CN117239159A - Carbon paper electrode of flow battery and preparation method thereof - Google Patents
Carbon paper electrode of flow battery and preparation method thereof Download PDFInfo
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- CN117239159A CN117239159A CN202311002418.1A CN202311002418A CN117239159A CN 117239159 A CN117239159 A CN 117239159A CN 202311002418 A CN202311002418 A CN 202311002418A CN 117239159 A CN117239159 A CN 117239159A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001721 carbon Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229920001690 polydopamine Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- -1 super P Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 8
- 230000010287 polarization Effects 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960003638 dopamine Drugs 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
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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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Abstract
The invention discloses a flow battery carbon paper electrode, which is obtained by immersing a substrate layer of the flow battery carbon paper electrode in a modifying slurry for a period of time, then taking out, and carrying out high Wen Xiushi in inert gas. The thickness of the carbon paper electrode is thin, so that the volume of the liquid flow energy storage pile is greatly reduced, the pile with the same volume can achieve larger power, the carbon paper electrode has good oxidation-reduction reaction catalytic performance on active substances, concentration polarization in the pile can be reduced, the conductivity of the carbon paper is better, ohmic polarization is reduced, and the voltage efficiency and the energy efficiency of the liquid flow battery are improved. The carbon paper electrode has the advantages of simple preparation process, no pollution, no corrosiveness, low cost of the selected substrate layer, low requirement on equipment precision, batch 'roll-to-roll' preparation and high practical value.
Description
Technical Field
The invention belongs to the technical field of battery electrodes, and particularly relates to a carbon paper electrode of a flow battery and a preparation method thereof.
Background
The energy storage of the flow battery is taken as one of novel energy storage technologies, the energy storage of the flow battery is various, and the flow battery mainly comprises an all-vanadium flow battery, a zinc-bromine flow battery, an iron-chromium flow battery, an all-iron flow battery, an aqueous organic flow battery and the like, wherein the all-vanadium flow battery is fastest in development and the technology is most mature. With the development of green power generation technologies such as wind energy, photovoltaic and the like and the large-scale application, due to the fact that the power generation has volatility, matching of corresponding energy storage systems is needed urgently, the volatility of the intermittent green power generation technology is guaranteed to be smooth in each link of a power grid, the running stability of the power grid system is improved, the effects of peak shaving and valley filling of electricity consumption are achieved, the impact of the power grid is reduced, the power investment is saved, and the equipment utilization rate of a power transmission and distribution system and the permeability of wind and light energy are improved.
The flow battery energy storage has the advantages of high safety, low self-discharge performance, high battery reaction speed and deep discharge, and the capacity of the electrolyte liquid storage tank and the power of the electric pile can be independently designed in a modularized manner, so that the flow battery energy storage device is suitable for large-scale long-time energy storage. The electric pile is a core part of energy storage of the flow battery, and is not only an electrochemical reaction place but also a place for converting electric energy and chemical energy in the energy storage system. The pile is formed by connecting collector plate, flow frame, bipolar plate, proton exchange membrane, electrode, etc. The proton exchange membrane plays roles of blocking positive and negative electrolyte and conducting protons, and the electrode is a main place for the active substance to generate oxidation-reduction chemical reaction. The performance of the electrode directly influences the performance of the liquid flow energy storage battery, and the electrode used as the liquid flow energy storage battery has the advantages of low cost, easy preparation, good conductivity, excellent mechanical performance, corrosion resistance, higher electrochemical activity and the like. The current commercial electrode products are mainly graphite felt or carbon felt, and although the cost is relatively low, the conductivity and the corrosion resistance are good, the electrochemical activity is poor, the thickness is thick, and secondary treatment is generally needed. And further, the electrochemical activity of the electrode is improved, the internal polarization phenomenon of the battery is reduced, the battery has higher working current density, and better voltage efficiency and energy efficiency are ensured.
The current methods for activating and modifying the flow battery electrode mainly comprise an acidification method, an oxidation method, a deposition catalytic metal ion, a heteroatom doping method and the like. Patent CN103633330a discloses a composite electrode for a flow battery and a flow energy storage battery, which are prepared by bonding a graphite plate and a catalytic layer (carbon felt, carbon paper, carbon cloth or graphite felt) by conductive adhesive, wherein the preparation process does not carry out high-temperature oxidation treatment so as to improve voltage efficiency and energy efficiency; patent CN 112234215A discloses an electrode applied to an iron-chromium redox flow battery, wherein the conductivity of carbon cloth is improved by a method of treating the carbon cloth with concentrated sulfuric acid and then impregnating zinc salt aqueous solution, so that the internal resistance of the battery is reduced; patent CN 111261881A discloses an electrode with a thinner thickness prepared by modifying industrial filter paper as a substrate through acid treatment, alkali treatment and high-temperature oxidation treatment, which reduces the body resistance and improves the voltage efficiency and the energy efficiency of the vanadium redox flow battery; patent CN 113809338A discloses a method that graphite felt is used as a substrate to be immersed in a mixed solution of graphene and dopamine, and then high-temperature carbonization treatment is carried out to realize doping of N element, so that electronegativity of an electrode is improved to attract vanadium ions to the surface of the electrode to participate in a reaction, conductivity of the electrode material for transmitting ions is improved, and energy conversion efficiency of a battery is improved. Although the above means can improve the performance of the electrode, it is difficult to realize mass production. The commercialized carbon felt or graphite felt electrode greatly increases the volume and internal resistance of the galvanic pile due to the thicker thickness, and has a great influence on the efficiency of the galvanic pile.
Disclosure of Invention
The invention aims to provide a carbon paper electrode of a flow battery and a preparation method thereof, which solve the problems of thick carbon felt or graphite felt electrode, high resistance, poor electrochemical activity, complex process for performing secondary activation modification on electrode performance and the like in the prior art, and can realize batch roll-to-roll production.
The technical scheme of the invention is as follows: a carbon paper electrode of a flow battery is obtained by dipping a carbon paper substrate layer in a modification slurry, taking out and drying, carrying out high-temperature oxidation reaction, and carrying out high Wen Xiushi in inert gas.
The preparation method of the carbon paper electrode of the flow battery comprises the following steps:
(1) Immersing the carbon paper substrate layer in the modified slurry for 1-10 min, placing in a baking oven at 50-100 ℃ and drying for 10-100 min to obtain a product A;
(2) Placing the product A in a high-temperature oxidation furnace at 300-500 ℃, preserving heat for 10-100 min, and performing pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer, thus obtaining a product B;
(3) And (3) placing the product B in an inert gas protection high-temperature carbonization furnace for graphitization treatment, and rolling after naturally cooling to room temperature to obtain the carbon paper electrode of the flow battery.
The thickness of the carbon paper substrate layer in the step (1) is 100-2000 mu m, the pore diameter is 10-150 mu m, and the porosity is more than 70%.
The modified slurry in the step (1) consists of 5-10 parts by weight of carbon materials, 5-10 parts by weight of N-containing organic compounds and 80-90 parts by weight of solvents.
Specifically, the carbon material is one or more of graphite, graphene, acetylene black, superconducting carbon black, superP, ketjen black and carbon nanotubes.
Specifically, the N-containing organic compound is one or more of polyvinylpyrrolidone, sodium carboxymethylcellulose, polypyrrole, polydopamine and polyaniline.
Specifically, the solvent is one or more of deionized water, ethanol, methanol, N-methylpyrrolidone and isopropanol.
In the step (3), the graphitization treatment temperature is 2000-2500 ℃; the graphitization treatment time is 10-100 min.
In the step (3), the inert gas is N 2 One or more of gas, ar gas and carbon dioxide.
Compared with the prior art, the invention has the following beneficial effects:
(1) The thickness of the carbon paper is thinner and the surface is flat, and the thickness of the carbon paper is about that of a carbon felt or a graphite feltThe value of the surface roughness Sa is about 1/20 to 1/100 of that of the carbon felt or graphite felt. The thickness of the carbon paper electrode is thin, so that the volume of the liquid flow energy storage pile is greatly reduced, the pile with the same volume can achieve larger power, the carbon paper electrode has good oxidation-reduction reaction catalytic performance on active substances, concentration polarization in the pile can be reduced, the conductivity of the carbon paper is better, ohmic polarization is reduced, the voltage efficiency and the energy efficiency of the liquid flow battery are improved, and the current density is 110mA cm -2 Under the condition of current density of 200mA, the coulomb efficiency reaches 94.1%, the voltage efficiency reaches 87.91%, the energy efficiency reaches 82.72%, and the current density is 200mA -2 Under the condition, the coulomb efficiency reaches 96.33%, the voltage efficiency reaches 79.07%, and the energy efficiency reaches 76.17%.
(2) The flat surface is not easy to pierce the diaphragm, so that the cross contamination of positive and negative active substances in the galvanic pile is avoided, and the energy efficiency of the galvanic pile is reduced. Meanwhile, the carbon paper electrode has a certain catalytic effect and a certain hydrophilicity on active substances participating in oxidation-reduction reaction due to doping of N, O functional groups, so that electrochemical polarization of the liquid flow energy storage pile is reduced, and pile efficiency is improved.
(3) The carbon paper electrode has the advantages of simple preparation process, no pollution, no corrosiveness, low cost of the selected substrate layer, low requirement on equipment precision, batch 'roll-to-roll' preparation and high practical value.
Description of the drawings:
fig. 1: example 1 high definition magnification plot of carbon paper electrode;
fig. 2: example 2 high definition magnification plot of carbon paper electrode;
fig. 3: comparative example carbon felt electrode high definition magnification graph;
fig. 4: example 1 carbon paper electrode hydrophilicity;
fig. 5: example 2 carbon paper electrode hydrophilicity;
fig. 6: comparative example carbon felt was hydrophilic.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Example 1
(1) Selecting a carbon paper electrode basal layer with the thickness of 200 mu m, and cutting into the size of 100 multiplied by 200mm for later use;
(2) 8 parts of graphite, 2 parts of acetylene black, 6 parts of polyvinylpyrrolidone, 1.5 parts of sodium carboxymethylcellulose, 80 parts of deionized water and 2.5 parts of ethanol are taken according to parts by weight to prepare modified slurry;
(3) Immersing the carbon paper electrode substrate layer with the size of 100 multiplied by 200mm in the step (1) into the modified slurry in the step (2), immersing for 10min, taking out, placing in a 60 ℃ oven, and drying for 30min to obtain the carbon paper substrate layer after drying treatment;
(4) Placing the carbon paper substrate layer subjected to the drying treatment in the step (3) in a high-temperature oxidation furnace at 350 ℃, and preserving heat for 30min for pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer;
(5) Placing the carbon paper substrate layer modified by oxygen in the step (4) in N 2 Preserving the temperature for 30min in a high-temperature carbonization furnace with air protection at 2200 ℃. And cooling to room temperature to obtain the carbon paper electrode of the flow battery.
Example 2
(1) Selecting a carbon paper electrode basal layer with the thickness of 1000 mu m, and cutting into the size of 100 multiplied by 200mm for later use;
(2) 8 parts of graphite, 2 parts of acetylene black, 6 parts of polyvinylpyrrolidone, 1.5 parts of sodium carboxymethylcellulose, 80 parts of deionized water and 2.5 parts of ethanol are taken according to parts by weight to prepare modified slurry;
(3) Immersing the carbon paper electrode substrate layer with the size of 100 multiplied by 200mm in the step (1) into the modified slurry in the step (2), immersing for 10min, taking out, placing in a 60 ℃ oven, and drying for 30min to obtain the carbon paper substrate layer after drying treatment;
(4) Placing the carbon paper substrate layer subjected to the drying treatment in the step (3) in a high-temperature oxidation furnace at 350 ℃, and preserving heat for 30min for pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer;
(5) Placing the carbon paper substrate layer modified by oxygen in the step (4) in N 2 Preserving the temperature for 30min in a high-temperature carbonization furnace with air protection at 2200 ℃. And cooling to room temperature to obtain the carbon paper electrode of the flow battery.
Example 3
(1) Selecting a carbon paper electrode basal layer with the thickness of 200 mu m, and cutting into the size of 100 multiplied by 200mm for later use;
(2) According to parts by weight, 6 parts of graphene, 4 parts of superconducting carbon black, 6.5 parts of polypyrrole, 3.5 parts of polydopamine, 85 parts of deionized water and 5 parts of methanol are taken to prepare modified slurry;
(3) Immersing the carbon paper electrode substrate layer with the size of 100 multiplied by 200mm in the step (1) into the modified slurry in the step (2), immersing for 1min, taking out, placing in a 50 ℃ oven, and drying for 10min to obtain the carbon paper substrate layer after drying treatment;
(4) Placing the carbon paper substrate layer subjected to the drying treatment in the step (3) in a high-temperature oxidation furnace at 300 ℃, and preserving heat for 10min for pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer;
(5) And (3) placing the carbon paper substrate layer modified by oxygen in the step (4) into a high-temperature carbonization furnace protected by Ar gas at 2000 ℃ and preserving heat for 10min. And cooling to room temperature to obtain the carbon paper electrode of the flow battery.
Example 4
(1) Selecting a carbon paper electrode basal layer with the thickness of 1000 mu m, and cutting into the size of 100 multiplied by 200mm for later use;
(2) According to the weight parts, 3 parts of carbon nano tubes, 2 parts of Super P, 4 parts of polyvinylpyrrolidone, 1 part of polyaniline, 78 parts of deionized water and 2 parts of N-methyl pyrrolidone are taken to prepare modified slurry;
(3) Immersing the carbon paper electrode substrate layer with the size of 100 multiplied by 200mm in the step (1) into the modified slurry in the step (2), immersing for 10min, taking out, placing in a baking oven with the temperature of 100 ℃, and drying for 100min to obtain a carbon paper substrate layer after drying treatment;
(4) Placing the carbon paper substrate layer subjected to the drying treatment in the step (3) in a high-temperature oxidation furnace at 500 ℃, and preserving heat for 100min for pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer;
(5) And (3) placing the carbon paper substrate layer modified by oxygen in the step (4) into a high-temperature carbonization furnace protected by carbon dioxide at 2500 ℃, and preserving heat for 100min. And cooling to room temperature to obtain the carbon paper electrode of the flow battery.
Example 5
(1) Selecting a carbon paper electrode basal layer with the thickness of 200 mu m, and cutting into the size of 100 multiplied by 200mm for later use;
(2) According to the weight portions, 5 portions of graphite, 3 portions of Ketjen black (Ketjen black EC-300J), 6.5 portions of polyaniline, 80 portions of deionized water and 2.5 portions of isopropanol are taken to prepare modified slurry;
(3) Immersing the carbon paper electrode substrate layer with the size of 100 multiplied by 200mm in the step (1) into the modified slurry in the step (2), immersing for 5min, taking out, placing in an oven at 80 ℃, and drying for 50min to obtain a carbon paper substrate layer after drying treatment;
(4) Placing the carbon paper substrate layer subjected to the drying treatment in the step (3) in a high-temperature oxidation furnace at 400 ℃, and preserving heat for 50min for pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer;
(5) Placing the carbon paper substrate layer modified by oxygen in the step (4) in N 2 The temperature is kept for 50min in a high-temperature carbonization furnace protected by gas and Ar gas at 2200 ℃. And cooling to room temperature to obtain the carbon paper electrode of the flow battery.
Example 6
(1) Selecting a carbon paper electrode basal layer with the thickness of 200 mu m, and cutting into the size of 100 multiplied by 200mm for later use;
(2) According to the weight portions, 10 portions of graphite, 8 portions of polyvinylpyrrolidone, 80 portions of deionized water and 3.5 portions of ethanol are taken to prepare modified slurry;
(3) Immersing the carbon paper electrode substrate layer with the size of 100 multiplied by 200mm in the step (1) into the modified slurry in the step (2), immersing for 8min, taking out, placing in a 70 ℃ oven, and drying for 80min to obtain the carbon paper substrate layer after drying treatment;
(4) Placing the carbon paper substrate layer subjected to the drying treatment in the step (3) in a high-temperature oxidation furnace at 400 ℃, and preserving heat for 40min for pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer;
(5) And (3) placing the carbon paper substrate layer modified by oxygen in the step (4) into a high-temperature carbonization furnace protected by N2 gas and carbon dioxide, and preserving heat for 20min. And cooling to room temperature to obtain the carbon paper electrode of the flow battery.
Comparative example
Preparation of comparative example: a commercial carbon felt with a thickness of 2000 μm was selected and cut to 50X 50mm and assembled with a commercial proton exchange membrane (GH.Inc., PEM-50) to form an all-vanadium redox flow battery for efficiency testing.
The carbon paper electrode of the flow battery prepared in the example 1 and the example 2 is cut into 50X 50mm and assembled with a commercial proton exchange membrane (GH.Inc, PEM-50) to form an all-vanadium flow single battery, and the current density is 110mA cm in the comparative example -2 And a current density of 200110mA cm -2 The following experimental comparison of cell efficiencies was performed, and the comparison results are shown in tables 1 and 2:
table 1: efficiency of each electrode matching PEM-50 in an all-vanadium redox flow battery
Table 2: comparison of physical Properties of electrodes
| Name of the name | Unit (B) | Example 1 | Example 2 | Comparative example |
| Thickness @1MPa | μm | 137.21 | 692.01 | 623.87 |
| Bulk resistance @1MPa | mΩ*cm 2 | 3.39 | 6.49 | 17.16 |
| Surface resistance | Ω*mm | 0.243 | 0.218 | 0.972 |
| Surface conductivity | S/mm | 4.10 | 4.58 | 1.03 |
| Roughness of Sa | μm | 15.648 | 15.14 | 83.9 |
| Compression ratio @1Mpa | ％ | 25.8 | 27.1 | 36.2 |
| Contact angle | ° | 114.146 | 119.396 | 127.823 |
Claims (9)
1. The utility model provides a flow battery charcoal paper electrode which characterized in that: the carbon paper electrode of the flow battery is obtained by dipping a carbon paper substrate layer in the modified slurry, taking out and drying, carrying out high-temperature oxidation reaction, and carrying out high Wen Xiushi in inert gas.
2. The method for preparing the carbon paper electrode of the flow battery according to claim 1, which is characterized in that: the preparation method comprises the following steps:
(1) Immersing the carbon paper substrate layer in the modified slurry for 1-10 min, placing in a baking oven at 50-100 ℃ and drying for 10-100 min to obtain a product A;
(2) Placing the product A in a high-temperature oxidation furnace at 300-500 ℃, preserving heat for 10-100 min, and performing pre-oxidation treatment to obtain an oxygen-containing modified carbon paper substrate layer, thus obtaining a product B;
(3) And (3) placing the product B in an inert gas protection high-temperature carbonization furnace for graphitization treatment, and rolling after naturally cooling to room temperature to obtain the carbon paper electrode of the flow battery.
3. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 2, which is characterized by comprising the following steps: the thickness of the carbon paper substrate layer in the step (1) is 100-2000 mu m, the pore diameter is 10-150 mu m, and the porosity is more than 70%.
4. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 2, which is characterized by comprising the following steps: in the step (1), the modified slurry consists of 5-10 parts by weight of carbon materials, 5-10 parts by weight of N-containing organic compounds and 80-90 parts by weight of solvents.
5. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 4, which is characterized by comprising the following steps: the carbon material is one or more than two of graphite, graphene, acetylene black, superconductive carbon black, super P, ketjen black and carbon nano tube.
6. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 4, which is characterized by comprising the following steps: the N-containing organic compound is one or more than two of polyvinylpyrrolidone, sodium carboxymethylcellulose, polypyrrole, polydopamine and polyaniline.
7. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 4, which is characterized by comprising the following steps: the solvent is one or more of deionized water, ethanol, methanol, N-methyl pyrrolidone and isopropanol.
8. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 2, which is characterized by comprising the following steps: in the step (3), the graphitization treatment temperature is 2000-2500 ℃; the graphitization treatment time is 10-100 min.
9. The method for preparing the carbon paper electrode of the flow battery as claimed in claim 2, which is characterized by comprising the following steps: in the step (3), the inert gas is N 2 One or more of gas, ar gas and carbon dioxide.
Priority Applications (1)
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| CN202311002418.1A CN117239159A (en) | 2023-08-10 | 2023-08-10 | Carbon paper electrode of flow battery and preparation method thereof |
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