Zinc Blende Magnesium Sulfide in Rechargeable Magnesium-Sulfur Batteries

Nakayama, Yasuo; Matsumoto, Ryuhei; Kumagae, Kiyoshi; Mori, Daisuke; Mizuno, Yoshifumi; Hosoi, Suguru; Kamiguchi, Kazuhiro; Koshitani, Naoki; Inaba, Yuta; Kudo, Yoshihisa; Kawasaki, Hideki; Miller, Erin A.; Weker, Johanna Nelson; Toney, Michael F.

doi:10.1021/acs.chemmater.8b02105

Cited by 29 publications

(34 citation statements)

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“…In a recent report, Nakayama et al also observed the formation of a metastable zinc blende MgS phase during the discharge of a sulfur cathode in a Mg/S battery with sulfone-based magnesium electrolyte. 23 This, together with our experimental and computational ndings, makes us conclude that the nal discharge product is indeed MgS in the zinc blende structure type. For further comparison, we determined the theoretical average discharge voltage for the conversion of hcp-Mg and rhombic sulfur into the zinc blende MgS from our DFT calculations.…”

Section: àsupporting

confidence: 53%

“…5 Nakayama et al investigated the charge/discharge reaction mechanism of a Mg/S cell with sulfone-based magnesium electrolytes by various ex situ techniques like XPS, X-ray absorption near edge structure (XANES) spectroscopy, XRD, high-energy XRD (HE-XRD), transmission Xray microscopy (TXM) and solid-state NMR. 23 These studies conclude that MgS with the zinc blende (ZB) structure type forms as the nal discharge product on the cathode side. In another report, Robba et al investigated the reduction processes in Mg/S cells with Mg(TFSI) 2 -MgCl 2 electrolyte by operando XRD and S K-edge X-ray absorption (XANES) studies.…”

Section: Introductionmentioning

confidence: 96%

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Insights into the electrochemical processes of rechargeable magnesium–sulfur batteries with a new cathode design

et al. 2019

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Section: àsupporting

confidence: 53%

Section: Introductionmentioning

confidence: 96%

Insights into the electrochemical processes of rechargeable magnesium–sulfur batteries with a new cathode design

et al. 2019

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“…However, while the barriers for decomposition of the sulfones are lower than those of the glymes, they are still significantly large, indicating sulfone stability should be attainable if the relevant electrolyte interactions are controlled. To our knowledge, the only documented examples of high Mg plating Coulombic efficiency (>90%) in sulfone solvents have utilized MgCl 2 as the primary salt and in most cases require an ether co-solvent (Kang et al, 2017; Merrill and Schaefer, 2018; Nakayama et al, 2018). Because of the significant Mg 2+ complexation and interfacial activation tendencies of the Cl − anion (Shterenberg et al, 2015, 2017), these examples suggest that stabilization of a sulfone solvent is possible if the electrolyte composition is rationally designed such that the solvent is less exposed to the Mg + cation.…”

Section: Resultsmentioning

confidence: 99%

Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles

et al. 2019

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Rational design of novel electrolytes with enhanced functionality requires fundamental molecular-level understanding of structure-property relationships. Here we examine the suitability of a range of organic solvents for non-aqueous electrolytes in secondary magnesium batteries using density functional theory (DFT) calculations as well as experimental probes such as cyclic voltammetry and Raman spectroscopy. The solvents considered include ethereal solvents (e.g., glymes) sulfones (e.g., tetramethylene sulfone), and acetonitrile. Computed reduction potentials show that all solvents considered are stable against reduction by Mg metal. Additional computations were carried out to assess the stability of solvents in contact with partially reduced Mg cations (Mg 2+ → Mg + ) formed during cycling (e.g., deposition) by identifying reaction profiles of decomposition pathways. Most solvents, including some proposed for secondary Mg energy storage applications, exhibit decomposition pathways that are surprisingly exergonic. Interestingly, the stability of these solvents is largely dictated by magnitude of the kinetic barrier to decomposition. This insight should be valuable toward rational design of improved Mg electrolytes.

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“…Notably, MgS was found to be electrochemically virtually inactive in the chosen electrolyte. Recently, Nakayama et al elucidated the nature of the phase of the formed MgS after discharge, which is metastable zinc blende MgS rather than the rock salt phase. The high stability of both Mg 3 S 8 and MgS was made responsible for the high polarization and the unclear charge plateaus …”

Section: Cathode Materialsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rechargeable Magnesium–Sulfur Battery Technology: State of the Art and Key Challenges

Wang

Buchmeiser

2019

Adv Funct Materials

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abundant metal on earth. [19] In view of these merits and the high abundance of sulfur, increasing interest has been raised on post Li-S battery systems, including magnesium-selenium batteries, Mg-S batteries, which display higher energy density, low costs and improved safety in comparison to Li-S batteries. [11,[20][21][22][23] Despite the advantages of Mg-S batteries, major issues in this field are related to the severe overcharge behavior and low sulfur utilization of the cathode during charging and discharging in general, the formation of magnesium polysulfides and the slow diffusion of Mg 2+ , which all result in poor electrochemical behavior. [17,22,24,25] Substantial efforts have been made to improve cell performance so far, including the modification of cathode materials, anodes and separators, [25] the synthesis of novel electrolyte systems, [24,26] which all to some extent can improve the cell behavior. Figure 1d gives a timeline of all the novel findings in the area of Mg-S batteries in each year. Figure 1b demonstrates an overview of the topics addressed in the published research articles in Mg-S batteries. According to this survey, the research community developed a strong preference for investigating novel electrolyte systems, modifying sulfur cathode materials and carrying out mechanistic studies. By contrast, only few research groups devoted their work to the other components of a Mg-S battery, such as the anode and the separator. Major improvements related to the latter two will also be thoroughly discussed in the following sections.Several reviews already discussed the developments in Mg batteries based on intercalation cathode materials. [1,15,[27][28][29][30] By contrast, accounts on Mg batteries containing a sulfur-based conversion cathode, which benefits from high theoretical energy density, a reasonable potential difference with Mg, nontoxicity and high earth abundance [11,31,32] are rare. This review solely refers to Mg-S batteries that use sulfur-based conversion cathodes.The purposes of this review are to summarize and highlight the most up-to-date and novel findings for Mg-S batteries, addressing sulfur-based conversion cathodes and Mg anode materials, separator modifications as well as various electrolyte systems. Furthermore, since the research on Mg-S batteries is still at an initial stage, some challenges, including the capacity decay mechanism, a lack of suitable electrolyte systems and the passivation of the Mg anode, which so far impedes any superior electrochemical performance in Mg-S batteries, will also be addressed. In addition, we also listed and discussed some possible future prospects for high energy Mg-S batteries. Finally, the currently reported Mg-S systems have been summarized in a table for easy comparison.This review on rechargeable Mg-S batteries is arranged in the following sequences. In the first section, currently applied anode materials (various forms of Mg anodes) and prospective anodes are discussed. Next, various sulfur-based conversion cathodes, which mainly...

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Zinc Blende Magnesium Sulfide in Rechargeable Magnesium-Sulfur Batteries

Cited by 29 publications

References 32 publications

Insights into the electrochemical processes of rechargeable magnesium–sulfur batteries with a new cathode design

Insights into the electrochemical processes of rechargeable magnesium–sulfur batteries with a new cathode design

Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles

Rechargeable Magnesium–Sulfur Battery Technology: State of the Art and Key Challenges

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