CN109301258A - Fuel battery gas diffusion layer and preparation method thereof - Google Patents
Fuel battery gas diffusion layer and preparation method thereof Download PDFInfo
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- CN109301258A CN109301258A CN201811056404.7A CN201811056404A CN109301258A CN 109301258 A CN109301258 A CN 109301258A CN 201811056404 A CN201811056404 A CN 201811056404A CN 109301258 A CN109301258 A CN 109301258A
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- gas diffusion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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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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- Condensed Matter Physics & Semiconductors (AREA)
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- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Fuel Cell (AREA)
Abstract
The present invention provides a kind of fuel battery gas diffusion layers, sintering processes are made after coating gas diffusion layer slurry in the one side of carbon paper, it include PTFE, carbon dust and porous nano-fibre shape nickel powder in the gas diffusion layers slurry, the solid content of the gas diffusion layers slurry is 2.2%~3.75%, the mass ratio of the carbon dust and porous nano-fibre shape nickel powder is (1~5): 1, the quality of the PTFE is the 10%~25% of the gross mass of carbon dust and porous nano-fibre shape nickel powder, and the solid loadings on the carbon paper are 1~3mg/cm2.Additionally provide the preparation method of fuel battery gas diffusion layer of the present invention.Fuel battery gas diffusion layer of the invention, internal resistance is small, and water management properties are superior, and service life is longer, conductivity and porosity with higher, preparation method simple possible.
Description
Technical field
The present invention relates to a kind of fuel battery gas diffusion layers and preparation method thereof.
Background technique
The core component of Proton Exchange Membrane Fuel Cells (PEMFC) is membrane electrode (MEA), and membrane electrode is by gas diffusion
Layer, Catalytic Layer and proton exchange membrane composition.Gas diffusion layers (GDL) are between Catalytic Layer and bipolar plates, and main function is
Support Catalytic Layer, collected current, the water of transmission reaction gas and reaction generation.
General gas diffusion layers are usually made of supporting layer and microporous layers, and the matrix of supporting layer is mainly by carbon fiber paper
Etc it is porous constituted by material, and microporous layers are made of the polytetrafluoroethylene (PTFE) (PTFE) of carbon dust and hydrophobicity.Measure gas
Major parameter one of body diffused layer quality is electric conductivity, and electric conductivity is mainly determined by its material, another is exactly to drain to lead
Gas, it decides the discharge of reaction gas spread with react the water generated, to largely influence the performance of battery.
In order to meet the conductive function of draining, the PTFE emulsion of use impregnates and makes the gas diffusion layers being widely used at present
Carbon paper is used as matrix to solve.But still that there is porositys is low, gas passage is undesirable, the heavy-current discharge the case where
Under, battery performance decline.And under the long-term running environment of fuel cell, carbon black material is gradually aoxidized, and becomes microporous layers
Must be hydrophilic, increase mass transfer polarization, shortens the service life and stability of battery.
Summary of the invention
The present invention is intended to provide a kind of internal resistance is small, water management properties are superior, fuel cell gas with long service life diffusion
Layer, while additionally providing the preparation method of fuel battery gas diffusion layer of the present invention.
The present invention is realized by the following scheme:
A kind of fuel battery gas diffusion layer, the sintering processes system after coating gas diffusion layer slurry in the one side of carbon paper
, in the gas diffusion layers slurry include PTFE, carbon dust and porous nano-fibre shape nickel powder, the gas diffusion layers slurry
Solid content is 2.2%~3.75%, and the mass ratio of the carbon dust and porous nano-fibre shape nickel powder is (1~5): 1, the PTFE
Quality be carbon dust and porous nano-fibre shape nickel powder gross mass 10%~25%, the solid loadings on the carbon paper are 1
~3mg/cm2。
A kind of preparation method of fuel battery gas diffusion layer as described above, sequentially includes the following steps:
Nanometer fibrous FeNi powders are added into excessive acid solution to stir and filter after a certain period of time by I, later will filter
Wash heat is washed to neutrality, then filter residue is dried to obtain porous nano-fibre shape nickel powder；Mixing time is generally in acid solution solution
Ferrous metal in nanometer fibrous FeNi powders is dissolved in acid solution by 0.5~5h, and residue washing is generally using going
Ion water washing；Drying and processing technique is general are as follows: filter residue is placed in 3~5h in 70~90 DEG C of baking oven；
Porous nano-fibre shape nickel powder made from carbon dust and step I is extremely contained dispersing agent than being added with certain mass by II
It is dispersed with stirring in alcoholic solution and uniformly obtains suspension, mixing time general control is 2~5h, using ultrasonic disperse, jitter time
General control is 0.5~2h, and the quality accounting of dispersing agent is 0.1%~1% in the alcoholic solution, the solid content of the suspension
Control is 2~3%；The configuration technique of alcoholic solution containing dispersing agent specifically: dissolving the dispersant into mass concentration is 50%
In~90% alcoholic solution and stir evenly；
Hydrophober is added in suspension made from step II and is uniformly dispersed to obtain gas diffusion layers slurry by III, the gas
The solid content control of body diffused layer slurry is 2.2%~3.75%；Using ultrasonic disperse, jitter time general control is 0.5~
2h；
IV is coated in gas diffusion layers slurry made from step III through impregnating under the conditions of environment temperature is 60~90 DEG C
In the one side of carbon paper after sintering processes, the carbon paper for being finally coated with gas diffusion layers slurry is placed in full of protective gas and temperature
Degree is 3~5h of sintering processes in 300~450 DEG C of annealing device, and the solid loadings control on the carbon paper is 1~3mg/
cm2, solid loadings on carbon paper spray the spraying flow of instrument etc. by ultrasound and spraying number or time are controlled.
In the step II, the mass ratio of carbon dust and porous nano-fibre shape nickel powder is (1~5): 1.
In the step III, hydrophober is PTFE solution, and the quality of PTFE is that the carbon dust being added in step II is received with porous
The 10%~25% of the gross mass of rice fibrous nickel powder.The concentration of PTFE solution can be selected as needed, be typically chosen in
10%~25%.
In the step I, acid solution is hydrochloric acid solution or sulfuric acid solution；In the step II, alcoholic solution is that isopropanol is molten
One of liquid, ethanol solution, ethylene glycol solution are a variety of, and dispersing agent is polyvinylpyrrolidone or alkylphenol-polyethenoxy
Ether.
The impregnation sintering treatment process of the carbon paper specifically: it is 10%~25% to hate that carbon paper, which is immersed in mass concentration,
Vacuumize process 1~2 hour in aqua takes out drying and is placed on the heat treatment that full of protective gas and temperature is 300~450 DEG C
3~5h of sintering processes in device.
Protective gas is generally one of nitrogen, inert gas or a variety of.
Fuel battery gas diffusion layer of the invention, internal resistance is small, and water management properties are superior, and service life is longer, in slurry
In be added to porous nano-fibre shape nickel powder, and the mass ratio of carbon dust Yu porous nano-fibre shape nickel powder is controlled, so that fuel is electric
Porosity, the conductivity of pond gas diffusion layers are higher.The preparation method of fuel battery gas diffusion layer of the invention, simply may be used
Row.
Specific embodiment
The invention will be further described with reference to embodiments, but the invention is not limited to the statements of embodiment.
Embodiment 1
A kind of preparation method of fuel battery gas diffusion layer, sequentially includes the following steps:
I is immersed in mass concentration by 5cm × 5cm, with a thickness of 200 μm of carbon papers to vacuumize place in 10% PTFE solution
Reason 1 hour, taking-up drying is placed on full of nitrogen and temperature is sintering processes 5h in 300 DEG C of baking oven；
II by nanometer fibrous FeNi powders be added into excessive hydrochloric acid solution stirring 2h after filter, filter residue is made later
It is washed with deionized to neutrality, then filter residue is dried to obtain porous nano-fibre shape nickel powder；
Polyvinylpyrrolidone (PVP) is dissolved in the aqueous isopropanol that mass concentration is 50% and is stirred evenly by III,
The quality accounting control of PVP is 0.5%；
IV porous nano-fibre shape nickel powder made from 1.5g carbon dust and 1.5g step II is added to made from 97g step III
Elder generation high-speed stirred 2h re-ultrasonic dispersion 2h obtains suspension in aqueous isopropanol；
The PTFE solution that 3g mass concentration is 10% is added to ultrasonic disperse 1h in suspension made from step IV by V to be obtained
To gas diffusion layers slurry；
VI is sprayed gas diffusion layers slurry made from step V using ultrasound spraying instrument under the conditions of environment temperature is 80 DEG C
It is coated in the one side of the carbon paper handled through step I, the spraying flow of ultrasound spraying instrument is 5ml/min, reciprocal spray time
Control is 10min, and the carbon paper for being finally coated with gas diffusion layers slurry is placed in full of nitrogen and in the baking oven that temperature is 350 DEG C
Sintering processes 4h, obtains fuel battery gas diffusion layer.
Fuel battery gas diffusion layer made from embodiment 1 is detected, the solid loadings on carbon paper are 2mg/cm2。
Fuel battery gas diffusion layer made from embodiment 1 is fabricated to membrane electrode, measure membrane electrode internal resistance be 0.00008 ohm/
cm2。
Embodiment 2
A kind of preparation method of fuel battery gas diffusion layer, sequentially includes the following steps:
I is immersed in mass concentration by 5cm × 5cm, with a thickness of 200 μm of carbon papers to vacuumize place in 20% PTFE solution
Reason 2 hours, taking-up drying is placed on full of inert gas and temperature is sintering processes 3h in 450 DEG C of baking oven；
II by nanometer fibrous FeNi powders be added into excess sulfuric acid solution stirring 3.5h after filter, later by filter residue
Make to be washed with deionized to neutrality, then filter residue is dried to obtain porous nano-fibre shape nickel powder；
Alkyl phenol polyoxyethylene ether (APEO) is dissolved in the ethanol solution that mass concentration is 70% and is stirred evenly by III,
The quality accounting control of APEO is 0.2%；
IV porous nano-fibre shape nickel powder made from 3g carbon dust and 1g step II is added to second made from 156g step III
Elder generation high-speed stirred 3.5h re-ultrasonic dispersion 1h obtains suspension in alcoholic solution；
The PTFE solution that 10g mass concentration is 10% is added to ultrasonic disperse 2h in suspension made from step IV by V to be obtained
To gas diffusion layers slurry；
VI is sprayed gas diffusion layers slurry made from step V using ultrasound spraying instrument under the conditions of environment temperature is 90 DEG C
It is coated in the one side of the carbon paper handled through step I, the spraying flow of ultrasound spraying instrument is 5ml/min, reciprocal spray time
Control is 15min, and the carbon paper for being finally coated with gas diffusion layers slurry is placed in the baking that full of inert gas and temperature is 450 DEG C
Sintering processes 3h in case, obtains fuel battery gas diffusion layer.
Fuel battery gas diffusion layer made from embodiment 2 is detected, the solid loadings on carbon paper are 3mg/cm2。
Fuel battery gas diffusion layer made from embodiment 2 is fabricated to membrane electrode, measure membrane electrode internal resistance be 0.00012 ohm/
cm2。
Embodiment 3
A kind of preparation method of fuel battery gas diffusion layer, sequentially includes the following steps:
I is immersed in mass concentration by 5cm × 5cm, with a thickness of 200 μm of carbon papers to vacuumize place in 25% PTFE solution
Reason 2 hours, taking-up drying is placed on full of nitrogen and inert gas and temperature is sintering processes 4h in 350 DEG C of baking oven；
II by nanometer fibrous FeNi powders be added into excess sulfuric acid solution stirring 4h after filter, filter residue is made later
It is washed with deionized to neutrality, then filter residue is dried to obtain porous nano-fibre shape nickel powder；
Alkyl phenol polyoxyethylene ether (APEO) is dissolved in the ethylene glycol solution that mass concentration is 90% and is stirred equal by III
Even, the quality accounting control of APEO is 1%；
IV porous nano-fibre shape nickel powder made from 4g carbon dust and 0.8g step II is added to made from 235g step III
Elder generation high-speed stirred 5h re-ultrasonic dispersion 0.5h obtains suspension in ethylene glycol solution；
The PTFE solution that 7.2g mass concentration is 10% is added to ultrasonic disperse in suspension made from step IV by V
0.8h obtains gas diffusion layers slurry；
VI is sprayed gas diffusion layers slurry made from step V using ultrasound spraying instrument under the conditions of environment temperature is 60 DEG C
It is coated in the one side of the carbon paper handled through step I, the spraying flow of ultrasound spraying instrument is 5ml/min, reciprocal spray time
Control is 8min, and the carbon paper for being finally coated with gas diffusion layers slurry is placed in full of nitrogen and in the baking oven that temperature is 300 DEG C
Sintering processes 5h, obtains fuel battery gas diffusion layer.
Fuel battery gas diffusion layer made from embodiment 3 is detected, the solid loadings on carbon paper are 1.5mg/
cm2.Fuel battery gas diffusion layer made from embodiment 3 is fabricated to membrane electrode, the internal resistance for measuring membrane electrode is 0.0001 Europe
Nurse/cm2。
Claims (6)
1. a kind of fuel battery gas diffusion layer, sintering processes are made after coating gas diffusion layer slurry in the one side of carbon paper,
It is characterized by: including PTFE, carbon dust and porous nano-fibre shape nickel powder, the gas diffusion in the gas diffusion layers slurry
The solid content of layer slurry is 2.2%~3.75%, and the mass ratio of the carbon dust and porous nano-fibre shape nickel powder is (1~5): 1,
The quality of the PTFE is the 10%~25% of the gross mass of carbon dust and porous nano-fibre shape nickel powder, the solid on the carbon paper
Carrying capacity is 1~3mg/cm2。
2. a kind of preparation method of fuel battery gas diffusion layer as described in claim 1, it is characterised in that: according to the following steps
It carries out:
Nanometer fibrous FeNi powders are added into excessive acid solution to stir and filter after a certain period of time by I, later wash filter residue
It washs to neutrality, then filter residue is dried to obtain porous nano-fibre shape nickel powder；
II is more molten to the alcohol containing dispersing agent than being added with certain mass with porous nano-fibre shape nickel powder made from step I by carbon dust
It is dispersed with stirring in liquid and uniformly obtains suspension, the quality accounting of dispersing agent is 0.1%~1% in the alcoholic solution, the suspension
The solid content control of liquid is 2~3%；
Hydrophober is added in suspension made from step II and is uniformly dispersed to obtain gas diffusion layers slurry by III, and the gas expands
The solid content control for dissipating layer slurry is 2.2%~3.75%；
IV is coated in gas diffusion layers slurry made from step III through impregnation sintering under the conditions of environment temperature is 60~90 DEG C
In the one side of treated carbon paper, the carbon paper for being finally coated with gas diffusion layers slurry is placed in full of protective gas and temperature is
3~5h of sintering processes in 300~450 DEG C of annealing device, the solid loadings control on the carbon paper is 1~3mg/cm2。
3. the preparation method of fuel battery gas diffusion layer as claimed in claim 2, it is characterised in that: in the step II,
The mass ratio of carbon dust and porous nano-fibre shape nickel powder is (1~5): 1.
4. the preparation method of fuel battery gas diffusion layer as claimed in claim 3, it is characterised in that: in the step III,
Hydrophober is PTFE solution, and the quality of PTFE is the carbon dust being added in step II and the gross mass of porous nano-fibre shape nickel powder
10%~25%.
5. the preparation method of fuel battery gas diffusion layer as claimed in claim 2, it is characterised in that: in the step I, acid
Solution is hydrochloric acid solution or sulfuric acid solution；In the step II, alcoholic solution is aqueous isopropanol, ethanol solution, ethylene glycol solution
One of or it is a variety of, dispersing agent be polyvinylpyrrolidone or alkyl phenol polyoxyethylene ether.
6. the preparation method of the fuel battery gas diffusion layer as described in claim 2~5 is any, it is characterised in that: the carbon
The impregnation sintering treatment process of paper specifically: carbon paper is immersed in the hydrophober that mass concentration is 10%~25% and vacuumizes place
Reason 1~2 hour, taking-up drying is placed on full of protective gas and temperature is sintering processes in 300~450 DEG C of annealing device
3~5h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518259A (en) * | 2019-08-26 | 2019-11-29 | 浙江锋源氢能科技有限公司 | A kind of gas diffusion layers and preparation method thereof and fuel cell |
| CN111628183A (en) * | 2020-05-27 | 2020-09-04 | 先进储能材料国家工程研究中心有限责任公司 | Preparation method of fuel cell catalyst slurry |
| CN111900416A (en) * | 2020-07-31 | 2020-11-06 | 齐鲁工业大学 | Preparation method and application of carbon paper impregnating resin for fuel cell gas diffusion layer |
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| JP2011076848A (en) * | 2009-09-30 | 2011-04-14 | Dainippon Printing Co Ltd | Micro porous layer for fuel cell, gas diffusion electrode with micro porous layer, catalyst layer with micro porous layer, gas diffusion electrode with catalyst layer, membrane electrode assembly, and polymer electrolyte fuel cell |
| CN105014064A (en) * | 2015-07-22 | 2015-11-04 | 常州市好利莱光电科技有限公司 | Method for manufacturing nanofiber material by means of iron-nickel alloy pipe |
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Patent Citations (3)
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| CN101286564A (en) * | 2008-05-28 | 2008-10-15 | 中国科学院上海微系统与信息技术研究所 | Composite anode for direct methanol fuel cell and method for making the same |
| JP2011076848A (en) * | 2009-09-30 | 2011-04-14 | Dainippon Printing Co Ltd | Micro porous layer for fuel cell, gas diffusion electrode with micro porous layer, catalyst layer with micro porous layer, gas diffusion electrode with catalyst layer, membrane electrode assembly, and polymer electrolyte fuel cell |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518259A (en) * | 2019-08-26 | 2019-11-29 | 浙江锋源氢能科技有限公司 | A kind of gas diffusion layers and preparation method thereof and fuel cell |
| CN111628183A (en) * | 2020-05-27 | 2020-09-04 | 先进储能材料国家工程研究中心有限责任公司 | Preparation method of fuel cell catalyst slurry |
| CN111900416A (en) * | 2020-07-31 | 2020-11-06 | 齐鲁工业大学 | Preparation method and application of carbon paper impregnating resin for fuel cell gas diffusion layer |
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