the anode capacity, remains intact in the course of cycling
(Fig. 9b).
Nevertheless, Mohapatra et al. investigated the electrochemical
behaviors of two types of CuO porous materials [126]. While both
showed two distinctive pseudocapacitive behaviors at the potential
ranges of 02.3 and 2.33.0, the intensity of these regions was highly
dependent on the morphological structure. In general, the exact
electrochemical performance of electroactive materials such as these
transition metal oxides cannot be precisely predicted as the redox sites
with dierent reactivities can be formed via various synthesis routes.
Manganese oxide anode undergoes a conversion mechanism, which
is quite dierent from the straightforward intercalation of similar
cathode materials.
MnOx+2xLi++2xe=Mn+xLi2O
The theoretical capacity and redox potential directly depend on the
Mn/O ratio [127129]. MnO also can conduct the delithiation under
1.5 V vs. Li/Li+, though this performance is highly dependent on the
material structure [130133]. On contrast, Mn3O4 displays mostly
A. Eftekhari
Fig. 10. Possible formation of various intermediates in the course of lithiation/delithiation of a Mn-based anode. Reproduced with permission from Ref. [136]. Copyright 2013, Royal
Society of Chemistry.
pseudocapacitive behavior due to the existence of mixed-valence
manganese sites [134], though a at plateau due to the corresponding
redox system might be still distinguishable [135]. In this case, the
redox sites have dierent reactivities resulting in the electrochemical
behavior over a broad range of potential.
It should be taken into account that the mechanism of lithiation/
delithiation in an anode process is usually more complicated than
similar cathode performance, due to the possible structural changes at
low reductive potentials. The reaction at less positive potentials is
usually complicated for anode materials resulting in the formation of a
series of intermediates. For example, Lowe et al. discussed the
complexity of Li intercalation/deintercalation into LiMn3O4 [136].
Fig. 10 exhibits possible mechanism for the formation of Mn-based
species during the corresponding lithiation/delithiation.
Iron oxide has attracted considerable attention as an anode
material due to its abundance and low cost. The voltammetric peak
of delithiation occurs at 1.5 V vs. Li/Li+, and thus, the delithiation
process can be conducted below 2.0 V vs. Li/Li+ [137]. Utilizing carbon
conductive agent seems essential due to the low electrical conductivity
of Fe3O4. However, the presence of carbon component does not
signicantly change the delithiation potential or the specic capacity
[138]. If the carbon nanomaterial does not contribute a huge capaci-
tance due to an extremely high surface area, the presence of an excess
amount of carbon (e.g., over 10%) is harmful and reduces the overall
capacity [139].
TiNb2O7 has been recently introduced as a promising anode
material because its 33 crystal structure provides more open channels
for the Li diusion and its theoretical capacity is 388 mA h g1 [140].
Although the electrochemical behavior is involved with the redox
systems of Ti3+/Ti4+ and Nb3+/Nb5+, the delithiation occurs in a
relatively narrow potential window between 1.21.8, composed of
two merging plateaus [141143]. The capacity fading is still a major
issue of this anode material, which can be overcome by common
approaches such as metal doping [141].
NiO facilitates the delithiation via both a well-dened redox system
and pseudocapacitance. As a result, about half of the capacity is
delivered via a at plateau, but the distance between the lithiation
and delithiation potentials is massive. The lithiation occurs at poten-
tials less positive than 1 V, while the delithiation at more positive than
2 V [144].
Huang et al. synthesized a single phase Ni0.9Zn0.1O with high
crystallinity. Therefore, one could expect a well-dened electrochemi-
cal behavior [145]. Cyclic voltammetry exhibited a redox system with
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Energy Storage Materials 7 (2017) 157180
sharp peaks but large peak-to-peak separation. However, the CV was
not similar to the galvanostatic proles. While the lithiation peak
appeared in 1.2 V, the galvanostatic lithiation showed a at plateau at
0.5 V. On the other hand, the delithiation peak in the CV appeared at
2.3 V, but the galvanostatic delithiation was almost a pseudocapacitive
diagonal line in the range of 03.0 V. Nevertheless, depending on the
delithiation rate, the at plateau corresponding to the 2.3 V redox can
appear (see Table 1). The interesting point is that this observance is
limited to middle rates only, as the galvanostatic proles tend to be
pseudocapacitive at low and high rates.
MoO2 with a distorted rutile structure has a theoretical capacity of
209 mA h g1 for the stoichiometric composition of LiMoO2 [146
148]. The corresponding anode performance is composed of two
distinctive redox couples, and thus, the delithiation occurs at two steps
characterized by fairly at plateaus at about 1.4 and 1.7 V vs. Li/Li+.
The major issue of LiMoO2 is a phase transformation from monoclinic
to orthorhombic when x is between 0.4 and 0.8 [149]. However, the
electrochemical performance of Li2MoO3 is completely dierent dis-
playing an entirely pseudocapacitive delithiation over a wide potential
window, while the lithiation process occurs only at less positive
potentials below 0.7 V vs. Li/Li+ [150].
TiO2 is a common electrochemical material, which has been widely
employed in various systems. Its Li intercalation/deintercalation redox
system is also straightforward though its redox potential is slightly high
for an anode material. Mesoporous TiO2 spheres exhibited a well-
dened lithiation characterized by a at plateau at 2.0 V vs. Li/Li+
while having an excellent cyclability of the intercalation anode materi-
als [151]. Anatase has shown a well-dened electrochemical perfor-
mance with a at plateau for the delithiation at 1.8 V vs. Li/Li+ where
the overpotentials between the lithiation/delithiation at plateaus were
in order of 100 mV [152,153]. In a comparison of TiO2 bers and
particles, Damien et al. showed that a composite of TiO2 bers/
particles exhibits the best electrochemical performance with the high-
est specic capacity and lowest overpotentials between the lithiation
and delithiation plateaus [154].
Li et al. introduced PbLi2Ti6O14 as a novel anode material [155].
Fig. 11 shows that PbLi2Ti6O14 has the characteristics of the intercala-
tion anode materials delivering an excellent battery performance. Both
the CV and galvanostatic data suggest that the system under con-
sideration has two well-dened redox systems, which are very close
with least overpotentials. The schematic of the intercalation/deinter-
calation illustrates how the lithiation and delithiation processes are
conducted reversibly.
A. Eftekhari Energy Storage Materials 7 (2017) 157180

Fig. 11. (a) The 1st, 2nd and 100th charge/discharge curves of PbLi2Ti6O14. (b) CVs of PbLi2Ti6O14 recorded at a scan rate of 0.1 mV s1. (c) Crystal structure of PbLi2Ti6O14, lithium
ions insertion in 8f sites at the rst step, lithium ions insertion in 4a sites at the second step, lithium ions insertion in 4b and 8c sites at the third step. (d) Evolution of lattice parameters
(a, b, c and V) during charge/discharge process. Reproduced with permission from Ref. [229]. Copyright 2016, Elsevier.

Fig. 12. The prole of the electrochemistry with schematics representing the phase distribution at each stage of lithiation of RuO2. Reproduced with permission from Ref. [202].
Copyright 2013, Nature Publishing Group.

In the mixture of metal oxides, each redox center can display its middle range of potential.
performance at the given potential. This results in the formation of
multi-step plateaus [156]. If the redox potentials of the metal oxide
9. Intercalating lithium metal oxides
components are close to each other, it is possible to limit the potential
within a narrow potential window, which can be acceptable for the
Among the intercalation anode materials, Li4Ti5O12 is one of the
practical applications. Fig. 12 shows the battery performance of a
best choices for delivering a at plateau [157,158]. This anode can
simple mixture of Mn3O4, Fe3O4, and Co3O4. Although the plateaus
deliver a stable constant potential of ca. 1.55 V vs. Li/Li+ with a
associated with each redox center is distinguishable during the lithia-
theoretical capacity of 175 mA h g1, which is practically achievable
tion, the delithiation process is composed of a semi-at plateau at a
[159]. Owing to its rigid lattice structure, Li4Ti5O12 undergoes no

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A. Eftekhari
volume change in the course of lithiation/delithiation, which made it
famous because of its zero strain property [160]. Moreover, the
overpotentials for the charging and discharging processes are fairly
low, as the lithiation and delithiation at plateaus have only 72 mV
dierence, which can even be reduced further by doping [161,162]. The
dierence between the lithiation and delithiation plateaus is directly
proportional to the C-rate, as the peak-to-peak separation in the cyclic
voltammetry to the potential scan rate [163].
Although Li4Ti5O12 is famous because of its well-dened electro-
chemical behavior, there are reports of unusual performance. For
instance, Yang et al. synthesized a conventional Li4Ti5O12 via a solid-
state reaction; the pristine Li4Ti5O12 and its carbon-based composites
displayed two separate redox systems at about 0.4 and 1.7 V vs. Li/Li+
[164]. Since the cathodic process of the second peak (i.e., the main
redox system of Li4Ti5O12) was very weak, the delithiation occurred at
an extremely low potential. Therefore, the potential dierence between
the lithiation and delithiation plateaus was as large as 1 V. This
performance is similar to that of Li2ZnTi3O8 [165].
Lithium vanadium oxide is an intercalation anode material with a
high theoretical capacity of 394 mA h g1. The delithiation process
mainly occurs in a potential window of 0.31.5 V composed of two
redox systems characterized by dierent plateaus appearing between
0.31.0 and 1.01.5 V vs. Li/Li+ [166,167].
10. Metal suldes and phosphides
Nickel sulde (Ni3S2) has a well-dened redox system, though the
anodic and cathodic peaks are distinguishable separated (Fig. 13).
However, the peak-to-peak separation is still smaller than most anode
Fig. 13. (a) CVs of a Ni3S2/Ni electrode, and (b) galvanostatic proles. Reproduced with
permission from Ref. [168]. Copyright 2016, Elsevier.
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Energy Storage Materials 7 (2017) 157180
materials, and thus, the battery performance is accompanied by two at
plateaus for the lithiation and delithiation, which are 400 mV apart.
The interesting feature of nickel compounds is that nickel foam is now
a potential substrate with high electrochemically accessible area [168].
Therefore, nickel-based electroactive materials can be directly growing
on the nickel substrate, where there is no need for a binder or current
collector.
Iron sulde conducts the delithiation process at a potential of 1.7 V
vs. Li/Li+, and thus, the anode performance is accompanied by a at
plateau [169]. VS2 has an asymmetrical redox system, while the
lithiation mainly occurs between 0 and 2.0 V vs. Li/Li+, the delithiation
occurs at noticeably high potentials in the range of 1.53.0 V vs. Li/Li+
[170].
CoNi2S4 has two redox systems at about 0.3 and 1.7 V vs. Li/Li+;
while the high voltage redox system is weak and accompanied by a
large overpotential, the low potential redox system can deliver excellent
battery performance [171]. The rst redox system facilitates an anode
performance achieving 70% of the overall capacity under 0.5 V, and the
rest of the capacity can be achieved at 2.0 V vs. Li/Li+ by the second
redox system. Nevertheless, there are reports on the dominance of the
second redox system, and thus, the delithiation capacity is mostly
delivered at 2 V vs. Li/Li+ [172]. Such controversial reports suggest
that the battery performance of such electroactive materials are very
sensitive to the structure (both lattice and morphology) because of the
active composition between the dierent mechanisms for the lithia-
tion/delithiation.
Li et al. deposited Zn3P2 nanowires on a carbon cloth [173]. The
anode could deliver its delithiation capacity of almost 1200 mA h g1
fairly under 1.0 V vs. Li/Li+. The anode was also examined in a full cell
employing a LiFePO4 cathode, and the full battery delivered a steady
voltage declining from 3.3 to 2.8 V. Sn3P4 anode delivers a specic
capacity of over 1000 mA h g1 in the potential window of 0.51.5 V
vs. Li/Li+ [174]. The cyclability is poor during the rst 10 cycles, but no
noticeable capacity fading after the 30th cycle.
Similar results have also been reported for iron phosphide as the
anode could deliver a delithiation capacity of over 600 mA h g1 mainly
through a at plateau around 1.0 V vs. Li/Li+ [175]. The anode loses
30% of its capacity during the rst 10 cycles, but afterward, the capacity
fading is gradual. The specic capacity is directly related to the P
content and structure, as can substantially vary for similar electrodes.
This can somehow vanish the 1.0 V plateau. In general, metal suldes
deliver a relatively high specic capacity at a low voltage, but the initial
cyclability is poor due to the essential structural changes. Since metal
phosphides are novel candidates for the LIB anodes, the research is still
at its preliminary stage utilizing pristine electroactive materials.
However, stabilizing the anode structure by the common methods
can signicantly improve the cyclability of metal phosphides to make
them practical candidates for anode materials.
11. Transition metal hexacyanometallates
Prussian blue and its analogs (transition metal hexacyanoferrates)
are among the attractive battery materials due to their excellent
cyclability owing to the rigid cage-like lattice structure. They exhibit
excellent performance for the K intercalation/deintercalation, and
thus, are still the most common cathode material for potassium-ion
batteries [176,177]. Since the operating potential is directly dependent
on the redox systems of the transition metals, the electrode potential
can be adjusted by changing the transition metal. Sun et al. reported
that titanium hexacyanoferrate can have an extremely low redox
potential suitable for the LIB anodes [178]. Fig. 14 shows that anode
performance and the electrode potential as a function of the depth of
lithiation/delithiation. The results suggest that 90% of the electrode
capacity can be achieved by delithiation under 1.0 V vs. Li/Li+.
The interesting features of this class of electroactive materials are
that they normally deliver a well-dened redox system and excellent
A. Eftekhari Energy Storage Materials 7 (2017) 157180

Fig. 14. (a) The 2nd (black), 10th (red) and 50th (blue) galvanostatic proles of Li/TFCN half-cell. (b) The dependency of the electrode potential to the degree of lithiation/delithiation.
Reproduced with permission from Ref. [178]. Copyright 2016, Elsevier. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this
article.)

cyclability owing to the rigid lattice structure. In addition to the increasing the slope of the at plateaus in the charge/discharge
common hexacyanoferrates, other transition metal can also be em- proles).
ployed in designing this cage-like architecture. It has been reported Many candidate anode materials mainly show pseudocapacitive
that other transition metal hexacyanometallates can have noticeably behaviors. This does not make them unsuitable for electrochemical
low potentials, which make them suitable materials as an anode. For energy storage, but this dierence should be carefully taken into
instance, changing the lattice arrangement from chromium hexacya- account in designing the practical applications. Owing to the rapidly
noferrate (Cr{Fe(CN)6}) to iron hexacyanochromate (Fe{Cr(CN)6}) growing interest in hybrid battery/supercapacitor systems [183,184],
transforms a cathode material into an anode material with a well- this class of anode materials can be of particular interest for specic
dened redox system below 2.0 V vs. Li/Li+ [179], which has also been applications, but they are not appropriate candidates for conventional
employed to build a full battery [180]. lithium-ion batteries. Some authors appropriately classify them as
pseudocapacitive anode materials [185].
MoS2 is, for example, one of the common candidates for LIB anode
12. Pseudocapacitive anode materials
materials. However, MoS2 or its carbon-based nanocomposites exhibit
a pseudocapacitive behavior as characterized by diagonal lines in the
Since the birth of supercapacitors, the actual boundary between
galvanostatic proles during both lithiation and delithiation process
batteries and supercapacitors were subject to debates [181,182].
over a potential window of 02.5 V vs. Li/Li+ [186], though the prole
However, this concept is now of practical importance.
is bent to form a at plateau between 2.0 and 2.5 V due to the
Pseudocapacitance, as the name suggests, is not a capacitance by
corresponding redox system [187,188]. The latter transformation is
nature. Instead, it is the same old redox system displaying an
highly dependent on the material structure but should be distinguish-
electrochemical behavior, which looks like double layer capacitance.
able in general. The inuence of pseudocapacitive contribution is
The key dierence between and a pseudocapacitive material and a
evident when comparing a bulk MoS2 anode with a mesoporous
battery material is that the latter is based on a well-dened redox
MoS2 with a high surface area; while the delithiation capacity is almost
system, but the former has a collection of redox sites which participate
the same, the former shows a at plateau at 2.2 V vs. Li/Li+ but the
in the electrochemical reactions at various potentials. Therefore, the
latter only pseudocapacitive behavior [189]. It has been discussed that
electrochemical behavior of a battery material is characterized by a
the lattice structure of MoSe2 provides a better opportunity for the
sharp peaks in cyclic voltammetry and at plateaus in charge/discharge
appearance of the at plateau, while the tendency of MoS2 is toward a
proles; but that of a pseudocapacitive material is characterized by a
pseudocapacitive behavior [190].
broad peak or several overlapped peaks (as wide as the potential
Although cyclic voltammetry of Fe2O3 suggests the occurrence of a
window) or diagonal lines in the charge/discharge proles. In a general
well-dened (though with a large peak-to-peak separation) redox
comparison (though it varies from cases to case), battery performance
couple, the galvanostatic proles of the anode performance is over-
is based on solid state diusion in which the counter ion is smoothly
shadowed by the pseudocapacitance, and the overall performance
diusion among the equal redox sites across the lattice, while
seems like a pseudocapacitive behavior over a wide range of 03 V
pseudocapacitance is based on reaction usually at the surface or sub-
vs. Li/Li+ [191].
surface.
Various transition metal oxides such as WO3 [192194], Co3O4
In a battery material, all the redox sites within the crystal structure
[195197], and so forth conduct the delithiation process through a
are reacting at the same potential. Increasing the material crystallinity
well-dened pseudocapacitive behavior over a wide potential window
makes the redox sites more similar, and as a result, sharper peaks are
of 03.0 V vs. Li/Li+. However, their lithiation process usually occurs
observed in the XRD patterns as well as sharper peaks in the cyclic
at a constant potential following a well-dened redox [197]. Nickel
voltammetry (or atter plateaus in the charge/discharge proles). This
oxide exhibits a pseudocapacitive-like performance over 03.0 V
is the reason that single-crystals normally show better well-dened
despite its redox system, but the at plateau appears above 2.0 V vs.
battery performance at suciently low charge/discharge rates (because
Li/Li+ when compositing the electroactive material with carbon [198].
they have poor rate capacity due to long solid-state diusion lengths).
This is due to the failure of the low electrical conductivity of such metal
However, the redox sites at the surface are non-uniform due to the
oxides. However, it should be taken into account that most of the
crystal defects, dangling bonds, etc. Increasing the surface to bulk ratio
corresponding redox systems, which are associated with the transition
improves the rate capability by reducing the solid-state lengths, but the
metal valences, occurs at fairly positive potentials (typically over 2 V vs.
battery performance tends to a pseudocapacitive behavior (as can be
Li/Li+). Depending on the material structure, such metal oxides can
characterized by broadening the peaks in cyclic voltammetry and

169
A. Eftekhari
Fig. 15. The rst three galvanostatic charge/discharge curves for LiTiOPO4@C cycling at the rate of C/20 in dierent potential ranges: (a) 0.53.0 V and (b) 0.13.0 V. The x denotes
the amount of the involved lithium ions as the theoretical capacity of LiTiOPO4@C electrode material is 161.5 mA h g1 which corresponds to the uptake of one lithium ion. Reproduced
with permission from Ref. [201]. Copyright 2015, Elsevier.
show a at plateau at a high potential range (e.g., 2.02.5 V vs. Li/Li+)
instead of a pseudocapacitive behavior [199].
Mixed metal compounds normally tend to deliver a pseudocapaci-
tive behavior even in the presence of distinguishable redox systems
because of the presence of complicated redox sites which may
participate in the electrochemical reactions at quite dierent potentials.
For example, Cu2ZnSnS4 [200], and similar compounds have active
delithiation over a broad range of potential up to 3.0 V vs. Li/Li+.
Fu et al. reported quite interesting experimental results regarding a
peculiar change of the ideal battery performance of LiTiOPO4@C anode
characterized by a at plateau to ideal pseudocapacitive behavior
simply by extending the lithiation potential window [201]. When the
lower cuto is 0.5 V vs. Li/Li+, the lithiation occurs at a constant
potential of 1.5 V vs. Li/Li+, and the delithiation during the reverse
scan at a similar constant potential (Fig. 15). However, if continuing
the lithiation process in the potential window of 0.50 V, a huge
amount of lithium can be stored by the anode material. The interesting
point is that the delithiation behavior is no longer similar to the
characteristic battery performance of LiTiOPO4 or similar intercalation
materials. In this case, the system can reversibly store 2.5 mol of Li as
Li2.5TiOPO4. However, the battery performance is utterly transformed
into an ideal pseudocapacitive behavior. Although such phenomenon
has not been reported for this class of intercalation materials in
general, these experimental data reveal the possible of easy transfor-
mation between the battery performance and the pseudocapacitive
behavior in electroactive materials.
In fact, the lithiation process undergoes several stages, which can
control the anode electrochemistry. In a similar context, Grey and her
coworkers modeled the various structures of the anode and its SEI
formed during the lithiation of RuO2 [202]. As illustrated in Fig. 12, the
chemical conversion at low reductive potentials causes the formation of
new materials, which may undergo a dierent pathway during the
delithiation.
13. Low voltage pseudocapacitive anode materials
There are some candidate materials, which display a pseudocapa-
citive behavior but within a more negative potential window making
them potential anode materials. For instance, mixed metal oxide
spinels can show a well-dened pseudocapacitive behavior in the
potential range of 02.0 V vs. Li/Li+ [203209]. As a matter of fact,
the well-dened redox disappears in time while the pseudocapacitive
behavior remains almost intact [210]. However, this is not a general
statement for mixed metal oxide spinels, as it is highly dependent on
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Energy Storage Materials 7 (2017) 157180
the corresponding redox systems [211214].
In the case of CoFe2O4 nanowires, the main portion of the specic
capacity during the delithiation was achieved under 1.0 V vs. Li/Li+,
which is at the level of reactive anode materials [215]. Although the
lithiation process undergoes several steps as can be characterized by
fairly distinguishable peaks in cyclic voltammetry, the delithiation
occurs in one step, and this is the reason for the excellent battery
performance of CoFe2O4 with no noticeable overpotential. Again, it is
not possible to generalize the delithiation potential of this class of
materials, as it is highly dependent on the material structure. It has
been reported that the delithiation from CoFe2O4 nanotubes prepared
by electrospinning occurs mostly between 1.3 and 2.2 V vs. Li/Li+
[216].
Like most of the metal oxides, SnO2 has a pseudocapacitive
behavior, but the delithiation can be completed within the range of
02.0 V vs. Li/Li+. However, compositing with various types of carbon
is a common approach to enhance the electrochemical accessibility of
the electroactive SnO2 and improve the electrical conductivity between
the electroactive particles. In the resulting nanocomposite, which has a
high specic surface area, the carbon nanomaterial contributes a
capacitance to the overall electrochemical performance. As a result,
the specic capacity is improved but over a wider potential window of
03.0 V vs. Li/Li+ [217]. Similar behavior can be observed for other
anode materials too [218], and this is indeed the regular role of carbon
additives on the anode performance. In a comparison between SnO2, C,
and SnO2/C electrodes, the galvanostatic proles of the SnO2/C
nanocomposite are more similar to those of pure C rather than those
of pristine SnO2 [217]. In a sense, the SnO2/C nanocomposite is simply
a sum of the electrochemical behaviors observed for the composite
components.
There are also cases in which the delithiation prole seems
pseudocapacitive but in a narrow potential window, but these cases
should be somehow considered as at plateaus with a slope rather than
pseudocapacitance. However, it is dicult to draw a line between these
two behaviors. Liu et al. synthesized a core-shell architecture of ZnO@
C in which the carbon coating was smooth to form uniform nano-
spheres rather than increasing the specic capacity [219]. The anode
could deliver a specic capacity of over 600 mA h g1 at 82.5 mA g1
under 1.0 V vs. Li/Li+. Geng et al. examined NaLaTi2O6 as a potential
anode material [220]. Although the specic capacity was low at the
level of 100 mA h g1, the majority of this capacity was delivered for
delithiation under 1.0 V vs. Li/Li+.
A. Eftekhari
14. High voltage anode materials
A broad range of high-voltage anode materials is subject to
investigation, which can deliver the delithiation process at a potential
window of 2.03.0 V vs. Li/Li+. Obviously, these anode materials
cannot be employed in conventional LIBs, and no wonder that such
materials are considered as both anode and cathode materials. For
instance, MnO2, having a well-dened redox system and pseudocapa-
citance at fairly high potentials [3,4] is suitable for the cathode, but has
also been employed as an anode material too [221]. The misleading is
the charge/discharge labeling described above. They typically have
huge overpotentials for the lithiation or delithiation or both, as can be
characterized by a large gap between the lithiation and delithiation
plateaus. This means that an extremely negative potential is required
for the lithiation. When labeling the lithiation process as discharge, it
seems that it is favorable as the lithiation plateau has been shifted
towards more negative potentials.
15. The impact of morphology on the battery performance
Morphology has an enormous impact on the battery performance of
anode materials, as the surface structure plays particular roles in
various systems. In common anode materials, three categories should
be dened in which the morphology has distinguishable inuences:
intercalation mechanism, conversion mechanism, and compositing
with a high surface area material.
In an intercalation system, the specic surface area denes the ratio
of the surface reaction to the solid-state reaction, as the latter is
controlled by the rate-determining step of solid-state diusion [7]. This
eect can be seen in the rate capability of cathode materials (i.e., a
better rate capability for nanostructured cathodes), but the case is more
complicated for anode materials. In the latter case, surface redox
systems with dierent levels of energies result in the formation of a
strong pseudocapacitive behavior over a wide range of potential. For
example, FeNbO4 has also been employed as an anode material, which
can deliver a specic capacity of over 200 mA h g1 under 1.0 V vs. Li/
Li+ [222]. Increasing the specic surface area by reducing the particle
size from micro- to nano-scale does not aect the specic capacity
under 1.0 V but results in the appearance of strong pseudocapacitive
performance in the potential window of 1.02.0 V vs. Li/Li+.
Therefore, the overall capacity of nanosized FeNbO4 is doubled in
comparison with microparticles [222].
It should be taken into account that morphology is closely
entangled with crystallinity in the intercalation materials. The arrange-
ment of the lattice units is actually building the overall morphology.
While the lattice structure is dictating the accessibility and energy of
the redox sites facilitating the intercalation process, the nanoscale
morphology controls the diusion pathways. Fig. 16 compares a series
of Li4Ti5O12 samples prepared at dierent calcination temperatures.
Thermal treatment at a higher temperature enhances the crystallinity
(Fig. 16a) while the porosity is reduced [223]. This means that the
solid-state diusion is more facile within a crystalline structure but the
electrolyte cannot ow into the solid material. The latter phenomenon
can be recognized from the poor rate capability of the sample
calcinated at high temperature (Fig. 16l). As a result of this competi-
tion, the electrochemical performance is not simply predictable by
controlling the crystallinity and morphology, and these two parameters
should be optimized with respect to the overall diusion process.
In the conversion-based anode materials such as Si, reducing the
particle size enhances the reactivity. Contrary to the intercalation
system, the original lattice structure is not supported to be preserved
in the course of the anode reaction. Thus, regardless of the particle size,
the whole particle should participate in a conversion mechanism, which
will be faster for smaller particles. For such anode materials, nanos-
tructuring usually improves the specic capacity without altering the
overall battery performance [47]. Such behavior has been observed for
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Energy Storage Materials 7 (2017) 157180
various conversion-based anode materials such as metal oxides
[149,224].
As mentioned earlier, there are many cases in which compositing
the electroactive material with a carbon component simply results in a
pseudocapacitive contribution to the overall capacity over a high range
of potential [100,218,225]. Of course, the presence of carbon can
suppress the volume expansion, and the cyclability is improved as a
result of the attachment of the electroactive material to the solid carbon
matrix. However, carbon does not normally improve the specic
capacity of the original electroactive material. A possible misleading
is that the specic capacity is usually calculated according to the mass
of the electroactive material rather than the mass of the entire
composite.
16. Classication
It should be taken into account that the anode process is delithia-
tion when using a battery, regardless of labeling. Therefore, the
delithiation should be conducted at a less positive potential as much
as possible. The lithiation voltage is irrelevant to the full cell operating
voltage. Furthermore, a dierence between the lithiation and delithia-
tion potentials is the overall overpotential of the redox system. This is
the excess energy required for charging the battery. When the lithiation
occurs at 0.5 V vs. Li/Li+ and the delithiation occurs at 2.5 V vs. Li/Li+.
This means that in a regular setup with a typical LiCoO2 cathode, we
need a power supply of 4 V to charge the battery, but when using the
battery, it only delivers 2 V.
In general, the anode materials can be classied as listed in Table 1
with into the following classes
(i) Low-Voltage in which the majority of the delithiation capacity is
delivered under 1.0 V vs. Li/Li+. This category typically covers the
reactive elements of the IV and V groups of the Periodic Table.
(ii) Mid-Voltage in the range of 1.02.0 V, which covers a broad range
of intercalation materials including transition metal oxides and
chalcogenides.
(iii) High-Voltage in which the majority of the delithiation capacity
occurs over 2.0 V.
(iv) Wide Potential Window normally delivering a pseudocapacitive
behavior over the potential range of 03.0 V and includes a wide
variety of materials with nanostructured and mixed valences.
All the common materials in these categories might be of interest
for electrochemical energy storage, but a proper classication can
better lead us in this area of research. Therefore, similar anode
materials can be appropriately compared to take practical steps for
the improvement of the current candidates to meet the practical
requirements.
17. Redox potentials of the anode materials
The classication made above is merely based on the operating
voltage and does not reect the type of anode mechanism involved.
Cathode materials are mostly based on the intercalation mechanisms,
and thus, have similar thermodynamics. The electrode potential can be
thermodynamically expressed as
FE0 (x ) = G(x ) = H(x )TS(x )
where F is the Faraday constant, E the electrode potential, G the
Gibbs free energy, H the enthalpy, T temperature, and S the entropy.
The electrode potential changes during the lithiation/delithiation
process according to the changes in H(x) and S(x) as a result of
the changing Li concentration (x). In an intercalation mechanism such
as the performance of a graphite anode, the changes of H(x) and
S(x) can be predicted theoretically [226,227]. However, the case of
conversion-based anode materials is much more complicated, as the
A. Eftekhari Energy Storage Materials 7 (2017) 157180

Fig. 16. (a) XRD patterns of a series of Li4Ti5O12 samples prepared hydrothermally and subjected to thermal treatment. TEM and galvanostatic proles of the samples calcinated at (b,
c, d) 500, (e, f, g) 500, (h, i, j) 600, and (k, l) 700 C. The hydrothermal solvent was 60% ethanol in water, except the rst sample (b, c, d) which was without ethanol. The sample codes in
the XRD patterns (a) indicates the ratio of ethanol and the calcination temperature, respectively. Reproduced with permission from Ref. [223]. Copyright 2014, Royal Society of
Chemistry.

entire anode is subject to change. In addition to the substantial changes
in H(x) as a result of a chemical reaction (rather than the Li
intercalation into a solid lattice), one can anticipate the crucial changes
in S(x) as the entire structure is subject to change upon lithiation or
delithiation. This is the reason that conversion-based anode materials
have a less tendency to deliver a at plateau, as it is common for the
intercalation materials (see Table 1). Fig. 17 compares the structural
changes upon Li intercalation into graphene (as a typical intercalation
anode) and two Si/C nanocomposites (as a typical conversion anode).
When the ratio of Si (i.e., the anode material) is low, still the structural
changes is much more complicated than a regular intercalation system.
For high ratios of Si, the system undergoes severe structural changes

172
A. Eftekhari
Fig. 17. Schematic models illustrating the structural changes upon Li intercalation into (a) graphite, (b) Si/C nanocomposite with a low ratio of Si, and (c) Si/C nanocomposite with a
high ratio of Si. Reproduced with permission from Ref. [45]. Copyright 2016, Nature Publishing Group.
including volume expansion. Bearing in mind that the latter system is
much simpler than pure anode materials under investigation, this basic
scheme illustrates how much dicult is to calculate the thermodyna-
mical parameters for these anode materials in the course of lithiation/
delithiation.
Graphite is indeed an exceptional low-potential intercalation ma-
terial, as almost all intercalation materials have much higher redox
potentials. In high-voltage intercalation materials (including cathode
materials), the intercalation of Li ions facilitates the redox system
between two oxidation state of a core cation (for example Co3+/Co4+ in
LiCoO2). At the low-potential range ( < 1.0 V vs. Li/Li+), it is unlikely to
nd a redox system without involving a reduction of the core cation to
its elemental form. Hence, most of the anode materials undergo a
conversion mechanism. The essential structural changes accompanied
by severe volume changes are undesirable for the practical perfor-
mance, but having the less positive potentials is attractive. It is worth
noting that the electrode potential thermodynamically depends on the
base reaction, and not all conversion-based electrode materials can
deliver a low potential. There are elemental reactions with Li, which are
employed as the redox system for the cathode side such as lithium-
selenium battery [228].
The complexity of the thermodynamics of the pseudocapacitive
materials described above is even more severe because these materials
are based on a series of redox systems spread over a wide range of
potential. On the other hand, the redox systems are mostly based on
surface adsorption instead of diusion within the lattice. In a crystal-
line material, the unit cells are fairly similar and the redox sites can be
considered similar. However, the adsorption is highly sensitive to the
chemical and structural irregularities of the surface.
18. Designing the anode materials
Like cathode materials, three requirements for anode materials
should be met for the practical development: reasonably low potential,
specic capacity, and cyclability. None of them can be totally sacriced
in favor of others. Graphite is the dominant anode material in the
current LIBs, which can deliver a good performance at a potential
range close to that of Li/Li+ redox. However, graphite has reached its
theoretical capacity, and there is an active quest for nding high
capacity anodes. In this direction, the low potential of graphite is
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Energy Storage Materials 7 (2017) 157180
somewhat sacriced to consider new choices with a higher capability
for Li storage, but sometimes, the low potential requirement is
sacriced too much. The interesting point is that these materials are
indeed a new class viz. pseudocapacitive anode materials. This class of
anode materials is not appropriate candidates for the conventional
LIBs, but they are good choices for new types of electrochemical energy
storage systems such as hybrid battery/supercapacitor.
The importance of this classication is because of the easy
transformation between these classes. For example, most of the low
potential anode materials (e.g., based on IVA group elements) have
poor cyclability due to the essential volume changes in a conversion
mechanism. A practical approach is to mix these materials with carbon
nanomaterials to overcome the overall volume change, but carbon
additives transform a battery performance to a pseudocapacitive
behavior. While the resulting composite has a good cyclability but it
is not longer a low-potential anode material. Therefore, if the aim is to
improve the battery performance of a low-potential anode material, the
delithiation redox potential should be monitored when utilizing any
approach.
19. Perspective
The present manuscript aims to clarify that there are complicated
issues associated with the studies of anode materials, which are not the
case for cathode materials. In half-cell studies, an anode material is
simply examined as a cathode material in respect with a metallic Li
anode in the conventional coin-type cell. However, some points should
be subtly taken into account to make the half-cell studies applicable to
a full-cell.
First, the impact of the potential window on the specic capacity
recorded should be carefully considered. Studies of cathode materials
are usually conducted in a potential window of 2.54.5 V vs. Li/Li+, but
the majority of the specic capacity is delivered at a narrow potential
range around 4 V (for conventional cathode materials such as LiCoO2
and LiMn2O4, while this potential range is around 3.5 V for LiFePO4).
The reason for such a low potential cuto is to inspect the rapid
potential drop indicating that there is no other redox system. In a
similar fashion, anode materials are investigated in a broad potential
window to inspect the main redox potential, but a signicant number of
novel anode materials show a pseudocapacitive behavior over a wide
A. Eftekhari
potential window of 03.0 V. This means that lowering the upper cuto
substantially changes the specic capacity recorded, while a similar
specic capacity will be recorded for the cathode materials if changing
the lower cuto. Similar behavior can be observed for anode materials
delivering at plateaus such as Si or Li4Ti5O12.
Second, the process of interest is the anode delithiation rather than
lithiation. When a LIB is used, the cathode is subject to lithiation and
the anode delithiation. This means that the anode capacity for
delithiation is gained in a practical battery performance. The delithia-
tion capacity is always lower than that of lithiation because an anode
cannot deliver Li-ions more than what it has stored during the battery
charging. Therefore, it is of vital importance to pay particular attention
to the delithiation process.
Third, many of novel anode materials tend to show a pseudocapa-
citive behavior rather than the conventional battery performance
characterized by a at plateau. This is of utmost importance, as this
pseudocapacitive behavior is stronger in the course of delithiation.
While the lithiation process occurs at several stages but delivering
somewhat at plateaus, the delithiation process can be an ideal
pseudocapacitive behavior characterized by a diagonal line in the
galvanostatic proles (usually over a wide potential range of 03.0 V
vs. Li/Li+).
Fourth, the upper limit of the cathode charging is crucially
important, as might be accompanied by the electrolyte instability at
high oxidative potentials. However, reaching the low reductive poten-
tials close to the Li/Li+ redox potential is much more complicated. The
anode material can undergo a conversion mechanism resulting in the
formation of new materials, which may conduct the delithiation
process via a dierent pathway. In fact, choosing the lower cuto of
the potential window can signicantly alter the battery performance of
an anode material.
In general, the classication of anode materials is much more
complicated than cathode materials, which are normally based on
similar intercalation mechanisms with a redox potential around 4.0 V
vs. Li/Li+. Instead, anode materials should be categorized based on the
electrode potential and the redox mechanism. The lack of this
classication causes an inappropriate comparison between anode
materials, which have no connection whatsoever, except their potential
applications (though, some are not even appropriate anode materials).
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