Improving the performance of a deep eutectic solvent (DES)-electrolyte non-aqueous redox flow battery by antimony ion additive

doi:10.11949/0438-1157.20201483

Abstract

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

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

CLC Number:

TK 02

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.

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.

Figures/Tables 18

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

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

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

Fig.3 CV curve of ethaline electrolyte

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

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

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

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

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

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

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

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

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

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

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

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

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

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

References 27

1	Leung P, Li X, Poncedeleon C, et al. Progress in redox flow batteries, remaining challenges and their applications in energy storage[J]. RSC Advances, 2012, 2(27): 10125-10156.
2	Xu Q, Zhao T S. Fundamental models for flow batteries[J]. Progress in Energy & Combustion Science, 2015, 49: 40-58.
3	Xu Q, Zhao T S, Zhang C. Effects of SOC-dependent electrolyte viscosity on performance of vanadium redox flow batteries[J]. Applied Energy, 2014, 130: 139-147.
4	Soloveichik G L. Flow batteries: current status and trends[J]. Chemical Reviews, 2015, 115: 11533-11558.
5	Thaller L H. Electrically rechargeable redox flow cells[C]//Intersociety Energy Conversion Engineering Conference, 1974: 924-928.
6	Chalamala B R, Soundappan T, Fisher G R, et al. Redox flow batteries: an engineering perspective[J]. Proceedings of the IEEE, 2014, 102: 976-999.
7	Skyllas-Kazacos M, Chakrabarti M H, Hajimolana S A, et al. Progress in flow battery research and development[J]. Journal of the Electrochemical Society, 2011, 158: R55-R79.
8	Galus Z. Electrochemical reactions in nonaqueous and mixed solvents[M]//Advances in Electrochemical Science and Engineering: Volume 4. Wiley‐VCH Verlag GmbH, 2008.
9	Wei X, Duan W, Huang J, et al. A high-current, stable nonaqueous organic redox flow battery[J]. ACS Energy Letters, 2016, 1(4): 705-711.
10	Escalante-García I L, Wainright J S, Thompson L T, et al. Performance of a non-aqueous vanadium acetylacetonate prototype redox flow battery: examination of separators and capacity decay[J]. Journal of the Electrochemical Society, 2014, 162: A363-A372.
11	Abbott A P, Mckenzie K J. Application of ionic liquids to the electrodeposition of metals[J]. Physical Chemistry Chemical Physics, 2006, 8: 4265-4279.
12	Lin I J B, Vasam C S. Metal-containing ionic liquids and ionic liquid crystals based on imidazolium moiety[J]. Journal of Organometallic Chemistry, 2005, 690: 3498-3512.
13	Abbott A P, Barron J C, Ryder K S, et al. Eutectic-based ionic liquids with metal-containing anions and cations[J]. Chemistry - A European Journal, 2007, 13: 6495-6501.
14	Zhang Q, Vigier K D O, Royer S, et al. Deep eutectic solvents: syntheses, properties and applications[J]. Chemical Society Reviews, 2012, 41: 7108-7146.
15	Ding Y, Zhang C, Zhang L, et al. Molecular engineering of organic electroactive materials for redox flow batteries[J]. Chemical Society Reviews, 2018, 47: 69-103.
16	Zhang C K, Zhang L Y, Ding Y, et al. Progress and prospects of next-generation redox flow batteries[J]. Energy Storage Materials, 2018, 15: 324-350.
17	Lloyd D, Vainikka T, Murtomäki L, et al. The kinetics of the Cu²⁺/Cu⁺ redox couple in deep eutectic solvents[J]. Electrochimica Acta, 2011, 56: 4942-4948.
18	Xu Q, Zhao T S, Wei L, et al. Electrochemical characteristics and transport properties of Fe(Ⅱ)/Fe(Ⅲ) redox couple in a non-aqueous reline deep eutectic solvent[J]. Electrochimica Acta, 2015, 154: 462-467.
19	Xu Q, Qin L, Su H, et al. Electrochemical and transport characteristics of V(Ⅱ)/V(Ⅲ) redox couple in a nonaqueous deep eutectic solvent: temperature effect[J]. Journal of Energy Engineering, 2017, 143: 04017051.
20	Jiang H R, Zeng Y K, Wu M C, et al. A uniformly distributed bismuth nanoparticle-modified carbon cloth electrode for vanadium redox flow batteries[J]. Applied Energy, 2019, 240: 226-235.
21	Hwang J, Ha H Y. Method for preparing electrolyte for redox flow battery including organic molecules as additive and redox flow battery using the same: US20180013163[P]. 2018-01-11.
22	Leung P, Shah A A, Sanz L, et al. Recent developments in organic redox flow batteries: a critical review[J]. Journal of Power Sources, 2017, 360: 243-283.
23	Jiang J, Materna K, Hedström S, et al. Molecular antimony complexes for electrocatalysis: activity of a main group element in proton reduction[J]. Angewandte Chemie International Edition, 2017, 56: 9111-9115.
24	Bradwell D J, Kim H, Sirk A H C, et al. Magnesium-antimony liquid metal battery for stationary energy storage[J]. Journal of the American Chemical Society, 2012, 134: 1895-1897.
25	Shen J, Liu S, He Z, et al. Influence of antimony ions in negative electrolyte on the electrochemical performance of vanadium redox flow batteries[J]. Electrochimica Acta, 2015, 151: 297-305.
26	Liang X, Peng S, Lei Y, et al. Effect of L-glutamic acid on the positive electrolyte for all-vanadium redox flow battery[J]. Electrochimica Acta, 2013, 95: 80-86.
27	Xu Q, Ji Y N, Qin L Y, et al. Effect of carbon dioxide additive on the characteristics of a deep eutectic solvent (DES) electrolyte for non-aqueous redox flow batteries[J]. Chemical Physics Letters, 2018, 708: 48-53.

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