锑离子添加剂对低共熔溶剂（DES）电解液液流电池的性能改善研究

doi:10.11949/0438-1157.20201483

摘要/Abstract

摘要：

非水系氧化还原液流电池（NARFB）的广泛应用受制于其较低的性能。在电解液中加入一些金属离子添加剂是一种可能的解决方案。实验研究了Sb³⁺离子对低共熔溶剂（DES）电解液液流电池电化学性能的影响。结果表明，添加Sb³⁺离子可以强化V（Ⅲ）/V（Ⅱ）氧化还原离子对的电化学反应动力学（最高可达22.6％）过程，钒离子在DES中的扩散系数提高了63.3％，并且电荷转移电阻降低了11.9％。场发射扫描电子显微镜表明，Sb³⁺离子电沉积在石墨毡的表面，对电化学反应起催化作用，从而改善了电化学性能。考虑增强的动力学和降低的活性比表面积之间的平衡，确定了Sb³⁺的最佳浓度为15 mmol·L^-1。此外，当使用含有Sb³⁺的负极电解液液流电池时，液流电池的功率密度提高了31.2%，从含原始电解质的3.08 mW·cm^-2到含15 mmol·L^-1 Sb³⁺离子的4.04 mW·cm^-2。这些结果为改善NARFB的电池性能提供了一个便捷而有前景的方法。

关键词: 低共熔溶剂（DES）, 氧化还原液流电池（RFB）, 锑离子, 电池性能

Abstract:

The wide application of non-aqueous redox flow battery (NARFB) is restricted by its lower performance. Adding some metal ion additives to the electrolyte is a possible solution. In this study, the influence of Sb³⁺ ions on the electrochemical performance of non-aqueous redox flow batteries (NARFBs) was experimentally studied. The results showed that the electrochemical reaction kinetics of V(Ⅲ)/ V(Ⅱ) redox couple is enhanced by the addition of Sb³⁺ (up to 22.6%), the diffusion coefficient of vanadium ions also increases (up to 63.3%) and the charge transfer resistance decreases (up to 11.9%). The field emission scanning electron microscope shows that Sb ions are electrodeposited on the surface of graphite felt, which contributes a catalytic effect on the electrochemical reaction so as to improve the electrochemical performance. Due to the trade-off between the enhanced kinetics and reduced active surface area, the optimum concentration of Sb³⁺ ions is found to be 15 mmol·L^-1. In addition, the flow battery assembled with negative electrolyte containing Sb³⁺ ions exhibits 31.2% higher power density, from 3.08 mW·cm^-2 with pristine electrolyte, to 4.04 mW·cm^-2 with 15 mmol·L^-1 Sb³⁺ ions in the electrolyte. These results provide a convenient and promising method for improving the battery performance of NARFB.

Key words: deep eutectic solvent (DES), redox flow battery (RFB), antimony ions, cell performance

中图分类号:

TK 02

纪燕男, 孙培茁, 马强, 张玮琦, 苏华能, 徐谦. 锑离子添加剂对低共熔溶剂（DES）电解液液流电池的性能改善研究[J]. 化工学报, 2021, 72(6): 3368-3379.

JI Yannan, SUN Peizhuo, MA Qiang, ZHANG Weiqi, SU Huaneng, XU Qian. Improving the performance of a deep eutectic solvent (DES)-electrolyte non-aqueous redox flow battery by antimony ion additive[J]. CIESC Journal, 2021, 72(6): 3368-3379.

图/表 18

图1 含有不同浓度SbCl3的VCl3电解液A—原始溶液; B—5 mmol·L-1; C—10 mmol·L-1; D—15 mmol·L-1;

Fig.1 Electrolytes with different concentrations of SbCl3E—20 mmol·L-1; F—25 mmol·L-1

表1 含有不同浓度Sb3+离子的电解液的黏度和电导率值

Table 1 Viscosity and conductivity of electrolytes with different concentrations of Sb3+ ions

Sb³⁺浓度/(mmol·L^-1)	黏度/(mPa·s)	电导率/(mS·cm^-1)
pristine	62.4	6.64
5	61.6	6.70
10	61.5	6.72
15	61.2	6.75
20	61.9	6.69

图2 0.1 mol·L-1 V(Ⅲ)电解质中加入15 mmol·L-1 Sb3+离子前、后的拉曼光谱

Fig.2 The Raman spectra of 0.1 mol·L-1 V(Ⅲ) electrolyte with and without 15 mmol·L-1 Sb3+ ions

图3 ethaline电解液的CV曲线

Fig.3 CV curve of ethaline electrolyte

图4 含不同浓度Sb3+离子0.1 mol·L-1 V(Ⅲ)电解质在不同扫描速率下的CV曲线

Fig.4 CV curves of 0.1 mol·L-1 V(Ⅲ) electrolyte with different concentrations of Sb3+ ions at different scanning rates

表2 不同扫描速率下的峰电流密度

Table 2 Peak current density at different scanning rates

Sb³⁺浓度/(mmol·L^-1)	氧化峰电流密度/(mA·cm^-2)				还原峰电流密度/(mA·cm^-2)
Sb³⁺浓度/(mmol·L^-1)	10 mV·s^-1	25 mV·s^-1	50 mV·s^-1	100 mV·s^-1	10 mV·s^-1	25 mV·s^-1	50 mV·s^-1	100 mV·s^-1
pristine	2.252	3.583	5.085	7.189	-2.343	-3.691	-5.211	-7.340
5	2.650	4.176	5.901	8.221	-2.717	-4.197	-5.940	-8.406
10	2.703	4.254	6.029	8.389	-2.860	-4.342	-6.146	-8.770
15	2.898	4.589	6.481	9.072	-3.128	-4.764	-6.742	-9.514
20	2.754	4.371	6.192	8.645	-2.977	-4.526	-6.412	-9.065

图5 阳极峰值电流密度与扫描速率平方根之间的关系

Fig.5 The relationship between anode peak current density and the square root of scanning rates

表3 具有不同浓度Sb3+离子的0.1 mol·L-1 V(Ⅲ)离子的扩散系数

Table 3 Diffusion coefficients of 0.1 mol·L-1 V(Ⅲ) ions with different concentrations of Sb3+ ions

Sb³⁺浓度/ (mmol·L^-1)	D_re/(cm²·s^-1)	D_irre/(cm²·s^-1)
pristine	7.009×10^-7	1.362×10^-6
5	9.705×10^-7	1.951×10^-6
10	1.010×10^-6	2.142×10^-6
15	1.161×10^-6	2.472×10^-6
20	1.048×10^-6	2.241×10^-6

图6 0.1 mol·L-1 V(Ⅲ)电解质在不同浓度Sb3+下的Nyquist图及相应的等效电路

Fig.6 Nyquist plot of 0.1 mol·L-1 V(Ⅲ) electrolyte with different concentrations of Sb3+ ions and corresponding equivalent circuit

图7 不同浓度Sb3+的影响(Nyquist图)

Fig.7 The influence of different concentrations of Sb3+ ions(Nyquist plot)

表4 用等效电路拟合EIS图得到的参数

Table 4 The parameters obtained from fitting the EIS plots with the equivalent circuit

Sb³⁺浓度/(mmol·L^-1)	R_s/Ω	R_t/Ω	CPE/F	W_s
pristine	22.03	11.57	7.22×10^-4	0.533
5	20.72	9.89	9.86×10^-4	0.538
10	20.67	9.50	1.01×10^-3	0.548
15	19.41	8.95	1.15×10^-3	0.558
20	21.15	9.11	1.06×10^-3	0.549

表5 在Nafion 115膜组装下含有不同浓度Sb3+离子电解质的电池的内阻及能量效率

Table 5 Internal resistance and energy efficiency of batteries with different concentrations of Sb3+ ions electrolyte under Nafion 115 membrane assembly

Sb³⁺浓度/(mmol·L^-1)	内阻/Ω	能量效率/%
pristine	14.38	78.39
5	11.71	80.57
10	11.39	82.86
15	10.34	87.01
20	11.28	84.01

图8 在Nafion 115膜组装下含有不同浓度Sb3+离子电解质的电池充放电曲线

Fig.8 The charge-discharge curves of batteries using electrolyte with different concentrations of Sb3+ ions under Nafion 115 membrane assembly

图9 在Nafion 115膜组装下含有不同浓度Sb3+离子电解质的电池的极化曲线(a)和最大功率密度(b)

Fig.9 Polarization curves(a) and maximum power densities (b) of batteries with different concentrations of Sb3+ ions under Nafion 115 membrane assembly

表6 含有不同浓度Sb3+离子电解质的电池在三次充放电循环中的能量效率

Table 6 Energy efficiency of batteries with different concentrations of Sb3+ ions electrolyte in three charge-discharge cycles

Sb³⁺浓度/(mmol·L^-1)	能量效率/%
Sb³⁺浓度/(mmol·L^-1)	第一次循环	第二次循环	第三次循环
pristine	78.39	75.42	73.50
5	80.57	78.26	76.06
10	82.86	80.90	78.99
15	87.01	86.52	84.93
20	84.01	83.48	82.11

图10 使用含有不同浓度Sb3+离子电解质的电池在2 mA·cm-2电流密度下的充放电曲线

Fig.10 The charge-discharge curves of batteries using electrolyte with different concentrations of Sb3+ ions at a current density of 2 mA·cm-2

图11 相同放大倍率下完成充放电循环后石墨毡电极的FESEM图像

Fig.11 The FESEM images of graphite felt electrode at the same magnifications after cycling

图12 石墨毡表面颗粒EDX谱图

Fig.12 EDX spectrogram of particles on the surface of graphite felts

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