Article

pubs.acs.org/crystal

Hydrothermal Synthesis of CoSb2O4: In Situ Powder X‑ray Diffraction,

Crystal Structure, and Electrochemical Properties
Peter Nørby, Martin Roelsgaard, Martin Søndergaard, and Bo B. Iversen*
Department of Chemistry and iNANO, Center for Materials Crystallography, Langelandsgade 140, DK-8000 Aarhus C, Denmark
*
S Supporting Information

ABSTRACT: MSb2O4 constitutes a relatively unexplored class

of multinary oxides that is traditionally synthesized by high-
temperature solid-state methods. Here, we report a facile
synthesis of CoSb2O4 under hydrothermal conditions (T =
135−300 °C, 256 bar). Using in situ synchrotron powder X-ray
diffraction (PXRD), the formation and growth of CoSb2O4
nanoparticles are followed in real time using different precursor
stoichiometries. Phase-pure CoSb2O4 can be formed at 135 °C,
although the formation mechanism changes with precursor
stoichiometry. The crystallite size can be fine-tuned between
14 and 17.5 nm under nonstoichiometric conditions, but crystallites twice as large are found in the stoichiometric case. An
activation energy of 65(12) kJ/mol is obtained for the crystallization from a nonstoichiometric precursor. Modeling of atomic
displacement parameters obtained from Rietveld refinement of multi-temperature high-resolution synchrotron PXRD data gives
a Debye temperature of 331(11) K. The thermal expansion coefficients for the material was found to be αa = 6.2(1) × 10−6 K−1
and αc = 3.1(4) × 10−6 K−1. Electrochemical measurement shows that CoSb2O4 displays a large irreversible capacity (1131 mAh/
g) on the first cycle in Li-ion half-cells and that the capacity decreases significantly in the following cycles.

■ INTRODUCTION
Transition metal antimony(III) oxides MSb2O4 (M: Mn, Fe,
Co, Ni, Zn) belonging to the schafarzikite mineral group have
been studied significantly less than many other binary oxides
(e.g., perovskites).1−21 This is mostly due to the current lack of
technological applications for these materials. It has previously
been shown that MnSb2O4,5 CoSb2O4,19 FeSb2O4,11,17 and
NiSb2O42,7,11 display antiferromagnetic ordering at low temper-
ature (highest TN = 79 K). More recently, their applicability as
anode materials in Li-batteries (LIBs) has been investigated.20
It is well-known that the performance of anode materials in
LIBs is correlated with materials’ characteristics such as
nanocrystallite size, crystallinity, and phase purity.22 The Li-
ion and electronic conductivities of electrode materials for LIBs
are increased with a reduction in the crystallite’s size, owing to
faster diffusion in the smaller crystallites and access to more
electrolyte.22 Hence, it is of key importance to develop
synthesis methods that allow full control of both the crystallite
size and phase purity.
So far, MSb2O4 materials have been mainly synthesized by a
traditional solid-state synthesis method, where the elements are
mixed and heated in a sealed ampule (700 °C for 12 h).17,19
Westin and Nygren investigated the decomposition of M2+-
Sb3−-alkoxide gels to both MSb2O6 and MSb2O4. The
formation of a gel is similar to the first step in a hydrothermal
synthesis, although the temperature used in the decomposition
of the gel to crystalline MSb2O4 is 620 °C,15 which is much
higher than typical hydrothermal synthesis temperatures (T >
100 °C). Furthermore, it is difficult to control the crystallite’s
size and purity with this method. In contrast, the low-
temperature hydrothermal synthesis method has proven to be
extremely versatile in the synthesis of many different
oxides.23−25 Here, we show for the first time that phase-pure
CoSb2O4 nanoparticles can be prepared via a hydrothermal
synthesis route. In order to gain size control on the nanometer
scale, it is important to understand the formation and growth
mechanisms taking place during the hydrothermal synthesis. In
situ studies give the experimentalist unique insight into the
formation mechanism and growth of crystalline materials
synthesized under hydrothermal conditions.26−32 A range of
techniques can provide information about hydro- and
solvothermal syntheses under sub- and supercritical con-
ditions.33−41 Here, in situ powder X-ray diffraction (PXRD)
is used to study the formation and growth of nanocrystalline
CoSb2O4 in real time from both a stoichiometric and
nonstoichiometric precursor. The results are compared with
those obtained from an ex situ hydrothermal synthesis
performed in an autoclave. In addition, the thermal expansion,
atomic displacement parameters, and Debye temperature are
obtained from Rietveld refinement of high-resolution multi-
temperature synchrotron PXRD data. Finally, the morphology
and electrochemical properties of microcrystalline CoSb2O4
were investigated.
Received: October 5, 2015
Revised: December 22, 2015
Published: January 5, 2016

© 2016 American Chemical Society 834 DOI: 10.1021/acs.cgd.5b01421

Cryst. Growth Des. 2016, 16, 834−841
Crystal Growth & Design Article

Table 1. Synthesis Conditions for in Situ Data Collection at p = 256 bar

compound M(Sb)/M(Co) 135 °C 150 °C 180 °C 220 °C 300 °C
CoSb2O4 1.33 × × × ×
2.00 × × ×

■ EXPERIMENTAL SECTION
Precursor Synthesis. SbCl3 (≥99.0%, Sigma-Aldrich), Co-
(CH3COO)2·4H2O (≥98.0%, Sigma-Aldrich), NaOH, and HCl were
used as purchased. For the in situ study, solutions of SbCl3 in 4 M HCl
and Co(CH3COO)2·4H2O in deionized water were utilized. The pH
value of the mixture was adjusted by addition of NaOH. Upon
addition of NaOH, the solution changed color from light red to dark
blue. In a typical synthesis, an aqueous 2.5 mL 1.00 M Co-
(CH3COO)2·4H2O solution was mixed with 2.5 mL of a 1.33 M SbCl3
solution; subsequently, 3.0 mL of 8 M NaOH was added. The molar
ratio between Sb and Co was modified to either 1.33 or 2.00 (Table 1)
in order to study the influence of excess Co on the formation and
growth of the nanocrystallites.
In Situ Experiments. A custom-made sapphire capillary setup was
charged with a constant current of 30 mA/g between 0.05 and 1.3 V vs
Li/Li+.
Data Integration and Analysis. Prior to integration in Fit2D,44
the 2D diffraction patterns from the in situ experiments were masked
in order to remove single-crystalline diffraction peaks from sapphire
and the beam stop. The integrated in situ PXRD patterns were
analyzed in the FullProf program package45 by sequential Rietveld
refinement. The volume-weighted crystallite size, scale factor, and
lattice parameters were extracted from each frame in the refinement.
The crystallite sizes were calculated based on the Scherrer equation
using the line profile parameters corrected for instrumental broad-
ening.46 The high-resolution multi-temperature PXRD patterns
measured on the ex situ synthesized sample were analyzed by Rietveld
refinement in the FullProf program package.45 Details on the Rietveld
refinements can be found in the Supporting Information.

■
used as described in detail by Becker et al.42 The experiments were
carried out at beamline I711 at MAX-LAB (Lund, Sweden).43 The RESULTS AND DISCUSSION
precursor was injected into a thin single-crystalline sapphire capillary
(inner diameter 0.7 mm), which was subsequently pressurized at 256 Precursor and Phase Identification. The contour plot of
bar. Heating was initiated by switching a valve directing a jet of the in situ PXRD data shown in Figure 1 and the Supporting
preheated hot air onto the sapphire capillary (see Table 1 for applied
temperatures). The desired temperature can be reached within
approximately 20 s (see Supporting Information, Figure S1), and
time-resolved X-ray patterns with a time resolution of 5 s were
recorded prior to and during the heating. Each experiment was allowed
to run for ∼20 min. The wavelengths, sample-to-detector distances,
and instrumental contribution to the peak broadening were calibrated
with a NIST LaB6 standard for each experiment (the wavelength was λ
= 0.992 Å). The scattered X-rays were detected by an Oxford
Diffraction Titan CCD detector. All PXRD data are presented in Q-
space (Q = (4π sin θ)/λ).
Ex Situ Experiments. A scaled-up synthesis was performed by
mixing 10 mL of a 0.667 M Co(CH3COO)2·4H2O aqueous solution
with 10 mL of 1.334 M SbCl3 (dissolved in 4 M HCl). Under
magnetic stirring, 16 mL of 8.0 M NaOH was added. The autoclave
was filled to half the volume with the precursor (total volume: 70 mL).
The precursor was heated at 220 °C for 53 h. High-resolution PXRD
patterns on the powdered sample were measured at beamline BL44B2,
SPring-8 (Japan), from 100 to 300 K in steps of 50 K. A homogeneous
sample for the PXRD measurements was obtained by floating two
times in ethanol (96%), which was subsequently packed into a 0.1 mm
glass capillary. The scattered X-rays were collected on an image plate
detector mounted in a Debye−Scherrer camera covering an angular 2θ
range of 2−77°, resulting in a Q-range from 0.44 to 15.6 Å−1. The
sample was further characterized by scanning electron microscopy
(SEM) on a FEI Nova NanoSEM 600 and by transmission electron
microscopy (TEM) on a Phillips CM20 with an acceleration voltage of Figure 1. Contour plot of raw PXRD in situ data for the nanocrystals
200 kV. SEM preparation was done by placing the powder on synthesized at 135 °C and with (a) M(Sb)/M(Co) = 1.33 and (b)
conducting carbon tape. TEM samples were prepared by making a M(Sb)/M(Co) = 2.00. Asterisks indicate CoSb2O4.
diluted suspension of the particles in ethanol and placing a droplet on
a carbon-coated copper grid.
Li-Battery Assembly and Measurements. Half-cells of type Information (Figures S2−S9) reveals an almost instantaneous
CR2032 were assembled with Li metal foil as both counter and formation of phase-pure CoSb2O4 under hydrothermal
reference electrodes. The scaled-up product was used as the active conditions when heat is turned toward the sample. CoSb2O4
material in the working electrode, and it was mixed with Super P can be synthesized at the lowest investigated temperature (135
carbon as the conductor and poly(vinylidene difluoride) (PVDF) as °C) for both stoichiometries. The rapid formation indicates
the binder in a weight ratio of 76:12:12 and coated onto Cu-foil. The that the synthesis temperature can be reduced even further.
typical loading of a dry electrode was ∼30 μm or ∼2 mg/cm2. The
After 1000 s, the sample is phase-pure independent of the ratio
working electrodes were compressed with ∼50 kN/cm2. Two pieces of
25 μm thick porous polypropylene membranes were employed as of cobalt to antimony in the precursor. Surprisingly, there is an
separators, and the electrolyte solution was composed of 1 M LiPF6 in unidentified impurity in the synthesis performed at 180 °C
ethylene carbonate (EC) and dimethyl carbonate (DMC) in a ratio of under stoichiometric (M(Sb)/M(Co) = 2.00) conditions. It is
1:1 by volume. The cells were assembled in a glovebox with water and not present when the synthesis temperature is increased or
oxygen levels at ∼1 ppm. After assembly, the cells were discharged and decreased.
835 DOI: 10.1021/acs.cgd.5b01421
Cryst. Growth Des. 2016, 16, 834−841
Crystal Growth & Design
The formation mechanism differs under the nonstoichio-
metric (M(Sb)/M(Co) = 1.33) and stoichiometric (M(Sb)/
M(Co) = 2.00) synthesis conditions (Figure 2). The
Figure 2. PXRD patterns at three different times for the reaction at
135 °C with a Sb to Co ration of (a) 1.33 and (b) 2.00. (c) Standard
CoSb2O4 PXRD pattern. The precursor is amorphous for Sb/Co =
1.33 and crystalline for Sb/Co = 2.00.
stoichiometric precursor contains both crystalline orthorhom-
bic Sb2O3 (Pccn) and nanocrystalline cubic Sb2O3 (Fd3̅m) (see
the Supporting Information, Figure S8). Switching the heat
toward the sample dissolves the crystalline precursor over a
time period of approximately 100 s at 135 °C. The intensity of
the reflections of CoSb2O4 increases at the expense of a
decrease in intensity of the reflections of Sb2O3. Increasing
synthesis temperature results in a faster dissolution of the
crystalline precursor, and even at 180 °C the transformation
from Sb2O3 to CoSb2O4 is faster than the resolution time (5 s)
(see the Supporting Information). The in situ results show that
in the nonstoichiometric case the precursor is amorphous,
which indicates that the formation of Sb2O3 in the precursor is
suppressed when the relative concentration of antimony is
lowered. Since CoSb2O4 in this case is formed from an
amorphous precursor, it crystallizes instantaneously when heat
is applied. This is seen as a sharp transition in Figure 1. This
indicates a strong dependence on reactive antimony species in
solution in order to form CoSb2O4. Hence, it is advantageous
to have an amorphous precursor where the antimony atoms
seem to be more loosely bonded. It can be rationalized that the
mechanism most likely is a dissolution recrystallization
mechanism where CoSb2O4 is formed as more antimony is
released to the solution, which in the stoichiometric and
nonstoichiometric cases is from crystalline Sb2O3 and
amorphous antimony material, respectively.
Size Evolution and Growth Kinetics. The crystallite size
is calculated from the sequential Rietveld refinement data
corrected for instrumental broadening. It is extracted as a
function of synthesis temperature for the nonstoichiometric
precursor as shown in Figure 3. It should be noted that in a
diffraction experiment the volume-averaged crystallite size value
is obtained, which is inversely proportional to the broadening
of the Bragg peaks. The inset in Figure 3 shows that the overall
growth rate of CoSb2O4 nanoparticles is almost independent of
the synthesis temperature, although slight differences are seen
in how fast zero growth rate is achieved. At 135 °C, the
crystallite size stabilizes at 14 nm after approximately 300 s.
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Figure 3. Crystallite size for CoSb2O4 nanoparticles (Sb/Co = 1.33) as
a function of time. The uncertainties are smaller than the marks. The
inset show the growth rate as a function of time.
Increasing the synthesis temperature to 220 °C results in fast
initial growth, and the final crystallite size (17.5 nm) is reached
within 150 s after the heat has been applied. It should be noted
that the estimated standard deviation in Figure 3 is smaller than
the symbols.
The Johnson−Mehl−Avrami equation47,48 is utilized here to
model the growth of nanocrystalline CoSb2O4 from an
amorphous precursor. Although the model was initially
developed for solid-state reactions, it has proven to give
valuable information from experiments performed under hydro-
and solvothermal conditions.49−52 Both the reaction mecha-
nism and activation energy are extractable parameters from the
model. The extent of the reaction (f) is plotted as a function of
time after the first appearance of the first nanocrystallites (t −
t0). The data are subsequently modeled by the equation f = 1 −
exp[−k(t − t0)n], where the extent of the reaction is defined as
V(t)/Vinf (Vinf is equal to the final stable nanocrystal volume at
the specific synthesis temperature). It is assumed that the
crystallites are spherical in morphology, which is supported by
the modeling of the peak shape (see Supporting Information).
The two parameters in the equation are related to the rate
constant (k) and to the mechanism (n). If the value of n is in
the range from 0.54 to 0.62, then this typically corresponds to a
diffusion-controlled reaction mechanism, 1.0−1.24, to a zero-
order, first-order, or phase-boundary-controlled mechanism,
and 2.0−3.0, to a nucleation- and growth-controlled mecha-
nism.53
Figure 4a−d shows t − t0 as a function of the extent of the
reaction with fits for the four different synthesis temperatures.
The rate constant (k) and mechanism-dependent parameter
(n) are obtained from the fits. It can be seen that the value of n
decreases with temperature and varies from 0.9 to 0.4; however,
all four data points fall outside of physically meaningful ranges,
as indicated with gray in Figure 4e. It can be concluded that the
reaction mechanism presumably changes from something that
is close to either zero- or first-order kinetics to a more diffusion-
controlled reaction mechanism with increasing temperature,
albeit the specific mechanism is uncertain. It could also be
caused by different reactions occurring in parallel, and further
total scattering experiments may clarify the formation
mechanism from amorphous to crystalline CoSb2O4.
The activation energy (Ea) can be calculated by the
Arrhenius equation k = A exp(Ea/RT), and it is obtained as
the slope when ln(k) vs 1000/T is plotted (Figure 4f). An
activation energy of 65(12) kJ/mol is obtained for the
crystallization of CoSb2O4 from an amorphous precursor.
This is in good agreement with activation energies obtained in
DOI: 10.1021/acs.cgd.5b01421
Cryst. Growth Des. 2016, 16, 834−841
Crystal Growth & Design
Figure 4. (a−d) Johnson−Mehl−Avrami plots for syntheses at (a)
135, (b) 150, (c) 180, and (d) 220 °C in the nonstoichiometric case.
(e) n values obtained from the fits at different synthesis temperatures
with gray areas indicating physically meaningful n values. (f) Arrhenius
plot.
other oxide systems synthesized under hydrothermal con-
ditions. For the formation of Fe2O3, TiO2, and α-Li2TiO3
nanocrystallites, activation energies of 67(15), 66(19), and
66(7) kJ/mol were estimated, respectively.49,51,54 Rossetti et al.,
by a pseudo in situ method, found an activation energy of the
apparent crystallization of PbTiO3 of 30 kJ/mol;52 however, the
initial formation was omitted in this case. The activation energy
for a phase transition in nanocrystals is a larger by a factor of 2,
e.g., the phase transition from β-chalcocite Cu2S to high
digenite Cu2−xS has an activation energy of 171(27) kJ/mol.50
Hence, the similarity found for the activation energy for the
oxides synthesized under analogous conditions is interesting,
but on the basis solely of these values, a conclusion for the
mechanism governing the formation cannot be drawn. Recent
total X-ray scattering studies of the hydrothermal formation of
nanoparticles have shown that the formation mechanism for
relatively simple oxides can be very complex: going from a
polymeric precursor to a highly disordered amorphous
precipitate before crystallizing in the desired phase.55−57
The changes in unit cell parameters obtained from the
sequential Rietveld refinement are plotted as a function of
crystallite size (Figure 5). Only changes in unit cell parameters
(a − afinal, c − cfinal, and V − Vfinal) are considered, owing to the
lack of an internal standard in the in situ experiments. It can be
seen that both the a and c axes decrease as the crystallite grows.
The change in unit cell parameters is anisotropic, as the
decrease is larger along the c axis than along the a axis. This
anisotropy is also seen in the formation of SnO2 nano-
particles.58 Furthermore, there is a clear enlargement of the unit
cell when the nanocrystallites are below 7 nm. At larger
crystallite sizes, the unit cell has almost relaxed to its final value,
which indicates that the internal atomic structure changes as a
function of crystallite size. The origin of this unit cell expansion
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Figure 5. Changes in the unit cell parameters as a function of
crystallite size. The color of the markers indicates a different synthesis
temperature (red, 135 °C; blue, 150 °C; purple, 180 °C; and black,
220 °C).
with decreasing crystallite size has been ascribed to the
softening of lattice vibration.59 In the present study, it is not
possible to distinguish between the mechanisms involved in the
softening of the lattice vibration because reliable values of the
correlated occupancy, atomic thermal displacements, and
atomic positions cannot be extracted due to insufficient data
quality.
The in situ PXRD data show that changing the ratio between
antimony and cobalt from nonstoichiometric to stoichiometric
affects the formation mechanism, as shown in Figures 1 and 2.
Analysis of the stoichiometric data shows that the crystallite size
is more than doubled when the ratio is stoichiometric
compared with that for the nonstoichiometric case (Figure
6). Furthermore, the growth is significantly different when the
Figure 6. Crystallite size for CoSb2O4 nanoparticles (M(Sb)/M(Co)
= 2.00).
ratio is changed, as seen when comparing Figure 3 with Figure
6. In the stoichiometric case, the final crystallite size at 135 °C
is reached within the first 150 s; subsequently, the crystallite
size stabilizes around 34 nm. Upon an increase in the synthesis
temperature, the initial crystallite size of approximately 35 nm
increases to 44 and 52 nm at 180 and 300 °C, respectively.
Hence, the ratio of antimony to cobalt influences the final
crystallite size. Furthermore, there is both a temperature and
compositional dependence for the nanoparticles to grow by
Ostwald ripening (see the Supporting Information, Figure
S10).58 In the stoichiometric case at 135 °C, no Ostwald
ripening is observed since the scale factor can be superimposed
DOI: 10.1021/acs.cgd.5b01421
Cryst. Growth Des. 2016, 16, 834−841
Crystal Growth & Design
with the crystallite volume. Hence, the nanoparticles grow
because more CoSb2O4 can be formed from the precursor in
solution; thus, the growth and scale factor stagnate when the
precursor is depleted. When increasing the temperature to 180
°C or changing to nonstoichiometric conditions, Ostwald
ripening is observed (see the Supporting Information, Figure
S10).
Ex Situ Autoclave Study. The scaled-up autoclave-
synthesized ex situ product has a small impurity present, as
seen by the Rietveld refinement in Figure 7. It is speculated that
Figure 7. Rietveld refinement of high-resolution PXRD data measured
at 100 K. It is clear from the difference curve that an impurity is
present in the measured sample. RBragg = 4.50; RF = 2.41.
the prolonged synthesis time (53 h) might have induced
decomposition of the phase-pure CoSb2O4 since, as we have
just shown, CoSb2O4 can be synthesized in seconds from a
similar starting solution. It should be noted that there are small
differences between the two methods, especially the heating
rate and pressure. It has not been possible to identify the
impurity phase. The impurity might also explain the light blue
or greyish color of the material, which is in contrast with the
previous reported pinkish brown.3,19
Figure 8 display a TEM picture of the sample from the
autoclave synthesis, and it can be seen that at long synthesis
times the particles grow into rods and cubes. The largest rods
are around 400 nm in length and 100 nm in diameter, although
much smaller rods are also observable. The cubes have a similar
Figure 8. TEM picture of an autoclave synthesis sample used as the
anode material in Li-ion half-cells.
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large size distribution, with the smallest and largest being
around 80 and 300 nm in one dimension, respectively. No
micrometer-sized particles were found by SEM (see the
Supporting Information, Figure S15).
Rietveld refinements similar to those depicted in Figure 7
were performed for the five different temperatures on the high-
resolution PXRD patterns, ignoring the impurity phase (see the
Supporting Information, Figures S12 and S13). From these
multi-temperature Rietveld refinements, different physical
parameters can be extracted and evaluated as a function of
temperature, e.g., unit cell parameters. Figure 9 shows that
Figure 9. Thermal evolution of the unit cell as extracted from multi-
temperature Rietveld refinement. The linear fits show the region where
the thermal expansion coefficients are calculated.
there is a linear thermal expansion of the unit cell, although the
c parameter displays a deviation from linearity when compared
with the a parameter. Similarly, the unit cell’s thermal
expansion also shows this nonlinearity. The linear thermal
expansion coefficients with respect to 300 K are 6.2(1) × 10−6,
3.1(4) × 10−6, and 1.55(7) × 10−5 K−1 in the a and c directions
and for the unit cell, respectively. Comparing the absolute
values at 300 K obtained in this study of the a axis (8.5031(1)
Å) and c axis (5.9288(1) Å) with those reported by Koyama et
al. (a = 8.500(1) Å and c = 5.931(1) Å)3 and de Laune et al. (a
= 8.49340(9) Å and c = 5.92387(8) Å)19 reveals that the values
are slightly larger in this study. This discrepancy might be
explained by the difference in the synthesis methods used in
this study and the previous ones; although the absolute values
differ, the relative changes investigated in this study should still
be valid. None of the previously reported studies investigated
the thermal expansion of CoSb2O4. Comparing the thermal
expansion coefficients with those for MnSb2O4 shows that the
result found in this study is slightly lower but is of the same
order of magnitude.10
The atomic displacement parameters (ADPs) for all atoms
are shown in Figure 10. The best model is achieved when
antimony is allowed to vibrate anisotropically. Independent of
temperature, the oxygen atoms have the smallest ADP
(constrained to be identical for the two sites), whereas cobalt
display the largest ADP. The isotropic equivalent ADP value for
antimony is in between these two values. This is rather
surprising since de Laune et al. observed by neutron powder
diffraction that antimony has a larger ADP than cobalt.19 The
absolute values at 300 K are also slightly larger in the study
presented here. It should be noted that antimony is surrounded
by four O2− anions. The u11 for antimony is twice as large as all
other ADP elements, and upon extrapolation to 0 K, it
approaches a finite value, which could indicate that static
DOI: 10.1021/acs.cgd.5b01421
Cryst. Growth Des. 2016, 16, 834−841
Crystal Growth & Design
Figure 10. Atomic displacement parameters (ADPs) for (a) isotropic
(Co and O) or equivalent (Sb) and (b) anisotropic for antimony as a
function of temperature.
disorder contributes to u11. This could be a consequence of the
lone electron pair present in antimony, but detailed analysis is
beyond the scope of this article.60 Furthermore, there is a
decrease in electron density (void) in the center of the unit cell.
However, the long axis of the ellipsoid representing the
anisotropic vibration is in the ab plane, as shown in Figure 11.
Hence, it is not in the direction of the center.
Figure 11. Illustration of the unit cell with thermal ellipsoids shown
for antimony and octahedra for the cobalt atoms. The long axes for the
Sb ellipsoids point either in the a or b direction.
The lattice dynamics of the structure can be analyzed from
the ADPs, and here we approximate that the motion of the
atoms can be represented by a Debye model:
3ℏ2T ⎡ T θD/ T x θ ⎤
Uiso(T ) = ⎢
mkBθD2 ⎣ θD
∫0 exp(x) − 1
dx + D ⎥
4T ⎦
+ d2
Fitting the ADPs to this formula provides an estimate of the
Debye temperature (see the Supporting Information, page 12,
for details), which is also related to the average sound velocity
in the material. If an average atomic mass of 52.3 amu is used,
then a Debye temperature of 331(11) K is obtained for
CoSb2O4. If the ADPs of the individual atoms are fitted to the
Debye formula, then Debye temperature for the Co, Sb, and O
sublattices are 255(9), 208(2), 656(57) K, respectively.
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Electrochemical Measurements. Half-cells of type
CR2032 were measured in order to investigate the potential
of CoSb2O4 for use as an anode in LIBs. The galvanostatic
cycling of CoSb2O4 can be seen in Figure 12. The initial
Figure 12. Potential (vs Li/Li+) vs capacity for CoSb2O4 under
galvanostatic charge/discharge at 30 mA/g between 0.05 and 1.3 V for
the second, third, and tenth cycles. The inset shows the initial
discharge and charge curves.
discharge reached 1131 mAh/g, corresponding to ∼15 Li atoms
reacting with CoSb2O4. This is comparable to the 1127 mAh/g
reported by Jibin et al.20 and concurs with the formation of
Li2O and Li3Sb leaving one Li, e.g., for formation of the SEI
layer. The initial charge capacity was 417 mAh/g, which
corresponds to dealloying of slightly below two formula units of
Li3Sb. Furthermore, it should be noted that the unreacted
cobalt in the half-cells is electrochemically inactive. Future
studies might reveal how cobalt is bonded in the decomposed
compound and why this unusual inactivity is seen. On
subsequent cycling, the capacity fade was relatively fast, with
only ∼20 mAh/g reversible capacity remaining after the tenth
cycle.
■ CONCLUSIONS
We have demonstrated by in situ PXRD studies that phase-pure
CoSb2O4 nanoparticles can be synthesized under hydrothermal
conditions at temperatures ranging from 135 to 300 °C. The
dependence of the starting solution on stoichiometry was
investigated, and it was found that with the nonstoichiometric
precursor the nanoparticle sizes range from 14.5 to 17 nm. In
the case of a stoichiometric precursor, the sizes are twice as
large. The formation mechanism is different in the two cases, as
it was found that the nonstoichiometric precursor is
amorphous, whereas the stoichiometric precursor is crystalline.
The unit cell shows a clear enlargement for nanoparticles below
7 nm. Fitting growth curves with a Johnson−Mehl−Avrami
model yields an activation of 65(12) kJ/mol for the
crystallization of CoSb2O4 from a nonstoichiometric precursor.
A scaled-up ex situ autoclave synthesis gave submicrometer
CoSb2O4 particles, and Rietveld refinements of multi-temper-
ature high-resolution PXRD patterns reveal that the a axis
expands linearly with temperature, whereas the c axis deviates
slightly from linearity. The following linear thermal expansion
coefficients with respect to 300 K were obtained: αa = 6.2(1) ×
10−6 K−1 and αc = 3.1(4) × 10−6 K−1. Modeling the ADPs gives
a Debye temperature of 331(11) K for CoSb2O4. Its potential
for use as the anode material in LIBs is not promising, as the
material exhibits a large irreversible capacity on the first cycle
DOI: 10.1021/acs.cgd.5b01421
Cryst. Growth Des. 2016, 16, 834−841
Crystal Growth & Design
and the reversible capacity fades substantially on the following
cycles, resulting in a capacity of ∼20 mAh/g after the tenth
cycle. Further material improvements have to be conducted
before CoSb2O4 can be used in battery applications.
■
ASSOCIATED CONTENT
* Supporting Information
S (17) Whitaker, M. J.; Bayliss, R. D.; Berry, F. J.; Greaves, C. J. Mater.
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.5b01421.
Details of in situ data analysis, sequential Rietveld
refinement, and how the crystallite size is calculated from
spherical harmonics; contour plots for all in situ PXRD
data along with verification of precursor composition and
Ostwald ripening; temperature profile for the in situ
setup and examples of Rietveld refinements for two
frames; details of ex situ data analysis and Debye
temperature calculations together with representation of
the whole data range for the ex situ multitemperature
high-resolution data; and SEM picture of the obtained
particles synthesized ex situ (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: bo@chem.au.dk.
Funding
The work was supported by the Danish National Research
Foundation (Center for Materials Crystallography, DNRF93),
the Danish Research Council for Nature and Universe
(Danscatt), and the European Community’s Seventh Frame-
work Programme (FP7/2007-2013) CALIPSO under Grant
Agreement No. 312284
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Beamline I711 at MAX-LAB and RIKEN beamline BL4402 at
SPring-8 are gratefully acknowledged for beam time. Henrik L.
Andersen, Dr. Espen D. Bøjesen, and Dr. Mogens Christensen
are thanked for assistance during the experiments at MAX-LAB.
■
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841 DOI: 10.1021/acs.cgd.5b01421

Cryst. Growth Des. 2016, 16, 834−841