Wang Yongqing, Zhao Fengyue, Qian Yumin, Ji Hongbing
Fine Chemical Industry Research Institute, School of Chemistry , Sun Yat-Sen University , Guangzhou 510275 , China.
Materials Science and Engineering Program and Department of Mechanical Engineering , The University of Texas at Austin , Austin , Texas 78712 , United States.
ACS Appl Mater Interfaces. 2018 Dec 12;10(49):42380-42386. doi: 10.1021/acsami.8b15693. Epub 2018 Dec 3.
Room-temperature sodium-ion batteries (NIBs) using a manganese-based layered cathode have been considered promising candidates for grid-scale energy storage applications. However, manganese-based materials suffer from serious Jahn-Teller distortion, phase transition, and unstable interface, resulting in severe structure degradation, sluggish sodium diffusion kinetics, and poor cycle, respectively. Herein, we demonstrate a Zr-doped NaMnCoZrO material with much improved specific capacity and rate capability compared with Zr-free NaMnCoO when used as cathode materials for NIBs. The material delivers a reversible capacity of 173 mA h g at 0.1 C rate, corresponding to approximately 72% of the theoretical capacity (239 mA h g) based on a single-electron redox process, and a capacity retention of 88% after 50 cycles was obtained. Additionally, a homogenous solid-state interphase (SEI) film was revealed directly by high-resolution transmission electron microscopy in Zr-doped material after battery cycling. Electrochemical impedance spectroscopy proves that the formation of SEI films provides the Zr-doped material with special chemical/electrochemical stability. These results here give clear evidence of the utility of Zr-doping to improve the surface and environmental stability, sodium diffusion kinetics, and electrochemical performance of P2-type layered structure, promising advanced sodium-ion batteries with higher energy density, higher surface stability, and longer cycle life compared with the commonly used magnesiumdoping method in electrode materials.
使用锰基层状阴极的室温钠离子电池(NIBs)被认为是电网规模储能应用的有前途的候选者。然而,锰基材料存在严重的 Jahn-Teller 畸变、相变和不稳定界面,分别导致严重的结构退化、缓慢的钠扩散动力学和较差的循环性能。在此,我们展示了一种 Zr 掺杂的 NaMnCoZrO 材料,当用作 NIBs 的阴极材料时,与无 Zr 的 NaMnCoO 相比,其比容量和倍率性能有了很大提高。该材料在 0.1 C 倍率下具有 173 mA h g 的可逆容量,基于单电子氧化还原过程,约占理论容量(239 mA h g)的 72%,并且在 50 次循环后获得了 88%的容量保持率。此外,通过高分辨率透射电子显微镜直接揭示了电池循环后 Zr 掺杂材料中均匀的固态界面(SEI)膜。电化学阻抗谱证明,SEI 膜的形成赋予了 Zr 掺杂材料特殊的化学/电化学稳定性。这些结果清楚地证明了 Zr 掺杂在改善 P2 型层状结构的表面和环境稳定性、钠扩散动力学以及电化学性能方面的效用,有望制备出与电极材料中常用的镁掺杂方法相比具有更高能量密度、更高表面稳定性和更长循环寿命的先进钠离子电池。