金属有机框架衍生的C-Bi/CC电极制备及其在铁铬液流电池中的电化学性能

doi:10.19799/j.cnki.2095-4239.2023.0607

摘要/Abstract

摘要：

电极是铁铬液流电池的重要组成部分，是电解液中活性组分发生电化学反应的场所。理想的电极材料应具备高电导率、大比表面积、高电化学活性、低成本等特性，而目前的电极材料往往不能兼顾。金属有机框架（MOF）兼具高导电性、高催化性能的优点，能够为电化学反应提供更多的活性位点，因此被广泛应用在电极材料中。此项工作通过水热法制备了以碳布负载Bi-MOF为前驱体（Bi-MOF/CC）的铋基碳布（CC）电极（C-Bi/CC）。通过探究金属盐的添加量与电极性能的耦合关系，提升了电极的性能，结果显示，使用90 mg金属盐的电极样品极化电阻仅1.069 Ω，相较于原始碳布降低了8.5%、Cr³⁺还原过电位为0.25 V，使用普通碳布作为正极，改性过的电极作为铁铬液流电池负极进行电池循环性能测试，在电流密度为80 mA/cm²时能量效率达89.7%，库仑效率达97.2%，电压效率达92.3%；在电流密度为140 mA/cm²时能量效率达到83.8%，库仑效率达98.1%，电压效率达85.5%。

关键词: 铁铬液流电池, 电极材料, 电化学性能, 能量效率

Abstract:

The electrode is an important part of the iron-chromium flow battery, serving as the site where the active components in the electrolyte undergo electrochemical reactions. The ideal electrode material should have high conductivity, large specific surface area, high electrochemical activity, low cost, among other characteristics. However, current electrode materials often lack a balance of these characteristics. Metal-organic frameworks (MOFs) combine their advantages of high conductivity and high catalytic performance, providing additional active sites for electrochemical reactions and finding widespread use in electrode materials. Herein, bismuth-based carbon cloth (CC) electrodes (C-Bi/CC) with carbon cloth-supported Bi-MOF as a precursor (Bi-MOF/CC) were prepared using a hydrothermal method. The electrode performance was improved by exploring the coupling correlation between the addition of metal salts and the electrode performance. The results showed that the electrode sample using 90 mg of metal salt and the ordinary carbon cloth as the positive electrode exhibited the best electrochemical performance, with a reduced polarization resistance of 1.069 Ω (an 8.5% reduction), an enhanced electrochemical active area, a low Cr³⁺ reduction overpotential of 0.25 V (a 59.7% decrease). The modified electrode was used as the negative electrode of the iron-chromium flow battery for the battery cycling performance test. At a current density of 80 mA/cm², the energy efficiency reached 89.7%, the Coulombic efficiency was 97.2%, and the voltage efficiency was 92.3%. At a current density of 140 mA/cm², the energy efficiency remained high at 83.8%, with the Coulomb efficiency reaching 98.1% and the voltage efficiency reaching 85.5%.

Key words: iron-chromium flow batteries, electrode material, electrochemical performance, energy efficiency

中图分类号:

TQ 02

周洋, 韩培玉, 牛迎春, 徐春明, 徐泉. 金属有机框架衍生的C-Bi/CC电极制备及其在铁铬液流电池中的电化学性能[J]. 储能科学与技术, 2024, 13(2): 381-389.

Yang ZHOU, Peiyu HAN, Yingchun NIU, Chunming XU, Quan XU. Fabrication of metal-organic framework-derived C-Bi/CC electrode materials and their electrochemical properties in ICRFB[J]. Energy Storage Science and Technology, 2024, 13(2): 381-389.

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参考文献 22

1	南明君, 乔琳, 刘玉琴, 等. 无机水系液流电池研究[J]. 化学进展, 2022, 34(6): 1402-1413.
	NAN M J, QIAO L, LIU Y Q, et al. A review of inorganic aqueous flow battery[J]. Progress in Chemistry, 2022, 34(6): 1402-1413.
2	谢聪鑫, 郑琼, 李先锋, 等. 液流电池技术的最新进展[J]. 储能科学与技术, 2017, 6(5): 1050-1057.
	XIE C X, ZHENG Q, LI X F, et al. Current advances in the flow battery technology[J]. Energy Storage Science and Technology, 2017, 6(5): 1050-1057.
3	张君慧, 曾义凯, 袁雨峰, 等. 铁铬液流电池关键材料研究进展[J]. 制冷与空调(四川), 2023, 37(1): 129-136.
	ZHANG J H, ZENG Y K, YUAN Y F, et al. Research progress on key materials of the iron-chromium flow battery[J]. Refrigeration & Air Conditioning, 2023, 37(1): 129-136.
4	TIEMANN P H, BENSMANN A, STUKE V, et al. Electrical energy storage for industrial grid fee reduction-A large scale analysis[J]. Energy Conversion and Management, 2020, 208: 112539.
5	M GÜR T. Correction: Review of electrical energy storage technologies, materials and systems: Challenges and prospects for large-scale grid storage[J]. Energy & Environmental Science, 2018, 11(10): 3055.
6	JAVED M S, MA T, JURASZ J, et al. Solar and wind power generation systems with pumped hydro storage: Review and future perspectives[J]. Renewable Energy, 2020, 148: 176-192.
7	LEI J Z, GONG Q W. Optimal allocation of a hybrid energy storage system considering its dynamic operation characteristics for wind power applications in active distribution networks[J]. International Journal of Energy Research, 2018, 42(13): 4184-4196.
8	SUN C Y, ZHANG H. Review of the development of first-generation redox flow batteries: Iron-chromium system[J]. ChemSusChem, 2022, 15(1): e202101798.
9	CHENG D S, REINER A, HOLLAX E. Activation of hydrochloric acid-CrCl₃ ·6H2 solutions with N-alkyfamines[J]. Journal of Applied Electrochemistry, 1985, 15(1): 63-70.
10	GAHN R F, HAGEDORN N, LING J S. Single cell performance studies on the Fe/Cr Redox Energy Storage System using mixed reactant solutions at elevated temperature[C]//Intersoc. Energy Conversion Engr. Conf, 1983
11	AHN Y, MOON J, PARK S E, et al. High-performance bifunctional electrocatalyst for iron-chromium redox flow batteries[J]. Chemical Engineering Journal, 2021, 421: 127855.
12	REN H L, SU Y, ZHAO S, et al. Research on the performance of cobalt oxide decorated graphite felt as electrode of iron-chromium flow battery[J]. ChemElectroChem, 2023, 10(5): e202201146.
13	JIANG Y Q, CHENG G, LI Y H, et al. Promoting vanadium redox flow battery performance by ultra-uniform ZrO₂@C from metal-organic framework[J]. Chemical Engineering Journal, 2021, 415: 129014.
14	NGUYEN V H, NGUYEN T D, VAN NGUYEN T. Microwave-assisted solvothermal synthesis and photocatalytic activity of bismuth(III) based metal-organic framework[J]. Topics in Catalysis, 2020, 63(11): 1109-1120.
15	XU J Y, XIE Y Y, ZHENG J Q, et al. A sodiophilic carbon cloth decorated with Bi-MOF derived porous Bi@C nanosheets for stable Na metal anode[J]. Journal of Electroanalytical Chemistry, 2021, 903: 115853.
16	TRÖBS L, WILKE M, SZCZERBA W, et al. Mechanochemical synthesis and characterisation of two new bismuth metal organic frameworks[J]. CrystEngComm, 2014, 16(25): 5560-5565.
17	GAO Y, YI X H, WANG C C, et al. Effective Cr(VI) reduction over high throughput Bi-BDC MOF photocatalyst[J]. Materials Research Bulletin, 2023, 158: 112072.
18	SCHALENBACH M. Impedance spectroscopy and cyclic voltammetry to determine double layer capacitances and electrochemically active surface areas[DB/OL]. (2018-12-31) https://api.semanticscholar.org/CorpusID:239437296.
19	FRANZ S, ARAB H, CHIARELLO G L, et al. Single-step preparation of large area TiO₂ photoelectrodes for water splitting[J]. Advanced Energy Materials, 2020, 10(23): 2000652.
20	冯晓健. 全钒液流电池碳纤维/金属氧化物复合电极的构建及性能研究[D]. 唐山: 华北理工大学, 2022.
	FENG X J. Construction and properties of carbon fiber/metal oxide composite electrode for vanadium flow battery[D]. Tangshan: North China University of Science and Technology, 2022.
21	褚夫军. Cr³⁺/Cr²⁺氧化还原电对性能及其在液流电池中的应用研究[D]. 北京: 北京化工大学, 2022.
	CHU F J. Performance of Cr³⁺/Cr²⁺ redox couple and its application in flow battery[D]. Beijing: Beijing University of Chemical Technology, 2022.
22	ZHANG F F, HUANG S P, WANG X, et al. Redox-targeted catalysis for vanadium redox-flow batteries[J]. Nano Energy, 2018, 52: 292-299.

样品/元素	C	O	Bi
C-Bi/CC	89.1%	10.3%	0.6%
Bi-MOF/CC	67.8%	28.3%	3.9%
CC	79.9%	20.1%	0

电极	R_s/Ω	R_ct/Ω
CC	1.187	1.169
Bi-MOF/CC	1.122	1.069
C-Bi/CC	1.121	1.106

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