CN110614742A - Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof - Google Patents
Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof Download PDFInfo
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- CN110614742A CN110614742A CN201910898689.7A CN201910898689A CN110614742A CN 110614742 A CN110614742 A CN 110614742A CN 201910898689 A CN201910898689 A CN 201910898689A CN 110614742 A CN110614742 A CN 110614742A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/02—Moulding by agglomerating
- B29C67/04—Sintering
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0092—Other properties hydrophilic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0093—Other properties hydrophobic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3468—Batteries, accumulators or fuel cells
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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
Abstract
The invention relates to the field of proton exchange membrane fuel cells, and discloses a microporous layer with alternately distributed surface hydrophilic and hydrophobic characteristics and a preparation method thereof. The preparation steps are as follows: preparing hydrophobic carbon slurry, preparing hydrophilic carbon slurry, coating and sintering the hydrophobic carbon slurry, and coating and sintering the hydrophilic carbon slurry. Compared with the prior art, the product of the invention can realize effective water and gas management in the proton exchange membrane fuel cell, form distribution with different wetting characteristics in the microporous layer, control the distribution of water in the microporous layer and the gas diffusion layer, form an effective oxygen diffusion channel and a water drainage channel, and improve the running performance and the low-temperature starting performance of the fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties and a preparation method thereof.
Background
Fuel cells are increasingly widely used in many fields due to their advantages such as high efficiency and no pollution. Among them, the most common proton exchange membrane fuel cell, which uses hydrogen and oxygen as reaction gas, has the advantages of high power generation efficiency, no chemical hazard, only producing pure water and heat after power generation, environmental friendliness and the like, which cannot be achieved by other power sources at present. The proton exchange membrane fuel cell is composed of a proton exchange membrane, a catalyst layer, a microporous layer, a gas diffusion layer, a bipolar plate (the surface of which is provided with a flow channel), a collector plate and the like in sequence from inside to outside, and each component of a cathode and an anode of the cell is symmetrically distributed relative to the proton exchange membrane. When the anode and the cathode of the cell are respectively fed with hydrogen and air, the cell generates electrochemical reaction and generates water in the cathode catalyst layer, and the generated water is discharged out of the cell through the cathode microporous layer, the gas diffusion layer and the flow channel.
When the proton exchange membrane fuel cell works, the control of reasonable water distribution in the proton exchange membrane fuel cell is one of the important conditions for high-efficiency and stable work of the cell. The reasonable water distribution can ensure the conductivity of the proton exchange membrane, ensure that the water in the battery can be smoothly discharged and simultaneously ensure that reaction gas can smoothly reach the catalyst layer, avoid the occurrence of flooding phenomenon and effectively carry out the electrochemical reaction. At the same time, reasonable water distribution is also of great importance to improve the ability of fuel cells to start at low temperatures.
However, water generated by the reaction of the fuel cell is uniformly distributed on the surface of the catalyst layer, and if the generated water cannot be discharged out of the cell through the microporous layer, the gas diffusion layer and the flow channel in time, a 'flooding' phenomenon is caused in the cell, so that a path for the reaction gas to enter the catalyst layer is blocked, and the electrochemical reaction efficiency is reduced or even stopped; in addition, when the cell is operated in a low-temperature environment, once water produced by the reaction freezes in the cell, the diffusion of the reaction gas into the catalytic layer is also inhibited. In the current domestic and foreign research, although some solutions are provided for the 'water flooding' problem and the low-temperature starting problem of the fuel cell, no good solution is provided for the water distribution problem in the plane direction inside the cell, and the blocking phenomenon still exists in the high-current density or low-temperature environment.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties and a preparation method thereof. The microporous layer with the surface alternately distributed hydrophilic and hydrophobic properties can form distribution with different wetting properties in the microporous layer; due to the existence of capillary pressure between water and different materials, the distribution mode of the microporous layer can form capillary pressure difference between the different materials, so that water generated by reaction of the catalyst layer directly enters the hydrophilic microporous layer, and a gas diffusion channel is left in the hydrophobic microporous layer, so that the distribution of the water in the microporous layer and the gas diffusion layer is controlled, an effective oxygen diffusion channel and a water drainage channel are formed, the phenomenon that the gas diffusion channel is blocked is avoided, and the running performance and the low-temperature starting performance of the fuel cell are improved.
The technical scheme adopted by the invention is as follows: the microporous layer with the surface hydrophilic and hydrophobic characteristics alternately distributed comprises a substrate layer, wherein a hydrophobic microporous layer and a hydrophilic microporous layer are arranged on the substrate layer, the hydrophobic microporous layer and the hydrophilic microporous layer are in a strip shape with the width of W and are alternately distributed in the plane direction, and the thickness of the hydrophobic microporous layer is equal to that of the hydrophilic microporous layer.
The invention also provides a die for preparing the microporous layers with the surface hydrophilic and hydrophobic characteristics alternately distributed, the die is made of a stainless steel plate material, the thickness of the stainless steel plate material is equal to that of the microporous layers, the stainless steel plate material is provided with a plurality of strip-shaped grooves which are hollowed and arranged in parallel, and the width of each strip-shaped groove and the distance between every two adjacent strip-shaped grooves are W.
The preparation method of the microporous layer with the surface hydrophilic and hydrophobic characteristics alternately distributed comprises the following steps:
step one, preparation of hydrophobic carbon slurry: mixing carbon black, a hydrophobic additive, an organic solvent and deionized water according to a certain proportion, stirring and mixing uniformly, and then dispersing by using an ultrasonic cleaner to prepare hydrophobic carbon slurry;
step two, preparation of hydrophilic carbon slurry: mixing carbon black, a hydrophilic additive, an organic solvent and deionized water according to a certain proportion, stirring and mixing uniformly, and then dispersing by using an ultrasonic cleaner to prepare hydrophilic carbon slurry;
step three, coating and sintering of hydrophobic carbon slurry: covering a mold according to claim 2 on a carbon paper with a carbon paper as a substrate layer, spraying a layer of hydrophobic additive with a spray pen, then uniformly coating the hydrophobic carbon paste prepared in the step one on the carbon paper, wherein the thickness of the hydrophobic carbon paste is equal to that of the mold, removing the mold, and sintering the carbon paper covered with the hydrophobic carbon paste stripes in an environment at 375 ℃ to form a hydrophobic microporous layer;
step four, coating and sintering hydrophilic carbon slurry: covering the mold on the carbon paper with the hydrophobic microporous layer after the treatment of the third step, wherein the strip-shaped groove of the mold is opposite to the region without the hydrophobic microporous layer, firstly mixing and stirring the hydrophilic additive and the organic solvent until the hydrophilic additive is fully dissolved to obtain a solution A, then spraying the solution A on the carbon paper with the hydrophobic microporous layer by using a spray pen, then uniformly coating the hydrophilic carbon pulp prepared in the second step on the carbon paper with the hydrophobic microporous layer, wherein the thickness of the hydrophilic carbon pulp is equal to the sum of the thicknesses of the mold and the hydrophobic microporous layer, removing the mold, and sintering the carbon paper covered with the hydrophilic carbon pulp stripes in an environment at 300 ℃ to form the hydrophilic microporous layer;
and fifthly, scraping off the part of the hydrophilic microporous layer higher than the hydrophobic microporous layer along the direction of the stripes of the hydrophilic microporous layer by using a blade to ensure that the thickness of the whole microporous layer is uniform, thus obtaining the microporous layer with alternately distributed surface hydrophilic and hydrophobic characteristics.
Further, the invention is regarded as a preparation method, wherein the carbon paper is provided with hydrophobic areas and hydrophilic areas which are alternately distributed in parallel, so that the substrate layer is a gas diffusion layer with the hydrophilic and hydrophobic characteristics alternately distributed in the plane direction.
In the second step of the preparation method, the mass volume ratio of the carbon black, the hydrophobic additive, the organic solvent and the deionized water is 1g: 0.1-0.5 g:10mL:3 mL; in the third step, the mass volume ratio of the carbon black, the hydrophilic additive, the organic solvent and the deionized water is 1g: 0.1-0.5 g:10mL:3mL.
The carbon Black is one of Vulcan XC-72, acetylene Black, Black Pearl and Ketjen Black.
The hydrophobic additive is polytetrafluoroethylene concentrated dispersion.
The hydrophilic additive is one of polyamide resin and polyvinyl alcohol.
The organic solvent is one or two of ethanol, isopropanol and glycol.
And in the coating process of the hydrophobic carbon slurry and the hydrophilic carbon slurry, a blade coating or spraying mode is used.
The microporous layer with the hydrophilic and hydrophobic characteristics alternately distributed in the plane direction can be applied to single cells of a proton exchange membrane fuel cell and can also be applied to a proton exchange membrane fuel cell stack. When the electrochemical reaction of the battery occurs, water generated on the surface of the cathode catalytic layer can directly enter the hydrophilic microporous layer, and a small part of water entering the hydrophobic microporous layer can also be discharged to the hydrophilic microporous layer under the action of capillary pressure, so that the interior of the hydrophobic microporous layer is kept in an anhydrous state, and a gas diffusion channel is left in the hydrophobic microporous layer.
Compared with the prior art, the invention has the beneficial effects that:
(1) the whole preparation process is simple to operate, and the required materials and the required dies are cheap and easy to obtain.
(2) The mode of alternately distributing hydrophilic and hydrophobic characteristics is formed in the plane direction of the microporous layer, so that water generated by the reaction of the fuel cell can be effectively managed, and the gas diffusion channel can be reserved while the cell discharges the water, thereby avoiding the flooding phenomenon of the cell during operation, improving the operation performance of the fuel cell and improving the low-temperature starting capability of the cell.
Drawings
FIG. 1 is a schematic diagram of a microporous layer with alternating hydrophilic and hydrophobic properties on the surface according to the present invention;
FIG. 2 is a schematic view of a microporous layer with alternate hydrophilic and hydrophobic properties on the surface thereof combined with a gas diffusion layer with alternate hydrophilic and hydrophobic properties in the planar direction according to the present invention;
FIG. 3 is a schematic diagram of the movement of water within a microporous layer with alternating surface hydropathic and hydrophobic properties according to the present invention;
fig. 4 is a schematic view of a mold used for coating hydrophilic carbon slurry and hydrophobic carbon slurry according to the present invention.
The reference numbers in the figures illustrate: 1-hydrophilic microporous layer, 2-hydrophobic microporous layer, 3-gas diffusion layer, 4-water moving path, 5-water, 6-gas diffusion path, 7-catalytic layer, 8-hydrophobic region, and 9-hydrophilic region.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention.
As shown in FIG. 1, the microporous layer with alternately distributed surface hydrophilic and hydrophobic characteristics provided by the invention comprises a substrate layer 3, wherein a hydrophobic microporous layer 2 and a hydrophilic microporous layer 1 are arranged on the substrate layer 3, the hydrophobic microporous layer 2 and the hydrophilic microporous layer 1 are in a strip shape with the width W and are alternately distributed in the plane direction, and the thickness of the hydrophobic microporous layer 2 is equal to that of the hydrophilic microporous layer 1.
The substrate layer 3 in the present invention may be a common carbon paper with uniform hydrophilic and hydrophobic properties, or a carbon paper with alternate hydrophilic and hydrophobic properties in the plane direction, as shown in fig. 2, the carbon paper with alternate hydrophilic and hydrophobic properties in the plane direction is a carbon paper (substrate layer 3) with an entire area provided with hydrophobic regions 8 and hydrophilic regions 9 alternately distributed in parallel, so that the substrate layer 3 forms a gas diffusion layer with alternate hydrophilic and hydrophobic properties in the plane direction.
As shown in fig. 3, the microporous layers with alternately distributed hydrophilic and hydrophobic surfaces according to the present invention can be applied to single cells of a pem fuel cell, and can also be applied to a pem fuel cell stack. The microporous layer with the surface hydrophilic and hydrophobic characteristics alternately distributed can realize effective water and gas management in the proton exchange membrane fuel cell, a distribution of different wetting characteristics is formed in the microporous layer, which, due to the capillary pressure between the water 5 and the different materials, the distribution mode of the microporous layer can form capillary pressure difference between different materials, so that water 5 generated by the reaction of the catalytic layer 7 directly enters the hydrophilic microporous layer 1, leaving gas diffusion channels in the hydrophobic microporous layer 2, gas diffusion paths are shown by reference numeral 6 in the figure, thereby controlling the distribution of water in the gas diffusion layer formed by the microporous layer and the substrate layer 3, forming effective oxygen diffusion channels and water drainage channels, the arrows 4 in the figure show the water moving route, so that the phenomenon that the gas diffusion channel is blocked is avoided, and the running performance and the low-temperature starting performance of the fuel cell are improved.
The die used in the preparation method of the invention is shown in figure 4, the die is a stainless steel plate material, the thickness of the stainless steel plate material is equal to the thickness of the microporous layer, the stainless steel plate material is provided with a plurality of strip-shaped grooves which are hollowed out and arranged in parallel, and the width of each strip-shaped groove and the distance between every two adjacent strip-shaped grooves are W. In this example, W is 1mm, and the thickness of the mold is 0.05 mm.
Example 1
Mixing 1g of acetylene black, 0.2g of PTFE concentrated dispersion liquid, 10mL of isopropanol and 3mL of deionized water in a beaker in sequence, uniformly stirring by using a glass rod, and then dispersing by using an ultrasonic cleaner to prepare hydrophobic carbon slurry;
and step two, mixing 0.2g of soluble polyamide resin and 10mL of ethanol in another clean beaker, stirring until the polyamide resin is fully dissolved, adding 1g of acetylene black and 3mL of deionized water into the beaker, stirring and mixing uniformly by using a glass rod, and dispersing by using an ultrasonic cleaner to prepare the hydrophilic carbon slurry.
Step three, taking a piece of Toray 060 carbon paper, covering a mould on the carbon paper, wherein the area of the mould is equal to that of the carbon paper; spraying a layer of PTFE concentrated dispersion on the carbon paper by using a spray pen, then uniformly coating the hydrophobic carbon paste on the carbon paper by using a scraper, wherein the thickness of the hydrophobic carbon paste is equal to that of a mould, removing the mould, and sintering the carbon paper covered with the hydrophobic carbon paste stripes in a high-temperature blast drying box at 375 ℃ to form a hydrophobic microporous layer;
step four, covering a mould on the carbon paper containing the hydrophobic microporous layer after the treatment of the step, wherein the groove of the mould is opposite to the area without the hydrophobic microporous layer, then evenly coating the hydrophilic carbon pulp on the carbon paper containing the hydrophobic microporous layer by a scraper, wherein the thickness of the hydrophilic carbon pulp is equal to the sum of the thicknesses of the mould and the hydrophobic microporous layer, removing the mould, and sintering the carbon paper covered with the hydrophilic carbon pulp stripes in a high-temperature air drying box at 300 ℃ to form the hydrophilic microporous layer.
And fifthly, scraping off the part of the hydrophilic microporous layer higher than the hydrophobic microporous layer along the direction of the stripes of the hydrophilic microporous layer by using a blade to ensure that the thickness of the whole microporous layer is uniform, thus preparing the microporous layer with the surface hydrophilic and hydrophobic characteristics alternately distributed.
Example 2
Mixing acetylene black, PTFE concentrated dispersion liquid, isopropanol and deionized water in a beaker in sequence, wherein the content of the isopropanol and the content of the deionized water are far higher than that of the acetylene black and the like, uniformly stirring by using a glass rod, and then dispersing by using an ultrasonic cleaner to prepare hydrophobic carbon slurry; mixing soluble polyamide resin and ethanol in another clean beaker, stirring until the polyamide resin is fully dissolved, adding acetylene black and deionized water into the beaker, wherein the content of the ethanol and the deionized water is far higher than that of the acetylene black, stirring and mixing uniformly by using a glass rod, and dispersing by using an ultrasonic cleaner to prepare the hydrophilic carbon slurry.
Covering a piece of Toray 060 carbon paper with a mold, wherein the area of the mold is equal to that of the carbon paper, and through grooves are distributed in parallel on the surface of the mold; spraying a layer of PTFE concentrated dispersion on the carbon paper by using a spray pen, then uniformly spraying the hydrophobic carbon paste on the carbon paper by using the spray pen, wherein the thickness of the hydrophobic carbon paste is equal to that of the mould, removing the mould, and sintering the carbon paper covered with the hydrophobic carbon paste stripes in a high-temperature air-blast drying box at 375 ℃ to form a hydrophobic microporous layer; covering a mould on the carbon paper containing the hydrophobic microporous layer after the treatment in the step, wherein the groove of the mould is opposite to the region without the hydrophobic microporous layer, then uniformly spraying the hydrophilic carbon slurry on the carbon paper containing the hydrophobic microporous layer by using a spray pen, wherein the thickness of the hydrophilic carbon slurry is equal to the sum of the thicknesses of the mould and the hydrophobic microporous layer, removing the mould, and sintering the carbon paper covered with the hydrophilic carbon slurry stripes in a high-temperature air drying box at 300 ℃ to form the hydrophilic microporous layer.
And scraping off the part of the hydrophilic microporous layer higher than the hydrophobic microporous layer along the direction of the stripes of the hydrophilic microporous layer by using a blade to ensure that the thickness of the whole microporous layer is uniform, thus preparing the microporous layer with alternately distributed hydrophilic and hydrophobic characteristics on the surface.
Example 3
Toray 060 carbon paper was placed on a device that could create a negative pressure on the back of the carbon paper; obliquely inserting a glass capillary into the PTFE concentrated dispersion liquid, and sucking the PTFE solution into the capillary by using the capillary force between the capillary and the PTFE solution; covering a mold on the carbon paper, wherein the area of the mold is equal to that of the carbon paper, and through grooves are distributed in parallel on the surface of the mold; then coating the PTFE solution in the capillary on the carbon paper along the direction of the groove of the die; the coating is repeated for 2 times or 3 times, so that the PTFE emulsion can completely permeate the carbon paper to form a hydrophobic area 8, and other areas which are not coated with the PTFE emulsion are hydrophilic areas 9, namely, the hydrophobic area 8 and the hydrophilic area 9 which are alternately distributed in parallel are formed on the surface of the carbon paper, so that the gas diffusion layer with the substrate layer 3 which is alternately distributed in the hydrophilic and hydrophobic characteristics in the plane direction is prepared.
Hydrophobic carbon slurry and hydrophilic carbon slurry were prepared according to the method of example 1.
Covering a mould on the gas diffusion layers with the hydrophilic and hydrophobic characteristics alternately distributed in the plane direction, enabling the groove of the mould to be opposite to the PTFE-treated area, uniformly coating the hydrophobic carbon slurry on carbon paper by using a scraper, wherein the thickness of the hydrophobic carbon slurry is equal to that of the mould, removing the mould, and sintering the carbon paper covered with the hydrophobic carbon slurry stripes in a high-temperature air drying box at 375 ℃ to form a hydrophobic microporous layer; covering a mould on the carbon paper containing the hydrophobic microporous layer after the treatment in the step, wherein the groove of the mould is opposite to the region without the hydrophobic microporous layer, uniformly coating the hydrophilic carbon pulp on the carbon paper containing the hydrophobic microporous layer by a scraper, wherein the thickness of the hydrophilic carbon pulp is equal to the sum of the thicknesses of the mould and the hydrophobic microporous layer, removing the mould, and sintering the carbon paper covered with the hydrophilic carbon pulp stripes in a high-temperature forced air drying box at 300 ℃ to form the hydrophilic microporous layer.
And scraping off the part of the hydrophilic microporous layer higher than the hydrophobic microporous layer along the direction of the stripes of the hydrophilic microporous layer by using a blade to ensure that the thickness of the whole microporous layer is uniform, thus preparing the microporous layer with alternately distributed hydrophilic and hydrophobic characteristics on the surface.
Example 4
Gas diffusion layers having hydrophilic and hydrophobic properties alternately distributed in the plane direction were prepared according to the method of example 3, and then hydrophobic carbon slurry and hydrophilic carbon slurry were prepared according to the method of example 2.
Covering a mould on the gas diffusion layers with the hydrophilic and hydrophobic characteristics alternately distributed in the plane direction, enabling the grooves of the mould to be opposite to the PTFE-treated area, then uniformly spraying the hydrophobic carbon slurry on carbon paper by using a spray pen, wherein the thickness of the hydrophobic carbon slurry is equal to that of the mould, removing the mould, and sintering the carbon paper covered with the hydrophobic carbon slurry stripes in a high-temperature air drying box at 375 ℃ to form a hydrophobic microporous layer; covering a mould on the carbon paper containing the hydrophobic microporous layer after the treatment in the step, wherein the groove of the mould is opposite to the region without the hydrophobic microporous layer, then uniformly spraying the hydrophilic carbon slurry on the carbon paper containing the hydrophobic microporous layer by using a spray pen, wherein the thickness of the hydrophilic carbon slurry is equal to the sum of the thicknesses of the mould and the hydrophobic microporous layer, removing the mould, and sintering the carbon paper covered with the hydrophilic carbon slurry stripes in a high-temperature air drying box at 300 ℃ to form the hydrophilic microporous layer.
And scraping off the part of the hydrophilic microporous layer higher than the hydrophobic microporous layer along the direction of the stripes of the hydrophilic microporous layer by using a blade to ensure that the thickness of the whole microporous layer is uniform, thus preparing the microporous layer with alternately distributed hydrophilic and hydrophobic characteristics on the surface.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (10)
1. A microporous layer with alternately distributed surface hydrophilic and hydrophobic characteristics is characterized in that: the microporous membrane comprises a substrate layer (3), wherein a hydrophobic microporous layer (2) and a hydrophilic microporous layer (1) are arranged on the substrate layer (3), the hydrophobic microporous layer (2) and the hydrophilic microporous layer (1) are strips with the width of W and are alternately distributed in the plane direction, and the thicknesses of the hydrophobic microporous layer (2) and the hydrophilic microporous layer (1) are equal.
2. The mold is characterized in that the mold is made of a stainless steel plate material, the thickness of the stainless steel plate material is equal to that of the microporous layer, the stainless steel plate material is provided with a plurality of strip-shaped grooves which are hollowed out and arranged in parallel, and the width of each strip-shaped groove and the distance between every two adjacent strip-shaped grooves are W.
3. The method of claim 1, wherein the microporous layer with an alternating distribution of hydrophilic and hydrophobic properties on the surface is prepared by: the method comprises the following steps:
step one, preparation of hydrophobic carbon slurry: mixing carbon black, a hydrophobic additive, an organic solvent and deionized water according to a certain proportion, stirring and mixing uniformly, and then dispersing by using an ultrasonic cleaner to prepare hydrophobic carbon slurry;
step two, preparation of hydrophilic carbon slurry: mixing carbon black, a hydrophilic additive, an organic solvent and deionized water according to a certain proportion, stirring and mixing uniformly, and then dispersing by using an ultrasonic cleaner to prepare hydrophilic carbon slurry;
step three, coating and sintering of hydrophobic carbon slurry: covering a carbon paper as a substrate layer with the mold as claimed in claim 2, spraying a layer of hydrophobic additive with a spray pen, then uniformly coating the hydrophobic carbon paste prepared in the step one on the carbon paper, wherein the thickness of the hydrophobic carbon paste is equal to that of the mold, removing the mold, and sintering the carbon paper covered with the hydrophobic carbon paste stripes in an environment at 375 ℃ to form a hydrophobic microporous layer;
step four, coating and sintering hydrophilic carbon slurry: covering the mold on the carbon paper with the hydrophobic microporous layer after the treatment of the third step, wherein the strip-shaped groove of the mold is opposite to the region without the hydrophobic microporous layer, firstly mixing and stirring the hydrophilic additive and the organic solvent until the hydrophilic additive is fully dissolved to obtain a solution A, then spraying the solution A on the carbon paper with the hydrophobic microporous layer by using a spray pen, then uniformly coating the hydrophilic carbon pulp prepared in the second step on the carbon paper with the hydrophobic microporous layer, wherein the thickness of the hydrophilic carbon pulp is equal to the sum of the thicknesses of the mold and the hydrophobic microporous layer, removing the mold, and sintering the carbon paper covered with the hydrophilic carbon pulp stripes in an environment at 300 ℃ to form the hydrophilic microporous layer;
and fifthly, scraping off the part of the hydrophilic microporous layer higher than the hydrophobic microporous layer along the direction of the stripes of the hydrophilic microporous layer by using a blade to ensure that the thickness of the whole microporous layer is uniform, thus obtaining the microporous layer with alternately distributed surface hydrophilic and hydrophobic characteristics.
4. The method for preparing a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties according to claim 3, wherein the method comprises the following steps: the carbon paper is provided with hydrophobic areas (8) and hydrophilic areas (9) which are alternately distributed in parallel, so that the substrate layer (3) is a gas diffusion layer with the hydrophilic and hydrophobic characteristics alternately distributed in the plane direction.
5. The method for preparing a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties according to claim 3, wherein the method comprises the following steps: in the second step, the mass volume ratio of the carbon black, the hydrophobic additive, the organic solvent and the deionized water is 1g: 0.1-0.5 g:10mL:3 mL; in the third step, the mass-volume ratio of the carbon black, the hydrophilic additive, the organic solvent and the deionized water is 1g: 0.1-0.5 g:10mL:3mL.
6. The method for preparing a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties according to claim 3, wherein the method comprises the following steps: the carbon Black is one of Vulcan XC-72, acetylene Black, Black Pearl and Ketjen Black.
7. The method for preparing a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties according to claim 3, wherein the method comprises the following steps: the hydrophobic additive is polytetrafluoroethylene concentrated dispersion; the hydrophilic additive is one of polyamide resin and polyvinyl alcohol.
8. The method for preparing a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties according to claim 3, wherein the method comprises the following steps: the organic solvent is one or two of ethanol, isopropanol and glycol.
9. The method for preparing a microporous layer with alternately distributed surface hydrophilic and hydrophobic properties according to claim 3, wherein the method comprises the following steps: and in the coating process of the hydrophobic carbon slurry and the hydrophilic carbon slurry, a blade coating or spraying mode is used.
10. Use of a microporous layer with alternating hydrophilic and hydrophobic surface properties according to claim 1, wherein: the microporous layer is used for preparing a proton exchange membrane fuel cell.
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| CN201910898689.7A CN110614742A (en) | 2019-09-23 | 2019-09-23 | Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof |
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| CN201910898689.7A CN110614742A (en) | 2019-09-23 | 2019-09-23 | Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof |
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| CN201910898689.7A Pending CN110614742A (en) | 2019-09-23 | 2019-09-23 | Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof |
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| CN113140768A (en) * | 2021-04-12 | 2021-07-20 | 上海交通大学 | Cathode side structure of integrated reversible fuel cell membrane electrode |
| CN113948719A (en) * | 2021-08-30 | 2022-01-18 | 东风汽车集团股份有限公司 | Gas diffusion layer with high air permeability and preparation method thereof |
| CN114512682A (en) * | 2022-02-21 | 2022-05-17 | 浙江高成绿能科技有限公司 | Carbon-supported platinum catalyst, fuel cell membrane electrode and preparation method thereof |
| CN114744215A (en) * | 2022-03-15 | 2022-07-12 | 昀际科技(上海)有限责任公司 | Fuel cell gas diffusion layer with novel structure and preparation method |
| WO2022222220A1 (en) * | 2021-04-21 | 2022-10-27 | 华东理工大学 | Gas diffusion layer, preparation method therefor and application thereof, and fuel cell |
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