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通过掺杂锰构建多电子反应以提高钾离子电池磷酸盐阴极KVMn(PO)/C的容量和稳定性

Constructing Multi-Electron Reactions by Doping Mn to Increase Capacity and Stability in KVMn(PO)/C of Phosphate Cathodes for Potassium-Ion Batteries.

作者信息

Wang Shengmei, Xiong Shuangsheng, Li Zheng, Zhao Yueqi, Tao Xiwen, Gao Faming, Gao Yuan, Hou Li

机构信息

Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao, 066004, China.

College of Chemical Engineering and Materials science, Tianjin University of Science and Technology, Tianjin, 300457, China.

出版信息

Small. 2024 Nov;20(46):e2308628. doi: 10.1002/smll.202308628. Epub 2024 Aug 1.

Abstract

Vanadium-based phosphate cathode materials (e.g., KV(PO)) have attracted widespread concentration in cathode materials in potassium-ion batteries owing to their stable structure but suffer from low capacity and poor conductivity. In this work, an element doping strategy is applied to promote its electrochemical performance so that KVMn(PO)/C is prepared via a simple sol-gel method. The heterovalent Mn is introduced to stimulated multiple electron reactions to improve conductivity and capacity, as well as interlayer spacing. Galvanostatic intermittent titration technique (GITT) and in situ X-ray diffraction results further confirm that Mn-doping in the original electrode can obtain superior electrode process kinetics and structural stability. The prepared KVMn(PO)/C exhibits a high-capacity retention of 80.8% after 1 500 cycles at 2 C and an impressive rate capability, with discharge capacities of 87.6 at 0.2 C and 45.4 mA h g at 5 C, which is superior to the majority of reported vanadium-based phosphate cathode materials. When coupled KVMn(PO)/C cathode with commercial porous carbon (PC) anode as the full cell, a prominent energy density of 175 Wh kg is achieved based on the total active mass. Overall, this study provides an effective strategy for meliorating the cycling stability and capacity of the polyanion cathodes for KIB.

摘要

钒基磷酸盐正极材料(如KV(PO))因其结构稳定,在钾离子电池正极材料中受到广泛关注,但存在容量低和导电性差的问题。在这项工作中,采用元素掺杂策略来提升其电化学性能,通过简单的溶胶-凝胶法制备了KVMn(PO)/C。引入异价态的Mn以激发多电子反应,从而提高导电性和容量以及层间距。恒电流间歇滴定技术(GITT)和原位X射线衍射结果进一步证实,在原始电极中掺杂Mn可获得优异的电极过程动力学和结构稳定性。制备的KVMn(PO)/C在2 C下1500次循环后展现出80.8%的高容量保持率以及令人印象深刻的倍率性能,在0.2 C下放电容量为87.6 mA h g,在5 C下为45.4 mA h g,优于大多数已报道的钒基磷酸盐正极材料。当将KVMn(PO)/C正极与商业多孔碳(PC)负极耦合作为全电池时,基于总活性质量实现了175 Wh kg的突出能量密度。总体而言,本研究为改善钾离子电池聚阴离子正极材料的循环稳定性和容量提供了一种有效策略。

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