Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

Li, Zhenyou; Vinayan, B. P.; Jankowski, Piotr; Njel, Christian; Roy, Ananyo; Vegge, Tejs; Maibach, Julia; Lastra, Juan Maria García; Fichtner, Maximilian; Zhao‐Karger, Zhirong

doi:10.1002/anie.202002560

Cited by 111 publications

(118 citation statements)

References 40 publications

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“…[16] Recently,Saha et al presented fundamental research on the bottlenecks of Sr edox, [17] in which an ew material Li 1.33À2y/3 Ti 0.67Ày/3 Fe y S 2 (y = 0.3) was capable of ar eversible capacity as high as 245 mAh g À1 .T he high capacity resulted from the existence of 3d 6 electrons in the Fe 2+/3+ redox couple that activated the anionic Sr edox. During the final review stage of this manuscript, See et al revealed the electrochemistry of aL i-rich layered iron sulfide Li 2 FeS 2 , [18] whereas Zhao-Karger reported on multivalent cation storage in VS 4 , [19] further emphasizing the rising importance of this class of materials.…”

Section: Introductionmentioning

confidence: 99%

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

et al. 2020

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We report the electrochemistry of a hitherto unexplored Na2MoS4 phase as a conversion electrode material for Na‐ and Li‐ion batteries. The material adopts an amorphous coordination polymer structure with mixed Mo and S valences. XPS and XRD analysis reveal a complex interplay between Mo and S redox chemistry, while excluding the formation of free sulfur, lithium sulfide, or other crystalline phases. Na2MoS4 behaves as a mixed ionic–electronic conductor, with electronic conductivity of 6.1×10−4 S cm−1, that permits carbon‐free application in an electrochemical cell. A reversible capacity of up to 500 mAh g−1 was attained, corresponding to a five‐electron redox exchange, with species ranging from (highest oxidized state) to 5MoS4> (lowest oxidized state). This study emphasizes the excellent charge‐storage performances of Na2MoS4 for Li‐ or Na‐ion batteries, and enriches the emerging library and knowledge of sulfide phases with mixed anionic and cationic redox properties.

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Section: Introductionmentioning

confidence: 99%

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

et al. 2020

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“…In fact, this anion-based redox chemistry (anionic redox) has recently drawn quite some attention with respect to the increase in the energy density of Li-, Na-and Mg-ion batteries, see, e.g., Refs. 62,63 To elucidate this anionic redox, we performed a Bader charge analysis 64 and calculated charge density differences 65 for MgSc 2 S 4 . Details of this charge analysis can be found in the Supplementary Information.…”

Section: Resultsmentioning

confidence: 99%

Mechanism of magnesium transport in spinel chalcogenides

Sotoudeh¹,

Dillenz²,

Groß³

2021

Preprint

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In the area of sustainable energy storage, batteries based on multivalent ions such as magnesium have been attracting considerable attention due to their potential for high energy densities. Furthermore, they are typically also more abundant than, e.g., lithium. However, as a challenge their low ion mobility in electrode materials remains. This study addresses the ionic conductivity in spinel host materials which represent a promising class of cathode and solid-electrolyte materials in Mg-ion batteries. Based on periodic density functional theory calculations, we identify the critical parameters which determine the mobility and insertion of ions. We will in particular highlight the critical role that trigonal distortions of the spinel structure play for the ion mobility. In detail, we will show that it is the competition between coordination and bond length that governs the Mg site preference in ternary spinel compounds upon trigonal distortions. This can only be understood by also taking covalent interactions into account. Furthermore, our calculations suggest that anionic redox plays a much more important role in sulfide and selenide spinels than in oxide spinels. Based on our theoretical study, we rationalize the impact of the metal distribution in the host material and the ion concentration on the diffusion process. Furthermore, cathode-related challenges for practical devices will be addressed. Our findings shed light on the fundamentional mechanisms underlying ionic conductivity in solid hosts and thus may contribute to improve ion transport in battery electrodes.

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“…Although a significant drop in reversible capacity was observed when the temperature was lowered (≈80 mAh g −1 at room temperature vs 170 mAh g −1 at 60 °C), it is still far better than micrometer-sized TiS 2 , which exhibited extremely poor electrochemical performance at room temperature. These results showed that obtaining a reversible reaction of Mg cathode is far difficult compared to that of Li cathode and hence nanosizing of cathode materials [12,27,29,31,36,39,42,43,[45][46][47][48]50,68,70,[86][87][88]90,[92][93][94][95][96][97][98].…”

Section: Tmdsmentioning

confidence: 99%

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries

Regulacio

Nguyen

Horia

et al. 2021

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Rechargeable magnesium batteries (RMBs) are regarded as promising candidates for beyond‐lithium‐ion batteries owing to their high energy density. Moreover, as Mg metal is earth‐abundant and has low propensity for dendritic growth, RMBs have the advantages of being more affordable and safer than the currently used lithium‐ion batteries. However, the commercial viability of RMBs has been negatively impacted by slow diffusion kinetics in most cathode materials due to the high charge density and strongly polarizing nature of the Mg2+ ion. Nanostructuring of potential cathode materials such as metal chalcogenides offers an effective means of addressing these challenges by providing larger surface area and shorter migration routes. In this article, a review of recent research on the design of metal chalcogenide nanostructures for RMBs’ cathode materials is provided. The different types and structures of metal chalcogenide cathodes are discussed, and the synthetic strategies through which nanostructuring of these materials can be achieved are described. An organized summary of their electrochemical performance is also presented, along with an analysis of the current challenges and future directions. Although particular focus is placed on RMBs, many of the nanostructuring concepts that are discussed here can be carried forward to other next‐generation energy storage systems.

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Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

Cited by 111 publications

References 40 publications

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Mechanism of magnesium transport in spinel chalcogenides

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries

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