Ziming Wang, Hao Chen, Qi Zhao, Yu Shi, Haiyang Wang, Yuxuan Ye, Yu Guo, Zhiguo Du, Shubin Yang
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引用次数: 0
摘要
尽管 O3 型层状氧化物因其能量密度高而成为钠离子电池(SIB)的可行正极材料,但它们仍然存在离子通道狭窄、结构退化严重等问题,严重危害了其电化学性能。本文采用高熵掺杂策略合成了一种稳定的 O3 型层状氧化物 NaNi0.4Mn0.4M0.2O2(M= Fe、Cu、Mg、Ti、Sn)(HE-NaNM)。由于在层状结构中引入了离子半径在 0.61-0.73 Å 范围内的金属阳离子,晶格在 c 轴上从 15.94 Å 扩展到 16.03 Å,这与 TMO6 八面体的高度畸变有关,为钠离子在晶格中的传输提供了宽广的通道。此外,这种扩展的晶格和高度扭曲的 TMO6 八面体能够有效抑制 TM 离子的迁移和 TMO2 板的严重滑动,从而在钠萃取/插入过程中实现 O3 相和 P3 相之间的一步可逆结构演化,而不会形成有害的相间。因此,在钠存储方面实现了 10 C 下 77.9 mAh g-1 的良好速率能力和 5 C 下高达 400 次循环的长期循环稳定性。
High entropy induced lattice expansion in layered oxide cathode towards fast sodium storage
Although O3-type layered oxides have become viable cathode materials for sodium-ion batteries (SIBs) due to their high energy densities, they still suffer from narrow ion channels and serious structure degradation, severely jeopardizing their electrochemical properties. Here, a stable O3-type layered oxide NaNi0.4Mn0.4M0.2O2 (M= Fe, Cu, Mg, Ti, Sn) (HE-NaNM) was synthesized by a high-entropy doping strategy. Owing to the introduction of the metal cations with ionic radiuses in a range of 0.61-0.73 Å into the layered structure, the lattice is expanded from 15.94 to 16.03 Å in c-axis, associated with a high distortion of TMO6 octahedrons, offering broad channels for sodium-ion transport in the lattices. Moreover, such expanded lattices and highly distorted TMO6 octahedrons enable to efficiently restrain the migration of TM ions and the severe sliding of TMO2 slabs, affording one-step reversible structure evolution between O3 and P3 phase during sodium extraction/insertion without formation of harmful interphases. As a result, a good rate capability of 77.9 mAh g-1 at 10 C and a long-term cycling stability up to 400 cycles at 5 C are achieved for sodium storage.
期刊介绍:
Energy Storage Materials is a global interdisciplinary journal dedicated to sharing scientific and technological advancements in materials and devices for advanced energy storage and related energy conversion, such as in metal-O2 batteries. The journal features comprehensive research articles, including full papers and short communications, as well as authoritative feature articles and reviews by leading experts in the field.
Energy Storage Materials covers a wide range of topics, including the synthesis, fabrication, structure, properties, performance, and technological applications of energy storage materials. Additionally, the journal explores strategies, policies, and developments in the field of energy storage materials and devices for sustainable energy.
Published papers are selected based on their scientific and technological significance, their ability to provide valuable new knowledge, and their relevance to the international research community.