CN107863536B - Multi-scale porous electrode applied to flow battery and preparation method and application thereof - Google Patents
Multi-scale porous electrode applied to flow battery and preparation method and application thereof Download PDFInfo
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- CN107863536B CN107863536B CN201710960189.2A CN201710960189A CN107863536B CN 107863536 B CN107863536 B CN 107863536B CN 201710960189 A CN201710960189 A CN 201710960189A CN 107863536 B CN107863536 B CN 107863536B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- -1 alkali metal salt Chemical class 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- FYMBCBXJSPPHJQ-UHFFFAOYSA-N [Br].[V] Chemical compound [Br].[V] FYMBCBXJSPPHJQ-UHFFFAOYSA-N 0.000 claims description 3
- SKAXWKNRKROCKK-UHFFFAOYSA-N [V].[Ce] Chemical compound [V].[Ce] SKAXWKNRKROCKK-UHFFFAOYSA-N 0.000 claims description 3
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009941 weaving Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a multi-scale porous electrode applied to a flow battery and a preparation method and application thereof. The multi-scale porous electrode can be applied to an all-vanadium redox flow battery, and when the multi-scale porous electrode is applied to the all-vanadium redox flow battery, the current efficiency of the battery can reach more than 98%, the energy efficiency can reach 89%, and the operating current density can reach 200mAcm‑2Above, the effective run time exceeded 500 hours.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to a multi-scale porous electrode applied to a flow battery and a preparation method and application thereof.
Background
The energy is the basis of human survival, is the power of social development, and has attracted great attention to the reasonable development and utilization of the energy. The use of traditional fossil energy in large quantities brings about a plurality of problems such as environmental pollution, climate change and the like. The vigorous development of renewable energy sources represented by wind energy and solar energy is an effective way to realize clean and sustainable energy supply. However, renewable energy has the characteristics of intermittency, volatility and the like, and often causes great impact on a power grid, so that the renewable energy becomes a bottleneck limiting large-scale application of the renewable energy. The development of grid-level power storage systems is an effective way to solve this problem. In the existing large-scale electricity storage technology, the flow battery has a wide development prospect due to good expandability, good safety, long service life and low full-cycle service life.
In flow batteries, the active material is typically dissolved in ionic form in the liquid electrolyte. The positive and negative electrolytes are stored in an external liquid storage tank, and when the battery runs, the positive and negative electrolytes are respectively pumped to the positive and negative electrodes to generate electrochemical reaction so as to store or release electric energy. According to different active material classifications, the existing flow batteries mainly include all vanadium flow batteries, iron chromium flow batteries, zinc bromine flow batteries, hydrogen bromine flow batteries, and the like. The existing flow battery electrode generally adopts carbon fiber lap-joint-based porous electrode materials such as carbon felt, graphite felt, carbon paper and carbon cloth. Compared with a plane electrode, the porous electrode can improve the specific surface area and the electrochemical catalytic activity and has stabilityGood qualitative performance, high permeability, low cost and the like. Flow batteries based on existing electrodes, such as all-vanadium flow batteries, operate at lower current densities (40-80mA cm)-2) And the charge-discharge energy efficiency can reach 70-80%. However, the existing flow battery has low operating current density and low output power, so that the galvanic pile has the disadvantages of more materials, high manufacturing cost and difficult popularization.
The development of a high specific surface area and high activity electrode is crucial to the improvement of the operating current density and power density of the flow battery, which will significantly reduce the cost of the energy storage system and promote the commercialization process thereof. In the design of the flow battery electrode, the electrode activity and the electrode mass transfer characteristic need to be considered at the same time, but the specific surface area and the electrode permeability are often mutually restricted and are difficult to be improved at the same time. In general, reducing the diameter of carbon fibers can increase the specific surface area of an electrode, but at the same time, the permeability of the electrode is greatly reduced, resulting in a significant increase in the electrolyte flow resistance and pumping work, which deteriorates the battery performance.
Therefore, there is a need for improvements in the prior art.
Disclosure of Invention
Based on this, it is an object of the present invention to provide a multi-scale porous electrode for use in a flow battery.
The specific technical scheme is as follows:
a multi-scale porous electrode applied to a flow battery comprises a porous electrode framework formed by lapping, bonding or weaving carbon fibers, wherein secondary holes are distributed on the surface of the carbon fibers, and tertiary holes are distributed on the inner surface of the secondary holes.
In some of these embodiments, the carbon fibers have a diameter of 2 μm to 20 μm and a length of 10 μm to 10 mm.
In some of these embodiments, the secondary pores have a diameter of 50nm to 500nm, a pore depth of 50nm to 500nm, and a pore spacing of 50nm to 500 nm.
In some of these embodiments, the tertiary pores have a diameter of 5nm to 10nm, a pore depth of 10nm to 30nm, and a pore spacing of 5nm to 10 nm.
Another object of the present invention is to provide a method for preparing the above multi-scale porous electrode for a flow battery.
The preparation method of the multi-scale porous electrode applied to the flow battery comprises the following steps:
(1) immersing an initial carbon material into a nickel salt, iron salt or cobalt salt solution (the solvent can be water, ethanol, acetone or isopropanol) and carrying out ultrasonic treatment for 5-60min, wherein the mass fraction of the nickel salt, the iron salt or the cobalt salt in the solution is 3-30%; drying at 60-120 deg.C;
(2) carrying out heat treatment on the carbon material obtained in the step (1), wherein the atmosphere is a mixed gas of inert gas and oxidizing gas, the volume fraction of the oxidizing gas is 2-50%, the heating rate is 2-10 ℃/min, the heat treatment temperature is 500-;
(3) repeatedly cleaning the carbon material obtained in the step (2) in dilute nitric acid, and then soaking in an alkali solution or an alkali metal salt solution; soaking and ultrasonically treating 5-70 wt% of alkali or alkali metal salt in the solution for 5-60min, taking out and drying;
(4) carrying out heat treatment on the carbon material obtained in the step (3) in an inert gas atmosphere, wherein the heating rate is 2-10 ℃/min, the heat treatment temperature is 600-900 ℃, the heat treatment time is 1-3h, and naturally cooling to room temperature after heat treatment; and then sequentially washing and drying by using distilled water and dilute nitric acid to obtain the multi-scale porous electrode applied to the flow battery.
In some of these embodiments, the initial carbonaceous material is selected from the group consisting of carbon felt, graphite felt, carbon paper, and carbon cloth, and has a thickness of 0.1 to 3 mm.
In some of these embodiments, the nickel salt is selected from nickel chloride, nickel acetate, nickel formate, nickel sulfate, or nickel nitrate; the ferric salt is selected from ferric chloride, ferric acetate, ferric formate, ferric sulfate or ferric nitrate; the cobalt salt is selected from cobalt chloride, cobalt acetate, cobalt formate, cobalt sulfate or cobalt nitrate.
In some of these embodiments, the oxidizing gas is one or more of water vapor, oxygen, or carbon dioxide; the inert gas is nitrogen, helium or argon.
In some of these embodiments, the alkali solution is a lithium hydroxide, sodium hydroxide, or potassium hydroxide solution, and the alkali metal salt solution is a lithium carbonate, lithium sulfate, lithium nitrate, lithium formate, lithium acetate, sodium carbonate, sodium sulfate, sodium nitrate, sodium formate, sodium acetate, potassium carbonate, potassium sulfate, potassium nitrate, potassium formate, or potassium acetate solution.
Another object of the present invention is to provide a flow battery.
A flow battery comprises the multi-scale porous electrode applied to the flow battery.
In some of these embodiments, the flow battery is selected from an all vanadium flow battery, a ferro-chromium flow battery, a ferro-vanadium flow battery, a zinc-bromine flow battery, a vanadium-bromine flow battery, or a vanadium-cerium flow battery.
The principle and advantages of the invention are as follows:
the invention aims to solve the problem that the permeability of a porous electrode and the specific surface area of the porous electrode in a flow battery are mutually restricted and are difficult to simultaneously improve.
The invention breaks through the structural design and preparation process of the electrode in the traditional flow battery, and realizes the preparation of the multi-scale porous electrode by adopting a method of carrying out two times of pore forming on the surface of the carbon fiber by adopting the catalytic oxidation reaction of the iron-cobalt-nickel metal oxide and the oxidation reaction of the alkali metal ions. On the premise of not influencing the permeability of the electrode, the specific surface area and the catalytic activity of the electrode are greatly improved through two pore-forming reactions on different scales; because the secondary hole and the tertiary hole formed by the two times of pore-forming reaction have different scales and have no influence on each other, the amplification factor of the electrode area after the two times of continuous pore-forming is the product of the amplification factors of the electrode area after the first time and the second time of independent pore-forming.
The multi-scale porous electrode prepared by the invention has the advantages of high specific surface area, high catalytic activity, high permeability and the like. The preparation method is simple in preparation process, low in production cost, easy to operate and suitable for large-scale production.
The multi-scale porous electrode prepared by the invention can be applied to all-vanadium redox flow batteries, iron-chromium redox flow batteries, iron-vanadium redox flow batteries, zinc-bromine redox flow batteries, vanadium-bromine redox flow batteries or vanadium-cerium redox flow batteries. When the method is applied to the all-vanadium redox flow battery, the battery can be ensuredThe current efficiency reaches more than 98 percent, the energy efficiency reaches 89 percent, and the operating current density reaches 200mA cm-2Above, the effective run time exceeded 500 hours.
Drawings
FIG. 1 is a schematic diagram of a multi-scale porous electrode structure;
FIG. 2 is a scanning electron micrograph of the multi-scale porous electrode prepared in example 1;
FIG. 3 shows the voltage of 200-500mA cm for the all-vanadium redox flow battery based on the electrode of example 1-2Constant current charging and discharging curves under different operating current densities;
FIG. 4 shows the voltage at 200-500mA cm of the all-vanadium redox flow battery based on the electrode of example 1-2The efficiency of constant current charging and discharging and the utilization rate of electrolyte under different operating current densities;
FIG. 5 shows the full vanadium redox flow battery based on the electrode of example 1 at 400mA cm-2Cycling performance under constant current charge and discharge conditions.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
The multi-scale porous electrode (the structural schematic diagram is shown in figure 1) applied to the flow battery comprises a porous electrode framework formed by carbon fibers, secondary holes are distributed on the surface of the carbon fibers, and tertiary holes are distributed on the inner surface of the secondary holes. The diameter of the carbon fiber is 8 μm, and the length is 9 mm; the diameter of the secondary hole is 300-500nm, the depth of the hole is 50-100nm, and the distance between the holes is 50-100 nm; the diameter of the tertiary pore is 5-10nm, the depth of the pore is 10-30nm, and the distance between pores is 5-10mm (scanning electron micrograph, scanning electron micrograph is shown in figure 2).
The preparation method of the multi-scale porous electrode applied to the flow battery comprises the following steps:
the method comprises the steps of taking carbon cloth as an initial material, placing the initial material in an acetone solution containing nickel nitrate (mass fraction is 15%), dipping and carrying out ultrasonic treatment for 30min, taking out and drying at 60 ℃. Putting the obtained material into a tubular furnace for heat treatment, wherein the atmosphere is a mixed gas of water vapor and nitrogen, the volume fraction of the water vapor is 3%, the heating rate is 5 ℃/min, the heat treatment temperature is 850 ℃, and the heat treatment time is 1.5 h. And (3) performing heat treatment and natural cooling to room temperature, repeatedly cleaning the solution by using dilute nitric acid, soaking the solution in 60 mass percent of potassium hydroxide aqueous solution and performing ultrasonic treatment for 20min, taking the solution out and drying the solution, then placing the dried solution into a tubular furnace in nitrogen atmosphere for heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment temperature is 800 ℃, the heat treatment time is 1.5h, and naturally cooling the solution to room temperature after heat treatment. Taking out, sequentially washing and drying by using distilled water and dilute nitric acid to obtain the target electrode.
Example 2
The embodiment of the invention relates to assembly of an all-vanadium redox flow battery.
The all-vanadium redox flow battery assembled by the multi-scale porous electrode prepared in example 1 adopts an aluminum end plate, a gold-plated copper current collecting plate, a graphite plate with an interdigital flow field, a polytetrafluoroethylene gasket and
and NR-211 diaphragm, and stacking the end plate, the current collecting plate, the graphite plate, the electrode, the gasket, the diaphragm, the gasket, the electrode, the graphite plate, the current collecting plate and the end plate in sequence, and fastening and assembling the stack through bolts and nuts to form the battery. Performing constant-current charge and discharge test on the assembled all-vanadium redox flow battery at 200 mA-cm-2At current density, the energy efficiency was 89.8%. And the traditional carbon cloth electrode is assembled into the all-vanadium redox flow battery under the same condition, and the total vanadium redox flow battery is 200 mA-cm-2At a current density, the energy efficiency is only73.4％。
The all-vanadium redox flow battery based on the electrode of the embodiment 1 is 200-500mAcm-2Constant current charge and discharge curves under different operating current densities are shown in FIG. 3;
the all-vanadium redox flow battery based on the electrode of the embodiment 1 is 200-500mAcm-2The constant current charging and discharging efficiency and the electrolyte utilization rate under different operating current densities are shown in fig. 4;
all-vanadium redox flow battery based on the electrode of example 1 at 400mA cm-2The cycle performance under constant current charge and discharge conditions is shown in fig. 5.
Example 3
The embodiment of the invention provides a multi-scale porous electrode applied to a flow battery, which comprises a porous electrode framework formed by carbon fibers, wherein secondary holes are distributed on the surface of the carbon fibers, and tertiary holes are distributed on the inner surface of the secondary holes. The diameter of the carbon fiber is 9 μm, and the length is 5 mm; the diameter of the secondary hole is 400-600nm, the depth of the hole is 80-110nm, and the distance between the holes is 70-110 nm; the diameter of the third-level hole is 5-10nm, the depth of the hole is 10-30nm, and the distance between the holes is 5-10 mm.
The preparation method comprises the following steps:
the method comprises the steps of taking a carbon felt as an initial material, placing the initial material in an aqueous solution containing ferric chloride (the mass fraction is 25%), dipping and carrying out ultrasonic treatment for 20min, taking out, and drying at 80 ℃. And putting the obtained material into a tubular furnace for heat treatment, wherein the atmosphere is a mixed gas of carbon dioxide and nitrogen, the volume fraction of the carbon dioxide is 20%, the heating rate is 5 ℃/min, the heat treatment temperature is 900 ℃, and the heat treatment time is 2 h. And (3) performing heat treatment, naturally cooling to room temperature, repeatedly cleaning with dilute nitric acid, soaking in 50% sodium hydroxide aqueous solution, performing ultrasonic treatment for 30min, taking out, drying, placing in a tubular furnace containing nitrogen atmosphere, performing heat treatment at a heating rate of 5 ℃/min and a heat treatment temperature of 850 ℃ for 1.5h, and naturally cooling to room temperature after heat treatment. Taking out, sequentially washing and drying by using distilled water and dilute nitric acid to obtain the target electrode.
Example 4
The embodiment of the invention relates to assembly of an all-vanadium redox flow battery.
Application of the inventionExample 3 an all vanadium redox flow battery was fabricated using aluminum end plates, gold plated copper collector plates, graphite plates with interdigitated flow fields, teflon spacers and
and NR-211 diaphragm, and stacking the end plate, the current collecting plate, the graphite plate, the electrode, the gasket, the diaphragm, the gasket, the electrode, the graphite plate, the current collecting plate and the end plate in sequence, and fastening and assembling the stack through bolts and nuts to form the battery. Performing constant-current charge and discharge test on the assembled all-vanadium redox flow battery at 300 mA-cm-2At current density, the energy efficiency was 86.1%.
Example 5
The embodiment of the invention provides a multi-scale porous electrode applied to a flow battery, which comprises a porous electrode framework formed by carbon fibers, wherein secondary holes are distributed on the surface of the carbon fibers, and tertiary holes are distributed on the inner surface of the secondary holes. The diameter of the carbon fiber is 10 μm, and the length is 3 mm; the diameter of the secondary hole is 200-300nm, the depth of the hole is 70-120nm, and the distance between the holes is 60-100 nm; the diameter of the third-level hole is 5-10nm, the depth of the hole is 10-30nm, and the distance between the holes is 5-10 mm.
The preparation method comprises the following steps:
carbon paper is used as an initial material, the initial material is placed in an aqueous solution containing cobalt acetate (the mass fraction is 10%), the initial material is soaked and subjected to ultrasonic treatment for 20min, and the initial material is taken out and dried at 50 ℃. Putting the obtained material into a tubular furnace for heat treatment, wherein the atmosphere is mixed gas of water vapor and nitrogen, the volume fraction of the water vapor is 5%, the heating rate is 5 ℃/min, the heat treatment temperature is 800 ℃, and the heat treatment time is 1.5 h. And (3) performing heat treatment, naturally cooling to room temperature, repeatedly cleaning with dilute nitric acid, soaking in 70% by mass of potassium hydroxide aqueous solution, performing ultrasonic treatment for 30min, taking out, drying, placing in a tubular furnace containing nitrogen atmosphere for heat treatment at a heating rate of 5 ℃/min and a heat treatment temperature of 800 ℃ for 1.5h, and naturally cooling to room temperature after heat treatment. Taking out, sequentially washing and drying by using distilled water and dilute nitric acid to obtain the target electrode.
Example 6
The embodiment of the invention relates to assembly of an all-vanadium redox flow battery.
The all-vanadium redox flow battery assembled by the multi-scale porous electrode prepared in example 5 adopts an aluminum end plate, a gold-plated copper current collecting plate, a graphite plate with an interdigital flow field, a polytetrafluoroethylene gasket and
and NR-211 diaphragm, and stacking the end plate, the current collecting plate, the graphite plate, the electrode, the gasket, the diaphragm, the gasket, the electrode, the graphite plate, the current collecting plate and the end plate in sequence, and fastening and assembling the stack through bolts and nuts to form the battery. Performing constant-current charge and discharge test on the assembled all-vanadium redox flow battery at 400 mA-cm-2At current density, the energy efficiency was 82.3%.
Example 7
The embodiment of the invention provides a multi-scale porous electrode applied to a flow battery, which comprises a porous electrode skeleton formed by carbon fibers, a secondary hole and a tertiary hole. The diameter of the carbon fiber is 13 μm, and the length is 5 mm; the diameter of the secondary hole is 200-400nm, the depth of the hole is 90-150nm, and the distance between the holes is 80-130 nm; the diameter of the third-level hole is 5-10nm, the depth of the hole is 10-30nm, and the distance between the holes is 5-10 mm.
The preparation method comprises the following steps:
carbon paper is used as an initial material, the initial material is placed in acetone solution containing cobalt acetate (mass fraction is 20%), dipping and ultrasonic treatment are carried out for 20min, and the carbon paper is taken out and dried at 70 ℃. Putting the obtained material into a tubular furnace for heat treatment, wherein the atmosphere is mixed gas of water vapor and nitrogen, the volume fraction of the water vapor is 5%, the heating rate is 5 ℃/min, the heat treatment temperature is 800 ℃, and the heat treatment time is 1.5 h. And (3) performing heat treatment, naturally cooling to room temperature, repeatedly cleaning with dilute nitric acid, soaking in 70% sodium hydroxide aqueous solution, performing ultrasonic treatment for 30min, taking out, drying, placing in a tubular furnace containing nitrogen atmosphere, performing heat treatment at a heating rate of 5 ℃/min and a heat treatment temperature of 850 ℃ for 2h, and naturally cooling to room temperature after heat treatment. Taking out, sequentially washing and drying by using distilled water and dilute nitric acid to obtain the target electrode.
Example 8
The embodiment of the invention relates to assembly of an all-vanadium redox flow battery.
An all vanadium redox flow battery was assembled using the multi-scale porous electrode prepared in example 7 using aluminum end plates, gold plated copper collector plates, graphite plates with interdigitated flow fields, teflon spacers and
and NR-211 diaphragm, and stacking the end plate, the current collecting plate, the graphite plate, the electrode, the gasket, the diaphragm, the gasket, the electrode, the graphite plate, the current collecting plate and the end plate in sequence, and fastening and assembling the stack through bolts and nuts to form the battery. Performing constant-current charge and discharge test on the assembled all-vanadium redox flow battery at 500 mA-cm-2At current density, the energy efficiency was 78.2%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A multi-scale porous electrode applied to a flow battery is characterized by comprising a porous electrode framework formed by lapping, bonding or weaving carbon fibers, wherein secondary holes are distributed on the surface of the carbon fibers, and tertiary holes are distributed on the inner surface of the secondary holes; the diameter of the secondary hole is 50nm-500nm, the hole depth is 50nm-500nm, and the hole distance is 50nm-500 nm; the diameter of the tertiary pore is 5nm-10nm, the pore depth is 10nm-30nm, and the pore spacing is 5nm-10 nm.
2. The multi-scale porous electrode applied to a flow battery as recited in claim 1, wherein the carbon fibers have a diameter of 2 μm to 20 μm and a length of 10 μm to 10 mm.
3. The method for preparing the multi-scale porous electrode applied to the flow battery in claim 1 or 2 is characterized by comprising the following steps of:
(1) immersing the initial carbon material into a nickel salt, iron salt or cobalt salt solution and carrying out ultrasonic treatment for 5-60min, wherein the mass fraction of the nickel salt, the iron salt or the cobalt salt in the solution is 3-30%; drying at 60-120 deg.C;
(2) carrying out heat treatment on the carbon material obtained in the step (1), wherein the atmosphere is nitrogen or mixed gas of inert gas and oxidizing gas, the volume fraction of the oxidizing gas is 2-50%, the heating rate is 2-10 ℃/min, the heat treatment temperature is 500-;
(3) repeatedly cleaning the carbon material obtained in the step (2) in dilute nitric acid, and then soaking in an alkali solution or an alkali metal salt solution; soaking and ultrasonically treating 5-70 wt% of alkali or alkali metal salt in the solution for 5-60min, taking out and drying;
(4) carrying out heat treatment on the carbon material obtained in the step (3) in an inert gas atmosphere, wherein the heating rate is 2-10 ℃/min, the heat treatment temperature is 600-900 ℃, the heat treatment time is 1-3h, and naturally cooling to room temperature after heat treatment; and then sequentially washing and drying by using distilled water and dilute nitric acid to obtain the multi-scale porous electrode applied to the flow battery.
4. The method of claim 3, wherein the initial carbonaceous material is selected from the group consisting of carbon felt, graphite felt, carbon paper and carbon cloth, and has a thickness of 0.1 to 3 mm.
5. The method according to claim 3, wherein the nickel salt is selected from nickel chloride, nickel acetate, nickel formate, nickel sulfate, or nickel nitrate; the ferric salt is selected from ferric chloride, ferric acetate, ferric formate, ferric sulfate or ferric nitrate; the cobalt salt is selected from cobalt chloride, cobalt acetate, cobalt formate, cobalt sulfate or cobalt nitrate.
6. The preparation method according to claim 3, wherein the oxidizing gas is one or more of water vapor, oxygen or carbon dioxide; the inert gas is helium or argon.
7. The production method according to claim 3, wherein the alkali solution is a lithium hydroxide, sodium hydroxide or potassium hydroxide solution, and the alkali metal salt solution is a lithium carbonate, lithium sulfate, lithium nitrate, lithium formate, lithium acetate, sodium carbonate, sodium sulfate, sodium nitrate, sodium formate, sodium acetate, potassium carbonate, potassium sulfate, potassium nitrate, potassium formate or potassium acetate solution.
8. A flow battery comprising the multi-scale porous electrode of claim 1 or 2 applied to a flow battery.
9. The flow battery of claim 8, wherein the flow battery is selected from an all vanadium flow battery, an iron chromium flow battery, an iron vanadium flow battery, a zinc bromine flow battery, a vanadium bromine flow battery, or a vanadium cerium flow battery.
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| CN109873187A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
| CN109167082B (en) * | 2018-08-27 | 2021-11-23 | 成都先进金属材料产业技术研究院股份有限公司 | Electrode for vanadium cell and vanadium cell |
| CN109167071B (en) * | 2018-08-31 | 2021-09-07 | 深圳大学 | Electrode for all-vanadium redox flow battery and preparation method thereof |
| CN111769300B (en) * | 2020-02-28 | 2023-06-30 | 上海市机电设计研究院有限公司 | Preparation method of aluminum-based copper-plated current collector for all-vanadium redox flow battery |
| CN111883781B (en) * | 2020-06-05 | 2021-10-29 | 辽宁科技大学 | Activation method for nickel salt etched graphite felt electrode |
| US11901598B2 (en) * | 2022-02-15 | 2024-02-13 | Saudi Arabian Oil Company | Increasing reactant utilization in Fe/V flow batteries |
| CN114671514B (en) * | 2022-04-20 | 2023-03-17 | 浙江大学 | Sewage electrochemical nitrogen and phosphorus removal device and method based on intelligent conductivity judgment |
| CN117525447B (en) * | 2024-01-05 | 2024-03-15 | 天津泰然储能科技有限公司 | Three-stage gradient porous electrode for all-vanadium redox flow battery and preparation method thereof |
| CN117913301B (en) * | 2024-03-18 | 2024-07-05 | 中海储能科技(北京)有限公司 | Method for modifying battery carbon cloth electrode by metal carbide nano material |
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