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材料研究学报  2026, Vol. 40 Issue (4): 313-320    DOI: 10.11901/1005.3093.2025.155
  研究论文 本期目录 | 过刊浏览 |
稀土镧离子掺杂二氧化钒的制备和电化学性能
赵睿泽, 田俐(), 宋佩媛, 方瑶, 孙萌, 樊赛男, 欧治民, 朱海博, 黄容姣, 阳立
湖南科技大学材料科学与工程学院 新能源储存与转换先进材料湖南省重点实验室 湘潭 411201
Preperation and Electrochemical Performance of Rare Earth La3+-doped Vanadium Dioxide
ZHAO Ruize, TIAN Li(), SONG Peiyuan, FANG Yao, SUN Meng, FAN Sainan, OU Zhimin, ZHU Haibo, HUANG Rongjiao, YANG Li
School of Materials Science and Engineering, Hunan Provincial Key Laboratory of Advanced Materials for New Energy Storage and Conversion, Hunan University of Science and Technology, Xiangtan 411201, China
引用本文:

赵睿泽, 田俐, 宋佩媛, 方瑶, 孙萌, 樊赛男, 欧治民, 朱海博, 黄容姣, 阳立. 稀土镧离子掺杂二氧化钒的制备和电化学性能[J]. 材料研究学报, 2026, 40(4): 313-320.
Ruize ZHAO, Li TIAN, Peiyuan SONG, Yao FANG, Meng SUN, Sainan FAN, Zhimin OU, Haibo ZHU, Rongjiao HUANG, Li YANG. Preperation and Electrochemical Performance of Rare Earth La3+-doped Vanadium Dioxide[J]. Chinese Journal of Materials Research, 2026, 40(4): 313-320.

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摘要: 

用水热法制备一系列稀土La3+掺杂二氧化钒(La3+-VO2)并用XRD、EDS和SEM等手段对其表征以研究La3+-VO2电极的电化学性能。结果表明,在VO2中掺入适量的稀土La3+有利于提高La3+-VO2电极的倍率性能和循环稳定性。V∶La摩尔比为2∶0.3的La3+-VO2样品电极在电流密度为0.1 A·g-1时比容量为160.2 mAh·g-1,循环100次后其放电比容量为131.9 mAh·g-1,保持率为82%;电流密度为0.1 A·g-1时La3+-VO2电极的最大比容量达到209.8 mAh·g-1,电流密度为5.0 A·g-1时比容量为60.8 mAh·g-1,电流密度恢复到0.1 A·g-1时比容量可达217.6 mAh·g-1,表明其可逆性良好和结构稳定;电流密度为1.0 A·g-1时循环1000次后比容量为52.2 mAh·g-1,表明这种电极在大电流密度下也呈现出较好的循环性能。电化学动力学分析结果表明,La3+-VO2电极的充放电过程同时受电容和扩散反应的控制,扫描速度为0.2 mV·s-1和1.0 mV·s-1时其高赝电容占比分别为77%和88%,表明其具有高速动力学行为。电容性电荷存储机制使La3+-VO2电极在大容量和高扫描速率下具有良好的循环稳定性。

关键词 无机非金属材料水系锌离子电池水热法二氧化钒    
Abstract

Regarding the structural instability and poor cycling performance of vanadium-based oxide cathode materials during the charge-discharge processes in aqueous zinc-ion batteries, a series of La3+-doped VO2 materials (La3+-VO2) have been synthesized via a simple hydrothermal method. The results of electrochemical measurement indicate that an appropriate amount of rare-earth La3+-doping could enhance the rate capability and cycling stability of VO2 electrodes. When the V:La molar ratio is 2:0.3, the prepared La3+-VO2 electrode exhibits a specific capacity of 160.2 mAh·g-1 at a current density of 0.1 A·g-1 and a discharge specific capacity of 131.9 mAh·g-1 with a capacity retention rate of 82% after 100 cycles. The rate capability tests reveal the electrode with a maximum specific capacity of 209.8 mAh·g-1 at a current density of 0.1 A·g-1 and with a capacity of 60.8 mAh·g-1 at a high current density of 5.0 A·g-1, and with a maximum specific capacity of 217.6 mAh·g-1 when the current density returned 0.1 A·g-1, showing good reversibility and structural stability of the La3+-VO2 electrodes. The electrode maintains a specific capacity of 52.2 mAh·g-1 after 1000 cycles at 1.0 A·g-1 demonstrating good cycling performance even at high current densities. The electrochemical kinetic analysis indicates that the charge-discharge process of the La3+-VO2 electrode is simultaneously governed by both capacitive and diffusion-controlled reactions with the pseudocapacitive contribution percentages of 77% and 88% at scan rates of 0.2 mV·s-1 and 1.0 mV·s-1, respectively showing its fast kinetic behavior. The contribution of the capacitive charge storage mechanism ensures the excellent cycling stability of the La3+-VO2 electrode at high capacity and high-rate conditions.

Key wordsinorganic non-metallic materials    aqueous zinc-ion battery    hydrothermal method    vanadium dioxide
收稿日期: 2025-04-24     
ZTFLH:  TQ152  
基金资助:国家自然科学基金(51202066);教育部新世纪优秀人才支持计划(NCET-13-0784);全国大学生创新创业训练计划(202510534057);湖南省研究生科研创新项目(CX20251560);大学生创新训练计划(S202510534131);湖南科技大学教学改革研究项目(G325E3)和大学生科研创新计划(YZ2553)(G325E3)
通讯作者: 田俐,教授,849050031@qq.com,研究方向为光电功能材料;
Corresponding author: TIAN Li, Tel: 18627323439, E-mail: 849050031@qq.com
作者简介: 赵睿泽,男,2004年生,本科生
图1  La3+预嵌VO2电极材料的XRD谱
图2  La3+掺杂VO2电极材料(0.30La3+-VO2)的EDS谱和元素分布
图3  0La3+-VO2和0.3La3+-VO2样品的SEM照片
图4  扫速为0.1 mV·s-1时电极试样的前3次循环CV曲线
图5  La3+-VO2电极在0.1 A·g-1的循环性能曲线和0.30La3+-VO2电极的充放电曲线
图6  La3+-VO2在不同电流密度下的倍率性能和0.30La3+-VO2在0.1~5.0 A·g-1电流密度下的GCD曲线
图7  电流密度为1.0 A·g-1时La3+-VO2电极的循环性能
图8  La3+-VO2电极的首圈Nyquist曲线
图9  0.30La3+-VO2 和0.45La3+-VO2样品在不同扫描速率下的CV曲线以及0.30La3+-VO2和0.45La3+-VO2样品的b值拟合图
图10  0.30La3+-VO2和0.45La3+-VO2样品在0.2 mV·s-1下的赝电容占比贡献以及0.30La3+-VO2和0.45La3+-VO2样品在不同扫描速率下的电容贡献率
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