K0.5V2O5: A Novel Li Intercalation Compound As Positive Electrode Material For Rechargeable Lithium Batteries
K0.5V2O5: A Novel Li Intercalation Compound As Positive Electrode Material For Rechargeable Lithium Batteries
K0.5V2O5: A Novel Li Intercalation Compound As Positive Electrode Material For Rechargeable Lithium Batteries
Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
a r t i c l e i n f o a b s t r a c t
Article history: We report here for the first time the reversible electrochemical lithium insertion in the potassium vana-
Received 25 October 2013 dium bronze K0.5 V2 O5 leading to Lix K0.5 V2 O5 with 0 < x ≤ 1.5. Long and thin platelets of K0.5 V2 O5 are
Received in revised form 2 December 2013 prepared by a fast and facile synthesis route. A specific capacity of 210 mAh g−1 is available at an average
Accepted 5 December 2013
voltage of 2.6 V without any significant structural changes even after extended cycling experiments. This
Available online 19 December 2013
vanadium bronze exhibits an excellent capacity retention with still 200 mAh g−1 at C/10 after 70 cycles
and a good rate capability with 140 and 120 mAh g−1 at 1 C and 1.4 C respectively. The electrochemical
Keywords:
performance of this cathode material is one of the best among vanadium bronzes.
lithium batteries
layered lithium intercalation compound © 2013 Elsevier Ltd. All rights reserved.
potassium vanadium bronze.
0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.12.039
S. Bach et al. / Electrochimica Acta 119 (2014) 38–42 39
the cathode material was pressed (5 t/cm2 ). The cathode was made observed from SEM micrographs showing a stacking of platelets to
of a mixture of active material (80% wt), acetylene black (7.5% wt), form long and thin particles. The structure can be viewed as one-
graphite (7.5% wt) and teflon as binder agent (5% wt). A typical dimensional stacking of atomic sheets along the c axis (Fig. 1) and
mass loading of ≈ 10 mg cm−2 is used for each positive electrode. A is designed as a double-sheet V2 O5 layers with interstitial K atoms
stainless steel 2025 coin-type cell was assembled using this pos- (Fig. 3).
itive electrode and Li sheet as negative electrode. The cell was The Raman fingerprint of K0.5 V2 O5 is reported here for the
filled with a commercial grade LP71 electrolyte (Merck) that means first time (Fig. 4a). It Exhibits 21 modes in the 90-1020 cm−1
1 M LiPF6 (EC/DEC/DMC = 1:1:1). Galvanostatic experiments and wavenumber range located at 96, 115,165, 233, 271, 330, 347, 407,
impedance measurements were made with a VMP3 Biologic appa- 431, 471, 509, 604, 702, 784, 850, 887, 946, 960, 980, 1008 and
ratus. Impedance measurements were performed using a three 1020 cm−1 . K0.5 V2 O5 framework is made of VO6 distorted units
electrode cell in the frequency range 4 10−4 -10−3 Hz. The excita- which are also involved to describe the structure of V2 O5 [9]
tion signal was 10 mV peak to peak. For the GITT measurements Although K0.5 V2 O5 belongs to a different point symmetry group
allowing a quasi OCV curve to be obtained the cell was discharged (C2 h) than does V2 O5 (D2h ), many of the internal optic modes
and charged at a current pulse of 100 A for 30 min followed by a wavenumbers are determined by the vanadium-oxygen covalent
relaxation period for 5 h. bonds and the basic structure of the V-O polyhedra, both of which
are quite similar in the crystals. Therefore, a first interpretation
of the Raman spectrum of K0.5 V2 O5 can be proposed by compari-
3. Results and discussion
son with the spectrum of V2 O5 . In the 100-900 cm−1 wavenumber
region, most of the bands have their counterpart in the Raman spec-
SEM images of K0.5 V2 O5 reveal well defined and regular platelets
trum of V2 O5 and may be assigned to the different V-O-V bending
about 10 m long, 1 m wide and 0.5 m thick (Fig. 1). The size
distribution seems homogeneous throughout the sample. It is out-
standing that the shape of K0.50 V2 O5 particles resembles that
obtained for the microwave synthesized K0.51 V2 O5 bronze [7].
001
However in the latter case larger particles with many defects and
a heterogeneous size distribution were obtained.
The typical XRD pattern of the powder obtained is shown in
Intensity
004
31-1
11-1
110
600
Fig. 3. Schematic representation of the layered structure of K0.5 V2 O5 with interlayer potassium ions in green, oxygen atoms in red and vanadium atoms in blue.
and V-O stretching vibrations in the VO6 octahedra [9] Table 1. In We describe now the electrochemical Li insertion-extraction
the 900-1020 cm−1 range, the stretching vibrations of the shortest reaction in K0.5 V2 O5 which has never been reported as yet. The evo-
V = O bonds are observed. Multiple features (at 946, 960, 980, 1008 lution of the equilibrium potential of Lix K0.5 V2 O5 vs. x is obtained
and 1020 cm−1 ) are clearly highlighted in this region for K0.5 V2 O5 from GITT measurements and shown in Fig. 5. The resulting pro-
compared to one single band at 995 cm−1 in V2 O5 . This multiplic- file can be considered as a quasi OCV curve. Three insertion steps
ity may be due to the presence of two V-O short bonds of 1.6 Å appear at 3 V, 2.8 V and 2.55 V with variable Li uptakes of 0.2, 0.6
[8] in K0.5 V2 O5 combined with the existence of both V4+ = O and and 0.7 Li per mole of bronze respectively. The total faradaic yield
V5+ = O species in the bronze. Worth is also noticing intense Raman of 1.5 F/mole of bronze involved in the overall reduction process
features at 784 and 887 cm−1 which probably correspond to the exactly correspond to the number of available V5+ ions in K0.5 V2 O5 .
stretching vibrations of strongly asymmetric V-O-V bridges in the The related specific capacity is high since it reaches 210 mAh g−1 .
double layer structure of K0.5 V2 O5 . It is commonly recognized that Worth noting is the highly reversible behaviour evidenced during
this mode is not observable in Raman spectra of V2 O5 because of Li extraction up to 3.70 V leading to the Li free host structure. The
its low intensity. Low Raman intensity of this mode is due to the layered structure of K0.5 V2 O5 characterized by a large interlayer
antisymmetric stretching character of the V-O bonds vibration in ´ about twice that encountered in the V O par-
spacing of 7.7 Å, 2 5
nearly linear V-O-V bridge that leads to compensation effect [9]. ´ probably explains a facile and reversible Li
ent oxide (≈ 4.37 Å),
Ab initio calculations are in progress to complete this preliminary
insertion-extraction process.
spectroscopic analysis.
The electrochemical fingerprint of K0.5 V2 O5 strongly differs
from that known for other potassium bronzes and mixed oxides. In
the tunnel structure of K0.25 V2 O5 , Li accommodation occurs in par-
ticular sites with strong repulsive coulombic interactions leading
782
163
4
Raman Intensity
329
700
942
405
884
505
3.5
1007
266
230
922
958
E vs (Li/Li )/V
(b)
+
165
784
887
3
330
509
704
271
407
1009
233
347
946
2.5
850
604
431
960
980
(a)
100 200 300 400 500 600 700 800 900 1000
2
-1 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Wavenumber / cm
x in Li K V O
x 0.5 2 5
Fig. 4. Raman fingerprint of K0.5 V2 O5 powder before (a) and after 100 cycles at C/10
(b). Fig. 5. OCV curve of K0.5 V2 O5 vs.x in Lix K0.5 V2 O5 obtained from GITT experiments.
S. Bach et al. / Electrochimica Acta 119 (2014) 38–42 41
001
* b
003
002
Intensity
004
110
* *
001
* a
003
*
002
004
110
*
10 20 30 40 50 60
2θ (Co Kα , °)
Fig. 7. XRD pattern of the K0.5 V2 O5 powder after (a) 1 cycle and (b) 100 cycles at
b C/10 (*: Teflon and Graphite).
and short range structure of K0.5 V2 O5. Indeed, the main diffraction
lines as well Raman bands still appear without any shift or inten-
sity decrease. In addition, the Raman spectrum obtained after 100
cycles does not make evidence of any new bands due to the pres-
ence of parasite phase formed at the surface of the electrode during
cycling. Only a decrease in the relative intensity of the 887 cm−1
band is observed, which suggests some change in the geometry of
the V-O-V bridges in the double layer structure of K0.5 V2 O5 upon
cycling. Such findings support the high capacity retention observed
c during cycles (Fig. 6c). Such a behaviour is better than that reported
for K3 V5 O14 , KV3 O8 and K0 .25 V2 O5 . This specific capacity of 200
mAh g−1 remains lower than that of the best potassium vanadium
oxide KV5 O13 investigated so far but can be due to a larger amount
of carbon (33% wt) used in the case of KV5 O13 and to the different
V5+ contents in the two compounds [4].
Fig. 8 shows the results of rate tests for K0.5 V2 O5 from C/7 to 2 C.
Whatever the C rate, a remarkable stability is obtained. The capacity
changes from 210 mAh g−1 at C/7 to 160 mAh g−1 at 0.7 C and 120
mAh g−1 at 1.4 C. A significant drop in capacity is seen only for 2.8 C
(≈70 mAh g−1 ). The cycling properties of K0.5 V2 O5 at high current
densities (≥ 2 C) would require an optimization of the electrode
technology. Owing to the particular morphology of the particles
(Fig. 1), the use of NTCs as carbon matrix should favor the electron
Fig. 6. Discharge-charge curves of K0.5 V2 O5 at (a) C/10 and (b) C/2 measurements in percolation.
the 4V-2 V range; (c) Evolution of the specific capacity versus cycle number at C/10
The kinetics of Li transport is known to impact the rate capa-
and C/2. For comparison results achieved for K0.25 V2 O5 at C/10 are reported.
bility. A typical ac impedance diagram is shown Fig. 9. A well
defined high frequency semi-circle is followed at medium frequen-
cies by a straight line with a phase angle of 45◦ from the real axis
to sharp discontinuities in the discharge-charge profile and a little
bit larger specific capacity of 230 mAh g−1 . A very low capacity of
70 mAh g−1 is achieved with KV3 O8 . The large interlayer spacing
in K0.5 V2 O5 probably levels the mean working voltage leading to 2
250
a sloped curve. A detailed study of its structural response is under
investigation by XRD and Raman spectroscopy. 100 A (C/7)
Specific capacity /mAh g
100 A
-1
1.5
potential range are depicted in Fig. 6a. During the first ten cycles at 500 A
500 A
C/10 the discharge capacity slightly increases with cycles from 1.5 750 A 150
to 1.6 F/mole of bronze. This can be explained by an extraction of a 1 1mA
small amount of potassium ions. In addition to the full Li extraction,
100
the larger capacity in charge indicates the possible oxidation of a
2mA
limited amount of V4+ into V5+ combined with a release of K+ ions. 0.5
50
This progressive but limited process allows a maximum capacity of
-1
60 *
References
f =0.03Hz
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