CN1734812A - Gas diffusion layer material for fuel cell and preparation method thereof - Google Patents
Gas diffusion layer material for fuel cell and preparation method thereof Download PDFInfo
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- CN1734812A CN1734812A CNA2005100188825A CN200510018882A CN1734812A CN 1734812 A CN1734812 A CN 1734812A CN A2005100188825 A CNA2005100188825 A CN A2005100188825A CN 200510018882 A CN200510018882 A CN 200510018882A CN 1734812 A CN1734812 A CN 1734812A
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- carbon black
- binding agent
- carbon fiber
- fiber felt
- diffusion layer
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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
- Y02E60/10—Energy storage using batteries
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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
This invention provides gas diffusion layer material and preparation method for fuel cell, which is characterized in that the material comprises carbon fiber felt as base, carbon black as filling phase, and adhesive agent. The preparation technique comprises, dipping carbon black with nitric acid or hydrochloric acid, drying, mixing the dried carbon black and adhesive agent to prepared solution, dipping and treating the felt in the mixed solution, smoothing and high temperature thermal treating, and obtaining the product. The product has well monocell property and needs low cost.
Description
Technical field
The present invention relates to a kind of gas diffusion layer material for fuel cell and preparation method thereof, particularly gas diffusion layer material for fuel cell and the preparation method who is composited by carbon fiber felt, carbon black and binding agent.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has advantages such as low, pollution-free, the no burn into specific power of working temperature is big, startup is rapid as a kind of novel energy processing mode, has become one of focus of energy field research.In Proton Exchange Membrane Fuel Cells, gas diffusion layers (GDL) plays the support catalyst layer and provides gas passage, electron channel and drainage channel effect for electrode reaction.Therefore, select for use high performance gas diffusion layer material to help improving the combination property of electrode.
Carbon fiber paper is a kind of gas diffusion layer material that is widely used in the proton exchange membrane fuel cell electrode, it not only has uniform porous matter laminate structure, and, make it possess excellent conductivity, chemical stability and thermal stability because primary raw material uses graphitized carbon fibre.At present domestic PEMFC research unit all is to use the carbon paper that Japanese TORAY company, German SGL technology company, Canadian Ballard company or E-Tek company produce basically.People such as Japan Teruaki mix carbon fiber, paper pulp, organic fiber, four kinds of materials of organic polymer binder papermaking then; People such as the Wang Shujun of China's oil university, Zhang Wei adopt cellulose, activated carbon fiber and carbon dust to be feedstock production to meet the carbon fibre composite paper that the proton exchange membrane fuel cell electrode diffusion layer requires.People such as Wang Shujun also adopt another method to prepare the function carbon paper that a kind of two sides has the different hydrophilic performance, and it is by two-layer carbon paper compacting composite molding after the moulding of wet papermaking technology, makes after carbonization treatment again.But carbon fiber paper surface can appear in these methods inevitably produces wrinkle, problem such as cause the product mechanical strength to descend or the bulk density of carbon fiber paper is big inadequately.
People such as Wang Shuzhong, Li Lingxin prescinds high carbon fiber polyacrylonitrile-based carbon fibre and asphalt base carbon fiber, and the length of the high carbon fiber of weak point after prescinding is 0.5mm～5.0mm, and its average length is 1.0mm～3.0mm; Select for use mass concentration less than 1% polyvinyl alcohol or poly-propionamide dispersant, short high-carbon fiber dispersion in aqueous phase, is formed the slurries raw material, its medium high carbon quality of fiber content utilizes the wet papermaking method of forming to make carbon fiber paper material between 96%～99%.
Summary of the invention
The purpose of this invention is to provide a kind of gas diffusion layer material for fuel cell and preparation method thereof, particularly composite modified by carbon fiber felt is carried out, prepare low-cost and well behaved gas diffusion layer material.
A kind of gas diffusion layer material for fuel cell of the present invention is composited by carbon fiber felt, carbon black and binding agent, and wherein the mass ratio of carbon fiber felt and carbon black and binding agent is 0.1～1: 1: 1～30, preferred 0.2～0.5: 1: 1～5.Described carbon fiber felt is active carbon fiber felt or celion felt, and thickness is 100～200 μ m, and porosity is more than 50%, and average pore size is 0.1-100 μ m; Carbon black is activated carbon or is conductive carbon black that the carbon black granules particle diameter is 30～200nm; Binding agent is any in phenolic resins, polytetrafluoroethylene or the polyvinyl alcohol.
The preparation method of gas diffusion layer material of the present invention, carry out according to the following steps:
1st, carbon black is put into the nitric acid of 0.5-2mol/L or hydrochloric acid and handled 2-6 hour, molar ratio of its acid and carbon black is greater than 5: 1, under 90-100 ℃ of temperature dry 2-8 hour then, obtains pretreated carbon black;
2nd, binding agent is dissolved as binder solution in solvent, the mass ratio of binding agent and solvent is 1: 1-10: its concrete preparation method is: if binding agent is a phenolic resins, then phenolic resins is joined reflux in the absolute ethyl alcohol, make binding agent dissolve the acquisition binder solution fully; If binding agent is a polytetrafluoroethylene, then polytetrafluoroethylene and absolute ethyl alcohol are put into autoclave, under 200-300 ℃ of temperature and 10-20MPa pressure, dissolve, perhaps directly use business-like ptfe emulsion; If binding agent is a polyvinyl alcohol, then polyvinyl alcohol is joined reflux in the absolute ethyl alcohol, make binding agent dissolve the acquisition binder solution fully;
3rd, the pretreated carbon black of step 1 is mixed with the binder solution that step 2 obtains, stirred 2-12 hour, sonicated 10～60 minutes, wherein the mass ratio of binding agent and solid-state carbon black is 1-30: 1, preferred 1～5: 1;
4th, carbon fiber felt is fastened on polyester frame, aluminium frame or the stainless steel framework, and immerse carbon black and binding agent mixed solution 1-10 second, taking-up is dried then, wherein the mass ratio of carbon fiber felt and carbon black and binding agent is 0.1～1: 1: 1～30, preferred 0.2～0.5: 1: 1～5;
5th, the carbon fiber felt that step 4 has been soaked carbon black and binding agent mixed solution after dry 0.5-4 hour, is sloughed fixed frame under 70-100 ℃ of temperature, hot pressing in flat press, and hot pressing temperature is 120-150 ℃, the time is 50-120 second;
6th, the carbon fiber felt after smooth is inserted in the high-temperature atmosphere furnace with hot pressing, feeds N
2Gas was handled 1-3 hour under 2000-2500 ℃ of high temperature, promptly obtained being used for the gas diffusion layer material of fuel cell.
Compare with background technology, the present invention is to be matrix with the carbon fiber felt, carbon black is for filling phase, phenolic resins, polytetrafluoroethylene or polyvinyl alcohol are bonding agent, adopt the liquid impregnation method that carbon fiber felt is carried out carbon black-filled synthetic fuel battery gas diffusion layer material, its synthesis technique is simple, low production cost, but also have good cell output.
Description of drawings
Accompanying drawing 1 is the monocell performance curve of gas diffusion layer material for fuel cell of the present invention.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
The preparation of gas diffusion layer material for fuel cell the steps include:
1. get 10g Vulcan XC72 conductive carbon black and put into there-necked flask, adding concentration is the hydrochloric acid 1000mL of 1.5mol/L, stirs 2 hours, pour out then, use the Buchner funnel filtration under diminished pressure, put into the drying box drying with filtering good carbon black, dry carbon black grinds to form-200 purpose powder;
Get the 100g polytetrafluoroethylgranule granule and put into autoclave, add the 250ml absolute ethyl alcohol, dissolving is 2 hours under 300 ℃ of temperature and 20MPa pressure;
2. be after 10% the solids content with the polytetrafluoroethylene ethanolic solution with absolute ethyl alcohol dilution, with the carbon black of handling well be to add in there-necked flask at 1: 1 according to polytetrafluoroethylene and carbon black mass ratio, stirred 10 hours, again carbon black granules is pulverized with ultrasonic cell disruptor then, it is uniformly dispersed;
3. get the celion felt of 10cm * 10cm, thickness is 1801 μ m, and porosity is 75%, and average pore size is 20 μ m.Carbon fiber felt is bonded on the aluminium frame, after fixing, immerses 5 seconds in carbon black, the phenolic resins mixed liquor, the mass ratio of its carbon fiber felt and carbon black, polytetrafluoroethylene is 1: 1: 1, takes out then and dries, and hot pressing in platen-press, hot pressing temperature is 120 ℃, and the time was 90 seconds.Carbon fiber felt with hot pressing after smooth places high-temperature atmosphere furnace, feeds N
2, 15 ℃/minute of heating rates, be warming up to 2500 ℃ after the insulation 1 hour, make gas diffusion layer material for fuel cell after the cooling.
Adopt gas diffusion layer material and self-control fuel cell chip CCM (catalyst coated membrane, Pt carrying capacity 0.6mg/cm
2) the preparation membrane electrode, at H
2/ Air normal pressure, 60 ℃ of battery testings that place an order the results are shown in Figure 1.
Embodiment 2
The preparation of gas diffusion layer material for fuel cell the steps include:
1. getting 15g Vulcan XC72 conductive carbon black puts into there-necked flask to add concentration is the hydrochloric acid 1000ml of 2mol/L, stirred 2 hours, and poured out then, use the Buchner funnel filtration under diminished pressure, put into the drying box drying with filtering good carbon black, and grind to form-200 purpose powder.
Get 150g phenolic resins and put into there-necked flask, add the 200ml absolute ethyl alcohol, add thermal agitation, till phenolic resins all dissolves.
2. be after 15% the solids content with the phenolic resins ethanolic solution with absolute ethyl alcohol dilution, with the carbon black of handling well be to add in there-necked flask at 5: 1 according to phenolic resins and carbon black mass ratio, stirred 12 hours, again carbon black granules is pulverized with ultrasonic cell disruptor then, it is uniformly dispersed.
3. get the active carbon fiber felt of 10cm * 10cm, thickness is 150 μ m, and porosity is 75%, and average pore size is 20 μ m.Carbon fiber felt is bonded on the stainless steel framework, after fixing, immerses 10 seconds in carbon black, the phenolic resins mixed liquor, the mass ratio of its carbon fiber felt and carbon black and phenolic resins thereof is 0.5: 1: 5, takes out dry.Afterwards, the carbon fiber felt of drying is put into platen-press hot pressing, hot pressing temperature is 120 ℃, and the time was 120 seconds.Carbon fiber felt after smooth is placed high-temperature atmosphere furnace, feed N
2, 15 ℃/minute of heating rates are swollen, and insulation was 2 hours after temperature rose to 2200 ℃, made gas diffusion layer material for fuel cell after the cooling.
The monocell method of testing of gas diffusion layer material is identical with embodiment 1, and test result is seen Fig. 1.
Embodiment 3
The preparation of gas diffusion layer material for fuel cell the steps include:
1. get 10g Vulcan XC72 and put into there-necked flask, adding concentration is the hydrochloric acid 1000ml of 2mol/L, stirs 2 hours, pours out then, uses the Buchner funnel filtration under diminished pressure, puts into the drying box drying with filtering good carbon black, and grinds to form-200 purpose powder.
Get the 100g polyvinyl alcohol and put into there-necked flask, add the 400ml absolute ethyl alcohol, reflux makes binding agent dissolve the acquisition binder solution fully, polyvinyl alcohol and ethanol mass ratio=and 1: 4.
2. be after 15% the solids content with poly-vinyl alcohol solution dilution, with the carbon black of handling well be to add in there-necked flask at 30: 1 according to polyvinyl alcohol and carbon black ratio, stirred 12 hours, and again carbon black granules was pulverized with ultrasonic cell disruptor then, it is uniformly dispersed.
3. get the active carbon fiber felt of 10cm * 10cm, thickness is 150 μ m, and porosity is 75%, and average pore size is 20 μ m.Carbon fiber felt is bonded on the aluminium frame, after fixing, immerses 10 seconds in carbon black, the polyvinyl alcohol mixing liquid, the mass ratio of its carbon fiber felt and carbon black, polyvinyl alcohol is 0.2: 1: 30, takes out dry.Afterwards, the active carbon fiber felt of drying is put into platen-press hot pressing, hot pressing temperature is 120 ℃, and the time was 120 seconds.Carbon fiber felt after smooth is placed high-temperature atmosphere furnace, feed N
2, 15 ℃/minute of heating rates, insulation was 2 hours after temperature rose to 2200 ℃, made gas diffusion layer material for fuel cell after the cooling.
The monocell method of testing of gas diffusion layer material is identical with embodiment 1, and test result is seen Fig. 1.
Claims (4)
1, a kind of gas diffusion layer material for fuel cell, it is characterized in that this material is composited by carbon fiber felt, carbon black and binding agent, the mass ratio of its carbon fiber felt and carbon black and binding agent is 0.1～1: 1: 1～30, described carbon fiber felt is active carbon fiber felt or celion felt, thickness is 100～200 μ m, porosity is more than 50%, and average pore size is 0.1-100 μ m; Carbon black is activated carbon or is conductive carbon black that the carbon black granules particle diameter is 30～200nm; Binding agent is any in phenolic resins, polytetrafluoroethylene or the polyvinyl alcohol.
2, gas diffusion layer material as claimed in claim 1, the mass ratio that it is characterized in that described carbon fiber felt and carbon black and binding agent is 0.2～0.5: 1: 1～5.
3, the preparation method of the described gas diffusion layer material of claim 1 is characterized in that carrying out according to the following steps:
1st, carbon black is put into the nitric acid of 0.5-2mol/L or hydrochloric acid acid treatment 2-6 hour, molar ratio of its acid and carbon black is greater than 5: 1, under 90-100 ℃ of temperature dry 2-8 hour then, obtains pretreated carbon black;
2nd, binding agent is dissolved as binder solution in solvent, the mass ratio of binding agent and solvent is 1: 1-10: its concrete preparation method is: if binding agent is a phenolic resins, then phenolic resins is joined reflux in the absolute ethyl alcohol, make binding agent dissolve the acquisition binder solution fully; If binding agent is a polytetrafluoroethylene, then polytetrafluoroethylene and absolute ethyl alcohol are put into autoclave, under 200-300 ℃ of temperature and 10-20MPa pressure, dissolve, perhaps directly use business-like ptfe emulsion; If binding agent is a polyvinyl alcohol, then polyvinyl alcohol is joined reflux in the absolute ethyl alcohol, make binding agent dissolve the acquisition binder solution fully;
3rd, the pretreated carbon black of step 1 is mixed with the binder solution that step 2 obtains, stirred 2-12 hour, sonicated 10～60 minutes, the mass ratio of wherein solid-state carbon black and binding agent is 1: 1～30;
4th, carbon fiber felt is fastened on polyester frame, aluminium frame or the stainless steel framework, and immerses 1-10 second in carbon black and the binding agent mixed solution, take out then, dry, wherein the mass ratio of carbon fiber felt and carbon black and binding agent is 0.1～1: 1: 1～30;
5th, the carbon fiber felt that step 4 has been soaked carbon black and binding agent mixed solution after dry 0.5-4 hour, is sloughed fixed frame under 70-100 ℃ of temperature, hot pressing in flat press, and hot pressing temperature is 120-150 ℃, the time is 50-120 second;
6th, the carbon fiber felt after smooth is inserted in the high-temperature atmosphere furnace with hot pressing, feeds N
2Gas was handled 1-3 hour under 2000-2500 ℃ of high temperature, promptly obtained being used for the gas diffusion layer material of fuel cell.
4, the preparation method of gas diffusion layer material as claimed in claim 3 is characterized in that the mass ratio of solid-state carbon black and binding agent is 1: 1～5 in the binder solution mixed liquor that pretreated carbon black of step 1 and step 2 obtain.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100188825A CN1331261C (en) | 2005-06-08 | 2005-06-08 | Gas diffusion layer material for fuel cell and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591868B (en) * | 2009-06-23 | 2011-04-27 | 东华大学 | Preparation for carbon fiber paper used for gas diffusion layer of proton exchange membrane fuel cell |
| CN101425583B (en) * | 2007-11-02 | 2011-06-08 | 清华大学 | Fuel cell membrane electrode and preparation thereof |
| CN102110822A (en) * | 2009-12-25 | 2011-06-29 | 南京大学 | Gas diffusion layer and preparation method and application thereof |
| CN102203995A (en) * | 2008-10-31 | 2011-09-28 | 松下电器产业株式会社 | Gas diffusion layer for fuel cell, manufacturing method therefor, membrane electrode assembly, and fuel cell |
| US8343452B2 (en) | 2006-03-20 | 2013-01-01 | GM Global Technology Operations LLC | Acrylic fiber bonded carbon fiber paper as gas diffusion media for fuel cell |
| US8859165B2 (en) | 2008-07-25 | 2014-10-14 | Tsinghua University | Membrane electrode assembly and fuel cell using the same |
| US8951697B2 (en) | 2008-12-17 | 2015-02-10 | Tsinghua University | Membrane electrode assembly and fuel cell using the same |
| US9077012B2 (en) | 2008-12-17 | 2015-07-07 | Tsinghua University | Membrane electrode assembly and biofuel cell using the same |
| US9077042B2 (en) | 2008-07-25 | 2015-07-07 | Tsinghua University | Membrane electrode assembly and biofuel cell using the same |
| CN106395814A (en) * | 2016-08-30 | 2017-02-15 | 浙江大维高新技术股份有限公司 | Preparation method of special activated-carbon electrode block for capacitive deionizing equipment |
| CN109273724A (en) * | 2018-07-26 | 2019-01-25 | 同济大学 | A kind of fuel battery gas diffusion layer and preparation method thereof |
| CN112609452A (en) * | 2020-12-15 | 2021-04-06 | 深圳市通用氢能科技有限公司 | Gas diffusion layer material and preparation method thereof |
| CN114551920A (en) * | 2022-02-21 | 2022-05-27 | 一汽解放汽车有限公司 | Gas diffusion layer slurry and preparation method and application thereof |
| CN115000419A (en) * | 2022-04-27 | 2022-09-02 | 深圳市通用氢能科技有限公司 | Gas diffusion layer and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7144476B2 (en) * | 2002-04-12 | 2006-12-05 | Sgl Carbon Ag | Carbon fiber electrode substrate for electrochemical cells |
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2005
- 2005-06-08 CN CNB2005100188825A patent/CN1331261C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8343452B2 (en) | 2006-03-20 | 2013-01-01 | GM Global Technology Operations LLC | Acrylic fiber bonded carbon fiber paper as gas diffusion media for fuel cell |
| CN101425583B (en) * | 2007-11-02 | 2011-06-08 | 清华大学 | Fuel cell membrane electrode and preparation thereof |
| US9077042B2 (en) | 2008-07-25 | 2015-07-07 | Tsinghua University | Membrane electrode assembly and biofuel cell using the same |
| US8859165B2 (en) | 2008-07-25 | 2014-10-14 | Tsinghua University | Membrane electrode assembly and fuel cell using the same |
| CN102203995A (en) * | 2008-10-31 | 2011-09-28 | 松下电器产业株式会社 | Gas diffusion layer for fuel cell, manufacturing method therefor, membrane electrode assembly, and fuel cell |
| US8999603B2 (en) | 2008-10-31 | 2015-04-07 | Panasonic Corporation | Gas diffusion layer for fuel cell, manufacturing method therefor, membrane electrode assembly, and fuel cell |
| US9077012B2 (en) | 2008-12-17 | 2015-07-07 | Tsinghua University | Membrane electrode assembly and biofuel cell using the same |
| US8951697B2 (en) | 2008-12-17 | 2015-02-10 | Tsinghua University | Membrane electrode assembly and fuel cell using the same |
| CN101591868B (en) * | 2009-06-23 | 2011-04-27 | 东华大学 | Preparation for carbon fiber paper used for gas diffusion layer of proton exchange membrane fuel cell |
| CN102110822B (en) * | 2009-12-25 | 2015-05-06 | 南京大学 | Gas diffusion layer and preparation method and application thereof |
| CN102110822A (en) * | 2009-12-25 | 2011-06-29 | 南京大学 | Gas diffusion layer and preparation method and application thereof |
| CN106395814A (en) * | 2016-08-30 | 2017-02-15 | 浙江大维高新技术股份有限公司 | Preparation method of special activated-carbon electrode block for capacitive deionizing equipment |
| CN106395814B (en) * | 2016-08-30 | 2018-04-10 | 浙江大维高新技术股份有限公司 | A kind of preparation method of capacitive deionization device-specific activated carbon electrodes block |
| CN109273724A (en) * | 2018-07-26 | 2019-01-25 | 同济大学 | A kind of fuel battery gas diffusion layer and preparation method thereof |
| CN112609452A (en) * | 2020-12-15 | 2021-04-06 | 深圳市通用氢能科技有限公司 | Gas diffusion layer material and preparation method thereof |
| CN114551920A (en) * | 2022-02-21 | 2022-05-27 | 一汽解放汽车有限公司 | Gas diffusion layer slurry and preparation method and application thereof |
| CN115000419A (en) * | 2022-04-27 | 2022-09-02 | 深圳市通用氢能科技有限公司 | Gas diffusion layer and preparation method thereof |
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