CN109868487A - A kind of metallic substrates gas diffusion layers and its preparation and application - Google Patents
A kind of metallic substrates gas diffusion layers and its preparation and application Download PDFInfo
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- CN109868487A CN109868487A CN201711257378.XA CN201711257378A CN109868487A CN 109868487 A CN109868487 A CN 109868487A CN 201711257378 A CN201711257378 A CN 201711257378A CN 109868487 A CN109868487 A CN 109868487A
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a kind of preparation methods for being used for proton exchange membrane (PEM) electrolyte water electrolysis gas diffusion layers, belong to the optimization field of the gas diffusion layers of metallic substrates.The present invention, as matrix, is modified using the method modification hydrophobic layer of brushing on its surface using titanium net, with conductive agent filler, is made into slurry with binder, hydrophobing agent, brushes onto titanium net matrix, preparation is supported on the gas diffusion layers of metallic substrates.By the proportion of control conductive agent, binder and hydrophobic aqua, enhance the corrosion resistance, electrical conductance and gas-liquid transmission process of gas diffusion layers.The problem of seriously corroded under the high position in PEM water electrolysis can be effectively improved.
Description
Technical field
The present invention designs the technical field of proton exchange membrane electrolyte water electrolysis, specially a kind of to be used for PEM (proton exchange
Film) water electrolysis gas diffusion layers preparation method.Use titanium net as matrix, it is hydrophobic using the method modification brushed on its surface
Layer is modified, and with conductive agent filler, is made into slurry with binder, hydrophobing agent, is brushed onto titanium net matrix, be formed in metal
The gas diffusion layers of substrate.Mechanical performance, corrosion resistance and the drain function of gas diffusion layers can effectively be enhanced.
Background technique
Proton exchange membrane (PEM) electrolyte water electrolysis as in one efficiently, cleaning, carbon-free hydrogen production process increasingly by
The concern of energy circle.As the key component in PEM water electrolytic cell, the main function of gas diffusion layers is the gas to participate in reaction
Body and the water of generation provide transmission channel, and support catalyst.Therefore, the performance of diffusion layer base material will directly affect electrolysis
The performance in pond.The gas diffusion layer substrate of selection function admirable can directly improve the working performance of PEM water electrolytic cell.It has excellent performance
Diffusion layer substrate should meet it is claimed below:
1) high resistivity.Gas diffusion layers will provide the conduction pathway between bipolar plates and Catalytic Layer for electronics, and collect
Electric current, therefore gas diffusion layers must have low resistivity, i.e. electric good conductor.
2) high porosity and a certain range of pore-size distribution.In the mea, reaction gas and generate water transmission channels all
There is provided by gas diffusion layers, so, diffusion layer substrate need high porosity guarantee electrode operation when reactant transmission,
And the water energy generated at electrode is smoothly discharged enough, prevent " water logging " phenomenon.
3) good chemical stability and heating conduction.In oxidation or reducing environment, gas diffusion layers are able to maintain stabilization,
Do not occur to corrode and degrade；It is able to maintain pile operating temperature in battery operation to stablize, guarantees the heat dissipation and temperature of battery
Distribution is hooked, there is good heat management system, the service life of pile could be extended.
4) higher cost performance.
By research in recent years, multiple gases diffusion layer base material has been developed, has been had respectively using more at present
Kind Carbon fibe material, but carbon material oxidation reaction under the higher current potential of electrolytic cell can aggravate, and the mechanicalness of carbon material
Can be poor, therefore it is impossible to meet the stability requirements of PEM water electrolysis.Existed with the oxide gas diffusion layer of porous metal matrix
Mechanical performance, gas cellular structure and corrosion resistance etc. have excellent performance etc..
Summary of the invention
The bad mechanical property that is encountered for the gas diffusion layers of existing carbon fibre material, it is perishable the problems such as, the present invention
There is provided corrosion-resistant one kind, high conductivity, hydrophobic performance good gas diffusion layers.The main structure of gas diffusion layers is Sb doped
Stannic oxide, the substance frequently as the anode catalyst of PEM water electrolysis substrate, it is with good stability, corrosion-resistant, conductive
Property.Gas passage is constructed using the polytetrafluoroethylene (PTFE) (PTFE) of hydrophobic material in gas duct.
The raw material for preparing GDL is brushed after decontamination, surface acid etch by several times using a kind of simple spread coating
On porous titanium net thin slice, the gas diffusion layers of a corrosion resistance with porous gas transmission channel are formed.It can satisfy PEM
The technical requirements of water electrolysis.Operating process are as follows:
(1) metal pretreated matrix:
A. by washing powder and natrium carbonicum calcinatum in mass ratio 1: 1, total 20g is added in 200ml deionized water, be put into 80 mesh,
The titanium net matrix of the 0.5g of 0.24mm thickness boils 15~60min, then rinses matrix, the vacuum drying at 80 DEG C with deionized water
12h carries out alkaline degreasing；
B., titanium net matrix after oil removing is placed in the mass concentration for being heated to 90 DEG C to impregnate 2h in 30%HCl solution, is used
Deionized water is rinsed, then is placed in methanol and is impregnated, spare.
(2) preparation of gas diffusion layers:
A. by the stibium doping stannic oxide prepared in advance (conductive agent, filler, ATO), Kynoar (binder,
PVDF), polytetrafluoroethylene (PTFE) (hydrophobing agent, PTFE) is mixed according to the mass ratio of 15:1~3:1~3, is ground in mortar
It is even.
B. powder is dissolved in n-methyl-2-pyrrolidone (NMP) to be gradually uniformly painted on that treated Ti is online, is brushed
It is dried in vacuo at 80 DEG C later, finally obtains gas diffusion layers.
Advantages of the present invention:
1) metallic substrates are used, it is possible to prevente effectively from the mechanical performances such as frangible, not resistance to compression of traditional carbon material gas diffusion layers
The disadvantage of difference.
2) preparation method is simple, and equipment requirement is low.
3) by the component ratio of regulation filler, binder and hydrophobing agent, corrosion resistance, the optimization hole of diffusion layer are improved
Road structure reduces the resistance value of diffusion layer, so that the performance of diffusion layer is best.
Detailed description of the invention
Fig. 1 is shown, when three kinds of ATO:PVDF:PTFE proportions are respectively 15:1:2,15:1.5:1.5,15:0.5:2.5
Obtained GDL, with homemade membrane electrode (anode 0.5mg/cm2IrO2, cathode 1.5mg/cm2Pt/C) be assembled into list
Battery, obtained polarization curve.
Specific embodiment
Embodiment 1
Metal pretreated matrix:
A. by washing powder and natrium carbonicum calcinatum in mass ratio 1: 1, total 20g is added in 200ml deionized water, be put into 80 mesh,
The titanium net matrix of the 0.5g of 0.24mm thickness boils 15~60min, then rinses matrix, the vacuum drying at 80 DEG C with deionized water
12h carries out alkaline degreasing；
B., titanium net matrix after oil removing is placed in the mass fraction for being heated to 90 DEG C to impregnate 2h in 30%HCl solution, is used
Deionized water is rinsed, then is placed in methanol and is impregnated, spare.
(2) preparation of gas diffusion layers:
A. by the stibium doping stannic oxide prepared in advance (conductive agent, filler, ATO), Kynoar (binder,
PVDF), polytetrafluoroethylene (PTFE) (hydrophobing agent, PTFE) is mixed according to the mass ratio of 15:1:2, is ground in mortar uniformly.
B. the uniformly mixed raw material of 0.1g is weighed, powder is dissolved in 10mlN- N-methyl-2-2-pyrrolidone N (NMP), benefit
With in the brushing method titanium net that is coated uniformly on that treated, it is dried in vacuo for 24 hours at 80 DEG C after brushing, finally obtains gas diffusion
Layer, is denoted as GDL-1.Gas diffusion layers with a thickness of 0.015mm.
Embodiment 2
1, metal pretreated matrix:
A. by washing powder and natrium carbonicum calcinatum in mass ratio 1: 1, total 20g is added in 200ml deionized water, be put into 80 mesh,
The titanium net matrix of the 0.5g of 0.24mm thickness boils 15~60min, then rinses matrix, the vacuum drying at 80 DEG C with deionized water
12h carries out alkaline degreasing；
B., titanium net matrix after oil removing is placed in the mass fraction for being heated to 90 DEG C to impregnate 2h in 30%HCl solution, is used
Deionized water is rinsed, then is placed in methanol and is impregnated, spare.
2, the preparation of gas diffusion layers:
A. by the stibium doping stannic oxide prepared in advance (conductive agent, filler, ATO), Kynoar (binder,
PVDF), polytetrafluoroethylene (PTFE) (hydrophobing agent, PTFE) is mixed according to the mass ratio of 15:1.5:1.5, is ground in mortar uniformly.
B. it weighs 0.1g and is pre-mixed uniform raw material, powder is dissolved in the n-methyl-2-pyrrolidone (NMP) of 10ml
In, using in the brushing method titanium net that is coated uniformly on that treated, it is dried in vacuo for 24 hours at 80 DEG C after brushing, finally obtains gas
Diffusion layer is denoted as GDL-2.The thickness of gas diffusion layers is respectively 0.018mm.
Embodiment 3
(1) metal pretreated matrix:
A. by washing powder and natrium carbonicum calcinatum in mass ratio 1: 1, total 20g is added in 200ml deionized water, is put into 80 mesh,
The titanium net matrix of the 0.5g of 0.24mm thickness boils 15~60min, then rinses matrix, the vacuum drying at 80 DEG C with deionized water
12h carries out alkaline degreasing；
B., titanium net matrix after oil removing is placed in the mass fraction for being heated to 90 DEG C to impregnate 2h in 30%HCl solution, is used
Deionized water is rinsed, then is placed in methanol and is impregnated, spare.
(2) preparation of gas diffusion layers:
A. by the stibium doping stannic oxide prepared in advance (conductive agent, filler, ATO), Kynoar (binder,
PVDF), polytetrafluoroethylene (PTFE) (hydrophobing agent, PTFE) is mixed according to the mass ratio of 15:0.5:2.5, is ground in mortar uniformly.
B. it weighs 0.1g and is pre-mixed uniform raw material, powder is dissolved in the n-methyl-2-pyrrolidone (NMP) of 10ml
In, using in the brushing method titanium net that is coated uniformly on that treated, it is dried in vacuo for 24 hours at 80 DEG C after brushing, finally obtains gas
Diffusion layer is denoted as GDL-3.The thickness of gas diffusion layers is respectively 0.016mm.
Claims (8)
1. a kind of metallic substrates gas diffusion layers, which is characterized in that substrate is metal mesh, is prepared on its surface with hydrophobic duct
Gas diffusion layers.
2. metallic substrates gas diffusion layers according to claim 1, which is characterized in that the metallic matrix of use with a thickness of
0.1~0.3mm, gas diffusion layers with a thickness of 0.015~0.018mm.
3. metallic substrates gas diffusion layers according to claim 1 or 2, which is characterized in that one in metal mesh Ti, Sn
Kind metal simple-substance or two kinds of alloy networks.
4. metallic substrates gas diffusion layers according to claim 1 or 2, which is characterized in that metal mesh mesh number be 50~
100。
5. metallic substrates gas diffusion layers according to claim 1 or 2, diffusion layer using serve as conductive agent, binder and
The mixture of the different polymer of hydrophobing agent is as raw material；Quality proportioning is conductive agent: binder: hydrophobing agent=15:1~3:1
~3；Conductive agent is stibium doping stannic oxide, and binder is Kynoar, and hydrophobing agent is polytetrafluoroethylene (PTFE)；
The mass ratio of SnO2:Sb2O3 is 60:40 in stibium doping stannic oxide.
6. a kind of preparation method of any metallic substrates gas diffusion layers of claim 1-5, the method that diffusion layer supports
Using spread coating, by raw material mixed dissolution in organic solvent, obtained by brushing, drying, the specific steps are as follows:
Metal pretreated matrix: by washing powder and natrium carbonicum calcinatum in mass ratio 1: 1, total 20g is added in 200ml deionized water,
Be put into 80 mesh, 0.24mm thickness 0.5g titanium net matrix, 15~60min is boiled, then rinse matrix with deionized water, at 80 DEG C
Vacuum drying 12h carries out alkaline degreasing；
Titanium net matrix after oil removing is placed in the mass concentration 30%HCl solution for be heated to 90 DEG C and impregnates 2h, uses deionized water
It rinses, then is placed in methanol and impregnates, it is spare；
The preparation of gas diffusion layers: by the stibium doping stannic oxide prepared in advance (conductive agent, filler, ATO), polyvinylidene fluoride
Alkene (binder, PVDF), polytetrafluoroethylene (PTFE) (hydrophobing agent, PTFE) are mixed according to required ratio, are ground in mortar uniformly, will
Powder is dissolved in n-methyl-2-pyrrolidone (NMP), using the method gradually brushed, is dried in vacuo at 80 DEG C, is obtained gas
Diffusion layer.
7. the preparation method of metallic substrates gas diffusion layers according to claim, the composition quality proportion of gas diffusion layers
For conductive agent: binder: hydrophobing agent=15:1~3:1~3.
8. a kind of application of any metallic substrates gas diffusion layers of claim 1-5 in PEM water electrolytic cell.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993265A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Gas diffusion layer for fuel cell and preparation method thereof |
| CN114507873A (en) * | 2022-03-30 | 2022-05-17 | 北京化工大学 | Hydrogen diffusion anode and preparation method and application thereof |
| CN114725399A (en) * | 2022-04-28 | 2022-07-08 | 一汽解放汽车有限公司 | Low-temperature cold start adaptive gas diffusion layer, preparation method thereof and fuel cell |
| CN114725398A (en) * | 2022-04-28 | 2022-07-08 | 一汽解放汽车有限公司 | High-pressure-resistant long-life gas diffusion layer, preparation method and fuel cell |
| CN114934290A (en) * | 2022-03-09 | 2022-08-23 | 氢克新能源技术(上海)有限公司 | Gas diffusion layer and processing technology thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105119007A (en) * | 2015-08-05 | 2015-12-02 | 黄河科技学院 | Preparing method for corrosion-resistant gas diffusion layer of fuel cell |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105119007A (en) * | 2015-08-05 | 2015-12-02 | 黄河科技学院 | Preparing method for corrosion-resistant gas diffusion layer of fuel cell |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993265A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Gas diffusion layer for fuel cell and preparation method thereof |
| CN114934290A (en) * | 2022-03-09 | 2022-08-23 | 氢克新能源技术(上海)有限公司 | Gas diffusion layer and processing technology thereof |
| CN114507873A (en) * | 2022-03-30 | 2022-05-17 | 北京化工大学 | Hydrogen diffusion anode and preparation method and application thereof |
| CN114725399A (en) * | 2022-04-28 | 2022-07-08 | 一汽解放汽车有限公司 | Low-temperature cold start adaptive gas diffusion layer, preparation method thereof and fuel cell |
| CN114725398A (en) * | 2022-04-28 | 2022-07-08 | 一汽解放汽车有限公司 | High-pressure-resistant long-life gas diffusion layer, preparation method and fuel cell |
| CN114725398B (en) * | 2022-04-28 | 2023-10-13 | 一汽解放汽车有限公司 | High-pressure-resistant long-life gas diffusion layer, preparation method and fuel cell |
| CN114725399B (en) * | 2022-04-28 | 2023-10-17 | 一汽解放汽车有限公司 | Low-temperature cold start adaptive gas diffusion layer, preparation method thereof and fuel cell |
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