工作温度对钠-氯化镍电池正极结构及电化学性能的影响

doi:10.15541/jim20170171

摘要/Abstract

摘要：

钠-氯化镍电池是一种中温电池, 研究温度对电池性能的影响具有重要意义。本工作研究了工作温度对含硫电池和不含硫电池的正极结构和电化学性能的影响。研究发现, 无论电池的正极中是否含有单质硫, 适当地降低电池工作温度都能提高电池的循环性能。降低电池工作温度能降低颗粒的表面活性, 减缓金属镍颗粒的团聚长大, 进而提高电池循环性能。但当工作温度进一步降低时, 电化学反应速率、Na⁺迁移速率和熔融金属钠与β″-Al₂O₃的润湿性也会随之变差, 电池性能反而会下降。无论电池正极中是否含硫, 钠-氯化镍电池最佳的工作温度约为260℃。

关键词: 钠-氯化镍电池, 工作温度, 正极结构, 电化学性能, 硫添加剂

Abstract:

Na-NiCl₂ battery is an intermediate temperature battery of which the operating temperature is one of the crucial factors for its electrochemical performance and needs to be fully understand. The effects of operating temperature on electrochemical performance of Na-NiCl₂ batteries and morphology of the cathode material under different temperatures were studied based on the results of cell test, EIS and SEM measurements. It was found that the reduction of the operating temperature of the Na-NiCl₂ battery within a certain range suppressed the growth of nickel particles during cycling and improved the cycle performance of the cell with and without sulfur in the cathode. The surface activity of the nickel particles decreased with reduction of the operating temperature, while the growth rate of nickel particles slow down at low temperature, resulting in improved cell cycle performance of the cell improves. However, much lower operating temperature leads to poor electrochemical performance due to slow electrochemical reaction rate, migration rate of Na⁺ and poor wettability of sodium on ceramic electrolyte. Based on above tests, the optimum operating temperatures of the cell no matter with or without sulfur are about 260℃.

Key words: Na-NiCl₂ battery, operating temperature, cathode material, electrochemical performance, sulfur additive

中图分类号:

TM911

敖昕, 吴相伟, 吴田, 吴梅芬, 温兆银. 工作温度对钠-氯化镍电池正极结构及电化学性能的影响[J]. 无机材料学报, 2017, 32(12): 1243-1249.

AO Xin, WU Wei-Xiang, WU Tian, WU Mei-Fen, WEN Zhao-Yin. Operating Temperature on Cathode Material and Electrochemical Performance of Na-NiCl₂ Batteries[J]. Journal of Inorganic Materials, 2017, 32(12): 1243-1249.

图/表 6

图1 不含硫电池和含硫5%电池在不同工作温度下的(a, c)循环曲线及(b, d)首周充放电曲线

Fig. 1 (a, c) Cycle performance and (b, d) the first charge and discharge curve of the Na-NiCl2 battery without sulfur and with 5% sulfur which were tested at 220℃, 260℃ and 300℃

图2 不含硫电池和含硫5%电池在(a,b)220℃、(c,d)260℃、(e,f)300℃工作时的前5周充放电曲线

Fig. 2 First 5 charge and discharge curves of the cell without sulfur and with 5% sulfur in NaAlCl4 tested at (a,b) 220℃, (c,d) 260℃ and (e,f) 300℃

图3 (a)不含硫电池和(b)含硫5%的电池在300℃、260℃及220℃工作时第5周放电态的电化学阻抗谱图

Fig. 3 Electrochemical impedance spectroscopy plots of the Na-NiCl2 battery (a) without sulfur and (b) with 5% sulfur in NaAlCl4 which were tested at 300℃, 260℃, 220℃ after 5 cycles at discharge state

图4 不含硫电池在(a, b)260℃和(c, d)300℃循环10周后金属镍的形貌

Fig. 4 Morphologies of the nickel in the cell without sulfur after 10 cycles which are tested at 260℃ (a,b) and 300℃ (c,d)

图5 不含硫电池在(a,b)220℃、(c,d)260℃和(c,d)300℃循环100周后金属镍的形貌

Fig. 5 Morphologies of the nickel in the cell without sulfur after 100 cycles which are tested at 220℃, 260℃, 300℃

图6 含硫5%的电池在(a)220℃、(b)260℃、(c)300℃下循环100周后金属镍的形貌以及(d)初始镍颗粒的形貌

Fig. 6 Morphologies of nickel in the cell with 5% sulfur in the NaAlCl4 tested at (a) 220℃, (b) 260℃, (c) 300℃ after 100 cycles; (d) pristine nickel particles

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