Electrochimica Acta 119 (2014) 38–42

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

K0.5 V2 O5 : A novel Li intercalation compound as positive electrode

material for rechargeable lithium batteries
S. Bach a,b,∗ , A. Boudaoud a , N. Emery a , R. Baddour-Hadjean a , J.-P. Pereira-Ramos a
a
Institut de Chimie et des Matériaux Paris-Est, GESMAT, UMR 7182 CNRS-Université Paris Est Créteil, 2, rue Henri-Dunant 94320 Thiais
b
Université d’Evry Val d’Essonne, Département Chimie, Bld François Mitterrand, 91025 Evry Cedex, France

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.

1. Introduction or the hydrothermal route [8]. However, in spite of an open

structure made of double-sheet V2 O5 layers particularly suitable
The idea of employing potassium vanadates as insertion com- for reversible Li accommodation, the electrochemical behaviour
pounds in positive electrodes for lithium batteries was introduced of K0.5 V2 O5 has never been evaluated as cathodic material for
nearly three decades ago by Raistrick and Huggins [1,2]. These rechargeable Li batteries. Here we demonstrate the attractive
works focused on thermodynamic data for Li intercalation reac- electrochemical properties of K0.5 V2 O5 synthesized via a solution
tion in the tunnel structure of K0.25 V2 O5 synthesized by a solid route leading to a fine powder of active material with a specific
state reaction. Maingot et al. [3] proposed a filling scheme of crys- platelet-like morphology. This reproducible rapid synthesis allows
tallographic sites by Li ions to account for the electrochemical to prepare few grams at laboratory scale. This active material deliv-
behavior of the same compound prepared by the sol-gel route. ers nearly 200 mAh g−1 at C/10 in the 4 V/2 V potential range with
However the cycle life of this sol-gel vanadium bronze was rather an excellent capacity retention which makes it one of the best can-
poor. Various potassium vanadium mixed oxides, K3 V5 O14 , KV3 O8 , didates among the potassium vanadium bronzes and oxides.
KV5 O13 and bronzes phases such as K2 V8 O21 have been tested
in view of their possible use as positive electrodes for secondary
cells at room temperature [4] and at 120 ◦ C [5]. K2 V8 O21 and 2. Experimental
KV5 O13 showed interesting capacities in the range 150-200 mAh
g−1 with a low capacity retention for K2 V8 O21 while only a lit- 1 g of V2 O5 (Alfa Aesar 99.995%) and 0.5 g of KVO3 (Alfa Aesar
tle Li amount reversibly entered the K3 V5 O14 and KV3 O8 layered >99.9%) were dissolved in 10 cm3 aqueous solution with 30 cm3
compounds [4]. The Kx V2 O5 compounds with 0 < x < 2 comprise H2 O2 (30%). A fast and violent exothermic reaction takes place
various phases whose homogeneity range is generally narrow due leading to a fine orange precipitate. The solid compound was then
to the large size of potassium ion [6]. Among them the K0.5 V2 O5 heat-treated at 570 ◦ C for 5 h under argon atmosphere. An elemen-
phase prepared from a solid state reaction between the appro- tal analysis by atomic absorption spectroscopy combined with a
priate amounts of reactants V2 O5 /VO2 /KVO3 at 550 ◦ C in a sealed redox titration analysis to determine the oxidation state of vana-
evacuated quartz ampoule was proved to exist [6]. This K0.5 V2 O5 dium ions lead to the chemical composition K0.5+/-0.02 V2 O5 . XRD
compound can be also prepared using microwave irradiation [7] experiments were performed using a Panalytical XPert pro appara-
tus equipped with a X’Celerator detector and using Co K␣ radiation
(␭K␣ =1.789 Å). The SEM experiments were carried out using a LEO
1530 instrument.
∗ Corresponding author. The working electrode consisted of a stainless steel grid (12 mm
E-mail address: [email protected] (S. Bach). diam., 0.2 mm thickness) with a geometric area of 1 cm2 on which

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

Fig. 1. SEM micrograph of the K0.5 V2 O5 powder.

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

Fig. 2. It compares very well with the literature reports of XRD

samples for K0.50 V2 O5 prepared using microwave irradiation [7]
and hydrothermal synthesis [8] and also with data of JCPDS file
039-0890. The chemical composition of the potassium bronze is in
40-1, 112
003

good accord with the elemental analysis leading to a K/V ratio of

002

004
31-1
11-1
110

600

0.25. The structure of K0.50 V2 O5 was determined by a single-crystal

study [8]. The material adopts a monoclinic symmetry (space group
´
C2/m, Z = 4) with the following unit cell parameters: a = 11.688 Å;
10 20 30 40 50 60
2θ (Co Kα, °)
´ c = 9.505 Å;
b = 3.668 Å; ´ Vm = 407 Å´ 3 ; ␤ = 92.24◦ . It exhibits a strong
preferred 00l orientation in good accordance with the morphology Fig. 2. XRD pattern of the K0.5 V2 O5 powder.
40 S. Bach et al. / Electrochimica Acta 119 (2014) 38–42

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

The discharge-charge cycles of K0.5 V2 O5 at C/10 in the 4V-2 V 200

Faradaic yield /F.mol

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

220 mAh g−1 to be reached after 10 cycles. Further cycling results

in an excellent capacity stability since 200 mAh g−1 are still recov- 0 0
0 10 20 30 40 50 60 70
ered after 70 cycles at C/10 and all the discharge-charge profiles
Number of Cycles
recorded superimpose whatever the C rate, C/10 and C/2 (Fig. 6).
The XRD pattern (Fig. 7) and Raman spectrum (Fig. 4b) of an elec- Fig. 8. Evolution of faradaic yield and specific capacity as a function of cycles and
trode after cycling do not indicate any change in the long range charge-discharge rates.
42 S. Bach et al. / Electrochimica Acta 119 (2014) 38–42

Table 1 corresponding to the Warburg impedance and then at low frequen-

Raman frequencies (cm−1 ) of K0.5 V2 O5 , and those previously reported for V2 O5 [9].
a
cies by a capacitive line related with the finite diffusion process. The
non observed experimentally.
apparent chemical diffusion DLi has been calculated from the War-
Vibrational modes V2 O5 From [9] K0 .5 V2 O5 [this work] burg region [10] and found to be equal to DLi ≈ 3.10−9 cm2 .s−1 .
Ag 104 96, 115 Using this relatively high value of DLi in the relation between the
B1g , B3g 144 165 limiting frequency ␻l , DLi and the maximum length for the Li diffu-
Ag , B2g 195 sion pathway (L), (␻l = 2␲f* l ≈ DLi /L2 ) (Fig. 9), the maximum length
B3g 220a 233
for the Li diffusion pathway L is found to be ≈ 1.3 ␮m. It clearly cor-
B1g , B3g 282 271
Ag 302 responds to the width of platelets. This indicates Li flow is probably
B2g 310a 330 perpendicular to the platelets thickness which promotes a fast and
B2g 350a 347 homogeneous lithiation process in the particles and then a good
Ag 403 407
rate capability.
431
Ag 480 471
B2g Ag 502a 526 509 4. Conclusion
604
B1g , B3g 700 702 We have reported the existence of K0.5 V2 O5 as new cathode
784
B2g 848a 850
material for rechargeable Li batteries in the K-V2 O5 system. Oper-
887 ating at an average voltage of 2.6 V, it delivers a reversible capacity
946 of 210 mAh g−1 with a good rate capability (120 mAh g−1 at 1.4 C).
960 These values are to the best of our knowledge the most attractive
B2g 976a 980
reported to date for a potassium vanadium bronze and compete
Ag 994 1008, 1020
with the KV5 O13 mixed oxide. The unusual large interlayer spac-
ing of 7.7 Å´ combined with K+ ions which stabilize the stacking of
double-sheet V2 O5 layers ensures a reversible Li accommodation-
extraction without any significant structural damage, as evidenced
by XRD and Raman measurements after 100 cycles. Moreover with
120
its fast, facile and low cost synthesis, and excellent cycle life (200
mAh g−1 at C10 after 70 cyles), K0.5 V2 O5 is a promising material for
100 rechargeable Li batteries. We believe that further improvements
might be possible through thorough tailoring of microstructure or
by using CNT as conductive agent well adapted to the particular
80
shape of particles.
-Z(im)/(Ω)

60 *
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l

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