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High-nickel content cathode materials offer high energy density. However, the structural and surface instability may cause poor capacity retention and thermal stability of them. To circumvent this problem, nickel concentration-gradient materials have been developed to enhance high-nickel content cathode materials' thermal and cycling stability. Even though promising, the fundamental mechanism of the nickel concentration gradient's stabilization effect remains elusive because it is inseparable from nickel's valence gradient effect. To isolate nickel's valence gradient effect and understand its fundamental stabilization mechanism, we design and synthesize a LiNi0.8Mn0.1Co0.1O2 material that is compositionally uniform and has a hierarchical valence gradient. The nickel valence gradient material shows superior cycling and thermal stability than the conventional one. The result suggests creating an oxidation state gradient that hides the more capacitive but less stable Ni3+ away from the secondary particle surfaces is a viable principle towards the optimization of high-nickel content cathode materials.

The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2− and (S2)2− through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g−1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n− species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction. Anionic redox reactions are gaining interest as a means to optimize capacities of alkaline ion batteries. Here, the authors investigate various charge compensation mechanisms and report S–S dimerization and the formation of electron holes on sulfur in a model sulfide cathode. [ABSTRACT FROM AUTHOR]