Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016) A2943

0013-4651/2016/163(14)/A2943/8/$33.00 © The Electrochemical Society

Learning from Overpotentials in Lithium Ion Batteries: A Case

Study on the LiNi1/3 Co1/3 Mn1/3 O2 (NCM) Cathode
Johannes Kasnatscheew,a,z Uta Rodehorst,a Benjamin Streipert,a Simon Wiemers-Meyer,a
Rene Jakelski,a Ralf Wagner,a Isidora Cekic Laskovic,a and Martin Wintera,b,∗,z
a MEET Battery Research Center / Institute of Physical Chemistry, University of Münster, 48149 Münster, Germany
b Helmholtz-Institute Münster (HI MS), IEK-12, Forschungszentrum Jülich GmbH, 48149 Münster, Germany

The practically available specific energy of Li ion batteries (LIB) is highly depending on the used specific charge/discharge current,
since the respective overpotentials of each electrode affect the two vital specific energy parameters, specific capacity and voltage.
Focusing on the positive composite electrode as the specific energy bottleneck, the overall nature of the overpotential is discussed
for the LiNi1/3 Co1/3 Mn1/3 O2 (NCM) active material. It is shown that the characteristic overpotentials during charge (delithiation)
and discharge (lithiation) is state of charge (SOC) and depth of discharge (DOD) dependent, respectively. It was demonstrated
that the discharge characteristics are intertwined with the previous charge conditions, particularly with the charging time and the
specific charge capacity. Increasing both in parallel can even lead to a deterioration of the subsequent specific discharge capacity.
Furthermore, Li+ transport pathways within the NCM composite electrode are discussed and their influence on the observed
overpotential evaluated. Changes of the overpotential are found to be mainly associated with changes within the NCM crystal
structure, which is experimentally supported by the correlation of the SOC dependent overpotential with the XRD determined c-axis
lattice parameter. Consequently, the Li+ transport within the active material is mostly responsible for limiting the practically available
specific energy.
© 2016 The Electrochemical Society. [DOI: 10.1149/2.0461614jes] All rights reserved.

Manuscript submitted August 24, 2016; revised manuscript received September 27, 2016. Published November 2, 2016.

For economic exploitation of renewable energy sources, the
development of effective and efficient energy storage devices is
indispensable.1 In this regard the lithium ion battery (LIB) is con-
sidered as key technology thanks to its outstanding characteristics in
terms of high energy density and in most cases high energy efficiency.2
In general, the output specific energy (Edis ) of any battery cell is
determined by the discharge voltage (Vdis ) as well as the discharge
capacity (Qdis ):
 Q dis  tdis
E dis = Vdis (q) dq = Idis Vdis (t) dt [1]
0 0
where q represents the specific capacity and tdis is the time in which
the constant current Idis is drawn from the cell (we neglect in this
discussion that typically the output power and not the output current
is the practically relevant parameter).3 During discharge of the cell, an
internal cell resistance (Ri ) reduces Vdis compared to the open-circuit
voltage (Voc ) by an overvoltage (η).
η = Ri Idis [2]
Vdis = Voc − η (q, Idis ) [3]
According to Eqs. 1 and 3, the output specific energy is strongly
dependent on the output current, indicating the important role of the
occurring kinetics within a working LIB cell.4 These kinetic limi-
tations decrease the thermodynamically achievable specific energy
values by lowering Vdis and in turn Qdis . For a given LIB cell, it is con-
sequently possible to enhance the practically available specific energy
by enhancing the responsible kinetics.
Several assessments for rate investigations are known in literature.5
However, the elucidation of the aforementioned kinetic processes is a
challenge. In a multi component LIB cell there are numerous kinetic
processes taking place simultaneously including kinetically determin-
ing Li+ transport processes and pathways that can theoretically affect
the overpotentials. These Li+ transport processes/pathways have al-
ready been intensively investigated from a theoretical point of view.6–8
However, to the best of our knowledge there is no investigation of these
processes according to their significance during practical LIB cell ap-
plication. In this regard, it is important to determine the kinetically
∗ Electrochemical Society Fellow.
z
E-mail: jkasnatscheew@uni-muenster.de; martin.winter@uni-muenster.de;
m.winter@fz-juelich.de
limiting processes as a basis to further increase the specific energy
and specific power of the LIB cell.
For the sake of reduction of complexity, we focused our investiga-
tions on the positive electrode (= cathode), which is considered to be
the bottleneck for the increase in cell capacity and specific energy.9,10
Among the various positive electrode materials, the layered oxide
LiNi1/3 Co1/3 Mn1/3 O2 (NCM) was intensively investigated in literature
and is of high present and future commercial interest, in particular
when the Ni content is increased.11–19
As starting point, the data in this study was evaluated based on our
previous insights.20 By thoroughly investigation of the specific capac-
ity loss in the initial cycle (responsible for the decreased Coulombic
efficiency) for NCM/Li half cell in the potential range of 4.6–3.0 V
vs. Li/Li+ and a used specific current of 30 mA g−1 , it could be shown
that the initial specific capacity loss is solely the result of incomplete
relithiation during discharge.20 Contrary to the common belief where
the specific capacity loss was attributed to electrolyte oxidation and
surface layer formation,21–23 it could be concluded that for the given
conditions the “parasitic charge capacity” (which is related to charge
reactions not resulting into delithiation, e.g. electrolyte oxidation) of
NCM is negligible.20
As a consequence a significant contribution of oxidative electrolyte
decomposition reactions to the total specific charge capacity could be
neglected and the specific charge capacity could be solely assigned to
Li+ removal from the NCM structure, i.e., as true “Li+ delithiation
capacity”. The specific discharge capacity is analogously called “lithi-
ation capacity” and the observed specific capacity loss (= the differ-
ence between the specific charge and the specific discharge capacity)
could be denominated to “non re-lithiation capacity loss”, which does
regard that those Li+ site vacancies in the NCM host structure that
can be not re-lithiated during the discharge (lithiation) step.20 The
total specific capacity loss can have a kinetic (thus reversible) and
an irreversible origin. It is possible to distinguish between these both
types of specific capacity loss by introducing a constant potential (CP)
step during lithiation at the discharge cutoff potential, which enables
the recovery of the reversible (recoverable) specific capacity loss. The
residual (non recoverable) specific capacity loss indicates the irre-
versible part.20 According to these insights, the cathode relevant Li+
extraction ratio parameter can thus be easily determined by the ra-
tio of the experimentally determined specific charge capacity and the
respective calculated specific theoretical capacity.20
In this work, the influence of the specific current on the electro-
chemical behavior of a NCM composite electrode is investigated in
detail. Literature known kinetic factors are discussed and classified

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 A2944 Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016)
Figure 1. Potential profiles of the first charge using a fixed upper cutoff po-
tential of 4.6 V vs. Li/Li+ of NCM/Li half cells at varied specific currents.
according to their significance, thus offering an overview and practical
assessment for battery application. This diagnostic work should act as
basis to overcome one of the main challenges of the LIB cell, namely
enhancing its gravimetric and volumetric energy at elevated rates.
Experimental
The LiNi1/3 Co1/3 Mn1/3 O2 (NCM) electrodes were provided by
BMW Group. NCM working electrodes had an active mass load-
ing of 15 mg cm−2 . Battery grade electrolyte 1 M LiPF6 in EC:EMC
(1:1, by wt) (LP50 Selectilyte) from BASF was used in all inves-
tigations. Galvanostatic charge/discharge cycling experiments were
performed in a three electrode cell set-up (Swagelok). Lithium metal
(Rockwood Lithium) was chosen as counter- and reference electrode.
A Maccor Series 4000 was used as battery cell test system. Galvano-
static charge/discharge cycling conditions have been varied in this
work and are mentioned in the caption of each figure. The discharge
cutoff potential was set to 3.0 V vs. Li/Li+ . In several experiments, a
constant potential (CP) step at the discharge cutoff potential was set
for 24 h for the initial cycle. For further galvanostatic charge/discharge
cycling the CP step length was set to 6 h for the next two formation
cycles and 2 h for the following cycles.
Lattice parameters in the XRD measurement were obtained by
Rietveld refinement (Topas) using powder diffraction data from a D8
Advance (Bruker) with Bragg-Brentano-Geometry and Ni-filtered Cu
Kα radiation. The corresponding Li concentration of the electrodes
was determined by ICP-OES.
Results and Discussion
For clarity reasons, the specific current dependent overpotential
behavior of the delithiation (charge) and lithiation (discharge) pro-
cess is discussed individually. Here, we charge the NCM up to 4.6 V
vs. Li/Li+ which is a substantially higher cutoff potential than the
typically used 4.2 V vs. Li/Li+ .20,24 As depicted in Figure 1, the indi-
vidual potential profiles (including the overpotentials) are dependent
not only on the specific current, but also on the specific charge capac-
ity (delithiation capacity; see introductory remarks) and thus on the
state of charge (SOC). The highest overpotential is observed at the
beginning of the delithiation process, which then steadily decreases
until a minimum is reached at a specific charge capacity of ≈140 mAh
g−1 . After this point, the difference in overpotential slightly increases
again. Hence, the internal cell resistance during the initial charging
process apparently reaches its minimum at a specific charge capac-
ity of ≈140 mAh g−1 , which corresponds to a Li+ extraction ratio
of ≈50% when considering that the theoretical specific capacity of
NCM is 278 mAh g−1 .20 Since this trend is also visible at lower spe-
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Figure 2. Potential profiles of the first discharge of NCM/Li half cells at varied
specific currents with a fixed discharge cutoff potential of 3.0 V vs. Li/Li+ . In
all experiments the NCM/Li cells have been charged with a specific current of
30 mA g−1 and up to a charge cutoff potential of 4.6 V vs. Li/Li+ .
cific currents, any issues associated with uneven delithiation/internal
gradients can be excluded. The presence of such internal gradients
is observable at significantly higher rates/specific currents,25,26 so the
relevance can thus be excluded for the given conditions.
The potential profiles reflecting the overpotential during discharge
are depicted in Figure 2. In the experimental setup, the charging con-
ditions of the NCM/Li half cells were fixed to the specific current of
30 mA g−1 and the charge cutoff potential to 4.6 V vs. Li/Li+ , which
yields a specific charge capacity of ≈220 mAh g−1 (equal SOC). In
the specific discharge capacity range from 0 to 60 mAh g−1 the over-
potential is small and almost constant, contrary to the overpotential
observed during charge (= delithiation, Figure 1). Only at the end of
the lithiation process at a high depth of discharge (DOD), a strongly
sloping potential profile down to the discharge cutoff potential and
a steadily increasing potential differences (= overpotentials) are ob-
served. The increase in specific capacity loss with increasing specific
current can be correlated to a “lithiation hindrance” i.e., a kinetically
limited Li+ uptake of NCM, which according to our previous re-
port induces the observed change in overpotential.20 The increase in
specific discharge current leads to higher overpotentials and thus to
lower specific discharge capacities, resulting in decreased Coulombic
efficiencies.
In its entirety, the lithiation (discharge) kinetics seem to be slower
than the delithiation (charge) kinetics as the value of the specific
discharge capacity (<200 mAh g−1 ) is lower than the value of the
specific charge capacity (= 220 mAh g−1 ). However, as seen in Figure
2, over a wide potential range the lithiation kinetics are good up to a
certain DOD threshold value. One can conclude, that the overpotential
increase at the end of the lithiation process is in majority responsible
for the incomplete lithiation, thus leading to the specific capacity
loss (non relithiation capacity loss). This phenomenon is only present
for cycles after a specific discharge current increase compared to
the previous cycle, as it is the case for the investigated initial cycle,
where formally the specific current is higher compared to the pristine
state (zero specific discharge current). Keeping the specific discharge
current constant during galvanostatic charge/discharge cycling, the
specific discharge capacity is practically equal to the specific charge
capacity leading to a CE of almost 100% (independent of the applied
constant specific current). For the case that the specific discharge
current is even lower than the previous cycle specific discharge current,
the CE can even be higher than 100%.20
Obviously, a lower overpotential leads to a higher lithiation amount
into the available vacant Li+ sites, which increases the specific dis-
charge capacity (Figure 2). By analogy, a low overpotential during
charge also leads to a higher delithiation amount, which increases
 Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016)
Figure 3. Specific charge and discharge capacities in the first cycle as a func-
tion of the specific charge current for NCM/Li half cells in the potential range
of 3.0 V – 4.6 V vs. Li/Li+ at a fixed specific discharge current of 30 mA g−1.
the specific charge capacity (Figure 1). The increase of vacant Li+
sites by a higher delithiation degree should in turn also lead to a
subsequent higher lithiation degree and thus to a higher specific dis-
charge capacity.21 Referring to Figure 1, the obtained specific charge
capacities are strongly dependent on the applied specific currents.
The subsequent specific discharge capacities under fixed discharging
conditions (30 mA g−1 ) are depicted in Figure 3 as a function of the
specific charge current. As expected, the lower the specific charge
current, the higher is the specific charge capacity. In literature, a pro-
portional correlation between the charge capacity and the subsequent
discharge capacity was reported.21 As depicted in Figure 3, in our
investigations this trend holds only true for specific charge currents
higher than ≈75 mA g−1 , thus at low specific charge capacities. How-
ever, at higher specific charge capacities, i.e., using lower specific
charge currents, the corresponding specific discharge capacity does
not follow the trend of the specific charge capacity. The obtained spe-
cific discharge capacity reaches a maximum and then even decreases
at very low specific charge currents (1.5 mA g−1 ). It can be concluded
that lowering the specific charge current, resulting in an increased spe-
cific charge capacity, is only beneficial for a corresponding increase in
the subsequent specific discharge capacity down to a certain threshold
value.
As depicted in Figure 3, a maximum specific discharge capacity of
187.0 mAh g−1 observed for a specific charge current of 15.0 mA g−1
(and a fixed specific discharge current of 30.0 mA g−1 ) corresponds to
a specific charge capacity of 226.0 mAh g−1 . At an one order of mag-
nitude lower specific charge current of 1.5 mA g−1 , a lower specific
discharge capacity of 177.7 mAh g−1 is observed despite to a higher
specific charge capacity of 237.2 mAh g−1 . Consequently, the addi-
tional specific charge capacity increase of 11.2 mAh g−1 (237.2–226.0
mAh g−1 ) is even lower than the total (reversible + irreversible) spe-
cific capacity loss in the first cycle, which increases by 20.5 mAh g−1
(from 39 to 59.5 mAh g−1 , when the charge current is lowered from
15.0 to 1.5 mA g−1 ). The obtained results cannot be simply explained
by the common attribution of the total specific capacity loss to solely
parasitic reactions, such as oxidative electrolyte decomposition, since
the increase in specific charge capacity should be at least as high as
the increase in specific capacity loss following this reason.21,22,27 Fol-
lowing common understanding, electrolyte oxidation increases solely
the charge capacity.20 The increase in specific charge capacity of 11.2
mAh g−1 at low specific currents is rather attributable to an increase of
the delithiation capacity (= increase in lithium extraction ratio) than
to electrolyte oxidation. One might conclude, that at low overpoten-
tials, as it is the case for low specific charge currents (Figure 1), a
higher delithiation capacity should be observed, since with decreas-
ing overpotential more delithiation must occur in order to achieve the
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A2945
Figure 4. Detailed insight in the specific capacity losses in the first cycle of
NCM/Li half cells as a function of the applied specific charge current. The
specific discharge current was fixed to 30 mA g−1 . Cells were cycled in the
potential range of 3.0 V – 4.6 V vs. Li/Li+ .
set charge cutoff potential of 4.6 V vs. Li/Li+ . Electrolyte oxidation
would counteract the electrode potential increase during delithiation
leading to a higher specific charge capacity increase.20 Overall, only
a marginal and thus insignificant part of electrolyte oxidation can be
expected in the specific charge capacity increase of 11.2 mAh g−1 .
Furthermore, the LiPF6 /carbonate based electrolytes have been proven
to be almost completely electrochemically stable at the upper cutoff
potential of 4.6 V vs. Li/Li+ .20 The assumption of sufficient oxida-
tive stability of the electrolyte is also supported by other reports, that
claimed an electrochemical stability up to 4.8 V vs. Li/Li+ ,28 or even
up to 5.0 V vs. Li/Li+ .29–32 Consequently, it is reasonable to exclude
any significant contributions from electrolyte oxidation to the specific
charge capacity and to assign the specific charge capacity increase
to an increase of the delithiation capacity; and the specific capacity
loss to an incomplete re-lithiation of the vacant Li+ sites, as previ-
ously reported.20 The specific capacity loss can be either induced by
kinetic limitations (i.e., being a reversible, recoverable capacity loss),
such as a more resistive cathode electrolyte interphase (CEI) layer,
or the formation of electrochemically inactive structural domains in
the NCM host material at high lithium extraction amounts (visible as
non recoverable capacity loss indicating the irreversible part). This
inactive domains can also impede the lithiation reaction thus addi-
tionally increasing the reversible capacity loss and increase the total
specific capacity loss.20 It is repeated here, that it is possible to dis-
tinguish between both types of specific capacity loss by introducing
a constant potential (CP) step during lithiation at the discharge cutoff
potential, which enables the recovery of the reversible part of the total
specific capacity loss. The residual, non recoverable specific capacity
loss indicates the irreversible part.20
The corresponding specific capacity losses are summarized in
Figure 4 as a function of the specific charge current. The aforemen-
tioned increase of the total specific capacity loss of 20.4 mAh g−1
when the specific charge current is decreased from 15.0 to 1.5 mA
g−1 is mostly of irreversible nature. The additional specific charge
capacity increase of 11.2 mAh g−1 is accompanied by an irreversible
specific capacity loss increase of 15.3 mAh g−1 . Hence, only 5.1 mAh
g−1 (20.4–15.3 mAh g−1 ) of the total specific capacity loss increase is
reversible. The reversible specific capacity loss alone would not lead to
a specific discharge capacity decrease of 9.3 mAh g−1 (187.0−177.7
mAh g−1 ) displayed in Figure 3. Hence, a solely kinetic hindrance,
by e.g. the presence of a more resistive CEI layer, can be excluded
as main reason for the specific discharge capacity decay in Figure
3. It is therefore concluded that structural changes of the cathode at
high delithiation degrees lead to an increased total specific capacity
loss. These findings are in agreement with our previous work, where
 A2946 Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016)
we showed that the irreversible specific capacity losses of the first
cycle increase exponentially after a threshold Li+ extraction value,
i.e. beyond a certain electrode potential during charge.20 Additionally,
the reversible specific capacity losses slightly increase, as well.20 An
even only minor additional delithiation amount beyond the threshold
value during charge can thus lead to a lower lithiation capacity during
subsequent discharge. This can also explain the above observation
that the specific capacity loss increase is even higher than the specific
charge capacity increase.
The higher specific charge capacity thus leads to a reduced specific
discharge capacity, probably due to irreversible structural changes of
the host material and a concomitant increase of the kinetic hindrance
for Li+ transport.
We conclude up to here, that for diminishing the first cycle specific
capacity loss the charging process needs to be re-evaluated. Three pos-
sible charging strategies are pursued within this study are as follows:
(i) a targeted specific charge capacity can be achieved by adjusting
the applied specific charge current at fixed charge cutoff potential cri-
teria as has been described in Figure 1. Due to overpotentials, higher
specific charge capacities can be reached only by lowering the spe-
cific charge current. This is beneficial regarding the charge/discharge
energy efficiency of the cell but prolongs the charging time; (ii) a
targeted specific charge capacity can also be achieved by the addition
of a defined CP step at the charge cutoff potential. This approach would
lead to a relatively reduced the charging time; (iii) a specific charge
capacity can be targeted by varying the charge cutoff potential at fixed
specific charge current. Because of higher overpotentials at higher
specific charge currents (Figure 1), a higher charge cutoff potential
must be set. This approach would be beneficial regarding the charging
time but unfavorable with respect to the charge/discharge energy effi-
ciency due to the increased overpotentials. The trade-off between fast
charging time (but higher electrode potentials due to overpotentials)
and low charge cutoff potentials (longer charging time) has to be opti-
mized. In this context, it is worth noting that structurally related safety
limitations of layered positive LIB electrode materials are predomi-
nantly attributable to the Li+ extraction ratio.33 This value is mainly
determined by the both the charge cutoff potential and the specific
charge current, as depicted in Figure 1. Consequently, the attribution
of structurally related safety hazards solely to the electrode potential
as often pursued in literature is not correct.
Even though a clear correlation between structural stability and
the delithiation capacity was reported,20 the influence of the corre-
sponding charging time needs to be considered. The reason is that
any possible structural changes at highly delithiated SOC can have
a more severe influence on the host material stability with longer
charging times,33 which thus might lead to larger specific capacity
losses. For each aforementioned charging strategy, the corresponding
total specific capacity loss is depicted in Figure 5 as a function of
the Li+ extraction ratio (specific charge capacity divided by specific
theoretical capacity, according to Ref. 20). At a similar Li+ extraction
ratio (for e.g. ≈85%, dotted line in Figure 5), the specific capacity
losses increase with a longer charging time. At a charging time of
< 8.1 h the specific capacity loss amounts to ≈40 mAh g−1 , whereas
(i) it further increases to ≈50 mAh g−1 at a charging time of 12 h (ii),
and finally reaches ≈60 mAh g−1 at a charging time of 158 h (iii)
(the impact of electrolyte oxidation is negligible as discussed above).
In other words, the structural changes (e.g. rock salt formation)34 at
the respective delithiated and thermodynamically instable SOC (, i.e.,
at high Li+ extraction ratios) have a more severe impact on the total
specific capacity loss with increasing the charging time.9
The identification of the limiting kinetic processes during
charge/discharge of the cell is of high interest, as the respective im-
provement efforts could be conducted in a more systematic way. The
challenge in this regard is the complex nature of a composite electrode
including essentially different kinetic processes during its application.
The main kinetic processes taking place on/in a composite positive
electrode are schematically depicted in Figure 6. In general, a positive
composite electrode consists of an active material, conductive car-
bon additive to enable a sufficient electronic conductivity,35 a binder,
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Figure 5. Total specific capacity loss as a function of Li+ extraction ratio for
three different charging strategies. (i) Variation of the specific charge current
(from 1.5 to 600 mA g−1 ) using the fixed charge cutoff potential of 4.6 V vs.
Li/Li+ . (ii) Variation of the CP step time (0, 1, 5, 15, 24 h) using the fixed
charge cutoff potential of 4.6 V vs. Li/Li+ and the fixed specific charging
current of 30 mA g−1 . (iii) Variation of the charge cutoff potential using the
fixed specific charging current of 30 mA g−1 . The total capacity loss was
determined after subsequent discharging to 3.0 V vs. Li/Li+ using a specific
discharge current of 30 mA g−1 .
which plays an important role in maintaining the structural integrity of
the electrode,36 and an Al current collector acting as substrate for the
electrode coating and as electronic conductor to the cell terminal.37
For a NCM electrode, delithiation occurs via Li+ de-insertion and
concomitant electron transfer. Thereby, both charge carriers have sep-
arate pathways, which are “electron pathway” and “Li+ ion transport
pathway”. During charge of the cell, electrons move from the active
material particle (possibly involving the conductive carbon particles)
further to the Al current collector and through the external circuit to
the negative electrode, therefore experiencing ohmic resistance. Dur-
ing discharge, the electron pathway is reversed. In both directions, the
electron movement should encounter the same electronic resistance,
whereas the Li+ transport pathway kinetics within the composite elec-
trode reveals differences between the charge and discharge processes.
During charge (delithiation) of the cell, Li+ ions move within the active
material particle bulk through the surface layer on the particle7 and the
electrode/electrolyte interface to the electrolyte medium, where they
are solvated before finally reaching the negative electrode. The dis-
charge pathway (lithiation) is reversed, but includes the de-solvation
process of Li+ ions before entering the active material.8 The de-
solvation process is supposed to have a significant influence on the
Li+ transport kinetics as thoroughly studied on the graphite negative
electrode.38,39
The significance of each aforementioned Li+ and electron transfer
step on the overpotential is systematically discussed in the following.
The electronic conductivity of the layered positive electrode materi-
als alone is too low for application.12,40,41 These materials have an
intrinsic electronic conductivity in the range from 10−3 to 10−5 S
cm−1 , depending on the transition metal composition of the layered
oxide active material and the SOC.12,42 This is the reason behind the
necessity of adding a conductive agent, commonly a conductive car-
bon. Despite lowering specific energy and energy density of the cell
due to a higher amount of inactive electrode material, it increases
the electronic conductivity in the composite up to ≈10−1 S cm−1 .22,43
This value is almost two orders of magnitude higher than the ionic
conductivity of the commonly used LiPF6 /organic carbonate based
electrolytes.22,44 Therefore, in case of a conductive additive containing
composite electrode, any impact of the limited electronic conductivity
of the host material on the overpotential is usually neglected as long as
the conductivity of the overall composite electrode is higher than the
 Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016)
Figure 6. Positive composite electrode of a LIB including the kinetic processes and Li+ pathways discussed in the text.
ionic conductivity of the electrolyte.22 Moreover, it has been reported
that even when only 1% (by weight) conductive carbon is used, the
electronic conductivity is still above the ionic conductivity value of
the electrolyte.43 Additionally, the significance of the electronic bulk
conductivity can be disproved by comparing different layered oxide
active materials. When adding Cobalt to LiNiO2 yielding for example
LiNi0.8 Co0.2 O2 , the electronic conductivity decreases by an order of
magnitude.45 Nevertheless, despite decreased electronic conductivity,
the overall electrochemical performance in terms of rate capability
even increases.12 This further reveals that performance changes at
increased current rates are not primarily related to electronic conduc-
tivity limitations but rather to factors, which will be discussed in the
following.
The two orders of magnitude lower ionic conductivity value of
a common LiPF6 /organic carbonate based electrolyte may indicate a
more significant impact on the overpotential. However, when decreas-
ing the ionic conductivity value by around a third via decreasing the
LiPF6 molarity from 1.0 M to 0.2 M,44 no apparent changes in the
potential profile are observable, when using a specific current of 30
mA g−1 (Figure 7). However, when increasing the specific current to
150 mA g−1 , slight changes are becoming evident. Compared to the
1.0 M electrolyte solution, the 0.2 M electrolyte with the lower ionic
Figure 7. 1st and 4th cycle of NCM/Li half cells using the specific currents of
30 (1st cycle) and 150 mA g−1 (4th cycle) in the potential range from 3.0 V –
4.6 V vs. Li/Li+ for a 0.2 and 1.0 M LiPF6 /organic carbonate solvent-based
electrolyte.
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A2947
conductivity displays a similar delithiation overpotential but a slightly
earlier begin of the potential slope resulting in a higher specific ca-
pacity loss and lower specific discharge capacity. This indicates that
a too slow ion transport can indeed affect the electrochemical perfor-
mance at higher specific currents, but only at higher DODs during the
lithiation process. This characteristic range seems to be sensitive with
respect to additional impedances induced by e.g. insufficient ionic
transport or by other impeding processes within the cell, that depend
on the ion concentration in the electrolyte, as may be the ionic charge
transfer from the electrolyte into the electrode.4,6 Overall, this leads to
the conclusion that ionic transport within the commonly used 1.0 M
LiPF6 /organic carbonate solvent based electrolytes cannot be made
responsible for the delithiation overpotential, but indeed can slightly
affect the lithiation kinetics at higher DOD in the case of small LiPF6
molarities.
Both, the porosity and the inactive materials (binder, conductive
carbon) within the positive composite electrode can kinetically affect
the Li+ transport. The influence of the porosity on the Li+ transport
has already been intensively reported by Zheng et al.22 Decreasing
the porosity via calendaring of the electrode has been found to be
beneficial regarding mechanical strength and practical energy density.
However, an extreme porosity decrease can also deteriorate the elec-
trochemical performance. With respect to the initial charge/discharge
cycle, an apparent overpotential increase was observed merely for the
electrode with no porosity (0%). The discharge rate test confirmed a
significant specific discharge capacity dependence just for porosities
lower than 20%. It is worth noting that in order to observe any effects
the authors used a high active material mass loading of 30 mg cm−2 ,
which is higher than the mass loading of commercial electrodes.22
Indeed, electrodes with lower mass loadings reveal better rate perfor-
mance at elevated discharge currents.46,47 It is therefore assumed that
electrode porosity cannot significantly influence the Li+ ion transport
as long typical porosities and mass loadings are used.
The influence of the inactive components within a composite cath-
ode on the impedance was clarified by Liu et al.43 The authors revealed
that two factors can increase the impedance within a composite pos-
itive electrode: on the one hand, the ratio of conductive carbon to
binder and on the other hand the ratio of the inactive to active ma-
terial. The most beneficial mass compositional ratio for conductive
carbon (acetylene black) to binder (PVDF) was found to be higher
than 0.6:1. The advantage of this optimized compositional ratio is
related to its low impedance even at small overall inactive ingredient
mass loading of below 5%. With commonly used positive electrodes,
applying compositional ratios above 0.6:1 the measured impedances
display the lowest values, especially at a sufficient inactive compo-
nent mass loading. The impedance increase associated with altering
 A2948 Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016)
Figure 8. Left: Schematic showing the de-solvation process during lithiation (discharge) of layered NCM. The solvent characteristic Li+ solvation strength can
retard the lithiation process resulting in an overpotential (activation energy EA ) increase of this reaction (charge transfer). Right: 1st cycle potential profile of a
NCM/Li half cell containing 1.0 M LiPF6 in different electrolyte solvents. The varied solvation strengths do not significantly influence the lithiation potential,
which indicates sufficient de-solvation kinetics.
the compositional ratios does not affect the performance at moderate
currents, which consequently disproves its significant influence on the
observed overpotentials.48
With regard to charging of the graphite anode, the charge transfer
process, which includes the Li+ de-solvation from a carbonate based
solvent, was considered as a rate determining step.38,39 Even for the
positive electrode, some reports assign the Li+ de-solvation process a
rate determining step due to the observed large activation energy (EA )
values.49–55 With respect to a full charge/discharge cycle of the NCM
cathode, the Li+ de-solvation process can only influence the lithiation
process (discharge) as schematically depicted in Figure 8 (left). Since
no de-solvation is required during delithiation, an influence on the
delithiation overpotential during charge can be excluded. As described
above, a significant lithiation hindrance is only observed beyond a
certain DOD at the end of discharge (Figure 2), which has been
attributed to structurally reasoned lithiation hindrances.20
Rather fundamental studies focused on the Li+ de-solvation phe-
nomenon from a theoretical point of view.56,57 In one report the coor-
dination strength of LIB electrolyte solvents to Li+ was determined.58
It was claimed that Li+ is equally coordinated in ethylene carbonate
(EC) and γ-butyrolactone (GBL) solvents and experiences a stronger
coordination in propylene carbonate (PC). A possible influence of the
aforementioned solvents, including fluoroethylene carbonate (FEC)
and vinylene carbonate (VC) as solid electrolyte interphase (SEI)59
forming electrolyte additives, on the overpotential was investigated
in this work. The charge/discharge potential curve of the 1st cycle
for selected 1.0 M LiPF6 electrolytes is depicted in Figure 8 (right).
The lithiation overpotential is similar for each solvent, thus indicating
a rather insignificant impact of the Li+ de-solvation process on the
overpotential.
According to literature, a further performance influencing process
is associated with Li+ transport through the CEI.15,60,61 CEI formation
is attributed to electrochemically induced changes of a native surface
passivation layer7,30 via precipitation of oxidatively decomposed elec-
trolyte components. However, such CEI formation is unlikely to oc-
cur for the here applied electrochemical conditions, because a major
electrochemical oxidation of the commonly used LiPF6 in carbon-
ates based electrolytes was disproved by our previous work.20 Other
reports claimed an electrochemical stability of LiPF6 in carbonate
based electrolytes even above 5.0 V vs. Li/Li+ .29–32 The fact that for
the high voltage spinel LiNi1/2 Mn3/2 O4 (LNMO) a rather low irre-
versible specific capacity loss was observed at the cutoff potential of
4.95 V vs. Li/Li+ supports the assumption of a rather electrochem-
ically stable LiPF6 carbonate solvent based electrolyte.20 Even if a
CEI would be formed on LNMO according to the definition above, its
influence on the overpotential contribution in the initial cycle cannot
be large due to the observed good electrochemical data and low po-
tential hysteresis in the initial cycle.20 Indeed, surface changes have
been observed, but already after simple exposure to the electrolyte
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without any electrochemical treatment.34,62 Nevertheless, the reported
associated impedances were insignificantly low compared to the total
cell impedance excluding such surface layer significance. Hence, the
reported surface layer changes are more likely attributable to intrin-
sic thermal or chemical (e.g., by electrode surface impurities such
as moisture or hydroxide) electrolyte decomposition than to oxidative
electrochemical decomposition.7,23,30,63,64 The fact that LiF is reported
to be the surface layer (or CEI layer) dominating species supports this
assumption, since LiF cannot be an oxidation product of LiPF6 .65–67
Furthermore, it was reported that there is no potential dependence for
the resistance associated with the surface layer.7 On the one hand this
neglects any electrochemical origin of the surface layer and on the
other hand disconfirms the observed significant influence on the SOC
dependent overpotential in Figure 1. Considering these thoughts, it is
unlikely to assign changes in electrochemical performance to changes
of the cathode surface layer (or CEI) caused by electrolyte oxida-
tion, especially for the initial charge/discharge cycle, when using a
common LiPF6 carbonate based electrolyte.
The Li+ transport through solids may be assumed as the slowest
Li transport pathway. In NCM cathodes, the Li+ resides in the 3b
+
layer (Li+ layer) on the Li+ sites, octahedrally coordinated by oxygen
anions. Meanwhile, the transition metal ions reside in an 3a layer
(TM layer) on the TM sites, also octahedrally coordinated by oxygen
anions.13 The Li+ movement during lithiation and delithiation occurs
within this two dimensional Li+ layer via octahedral and tetrahedral
vacancy hopping.18,68 The strength of the Coulombic interactions and
respective coordination of Li+ by surrounded oxygen anions dictates
the ease of the Li+ movement. The bigger the interlayer distance,
the easier the movement.13 This Li+ transport property is affected
by the oxidation state i.e. with the SOC. The SOC determines the
crystallographic parameter and thus the interlayer distances for the
Li+ layer, as well. Applying the HSAB concept, the oxidation of the
corresponding TM ions during charging of NCM leads to harder TM
ionic species, which in turn better attracts the oxygen ions in the a
axis and simultaneously stronger repels the oxygen ions from each
other in the c axis.12,69 The resulting steady increase of the c axis
lattice parameter during charge increases the responsible interlayer
distance for Li+ movement. Such SOC dependent c axis development,
as measured by XRD, is depicted in Figure 9. It is shown that the c axis
lattice parameter, as indication for the interlayer distance and thus Li+
mobility within NCM, is increasing up to a maximum as a delithiation
degree of 0.5 is reached. After this threshold value, the c axis lattice
parameter decreases again. This might be attributed to the presence
of Ni2+ ions within the Li+ layer due to the NCM characteristic
Li/Ni mixing phenomenon.70 Beyond a certain electrode potential the
divalent Ni2+ starts to irreversibly oxidize and become trivalent.71,72
The harder trivalent Ni species probably counteracts the c axis lattice
parameter increase. These c axis lattice parameter developments are
in agreement with previous reports for NCM based electrodes.12,73
 Journal of The Electrochemical Society, 163 (14) A2943-A2950 (2016)
Figure 9. Ex situ XRD measurement of the c axis parameter development
as a function of the delithiation degree of NCM. With increasing delithiation
during charging the c axis lattice parameter increases and reaches a maximum
at a delithiation degree (1-x) of ≈0.5, which corresponds to a specific charge
capacity of ≈140 mAh g−1 . The c axis lattice parameter correlates with the
interlayer distance and hence with the facility of Li+ movement within the Li+
layer in the NCM material. This result is in accordance with the overpoten-
tial investigation reported in Figure 1, where the minimum overpotential was
determined at ≈140 mAh g−1 (1-x = 0.5).
Interestingly, the overpotentials observed in Figure 1 clearly correlate
with the observed c axis lattice parameter development having the
lowest overpotential at a delithiation degree of 0.5, which corresponds
to a specific charge capacity of 140 mAh g−1 . Any time duration
impacts at the delithiated state (as shown in Figure 5) can be excluded
since the lithiation degree in this experiment is higher than 0.3 (or Li+
extraction ratio lower that 70%). Furthermore, since the c axis lattice
parameter development represents the bulk behavior, we suppose that
predominately the Li+ solid state transport is responsible for the shown
overpotential behavior in the initial charge, rather than only the surface
of the active material.
This correlation leads to the conclusion that the Li+ transport
within the active material itself must be the limiting process among the
different Li+ transportation pathways discussed above. In accordance
to the literature, the electrodes with the highest lithium diffusion
coefficients (D), acting as indication for Li+ mobility within the active
material, e.g. LiTiS2 (D = 10−8 cm2 s−1 ) are also materials with
the best rate performance.74 Among the currently investigated and
commercially used lithium transition metal layered oxides, LiCoO2
has the highest lithium diffusion coefficient (D = 10−9 cm2 s−1 )
and shows the best rate capability.12 Finally, among all the kinetic
processes taking place merely the variation of the active material Li+
transport associated parameters such as size, shape and morphology
can lead to different rate performances and are key for the practical
specific energy and energy density improvements.
Conclusions
The thermodynamic specific energy of a lithium ion battery (LIB)
cell is reduced under current flow. The rate limiting processes within
a LIB cell at practical specific currents induce overpotentials, which
reduce the two specific energy determining cell parameters, i.e., the
cell capacity and the cell voltage. The influence of the specific cur-
rent as well as possible kinetic limitations were investigated for
LiNi1/3 Co1/3 Mn1/3 O2 (NCM) based electrodes. It was shown that over-
potentials during the initial delithiation process (charge) are state of
charge (SOC) dependent, approaching the lowest overpotential at 50%
SOC, which corresponds to a specific charge capacity of ≈140 mAh
g−1 . The observed overpotentials during lithiation (discharge) were in
total lower than during charge, however, only up to a certain depth of
discharge (DOD) value; at the end of discharge a strong overpotential
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A2949
was observed. This overpotential is due to an incomplete lithiation in
the NCM structure, thus resulting into a specific capacity loss. How-
ever, these specific capacity losses are only present for cycles after a -
compared to the previous cycle - specific discharge current increase.
Furthermore, it was shown that the charging conditions signifi-
cantly affect the subsequent specific discharge capacity. At fixed cut
off potentials, higher delithiation overpotentials, e.g. due to higher
specific charge currents, lead to lower specific charge and discharge
capacities as well as lower charge/discharge energy efficiencies. In
analogy, the decrease of the overpotentials, e.g. due to lowering the
specific charge currents, results in an increase of the specific charge
capacities and better charge/discharge energy efficiencies, but at the
expense of prolonged charging times. However, the subsequent spe-
cific discharge capacities are not increasing with the same amount,
but instead reach a maximum and even decrease at very low prior
charging currents. It is proposed that the structural instability of the
NCM material at higher delithiation amounts leads to irreversible
structural changes, resulting in electrochemically inactive domains,
thus hindering the subsequent lithiation process. Exceeding a cer-
tain delithiation amount can even lead to a higher hindrance for the
subsequent lithiation, resulting in higher specific capacity losses and
lower specific discharge capacities. It was additionally proven that
the subsequent specific capacity losses were strongly dependent on
the previous charging time duration. In this regard, different charg-
ing strategies were compared and discussed. Achieving the targeted
Li+ extraction ratio at fast-charging seems to be most beneficial with
respect to small total capacity losses and high specific discharge ca-
pacity. Furthermore, the influence of several Li+ ion and electron
transport processes on the overpotentials was discussed and ranked
according to their significance. It was concluded that the Li+ ion trans-
port within the active NCM material is the most influential factor. The
evolution of the c-lattice parameter as a function of the lithium con-
tent supported this conclusion and could even explain the observed
dependence of the overpotential on the SOC.
Consequently, a significant enhancement of the practical specific
energy can be most effectively achieved by systematically improving
the material-intrinsic and experimental-operational parameters, which
are enhancing Li+ ion transport within the active material.
Acknowledgment
Financial and material support from the BMW group as well as
additional material support from BASF are gratefully acknowledged.
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