氮掺杂碳包覆的ZnO/CuO微球作为锂离子电池负极材料的性能研究

doi:10.15541/jim20250409

摘要/Abstract

摘要： 过渡金属氧化物ZnO做为锂电池负极材料,具有978.0 mAh·g^-1的高理论比容量,但是ZnO的循环稳定性与比容量保持率仍有待提高。因此,本研究采用Cu-ZnSe微米球为模板,盐酸多巴胺为原料制备了氮掺杂碳包覆的ZnO/CuO微米球。该合成策略同步实现了活性物质转化、内部孔隙结构构建以及外部导电碳层包覆。氮掺杂形成的吡啶氮、吡咯氮、石墨氮可以增加表面活性位点,促进离子电子转移。碳包覆后,在材料内部产生大量的缺陷,可以为表面氧化还原反应提供大量活性位点。ZnO/CuO/N-C微米球作为锂离子电池负极材料表现出出色的电化学性能。在0.1 A·g^-1电流密度下200次循环后表现出高比容量为1010.4 mAh·g^-1。在1 A·g^-1高电流密度下1000次循环后比容量为447.1 mAh·g^-1。其储锂过程具有较高的赝电容贡献,确保了优异的倍率性能。性能的提升主要归因以下因素：氮掺杂碳层有效缓冲了体积膨胀并维持了结构完整性;内部孔隙促进了电解液浸润与离子传输;ZnO与CuO的转化与合金化反应产生了高容量。

关键词: ZnO/CuO, 氮掺杂碳包覆, 微米球, 锂电池负极

Abstract: ZnO, a transition metal oxide, possesses a high theoretical capacity of 978 mAh·g^-1 as an anode for lithium batteries. However, its cycling stability and capacity retention still need to be improved. Therefore, ZnO/CuO microspheres modified with nitrogen-doped carbon-coating (ZnO/CuO/N-C) were synthesized using Cu-ZnSe microspheres as a template and dopamine hydrochloride as raw material. This synthesis strategy simultaneously achieves the conversion of active materials, construction of internal pore structure, and coating of external conductive carbon layer. The electrochemical properties of ZnO/CuO microspheres anode are greatly improved after the treatment of nitrogen-doped carbon-coating. The pyridine nitrogen, pyrrole nitrogen, and graphite nitrogen are formed after nitrogen-doped into ZnO/CuO microspheres, significantly increasing surface active sites and promoting ion electron transfer. A large number of defects are generated in the inner composites after carbon coating, advantageous for providing more active sites for surface redox reactions. The ZnO/CuO/N-C microspheres as anode material of Li-ion battery exhibit excellent electrochemical properties. They still display a high specific capacity of 1010.4 mAh·g^-1 at 0.1 A·g^-1after 200 cycles. The specific capacity of ZnO/CuO/N-C microspheres anode could reach 447.1 mAh·g^-1 at a high current density of 1 A·g^-1after 1000 cycles. The excellent rate performance is exhibited in the process of Li⁺ ions insertion, ascribed to a high contribution of pseudocapacitance. The improved electrochemical properties of ZnO/CuO/N-C microspheres can be ascribed to the following factors. The structural integrity of composites could maintain by buffering volume expansion after carbon-coating. The electrolyte infiltration and ion transport can be promoted due to the existence of internal pores. A high capacity is caused through the conversion and alloying reactions of between ZnO and CuO.

Key words: ZnO/CuO, N-doped carbon, microspheres, lithium-ion battery

中图分类号:

TB332

张高举, 任海波, 李文正, 王刚. 氮掺杂碳包覆的ZnO/CuO微球作为锂离子电池负极材料的性能研究[J]. 无机材料学报, DOI: 10.15541/jim20250409.

ZHANG Gaoju, REN Haibo, LI Wenzheng, WANG Gang. ZnO/CuO Microspheres Modified with Nitrogen-doped Carbon-coating for Lithium-ion Batteries[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250409.

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