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Electrochemical Delithiation/Relithiation of
LiCoPO4: A Two-Step Reaction Mechanism
Investigated by in Situ...

Article in The Journal of Physical Chemistry C · August 2014

DOI: 10.1021/jp503306v

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 Article

pubs.acs.org/JPCC

Electrochemical Delithiation/Relithiation of LiCoPO4: A Two-Step

Reaction Mechanism Investigated by in Situ X‑ray Diffraction, in Situ
X‑ray Absorption Spectroscopy, and ex Situ 7Li/31P NMR
Spectroscopy
Maximilian Kaus,† Ibrahim Issac,† Ralf Heinzmann,†,‡ Stephen Doyle,§ Stefan Mangold,§ Horst Hahn,†,#
Venkata Sai Kiran Chakravadhanula,# Christian Kübel,†,# Helmut Ehrenberg,#,∥ and Sylvio Indris*,†,#,∥
†
Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
‡
Bruker Biospin GmbH, Silberstreifen 4, 76287 Rheinstetten, Germany
§
ANKA Synchrotron Radiation Facility, Karlsruhe Institute of Technology, P.O. Box 3640, 76021Karlsruhe, Germany
#
Helmholtz Institute Ulm for Electrochemical Energy Storage, P.O. Box 3640, 76021 Karlsruhe, Germany
∥
Institute for Applied Materials − Energy Storage Systems, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe,
Germany

ABSTRACT: LiCoPO4 was synthesized by a solid-state and a supercritical solvo-thermal

method. In situ X-ray absorption near-edge structure (XANES) experiments were
evaluated on the basis of full-cycle experiments confirming the predominantly reversible
character of the redox reaction. In situ X-ray diffraction (XRD) measurements were
performed to follow structural changes during cycling indicating the existence of an
intermediate phase upon cycling. The local phosphorus and lithium environments were
studied by ex situ 31P and 7Li NMR at different states of charge proving the existence of an
intermediate phase of the composition Li2/3CoPO4. On the basis of these findings, a model
of the (de)lithiation process of LiCoPO4 is developed and discussed.

1. INTRODUCTION
LiCoPO4 has attracted a lot of interest in recent years as a
cathode material for Li-ion batteries due to its high redox
potential (4.8 V vs Li/Li+), large theoretical specific capacity
(167 mAh/g), and appealing energy density of about 802 Wh
kg−1.1−5 The two major challenges for this material have been
the intrinsically low electronic conductivity6,7 and the
pronounced capacity fading upon cycling.2,8 Several different
strategies have been employed in the past to enhance the cyclic
stability and rate performance. Most notably, doping with metal
ions,9−12 application of different synthesis procedures,13−16 and
the processing of electrically conductive additives17−20 all
proved to be effective methods for further optimizing the
material. As reported by Markevich et al.,21 the electrolyte used
for this high-voltage cathode material is of key importance and
numerous studies were dealing with the modification of the
same.22−29 More recently, major advancements have been
made identifying the nucleophilic attack of F− anions on the P
atoms in LiPF6 containing electrolytes as the underlying cause
for the strong degradation of this material.21 This nucleophilic
attack causes the P−O bonds of the LiCoPO4 to break,
eventually leading to rapid capacity fading. Subsequent studies
tried to alleviate this problem by introducing HF scavengers30
or the utilization of electrolyte additives forming protective
surface films on the cathode side.31 Though LiCoPO4 has been
extensively studied in recent years, very little is known about
the nature of the intermediate phase LixCoPO4. A first detailed
analysis of this intermediate phase was published by Bramnik et
al.32 suggesting a composition of Li0.7CoPO4. These results
were reconfirmed by Ehrenberg et al.33 who employed neutron
and X-ray powder diffraction simultaneously to determine the
Li content of the intermediate phase LixCoPO4 to be x =
0.60(10). These findings, however, are contradicted by a recent
work by Ju et al. 3 4 suggesting a composition of
Li0.20−0.45CoPO4. In the present work, the reversible character
of the (de)lithiation process is proven by in situ X-ray
absorption spectroscopy (XAS) and a model of the same is
developed on the basis of ex situ 31P/7Li nuclear magnetic
resonance (NMR) spectroscopy. The utilization of in situ
techniques is of key importance especially when dealing with
metastable phases such as the investigated CoPO4 phase which
undergoes amorphization when exposed to air.32 All the ex situ
samples must be dealt with great care in order to prevent any
exposure to atmospheric conditions.
Received: April 3, 2014
Revised: June 16, 2014
Published: July 9, 2014

© 2014 American Chemical Society 17279 dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C
2. EXPERIMENTAL SECTION
2.1. Synthesis. LiCoPO4 was synthesized by (a) a solid-
state reaction and (b) a supercritical solvo-thermal method.
The sample obtained via the solid-state reaction (labeled in the
following as ss-LiCoPO4) was prepared by mixing stoichio-
metric amounts of (NH4)Co(PO4)·H2O and Li2CO3 which
were then ground in a mortar. The powder was calcined in air
for 16 h at 600 °C, reground, and again calcined in air for 8 h at
600 °C.
The precursors for the supercritical solvo-thermal synthesis
(sc-LiCoPO4) were Co(CH3CO2)2·4H2O, LiOOCCH3, and
phosphoric acid. LiCoPO4 was prepared by mixing stoichio-
metric amounts of Co(CH3CO2)2·4H2O and phosphoric acid
in 40 mL of ethylene glycol after which lithium acetate was
added to the solution and left stirring for 30 min. The solution
was then transferred to a 100 mL Hastelloy-C276 autoclave
(Parr Instrument Co., IL, USA, Model 4793), which was
subsequently purged with argon. The solution was then heated
to 400 °C and 30 MPa and was kept under supercritical
conditions for 10 min followed by quenching the autoclave.
The product was obtained by filtration and repeated washing
with distilled water and ethanol. Finally, the powder was
calcined at 650 °C for 4 h in an argon atmosphere.
2.2. Materials Characterization. Electrochemical meas-
urements were performed using Swagelok type cells comprising
a Li metal (Goodfellow, 99.9%, 200 mm thickness) counter
electrode, 2 sheets of Whatman GF/B separator, LP-30
electrolyte (BASF, EC/DMC 1:1 w/w, 1 M LiPF6), and a
working electrode based on 80% LiCoPO4, 20% carbon black
(Super P, Timcal). Tris(hexafluoro-iso-propyl)phosphate
(HFiP) was purchased from Suzhou Fluolyte and used as an
electrolyte additive in a selected case (see Figure 5).
Galvanostatic cycling experiments were carried out on a
VMP3 multipotentiostat (Biologic Science Instruments,
France).
Ex situ crystal structure analysis was performed by X-ray
diffraction (XRD) analysis using a Bruker D8 advance
diffractometer with Cu Kα1,2 radiation (40 kV, 40 mA) in the
2θ range 10−80° (Bragg−Brentano geometry). Structural
refinements of the different materials were performed by
Rietveld analysis using the FULLPROF program.
In situ XAS measurements were performed using a custom-
built transmission cell composed of two aluminum plates, each
with a central aperture of 14 × 2 mm. Both aluminum plates
were isolated using a Kapton foil of 25 μm thickness. The
cathode film was prepared by mixing the active material, carbon
black, and poly(vinylidene fluoride) (PVDF, Arkema Inc.) in
weight ratios of 80:10:10 and using N-methylpyrrolidone
(NMP, Sigma-Aldrich) as a solvent. The slurry was then
doctor-bladed at a wet thickness of 200 μm onto an Al foil and
kept in the glovebox for drying. Li foil was used as the counter
electrode, which was pressed onto a ring-shaped Cu current
collector. LP-30 was used as the electrolyte, and the electrodes
were separated by a microporous trilayer membrane (Celgard
2325). XAS measurements were performed at the XAS
beamline (2.5 GeV, injection current 80−150 mA) of the
ANKA Synchrotron Light Source, Karlsruhe (Germany), both
in transmission and fluorescence modes. The transmitted
radiation was measured by three consecutive ionization
chambers, which were filled with an appropriate partial pressure
of N2, He, and Ar to reach an absorption of 15% in the first
ionization chamber and 40% and 60% in the second and third
17280
Article
chamber, respectively. Fluorescence radiation was measured by
a 5-element germanium detector. The cell was located between
the first and the second ionization chamber, and the energy
calibration was realized by a Co reference foil located between
the second and third ionization chamber. XAS scans of the Co
K-edge were taken every 5 min during cell cycling at a rate of
C/10, i.e., charging or discharging within 10 h.
In situ XRD was performed at the PDIFF beamline at the
ANKA Synchrotron Light Source, Karlsruhe, (Germany), at an
energy of 16 keV (λ = 0.77490 Å) using the same transmission
cell as described above. XRD powder patterns were collected
within 5 min during galvanostatic cycling at a current density of
16.7 mA g−1 (i.e., C/10 with respect to the theoretical capacity
of 167 mA h g−1) using a Princeton 165 mm diameter 2D-CCD
detector.
7
Li and 31P magic-angle spinning (MAS) NMR was
performed on a Bruker Avance 200 MHz spectrometer (B0 =
4.7 T) using 1.3 mm zirconia rotors in a dry nitrogen
atmosphere. An aqueous 1 M LiCl solution was used as the
reference for the chemical shift of 7Li (0 ppm). 85% H3PO4 was
used as the reference for the chemical shift of 31P (0 ppm).
Typical values for the recycle delay and the π/2 pulse length
were 5 s and 2 μs, respectively. The experiments were
performed at 298 K and a spinning speed of 60 kHz with a
rotor synchronized Hahn-echo sequence (π/2-τ-π-τ-acquis-
ition).
The carbon content of the samples was determined by a
CHNS elemental analyzer (Elementar Vario MICRO CUBE).
The morphology of the samples was analyzed by scanning
electron microscopy (SEM, LEO 1530).
Transmission electron microscopy (TEM) characterization
was carried out on an image-corrected FEI Titan 80-300
microscope operated at 80 kV and equipped with a Gatan
Tridiem energy filter, providing an information limit of 0.08 nm
in TEM mode. TEM samples were prepared by dispersing the
powdered cathode material on holey carbon coated copper
grids (Quantifoil GmbH).
3. RESULTS AND DISCUSSION
3.1. Physicochemical Properties. Structural refinements
based on the ex situ XRD data were performed on both
samples, and the results are presented in Figure 1.
Both samples contain small amounts of impurities. The
refinement results of ss-LiCoPO4 exhibit a phase impurity of
Co2P2O7 (4.0 wt %). In contrast to that, sc-LiCoPO4 contains
9.1 wt % of Co2P. The results of the structural refinement of
the LiCoPO4 phase together with other physicochemical
properties are detailed in Table 1 for both materials.
Figure 2 displays the particle size distribution for both
materials confirming a much broader size distribution as well as
a distinct increased d50 value in the case of sc-LiCoPO4.
TEM brightfield images (inset: selected area electron
diffraction, SAED pattern) and HRTEM micrograph (inset:
fast Fourier transformation, FFT) of ss-LiCoPO4 are shown in
Figure 3a,b, respectively. Both the SAED pattern and the FFT
reveal reflections corresponding to the (110) LiCoPO 4 ,
(120)LiCoPO4, and (11̅0)Co2P2O7 in good agreement with Rietveld
refinement results of Figure 1.
3.2. Electrochemical Characterization. The voltage
profiles obtained during the first charge−discharge cycle of
ss-LiCoPO4 and sc-LiCoPO4 are depicted in Figure 4.
dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C Article

Figure 1. Rietveld refinement results of (a) ss-LiCoPO4 and (b) sc- Figure 2. Particle size distribution (obtained from SEM image
LiCoPO4. analysis) for (a) ss-LiCoPO4 and (b) sc-LiCoPO4.

Table 1. Physicochemical Properties of the LiCoPO4 Phase explained by the Co2P impurity phase present in sc-LiCoPO4
for ss-LiCoPO4 and sc-LiCoPO4 (see Figure 1).
A similar effect was already reported by Wolfenstine et al.35
solid state supercritical
They observed that the Co2P impurity phase enhances the
space group Pnma Pnma electronic conductivity and in smaller concentrations of up to
a (Å) 10.2027(1) 10.2074(1) 4% leads to an increase in capacity. However, for higher
b (Å) 5.9219(1) 5.9229(1) concentrations of Co2P, a drastic decline in capacity was
c (Å) 4.6998(1) 4.7008(1) observed caused by the electrochemically inert Co2P phase,
V (Å3) 283.960(7) 284.209(8) which on the one hand improves the electronic conductivity
RBragg 7.32 7.99 but on the other hand tends to obstruct the Li+ insertion/
RF 7.12 12.31 extraction. Similar observations were also recently made by Xu
χ2 5.54 0.97
et al.36 The reason for the distinct content of Co2P in the case
d50a (μm) 0.577 0.859
of sc-LiCoPO4 is the fact that carbon containing precursors and
carbon content (wt %) n/a 1.08
a
an organic solvent were chosen for the synthesis, which led to
d50 is the median of the particle size distribution as obtained from the formation of the Co2P phase on the surface of the particles
SEM analysis. by carbothermal reduction of LiCoPO4 during heat treatment.
One important characteristic of the charging curve of ss-
Cycling was performed at C/20 at room temperature in the LiCoPO4 is the distinct occurrence of two plateaus. These two
potential range of 2−5 V (vs Li+/Li). The initial specific charge plateaus however can no longer be clearly distinguished during
capacities for ss-LiCoPO4 and sc-LiCoPO4 are 119 and 152 the discharge process. In general, the two step characteristics
mAh g−1, respectively (with respect to the mass of the active can also be observed for the discharge cycle at low C-rates (C/
material). For the subsequent discharge of ss-LiCoPO4, a 10).16 At higher C-rates, this feature becomes less obvious and
specific discharge capacity of about 101 mAh g−1 is observed eventually the two plateaus are indistinguishable. The severe
while sc-LiCoPO4 shows only low electrochemical activity (14 capacity fade of the solid-state sample in the subsequent cycles
mAh g−1). This electrochemical inactivity can most likely be is commonly observed for this cathode material. Markevich et
17281 dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C Article

Figure 3. (a) TEM image of ss-LiCoPO4 with corresponding SAED

pattern; (b) HRTEM micrograph.

al. discovered that LiCoPO4 in its charged state is prone to

nucleophilic attack of F− anions (originating from the presence Figure 4. Charge−discharge profiles of LiCoPO4 synthesized by (a)
of HF in LiPF6 based electrolytes) on the P atoms causing a solid state and (b) supercritical route.
breakdown of the P−O bonds leading to the structural
degradation of this material.21,37 One possible way to alleviate
this problem can be realized by electrolyte additives like HFiP
which form a protective surface film on the cathode side
resulting in an enhanced cyclability.38,39 The improvement of
the cyclability due to the addition of 1 wt % HFiP to the
standard LP30 electrolyte is shown in Figure 5.
3.3. In Situ XAS. First Co K-edge X-ray absorption near-
edge structure (XANES) measurements on LiCoPO4 were
reported by Okada et al.40 These measurements, though only
performed ex situ on three (initial, charged, and discharged)
samples, already hinted qualitatively at a partially reversible
redox reaction of Co. For the first time, the present work sheds
further light on the reversibility of the electrochemical reaction
processes occurring in the course of delithiation and relithiation
by collecting in situ XAS spectra of the Co K-edge during the
initial full cycle. As charging of LiCoPO4 commences, one
would expect an oxidation of the Co2+ to Co3+ which would
cause a shift of the XANES spectra to higher energies. The Figure 5. Impact of 1 wt % HFiP as an electrolyte additive to LP30 on
evolution of the XANES spectra for the ss-LiCoPO4 and sc- the cyclability of LiCoPO4.
LiCoPO4 cell is displayed in Figure 6.
Qualitatively, several observations can already be drawn from
the measurements of ss-LiCoPO4. (i) Upon charging, a distinct profile most likely caused by the decomposition reaction of the
shift of the edge position to higher energies is observable, electrolyte during the charging process. The issue of the
confirming the partial oxidation of Co from 2+ to 3+. (ii) There electrolyte instability at higher voltages is worsened by the
is a notable asymmetry of the charging−discharging voltage increased overpotential of the in situ cell and the concomitant
17282 dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C Article

Figure 6. (a) Voltage profile of the first full cycle combined with a PCA of the Co K-edge for ss-LiCoPO4. Corresponding XAS absorption and
fluorescence spectra of the solid-state sample during (b) charge and (c) discharge. Respective plots for sc-LiCoPO4 (d), (e), and (f). The numbered
markers in the voltage profiles correspond to the XAS scan numbers shown below.

need for a higher cutoff voltage. (iii) The pronounced
overpotential in combination with the onset of the electrolyte
decomposition at higher voltages causes the apparent
disappearance of the two charging plateaus observed for the
Swagelok based cells (Figure 4a). (iv) The initial and final (at
the end of discharge) XANES spectra are not completely
congruent. This is a clear indication for incomplete reversibility
of the delithiation/lithiation process. Arguably, one of the most
dominating factors for this capacity fade upon cycling is the
structural degradation of the cathode material caused by the
decomposition of the electrolyte at elevated potentials and the
17283
generation of HF in LiPF6 based organic carbonate electro-
lytes.21,41 The presence of a pre-edge feature in the spectra
hints at the asymmetry of the oxygen octahedron around the
Co ions which is also confirmed by the XRD measurements.
The XANES spectra of the sc-LiCoPO4 cell vary significantly
from the ss-LiCoPO4 cell. Several points are apparent: (i)
Almost no features of a XANES shift to higher energies
throughout the charging process were observed most likely
caused by the distinct presence of the electrochemically inert
Co2P impurity phase inhibiting the Li extraction.35 (ii)
Therefore, the occurrence of the plateau-like profile of the
dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C
Figure 7. XRD diffraction patterns acquired in situ during the first full
cycle illustrating the appearance/disappearance of the three phases
“A”, “B” and “C”.
Figure 8. Residual value RBragg and χ2 as a measure for the quality of
the Rietveld refinement as a function of the Li occupation in the
intermediate phase.33
supercritical sample has to be attributed to the electrolyte
decomposition. (iii) The lack of Co oxidation during the
charging of sc-LiCoPO4 brings about the absence of any
reduction reaction during the discharge process.
To gain a more quantitative measure for the redox-reaction
occurring upon cycling, principle component analysis (PCA)42
was performed on all XANES spectra which provides deeper
knowledge about the degree of reversibility. In order to perform
a PCA, a background subtraction, interpolation, and a
normalization of the measured spectra have to be done with
extremely high reproducibility. The code is highly efficient and
can therefore also be used for full field spectroscopic imaging.43
The asymmetric charging profile of ss-LiCoPO4 is even more
obvious in the 80% recovery of the first component of the PCA
(Figure 6a). The results based on the fluorescence and
absorption data (blue and green) are nearly identical, which
excludes any depth dependent reaction activities. An additional
component of the PCA contains only changes within ±50 eV
around the absorption edge and demonstrates an overall
strongly nonreversible behavior but also two different regimes
during charging. The latter effect might hint at the two reaction
steps also observed by XRD and NMR (see below).
17284
Article
Figure 9. Phase evolution of the phases “A”, “B”, and “C” as a function
of scan numbers.
The results of the PCA (Figure 6d) confirm the highly
irreversible process of the charging/discharging-cycle of sc-
LiCoPO4. This is in coincidence with the completely different
change in the spectra during charging. While the absorption
edge in the spectra of ss-LiCoPO4 shifts to higher energy, sc-
LiCoPO4 shows an increase in the first oscillation of the
spectrum (known as white line).
3.4. In Situ XRD. The structural changes occurring during
the first full cycle were investigated by in situ XRD on ss-
LiCoPO4. These measurements reveal the occurrence of two
two-phase regions upon charge/discharge first reported by
Bramnik et al.32 A qualitative overview of the occurring phase
changes during the de(lithiation) process is depicted in Figure
7.
Two apparent features can be seen in the charge/discharge
voltage profile of Figure 7. (i) Just like in the case of the
XANES measurements, there is a distinct asymmetry between
the charge and the discharge profile mainly caused by the
decomposition of the electrolyte which superimposes the
charging profile. (ii) The two well-defined plateaus seen in the
charging profile of Figure 4a can no longer be recognized due
to the increased overpotential of the in situ cell effectively
masking the two charging plateaus.
As charging (delithiation) of LiCoPO4 (indicated as “A”)
commences, the formation of another phase “B” can be clearly
identified. At this point, one can only make the statement that
this intermediate phase “B” most likely represents a partly
delithiated form of lithium cobalt phosphate. At the later stages
of the charging step, the reflections of this partly delithiated
phase LixCoPO4 are reduced in intensity while a third phase
“C” is formed. During the discharge step, these phase
transitions are qualitatively reversed. At the end of the
dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C
Figure 10. Exemplary Rietveld refinements at different states of
charge: (a) initial, (b) end of charge, and (c) end of discharge.
discharge step, however, the intermediate phase LixCoPO4 is
still present in a small amount. The most likely explanation for
this is the incomplete relithiation of the sample due to the slow
kinetics. In the course of the first full cycle, no signs of an
amorphization of the phases can be found. This was confirmed
by comparing the integrated intensities of the initial/final
patterns after correction for beam intensity.
17285
Article
Figure 11. Changes of unit cell volumes during (de)lithiation.
The nature of this intermediate phase is discussed
controversially in the literature. Bramnik et al.32 reported the
existence of Li0.70CoPO4 as an intermediate phase based on in
situ XRD while Ju et al. 34 stated a composition of
Li0.20−0.45CoPO4 as the intermediate phase. In the latter case,
the lithium content was solely derived from electrochemical
data, which can be very misleading since a non-negligible
amount of charge is consumed by side reactions (see Figure 6).
Therefore, it is not surprising that in this case the intermediate
phase is believed to have a relatively low lithium content of
0.2−0.45. In another study, Ehrenberg et al. employed neutron
and X-ray powder diffraction to uncover a lithiation state of x =
0.60(10) for the intermediate phase LixCoPO433 from the
optimum agreement between observed and calculated profiles;
see Figure 8.
The phase evolution of the phases “A”,“B”, and “C” was
evaluated by Rietveld refinement with the program FULL-
PROF. Thompson-Cox-Hastings Pseudo-Voigt was used as the
peak shape function. Scale factors, lattice parameters (a, b, c),
atomic positions (Co, P, O), overall isotropic displacement
factor, and Lorentzian/Gaussian size and strain parameters
were free parameters. The results are depicted in Figure 9.
It is important to point out that the statistics of the
diffraction patterns worsen toward the refilling of the
synchrotron ring (“beam dump”), which is the cause for the
increase in the standard deviation. At the initial stage of the
charging step, no phase transformation can be observed until
scan 14. This apparent inactivity can most likely be explained
by the initial onset of parasitic side reactions under the highly
oxidizing conditions. Subsequently, the formation of phase “B”
commences. The phase “C” can be evidenced at scan number
50 which continues to gain in intensity until scan 69. A clear
indication for a phase transformation of the nature “A” ↔ “B”
↔ “C” can be drawn from the discharge region. At the
beginning of the discharge step, phase “A” stays almost constant
while a decrease of phase “C” is accompanied by an increase of
phase “B” which hints at an exclusive phase transition between
“B” and “C”. After the beam dump, phase “C” can no longer be
evidenced and the phase transition between “B” and “A” is
progressing. It should be pointed out that the observed
coexistence of three phases at the end of the charge step and
the beginning of the discharge step is in violation of Gibbs’
dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C
Table 2. Unit Cell Parameters of the Three Investigated Phases
space group a (Å)
phase “A” Pnma 10.2005(3)
phase “B” Pnma 10.0860(14)
phase “C” Pnma 9.637(5)
Figure 12. Graphical estimation of the lithium content of phase “B”
determined from the value of the unit cell volume. The range of the
unit cell volumes corresponds to the scattering of all values obtained
from the Rietveld refinement.
phase rule. Therefore, the coexistence of these three phases has
to be ascribed to kinetic restraints. The reported weight percent
concentrations for the individual phases “A”, “B”, and “C” in
Figure 9 must be treated with some caution since different
absorption coefficients and/or preferred orientation of the
individual phases were not included in the model.
Comparing the electrochemical data of the in situ cell from
Figure 9 with the electrochemical data obtained from the
Swagelok cell (Figure 4a), it becomes apparent that the
discharge capacities show strong differences. The discharge
capacity of the Swagelok cell reaches 101.3 mAh g−1 which is
strikingly larger than the 46.8 mAh g−1 obtained in the case of
the in situ cell. The charge capacities on the other hand are
somewhat comparable: 119.7 mAh g−1 (Swagelok) and 96.2
mAh g−1 (in situ). In this context, it is important to recall that
these values are obtained by employing different boundary
conditions. The Swagelok based cell is cycled at C/20 with
potential limitations of 5 and 2.5 V while the in situ cell is set up
to cycle at C/10 in the voltage range of 5.2 to 2 V (accounting
for the increased overpotential of the cell). The pronounced
irreversible capacity of the in situ cell can be explained by the
extended voltage window which promotes parasitic side
reactions. Selected refinement results and the changes in the
unit cell volumes of the individual phases during the cycling can
be found in Figures 10 and 11.
Toward the end of the discharge step, the unit cell volume of
phase “B” markedly increases (Fig 11). This is a trend which
was also reported by Bramnik et al.32 and was discussed in
terms of the possible existence of a solid solution region.
Phase “A” represents the fully lithiated compound LiCoPO4,
and the lattice parameters are in good agreement with the
values obtained from the Bruker D8 advance diffractometer
(Tables 1,2). Values for the unit cell volume of CoPO4 have
been determined both experimentally32,33 and theoreti-
17286
Article
b (Å) c (Å) V (Å3)
5.9213(2) 4.6995(2) 283.85(2)
5.8585(6) 4.7187(9) 278.82(7)
5.813(3) 4.738 (2) 265.5(3)
cally44−47 but vary severely among themselves (261 Å3 45
compared to 275.8254 Å3 46). Phase “C” is identified to be
CoPO4 which has a unit cell volume similar to the 264.50 Å3
previously reported.33 On the basis of the assumption of a
linear correlation between the lithium content and the unit cell
volume of the olivine structure, a rough estimate of the lithium
content of phase “B” can be drawn from Figure 12.
On the basis of Figure 12, the lithiation state of the
intermediate phase can be estimated to be in the range between
0.68 and 0.82, in agreement with results from neutron powder
diffraction.33 In accordance with the pronounced irreversible
and limited (discharge) capacity of the in situ cell, the CoPO4
phase is only detectable in a small amount (17.7%) in the fully
charged state (Figure 9). A recently published theoretical work
by Osnis et al.45 suggests that the stability of LiCoPO4 upon
delithiation is by far lower compared to that of LiFePO4. The
reaction enthalpies of the two reactions differ by −128.79 kJ/
mol.45
Li + FePO4 → LiFePO4 (1)
Li + CoPO4 → LiCoPO4 (2)
The energetic unfavorable formation of the CoPO4 phase could
in turn affect the formation/existence of the investigated
intermediate phase. The thermal stability of LiCoPO4 at
different states of charge were analyzed by Bramnik et al.48
confirming a surprisingly low stability of the partly and fully
delithiated compounds. As charging progresses, the thermal
stability decreases further which indicates an even lower
thermal stability of CoPO4 compared to the intermediate
phase LixCoPO4.
3.5. Ex Situ 7Li and 31P NMR Spectroscopy. Both 7Li and
31
P NMR spectroscopy was performed on ss-LiCoPO4 with
different lithiation states. The results are shown in Figure 13.
The 7Li NMR spectrum of as prepared ss-LiCoPO4 is
characterized by a broad peak at about −105 ppm (labeled with
“A”). During charging, this peak successively disappears and
two new peaks at about 80 ppm (“B”) and −135 ppm (“C”)
appear. The ratio of the intensities of these two peaks is 1:1
(including the spinning sidebands that are not shown in this
picture). During further charging, the peaks “B” and “C”
disappear again and the spectrum obtained after full charge is
characterized by a structureless, flat line confirming the removal
of most of the lithium. Thus, these spectra reveal an
intermediate phase with two nonequivalent Li environments.
During discharging, the phase evolution is reversed. In the
beginning, the peaks “B” and “C” are reformed, and at later
stages, these peaks disappear again and are replaced by peak
“A”. The spectra of the completely discharged sample and of
the as-prepared sample show a high degree of congruence.
A very similar behavior is observed in the 31P NMR spectra.
The initial spectrum is characterized by a single peak “A” at
about 3000 ppm. In the course of the charging step, an
intermediate phase becomes apparent as can be seen by the
formation of two new peaks at about 2620 ppm (“B”) and 2230
ppm (“C”). In this case, the peak ratio is 2:1 representing two
dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C Article

Figure 13. 7Li and 31P NMR spectra of ss-LiCoPO4 at different states of charge. The sidebands of peaks “A”, “B”, and “D” in the 31P NMR spectra
are marked by ∗, +, and ×, respectively.

nonequivalent P environments with a corresponding ratio of

occupancies. At the end of the charge, the 31P NMR spectrum
is dominated by a new peak at 3210 ppm (labeled “D”). The
large 31P NMR shift in the charged state hints at a high-spin
state of Co3+ as it was also observed earlier by magnetic
measurements.33 Just like in the case of the 7Li NMR spectra,
the intermediate phase is then being reformed upon discharge
and vanishes again for the completely discharged sample. Both
the 7Li and the 31P NMR spectra show a good agreement
between the spectra of the as-prepard sample and the sample
obtained after one full cycle. In particular, no peak broadening
is visible. This hints at a preservation of the crystal structure,
and in accordance with our XRD findings, an amorphization
during cycling can be ruled out. On the basis of the 31P NMR
findings, the phase evolution during the (de)lithiation process
is displayed in Figure 14.
It should be pointed out that the “x” in Figure 14 should not
be taken literally since it merely indicates the progress of the
(dis-)charging step. A comparison of the phase evolution based
on NMR and in situ XRD (Figure 9) is worthwhile which are
Figure 14. Phase evolution based on 31P NMR results. consistent in many points:
17287 dx.doi.org/10.1021/jp503306v | J. Phys. Chem. C 2014, 118, 17279−17290
The Journal of Physical Chemistry C
Figure 15. Proposed charging/discharging mechanism of LiCoPO4.
(i) For the first two 31P NMR spectra, phase “B” cannot be
evidenced. This is in agreement with the observation that phase
“B” was only detectable after the 14th scan of the in situ XRD
experiment. (ii) The fully delithiated phase is only formed in
the final stages of the delithiation process at “x” = 0.25. This
trend is also reflected by the in situ XRD measurements. (iii)
Finally, the phase transformation of the nature “A” ↔ “B” ↔
“C” suggested on the basis of the XRD measurements is also
supported by the NMR results: In the first two NMR spectra of
the discharge step, the LiCoPO4 phase concentration remains
almost constant while a decrease in the CoPO4 phase
concentration is accompanied by a rise in the phase “B”
concentration. This is exactly the same behavior as observed in
the in situ XRD measurements.
The fact that we observe two nonequivalent Li environments
with a peak ratio of 1:1 and two nonequivalent P environments
with a peak ratio of 2:1 for the intermediate phase suggests a
lithiation state of 2/3. This value is in agreement with the
estimated lithiation state based on our XRD measurements
(Figure 12). According to these findings and the one-
dimensional character of lithium diffusion in this material
class,49 we propose the following (de)lithiation mechanism for
LiCoPO4 (Figure 15): The structure of the as-prepared
material LiCoPO4 contains a single Li site and a single P site.
Therefore, only one peak was observed in both the 7Li and the
31
P NMR spectrum. As charging commences, LiCoPO4 is
locally selectively delithiated forming the intermediate phase
Li2/3CoPO4 where one-third of the Li ions is removed from the
structure and correspondingly one-third of the Co2+ is oxidized
to Co3+ (dark green and light green octahedra). Different
arrangements of the Li vacancies are possible. In Figure 15, we
depicted an arrangement where complete channels along the b
axis are emptied in a way that alternating layers along the c
direction are formed with full or empty Li sites in a 2:1 stacking
sequence. Since the Co is partially oxidized, now two different
Li environments and two different P environments are present,
although the Li and P ions are still located on the same sites.
There are P ions with direct Co3+ neighbors (light purple
tetrahedra) and P ions without Co3+ neighbors (dark purple
tetrahedra), and the relative occupancy is 2:1. For the Li, there
are also environments with and without Co3+ neighbors (light
blue and dark blue spheres), but since here part of the Li is
removed, the relative occupancy of these two environments is
1:1. These ratios fit exactly to the relative intensities in the 7Li
and 31P NMR spectra. At the later stages of the charging
process, this intermediate phase then starts to be further
delithiated forming finally CoPO4. Again, this compound
contains only a single P site (and no Li). Since the number
17288
Article
of Co3+ neighbors is different from the sites in the LiCoPO4
and Li2/3CoPO4, the position of the 31P NMR peak is also
different for CoPO4 in comparison to the NMR peaks of the
other phases, although the P is always located on the same site
(neglecting the small changes in lattice constants and thus bond
lengths/angles). These outlined phase transformations differ
fundamentally from the established “domino-cascade” model in
the case of LiFePO4 in which only the end members are stable
and partly lithiated compounds are highly metastable at room
temperature.50−54
4. CONCLUSION
In situ XRD, ex situ 7Li/31P NMR spectroscopy, and to some
extent in situ XAS, all reveal the existence of two two-phase
redox reaction steps upon the (de)lithiation process of
LiCoPO4. For the first time, the lithiation state of the
intermediate phase is determined by ex situ 7Li and 31P NMR
spectroscopy to be Li2/3CoPO4 which is in good agreement
with our and previous XRD and neutron diffraction measure-
ments. On the basis of these findings, a model for the charge/
discharge process is proposed which differs greatly from the
well-established “domino-cascade” model for LiFePO4. The
existence of this intermediate phase Li2/3CoPO4 might be
explained by recent theoretical findings which suggest that the
formation of CoPO4 is energetically unfavorable compared to
the system of LiFePO4.
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: +49 721 608-28508. Fax: +49 721 608-28521. E-
mail: sylvio.indris@kit.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We are grateful to the German Federal Ministry of Education
and Research for financial support. Sample characterization was
partly carried out with the support of the Karlsruhe Nano
Micro Facility, a Helmholtz Research Infrastructure at
Karlsruhe Institute of Technology.
■
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