Journal of The Electrochemical Society, 160 (2) A351-A355 (2013) A3510013-4651/2013/160(2)/A351/5/$28.00 © The Electrochemical Society

A Scientific Study of Current Collectors for Mg Batteriesin Mg(AlCl2EtBu)2/THF ElectrolyteDongping 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

aNational Energy Technology Laboratory–Regional University Alliance (NETL-RUA), USAbDepartment of Mechanical & Nuclear Engineering, The Pennsylvania State University, University Park,Pennsylvania 16802, USAcDepartment of Bioengineering, Swanson School of Engineering, University of Pittsburgh, Pittsburgh,Pennsylvania 15261, USAdU.S. DOE NETL, Material Performance Division, Morgantown, West Virginia 26507, USAeMechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, Pittsburgh,Pennsylvania 15261, USAfDepartment of Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh,Pittsburgh, Pennsylvania 15261, USAgCenter 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(AlCl2EtBu)2/THF electrolyte have been investigated in boththree-electrode electrochemical cell and coin cell configurations. Linear sweep voltammetry and coin cell charge/discharge mea-surements indicate that copper, widely used in the literature as a current collector in this electrolyte, is not stable and undergoespitting corrosion above ∼1.8 V. Cyclic voltammetry shows that copper undergoes electrochemical oxidation and reduction in theelectrolyte, which was further confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electronmicroscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX) analyses. Among the current collectors studied, nickel showsexcellent electrochemical stability up to ∼2.2 V and high efficiency for magnesium deposition and dissolution processes in theelectrolyte, 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 bat-tery technologies for meeting the increasing global energy storagedemands of both electric vehicles and stationary energy storage sys-tems integrated into the electrical grids.1–3 Current batteries basedon lead acid, nickel-metal hydride, sodium-sulfur, lithium-ion, andvanadium flow systems are still not capable of meeting the grow-ing energy storage requirements due to various technical and costbarriers.4–6 Li-ion batteries presently offer a high energy density of∼200 Wh/kg, rendering them the best existing energy storage sys-tem for electric vehicles and small-scale stationary energy storagesystems. However, magnesium batteries have recently attracted greatinterest due to their high energy density and environmentally friendlycomponents, coupled with magnesium’s low cost (∼$ 2700/ton forMg compared to $64,000/ton for Li) and abundance in the earth’scrust (∼13.9% Mg compared to ∼0.0007% of Li).7–9 In addition, dueto the bivalent nature of the magnesium ion (Mg2+), a suitable inter-calation anode/cathode if identified could generate twice the capacityof the best intercalation hosts available for Li-ion (single-valent Li+)batteries. Theoretically, these Mg batteries can offer high volumetricspecific capacity compared to lithium (3833 mAh/cm3 for Mg vs.2046 mAh/cm3 for Li).10,11 Considering all these aspects, it is clearthat 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 sev-eral challenges pertaining to the use of cathodes, electrolytes, an-odes, and current collectors. With respect to electrolytes, electro-chemically driven, reversible magnesium deposition/dissolution wasfirst demonstrated only with Grignard reagents,12 amidomagnesiumhalides, or magnesium organoborates in ether solutions.13,14 Theseelectrolytes 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

∗Electrochemical Society Active Member.zE-mail: pkumta@pitt.edu; dwang@psu.edu

the reversible deposition and dissolution of magnesium in tetrahy-drofuran (THF) solution of magnesium organohalo-aluminate salt(Mg(AlCl2EtBu)2/THF, 0.25M), a Grignard reagent, with excellentcolumbic efficiency (∼100%) and wide electrochemical stability win-dow (i.e., up to ∼ 2.2 V vs. Mg reference electrode).1 Identificationof this electrolyte sparked renewed interest among researchers in thedevelopment of magnesium-based secondary batteries. Extensive re-search during the past fifteen years has focused on the developmentof a feasible system for rechargeable magnesium-ion batteries, in-cluding identification and development of new insertion/extractioncathode materials such as MgMo3S4, Mg1.03Mn0.97SiO4, and MoS2,new anodes, and a variety of electrolyte systems.3–8,10–23 However, thechemical instability of the Grignard reagent-based electrolyte2 couldlead to electrochemical incompatibility with the other components ofthe battery system, including the cathode, anode, separator, and cur-rent collectors. It is well known that compatibility between currentcollectors and electrolyte, particularly the stability of current collec-tors, is an important factor for designing a rechargeable battery witha long cycle life.24,25 Therefore, conducting a fundamental study andunderstanding the electrochemical behavior of current collectors inelectrolyte for Mg-ion batteries is critical for enabling viable, practicalapplications. This topic however, to date has received little attention.26

Hence, in this study, the electrochemical stability of potential currentcollectors for Mg-ion batteries, such as copper, nickel, stainless steel(SS 316L), aluminum, and titanium, has been investigated in detailusing the Mg(AlCl2EtBu)2/THF electrolyte. Our results indicate thatnickel is a good candidate as cathode and/or anode current collectorsfor Mg batteries in the present electrolyte due to its excellent electro-chemical stability up to ∼2.2 V and high efficiency for magnesiumdeposition and dissolution.

Experimental

Synthesis of Mg(AlCl2EtBu)2/THF electrolyte.— The electrolyte,Mg(AlCl2EtBu)2/THF (0.25M), was synthesized according to theliterature.1 A brief description of the procedure is provided below.The starting materials were MgBu2 (1M in heptane) and AlCl2Et

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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 with-out further purification. Stoichiometric amounts of MgBu2 (1.0 M inheptane) and AlCl2Et (1.0 M in hexane) (1:2 in volume) were mixedgradually in an argon-filled glove box (Mbraun Inc., Germany). Themixture was continuously stirred for 48 h at room temperature untilthe solvents were completely evaporated. The remaining white precip-itate was dissolved in inhibitor-free purified anhydrous THF, resultingin the formation of 0.25 M Mg(AlCl2EtBu)2/THF electrolyte.

Characterization.— Electrochemical analyzes, including linearsweep voltammetry (LSV) and cyclic voltammetry (CV) were carriedout in a three-electrode cell on a CHI660D electrochemical worksta-tion. 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 theMg(AlCl2EtBu)2/THF electrolyte. During LSV analyses conductedon the selected current collectors, the scan potential was controlledfrom open circuit potential (OCP) to 2.4 V. To verify the feasibility ofthe present electrolyte for reversible Mg deposition/dissolution, CVanalyses were carried out on Pt in the potential range of −1–2.3 V (startfrom OCP to −1 V, and then increase to 2.3 V). Similarly, reversibleMg deposition/dissolution on Ni was also studied by CV between −1and 2.2 V. The scan rates of the electrochemical tests in this paperwere all set to 1 mV/s within the various potential ranges. Deposi-tion/dissolution processes of Mg on Ni electrodes for efficiency calcu-lation was carried out in CR2016 coin cells. Briefly, Ni and Mg wereused as the working electrode and the counter electrode, respectively,and the coin cells were assembled using woven fiberglass (GFD) asthe separator and 0.25 M Mg(AlCl2EtBu)2/THF electrolyte. The elec-trochemical performance was measured by a galvanostatic dischargeprocess at a current density of 0.25 mAcm−2 for 1 h, followed by agalvanostatic 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-rayspectroscopy (EDX) were performed using a Hitachi S-3500N operat-ing at an accelerating voltage of 20 kV. It should be noted that the elec-trodes were washed with THF three times and dried in vacuum beforeconducting SEM and EDX analyses. The presence of any dissolved el-emental species in the electrolyte was further analyzed by inductivelycoupled plasma atomic emission spectroscopy (ICP-AES, iCAP duo6500 Thermo Fisher). The conductivity of the electrolyte was mea-sured using a portable conductivity meter (HI991301, HANNA).

Results and Discussion

The primary reasons for the selection of Mg(AlCl2EtBu)2/THF asthe electrolyte in the present study are its known excellent electro-chemical stability within a large electrochemical window and thehigh deposition-dissolution efficiency of magnesium in this elec-trolyte, as indicated in previous reports.1,27 In order to validate thequality of the as-synthesized electrolyte, it was first evaluated byCV using a three-electrode cell. Fig. 1 shows the first three CV cy-cles obtained from −1 V to 2.3 V using a Pt working electrode andMg(AlCl2EtBu)2/THF electrolyte. The cycling efficiency for magne-sium deposition/dissolution is determined from the ratio of the totalpeak area during dissolution and deposition for each CV cycle, asdescribed in an earlier publication.28 The deposition and dissolutionof magnesium is highly reversible, with an efficiency of almost 100%(Table I). The over-potentials for the first deposition and dissolutioncycle were observed to be −0.45 and 0.25 V, respectively, and dropped

Table I. Statistics of parameters during Mg deposition/dissolutionprocesses onto Pt calculated from cyclic voltammetry (CV) study.

Over-potential /V Peak area

Cycle Deposition Dissolution Deposition Dissolution Efficiency

1st −0.45 0.25 0.00191 0.00184 96.33%2nd −0.35 0.17 0.002253 0.00218 96.76%3rd −0.25 0.05 0.00272 0.00264 97.05%

Figure 1. Cyclic voltammetry showing magnesium deposition/dissolution ona Pt electrode in Mg(AlCl2EtBu)2/THF electrolyte collected at a voltage scanrate 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 inover-potential and the increase in deposition/dissolution efficiency ofmagnesium (Table I) may be ascribed to the desorption of the elec-trolyte on the working electrode after the first cycle.27 In addition,the measured conductivity of the electrolyte was 0.149 Sm−1, whichis similar to the published reports.2 The above analysis indicates thegood electrochemical activity and performance of the as-synthesizedelectrolyte comparable to the results reported in previous studies.1

This result also served to validate the quality and reproducibility ofthe synthesized electrolyte and hence justifies its further use to analyzethe electrochemical stability of the various current collectors.

The electrochemical performance of Cu as a current collector wasstudied 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 counterand reference electrodes. For comparison, an LSV scan was alsoperformed 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

Figure 2. Linear sweep voltammograms of Cu and Pt inMg(AlCl2EtBu)2/THF electrolyte within the potential range betweenOCP 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 sweepvoltammetry (LSV) using Cu electrode.

Elements (concentration) mgL−1

Mg 4770Al 2251Cu 15.68

2.4 V with a voltage scan speed of 1 mVs−1. With the Pt workingelectrode, only minimal anodic/oxidation current (due to electrolyteoxidation/decomposition) was observed in the positive scan until thepotential of 2.3 V, which is in good agreement with the previous cyclicvoltammetry 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 observedin the voltage range of 1.80–2.40 V, as shown in Fig. 2. The anodiccurrent begins to increase at about 1.80 V, and an obvious oxidationpeak was observed at 2.05 V. Considering the excellent stability ofthe electrolyte as proven by CV and LSV data with Pt, both of thesefeatures are likely due to the oxidation of Cu in the LSV process.In addition, ICP-AES analysis performed on the electrolyte after theLSV scan using Cu as the working electrode shows the presence of∼15.68 mgL−1of Cu (Table II), which further indicates and validatesthe electrochemical corrosion and dissolution of copper. Scanningelectron micrographs presented in Fig. 3 also clearly show that theinitially-smooth Cu electrode surface undergoes pitting during theLSV study, likely due to the corrosion of the Cu under a high potential.Digital photographs (inset in Fig. 3) of the same Cu electrodes beforeand after LSV scans also display the apparent change in color ofmetallic copper from pale red to grayish brown with distinct roughenedspots, suggesting the occurrence of electrochemical corrosion in thepresence of the electrolyte.

In order to further prove the oxidation of Cu, the Mg counterelectrode was also examined by SEM and EDX after the LSV mea-

Figure 3. Scanning electron micrographs of a Cu electrode before and afterLSV analysis. (inset: digital photographs of a Cu electrode before and afterLSV).

Figure 4. Scanning electron micrograph and corresponding EDX spectrum ofMg electrode after LSV analysis.

surement. Fig. 4 shows that after LSV scan the Mg electrode surfacewas covered by a rough solid layer, which may be caused by adsorp-tion/decomposition of the active components in the electrolyte.13,27

At the same time, a few clusters of aggregated particles were also ob-served on the surface of the Mg electrode. EDX analysis (point mode)reveals that these aggregates contained a large fraction of Cu. It shouldbe 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 magnesiumwhen the electrode was exposed to air during transfer of the samplefor examination in the microscope. Nevertheless, observation of thedeposited Cu on the Mg electrode combined with the obvious anodicpeak at 2.05 V in the LSV curves and the presence of copper in theelectrolyte as confirmed by ICP-AES results unequivocally demon-strates 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 Cuelectrode is oxidized to form cupric Cu2+ or cuprous Cu+ ions thatdissolve into the electrolyte and then diffuse to the Mg electrode. Ifthe Cu2+ or Cu+ reaches the Mg electrode, elemental Cu is producedvia 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 thepresent electrolyte, CV analyses were also performed using Cu asthe working electrode. As shown in Fig. 5, during the first posi-tive scan, the anodic current was observed beginning from 1.8 Vand there was an oxidation peak at 2.05 V, which is consistent withthe LSV analysis (Fig. 2) and ascribed to the electrochemical oxi-dation of Cu as illustrated in equation 3. In the negative scan pro-cess, a reduction peak was observed at about 1.0 V, which maybe ascribed to electrochemical reduction of Cu2+ or Cu+ to Cu asshown in equation 4. In the second and third cycles, the oxidationand reduction current (peak intensity) continued to increase, indi-cating the enhanced reversible oxidation/reduction of Cu. The pre-ceding results strongly suggest that copper is not a stable currentcollector above 1.80 V in Mg(AlCl2EtBu)2/THF electrolyte, since re-versible 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(AlCl2EtBu)2/THFelectrolyte within the potential range of 0.4–2.4 V (vs. Mg2+/Mg) collected ata 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 sta-ble current collectors for cathodes used in magnesium batteries. Weselected several common metals – Ni, SS 316L, Al, and Ti, and evalu-ated their electrochemical stability in the Mg(AlCl2EtBu)2/THF elec-trolyte. 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. LSVanalysis of Al suggests that it is not stable beyond 1.2 V with thepresent electrolyte. Similarly, a weak anodic current was observedfor SS 316L beginning at 1.6 V which continued to increase in thepositive scan direction. The anodic current may be induced by theelectrochemical corrosion of SS 316L, which is likely assisted by Cl−

present in the electrolyte.29 When Ti was used as the working elec-trode, a weak anodic current was also observed from OCP to 2.20 Vwith the current rising sharply thereafter. This indicates continuousoxidation of Ti in the electrolyte. In contrast, Ni exhibits a stable elec-trochemical window up to 2.20 V (Fig. 6), comparable with that ofPt.

CV was performed to further confirm the reversible deposi-tion/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 inthe Mg(AlCl2EtBu)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 inMg(AlCl2EtBu)2/THF electrolyte between −1 and 2.2 V (vs. Mg2+/Mg) at avoltage scan rate 1 mVs−1.

collector in the Mg(AlCl2EtBu)2/THF electrolyte (Fig. 7). In com-parison to the CV using Pt as the working electrode under the sameconditions (Fig. 1), Ni delivered lower and more stable over-potentialsof 0.3 V and 0.05 V for the magnesium deposition and dissolutionprocesses in the first cycle, respectively (Fig. 7). The decrease in over-potentials of Ni compared to Pt may be related to the chemical char-acteristics, crystal structure, and surface morphology of Ni,30 whichmay influence the adsorption of the electrolyte on the electrodes.27

The Ni electrodes also allow high reversibility of the deposition anddissolution reaction of Mg, with cycling efficiency close to 100%during galvanostatic charge/discharge tests in coin cells (inset ofFig. 8). The dissolution/deposition efficiency was calculated by di-viding the charge passed during dissolution by the charge passed

Figure 8. The first three cycles of deposition and dissolution of Mg on a Nielectrode 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) A355

during deposition (Fig. 8). For the first cycle, Mg displayed a rela-tively high over-potential (0.7 V) and low efficiency (92%), whichmay relate to the wetting of the electrode by the electrolyte in thecoin cell configuration and adsorption of electrolyte on both Mg andNi electrodes.27 However, the over-potentials decreased significantlyto 0.25 V and cycling efficiency increased to about 100% in the con-secutive cycles. The observed high deposition-dissolution efficiencyand decreased over-potentials in both CV and coin cell analyses againfurther demonstrate that Ni is indeed a suitable candidate as a cathodeand anode current collector for magnesium batteries.

Conclusions

Electrochemical evaluation combined with SEM and EDX ana-lyzes indicates that Cu is not a stable cathode current collector formagnesium batteries using Mg(AlCl2EtBu)2/THF electrolyte at po-tentials above 1.80 V. Electrochemical corrosion of Cu occurs in thepotential range of 1.80–2.40 V (vs. Mg2+/Mg) and an obvious ox-idation peak was observed at 2.05 V in the cyclic voltammograms,indicating the susceptibility of Cu to undergo oxidization and corro-sion under high potential in the electrolyte. Moreover, the oxidized Cuions could be reduced reversibly at about 1.0 V in the negative scanprocess of CV, or irreversibly by Mg. Stainless steel 316L, Al, and Tiwere also found to be electrochemically unstable in this electrolyte.In contrast, Ni exhibits an excellent stability up to 2.2 V in the elec-trolyte, which is comparable to the stable electrochemical windowof Pt. The observed high efficiency and decreased over-potentials forthe magnesium deposition/dissolution processes on Ni strongly sug-gest that Ni is an excellent current collector candidate for use as bothcathodes and anodes in magnesium batteries.

Acknowledgment

As part of the National Energy Technology Laboratory’s RegionalUniversity Alliance (NETL-RUA), a collaborative initiative of theNETL, this technical effort was performed under the RES contract4000.2.683.220.001. Financial support of Dr. Robert Romanosky isacknowledged. In addition, PNK acknowledges the Edward R. Wei-dlein Chair Professorship and the Center for Complex EngineeredMultifunctional Materials (CCEMM) for partial support of this re-search. This report was prepared as an account of work sponsoredby an agency of the United States Government. Neither the UnitedStates Government nor any agency thereof, nor any of their employ-ees, makes any warranty, express or implied, or assumes any legalliability or responsibility for the accuracy, completeness, or useful-ness 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-

vice by trade name, trademark, manufacturer, or otherwise does notnecessarily constitute or imply its endorsement, recommendation, orfavoring by the United States Government or any agency thereof. Theviews and opinions of authors expressed herein do not necessarilystate or reflect those of the United States Government or any agencythereof. Authors Dongping Lv and Partha Saha contributed equally tothis work.

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