CN102912670A - Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper - Google Patents
Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper Download PDFInfo
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- CN102912670A CN102912670A CN2012103774611A CN201210377461A CN102912670A CN 102912670 A CN102912670 A CN 102912670A CN 2012103774611 A CN2012103774611 A CN 2012103774611A CN 201210377461 A CN201210377461 A CN 201210377461A CN 102912670 A CN102912670 A CN 102912670A
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- Prior art keywords
- carbon fiber
- fiber paper
- carbon
- preparation
- idiosome
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000008187 granular material Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract 3
- 239000011231 conductive filler Substances 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006424 Flood reaction Methods 0.000 claims description 6
- 239000008135 aqueous vehicle Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 4
- 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 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 18
- 239000007789 gas Substances 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 7
- 230000035699 permeability Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000003746 surface roughness Effects 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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- Inert Electrodes (AREA)
- Paper (AREA)
Abstract
The invention relates to a preparation method of carbon fiber paper for a fuel cell, in particular to a carbon fiber paper preparing method capable of controlling the aperture size of carbon fiber paper. The carbon fiber paper preparing method is characterized in that pore-forming granules easily decomposed at a high temperature and having the granule diameter of 10-50 microns are added into carbon fiber pulp; a dispersant is a polymeric surfactant; and resin for impregnating a carbon fiber paper blank contains 0.1-10% of conductive filler carbon granules with the granule diameter of 10-30 nm. Compared with the prior art, the method has the advantages that the aperture size of the carbon fiber paper is easily controlled, and the uniformity of the aperture distribution of the carbon fiber paper is improved.
Description
Technical field
Carbon fiber paper is widely used in making gas diffusion layer material in the Proton Exchange Membrane Fuel Cells, can provide gas passage, drainage channel and electron channel for fuel cell.The present invention specifically relates to a kind of fuel cell with the preparation method of carbon fiber paper, belongs to fuel cell field.
Background technology
Gas diffusion layers is the significant components in the Proton Exchange Membrane Fuel Cells, plays support catalyst layer and stabilized electrodes structure function, also provides gas passage, electron channel and drainage channel for fuel cell reaction.Carbon fiber paper is one of most widely used gas diffusion layers base material in the fuel cell, the carbon fiber paper that uses at present is owing to added a large amount of resins, the carbon fiber paper surface can produce a kind of thinner resin film, this film can stop up the part hole in the carbon fiber paper, and this affects the air guide drainage performance of carbon fiber paper.Moreover, take conventional wet paper technology preparation carbon fiber paper since the skeleton of carbon fiber be to take at random knot to form, the pore size of the carbon fiber paper of preparing like this differs, pore-size distribution is also inhomogeneous.
Summary of the invention
The object of the invention is to solve existing fuel cell carbon fiber paper technical problem, a kind of preparation method of gas diffusion layer for fuel cell carbon fiber paper is provided.The carbon fiber paper paper of the inventive method preparation has good gas permeability, uniform pore size distributes and stable aperture size, when the fuel battery gas diffusion layer carbon fiber paper aperture size that adopts is in an OK range, the combination property of fuel cell is better, this is because when the aperture of carbon fiber paper is too small, surveys to be unfavorable for fuel battery gas diffusion layer carbon fiber paper air guide draining, when the carbon fiber paper aperture is excessive, survey and to increase the carbon fiber paper internal resistance, reduction electric transmission efficient.The carbon fiber paper of the present invention's preparation is except having good gas permeability, good pore-size distribution and suitable aperture size, also have simultaneously good electric conductivity, higher intensity concurrently, lower surface roughness, can satisfy the requirement of fuel battery gas diffusion layer, be suitable for the preparation of fuel cell membrane electrode.
The present invention adopts the interpolation pore creating material to send control carbon fiber paper aperture, specifically comprises the steps:
Be that 3～20mm diameter is that the polyacrylonitrile-based carbon fibre of 5～8nm is placed in 500～650 ℃ of air and carries out surface oxidation treatment with length, and the time is between 30 seconds～10 minutes.
To put into the dispersion liquid that contains pore creating material through the polyacrylonitrile-based carbon fibre of above-mentioned processing and carry out high-speed stirred, make that carbon fiber and pore-creating are evengranular to be dispersed in the aqueous vehicle.Wherein the dispersant concentration in the aqueous vehicle is 1%～3%.
Adopt the conventional wet papermaking technology to obtain the carbon fiber paper idiosome, the carbon fiber paper idiosome floods 3%～30% resin solution after drying, and wherein the carbon element particle accounts for 0.1%～5% in the resin solution.
Flooding the carbon fiber paper idiosome of above-mentioned resin behind 2～3 molded curings, is to carry out carbonization treatment under 900～2500 ℃ of nitrogen protection atmospheres in temperature, namely obtains carbon fiber paper.
Useful achievement of the present invention: the carbon fiber paper of the present invention preparation is except having good electric conductivity and intensity preferably, also have higher gas permeability, adopt the method for adding pore creating material to make the carbon fiber paper of preparation have stable aperture size and uniform pore-size distribution.Carbon fiber paper is one of critical material of fuel cell, for fuel cell provides gas passage, drainage channel and electron channel.Carbon fiber paper with suitable aperture dimensional structure can improve the combination property of fuel cell.
The specific embodiment
Example 1:
Be that the 10mm diameter is that the polyacrylonitrile-based carbon fibre of 7nm is placed in 500 ℃ of air and carries out surface oxidation treatment with length, the time is 5 minutes.
Take by weighing 70g/m
2The carbon fiber of handling well, 200g/m
2Particle diameter is 30 μ m calcium carbonate granules, and 2% sodium carboxymethylcellulose aqueous vehicle mixes this three by high-speed stirred.
Adopt the conventional wet papermaking technology to obtain the carbon fiber paper idiosome, the carbon fiber paper idiosome floods 20% phenol resin solution after drying, wherein contains the graphite granule that particle diameter is 15nm in the phenol resin solution, and mass ratio is for accounting for 1%.
The carbon fiber paper idiosome that floods above-mentioned resin is 150 ℃ of molded curings 2 times, and each clamp time is 15 minutes.Being placed at last temperature is to carry out carbonization treatment under 1500 ℃ of nitrogen protection atmospheres, namely obtains carbon fiber paper, and then water is removed pore creating material residue remaining in the carbon fiber paper, namely obtains our product carbon fiber paper.
The carbon fiber paper performance indications that obtain are as follows:
Surface resistivity 0.50g/cm
3, gas permeability is 2000mLmm/ (cm
2HrmmAq), surface resistivity is: 0.010 Ω cm.Tensile strength is: 20MPa, pore size are 28～32 μ m.
Example 2:
Be that the 6mm diameter is that the polyacrylonitrile-based carbon fibre of 7nm is placed in 600 ℃ of air and carries out surface oxidation treatment with length, the time is 1 minute.
Take by weighing 70g/m
2The carbon fiber of handling well, 200g/m
2Particle diameter is 20 μ m calcium carbonate granules, and 1.5% sodium carboxymethylcellulose aqueous vehicle mixes this three by high-speed stirred.
Adopt the conventional wet papermaking technology to obtain the carbon fiber paper idiosome, the carbon fiber paper idiosome floods 15% phenol resin solution after drying, wherein contains the graphite granule that particle diameter is 20nm in the phenol resin solution, and mass ratio is for accounting for 0.5%.
The carbon fiber paper idiosome that floods above-mentioned resin is 150 ℃ of molded curings 2 times, and each time is 15 minutes.Being placed at last temperature is to carry out carbonization treatment under 2000 ℃ of nitrogen protection atmospheres, namely obtains carbon fiber paper, and then water is removed pore creating material residue remaining in the carbon fiber paper, namely obtains our product carbon fiber paper.
The carbon fiber paper performance indications that obtain are as follows:
Surface resistivity 0.45g/cm
3, gas permeability is 2200mLmm/ (cm
2HrmmAq), surface resistivity is: 0.005 Ω cm.Tensile strength is: 15MPa, pore size are 15～25 μ m.
Claims (5)
1. carbon fiber paper preparation method who controls carbon fiber paper mesoporous size is characterized in that the process of the carbon fiber paper for preparing has adopted pore creating material, dispersant, electroconductive binder and nano-scale carbon crude granule.
According to claim 1 shown in a kind of carbon fiber paper preparation method who controls carbon fiber paper mesoporous size, it is characterized in that preparing that to have added a kind of particle diameter in the carbon fiber slurry be the labile pore-creating particles of 10～50 μ m high temperature, wherein to adopt high molecular surfactant, surfactant can be one or more of sodium carboxymethylcellulose, carboxymethyl cellulose, polyvinyl alcohol to dispersant.
According to claim 1 shown in a kind of carbon fiber paper preparation method who controls carbon fiber paper mesoporous size, it is characterized in that containing the conductive filler carbon element particle that 0.1%～10% particle diameter is 10～30nm in the resin that impregnation of carbon fibers paper idiosome uses.
According to claim 1 shown in a kind of carbon fiber paper preparation method who controls carbon fiber paper mesoporous size, it is characterized in that electroconductive binder can be one or more of phenolic resins, epoxy resin, pitch.
According to claim 1 shown in a kind of carbon fiber paper preparation method who controls carbon fiber paper mesoporous size, it is characterized in that the concrete steps that are the method are:
1) be that 3～20mm diameter is that the polyacrylonitrile-based carbon fibre of 5～8nm is placed in 500～650 ℃ of air and carries out surface oxidation treatment with length, and the time is between 30 seconds～10 minutes;
2) will put into the dispersion liquid that contains pore creating material through the polyacrylonitrile-based carbon fibre of above-mentioned processing and carry out high-speed stirred, make that carbon fiber and pore-creating are evengranular to be dispersed in the aqueous vehicle.Wherein the dispersant concentration in the aqueous vehicle is 1%～3%;
3) adopt the conventional wet papermaking technology to obtain the carbon fiber paper idiosome, the carbon fiber paper idiosome floods 3%～30% resin solution after drying, and wherein the carbon element particle accounts for 0.1%～5% in the resin solution;
4) the carbon fiber paper idiosome that flooded above-mentioned resin is to carry out carbonization treatment under 900～2500 ℃ of nitrogen protection atmospheres in temperature after 2～3 molded curing technique, namely obtains carbon fiber paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103774611A CN102912670A (en) | 2012-10-08 | 2012-10-08 | Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103774611A CN102912670A (en) | 2012-10-08 | 2012-10-08 | Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102912670A true CN102912670A (en) | 2013-02-06 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103774611A Pending CN102912670A (en) | 2012-10-08 | 2012-10-08 | Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102912670A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106549162A (en) * | 2015-09-22 | 2017-03-29 | 许昌学院 | Combination electrode material, its preparation method and its application in all-vanadium flow battery |
| CN107039192A (en) * | 2016-02-02 | 2017-08-11 | 昆明纳太科技有限公司 | The different Buckie paper of two sides hydrophobe, preparation method and applications |
| CN107785587A (en) * | 2016-08-26 | 2018-03-09 | Jntg有限公司 | Improve functional vanadium flow battery electrode and use its vanadium flow battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377930A (en) * | 2002-04-11 | 2002-11-06 | 石油大学(北京) | Producing carbon paper material functional adhesive using heavy petroleum component |
| CN101003956A (en) * | 2007-01-12 | 2007-07-25 | 东华大学 | Composite conductive paper of carbon fiber |
| CN101492895A (en) * | 2009-02-18 | 2009-07-29 | 程显军 | Carbon fibre cloth for gaseous diffusion layer of fuel cell electrode |
-
2012
- 2012-10-08 CN CN2012103774611A patent/CN102912670A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377930A (en) * | 2002-04-11 | 2002-11-06 | 石油大学(北京) | Producing carbon paper material functional adhesive using heavy petroleum component |
| CN101003956A (en) * | 2007-01-12 | 2007-07-25 | 东华大学 | Composite conductive paper of carbon fiber |
| CN101492895A (en) * | 2009-02-18 | 2009-07-29 | 程显军 | Carbon fibre cloth for gaseous diffusion layer of fuel cell electrode |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106549162A (en) * | 2015-09-22 | 2017-03-29 | 许昌学院 | Combination electrode material, its preparation method and its application in all-vanadium flow battery |
| CN106549162B (en) * | 2015-09-22 | 2020-08-11 | 许昌学院 | Composite electrode material, preparation method thereof and application of composite electrode material in all-vanadium redox flow battery |
| CN107039192A (en) * | 2016-02-02 | 2017-08-11 | 昆明纳太科技有限公司 | The different Buckie paper of two sides hydrophobe, preparation method and applications |
| CN107039192B (en) * | 2016-02-02 | 2019-04-26 | 昆明纳太科技有限公司 | The different Buckie paper of two sides hydrophobe, preparation method and applications |
| CN107785587A (en) * | 2016-08-26 | 2018-03-09 | Jntg有限公司 | Improve functional vanadium flow battery electrode and use its vanadium flow battery |
| CN107785587B (en) * | 2016-08-26 | 2021-09-03 | Jntg有限公司 | Electrode for vanadium redox flow battery with improved functionality and vanadium redox flow battery adopting same |
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