CN114824314A - Electrochemical modification method of vanadium battery electrode based on silane hydrolysate - Google Patents
Electrochemical modification method of vanadium battery electrode based on silane hydrolysate Download PDFInfo
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- CN114824314A CN114824314A CN202210464108.0A CN202210464108A CN114824314A CN 114824314 A CN114824314 A CN 114824314A CN 202210464108 A CN202210464108 A CN 202210464108A CN 114824314 A CN114824314 A CN 114824314A
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- felt
- silane hydrolysate
- vanadium
- silane
- acid
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 49
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 38
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000413 hydrolysate Substances 0.000 title claims abstract description 28
- 238000002715 modification method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000006184 cosolvent Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- 235000010289 potassium nitrite Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004146 energy storage Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 2
- 239000001257 hydrogen Substances 0.000 abstract 2
- 238000007086 side reaction Methods 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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- 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
- H01M4/8817—Treatment of supports before application of the catalytic active composition
-
- 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
-
- 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
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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)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an electrochemical modification method of a vanadium battery electrode based on silane hydrolysate, belonging to the field of novel flow battery energy storage materials. The method comprises the following steps: acid washing the polyacrylonitrile-based carbon felt/graphite felt; preparing silane hydrolysate; performing electrochemical treatment on the pickled polyacrylonitrile-based carbon felt/graphite felt by using the prepared silane hydrolysate; carbonizing the polyacrylonitrile-based carbon felt/graphite felt subjected to electrochemical treatment in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery. The carbon felt/graphite felt has low hydrogen evolution activity, is particularly suitable for a cathode electrode material of a vanadium battery, improves the battery efficiency and reduces the hydrogen evolution side reaction; the carbon felt/graphite felt electrode material is used as a vanadium battery electrode after being modified and is at 250mA/cm 2 The energy efficiency reaches 80%. The invention meets the requirement of environmental protection, has simple process and is easy to form industrialization.
Description
Technical Field
The invention relates to the technical field of novel flow battery energy storage materials, in particular to an electrochemical modification method of a vanadium battery electrode based on silane hydrolysate.
Background
An all-vanadium redox flow battery (vanadium battery) is a secondary energy system that utilizes redox reactions between vanadium ions of different valence states for energy storage and conversion. The method is characterized in that: no discharge pollution, adjustable capacity, long cycle life, deep heavy current density discharge, quick charge and high energy conversion rate. The vanadium battery is mainly applied to energy storage power supplies of power station peak shaving, large-scale photoelectric conversion and wind power generation as well as energy storage systems of remote areas, uninterrupted power supplies or emergency power supply systems.
At present, the electrode material used by the vanadium battery is mainly carbon graphite felt/carbon felt, and the material has the advantages of low resistivity, good stability and large specific surface area. But its electrochemical activity is relatively low, and it is necessary to perform an activation treatment for improving the electrochemical activity and the battery performance.
Currently, many methods of activation treatment are reported to include: noble metal modification, acid activation treatment, electrochemical anodization treatment and the like. Noble metal modification, complex steps, high-temperature sintering and limitation to the use in a laboratory range. The thermal activation treatment has small operation elasticity, the oxidation reaction is not easy to control, and the stability and the service life of the electrode material are reduced by excessive oxidation. The effect of the acid activation treatment is not very significant. The electrochemical treatment method is simple and easy to implement, and the effect is obvious. However, the oxidation reaction on the fiber surface is severe due to the use of sulfuric acid as an electrolyte, and the service life of the material is shortened due to the promotion effect of an acid medium on the oxidation degradation reaction and the severe etching phenomenon on the fiber surface.
Disclosure of Invention
In view of the above, the invention provides an electrochemical modification method of a vanadium battery electrode based on silane hydrolysate, which overcomes the technical limitations of methods such as heat treatment, acid treatment, noble metal modification and the like, and has the advantages of simple process, mild treatment conditions and obviously improved activity of electrode materials.
The invention discloses an electrochemical modification method of a vanadium battery electrode based on silane hydrolysate, which comprises the following steps:
step 1, acid washing is carried out on a polyacrylonitrile-based carbon felt/graphite felt;
step 2, preparing silane hydrolysate;
step 3, performing electrochemical treatment on the polyacrylonitrile-based carbon felt/graphite felt after acid washing in the step 1 by using the silane hydrolysate prepared in the step 2;
and 4, carbonizing the polyacrylonitrile-based carbon felt/graphite felt subjected to the electrochemical treatment in the step 3 in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery.
Further, the silane hydrolysate comprises the following components in percentage by weight: 5-30 g/L of silane; 5-40 g/L of cosolvent; 0.1-4 g/L of oxidant; 0.1-3 g/L of pH regulator; the balance of deionized water.
Further, the silane is one or more than two of KH540, KH550, KH560, KH561, KH570, KH571, KH580 and KH 590; the cosolvent is one or more of ethanol, isopropanol, ethylene glycol, propanol, dipropylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol.
Further, the oxidant is one or more than two of hydrogen peroxide, sodium nitrite, potassium nitrite, sodium hypochlorite, potassium permanganate, zinc nitrate, calcium nitrate, sodium perborate and potassium perborate.
Further, the pH regulator of the silane hydrolysate is one or more than two of sodium hydroxide, ammonia water, triethanolamine, hydrochloric acid, nitric acid and acetic acid.
Further, the pickling solution used for pickling the polyacrylonitrile-based carbon felt/graphite felt is formed by mixing hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid and water, and the pickling solution comprises the following components in percentage by weight: 30-150 g/L hydrochloric acid, 5-50 g/L nitric acid, 5-20 g/L hydrofluoric acid, 10-100 g/L sulfuric acid and the balance of water.
Further, the polyacrylonitrile-based carbon felt/graphite felt is used as a positive electrode, and the electrochemical treatment current density range is 10-200mA/cm 2 The voltage range is 1-50V, the treatment time is 1-30min, and the temperature is 10-70 ℃.
Further, when the electrochemical treatment is carried out, the electrode material of the negative electrode comprises at least one of a metal material, a carbon material and a conductive ceramic material; wherein the metal material comprises at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, tantalum, zirconium, tungsten, cerium, aluminum, bismuth, rhenium, barium, osmium, tin, lead, gold, silver, platinum, palladium, iridium, rhodium, molybdenum and ruthenium; the carbon material comprises any one of graphite, glassy carbon, boron-doped diamond, activated carbon, graphene, carbon fiber, carbon nanotube and carbon sponge.
Further, the electrode shape of the positive electrode and the negative electrode includes any one of a sheet, a rod, a filament, a granule, a sponge, a mesh, and a porous structure.
Further, the temperature of the nitrogen protection oxidation treatment in the tube furnace is 200-700 ℃, and the time is 1-10 h.
Due to the adoption of the technical scheme, the invention has the following advantages:
(1) according to the invention, after the carbon felt/graphite felt is electrochemically modified in silane hydrolysate, the activity of the graphite felt electrode is increased, and after the carbon felt/graphite felt is used as an electrode material of a vanadium battery, the battery performance is obviously improved, and under the current density of 300mA/cm2 at 25 ℃, the current efficiency is more than or equal to 98%, the voltage efficiency is more than or equal to 85%, and the energy efficiency is more than or equal to 80%.
(2) Compared with the existing activation treatment technology (heat treatment, acid treatment and precious metal modification), the method for electrochemically modifying the carbon felt/graphite felt in the silane hydrolysate has the advantages of simple process, low cost, mild and controllable conditions and good economic and environmental benefits.
(3) The method utilizes abundant hydroxyl groups contained in silane in the silane hydrolysate, is beneficial to forming more hydroxyl groups and carbonyl groups on the fiber surface of the electrode during electrochemical treatment, and improves the electrochemical reaction activity of the electrode.
(4) The invention provides a method for carrying out nitrogen protection carbonization in a tubular furnace after electrochemical treatment, which can further improve the conductivity of the surface of an electrode after electrochemical treatment, is favorable for electron conduction during electrode reaction and improves the battery performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments described in the embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings.
FIG. 1 is a schematic view of the microstructure of a treated carbon felt according to an embodiment of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples, it being understood that the examples described are only some of the examples and are not intended to be exhaustive. All other embodiments available to those of ordinary skill in the art are intended to be within the scope of the embodiments of the present invention.
Example 1:
(1) cutting the polyacrylonitrile-based graphite felt into 10cm multiplied by 10cm, and carrying out acid washing, wherein the acid washing solution comprises the following components in percentage by weight: 50g/L of hydrochloric acid; 30g/L of nitric acid; 5g/L of hydrofluoric acid; 10g/L of sulfuric acid; the balance of water
(2) Preparing silane hydrolysate, wherein the silane hydrolysate comprises the following components in percentage by weight: KH560 silane 5 g/L; 5g/L of cosolvent; 2g/L of oxidant; 2g/L of pH regulator; the balance of deionized water; the cosolvent is ethanol. The oxidant is hydrogen peroxide, and the pH regulator is sodium hydroxide.
(3) Carrying out electrochemical treatment on the graphite felt after acid washing: the graphite felt is used as a positive electrode, and the current density of electrochemical treatment is 50mA/cm 2 The voltage range is 1-8V, the treatment time is 20min, and the temperature is 30 ℃. The negative electrode material is titanium, and the electrode shapes of the positive electrode and the negative electrode are sheet-shaped.
(4) And taking out the graphite felt, airing, and carbonizing in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery, wherein the temperature of nitrogen protection oxidation treatment in the tubular furnace is 500 ℃ and the time is 50 hours.
The modified graphite felt (see figure 1) is used as the electrode of the vanadium battery and then is heated at 250mA/cm 2 The energy efficiency is improved to 82% at the current density of (2).
Example 2:
(5) cutting the polyacrylonitrile-based carbon felt into 10cm multiplied by 10cm, and carrying out acid washing, wherein the acid washing solution comprises the following components in percentage by weight: 20g/L of hydrochloric acid; 10g/L of nitric acid; 8g/L of hydrofluoric acid; 20g/L of sulfuric acid; the balance of water
(6) Preparing silane hydrolysate, wherein the silane hydrolysate comprises the following components in percentage by weight: 10g/L of KH550 silane; 20g/L of cosolvent; 5g/L of oxidant; 1g/L of pH regulator; the balance of deionized water; the cosolvent is ethylene glycol. The oxidant is potassium permanganate and the pH regulator is triethanolamine.
(7) And (3) carrying out electrochemical treatment on the carbon felt after acid washing: the carbon felt is used as a positive electrode, and the current density of electrochemical treatment is 60mA/cm 2 The voltage range is 4-15V, the treatment time is 40min, and the temperature is 70 ℃. The negative electrode material graphite, the positive electrode and the negative electrode are in a sheet shape.
(8) And taking out the carbon felt, airing, and carbonizing in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery, wherein the temperature of the nitrogen protection oxidation treatment in the tubular furnace is 600 ℃, and the time is 30 hours.
The modified carbon felt is used as the electrode of the vanadium battery and then is at 250mA/cm 2 The energy efficiency is improved to 81% at the current density of (2).
Example 3:
(1) cutting the polyacrylonitrile-based carbon felt into 10cm multiplied by 10cm, and carrying out acid washing, wherein the acid washing solution comprises the following components in percentage by weight: 80g/L of hydrochloric acid; 15g/L of nitric acid; 6g/L of hydrofluoric acid; 30g/L of sulfuric acid; the balance of water
(2) Preparing silane hydrolysate, wherein the silane hydrolysate comprises the following components in percentage by weight: KH590 silane 50 g/L; 10g/L of cosolvent; 4g/L of oxidant; 2g/L of pH regulator; the balance of deionized water; the cosolvent is a mixture of ethylene glycol and ethanol. The oxidant is sodium hypochlorite, and the pH regulator is ammonia water.
(3) And (3) carrying out electrochemical treatment on the carbon felt after acid washing: the carbon felt is used as the anode, and the current density of electrochemical treatment is 90mA/cm 2 The voltage range is 3-18V, the treatment time is 60min, and the temperature is 60 ℃. The negative electrode is made of titanium, the positive electrode is flaky, and the negative electrode is titanium sponge.
(4) And taking out the carbon felt, airing, and carbonizing in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery, wherein the temperature of nitrogen protection oxidation treatment in the tubular furnace is 700 ℃ and the time is 20 hours.
The modified carbon felt is used as the electrode of the vanadium battery and then is at 250mA/cm 2 The energy efficiency is improved to 85% at the current density of (2).
Example 4:
(1) cutting the polyacrylonitrile-based graphite felt into 10cm multiplied by 10cm, and carrying out acid washing, wherein the acid washing solution comprises the following components in percentage by weight: 10g/L of hydrochloric acid; 25g/L of nitric acid; 2g/L of hydrofluoric acid; 20g/L of sulfuric acid; the balance of water
(2) Preparing silane hydrolysate, wherein the silane hydrolysate comprises the following components in percentage by weight: KH570 silane 30 g/L; 30g/L of cosolvent; 5g/L of oxidant; 1g/L of pH regulator; the balance of deionized water; the cosolvent is a mixture of polypropylene glycol and glycerol. The oxidant is a mixture of hydrogen peroxide and zinc nitrate, and the pH regulator is ammonia water and sodium hydroxide.
(3) Carrying out electrochemical treatment on the graphite felt after acid washing: the graphite felt is used as a positive electrode, and the current density of electrochemical treatment is 180mA/cm 2 The voltage range is 5-25V, the treatment time is 30min, and the temperature is 50 ℃. The negative electrode material is carbon fiber, the positive electrode is sheet-shaped, and the negative electrode is porous carbon fiber.
(4) And taking out the carbon felt, airing, and carbonizing in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery, wherein the temperature of the nitrogen protection oxidation treatment in the tubular furnace is 600 ℃, and the time is 15 hours.
Modified carbon felt used as vanadium battery electrode and then is processed at 250mA/cm 2 The energy efficiency is improved to 85% at the current density of (2).
Example 5:
(1) cutting the polyacrylonitrile-based graphite felt into 10cm multiplied by 10cm, and carrying out acid washing, wherein the acid washing solution comprises the following components in percentage by weight: 15g/L of hydrochloric acid; 45g/L of nitric acid; 1g/L of hydrofluoric acid; 50g/L of sulfuric acid; the balance of water
(2) Preparing silane hydrolysate, wherein the silane hydrolysate comprises the following components in percentage by weight: KH571 silane 40 g/L; 10g/L of cosolvent; 3g/L of oxidant; 2/L of pH regulator; the balance of deionized water; the cosolvent is a mixture of ethylene glycol and glycerol. The oxidant is a mixture of hydrogen peroxide and sodium hypochlorite, and the pH regulator is ammonia water.
(3) Carrying out electrochemical treatment on the graphite felt after acid washing: the graphite felt is used as a positive electrode, and the current density of electrochemical treatment is 200mA/cm 2 The voltage range is 10-40V, the treatment time is 10min, and the temperature is 40 ℃. The negative electrode material is glassy carbon, the positive electrode is flaky, and the negative electrode is flaky.
(4) And taking out the carbon felt, airing, and carbonizing in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium redox flow battery, wherein the temperature of nitrogen protection oxidation treatment in the tubular furnace is 700 ℃ and the time is 20 hours.
The modified carbon felt is used as the electrode of the vanadium battery and then is at 250mA/cm 2 The energy efficiency is improved to 81% at the current density of (2).
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. An electrochemical modification method of a vanadium battery electrode based on silane hydrolysate is characterized by comprising the following steps:
step 1, acid washing is carried out on a polyacrylonitrile-based carbon felt/graphite felt;
step 2, preparing silane hydrolysate;
step 3, performing electrochemical treatment on the polyacrylonitrile-based carbon felt/graphite felt after acid washing in the step 1 by using the silane hydrolysate prepared in the step 2;
and 4, carbonizing the polyacrylonitrile-based carbon felt/graphite felt subjected to the electrochemical treatment in the step 3 in a tubular furnace under the nitrogen protection atmosphere to obtain the modified electrode of the all-vanadium flow battery.
2. The method for electrochemically modifying the vanadium battery electrode based on the silane hydrolysate of claim 1, wherein the silane hydrolysate comprises the following components in percentage by weight: 5-30 g/L of silane; 5-40 g/L of cosolvent; 0.1-4 g/L of oxidant; 0.1-3 g/L of pH regulator; the balance of deionized water.
3. The method for electrochemically modifying the vanadium battery electrode based on silane hydrolysate of claim 2, wherein the silane is one or more than two of KH540, KH550, KH560, KH561, KH570, KH571, KH580, KH 590; the cosolvent is one or more of ethanol, isopropanol, ethylene glycol, propanol, dipropylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol.
4. The electrochemical modification method of the vanadium battery electrode based on silane hydrolysate of claim 2, wherein the oxidant is one or more than two of hydrogen peroxide, sodium nitrite, potassium nitrite, sodium hypochlorite, potassium permanganate, zinc nitrate, calcium nitrate, sodium perborate, and potassium perborate.
5. The method for electrochemically modifying the vanadium redox battery electrode based on silane hydrolysate of claim 1, wherein the pH regulator of the silane hydrolysate is one or more of sodium hydroxide, ammonia water, triethanolamine, hydrochloric acid, nitric acid and acetic acid.
6. The electrochemical modification method of vanadium battery electrode based on silane hydrolysate as claimed in claim 1, wherein the pickling solution used for pickling the polyacrylonitrile-based carbon felt/graphite felt is formed by mixing hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid and water, and the contents of the components are as follows: 30-150 g/L hydrochloric acid, 5-50 g/L nitric acid, 5-20 g/L hydrofluoric acid, 10-100 g/L sulfuric acid and the balance of water.
7. The method for electrochemically modifying the vanadium battery electrode based on silane hydrolysate of claim 1, wherein the polyacrylonitrile-based carbon felt/graphite felt is used as a positive electrode, the electrochemical treatment current is 10 to 200mA/cm2, the voltage is 1 to 50V, the treatment time is 1 to 30min, and the temperature is 10 to 70 ℃.
8. The method for electrochemically modifying the vanadium battery electrode based on silane hydrolysis liquid as claimed in claim 7, wherein the electrode material of the negative electrode comprises at least one of a metal material, a carbon material and a conductive ceramic material; wherein the metal material comprises at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, tantalum, zirconium, tungsten, cerium, aluminum, bismuth, rhenium, barium, osmium, tin, lead, gold, silver, platinum, palladium, iridium, rhodium, molybdenum and ruthenium; the carbon material comprises any one of graphite, glassy carbon, boron-doped diamond, activated carbon, graphene, carbon fiber, carbon nanotube and carbon sponge.
9. The method for electrochemically modifying the vanadium battery electrode based on silane hydrolysate of claim 8, wherein the electrode shape of the positive electrode and the negative electrode comprises any one of a sheet, a rod, a wire, a granule, a sponge, a net and a porous structure.
10. The method for electrochemically modifying the vanadium battery electrode based on silane hydrolysate as claimed in claim 6, wherein the temperature of the nitrogen protection oxidation treatment in the tubular furnace is 200-700 ℃ and the time is 1-10 h.
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