Multi-Electron Reactions enabled by Anion-Based Redox Chemistry for High-Energy Multivalent Rechargeable Batteries

Z. Li , Bhaghavathi P. Vinayan , Piotr Jankowski , Christian Njel , Ananyo Roy , Tejs Vegge , Julia Maibach , Juan Maria García Lastra , Maximilian Fichtner , Zhirong Zhao-Karger


The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi-electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single-electron transfer, which are not ideal for multivalent-ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope-like voltage profiles with insertion/extraction redox of less than one electron. Taking VS4 as a model material, reversible two-electron redox with cationic–anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g−1 at a current density of 100 mA g−1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg−1 for RMBs and >500 Wh kg−1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg2+ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS4.

Author Z. Li
Z. Li,,
, Bhaghavathi P. Vinayan - [Helmholtz Institute Ulm]
Bhaghavathi P. Vinayan,,
, Piotr Jankowski (FC / CofIC)
Piotr Jankowski,,
- Chair Of Inorganic Chemistry
, Christian Njel - [Karlsruhe Institute of Technology, Campus North]
Christian Njel,,
, Ananyo Roy - [Helmholtz Institute Ulm]
Ananyo Roy,,
, Tejs Vegge - [Danmarks Tekniske Universitet]
Tejs Vegge,,
, Julia Maibach - [Karlsruhe Institute of Technology, Campus North]
Julia Maibach,,
, Juan Maria García Lastra - [Danmarks Tekniske Universitet]
Juan Maria García Lastra,,
, Maximilian Fichtner - [Helmholtz Institute Ulm]
Maximilian Fichtner,,
, Zhirong Zhao-Karger - [Helmholtz Institute Ulm]
Zhirong Zhao-Karger,,
Journal seriesAngewandte Chemie-International Edition, [Angewandte Chemie - International Edition], ISSN 1433-7851, e-ISSN 1521-3773
Issue year2020
ASJC Classification1503 Catalysis; 1600 General Chemistry
Languageen angielski
Score (nominal)200
Score sourcejournalList
ScoreMinisterial score = 200.0, 03-09-2020, ArticleFromJournal
Publication indicators Scopus Citations = 0; Scopus SNIP (Source Normalised Impact per Paper): 2018 = 2.132; WoS Impact Factor: 2018 = 12.257 (2) - 2018=12.359 (5)
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