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A ceramic/polymer composite solid electrolyte for

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sodium batteries
Cite this: J. Mater. Chem. A, 2016, 4,
15823
Zhizhen Zhang,a Qiangqiang Zhang,a Cheng Ren,a Fei Luo,a Qiang Ma,b
Received 2nd September 2016 Yong-Sheng Hu,*a Zhibin Zhou,b Hong Li,a Xuejie Huanga and Liquan Chena
Accepted 23rd September 2016

DOI: 10.1039/c6ta07590h

www.rsc.org/MaterialsA

Achieving high ionic conductivity in solid electrolytes and reducing the
interfacial resistance between solid electrolytes and electrode materials
are considered to be one of the biggest challenges in developing solid-
state batteries. The integration of the high ionic conductivity of inor-
ganic ceramics and the flexibility of organic polymers was attempted to
yield a solvent-free ceramic/polymer composite solid electrolyte for Na
batteries for the first time. The composite solid electrolytes exhibit
a Na+ ion conductivity as high as 2.4 mS cm
1 at 80  C. Meanwhile, this
composite membrane is thermally stable up to 150  C and maintains
the flexibility of polymer electrolytes. The solid-state Na3V2(PO4)3/CPE/
Na battery using this ceramic/polymer composite electrolyte exhibits
an initial reversible capacity of 106.1 mA h g
1 and excellent cycle
performance with negligible capacity loss over 120 cycles.
Introduction
Due to the huge abundance and low cost of sodium resources,
there has been a new upsurge of interest in sodium batteries,
especially in the eld of large-scale applications, such as electric
vehicles and energy storage systems.1–4 However, the contin-
uous pursuit for safe and high energy density batteries has
imposed stringent requirements on electrolyte materials. The
currently used organic liquid electrolytes suffer from an
intrinsic limited electrochemical window and safety issues. The
substitution of solid electrolytes for organic liquid electrolytes
can not only alleviate safety concerns,5,6 but may also enable the
use of Na metal anode and high voltage cathode materials to
achieve high energy density in batteries.
Inorganic ceramics and organic solid polymer electrolytes
are the commonly used solid electrolyte materials. Inorganic
a
Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy
Materials and Devices, Beijing National Laboratory for Condensed Matter Physics,
Institute of Physics, Chinese Academy of Sciences, School of Physical Sciences,
University of Chinese Academy of Sciences, Beijing 100190, China. E-mail: yshu@
aphy.iphy.ac.cn
b
Key Laboratory for Large-Format Battery Materials and System, Ministry of
Education, School of Chemistry and Chemical Engineering, Huazhong University of
Science and Technology, 1037 Luoyu Road, Wuhan 430074, China
ceramics such as NASICON and Na-b00 -Al2O3 possess many
advantages, including high ionic conductivity (>10
4 S cm
1),
a high Na+ ion transference number (t z 1), a wide electro-
chemical window (>5 V) and high thermal stability. However,
solid-state batteries using ceramic solid electrolytes always
show inferior electrochemical performance and limited cycle
life due to the poor interfacial conductance between ceramic
solid electrolytes and electrode materials.4,7 In addition,
ceramic materials have poor processability because of their
brittleness and hardness. In contrast, solid polymer electrolytes
are suitable for exible battery design, but suffer from other
defects, such as low ionic conductivity (<10
5 S cm
1 at ambient
temperature), a low cation transference number (t z 0.2–0.4)
and poor oxidation resistivity. The preparation of composites of
ceramic solid electrolytes and polymer electrolytes may achieve
a combination of high ionic conductivity, a high cation trans-
ference number and suitable mechanical properties.8–13 Exten-
sive efforts have been dedicated to investigate lithium ion
ceramic/polymer composite electrolytes (CPEs) and their elec-
trochemical performance in solid-state lithium-ion
batteries.14–16 Recently, attempts have also been made to explore
sodium ion hybrid electrolytes, including gel-polymer electro-
lytes based on cross-linked PMMA,17 gel-polymer/glass-ber
electrolytes,18 and hybrid electrolytes consisting of NASICON
ceramic, PVdF-HFP and ether-based electrolytes.19 Although the
batteries using these hybrid electrolytes exhibit good electro-
chemical properties, safety issues can't be ultimately eliminated
because of the liquid electrolyte contained in the hybrid
electrolytes.
Herein, we develop a solvent-free PEO based ceramic/poly-
mer composite electrolyte (CPE) for the rst time. Two different
ceramic llers, Na3Zr2Si2PO12 and Na3.4Zr1.8Mg0.2Si2PO12, with
different contents are attempted. The composite electrolytes
lled with Na3.4Zr1.8Mg0.2Si2PO12 ceramic exhibit better ionic
conducting properties. An excellent ionic conductivity of
2.4 mS cm
1 at 80  C can be obtained when 40 wt% of Na3.4-
Zr1.8Mg0.2Si2PO12 was included. These composite electrolytes
also show high thermal stability and exibility, which make

This journal is © The Royal Society of Chemistry 2016 J. Mater. Chem. A, 2016, 4, 15823–15828 | 15823

Journal of Materials Chemistry A
them feasible in solid state batteries. The electrochemical
performance of the composite electrolytes was evaluated by
using the solid-state Na3V2(PO4)3/CPE/Na cells.
Experimental section
Preparation and characterization of the Na+ ion ceramic/
polymer composite solid electrolyte
The NASICON structured Na3Zr2Si2PO12 and Na3.4Zr1.8Mg0.2-
Published on 23 September 2016. Downloaded by University of Waterloo on 08/12/2017 15:13:50.
Si2PO12 solid electrolyte was synthesized by a sol–gel method.
Firstly, tetraethyl orthosilicate (TEOS), ethanol and H2O were
mixed at a molar ratio of 1 : 10 : 20. An appropriate amount of
citric acid was added and the mixture was stirred at 60  C.
Secondly, NaNO3, ZrO(NO3)2 and Mg(NO3)2 were dissolved in
deionized water and added to the previous solution. Finally,
(NH4)2HPO4 aqueous solution was added and a clear collosol
was obtained. The collosol was heated at 80  C to get a gel. The
obtained precursor was rst sintered at 900  C for 24 h. Aer
a second mixing, the sintered powder was pressed to sample
discs (diameter 13 mm, thickness 1 mm) and calcined at 1100–
1200  C for 24 h. The resulting ceramic disk was crushed and
ground into powder for use.
The ceramic/polymer composite electrolyte was prepared
from PEO, NaFSI, and Na3Zr2Si2PO12/Na3.4Zr1.8Mg0.2Si2PO12
ceramic powder by using the solution-casting technique. The
PEO polymer (Mw ¼ 600 000) and sodium bis(uorosulfonyl)
imide (NaFSI) were dried at 50  C and 60  C, respectively, in
a vacuum oven for 24 h before use. PEO, as the matrix, and
NaFSI, as the sodium salt to give an [EO] : [Na] ratio of 12 : 1,
were weighed and dissolved in anhydrous acetonitrile in a glo-
vebox. The above mixture was sealed in a bottle and stirred at
60  C for 24 h. Aerwards, Na3Zr2Si2PO12/Na3.4Zr1.8Mg0.2Si2-
PO12, as a sodium ion conducting ceramic ller, was added and
the solution was mixed by ball milling for 12 h. The resulting
viscous solution was then cast onto a Teon plate and the
solvent was le to evaporate slowly at room temperature. The
obtained lm was nally dried at 60  C in a high vacuum oven
for 24 h to remove all the residual solvent. The nal lms with
a thickness of 200–400 mm were yielded.
XRD patterns of the ceramic electrolytes were collected on
a D8 Bruker ASX D8 advanced X-ray diffractometer equipped
with Cu Ka radiation at a scan rate of 1 min
1. TG measure-
ments were conducted on a Netzsch STA 449C differential
scanning calorimeter in an Ar atmosphere at a scanning rate of
10  C min
1 from room temperature to 150  C.
Linear sweep voltammetry (LSV) experiments were per-
formed to investigate the electrochemical window of the
ceramic/polymer composite electrolytes with stainless steel as
the working electrode and sodium foil as the counter electrode,
at a scanning rate of 0.1 mV s
1 and 60  C.
The cross-sectional morphology of the composite electrolytes
was observed on a scanning electron microscope (Hitachi
S-4800). The elemental distribution was calculated using energy
dispersive X-ray spectroscopy (EDX).
The ionic conductivity of the ceramic/polymer composite
electrolytes was measured using an impedance analyzer (Im6e)
in a frequency range of 4 MHz to 100 mHz from 20  C to 100  C.
15824 | J. Mater. Chem. A, 2016, 4, 15823–15828
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The composite electrolyte lms were cut into discs and sand-
wiched between two blocking stainless steel electrodes. For
conductivity tests at each temperature, the samples were
allowed to equilibrate for 4 h prior to measurements.
Electrochemical test
The cathode slurry was prepared by mixing the synthesized
carbon coated (5 wt%) Na3V2(PO4)3, Na3.4Zr1.8Mg0.2Si2PO12
ceramic powder, super P and PVDF binder in a weight ratio of
65 : 20 : 5 : 10. The slurry was then coated onto an aluminum
foil and dried in a vacuum at 120  C for 12 h. The cathode lms
were cut into 0.64 cm2 (0.8 cm  0.8 cm). Solid-state
Na3V2(PO4)3/CPE/Na and Na3V2(PO4)3/SPE/Na cells were then
assembled by sandwiching the CPE and SPE, respectively,
between the Na3V2(PO4)3 cathode and Na anode. All the cells are
assembled in 2032-type coin-type cells in an argon lled glove-
box ([H2O] < 0.1 ppm, [O2] < 0.1 ppm). The charge/discharge
tests of the cells were performed between 2.5 V and 3.8 V. The
mass loading of the cathode is about 2.5 mg cm
2.
Results and discussion
The XRD patterns of the NASICON structured Na3Zr2Si2PO12
and Na3.4Zr1.8Mg0.2Si2PO12 are presented in Fig. 1(c). The ob-
tained Na3Zr2Si2PO12 is phase pure and can be assigned to the
monoclinic C2/c space group. In the XRD pattern of Na3.4Zr1.8-
Mg0.2Si2PO12, a small peak appearing at 20.88 corresponds to
the NaMgPO4 (PDF#:32-1122) impurity. The crystal structural
and lattice parameters of both compositions are rened by the
Rietveld method,20 and the results are shown in Table 1. An
increase in the lattice parameters of the a axis, b axis and
volume can be clearly observed when Mg2+ was introduced into
the NASICON system (Table 1). The SEM image in Fig. 1(a)
shows that the particle size of the Na3.4Zr1.8Mg0.2Si2PO12
powder ranges from about 0.5 to 2 mm. Fig. 1(b) presents the
cross-sectional image of the Na3.4Zr1.8Mg0.2Si2PO12 ceramic
pellet. It can be seen clearly that a highly dense ceramic was
obtained when the Mg element was introduced into the NASI-
CON system. The impedance spectra of Na3Zr2Si2PO12 and
Na3.4Zr1.8Mg0.2Si2PO12 are displayed in Fig. 1(d). Both the bulk
and grain boundary resistances are reduced by Mg doping. As
a result, the total ionic conductivity can be enhanced from
0.67 mS cm
1 for Na3Zr2Si2PO12 to 1.6 mS cm
1 for Na3.4Zr1.8-
Mg0.2Si2PO12. The improvement in the bulk conductivity can be
attributed to the increased Na content. On the other hand, by
introducing the Mg element, the relative density of the ceramics
increases from 87.6% for Na3Zr2Si2PO12 to 97.6% for Na3.4-
Zr1.8Mg0.2Si2PO12. Therefore, the enhancement in the grain
boundary conductivity is caused by the densication of the
ceramics.
In order to investigate the distribution of the ceramic llers
in the polymer substrate, energy dispersive X-ray (EDX)
mapping analysis was performed. The photo image and the
cross-sectional image of 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–
NaFSI CPE are shown in Fig. 2(a) and (b), respectively. It can be
observed that Na3.4Zr1.8Mg0.2Si2PO12 ceramic powders are
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shown in Fig. 3. Table 2 shows the ionic conductivity values

under 25 C and 80 C of all these compositions. A conductivity
of 3.7  10
6 S cm
1 at 25  C is demonstrated by the PEO12–
NaFSI SPE (Fig. 3(a)). From Fig. 3(b) and (c), it can be observed
that the ionic conductivities of the Na3Zr2Si2PO12–PEO12–NaFSI
and Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI CPEs show an
increasing tendency when the ceramic ller content increases
until the maximum conductivities are reached at a content of
40 wt% (i.e. 2.2  10
5 S cm
1 at 25  C for Na3Zr2Si2PO12–
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PEO12–NaFSI and 4.4  10
5 S cm
1 at 25  C for Na3.4Zr1.8-

Fig. 1 (a) The SEM image of the nominal Na3.4Zr1.8Mg0.2Si2PO12
powder; (b) the cross-sectional image of the nominal Na3.4Zr1.8-
Mg0.2Si2PO12 ceramic pellet; (c) the XRD patterns of the Na3Zr2Si2PO12
and nominal Na3.4Zr1.8Mg0.2Si2PO12; (d) the impedance spectra of the
Na3Zr2Si2PO12 and nominal Na3.4Zr1.8Mg0.2Si2PO12 ceramic pellets at
25  C.
uniformly embedded in the polymer matrix. Fig. 2(c) displays
the EDX mapping of Na, Mg, Zr, Si, C and S elements. It can be
seen clearly that Na, Mg, Zr, and Si elements of the NASICON
powder are homogenously distributed in the composite elec-
trolyte. The distribution of the S element from the NaFSI salt
and the C element from PEO indicates that the salt is well dis-
solved in the PEO matrix.
The impedance spectra of the PEO12–NaFSI SPE, the Na3-
Zr2Si2PO12–PEO12–NaFSI and Na3.4Zr1.8Mg0.2Si2PO12–PEO12–
NaFSI CPEs with different contents of ceramic llers at 25  C are
Mg0.2Si2PO12–PEO12–NaFSI, respectively). Fig. 3(d) shows the
temperature dependence of the ionic conductivity of these
lms. The conductivity curves of the PEO12–NaFSI lm show
a break at 40–50  C due to the crystalline–amorphous transition
of the PEO component. In the temperature-dependent
conductivity curves of the composite lms, no signicant
transition can be observed. This indicates that the addition of
ceramic llers decreases the crystallinity of PEO. As a result, the
ratio of the amorphous area in the ceramic/polymer composite
electrolytes increased and the crystalline–amorphous transition
is weakened. The ionic conductivities of the composite elec-
trolytes are much higher than those of PEO12–NaFSI SPEs below
50  C. The total conductivity of the Na3.4Zr1.8Mg0.2Si2PO12–
PEO12–NaFSI CPE containing 40 wt% ceramic llers is about
one order of magnitude higher than that of the PEO12–NaFSI
SPEs over this temperature region. At temperatures above 50  C,
the ionic conductivity of the 40% Na3Zr2Si2PO12–PEO12–NaFSI
composite lm is only slightly higher than that of the PEO12–
NaFSI SPEs, while the 40% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI
composite lms still show a much higher conductivity
compared with PEO12–NaFSI SPEs. These results suggest that
the content of the ceramic ller affects the conductivities of the
composite electrolytes signicantly. A conductivity of

Table 1 Refined unit cell parameters of Na3Zr2Si2PO12 and nominal Na3.4Zr1.8Mg0.2Si2PO12

Composition a (Å) b (Å) c (Å) b ( ) V (Å3)

Na3Zr2Si2PO12 15.631(1) 9.039(1) 9.224(1) 123.680(1) 1084.50(4)

Na3.4Zr1.8Mg0.2Si2PO12 15.675(5) 9.071(8) 9.217(2) 123.880(3) 1088.17(9)

Table 2 The ionic conductivities of the PEO12–NaFSI SPE and of the Na3Zr2Si2PO12–PEO12–NaFSI and Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI
CPEs with different contents of ceramic filler

Conductivity (S cm
1)

Compositions Ceramic ller 25  C 80  C

PEO12–NaFSI 3.7  10
6 9.0  10
4

20% NZSP–PEO12–NaFSI Na3Zr2Si2PO12 1.4  10
5 1.2  10
3
30% NZSP–PEO12–NaFSI Na3Zr2Si2PO12 1.6  10
5 1.3  10
3
40% NZSP–PEO12–NaFSI Na3Zr2Si2PO12 2.2  10
5 1.1  10
3
50% NZSP–PEO12–NaFSI Na3Zr2Si2PO12 9.6  10
6 1.1  10
3
20% NZMSP–PEO12–NaFSI Na3.4Zr1.8Mg0.2Si2PO12 1.8  10
5 1.2  10
3
30% NZMSP–PEO12–NaFSI Na3.4Zr1.8Mg0.2Si2PO12 3.5  10
5 1.8  10
3
40% NZMSP–PEO12–NaFSI Na3.4Zr1.8Mg0.2Si2PO12 4.4  10
5 2.4  10
3
50% NZMSP–PEO12–NaFSI Na3.4Zr1.8Mg0.2Si2PO12 2.8  10
5 1.2  10
3

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Fig. 2 (a) The photo image of the ceramic/polymer composite electrolyte; (b) cross-sectional image of the 40% Na3.4Zr1.8Mg0.2Si2PO12–PEO–
NaFSI composite electrolytes; (c) EDX mapping of C, S, Na, Zr, Mg, and Si elements.

Fig. 3 Impedance spectra of (a) the PEO12–NaFSI SPE, (b) the Na3Zr2Si2PO12–PEO12–NaFSI CPEs with different contents of Na3Zr2Si2PO12 filler
and (c) the Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI CPEs with different contents of Na3.4Zr1.8Mg0.2Si2PO12 filler at 25  C; (d) temperature
dependence of the ionic conductivity of the PEO12–NaFSI SPEs, and 40 wt% Na3Zr2Si2PO12–PEO12–NaFSI and 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–
PEO12–NaFSI CPEs.

2.4 mS cm
1 at 80  C can be obtained for the 40 wt% Na3.4-
Zr1.8Mg0.2Si2PO12–PEO12–NaFSI composite lms.
The TG curve of the 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–
NaFSI composite lm is shown in Fig. 4(a). No weight loss
occurred below 150  C, indicating that the lm is thermally
stable up to this temperature. The electrochemical stability of
the composite solid electrolytes was evaluated by linear sweep
voltammetric measurements at 60  C. Fig. 4(b) displays the LSV
curve of the 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI CPE.
No peaks or noticeable oxidation current can be observed up to
4.37 V, which suggests that the composite electrolyte is stable
up to this potential.
The electrochemical performance of the composite lms was
evaluated in solid-state Na3V2(PO4)3/CPE-NZMSPO/Na cells
using the 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI
composite lm as the electrolyte and separator, Na3V2(PO4)3 as
the cathode and Na metal as the anode. For comparison, the
Na3V2(PO4)3/SPE/Na cells using the PEO12–NaFSI lm and
Na3V2(PO4)3/CPE-NZSPO/Na using the 40% Na3Zr2Si2PO12–
PEO12–NaFSI composite lm were also assembled. The cells

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Fig. 4 (a) The TG curve of the 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI CPE between room temperature and 150  C; (b) electrochemical
stability window of the 40 wt% Na3.4Zr1.8Mg0.2Si2PO12–PEO12–NaFSI CPE determined by linear-sweep voltammetry at a scan rate of 0.1 mV s
1
with stainless steel as the working electrode and a sodium foil as the counter electrode.
were cycled in the voltage range of 2.5–3.8 V at 80  C. Fig. 5(a)
shows the 1st charge–discharge curves of the Na3V2(PO4)3/CPE-
NZMSPO/Na and Na3V2(PO4)3/SPE/Na cells at 0.1C. The
Na3V2(PO4)3/CPE-NZMSPO/Na cell delivers a reversible capacity
of 106.1 mA h g
1, with an initial coulombic efficiency of 94.0%,
while the Na3V2(PO4)3/SPE/Na cell using the PEO12–NaFSI lm
exhibits a reversible capacity of 94.9 mA h g
1 with an initial
coulombic efficiency of 89.4%. The Na3V2(PO4)3/CPE-NZMSPO/
Na cell shows a very small polarization of 0.06 V, whereas, the
Na3V2(PO4)3/SPE/Na cell exhibits a large polarization of 0.16 V.
The rate performances of the Na3V2(PO4)3/SPE/Na and the
Na3V2(PO4)3/CPE-NZMSPO/Na cells are shown in Fig. 5(b) and
(c), respectively. The Na3V2(PO4)3/SPE/Na exhibits poor rate
performance, and no capacity can be obtained at a high rate of
0.5C. Aer cycling at 0.2C for another 35 cycles, a severe
degradation in the capacity occurred, which is consistent with
the results of our previous work.21 The Na3V2(PO4)3/CPE-
Fig. 5 (a) The 1st charge/discharge curves of the Na3V2(PO4)3/CPE-
NZMSPO/Na and Na3V2(PO4)3/SPE/Na batteries at 0.1C under 80  C;
(b) the rate performance of the Na3V2(PO4)3/SPE/Na batteries at 0.1C,
0.2C and 0.5C; (c) the rate performance of the Na3V2(PO4)3/CPE-
NZMSPO/Na batteries at 0.1C, 0.2C and 0.5C; (d) the cycling perfor-
mance of the Na3V2(PO4)3/CPE-NZMSPO/Na and the Na3V2(PO4)3/
CPE-NZSPO/Na batteries at a constant current density of 0.1C.
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NZMSPO/Na cell using the ceramic/polymer composite lm
displays an excellent rate performance, even at a high rate of
0.5C. When the current density goes back to 0.2C, the reversible
capacity can almost recover and no capacity degradation can be
observed aer another 10 cycles. The coulombic efficiency
increased steadily with the cycle number and remained at 99%
aer a few cycles. As depicted in Fig. 5(d), the Na3V2(PO4)3/CPE-
NZMSPO/Na cell shows superior cycling stability to the
Na3V2(PO4)3/CPE-NZSPO/Na cell and has no obvious capacity
loss aer 120 cycles. This outstanding electrochemical perfor-
mance of the solid state batteries can be ascribed to the high
ionic conductivity of the composite electrolyte and exible
interfacial contacts between the composite electrolyte and
electrode materials.
Conclusions
Ceramic/polymer composite solid electrolytes with exibility
and high ionic conductivity were studied for sodium solid state
batteries for the rst time. The content of the ceramic ller has
a signicant effect on the ionic conductivity of the composite
electrolytes. A high ionic conductivity of 2.4 mS cm
1 can be
obtained at 80  C. The composite electrolytes also show high
thermal stability and electrochemical stability. The
Na3V2(PO4)3/CPE/Na solid state battery using the composite
electrolyte shows good cycling performance at 80  C. The elec-
trochemical performance evidenced the advantages of utilizing
ceramic/polymer composite solid electrolytes in solid state
batteries.
Acknowledgements
This work was supported by the National Key Technologies R&D
Program (Grant No. 2016YFB0901504) and the National Natural
Science Foundation of China (Grant No. 51222210, No.
11234013, and No. 51421002).
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