CN118516852B - Chemical activation process for carbon fiber battery felt catalyst - Google Patents
Chemical activation process for carbon fiber battery felt catalyst Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 72
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 70
- 238000001994 activation Methods 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000000126 substance Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 22
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- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229920000742 Cotton Polymers 0.000 claims abstract description 4
- 229920006282 Phenolic fiber Polymers 0.000 claims abstract description 4
- 239000010426 asphalt Substances 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 4
- 244000198134 Agave sisalana Species 0.000 claims abstract description 3
- 240000008564 Boehmeria nivea Species 0.000 claims abstract description 3
- 229920000297 Rayon Polymers 0.000 claims abstract description 3
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 3
- 239000002025 wood fiber Substances 0.000 claims abstract description 3
- DOGFGDKIOOAKNQ-UHFFFAOYSA-N 1-prop-2-enylpyrrolidin-1-ium-2-carboxylate Chemical compound OC(=O)C1CCCN1CC=C DOGFGDKIOOAKNQ-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- -1 12-mercapto dodecyl cerium phosphate Chemical compound 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- MUUOUUYKIVSIAR-LURJTMIESA-N (2s)-2-but-3-enyloxirane Chemical compound C=CCC[C@H]1CO1 MUUOUUYKIVSIAR-LURJTMIESA-N 0.000 claims description 8
- 239000004254 Ammonium phosphate Substances 0.000 claims description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- MVQUCQUAYDBXMV-UHFFFAOYSA-N 12-sulfanyldodecyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCCCCCCCCCCS MVQUCQUAYDBXMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 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 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004146 energy storage Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- 238000002074 melt spinning Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
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- 238000007405 data analysis Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000012651 thiol-epoxy addition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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 provides a chemical activation process of a carbon fiber battery felt catalyst, and relates to the technical field of preparation of activated carbon fibers. The method comprises the following steps: immersing carbon fiber selected from polyacrylonitrile, asphalt fiber, phenolic fiber, viscose fiber, wood fiber, sisal fiber, ramie fiber and cotton fiber in a catalyst, and drying; after drying, slowly heating the carbon fiber, fully oxidizing the carbon fiber in air, and cooling the carbon fiber to room temperature; and (3) placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying. The combination of the high specific surface area and the yield of the carbon fiber battery felt prepared by the invention ensures that the activated carbon fiber has excellent performance in the fields of energy storage and conversion.
Description
Technical Field
The invention relates to the technical field of preparation of activated carbon fibers, in particular to a chemical activation process of a carbon fiber battery felt catalyst.
Background
The activated carbon fiber is an ideal and efficient adsorption material, and is developed on the basis of combining carbon fiber technology and activated carbon technology. The activated carbon fiber is a3 rd generation activated carbon product after granular activated carbon and powdery activated carbon, and is widely applied to the fields of environmental protection, medical sanitation, chemical industry and the like because of the special surface chemical structure and physical adsorption characteristic.
The patent with the publication number of CN103290526B discloses a method for preparing wood activated carbon fiber by physical activation by taking woody biomass as a raw material, which comprises the steps of placing wood powder in a liquefying device, adding a polyalcohol mixture as a liquefying agent, and preparing a liquefied product under the condition of acid catalysis; adding a synthetic agent to synthesize spinning solution, and performing melt spinning to obtain fiber precursor; finally, placing the precursor into a carbonization and activation device, and preparing the wood activated carbon fiber by taking water vapor as an activating agent.
Patent application publication No. CN105220275A discloses a method for preparing activated carbon fiber by using cellulose. Specifically, cellulose acetate is put into a liquefaction reaction kettle, phenol and an acidic catalyst are added to obtain cellulose phenol resin; adding a certain proportion of acetone into resin as a solvent to synthesize spinning solution, and carrying out thermal curing on the spinning solution under a certain condition after melt spinning to prepare and obtain cellulose precursor; and placing the precursor into a carbonization and activation device, and preparing and obtaining the cellulose-based activated carbon fiber through carbonization and activation processes.
Patent application with publication number CN109735830A discloses an activating solution, a preparation method and a preparation method of a carbon fiber composite material. An activating solution is prepared from the following components: dispersing agent, sodium citrate, nickel salt and boron-containing compound; the boron-containing compound is potassium borohydride or sodium borohydride; the pH value of the activating solution is 9-11. The dispersing agent in the activation liquid can avoid the aggregation of carbon fibers in the aqueous solution, can prevent the carbon fibers from being aggregated again after being activated and washed, integrates the activation liquid, and can finish the steps of carbon fiber dispersion, sensitization and activation only by placing the carbon fibers in the activation liquid.
However, the prior art has low production yield and high cost; although the chemical activation method can greatly improve the product yield, the chemical activation method needs multiple times of water washing, and the product is brittle and difficult to popularize in production.
Disclosure of Invention
The invention aims to provide a chemical activation process for a carbon fiber battery felt catalyst, and the combination of the high specific surface area and the yield of the carbon fiber battery felt prepared by the method ensures that the activated carbon fiber has excellent performance in the fields of energy storage and conversion.
The technical scheme adopted by the invention is as follows:
The chemical activation process of the carbon fiber battery felt catalyst comprises the following steps:
S1: immersing carbon fiber selected from polyacrylonitrile, asphalt fiber, phenolic fiber, viscose fiber, wood fiber, sisal fiber, ramie fiber and cotton fiber in a catalyst, and drying;
S2: after drying, slowly heating the carbon fiber to 240-250 ℃, fully oxidizing in air, and cooling to room temperature;
s3: placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying;
the preparation method of the catalyst comprises the following steps:
Adding 0.03-0.6 part of 12-mercapto dodecyl cerium phosphate complex and 0.05-0.5 part of 1-allyl pyrrolidine-2-nickel carboxylate complex into a reaction kettle, adding 2-6 parts of sodium ethoxide and 200-300 parts of acetone, uniformly stirring, and heating to 45-55 ℃ for reacting for 100-150 minutes; then adding 10-20 parts of ammonium phosphate and 1-6 parts of (S) -1, 2-epoxy-5-hexene, and mixing for 100-150 minutes under the heat preservation to obtain the required catalyst.
Further, the preparation method of the 12-mercapto dodecyl cerium phosphate complex comprises the following steps:
10-17 parts of 12-mercaptododecyl phosphate and 3-6 parts of cerium nitrate are weighed in a reaction kettle, added into 100-200 parts of water, reacted for 30-90 minutes at 30-40 ℃, and then distilled to remove water, thus obtaining the 12-mercaptododecyl cerium phosphate complex.
Further, the preparation method of the 1-allyl pyrrolidine-2-carboxylic acid nickel complex comprises the following steps:
Weighing 12-20 parts of 1-allyl pyrrolidine-2-carboxylic acid and 2-5 parts of nickel nitrate in a reaction kettle, adding into 200-300 parts of water, reacting for 20-40 minutes at 40-60 ℃, and then removing water through distillation to obtain the 1-allyl pyrrolidine-2-nickel carboxylate complex.
Further, the dipping time of the S1 is 30-60min.
Further, the oxidation time of S2 is 60-90min.
Further, the temperature rising rate of the S2 is 3-5 ℃/min.
Further, in the steam activation process of S3, the carbon fiber is kept at 800-900 ℃ for 1-3 hours to ensure that the surface of the carbon fiber is fully activated, so that the electrochemical performance of the carbon fiber in a battery is improved.
Reaction mechanism: thiol-ene addition reaction:
The addition reaction of the mercapto (-SH) group in the cerium 12-mercaptododecyl phosphate complex with the alkenyl group (c=c) in the nickel 1-allylpyrrolidine-2-carboxylate complex; the reaction may proceed by a michael addition mechanism in which a thiol group acts as a nucleophile to attack the beta carbon atom of an alkenyl group to form a carbon-sulfur bond.
Thiol-epoxy addition reaction:
The remaining mercapto group in the addition product undergoes a ring opening addition reaction with the epoxy group in (S) -1, 2-epoxy-5-hexene, the mercapto group attacks the less substituted carbon atom in the epoxy group, resulting in ring opening of the epoxy ring and formation of a new carbon-sulfur bond.
Compounding:
The addition product is complexed with ammonium phosphate, involving hydrogen bond formation or other non-covalent interactions, to produce the final catalyst structure; the combination can improve the thermal stability, mechanical strength or catalytic activity of the catalyst.
The beneficial effects are that: 1. modification of carbon fiber felt: the catalyst is used for modifying the carbon fiber felt, so that the porosity and average pore diameter of the carbon fiber felt can be remarkably improved; this modification allows for better electrolyte permeability and ion transport efficiency of the carbon fiber mat in battery applications.
2. Activated carbon fiber properties: the active carbon fiber prepared by the invention has the following characteristics:
the specific surface area is up to 2155m 2/g, which provides a very large surface active area for electrochemical reaction and enhances charge storage and transfer capability;
The yield reaches 59.37%, which shows that the effective utilization rate of raw materials is higher in the activation process, and the material waste is reduced;
comprehensive performance: the combination of high specific surface area and yield enables the activated carbon fiber to have excellent performance in the energy storage and conversion fields.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is made with reference to examples and comparative examples:
Specific surface area measurement: and (3) referring to a GB2596-81 nitrogen adsorption method, and adopting a JB-1 specific surface area tester for measurement.
Example 1: the chemical activation process of the carbon fiber battery felt catalyst comprises the following steps:
s1: immersing carbon fiber selected from polyacrylonitrile in a catalyst, and drying;
S2: after drying, slowly heating the carbon fiber to 240 ℃, fully oxidizing in air, and cooling to room temperature;
s3: and (3) placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying.
The preparation method of the catalyst comprises the following steps:
Adding 0.03g of a 12-mercapto dodecyl cerium phosphate complex and 0.05g of a 1-allyl pyrrolidine-2-carboxylic acid nickel complex into a reaction kettle, adding 2g of sodium ethoxide and 200g of acetone, uniformly stirring, and heating to 45 ℃ for reaction for 100 minutes; 10g of ammonium phosphate and 1g of (S) -1, 2-epoxy-5-hexene were then added and mixed for 100 minutes with a constant temperature to give the desired catalyst.
The preparation method of the 12-mercapto dodecyl cerium phosphate complex comprises the following steps:
10g of 12-mercaptododecyl phosphate and 3g of cerium nitrate were weighed in a reaction kettle, added into 100g of water, reacted at 30 ℃ for 30 minutes, and then distilled to remove water, thereby obtaining a 12-mercaptododecyl cerium phosphate complex.
The preparation method of the 1-allyl pyrrolidine-2-carboxylic acid nickel complex comprises the following steps:
12g of 1-allyl pyrrolidine-2-carboxylic acid and 2g of nickel nitrate were weighed in a reaction kettle, added into 200g of water, reacted at 40 ℃ for 20 minutes, and then distilled to remove water, thereby obtaining a 1-allyl pyrrolidine-2-carboxylic acid nickel complex.
The dipping time of the S1 is 30min.
The oxidation time of S2 is 60min.
The temperature rising rate of the S2 is 3 ℃/min.
In the steam activation process of S3, the carbon fiber is kept at the temperature of 800 ℃ for 1h, so that the surface of the carbon fiber is fully activated, and the electrochemical performance of the carbon fiber in a battery is improved.
Example 2: the chemical activation process of the carbon fiber battery felt catalyst comprises the following steps:
S1: immersing carbon fibers selected from asphalt fibers in a catalyst, and drying;
S2: after drying, slowly heating the carbon fiber to 245 ℃, fully oxidizing in air, and cooling to room temperature;
s3: and (3) placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying.
The preparation method of the catalyst comprises the following steps:
Adding 0.2g of a 12-mercapto dodecyl cerium phosphate complex and 0.2g of a 1-allyl pyrrolidine-2-carboxylic acid nickel complex into a reaction kettle, adding 3g of sodium ethoxide and 240g of acetone, uniformly stirring, and heating to 48 ℃ for reaction for 110 minutes; 13g of ammonium phosphate and 2g of (S) -1, 2-epoxy-5-hexene were then added and mixed for 110 minutes with heat preservation to give the desired catalyst.
The preparation method of the 12-mercapto dodecyl cerium phosphate complex comprises the following steps:
12g of 12-mercaptododecyl phosphate and 4g of cerium nitrate were weighed in a reaction vessel, added to 140g of water, reacted at 35℃for 50 minutes, and then distilled to remove water, thereby obtaining a 12-mercaptododecyl cerium phosphate complex.
The preparation method of the 1-allyl pyrrolidine-2-carboxylic acid nickel complex comprises the following steps:
14g of 1-allyl pyrrolidine-2-carboxylic acid and 3g of nickel nitrate were weighed in a reaction kettle, added to 240g of water, reacted at 45 ℃ for 25 minutes, and then distilled to remove water, thereby obtaining a 1-allyl pyrrolidine-2-carboxylic acid nickel complex.
The dipping time of the S1 is 40min.
The oxidation time of S2 is 70min.
The temperature rising rate of the S2 is 4 ℃/min.
In the steam activation process of S3, the carbon fiber is kept at the temperature of 840 ℃ for 2 hours, so that the surface of the carbon fiber is fully activated, and the electrochemical performance of the carbon fiber in a battery is improved.
Example 3: the chemical activation process of the carbon fiber battery felt catalyst comprises the following steps:
s1: immersing carbon fiber selected from phenolic fiber in a catalyst, and drying;
S2: after drying, slowly heating the carbon fiber to 245 ℃, fully oxidizing in air, and cooling to room temperature;
s3: and (3) placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying.
The preparation method of the catalyst comprises the following steps:
Adding 0.5g of a 12-mercapto dodecyl cerium phosphate complex and 0.4g of a 1-allyl pyrrolidine-2-carboxylic acid nickel complex into a reaction kettle, adding 5g of sodium ethoxide and 280g of acetone, uniformly stirring, and heating to 53 ℃ for reaction for 140 minutes; 18g of ammonium phosphate and 5g of (S) -1, 2-epoxy-5-hexene were then added and mixed for 40 minutes with a constant temperature to give the desired catalyst.
The preparation method of the 12-mercapto dodecyl cerium phosphate complex comprises the following steps:
16g of 12-mercaptododecyl phosphate and 5g of cerium nitrate were weighed in a reaction vessel, added to 180g of water, reacted at 35℃for 70 minutes, and then distilled to remove water, thereby obtaining a 12-mercaptododecyl cerium phosphate complex.
The preparation method of the 1-allyl pyrrolidine-2-carboxylic acid nickel complex comprises the following steps:
18g of 1-allyl pyrrolidine-2-carboxylic acid and 4g of nickel nitrate were weighed in a reaction kettle, added to 280g of water, reacted at 55 ℃ for 35 minutes, and then distilled to remove water, thereby obtaining a 1-allyl pyrrolidine-2-carboxylic acid nickel complex.
The dipping time of the S1 is 50min.
The oxidation time of S2 is 80min.
The temperature rising rate of the S2 is 4 ℃/min.
In the steam activation process of S3, the carbon fiber is kept at the temperature of 880 ℃ for 2 hours to ensure that the surface of the carbon fiber is fully activated, so that the electrochemical performance of the carbon fiber in a battery is improved.
Example 4: the chemical activation process of the carbon fiber battery felt catalyst comprises the following steps:
S1: immersing carbon fiber selected from cotton fiber in a catalyst, and drying;
S2: after drying, slowly heating the carbon fiber to 250 ℃, fully oxidizing in air, and cooling to room temperature;
s3: and (3) placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying.
The preparation method of the catalyst comprises the following steps:
Adding 0.6g of a 12-mercapto dodecyl cerium phosphate complex and 0.5g of a 1-allyl pyrrolidine-2-carboxylic acid nickel complex into a reaction kettle, adding 6g of sodium ethoxide and 300g of acetone, uniformly stirring, and heating to 55 ℃ for reaction for 150 minutes; subsequently, 20g of ammonium phosphate and 6g of (S) -1, 2-epoxy-5-hexene were added, and the mixture was kept warm and mixed for 150 minutes to obtain the desired catalyst.
The preparation method of the 12-mercapto dodecyl cerium phosphate complex comprises the following steps:
17g of 12-mercaptododecyl phosphate and 6g of cerium nitrate were weighed in a reaction vessel, added into 200g of water, reacted at 40℃for 90 minutes, and then distilled to remove water, thereby obtaining a 12-mercaptododecyl cerium phosphate complex.
The preparation method of the 1-allyl pyrrolidine-2-carboxylic acid nickel complex comprises the following steps:
20g of 1-allyl pyrrolidine-2-carboxylic acid and 5g of nickel nitrate were weighed in a reaction kettle, added into 300g of water, reacted at 60 ℃ for 40 minutes, and then distilled to remove water, thereby obtaining a 1-allyl pyrrolidine-2-carboxylic acid nickel complex.
The dipping time of the S1 is 60min.
The oxidation time of S2 is 90min.
The temperature rising rate of the S2 is 5 ℃/min.
In the steam activation process of S3, the carbon fiber is kept at the temperature of 900 ℃ for 3 hours, so that the surface of the carbon fiber is fully activated, and the electrochemical performance of the carbon fiber in a battery is improved.
Comparative example 1: the procedure of example 1 was repeated except that the cerium 12-mercaptododecyl phosphate complex was not added.
Comparative example 2: the procedure of example 1 was followed except that no 1-allylpyrrolidine-2-carboxylic acid nickel complex was added.
Comparative example 3: (S) -1, 2-epoxy-5-hexene was not added, and the same procedure as in example 1 was followed.
Table 1: test results for each example and comparative example
Through the data analysis of the above examples and comparative examples, the carbon fiber battery felt prepared by the invention has high specific surface area and yield, so that the activated carbon fiber has excellent performance in the energy storage and conversion fields.
The above embodiments are only illustrative of the invention and are not intended to be limiting, and any insubstantial modifications made by a person skilled in the art on the basis of the invention shall fall within the scope of the invention.
Claims (7)
1. The chemical activation process of the carbon fiber battery felt catalyst is characterized by comprising the following steps of: the method comprises the following steps:
S1: immersing carbon fiber prepared from one of polyacrylonitrile, asphalt fiber, phenolic fiber, viscose fiber, wood fiber, sisal fiber, ramie fiber and cotton fiber in a catalyst, and drying;
S2: after drying, slowly heating the carbon fiber to 240-250 ℃, fully oxidizing in air, and cooling to room temperature;
s3: placing the oxidized carbon fiber in a tubular high-temperature furnace, heating under the protection of nitrogen, performing activation treatment by using water vapor, and then drying;
the preparation method of the catalyst comprises the following steps:
Adding 0.03-0.6 part of 12-mercapto dodecyl cerium phosphate complex and 0.05-0.5 part of 1-allyl pyrrolidine-2-nickel carboxylate complex into a reaction kettle according to the parts by mass, adding 2-6 parts of sodium ethoxide and 200-300 parts of acetone, uniformly stirring, and heating to 45-55 ℃ for reacting for 100-150 minutes; then adding 10-20 parts of ammonium phosphate and 1-6 parts of (S) -1, 2-epoxy-5-hexene, and mixing for 100-150 minutes under the heat preservation to obtain the required catalyst.
2. The chemical activation process for carbon fiber battery felt catalyst according to claim 1, wherein: the preparation method of the 12-mercapto dodecyl cerium phosphate complex comprises the following steps:
10-17 parts of 12-mercaptododecyl phosphate and 3-6 parts of cerium nitrate are weighed according to parts by mass in a reaction kettle, added into 100-200 parts of water, reacted for 30-90 minutes at 30-40 ℃, and then distilled to remove water, thus obtaining the 12-mercaptododecyl cerium phosphate complex.
3. The chemical activation process for carbon fiber battery felt catalyst according to claim 1, wherein: the preparation method of the 1-allyl pyrrolidine-2-carboxylic acid nickel complex comprises the following steps:
weighing 12-20 parts by mass of 1-allyl pyrrolidine-2-carboxylic acid and 2-5 parts by mass of nickel nitrate in a reaction kettle, adding into 200-300 parts by mass of water, reacting for 20-40 minutes at 40-60 ℃, and then removing water by distillation to obtain the 1-allyl pyrrolidine-2-carboxylic acid nickel complex.
4. The chemical activation process for carbon fiber battery felt catalyst according to claim 1, wherein: the dipping time of the S1 is 30-60min.
5. The chemical activation process for carbon fiber battery felt catalyst according to claim 1, wherein: the oxidation time of the S2 is 60-90min.
6. The chemical activation process for carbon fiber battery felt catalyst according to claim 1, wherein: the temperature rising rate of the S2 is 3-5 ℃/min.
7. The chemical activation process for carbon fiber battery felt catalyst according to claim 1, wherein: in the water vapor activation process of the S3, the carbon fiber is kept at the temperature of 800-900 ℃ for 1-3h.
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| CN115122714A (en) * | 2022-05-30 | 2022-09-30 | 安徽天富环保科技材料有限公司 | Preparation process of activated carbon fiber cloth for electrode preparation |
| CN116770581A (en) * | 2023-08-28 | 2023-09-19 | 烟台奥森制动材料有限公司 | Method for preparing antioxidant carbon fiber solid felt by adopting metal ion purifying agent |
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| CN118326702B (en) * | 2024-06-17 | 2024-08-27 | 烟台奥森制动材料有限公司 | Preparation method for continuous steam activation of carbon fibers of battery felt |
| CN118345555B (en) * | 2024-06-18 | 2024-08-27 | 烟台奥森制动材料有限公司 | Dry forming process of short fiber solid heat-insulating felt |
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| CN116770581A (en) * | 2023-08-28 | 2023-09-19 | 烟台奥森制动材料有限公司 | Method for preparing antioxidant carbon fiber solid felt by adopting metal ion purifying agent |
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