论文标题
轨道分割在确定阴极潜力$ o3 $ $ $ natmo_2 $化合物中的主要作用
Dominant role of orbital splitting in determining cathode potential in $O3$ $NaTMO_2$ compounds
论文作者
论文摘要
为Na-ion电池设计高潜在的阴极，其性能与锂离子阴极相当，仍然是一项艰巨的任务。通过全面的密度功能计算，我们将阴极电位与$ tm-o $ $债券的离子性之间的关系取消，其中$ o3 $ $ $ natmo_2 $化合物，其中TM离子是第四或五轮过渡金属。我们证明，在TM离子的协调环境中的磁交换相互作用和局部扭曲在确定$ tm^{3+} $ $ \ to $ $ $ tm^{4+}+e^ - $反应的$ tm-o $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $的反应方面在确定$ tm^{3+} $ $ \ to $ tm^{3+} $ $ \ $ $ \ $ \ $ \ $ \ $ \ $ \ $ \ $ \ $ \ $ \ $ \ $ \ $ $ \ $ $ $ $ $ $ $ $中的磁性扭曲中起着重要作用。这些结果表明，仅基于经验电负性值以实现高电位的设计阴极材料可能不是一个可行的策略，而不必考虑详细的结构评估。
Designing high potential cathodes for Na-ion batteries, which are comparable in performance to Li-ion cathodes, remains a challenging task. Through comprehensive density functional calculations, we disentangle the relationship between the cathode potential and the ionicity of $TM-O$ bonds in $O3$ $NaTMO_2$ compounds in which TM ions is a fourth- or fifth-row transition metal. We demonstrate that the magnetic exchange interaction and the local distortions in the coordination environment of TM ions play more significant roles in determining the cathode potential of the $TM^{3+}$ $\to$ $TM^{4+}+ e^-$ reaction than the ionicity of the $TM-O$ bonds in these compounds. These results indicate that designing cathode materials solely based on empirical electronegativity values to achieve high potential may not be a feasible strategy without taking into account a detailed structural assessment.
