Journal of The Electrochemical Society, 160 (2) A351-A355 (2013)
0013-4651/2013/160(2)/A351/5/$28.00 © The Electrochemical Society
A351
A Scientific Study of Current Collectors for Mg Batteries
in Mg(AlCl2 EtBu)2 /THF Electrolyte
Dongping Lv,a,b Terrence Xu,a,b Partha Saha,a,c Moni Kanchan Datta,a,c
Mikhail L. Gordin,a,b Ayyakkannu Manivannan,a,d,∗ Prashant N. Kumta,a,c,e,f,g,∗,z
and Donghai Wanga,b,∗,z
a National Energy Technology Laboratory–Regional University Alliance (NETL-RUA), USA
b Department of Mechanical & Nuclear Engineering, The Pennsylvania State University, University
Park,
Pennsylvania 16802, USA
c Department of Bioengineering, Swanson School of Engineering, University of Pittsburgh, Pittsburgh,
Pennsylvania 15261, USA
d U.S. DOE NETL, Material Performance Division, Morgantown, West Virginia 26507, USA
e Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, Pittsburgh,
Pennsylvania 15261, USA
f Department of Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh,
Pittsburgh, Pennsylvania 15261, USA
g Center for complex Engineered Multifunctional Materials, Swanson School of Engineering, University of Pittsburgh,
Pittsburgh, Pennsylvania 15261, USA
The electrochemical behavior and stability of several current collectors (copper, nickel, stainless steel 316L, aluminum, titanium)
potentially employed in magnesium batteries with non-aqueous Mg(AlCl2 EtBu)2 /THF electrolyte have been investigated in both
three-electrode electrochemical cell and coin cell configurations. Linear sweep voltammetry and coin cell charge/discharge measurements indicate that copper, widely used in the literature as a current collector in this electrolyte, is not stable and undergoes
pitting corrosion above ∼1.8 V. Cyclic voltammetry shows that copper undergoes electrochemical oxidation and reduction in the
electrolyte, which was further confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron
microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX) analyses. Among the current collectors studied, nickel shows
excellent electrochemical stability up to ∼2.2 V and high efficiency for magnesium deposition and dissolution processes in the
electrolyte, indicating that it is a strong candidate as both cathode and anode current collectors in magnesium batteries.
© 2012 The Electrochemical Society. [DOI: 10.1149/2.085302jes] All rights reserved.
Manuscript submitted September 26, 2012; revised manuscript received November 26, 2012. Published December 19, 2012.
Advanced rechargeable batteries have emerged as the flagship battery technologies for meeting the increasing global energy storage
demands of both electric vehicles and stationary energy storage systems integrated into the electrical grids.1–3 Current batteries based
on lead acid, nickel-metal hydride, sodium-sulfur, lithium-ion, and
vanadium flow systems are still not capable of meeting the growing energy storage requirements due to various technical and cost
barriers.4–6 Li-ion batteries presently offer a high energy density of
∼200 Wh/kg, rendering them the best existing energy storage system for electric vehicles and small-scale stationary energy storage
systems. However, magnesium batteries have recently attracted great
interest due to their high energy density and environmentally friendly
components, coupled with magnesium’s low cost (∼$ 2700/ton for
Mg compared to $64,000/ton for Li) and abundance in the earth’s
crust (∼13.9% Mg compared to ∼0.0007% of Li).7–9 In addition, due
to the bivalent nature of the magnesium ion (Mg2+ ), a suitable intercalation anode/cathode if identified could generate twice the capacity
of the best intercalation hosts available for Li-ion (single-valent Li+ )
batteries. Theoretically, these Mg batteries can offer high volumetric
specific capacity compared to lithium (3833 mAh/cm3 for Mg vs.
2046 mAh/cm3 for Li).10,11 Considering all these aspects, it is clear
that magnesium battery systems could offer a significantly cheaper,
better-performing battery option in contrast to lithium.
Despite these attractive attributes of Mg batteries, there are several challenges pertaining to the use of cathodes, electrolytes, anodes, and current collectors. With respect to electrolytes, electrochemically driven, reversible magnesium deposition/dissolution was
first demonstrated only with Grignard reagents,12 amidomagnesium
halides, or magnesium organoborates in ether solutions.13,14 These
electrolytes showed electrochemical stability up to ∼1–1.5 V (vs.
Mg reference electrode) with poor magnesium cycling efficiencies.
It was the pioneering work of Aurbach et al. that first shed light on
∗
z
Electrochemical Society Active Member.
E-mail: [email protected]; [email protected]
the reversible deposition and dissolution of magnesium in tetrahydrofuran (THF) solution of magnesium organohalo-aluminate salt
(Mg(AlCl2 EtBu)2 /THF, 0.25M), a Grignard reagent, with excellent
columbic efficiency (∼100%) and wide electrochemical stability window (i.e., up to ∼ 2.2 V vs. Mg reference electrode).1 Identification
of this electrolyte sparked renewed interest among researchers in the
development of magnesium-based secondary batteries. Extensive research during the past fifteen years has focused on the development
of a feasible system for rechargeable magnesium-ion batteries, including identification and development of new insertion/extraction
cathode materials such as MgMo3 S4, Mg1.03 Mn0.97 SiO4 , and MoS2 ,
new anodes, and a variety of electrolyte systems.3–8,10–23 However, the
chemical instability of the Grignard reagent-based electrolyte2 could
lead to electrochemical incompatibility with the other components of
the battery system, including the cathode, anode, separator, and current collectors. It is well known that compatibility between current
collectors and electrolyte, particularly the stability of current collectors, is an important factor for designing a rechargeable battery with
a long cycle life.24,25 Therefore, conducting a fundamental study and
understanding the electrochemical behavior of current collectors in
electrolyte for Mg-ion batteries is critical for enabling viable, practical
applications. This topic however, to date has received little attention.26
Hence, in this study, the electrochemical stability of potential current
collectors for Mg-ion batteries, such as copper, nickel, stainless steel
(SS 316L), aluminum, and titanium, has been investigated in detail
using the Mg(AlCl2 EtBu)2 /THF electrolyte. Our results indicate that
nickel is a good candidate as cathode and/or anode current collectors
for Mg batteries in the present electrolyte due to its excellent electrochemical stability up to ∼2.2 V and high efficiency for magnesium
deposition and dissolution.
Experimental
Synthesis of Mg(AlCl2 EtBu)2 /THF electrolyte.— The electrolyte,
Mg(AlCl2 EtBu)2 /THF (0.25M), was synthesized according to the
literature.1 A brief description of the procedure is provided below.
The starting materials were MgBu2 (1M in heptane) and AlCl2 Et
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A352
Journal of The Electrochemical Society, 160 (2) A351-A355 (2013)
(1M in hexane), which were purchased from Aldrich and used without further purification. Stoichiometric amounts of MgBu2 (1.0 M in
heptane) and AlCl2 Et (1.0 M in hexane) (1:2 in volume) were mixed
gradually in an argon-filled glove box (Mbraun Inc., Germany). The
mixture was continuously stirred for 48 h at room temperature until
the solvents were completely evaporated. The remaining white precipitate was dissolved in inhibitor-free purified anhydrous THF, resulting
in the formation of 0.25 M Mg(AlCl2 EtBu)2 /THF electrolyte.
Characterization.— Electrochemical analyzes, including linear
sweep voltammetry (LSV) and cyclic voltammetry (CV) were carried
out in a three-electrode cell on a CHI660D electrochemical workstation. The three-electrode cell consisted of a working electrode (Cu, Ni,
SS 316L, Al, Ti or Pt purchased from Aldrich), a counter electrode
(Mg purchased from Aldrich), a reference electrode (Mg), and the
Mg(AlCl2 EtBu)2 /THF electrolyte. During LSV analyses conducted
on the selected current collectors, the scan potential was controlled
from open circuit potential (OCP) to 2.4 V. To verify the feasibility of
the present electrolyte for reversible Mg deposition/dissolution, CV
analyses were carried out on Pt in the potential range of −1–2.3 V (start
from OCP to −1 V, and then increase to 2.3 V). Similarly, reversible
Mg deposition/dissolution on Ni was also studied by CV between −1
and 2.2 V. The scan rates of the electrochemical tests in this paper
were all set to 1 mV/s within the various potential ranges. Deposition/dissolution processes of Mg on Ni electrodes for efficiency calculation was carried out in CR2016 coin cells. Briefly, Ni and Mg were
used as the working electrode and the counter electrode, respectively,
and the coin cells were assembled using woven fiberglass (GFD) as
the separator and 0.25 M Mg(AlCl2 EtBu)2 /THF electrolyte. The electrochemical performance was measured by a galvanostatic discharge
process at a current density of 0.25 mAcm−2 for 1 h, followed by a
galvanostatic charge process to the cutoff potential of 2.0 V vs. Mg,
using a Neware CT-3008W (Shenzhen, China) battery testing system.
Scanning electron microscopy (SEM) and energy-dispersive X-ray
spectroscopy (EDX) were performed using a Hitachi S-3500N operating at an accelerating voltage of 20 kV. It should be noted that the electrodes were washed with THF three times and dried in vacuum before
conducting SEM and EDX analyses. The presence of any dissolved elemental species in the electrolyte was further analyzed by inductively
coupled plasma atomic emission spectroscopy (ICP-AES, iCAP duo
6500 Thermo Fisher). The conductivity of the electrolyte was measured using a portable conductivity meter (HI991301, HANNA).
Results and Discussion
The primary reasons for the selection of Mg(AlCl2 EtBu)2 /THF as
the electrolyte in the present study are its known excellent electrochemical stability within a large electrochemical window and the
high deposition-dissolution efficiency of magnesium in this electrolyte, as indicated in previous reports.1,27 In order to validate the
quality of the as-synthesized electrolyte, it was first evaluated by
CV using a three-electrode cell. Fig. 1 shows the first three CV cycles obtained from −1 V to 2.3 V using a Pt working electrode and
Mg(AlCl2 EtBu)2 /THF electrolyte. The cycling efficiency for magnesium deposition/dissolution is determined from the ratio of the total
peak area during dissolution and deposition for each CV cycle, as
described in an earlier publication.28 The deposition and dissolution
of magnesium is highly reversible, with an efficiency of almost 100%
(Table I). The over-potentials for the first deposition and dissolution
cycle were observed to be −0.45 and 0.25 V, respectively, and dropped
Figure 1. Cyclic voltammetry showing magnesium deposition/dissolution on
a Pt electrode in Mg(AlCl2 EtBu)2 /THF electrolyte collected at a voltage scan
rate of 1 mVs−1 within the potential range of −1.0–2.3 V (vs. Mg2+ /Mg).
to −0.25 and 0.05 V, respectively, by the third cycle. The decrease in
over-potential and the increase in deposition/dissolution efficiency of
magnesium (Table I) may be ascribed to the desorption of the electrolyte on the working electrode after the first cycle.27 In addition,
the measured conductivity of the electrolyte was 0.149 Sm−1 , which
is similar to the published reports.2 The above analysis indicates the
good electrochemical activity and performance of the as-synthesized
electrolyte comparable to the results reported in previous studies.1
This result also served to validate the quality and reproducibility of
the synthesized electrolyte and hence justifies its further use to analyze
the electrochemical stability of the various current collectors.
The electrochemical performance of Cu as a current collector was
studied first, as it has been widely used in the magnesium batteries.3,6,8
LSV was first used to study the stability of Cu in the electrolyte,
where Cu was used as the working electrode and Mg as the counter
and reference electrodes. For comparison, an LSV scan was also
performed with Pt as the working electrode under the same conditions.
Fig. 2 shows the LSV scan curves of Cu and Pt taken from OCP to
Table I. Statistics of parameters during Mg deposition/dissolution
processes onto Pt calculated from cyclic voltammetry (CV) study.
Over-potential /V
Cycle
1st
2nd
3rd
Peak area
Deposition
Dissolution
Deposition
Dissolution
Efficiency
−0.45
−0.35
−0.25
0.25
0.17
0.05
0.00191
0.002253
0.00272
0.00184
0.00218
0.00264
96.33%
96.76%
97.05%
Figure 2. Linear sweep voltammograms of Cu and Pt in
Mg(AlCl2 EtBu)2 /THF electrolyte within the potential range between
OCP and 2.4 V (vs. Mg2+ /Mg) collected at a voltage scan rate at 1 mVs−1 .
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Journal of The Electrochemical Society, 160 (2) A351-A355 (2013)
A353
Table II. ICP-AES analysis of the electrolyte after linear sweep
voltammetry (LSV) using Cu electrode.
Elements
Mg
Al
Cu
(concentration) mgL−1
4770
2251
15.68
2.4 V with a voltage scan speed of 1 mVs−1 . With the Pt working
electrode, only minimal anodic/oxidation current (due to electrolyte
oxidation/decomposition) was observed in the positive scan until the
potential of 2.3 V, which is in good agreement with the previous cyclic
voltammetry of this electrolyte using Pt as working electrode (Fig. 1)
and confirms yet again the quality of the as-synthesized electrolyte.
However, with Cu, significant electrochemical corrosion was observed
in the voltage range of 1.80–2.40 V, as shown in Fig. 2. The anodic
current begins to increase at about 1.80 V, and an obvious oxidation
peak was observed at 2.05 V. Considering the excellent stability of
the electrolyte as proven by CV and LSV data with Pt, both of these
features are likely due to the oxidation of Cu in the LSV process.
In addition, ICP-AES analysis performed on the electrolyte after the
LSV scan using Cu as the working electrode shows the presence of
∼15.68 mgL−1 of Cu (Table II), which further indicates and validates
the electrochemical corrosion and dissolution of copper. Scanning
electron micrographs presented in Fig. 3 also clearly show that the
initially-smooth Cu electrode surface undergoes pitting during the
LSV study, likely due to the corrosion of the Cu under a high potential.
Digital photographs (inset in Fig. 3) of the same Cu electrodes before
and after LSV scans also display the apparent change in color of
metallic copper from pale red to grayish brown with distinct roughened
spots, suggesting the occurrence of electrochemical corrosion in the
presence of the electrolyte.
In order to further prove the oxidation of Cu, the Mg counter
electrode was also examined by SEM and EDX after the LSV mea-
Figure 3. Scanning electron micrographs of a Cu electrode before and after
LSV analysis. (inset: digital photographs of a Cu electrode before and after
LSV).
Figure 4. Scanning electron micrograph and corresponding EDX spectrum of
Mg electrode after LSV analysis.
surement. Fig. 4 shows that after LSV scan the Mg electrode surface
was covered by a rough solid layer, which may be caused by adsorption/decomposition of the active components in the electrolyte.13,27
At the same time, a few clusters of aggregated particles were also observed on the surface of the Mg electrode. EDX analysis (point mode)
reveals that these aggregates contained a large fraction of Cu. It should
be noted that several of the other elements detected (Mg, Al and Cl)
may originate from the residual electrolyte present on the specimen,
and the trace oxygen may be ascribed to the oxidation of magnesium
when the electrode was exposed to air during transfer of the sample
for examination in the microscope. Nevertheless, observation of the
deposited Cu on the Mg electrode combined with the obvious anodic
peak at 2.05 V in the LSV curves and the presence of copper in the
electrolyte as confirmed by ICP-AES results unequivocally demonstrates that oxidation of Cu occurs under high potential (1.80–2.40 V),
followed by its dissolution in the electrolyte. It is likely that the Cu
electrode is oxidized to form cupric Cu2+ or cuprous Cu+ ions that
dissolve into the electrolyte and then diffuse to the Mg electrode. If
the Cu2+ or Cu+ reaches the Mg electrode, elemental Cu is produced
via direct replacement reactions 1 and 2.
Cu2+ + Mg = Cu + Mg2+
[1]
Cu+ + 0.5Mg = Cu + 0.5Mg2+
[2]
To better understand the electrochemical behavior of Cu in the
present electrolyte, CV analyses were also performed using Cu as
the working electrode. As shown in Fig. 5, during the first positive scan, the anodic current was observed beginning from 1.8 V
and there was an oxidation peak at 2.05 V, which is consistent with
the LSV analysis (Fig. 2) and ascribed to the electrochemical oxidation of Cu as illustrated in equation 3. In the negative scan process, a reduction peak was observed at about 1.0 V, which may
be ascribed to electrochemical reduction of Cu2+ or Cu+ to Cu as
shown in equation 4. In the second and third cycles, the oxidation
and reduction current (peak intensity) continued to increase, indicating the enhanced reversible oxidation/reduction of Cu. The preceding results strongly suggest that copper is not a stable current
collector above 1.80 V in Mg(AlCl2 EtBu)2 /THF electrolyte, since reversible oxidation/reduction of Cu occurs during the charge/discharge
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A354
Journal of The Electrochemical Society, 160 (2) A351-A355 (2013)
Figure 5. Cyclic voltammograms of a Cu electrode in Mg(AlCl2 EtBu)2 /THF
electrolyte within the potential range of 0.4–2.4 V (vs. Mg2+ /Mg) collected at
a voltage scan rate of 1 mVs−1 .
processes.
Cu → Cu2+ /Cu+ + 2e/1e
[3]
Cu2+ /Cu+ + 2e/1e → Cu
[4]
Since Cu is not suitable, it is therefore important to identify stable current collectors for cathodes used in magnesium batteries. We
selected several common metals – Ni, SS 316L, Al, and Ti, and evaluated their electrochemical stability in the Mg(AlCl2 EtBu)2 /THF electrolyte. Fig. 6 shows the LSV curves obtained for Ni, SS 316L, Al,
Ti, and Pt (for comparison) in the voltage range of OCP-2.4 V. LSV
analysis of Al suggests that it is not stable beyond 1.2 V with the
present electrolyte. Similarly, a weak anodic current was observed
for SS 316L beginning at 1.6 V which continued to increase in the
positive scan direction. The anodic current may be induced by the
electrochemical corrosion of SS 316L, which is likely assisted by Cl−
present in the electrolyte.29 When Ti was used as the working electrode, a weak anodic current was also observed from OCP to 2.20 V
with the current rising sharply thereafter. This indicates continuous
oxidation of Ti in the electrolyte. In contrast, Ni exhibits a stable electrochemical window up to 2.20 V (Fig. 6), comparable with that of
Pt.
CV was performed to further confirm the reversible deposition/dissolution of Mg on Ni and the feasibility of Ni as a current
Figure 6. Linear sweep voltammograms of SS 316L, Al, Ti, Ni, and Pt in
the Mg(AlCl2 EtBu)2 /THF electrolyte between OCP and 2.4 V (vs. Mg2+ /Mg)
collected at a voltage scan rate of 1 mVs−1 .
Figure 7. Cyclic voltammetry curves of a Ni electrode in
Mg(AlCl2 EtBu)2 /THF electrolyte between −1 and 2.2 V (vs. Mg2+ /Mg) at a
voltage scan rate 1 mVs−1 .
collector in the Mg(AlCl2 EtBu)2 /THF electrolyte (Fig. 7). In comparison to the CV using Pt as the working electrode under the same
conditions (Fig. 1), Ni delivered lower and more stable over-potentials
of 0.3 V and 0.05 V for the magnesium deposition and dissolution
processes in the first cycle, respectively (Fig. 7). The decrease in overpotentials of Ni compared to Pt may be related to the chemical characteristics, crystal structure, and surface morphology of Ni,30 which
may influence the adsorption of the electrolyte on the electrodes.27
The Ni electrodes also allow high reversibility of the deposition and
dissolution reaction of Mg, with cycling efficiency close to 100%
during galvanostatic charge/discharge tests in coin cells (inset of
Fig. 8). The dissolution/deposition efficiency was calculated by dividing the charge passed during dissolution by the charge passed
Figure 8. The first three cycles of deposition and dissolution of Mg on a Ni
electrode acquired in a coin cell test and the corresponding efficiency (inset).
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Journal of The Electrochemical Society, 160 (2) A351-A355 (2013)
during deposition (Fig. 8). For the first cycle, Mg displayed a relatively high over-potential (0.7 V) and low efficiency (92%), which
may relate to the wetting of the electrode by the electrolyte in the
coin cell configuration and adsorption of electrolyte on both Mg and
Ni electrodes.27 However, the over-potentials decreased significantly
to 0.25 V and cycling efficiency increased to about 100% in the consecutive cycles. The observed high deposition-dissolution efficiency
and decreased over-potentials in both CV and coin cell analyses again
further demonstrate that Ni is indeed a suitable candidate as a cathode
and anode current collector for magnesium batteries.
Conclusions
Electrochemical evaluation combined with SEM and EDX analyzes indicates that Cu is not a stable cathode current collector for
magnesium batteries using Mg(AlCl2 EtBu)2 /THF electrolyte at potentials above 1.80 V. Electrochemical corrosion of Cu occurs in the
potential range of 1.80–2.40 V (vs. Mg2+ /Mg) and an obvious oxidation peak was observed at 2.05 V in the cyclic voltammograms,
indicating the susceptibility of Cu to undergo oxidization and corrosion under high potential in the electrolyte. Moreover, the oxidized Cu
ions could be reduced reversibly at about 1.0 V in the negative scan
process of CV, or irreversibly by Mg. Stainless steel 316L, Al, and Ti
were also found to be electrochemically unstable in this electrolyte.
In contrast, Ni exhibits an excellent stability up to 2.2 V in the electrolyte, which is comparable to the stable electrochemical window
of Pt. The observed high efficiency and decreased over-potentials for
the magnesium deposition/dissolution processes on Ni strongly suggest that Ni is an excellent current collector candidate for use as both
cathodes and anodes in magnesium batteries.
Acknowledgment
As part of the National Energy Technology Laboratory’s Regional
University Alliance (NETL-RUA), a collaborative initiative of the
NETL, this technical effort was performed under the RES contract
4000.2.683.220.001. Financial support of Dr. Robert Romanosky is
acknowledged. In addition, PNK acknowledges the Edward R. Weidlein Chair Professorship and the Center for Complex Engineered
Multifunctional Materials (CCEMM) for partial support of this research. This report was prepared as an account of work sponsored
by an agency of the United States Government. Neither the United
States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed,
or represents that its use would not infringe privately owned rights.
Reference herein to any specific commercial product, process, or ser-
A355
vice by trade name, trademark, manufacturer, or otherwise does not
necessarily constitute or imply its endorsement, recommendation, or
favoring by the United States Government or any agency thereof. The
views and opinions of authors expressed herein do not necessarily
state or reflect those of the United States Government or any agency
thereof. Authors Dongping Lv and Partha Saha contributed equally to
this work.
References
1. D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, R. Turgeman, Y. Cohen,
M. Moshkovich, and E. Levi, Nature, 407, 724 (2000).
2. C. Liebenow, J. Appl. Electrochem., 27, 221 (1997).
3. Y. Liang, R. Feng, S. Yang, H. Ma, J. Liang, and J. Chen, Adv. Mater., 23, 640 (2011).
4. H. S. Kim, T. S. Arthur, G. D. Allred, J. Zajicek, J. G. Newman, A. E. Rodnyansky,
A. G. Oliver, W. C. Boggess, and J. Muldoon, Nat. Commun., 2, 427 (2011).
5. T. Ichitsubo, T. Adachi, S. Yagi, and T. Doi, J. Mater. Chem., 21, 11764 (2011).
6. Y. NuLi, J. Yang, Y. Li, and J. Wang, Chem. Commun., 46, 3794 (2010).
7. B. Peng, J. Liang, Z. Tao, and J. Chen, J. Mater. Chem., 19, 2877 (2009).
8. Y. NuLi, Z. Guo, H. Liu, and J. Yang, Electrochem. Commun., 9, 1913 (2007).
9. W. Y. Li, C. S. Li, C. Y. Zhou, H. Ma, and J. Chen, Angew. Chem., Int. Ed., 45, 6009
(2006).
10. H. T. Yuan, L. F. Jiao, J. S. Cao, X. S. Liu, M. Zhao, and Y. M. Wang, J. Mater. Sci.
Tech., 20, 41 (2004).
11. Z. L. Tao, L. N. Xu, X. L. Gou, J. Chen, and H. T. Yuan, Chem. Commun., 2080
(2004).
12. M. Morita, N. Yoshimoto, S. Yakushiji, and M. Ishikawa, Electrochem. Solid-State
Lett., 4, A177 (2001).
13. D. Aurbach, Y. Cohen, and M. Moshkovich, Electrochem. Solid-State Lett., 4, A113
(2001).
14. E. Levi, Y. Gofer, Y. Vestfreed, E. Lancry, and D. Aurbach, Chem. Mater., 14, 2767
(2002).
15. W. Li, C. Li, C. Zhou, H. Ma, and J. Chen, Angew. Chem., Int. Ed., 45, 6009 (2006).
16. D. Imamura, M. Miyayama, M. Hibino, and T. Kudo, J. Electrochem. Soc., 150, A753
(2003).
17. D. Imamura and M. Miyayama, Solid State Ionics, 161, 173 (2003).
18. S. Mitra and S. Sampath, J. Mater. Chem., 12, 2531 (2002).
19. D. Aurbach, M. Moshkovich, A. Schechter, and R. Turgeman, Electrochem. Solid-State Lett., 3, 31 (2000).
20. L. F. Jiao, H. T. Yuan, Y. J. Wang, H. S. Cao, and Y. M. Wang, Electrochem. Commun.,
7, 431 (2005).
21. J. Giraudet, D. Claves, K. Guerin, M. Dubois, A. Houdayer, F. Masin, and A. Hamwi,
J. Power Sources, 173, 592 (2007).
22. J. Muldoon, C. B. Bucur, A. G. Oliver, T. Sugimoto, M. Matsui, H. S. Kim,
G. D. Allred, J. Zajicek, and Y. Kotani, Energy Environ. Sci., 5, 5941 (2012).
23. T. S. Arthur, N. Singh, and M. Matsui, Electrochem. Commun., 16, 103 (2012).
24. Y. F. Chen, T. M. Devine, J. W. Evans, O. R. Monteiro, and I. G. Brown, J. Electrochem. Soc., 146, 1310 (1999).
25. S. T. Myung, Y. Hitoshi, and Y. K. Sun, J. Mater. Chem., 21, 9891 (2011).
26. Z. Z. Feng, Y. Nuli, J. L. Wang, and J. Yang, J. Electrochem. Soc., 153, C689 (2006).
27. D. Aurbach, A. Schechter, M. Moshkovich, and Y. Cohen, J. Electrochem. Soc., 148,
A1004 (2001).
28. D. Aurbach, H. Gizbar, A. Schechter, O. Chusid, H. E. Gottlieb, Y. Gofer, and
I. Goldberg, J. Electrochem. Soc., 149, A115 (2002).
29. G. T. Burstein, C. Liu, R. M. Souto, and S. P. Vines, Corros. Eng., Sci. Technol., 39,
25 (2004).
30. C. Liebenow, Z. Yang, and P. Lobitz, Electrochem. Commun., 2, 641 (2000).
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