Superior Multielectron‐Transferring Energy Storage by π‐d Conjugated Frameworks. Issue 33 (29th June 2022)

• Record Type: Journal Article
• Authors: Xia, Dong; Sakaushi, Ken; Lyalin, Andrey; Wada, Keisuke; Kumar, Sonu; Amores, Marco; Maeda, Hiroaki; Sasaki, Sono; Taketsugu, Tetsuya; Nishihara, Hiroshi
• Is Part Of: Small. Volume 18:Issue 33(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-29
• Subjects: 2D coordination frameworks -- abundant elements -- carbon‐ and nitrogen‐frameworks -- multielectron‐transfer -- reversible energy storage -- sustainable materials; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.202202861
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract: Reversible multielectron‐transfer materials are of considerable interest because of the potential impact to advance present electrochemical energy storage technology by boosting energy density. To date, a few oxide‐based materials can reach an electron‐transfer number per metal‐cation ( e M ) larger than 2 upon a (de)intercalation mechanism. However, these materials suffer from degradation due to irreversible rearrangements of the cation–oxygen bonds, and are based on precious metals, for example, Ir and Ru. Hence, a design of the non‐oxide‐based reversible multielectron‐transfer materials with abundant elements can provide a promising alternative. Herein, it is demonstrated that the bis(diimino)copper framework can show e M = 3.5 with cation/anion co‐redox mechanism together with a dual‐ion mechanism. In this study, the role of the cation–anion interactions is unveiled by using an experiment/theory collaboration applied to a series of the model non‐oxide abundant electrode systems based on different metal–nitrogen bonds. These models provide designer multielectron‐transfer due to the tunable π‐d conjugated electronic structures. It is found that the Cu–nitrogen bonds show a unique reversible rearrangement upon Li‐intercalation, and this process responds to acquire a significant reversible multielectron‐transfer. This work provides new insights into the affordable multielectron‐transfer electrodes and uncovers an alternative strategy to advance the electrochemical energy storage reactions. Abstract : A significantly reversible multielectron‐transfer is demonstrated by using only abundant elements. The bis(diimino)copper framework shows an electron‐transfer number of 3.5. The CuN bonds show a unique reversible rearrangement upon Li‐intercalation, and this process is the key to superior electrochemical properties. This work provides insights into the affordable multielectron‐transfer electrodes and uncovers an alternative strategy to advance the electrochemical energy storage.