Yang Yang, Wang Zaifa, Du Congcong, Wang Bowen, Li Xinyan, Wu Siyuan, Li Xiaowei, Zhang Xiao, Wang Xubin, Niu Yaoshen, Ding Feixiang, Rong Xiaohui, Lu Yaxiang, Zhang Nian, Xu Juping, Xiao Ruijuan, Zhang Qinghua, Wang Xuefeng, Yin Wen, Zhao Junmei, Chen Liquan, Huang Jianyu, Hu Yong-Sheng
Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China.
Science. 2024 Aug 16;385(6710):744-752. doi: 10.1126/science.adm9223. Epub 2024 Aug 15.
Air sensitivity remains a substantial barrier to the commercialization of sodium (Na)-layered oxides (NLOs). This problem has puzzled the community for decades because of the complexity of interactions between air components and their impact on both bulk and surfaces of NLOs. We show here that water vapor plays a pivotal role in initiating destructive acid and oxidative degradations of NLOs only when coupled with carbon dioxide or oxygen, respectively. Quantification analysis revealed that reducing the defined cation competition coefficient (η), which integrates the effects of ionic potential and sodium content, and increasing the particle size can enhance the resistance to acid attack, whereas using high-potential redox couples can eliminate oxidative degradation. These findings elucidate the underlying air deterioration mechanisms and rationalize the design of air-stable NLOs.
空气敏感性仍然是钠（Na）层状氧化物（NLOs）商业化的一个重大障碍。由于空气成分之间相互作用的复杂性及其对NLOs体相和表面的影响，这个问题已经困扰了学术界几十年。我们在此表明，只有当水蒸气分别与二氧化碳或氧气结合时，才会在引发NLOs的破坏性酸降解和氧化降解中起关键作用。定量分析表明，降低定义的阳离子竞争系数（η）（该系数综合了离子势和钠含量的影响）并增加粒径可以增强对酸侵蚀的抗性，而使用高电势氧化还原对可以消除氧化降解。这些发现阐明了潜在的空气劣化机制，并为空气稳定的NLOs的设计提供了合理依据。
