Effect of hydrothermal reaction time on electrochemical properties of (NH4)2V4O9 as cathode material for aqueous zinc ion batteries
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摘要: 以NH4VO3和C2H2O4·2H2O为原料，采用简易的一步水热法制备出水系锌离子电池正极材料(NH4)2V4O9。利用X射线衍射仪（XRD）、扫描电子显微镜（SEM）、恒流充放电（GCD）、恒流间歇滴定技术（GITT）、循环伏安法（CV）以及电化学阻抗谱（EIS）等表征测试手段，研究不同水热反应时间（16、20和24 h）对 (NH4)2V4O9结构、形貌及电化学性能的影响。研究结果表明：水热反应20 h合成的(NH4)2V4O9拥有最高的结晶度，并表现出优异的电极反应动力学特性以及最佳的倍率性能和循环稳定性，其在0.1、0.2、0.5、1、2 A/g和5 A/g的电流密度下分别提供了554.6、472.2、386.6、322.6、266.2 mAh/g和199.5 mAh/g的高放电比容量，并且在5 A/g的大电流密度下长循环10 000圈后仍可保持159.7 mAh/g的放电比容量，容量保持率高达80.1%。
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关键词:
- 水系锌离子电池 /
- 钒基正极材料 /
- (NH4)2V4O9 /
- 水热反应时间 /
- 电化学性能
Abstract: (NH4)2V4O9 as cathode material for aqueous zinc ion batteries was prepared by a facile one-step hydrothermal method using NH4VO3 and C2H2O4·2H2O as raw materials. X-ray diffractometer (XRD), scanning electron microscope (SEM), galvanostatic charge-discharge (GCD), galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to investigate the effects of hydrothermal reaction time (16, 20 h and 24 h) on the structure, morphology and electrochemical properties of (NH4)2V4O9. The results show that (NH4)2V4O9 synthesized by hydrothermal reaction for 20 h has the highest crystallinity, electrode reaction kinetics, and rate capability as well as cyclic stability, delivering high discharge specific capacities of 554.6, 472.2, 386.6, 322.6, 266.2 and 199.5 mAh/g at current densities of 0.1, 0.2, 0.5, 1, 2 and 5 A/g, respectively. It can also maintain a discharge capacity of 159.7 mAh/g after 10 000 long-term cycles at a high current density of 5 A/g, showing a capacity retention of up to 80.1%. -
图 1 水热反应时间对样品的物相结构及形貌的影响
(a) 不同水热反应时间下样品的XRD 谱； (b) 2θ=10°附近衍射峰的强度对比； (c) (NH4)2V4O9的结构示意；水热反应时间为(d) 16 h,(e) 20 h和(f ) 24 h时样品的SEM形貌
Figure 1. Effect of hydrothermal reaction time on structures and morphologies of samples
图 2 样品的倍率性能及循环性能
(a)不同样品的倍率性能；(b)水热反应20 h样品的恒流充放电曲线；(c)不同样品在0.5 A/g电流密度下的循环性能；(d)不同样品在5 A/g电流密度下的的循环性能；(e)水热反应20 h样品的长循环性能曲线
Figure 2. Rate capability and cycle performance of samples
图 3 不同水热反应时间合成样品的(a)～(c) GITT曲线和(d)～(f) 锌离子扩散系数
Figure 3. (a)-(c) GITT curves and (d)-(f) zinc diffusion coefficient of samples synthesized under different hydrothermal reaction time
图 4 样品的电化学反应动力学
水热反应20 h的样品(a) 0.1 mV/s扫速下前三圈的CV曲线；(b) 100 mA/g电流密度下前三圈的充放电曲线；(c) 不同扫速下的CV曲线； (d) logi-logv曲线； (e) 电容贡献率柱状图；(f) 不同样品的EIS图
Figure 4. Electrochemical reaction kinetics of samples
表 1 试验原料规格与厂家
Table 1. Specifications and manufacturers of raw materials
名称 规格 厂家 偏钒酸铵（NH4VO3） 分析纯 成都市科隆化学品有限公司 草酸（C2H2O4·H2O） 分析纯 成都市科隆化学品有限公司 导电碳黑 电池级 东莞市科路得实验器材科技有限公司 聚偏氟乙烯（PVDF） 电池级 东莞市科路得实验器材科技有限公司 N-甲基吡咯烷酮（NMP） 电池级 成都市科隆化学品有限公司 锌箔（Zn） 电池级 东莞市科路得实验器材科技有限公司 钛箔（Ti） 电池级 东莞市科路得实验器材科技有限公司 三氟甲烷磺酸锌（Zn(CF3SO3)2） 分析纯 上海麦克林生化科技有限公司 玻璃纤维滤膜 GF/D 英国Whatman公司 
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