Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni-Rich Sodium Cathodes,Advanced Materials

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Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni-Rich Sodium Cathodes
Advanced Materials ( IF 27.4 ) Pub Date : 2023-12-22 , DOI: 10.1002/adma.202308380
Biwei Xiao ₁ , Yu Zheng _{2,

3} , Miao Song ₄ , Xiang Liu ₅ , Gi-Hyeok Lee _{6,

7} , Fred Omenya ₁ , Xin Yang ₁ , Mark H Engelhard ₈ , David Reed ₁ , Wanli Yang ₆ , Khalil Amine ₅ , Gui-Liang Xu ₅ , Perla B Balbuena _{2,

3,

9} , Xiaolin Li ₁

Affiliation

Protonation of oxide cathodes triggers surface transition metal dissolution and accelerates the performance degradation of Li-ion batteries. While strategies are developed to improve cathode material surface stability, little is known about the effects of protonation on bulk phase transitions in these cathode materials or their sodium-ion battery counterparts. Here, using NaNiO₂ in electrolytes with different proton-generating levels as model systems, a holistic picture of the effect of incorporated protons is presented. Protonation of lattice oxygens stimulate transition metal migration to the alkaline layer and accelerates layered-rock-salt phase transition, which leads to bulk structure disintegration and anisotropic surface reconstruction layers formation. A cathode that undergoes severe protonation reactions attains a porous architecture corresponding to its multifold performance fade. This work reveals that interactions between electrolyte and cathode that result in protonation can dominate the structural reversibility/stability of bulk cathodes, and the insight sheds light for the development of future batteries.

中文翻译：

质子化刺激富镍钠阴极的层状到岩盐相变

氧化物阴极的质子化会引发表面过渡金属溶解并加速锂离子电池的性能退化。虽然开发了提高阴极材料表面稳定性的策略，但人们对质子化对这些阴极材料或其钠离子电池对应物中体相变的影响知之甚少。在这里，使用具有不同质子生成水平的电解质中的NaNiO ₂作为模型系统，呈现了掺入质子的影响的整体图景。晶格氧的质子化刺激过渡金属迁移到碱性层并加速层状岩盐相变，从而导致体结构分解和各向异性表面重建层的形成。经历剧烈质子化反应的阴极会获得与其多重性能衰减相对应的多孔结构。这项工作揭示了电解质和阴极之间导致质子化的相互作用可以主导本体阴极的结构可逆性/稳定性，这一见解为未来电池的发展提供了线索。

更新日期：2023-12-22

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