Research progress on heteroatom-doped electrodes used in all vanadium redox flow batteries

doi:10.19799/j.cnki.2095-4239.2023.0929

Abstract

Abstract:

Flow batteries are indispensable technologies for large-scale energy storage, owing to their inherent safety and exceptionally long lifespan. In all-vanadium redox flow batteries (VRFBs), the electrode material is a crucial component, as its interface characteristics with the electrolyte substantially influence battery performance. Surface modification methods applied to the electrode facilitate enhancements in electrochemical activity, particularly under high current density conditions. Currently, electrode surface heteroatom doping technology is a focal point of research. This study summarizes the mechanisms and research progress of heteroatom doping in graphite felt (GF), specifically emphasizing two doping strategies: in-situ doping within the carbon framework and utilizing heteroatom catalysts on the electrode surface. This study also comprehensively summarizes doping types and performance differences associated with these two strategies. It explains the principles of in-situ doping in electrode materials based on the electronegativity and atomic size of heteroatoms, along with discussing how heteroatoms affect the electronic structure of carbon fibers. Additionally, it introduces the impact patterns of three carbon-based catalysts—heteroatom-doped porous carbon materials, carbon nanotubes, and graphene—on the electrochemical performance of electrode materials. The comprehensive analysis indicates that heteroatom doping on the electrode surface can increase active sites for electrode reactions, promote the migration of active ions, improve hydrophilicity, and enlarge the effective contact area between the electrode and electrolyte. Furthermore, the study suggests adopting methods such as regulating the charge distribution on the electrode surface, varying functional group types, and constructing defect sites to effectively enhance electrode materials' stability and electrochemical performance, ultimately leading to increased electrochemical activity at high current densities and higher conductivity.

Key words: vanadium redox flow battery, electrode, atomic doping, heteroatom catalyst

CLC Number:

TK 02

Ran XU, Baodong WANG, Shaoliang WANG, Qi ZHANG, Lei ZHANG, Ziyang FENG. Research progress on heteroatom-doped electrodes used in all vanadium redox flow batteries[J]. Energy Storage Science and Technology, 2024, 13(6): 1849-1860.

Figures/Tables 6

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References 47

1	贾传坤, 王庆. 高能量密度液流电池的研究进展[J]. 储能科学与技术,2015, 4(5): 467-475.
	JIA C K, WANG Q.The development of high energy density redox flow batteries[J].Energy Storage Science and Technology, 2015, 4(5): 467-475.
2	XUAN T, WANG L W. Eutectic electrolyte and interface engineering for redox flow batteries[J]. Energy Storage Materials, 2022, 48: 263-282.
3	GENCTEN M, SAHIN Y. A critical review on progress of the electrode materials of vanadium redox flow battery[J]. Energy Research, 2020, 44: 7903-7923.
4	KUMAR R, SAHOO S, JOANNI E, et al. Heteroatom doped graphene engineering for energy storage and conversion[J]. Materials Today, 2020, 39: 47-65.
5	李强, 王俊楠, 孙红, 等. 钒液流电池石墨毡电极的MWCNTs-COOH-NS修饰[J]. 储能科学与技术, 2021, 10(6): 2097-2105.
	LI Q, WANG J N, SUN H, et al. Graphite felt electrode modified with MWCNTs-COOH-NS for vanadium flow battery[J]. Energy Storage Science and Technology, 2021, 10(6): 2097-2105.
6	姚祯, 张琦, 王锐, 等. 生物质衍生碳材料在全钒液流电池电极方面的应用[J]. 储能科学与技术, 2022, 11(7): 2083-2091.
	YAO Z, ZHANG Q, WANG R, et al. Application of biomass derived carbon materials in all vanadium flow battery electrodes[J]. Energy Storage Science and Technology, 2022, 11(7): 2083-2091.
7	曾艳, 吕早生, 刘俞辰, 等. 全钒液流电池中石墨毡电极的改性研究[J]. 电镀与精饰, 2019, 41(1): 15-21.
	ZENG Y, LV Z S, LIU Y C, et al. Recent progress on graphite felt as electrode materials in vanadium redox flow battery[J]. Plating and Finishing, 2019, 41(1): 15-21.
8	SANKARALINGAM R K, SESHADRI S, SUNARSO J, et al. Overview of the factors affecting the performance of vanadium redox flow batteries[J]. Journal of Energy Storage, 2021, 41, 102857.
9	娄景媛, 尤东江, 李雪菁, 等. 全钒氧化还原液流电池用石墨毡电极的分步氧化活化[J]. 电化学, 2020, 26(6): 876-884.
	LOU J Y, YOU L J, LI X J, et al. Step-by-step modification of graphite felt electrode for vanadium redox flow battery[J]. Journal of electrochemistry, 2020, 26(6): 876-884.
10	QI S T, DAI L, HUO W J, et al. Doping engineering strategies for electrodes and catalysts in vanadium redox flow battery[J]. Composites Part B, 2023, doi: 10.1016/j.compositesb.2023.110947.
11	LIU JING, SONG P, NING Z G, et al. Recent advances in heteroatom-doped metal-free electrocatalysts for highly efficient oxygen reduction reaction[J]. Electrocatalysis, 2015, 6: 132-147.
12	ZHANG K Y, YAN C W, TANG A. Interfacial co-polymerization derived nitrogendoped carbon enables high-performance carbon felt for vanadium flow batteries[J]. Journal of Materials Chemistry A, 2021, 9, 17300-17310.
13	HE Z X, JIANG Y Q, ZHU J, et al., Phosphorus doped multi-walled carbon nanotubes: An excellent electrocatalyst for the VO²⁺/VO₂ ⁺ redox Reaction[J]. ChemElectroChem, 2018, 5(17): 2464-2474.
14	CHUNG Y, NOH C, KWON Y. Role of borate functionalized carbon nanotube catalyst for the performance improvement of vanadium redox flow battery[J]. Journal of Power Sources, 2019, 438, 227063.
15	苏秀丽, 杨霖霖, 周禹, 等, 全钒液流电池电极研究进展[J]. 储能科学与技术, 2019, 8(1): 65-74.
	SU X L, YANG L L, ZHOU Y, et al. Developments of electrodes for vanadium redox flow battery[J]. Energy Storage Science and Technology, 2019, 8(1): 65-74.
16	KIM H, PAICK J, YI J S, et al. Kinetic relevancy of surface defects and heteroatom functionalities of carbon electrodes for the vanadium redox reactions in flow batteries[J]. Journal of Power Sources, 2023, 557: 232612.
17	JIN J T, FU X G, LIU Y R, et al. Identifying the active site in nitrogen-doped graphene for the VO²⁺/VO₂ ⁺ redox reaction[J]. ACS Nano, 2013, 7(6): 4764-4773
18	WU L T, SHEN Y, YU L H, et al. Boosting vanadium flow battery performance by nitrogen-doped carbon nanospheres electrocatalyst[J]. Nano Energy, 2016, 28: 19-28.
19	LEE H J, KIM H. Graphite felt coated with dopamine-derived nitrogen-doped carbon as a positive electrode for a vanadium redox flow battery[J]. Journal of The Electrochemical Society, 2015, 162(8): A1675-A1681.
20	HE Z Q, ZHOU X J, ZHANG Y, et al. Low-temperature nitrogen-doping of graphite felt electrode for vanadium redox flow batteries[J]. Journal of The Electrochemical Society, 2019, 166(12): A2336-A2340.
21	KIM K J, LEE H S, KIM J, et al. Superior electrocatalytic activity of a robust carbon-felt electrode with oxygen-rich phosphate groups for all-vanadium redox flow batteries[J]. ChemSusChem, 2016, 9: 1329-1338.
22	WANG R, LI Y S, WANG Y N, et al. Phosphorus-doped graphite felt allowing stabilized electrochemical interface and hierarchical pore structure for redox flow battery[J]. Applied Energy, 2020, 261, 114369.
23	WU X W, XIE Z Y, ZHOU H K, et al. Designing high efficiency graphite felt electrode via HNO₃ vapor activation towards stable vanadium redox flow battery[J]. Electrochimica Acta 2023, 440, 141728.
24	HUANG Y Q, DENG Q, WU X W, et al. N, O co-doped carbon felt for high-performance all-vanadium redox flow battery[J]. International Journal of Hydrogen Energy, 2017, 42: 7177-7185.
25	KIM S, LIM H, KIM H, et al. Nitrogen and oxygen dual-doping on carbon electrodes by urea thermolysis and its electrocatalytic significance for vanadium redox flow battery[J]. Electrochimica Acta, 2020, 348: 136286.
26	PARK S E, LEE K, SUHARTO Y, et al. Enhanced electrocatalytic performance of nitrogen-and phosphorous-functionalized carbon felt electrode for VO²⁺/VO₂ ⁺ redox reaction[J]. International Journal of Energy Research, 2021, 45: 1806-1817.
27	OPAR D O, NANKYA R, RAJ C J, et al. In-situ functionalization of binder-free three-dimensional boron-doped mesoporous graphene electrocatalyst as a high-performance electrode material for all-vanadium redox flow batteries[J]. Applied Materials Today, 2021, 22: 100950.
28	JIANG H R, SHYY W, ZENG L, et al. Highly efficient and ultra-stable boron-doped graphite felt electrodes for vanadium redox flow batteries[J]. Journal of Materials Chemistry A, 2018, 6: 13244-13253.
29	LEE S, CHO S Y, CHUNG Y S, et al., High electrical and thermal conductivities of a PAN-based carbon fiber via boron-assisted catalytic graphitization[J]. Carbon, 2022, 199: 70-79.
30	YANG I, LEE S, JANG D, et al. Enhancing energy efficiency and long-term durability of vanadium redox flow battery with catalytically graphitized carbon fiber felts as electrodes by boron doping[J]. Electrochimica Acta, 2022, 429: 141033.
31	ZHANG J L, LIU Y Y, LU S F, et al. Nitrogen, phosphorus co-doped graphite felt as highly efficient electrode for VO²⁺/VO₂ ⁺ reaction[J]. Batteries, 2023, 9(40): 1-10.
32	SHI L, LIU S Q, HE Z, et al. Synthesis of boron and nitrogen co-doped carbon nanofiber as efficient metal-free electrocatalyst for the VO²⁺/VO₂ ⁺ redox reaction[J]. Electrochimica Acta, 2015, 178: 748-757.
33	ZHANG F J, ZHANG H T,et al. Applications of nanocarbons in redox flow batteries[J]. New Carbon Materials, 2021, 36(1): 82-92.
34	HUANG R J, WANG Y, LIU S Q. Non-precious transition metal based electrocatalysts for vanadium redox flow batteries: Rational design and perspectives[J]. Journal of Power Sources, 2021, 515: 230640.
35	XU J, ZHANG Y Q, HUANG Z F, et al. Surface modification ocarbon-based electrodes for vanadium redox flow batteries[J].Energy Fuels, 2021, 35: 8617-8633.
36	PARK M J, RYU J, CHO J, et al. Nanostructured electrocatalysts for all-vanadium redox flow batteries[J].Chemistry an Asian Journal, 2015, 10: 2096-2110.
37	LIU Y C, SHEN Y, YU L H, et al. Holey-engineered electrodes for advanced vanadium flow batteries[J]. Nano Energy, 2018, 43: 55-62.
38	LIU Y B, YU L H, LIU X, et al. ZIF-derived holey electrode with enhanced mass transfer and N-rich catalytic sites for high-power and long-life vanadium flow batteries[J]. Journal of Energy Chemistry, 2022, 72: 545-553.
39	JI J, NOH C, SHIN M, et al. Vanadium redox flow batteries using new mesoporous nitrogen-doped carbon coated graphite felt electrode[J]. Applied Surface Science, 2023, 611: 155665.
40	WANG S Y, ZHAO X S, COCHELL T, et al. Nitrogen-doped carbon nanotube/graphite felts as advanced electrode materials for vanadium redox flow batteries[J]. The Journal of Physical Chemistry Letters, 2012, 3: 2164-2167.
41	LIU L S, ZHANG X H, ZHANG D H, et al. Regulating the N/B ratio to construct B, N co-doped carbon nanotubes on carbon felt for high-performance vanadium redox flow batteries[J]. Chemical Engineering Journal, 2023, 473: 145454.
42	GONZÁLEZ Z, BOTAS C, BLANCO C, et al. Thermally reduced graphite and graphene oxides in VRFBs[J]. Nano energy, 2013, 2(6): 1322-1328.
43	LING W, WANG Z A, MA Q, et al. Phosphorus and oxygen co-doped composite electrode with hierarchical electronic and ionic mixed conducting networks for vanadium redox flow batteries[J].Chemical Communications, 2019: 1-4.
44	LI Q, WANG J N, ZHANG T Y, et al. Analysis of the performance of phosphorus and sulphur co-doped reduced graphene oxide as catalyst in vanadium redox flow battery[J]. Journal of Electrochemical Society, 2022, 169: 010523.
45	LI Q, LIU J Q, BAI A Y, et al. Preparation of a nitrogen-doped reduced graphene oxide-modified graphite felt electrode for VO²⁺/VO₂ ⁺reaction by freeze-drying and pyrolysis method[J]. Journal of Chemistry, 2019: 8958946.
46	XU A, SHI L, ZENG L, et al. First-principle investigations of nitrogen, boron, phosphorus-doped graphite electrodes for vanadium redox flow batteries[J]. Electrochimica Acta, 2019, 300: 389-395.
47	SHI L, LIU S Q, HE Z, et al. Nitrogen-doped graphene:Effects of nitrogen species on the properties of the vanadium redox flow battery[J]. Electrochimica Acta, 2014, 138: 93-100.

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