锡酸钾对流动锌酸钾碱液中锌沉积/溶解的影响

doi:10.7503/cjcu20180652

摘要/Abstract

摘要：

研究了在流动的高浓度锌酸钾溶液中锡酸钾添加剂对锌负极沉积/溶解行为的影响. 循环伏安测试结果表明, 扫描速度为1 mV/s时, 随着添加锡酸钾浓度的增加, 阴极分支更早出现沉积, 溶解峰的峰值逐渐减小; 随着扫描速度的增加, 这种规律变得不明显. 利用SEM观测电沉积500 s的沉积物形貌发现, 向基础溶液中添加锡酸钾有利于晶种的产生和晶粒的生长. EDS测试结果表明含锡酸钾的锌酸钾溶液中沉积层含有锌和锡. 自放电测试结果表明, 基础电解液加入锡酸钾后自放电现象得到了明显的改善, 充满电静置12 h后加入0.1 mol/L锡酸钾的电池放电库仑效率从基础溶液的60.0%提高到81.1%.

关键词: 锡离子, 锌镍单液流电池, 荷电保持

Abstract:

The effect of potassium stannate additive on the deposition/dissolution behavior of zinc anode in flowing high concentration potassium zincate solution was studied. Cyclic voltammetry results show that when the scanning speed is 1 mV/s, the cathode branch deposits earlier with the increase of potassium stannate concentration, that is, the co-deposition of tin and zinc leads to the gradual decrease of dissolution peak with the increase of potassium stannate concentration. With the increase of scanning speed, the law becomes less obvious. SEM analysis shows that the addition of potassium stannate to the base solution is beneficial to seed production and grain growth. EDS tests show that the deposit from potassium stannate solution containing potassium stannate do contain zinc and tin. The self-discharge test shows that the self-discharge phenomenon is improved obviously after adding potassium stannate to the basic electrolyte. The Coulomb efficiency of the battery with 0.1 mol/L potassium stannate is increased from 60.0% of the basic solution to 81.1% after 12 h static charge. Therefore, the addition of potassium stannate in high concentration potassium zincate solution can benefit the production of seed and the growth of grain, produce compact small grains, make the deposit surface smoother and more compact, slow down the self-dissolution of zinc to a certain extent, and thus inhibiting the self-discharge effect.

Key words: Stannum ion, Zinc-nickel single flow battery, Charge retention

中图分类号:

O646

TrendMD:

姚寿广, 陈勇, 程杰, 申亚举, 丁大培, 杨裕生. 锡酸钾对流动锌酸钾碱液中锌沉积/溶解的影响. 高等学校化学学报, 2019, 40(3): 481.

YAO Shouguang,CHEN Yong,CHENG Jie,SHEN Yaju,DING Dapei,YANG Yusheng. Effect of Potassium Stannate on the Deposition/Dissolution Behavior of Zinc Anode for Zinc-nickel Single-flow Battery^†. Chem. J. Chinese Universities, 2019, 40(3): 481.

图/表 8

Fig.1 Cyclic voltammetry curves of nickel-plated steel strip in alkaline solution at different scan rates(A), (B): The solution is 8 mol/L KOH+5 g/L LiOH+0.05 mol/L K2SnO3; (C), (D): the solution is 8 mol/L KOH+5 g/L LiOH; (A), (C) at 1 mV/s; (B), (D) at 5 mV/s. — First cycle; fifth cycle.

Fig.2 Constant-current charge-discharge curves of nickel-plated steel strip in 8 mol/L KOH+5 g/L LiOH+0.05 mol/L K2SnO3 aqueous solution at a current density of 5 mA/cm2

Fig.3 CV curves of the first cycle at scan rates of 1 mV/s(A), 5 mV/s(B) and 10 mV/s(C) on the nickel-plated steel strip electrodesElectrolyte: a. B; b. B+0.03 mol/L K2SnO3; c. B+0.05 mol/L K2SnO3; d. B+0.08 mol/L K2SnO3; e. B+0.1 mol/L K2SnO3. Enlarged curves in the insets, up: initial electroplate of the electrodes; down: another anode peak of control sample.

Fig.4 EDS of the surface of nickel-plated steel strip charged at current density of 10 mA/cm2 for 20 min in different electrolytesElectrolyte: (A) B; (B) B+0.05 mol/L K2SnO3; (C) B+0.1 mol/L K2SnO3.

Fig.5 The first charging curves of the nickel-plated steel strip electrodes in five different electrolytes(A) 5 mA/cm2, 1 h; (B) 10 mA/cm2, 0.5 h. Electrolyte: a. B; b. B+0.03 mol/L K2SnO3; c. B+0.05 mol/L K2SnO3; d. B+0.08 mol/L K2SnO3; e. B+0.1 mol/L K2SnO3.

Fig.6 Charge-discharge curves of nickel-plated steel strip electrodes in different electrolytes at 10 mA/cm2(A) 3rd Cycle; (B) 6th cycle; (C) 9th cycle; (D) amplification of the tin deposition potential of the negative electrode on the 9th cycle. Electrolyte: (A)—(C) a. B(control sample); b. B+0.03 mol/L K2SnO3; c. B+0.05 mol/L K2SnO3; d. B+0.08 mol/L K2SnO3; e. B+0.10 mol/L K2SnO3. (D) a. B; b. B+0.08 mol/L K2SnO3.

Fig.7 SEM images of the surface of the nickel-plated steel strip electrode charged at a current density of 10 mA/cm2 for 500 s in different electrolytesElectrolyte: (A) B; (B) B+0.03 mol/L K2SnO3; (C) B+0.05 mol/L K2SnO3; (D) B+0.08 mol/L K2SnO3; (E) B+0.10 mol/L K2SnO3.

Fig.8 Discharge curves of zinc-nickel single flow battery with nickel-plated steel strip as negative electrode after charging in different electrolytes and resting for different timeCharging and discharging current density is 10 mA/cm2, charged to capacity of 150 mA·h. (A) Discharging after resting of 12 h; (B) discharging after resting of 24 h; (C) discharging after resting of 48 h. Electrolyte: a. B; b. B+0.03 mol/L K2SnO3; c. B+0.05 mol/L K2SnO3; d. B+0.08 mol/L K2SnO3; e. B+0.10 mol/L K2SnO3.

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