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Superior Electrochemical Performance and Storage

Mechanism of Na3V2(PO4)3 Cathode for Room-Temperature
Sodium-Ion Batteries
Zelang Jian, Wenze Han, Xia Lu, Huaixin Yang, Yong-Sheng Hu,* Jing Zhou, Zhibin Zhou,
Jianqi Li, Wen Chen,* Dongfeng Chen,* and Liquan Chen

Energy storage and conversion remain significantly challenging could be used as a substitute for lithium to meet the demands
to the research community. Among the candidates, lithium-ion of rechargeable batteries. Furthermore, the sodium resources
batteries show great attraction and have been used in a wide are considered to be unlimited and sodium salts widely exist
range of applications, from small electronic devices, such as in the sea. Therefore, sodium-ion batteries demonstrate the
mobile phones and notebook computers, to increasing num- potential to substitute for lithium-ion batteries in the particular
bers of electric vehicles and large-scale energy storage equip- application in large-scale energy storage for renewable solar
ments.[1–6] However, the relatively high cost of lithium resources and wind power as well as smart grid.[7,8]
shows the potential problems in terms of the long-term and Tremendous attention has been paid to sodium-ion batteries
large-scale applications of lithium-ion batteries. Lithium in recent years. Many electrode materials, such as NaxCoO2,[9]
resources are limited; lithium makes up about 0.0065% of the NaCrO2,[10] Na1.0Li0.2Ni0.25Mn0.75Oδ,[11] NaNi1/3Mn1/3Fe1/3O2,[12]
earth′s crust and is unevenly distributed in South America. NaNi0.5Mn0.5O2,[13] Na2FePO4F,[14] V2O5,[15] Li4Ti5O12,[16]
Thus, development of alternative storage devices is not only Na2C8H4O4,[17] hard carbon[13,18,19] and TiO2[20] have been inves-
desirable but also necessary. Given this background, intense tigated for application in sodium-ion batteries. Very recently, we
interest in the use of sodium-ion batteries particularly for large- reinvestigated the sodium ion insertion/extraction into/from
scale energy storage has recently been rekindled. Sodium, an Na3V2(PO4)3 with a NASICON structure.[21] The NASICON
element of electrochemical equivalence and proper potential, structure features a highly covalent three-dimensional frame-
work that generates large interstitial spaces through which
sodium ions may diffuse.[22–24] Our previous study was the first
Dr. Z. L. Jian,[†] Dr. W. Z. Han,[†] X. Lu,[†] Prof. H. X. Yang, to demonstrate that carbon coating can significantly improve
Y.-S. Hu, J. Q. Li, L. Q. Chen its sodium storage performance.[21] Carbon-coated Na3V2(PO4)3
Key Laboratory for Renewable Energy electrodes show two flat plateaus at 3.4 V and 1.6 V vs. Na+/
Beijing Key Laboratory for New Na, respectively. The voltage plateau located at 3.4 V is relatively
Energy Materials and Devices, higher than that of other cathode materials for sodium-ion
Beijing National Laboratory for batteries in recent reports.[9–15] However, the coulombic effi-
Condensed Matter Physics ciency of the Na3V2(PO4)3 electrode in a half-cell is not as high
Institute of Physics as 99.5%, and does not even increase after the first cycle,[21]
Chinese Academy of Sciences
likely because of the NaClO4/PC electrolyte used. Moreover,
Beijing 100190, China
the storage capacity could also be enhanced by decreasing the
E-mail: yshu@aphy.iphy.ac.cn
carbon content of the composite and using optimized electro-
Dr. Z. L. Jian, Prof. J. Zhou, W. Chen
State Key Laboratory of Advanced Technology lyte system. In this contribution, Na3V2(PO4)3/C nanocompos-
for Materials Synthesis and Processing ites with different carbon contents were prepared by a one-step
School of Materials Science and Engineering solid state reaction and evaluated in different electrolyte sys-
Wuhan University of Technology tems. It was found that the sodium storage performance in
Wuhan 430070, China terms of capacity, coulombic efficiency and cyclability can be
E-mail: chenw@whut.edu.cn significantly improved in a new NaFSI/PC electrolyte which is
Dr. W. Z. Han, Prof. D. F. Chen introduced for the first time, bringing this material close to via-
China Institute of Atomic Energy bility as a promising cathode for room-temperature sodium-ion
Beijing 102413, China batteries. On the other hand, the mechanism of sodium inser-
E-mail: dongfeng@ciae.ac.cn
tion/extraction into/from Na3V2(PO4)3 lattice is firstly analyzed
Prof. Z. B. Zhou
by in situ XRD technique.
School of Chemistry and Chemical Engineering
Na3V2(PO4)3/C samples with different carbon contents
Huazhong University of Science and Technology
Wuhan 430074, China were synthesized by solid state reaction. The obtained sam-
[†]These authors contributed equally to this work. ples were denoted as sample 1 and sample 2, corresponding
to the samples with low and high carbon content, respec-
DOI: 10.1002/aenm.201200558 tively. The experimental details of the synthetic approach and

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Figure 1. a) XRD patterns of the Na3V2(PO4)3/C samples, b) TEM image
of sample 1 and c) TEM image of sample 2.

its characterizations are described in the Experimental Section.

Figure 1a presents the X-ray diffraction (XRD) patterns of the
resulting Na3V2(PO4)3/C samples. All of the diffraction peaks Figure 2. a) Raman spectra of the pristine Na3V2(PO4)3, sample 1 and
are indexed to the R-3c space group (2 Na in 18e position, sample 2, b) TG curves of sample 1 and sample 2.
1 Na in 6b position) and in good agreement with simulation
results deduced from the NASICON framework, including
the peak positions and intensities. The sharp peaks indicate (G band) were observed in both samples; these bands were
the good crystallinity in both samples. Figure 1b and 1c show the assigned to typical Raman features of carbon materials. The
high resolution transmission electron microscopy (HRTEM) disappearance or weakening of the Raman fingerprint char-
images of sample 1 and sample 2, respectively. Both samples acteristics of Na3V2(PO4)3 is caused by screening effects of
are uniformly coated with amorphous carbon layer which can the uniform conductive carbon layer coated on the surface of
be confirmed by XRD results where no diffraction peaks can Na3V2(PO4)3. Figure 2b shows the TG results, which indicate
be assigned to crystalline carbon. The thicknesses of the carbon that the carbon contents in the Na3V2(PO4)3/C nanocomposites
layer in sample 1 and sample 2 are estimated to be ca. 3 nm are 3.8 wt.% and 9.4 wt.%, respectively.
and 6 nm, respectively. Lattices are very obvious, further con- Our previous work showed that the coulombic efficiency of
firming the good crystallinity of the Na3V2(PO4)3 particles. Na3V2(PO4)3/C electrode in half-cells using NaClO4/PC elec-
Raman measurements and TG analyses were carried out trolyte is only about 94%. In order to further improve the cou-
to investigate the composition and carbon content in the lombic efficiency, several electrolyte systems including NaClO4/
resulting Na3V2(PO4)3/C nanocomposite. Figure 2a displays the PC, NaBF4/PC, NaPF6/EC+DEC, NaFSI/EC+DEC and NaFSI/
Raman spectra of the pristine Na3V2(PO4)3 and carbon coated PC systems were evaluated for the Na3V2(PO4)3/C electrodes;
Na3V2(PO4)3 (sample 1 and sample 2). The pristine sample the results are shown in Figure 3a. In the NaClO4/PC electrolyte
exhibits some bands located before 1200 cm−1, corresponding system, the coulombic efficiency for Na3V2(PO4)3/C electrode in
to the Raman fingerprint characteristics of Na3V2(PO4)3. The a half-cell is only 94.2% and does not increase in the following
bands located at around 1000 cm−1 and 442 cm−1 can be cor- cycles. (Note that in the case of non-carbon coated Na3V2(PO4)3
responded to the stretching vibrations and symmetric bending sample, the initial reversible capacity is only 82.6 mAh/g and
modes of the PO4, respectively. The bands below 400 cm−1 the coulombic efficiency is 82% in the NaClO4/PC electrolyte.
might be assigned to external modes of the PO4 tetrahedral In subsequent cycles, the capacity rapidly decreases and the
and/or modes arising from [VO6] octahedral.[25] After carbon coulombic efficiency is only 91% as shown in Figure S1.) The
coating, obvious bands at 1350 cm−1 (D band) and 1600 cm−1 initial coulombic efficiency is 94.4% and can be maintained at

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99.3% in subsequent cycles. Particularly in the NaFSI/PC elec-

trolyte system, the coulombic efficiency reaches 99.8% after the
first cycle. Given its excellent properties such as low melting
point (224.2 K), high dielectric constant, high chemical stability,
wide electrochemical window and low cost, as well as the results
of our electrochemical studies, PC appears to be an attractive
and promising non-aqueous electrolyte candidate that could be
used in stationary sodium-ion batteries operated at both high
and low temperatures.[26–28] NaFSI/PC was selected as optimal
electrolyte system.
Furthermore, the reversible capacity of sample 2 with 9.4 wt.%
carbon content as cathode is about 93 mAh/g. When the
carbon content in the nanocomposite is decreased, the initial
charge/discharge capacities of sample 1 with 3.8 wt.% carbon
content are 108.5 and 107.1 mAh/g at a current rate of C/10
(i.e., 25 μA/cm2) in NaFSI/PC electrolyte system (Note that
C/10 refers to two Na extraction from Na3V2(PO4)3 per formula
unit in 10 h); and corresponding initial coulombic efficiency is
98.7%. The potential polarization between the charge and dis-
charge curves of the first cycle is about 160 mV and the polariza-
tion shows an anomalistic decrease in subsequent cycles. After
10 cycles, the voltage polarization decreases to 50 mV. These
results are shown in Figure 3b. The phenomenon was also
observed in other electrolyte system, e.g., NaBF4/PC system.
However, this behavior is not obvious in NaClO4/PC and
NaPF6/EC+DEC systems. The stabilized NaFSI/PC electrolyte
could be partially responsible for the lower polarization (Note
that the polarizations for the 10th cycle are 70 mV, 100 mV and
80 mV in NaClO4/PC, NaBF4/PC, NaPF6/EC+DEC, respec-
tively, as shown in Figure S2, S3 and S4) though the specific
reasons are still unknown at this moment. The Na3V2(PO4)3/C
electrode also exhibits excellent cycling performance that its
reversible capacity is still kept at 99.5 mAh/g after 80 cycles (see
the Figure 3c). The capacity retention is 93%.
A full cell based on Na3V2(PO4)3/C nanocomposite as cathode
and hard carbon sphere as anode was initially constructued in
the NaFSI/PC electrolyte (Note that the discharge/charge pro-
files of hard carbon sphere were shown in the Figure S5.). A
preliminary result shows that the full cell delivers an average
operating voltage of about 2.7 V (Figure 4). It’s initial coulombic
efficiency is rather low at moment. However, we believe that the

Figure 3. a) Coulombic efficiencies for sample 2/Na cell in NaClO4/PC,

NaBF4/PC, NaPF6/EC+DEC, NaFSI/EC+DEC and NaFSI/PC; b) Charge/
discharge profiles sample 1/Na cell in NaFSI/PC, and c) Coulombic effi-
ciency and specific reversible capacity versus cycle number for sample 1/
Na cell in NaFSI/PC electrolyte at a current rate of C/10 in a voltage range
of 2.7–3.7 V vs. Na+/Na.

about 98% in the NaBF4/PC electrolyte. When the electrolyte

is changed to NaPF6/EC+DEC, the initial coulombic efficiency
is improved to 96.3%, and subsequent coulombic efficiency is
maintained at about 99%. The results may be ascribed to elec-
trolyte decomposition and other side reactions. However, the
coulombic efficiencies are significantly improved in the NaFSI-
based electrolyte systems. The initial coulombic efficiencies
were increased up to 98% and 98.2% in NaFSI/EC+DEC and Figure 4. The charge/discharge profiles for the Na3V2(PO4)3/hard carbon
NaFSI/PC electrolyte systems, respectively. In both electrolyte full cell in NaFSI/PC electrolyte at a current rate of C/10 in a voltage range
systems, subsequent coulombic efficiencies are larger than of 2.0 ∼ 3.4 V (the capacity is calculated based on the mass of cathode).

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The excellent electrochemical perform-
ance of the Na3V2(PO4)3/C electrode can be
ascribed to (i) the stable NaFSI/PC electro-
lyte; (ii) the open and immobile NASICON
structure of the Na3V2(PO4)3 host; and (iii)
small and reversible volume variation during
sodium insertion/extraction into/from the
Na3V2(PO4)3 host.
In summary, the sodium storage perform-
ances of Na3V2(PO4)3/C nanocomposites with
different carbon contents were optimized in
different electrolyte systems. It was found
that the sample with lower carbon content
exhibited the best performance in terms of
coulombic efficiency, storage capacity and
cyclability in the new NaFSI/PC electro-
Figure 5. In situ XRD patterns of the Na3V2(PO4)3/Na cell cycled between 3.7 and 2.7 V at a lyte. The initial coulombic efficiency for the
current rate of C/10, ♦ Na3V2(PO4)3, ♣ NaV2(PO4)3.
Na3V2(PO4)3/C electrode in NaFSI/PC system
can reach 98.7% and can be maintained at
initial coulombic efficiency and cycling performance could be 99.8% in subsequent cycles. The initial reversible capacity is
further improved by optimizing the mass ratio between cathode 107.1 mAh/g, close to its theoretical capacity, and its capacity
and anode materials. retention after 80 cycles is 93%. This significant progress makes
Figure 5 shows in situ XRD investigation on the this material close to viability as a promising cathode for room-
Na3V2(PO4)3/C electrode in an electrochemical cycle. The 2θ temperature sodium-ion batteries. The structure evolution of
ranges were recorded from 13.5° to 39.5°, a range that can well the Na3V2(PO4)3/C electrode during cycling was investigated by
reflects structural changes during sodium insertion/extraction in situ XRD measurement, whose results reveal a typical two-
into/from Na3V2(PO4)3/C electrode cycled between 2.7 and 3.7 V phase reaction between Na3V2(PO4)3 and NaV2(PO4)3 with a
at a current rate of C/10. At the beginning of charging the elec- small volume reversible change of 8.26%, thus leading to an
trode, all peaks are indexed to Na3V2(PO4)3 with the NASICON excellent cycling performance.
structure, except for some peaks from the current collector and
binder. Upon charging to 14 mAh/g, several new peaks appear.
The intensities of these new peaks increase while those from Experimental Section
Na3V2(PO4)3 decrease with continuous charging. The XRD pat- Na3V2(PO4)3/C samples were synthesized as follows: the 30 mmol
terns of chemically sodium extracted Na3V2(PO4)3 (see details NaH2PO4•2H2O (99.9%, Alpha), 10 mmol V2O3 (99.9%, Alpha) and
in experimental section) was recorded and shown in Figure S6 corresponding amounts of sugar (1 g and 2.5 g, respectively) were put
to identify these new diffraction peaks. ICP results show into an agate jar as precursors. The precursors were ball-milled in a
planetary ball mill (PM 200) at 400 rpm in a stainless steel vessel for
that the ratio of Na to V is 0.54:1, corresponding to the com-
8 h. After ball milling, the mixture was pressed into a pellet and then
position of NaV2(PO4)3 structure with a = 8.426 Å and c = heated at 800 °C for 24 h in an Ar atmosphere. The obtained samples
21.494 Å (space group: R-3c). Carefully analysis of the patterns were denoted as sample 1 and sample 2, corresponding to the samples
shows that new diffraction peaks are identical to those from chem- with low and high carbon content, respectively.
ically sodium extracted Na3V2(PO4)3. Thus, it can be concluded Chemically sodium extraction of the sample was accomplished by
that the new phase observed is the NaV2(PO4)3 phase. In the reaction with nitronium tetrafluoroborate (NO2BF4, Aldrich, 98%). Excess
NO2BF4 (Molar ratio, NO2BF4: Na3V2(PO4)3 = 3.2:1) was selected as the
charging plateau region at 3.4 V, all peaks from Na3V2(PO4)3 are
oxidant. Solid NO2BF4 was dissolved in acetonitrile and Na3V2(PO4)3
maintained and the intensities of their peaks gradually decrease, was added to the resulting solution. The slurry was stirred overnight
indicating a typical two-phase reaction between Na3V2(PO4)3 at room temperature, filtered under vacuum, and then finally washed
and NaV2(PO4)3. Nevertheless, the peaks of Na3V2(PO4)3 dis- several times with acetonitrile. The Na/V ratio of the obtained chemically
appear and all remaining peaks can be in accordance with the sodium extracted sample was measured by inductively coupled plasma
NaV2(PO4)3 phase at the end of charging to 3.7 V. During dis- (ICP).
charge, peaks from the Na3V2(PO4)3 phase appear again and Structural characterization was performed using an X’Pert Pro MPD
X-ray diffractometer (XRD) (Philips, Netherlands) with Cu Kα radiation
coexist with NaV2(PO4)3. Upon discharging to 2.7 V, only the (1.5405 Å). The morphology of the materials was observed with a
peaks of Na3V2(PO4)3 are observed while those from NaV2(PO4)3 transmission electron microscope (JEOL 2010). Thermogravimetric (TG)
phase completely disappear. The structure of the material com- analysis of the Na3V2(PO4)3/C sample was performed using a Diamond
pletely transforms back to the original NASICON Na3V2(PO4)3 TG thermoanalyzer in the oxygen atmosphere. Raman spectra were
phase at the end of discharge. Based on this, the calculated obtained using a Renishaw inVia micro-Raman spectroscopy system.
volume change from Na3V2(PO4)3 to NaV2(PO4)3 is ca. 8.26%, A slurry of the Na3V2(PO4)3/C sample, carbon black, and poly(vinyl
difluoride) (PVdF) at a weight ratio of 70: 20: 10 was spread onto pure
which is similar to that of an important cathode material,
Al foil (99.6%, Goodfellow) to prepare working electrodes. The electrode
LiFePO4 (ca. 6.8%),[29] used in lithium-ion batteries. This small material loading is about 3 mg/cm2. NaPF6 in ethylene carbonate (EC)
volume change could lead to excellent cycling performance as and diethyl carbonate (DEC) (1:1 by volume), NaBF4 in propylene
demonstrated by the above electrochemical studies. carbonate (PC), NaClO4 in PC, sodium bis(fluorosulfonyl) imides

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[8] P. Senguttuvan, G. Rousse, V. Seznec, J. M. Tarascon, M. R. Palacin,

China) in EC+DEC (1:1 by volume) and NaFSI in PC were employed as Chem. Mater. 2011, 23, 4109.
electrolytes for comparison. The concentration of all the electrolytes for [9] R. Berthelot, D. Carlier, C. Delmas, Nature Mater. 2011, 10, 74.
electrochemical tests is 1 mol/L. The water content in the electrolytes is [10] S. Komaba, C. Takei, T. Nakayama, A. Ogata, N. Yabuuchi, Electro-
below 15 ppm. Swagelok-type cells were assembled and disassembled chem. Commun. 2010, 12, 355.
with pure sodium foil as the counter electrode, a glass fiber as separator [11] D. Kim, S.-H. Kang, M. Slater, S. Rood, J. T. Vaughey, N. Karan,
in an argon-filled glove box (the water and oxygen contents are about M. Balasubramanian, C. S. Johnson, Adv. Energy Mater. 2011, 1,
0.5 ppm and 2 ppm, respectively.). The full cells were assembled by 333.
using Na3V2(PO4)3/C nanocomposite as cathode and hard carbon [12] D. Kim, E. Lee, M. Slater, W. Lu, S. Rood, C. S. Johnson, Electro-
as anode, where the mass ratio between cathode and anode is about
chem. Commun. 2012, 18, 66.
2:1. The hard carbon sphere was prepared according to our previous
[13] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki,
report.[30] Discharge and charge measurements were carried out on a
T. Nakayama, A. Ogata, K. Gotoh, K. Fujiwara, Adv. Funct. Mater.
Land BT2000 battery test system (Wuhan, China) at room temperature.
The voltage range was between 3.7 and 2.7 V vs. Na+/Na. For in situ XRD 2011, 21, 3859.
measurements, polytetrafluoroethylene (PTFE) was used as the binder [14] Y. Kawabe, N. Yabuuchi, M. Kajiyama, N. Fukuhara, T. Inamasu,
and the pure aluminum mesh was used as the current collector. R. Okuyama, I. Nakai, S. Komaba, Electrochem. Commun. 2011, 13,
1225.
[15] S. Tepavcevic, H. Xiong, V. R. Stamenkovic, X. B. Zuo,
M. Balasubramanian, V. B. Prakapenka, C. S. Johnson, T. Rajh, Acs
Supporting Information Nano 2012, 6, 530.
[16] L. Zhao, H. L. Pan, Y.-S. Hu, H. Li, L. Q. Chen, Chin. Phys. B 2012,
Supporting Information is available from the Wiley Online Library or
21, 028201.
from the author.
[17] L. Zhao, J. Zhao, Y.-S. Hu, H. Li, Z. Zhou, M. Armand, L.Q. Chen,
Adv. Energy Mater. 2012, 2, 962.
[18] S. Wenzel, T. Hara, J. Janek, P. Adelhelm, Energy Environ. Sci. 2011,
Acknowledgements 4, 3342.
[19] D. A. Stevens, J. R. Dahn, J. Electrochem. Soc. 2000, 147, 1271.
This work was supported by funding from “863” Project (2009AA033101), [20] H. Xiong, M. D. Slater, M. Balasubramanian, C. S. Johnson, T. Rajh,
“973” Projects (2010CB833102), NSFC (50972164, 51222210), CAS J. Phys. Chem. Lett. 2011, 2, 2560.
project (KJCX2-YW-W26), the 100 Talent Project of the Chinese Academy [21] Z. Jian, L. Zhao, H. Pan, Y.-S. Hu, H. Li, W. Chen, L. Chen, Electro-
of Sciences, Program for New Century Excellent Talents in University chem. Commun. 2012, 14, 86.
(NCET-09-0628) and Project-sponsored by SRF for ROCS, SEM. [22] C. Delmas, R. Olazcuaga, F. Cherkaoui, R. Brochu, C.R. Acad. Sc.
Paris, Série C t. 1978, 287, 169.
Received: July 24, 2012
[23] J. Gopalakrishnan, K. K. Rangan, Chem. Mater. 1992, 4, 745.
Revised: August 21, 2012
[24] B. L. Cushing, J. B. Goodenough, J. Solid State Chem. 2001, 162,
Published online: October 23, 2012
176.
[25] G. LePolles, J. J. Videau, R. Olazcuaga, M. Couzi, J. Solid State
Chem. 1996, 127, 341.
[1] M. Armand, J. M. Tarascon, Nature 2008, 451, 652. [26] Y. S. Hu, W. H. Kong, L. Hong, X. J. Huang, L. Q. Chen, Electrochem.
[2] J. B. Goodenough, Y. Kim, Chem. Mater. 2010, 22, 587. Commun. 2004, 6, 126.
[3] C. X. Zu, H. Li, Energy Environ. Sci. 2011, 4, 2614. [27] Y. S. Hu, W. H. Kong, Z. X. Wang, X. J. Huang, L. Q. Chen, Solid
[4] H. Li, Z. X. Wang, L. Q. Chen, X. J. Huang, Adv. Mater. 2009, 21, State Ionics 2005, 176, 53.
4593. [28] Y. S. Hu, W. H. Kong, Z. X. Wang, H. Li, X. J. Huang, L. Q. Chen,
[5] H. Q. Li, H. S. Zhou, Chem. Commun. 2012, 48, 1201. Electrochem. Solid-State Lett. 2004, 7, A442.
[6] A. Manthiram, J. Phys. Chem. Lett. 2011, 2, 176. [29] A. K. Padhi, K. S. Nanjundaswamy, J. B. Goodenough, J. Electrochem.
[7] V. Palomares, P. Serras, I. Villaluenga, K. B. Hueso, Soc. 1997, 144, 1188.
J. Carretero-González, T. Rojo, Energy Environ. Sci. 2012, 5, 5884. [30] Q. Wang, H. Li, L. Q. Chen, X. J. Huang, Carbon 2001, 39, 2211.

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