CN114149787A - Anti-ice hydrophobic agent for fuel cell, microporous layer slurry and GDL and preparation method thereof - Google Patents
Anti-ice hydrophobic agent for fuel cell, microporous layer slurry and GDL and preparation method thereof Download PDFInfo
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- CN114149787A CN114149787A CN202111177399.7A CN202111177399A CN114149787A CN 114149787 A CN114149787 A CN 114149787A CN 202111177399 A CN202111177399 A CN 202111177399A CN 114149787 A CN114149787 A CN 114149787A
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 53
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- 239000002904 solvent Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 27
- 239000006258 conductive agent Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- 239000002131 composite material Substances 0.000 abstract description 21
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- 230000003075 superhydrophobic effect Effects 0.000 abstract description 14
- 238000007710 freezing Methods 0.000 abstract description 5
- 230000008014 freezing Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- 239000011701 zinc Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 15
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- 235000012209 glucono delta-lactone Nutrition 0.000 description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 238000012935 Averaging Methods 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- 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
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention particularly relates to an anti-ice hydrophobic agent, microporous layer slurry and GDL for a fuel cell and a preparation method thereof, belonging to the technical field of fuel cells and comprising the following steps: adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution; reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder; drying the white powder to obtain an anti-icing hydrophobic agent; the composition of the anti-icing hydrophobic agent is Zn (NO)3)2With Co (NO)3)2The composite material is microspherical and has a structure with a super-smooth surface, so that the GDL has super-hydrophobic property, and meanwhile, the composite material is introducedThe freezing temperature of water can be significantly reduced, which will make the GDL ice resistant. Secondly, the introduction of the material can enable the GDL to be soaked without using a traditional hydrophobic agent in the preparation process, which can improve the preparation efficiency and the preparation cost. Finally, the anti-ice and super-hydrophobic GDL designed by the method has no obvious difference in conductivity with the commercial carbon paper, and other properties of the GDL are not reduced.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an anti-ice hydrophobic agent for a fuel cell, microporous layer slurry, GDL and a preparation method thereof.
Background
Energy safety is a crucial problem, and traditional chemical energy sources such as petroleum and coal are gradually exhausted, so that an alternative clean energy source is urgently needed. Hydrogen energy is a clean energy source that is considered to be a promising alternative to the above-mentioned chemical energy sources. A proton exchange membrane fuel cell is a device that generates electricity using hydrogen energy. It is composed of many membrane electrodes and bipolar plates. The membrane electrode is composed of a gas diffusion layer, a catalyst layer and a proton exchange membrane. The gas diffusion layer is a core component therein, and plays roles of gas conduction, water drainage and electric conduction. The bipolar plate can conduct gas required by reaction to the catalyst layer for reaction, can discharge water generated by the reaction to the outside of the membrane electrode, provides a high-efficiency reaction environment, and can conduct electrons generated by the reaction to the bipolar plate to form current so as to generate electricity. In conclusion, it plays an important role in the MEA.
In order to improve the diversity of the application of the proton exchange membrane power generation device, especially in the alpine region, it needs to have certain frost resistance. It is reported in the literature that water generated in a membrane electrode is prone to icing under low temperature conditions (Zhan Z G, Lyu Z Y, Huang Y, et al, research on PEMFC start-up at zero time and performance degree [ J ]. Journal of Wuhan University of Technology,2011,33(1): 151-. In addition, excessive water generated by the reaction not only increases the possibility of icing, but also causes flooding of the MEA, blocks the pores on the gas diffusion layer, and affects gas conduction. GDL failure will cause a dramatic decline in MEA performance, reducing the power generation efficiency of the PEMFC.
In the prior art, for example, chinese patent application CN200610047230.9 provides a method for improving the adaptability of a fuel cell to an environment below zero, which provides a method for vacuumizing a hydrogen cavity and an oxygen cavity of a fuel cell, removing water in a cell flow field and a gas diffusion layer, so that the cell can maintain integrity and sufficiently long life at a temperature below zero, and improve the freezing resistance of a PEMFC; however, the method needs to be provided with a vacuum pump, so that the cost is higher, and the matched vacuum pump increases the volume of the fuel cell and limits the application environment of the fuel cell.
Disclosure of Invention
The application aims to provide an anti-ice hydrophobic agent for a fuel cell, a microporous layer slurry and a GDL (gas diffusion layer) and a preparation method thereof, and solves the problem that additional vacuum equipment is required for increasing frost resistance at present.
The embodiment of the invention provides a preparation method of an anti-icing hydrophobic agent for a fuel cell, which comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
Optionally, said Zn (NO)3)2The mass ratio of the urea to the urea is 1: 1-5, said Zn (NO)3)2With said Co (NO)3)2The mass ratio of (A) to (B) is 1: 0.5-1; the Zn (NO)3)2And said NH4The mass ratio of F is 1: 0.2-1.
Optionally, the temperature of the hydrothermal reaction is 100-140 ℃.
Based on the same inventive concept, the embodiment of the invention also provides an anti-ice hydrophobic agent for the fuel cell, and the anti-ice hydrophobic agent is prepared by adopting the preparation method of the anti-ice hydrophobic agent for the fuel cell.
Based on the same inventive concept, the embodiment of the invention also provides a microporous layer slurry for a fuel cell, and the raw materials of the microporous layer slurry comprise: the preparation method of the anti-ice hydrophobic agent comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
Optionally, the raw materials of the microporous layer slurry further include: a conductive agent, a second solvent, and a binder;
the conductive agent comprises one of carbon nano tubes, graphene oxide and graphitized carbon;
the second solvent comprises absolute ethyl alcohol;
the binder comprises one of dopamine, KH-550, KH-540 and polyvinylidene fluoride.
Optionally, the mass ratio of the conductive agent to the second solvent is 1: 8-20; the mass ratio of the conductive agent to the anti-icing hydrophobic agent is 1: 0.5-1.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the microporous layer slurry for the fuel cell, which comprises the following steps:
dissolving a conductive agent in a second solvent to obtain a first solution;
mixing an adhesive with the first solution to obtain a second solution;
mixing an anti-icing hydrophobic agent with the second solution to obtain microporous layer slurry;
wherein the preparation method of the anti-icing hydrophobic agent comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the GDL for the fuel cell, which comprises the following steps:
coating the microporous layer slurry on a substrate layer, and then baking to obtain GDL; the raw materials of the microporous layer slurry comprise: a conductive agent, a second solvent, a binder and an anti-icing hydrophobic agent;
wherein the preparation method of the anti-icing hydrophobic agent comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
Based on the same inventive concept, the embodiment of the invention also provides a GDL for a fuel cell, and the GDL is prepared by adopting the method.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the embodiment of the invention provides a preparation method of an anti-ice hydrophobizing agent for a fuel cell, which comprises the following steps: adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution; reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder; drying the white powder to obtain an anti-icing hydrophobic agent; the composition of the anti-icing hydrophobic agent is Zn (NO)3)2With Co (NO)3)2The composite material is microspherical and has a structure with an ultra-smooth surface, so that the GDL has the super-hydrophobic property, and meanwhile, the introduction of the composite material can obviously reduce the icing temperature of water, which can enable the GDL to have the anti-icing property. Secondly, the introduction of the material can enable the GDL to be soaked without using a traditional hydrophobic agent in the preparation process, which can improve the preparation efficiency and the preparation cost. Most preferablyAnd then, the anti-ice and super-hydrophobic GDL designed by the method has no obvious difference in conductivity with the commercial carbon paper, and other properties of the GDL are not reduced.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
fig. 2 is a polarization graph of GDLs provided by various examples of the present invention and comparative examples.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Interpretation of terms: GDL: gas diffusion layer, MEA: membrane electrode, PEMFC: proton exchange membrane fuel cell, CCM: and a catalytic layer.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
the applicant finds in the course of the invention that: under the condition of low temperature, water generated in the membrane electrode is easy to freeze, and when the water turns into ice, the volume of the membrane electrode is increased, so that the gas diffusion layer is squeezed, and the gas diffusion layer is torn and damaged. In addition, excessive water generated by the reaction not only increases the possibility of icing, but also causes flooding of the MEA, blocks the pores on the gas diffusion layer, and affects gas conduction. GDL failure will cause a dramatic decline in MEA performance, reducing the power generation efficiency of the PEMFC. Therefore, it is important to design a GDL with super-hydrophobic properties that is resistant to icing.
In order to solve the problems, the applicant starts from the material level, redesigns the GDL without adding PEMFC supporting equipment, prepares the GDL which can resist ice and is super-hydrophobic, and ensures that the PEMFC can not be damaged under the severe cold condition and can be continuously used. And the redesigned GDL will not degrade in conductivity, gas transmission, etc.
According to an exemplary embodiment of the present invention, there is provided a method of manufacturing a GDL for a fuel cell, the method including:
s1, adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
s2, adding NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
s3, drying the white powder to obtain an anti-icing hydrophobic agent;
specifically, a certain amount of Zn (NO) is first weighed3)2Urea, Co (NO)3)2Dissolved in deionized water and stirred with a glass rod until completely dissolved. Adding a certain amount of NH into the solution4And F, continuing to use the glass rod until the glass rod is completely dissolved. Pouring the solution into a reaction kettle, placing the reaction kettle in an oven for reaction,after reacting for a certain time, taking the muffle furnace out of the oven, leaving white powder and drying to obtain ZnO/Co3O4Composite materials (i.e., anti-ice hydrophobing agents).
As an alternative embodiment, Zn (NO)3)2The mass ratio of the urea to the urea is 1: 1-5.
Control of Zn (NO)3)2The mass ratio of the urea to the urea is 1: 1-5 can be Zn (NO)3)2With Co (NO)3)2Sufficient nitrate was provided to ensure that they were sufficiently available for hydrothermal reaction. If the ratio is too large, nitrate radicals are introduced into the solution, side reactions are easy to occur, and byproducts are generated. If the ratio is too small, Zn (NO) cannot be obtained3)2With Co (NO)3)2Sufficient nitrate was provided, making hydrothermal reaction difficult to occur.
As an alternative embodiment, Zn (NO)3)2With Co (NO)3)2The mass ratio of (A) to (B) is 1:0.5-1,
control of Zn (NO)3)2With Co (NO)3)2The mass ratio of the cobalt oxide to the cobalt oxide is 1:0.5-1, so that the two materials can uniformly form a composite material, and if the ratio is too large, the cobalt oxide formed by hydrothermal reaction can be coated with zinc oxide, so that the performance of the composite material is reduced; if the ratio is too small, the zinc oxide coats the cobalt oxide, reducing the performance of the composite material.
As an alternative embodiment, Zn (NO)3)2And NH4Mass of F1: 0.2-1.
Control of Zn (NO)3)2And NH4Mass of F1: 0.2-1 can enable Zn2+Fully reacts with Co ions to carry out nucleation to obtain the microspherical composite material, thereby having the ice resistance and the super-hydrophobic performance. If the value is too large, Zn is present2+And the material and Co ions are excessively nucleated to form a strip-shaped composite material, the specific surface area of the material is reduced, the material is irregular in shape, and the ice resistance and the super-hydrophobic performance are poor. If the value is too small, Zn2+ and Co ions are hard to nucleate and form a microspherical shape; the irregular composite material has no ice resistance and super-hydrophobic performance.
As an alternative embodiment, the temperature of the oven should be set at 100-140 ℃.
At the temperature, the hydrothermal reaction can be fully carried out to obtain the target product. If the temperature is too low, hydrothermal conditions are insufficient, and the reaction cannot proceed. If the temperature is too high, side reactions occur, by-products are produced, and the yield is lowered.
S4, dissolving a conductive agent in a second solvent to obtain a first solution;
s5, adding an adhesive into the first solution to obtain a second solution;
s6, adding an anti-ice hydrophobic agent into the second solution to obtain microporous layer slurry;
specifically, a certain amount of conductive agent is dissolved in absolute ethyl alcohol, a certain amount of adhesive is added into the absolute ethyl alcohol, a certain amount of anti-icing and hydrophobic agent is added into the solution, and the solution is placed on a magnetic stirrer to be stirred, so that microporous layer slurry is obtained.
As an optional implementation manner, the conductive agent is one of carbon nanotubes, graphene oxide and graphitized carbon, and all the materials have excellent conductivity and are favorable for being compounded with the anti-ice and hydrophobic agent. It should be noted that the above list of conductive agents is only used to illustrate that the present invention can be implemented, and is not limited to the present invention.
As an alternative embodiment, the mass ratio of the conductive agent to the absolute ethyl alcohol is 1: 8-20.
The mass ratio of the conductive agent to the absolute ethyl alcohol is controlled to be 1:8-20, so that the conductive agent can be fully dissolved in the slurry. If the ratio is too large, the conductive agent will not be sufficiently dissolved; if the ratio is too small, the excess absolute ethyl alcohol will excessively dilute the conductive agent, not only increasing the cost, but also reducing the subsequent processing efficiency.
As an alternative embodiment, the binder is one of dopamine, KH-550, KH-540 and polyvinylidene fluoride. It should be noted that the above list of the adhesive is only for illustrating that the present invention can be implemented, and is not limited to the present invention, and in other embodiments, those skilled in the art can select other adhesives according to actual needs.
As an alternative embodiment, the mass ratio of the conductive agent to the anti-icing hydrophobic agent is 1: 0.5-1.
Controlling the mass ratio of the conductive agent to the anti-icing hydrophobic agent to be 1:0.5-1 enables the GDL obtained by subsequent processing to have ice resistance and conductivity. If the ratio is too large, the electrical conductivity of the GDL will be deteriorated, and if the ratio is too small, the anti-icing and hydrophobic properties of the GDL will be deteriorated
As an alternative embodiment, the magnetic stirrer is set at a rotation speed of 1000r/min for a stirring time of 60 min.
S7, coating the microporous layer slurry on a substrate layer, and then baking to obtain the GDL.
Specifically, the prepared microporous layer slurry is sprayed on a commercial substrate layer in a spraying mode, and then the sprayed product is baked in a muffle furnace to obtain the anti-icing and super-hydrophobic GDL.
The anti-ice hydrophobic agent for a fuel cell, the microporous layer slurry, and the GDL of the present application and the preparation method thereof will be described in detail below with reference to examples, comparative examples, and experimental data.
Example 1
A method of preparing a GDL for a fuel cell, the method comprising:
first, 1g of Zn (NO) is weighed3)21g of urea, 1g of Co (NO)3)2Dissolved in 20mL of deionized water and stirred using a glass rod until completely dissolved. 0.2g of NH4F was added to the solution and the glass rod was continued until complete dissolution. Pouring the solution into a reaction kettle, placing the reaction kettle in an oven for reaction, setting the temperature of the oven at 120 ℃, taking the muffle out of the oven after 4 hours of reaction, leaving white powder, drying, and obtaining ZnO/Co after drying3O4A composite material. Then 1g of graphene oxide is taken and poured into 8g of absolute ethyl alcohol, 0.2g of adhesive is added, stirring is carried out, and then 0.5g of ZnO/Co is added3O4Composite material, the mixed solution is stirred in magnetic forceStirring at the rotating speed of 1000r/min for 60min to obtain the microporous layer slurry.
And applying the obtained microporous layer slurry on a substrate layer by using a spraying process, and drying the substrate layer in a muffle furnace at the temperature of 300 ℃ for 2 hours.
Example 2
A method of preparing a GDL for a fuel cell, the method comprising:
first, 1g of Zn (NO) is weighed3)23g of urea, 0.8g of Co (NO)3)2Dissolved in 20mL of deionized water and stirred using a glass rod until completely dissolved. 0.4g of NH was added to the solution4And F, continuing to use the glass rod until the glass rod is completely dissolved. Pouring the solution into a reaction kettle, placing the reaction kettle in an oven for reaction, setting the temperature of the oven at 130 ℃, taking the muffle out of the oven after 4 hours of reaction, leaving white powder, drying, and obtaining ZnO/Co after drying3O4A composite material. Then 1g of graphene oxide is taken and poured into 15g of absolute ethyl alcohol, 0.4g of adhesive is added, stirring is carried out, and then 0.7g of ZnO/Co is added3O4And (3) stirring the mixed solution in magnetic stirring at the stirring speed of 1000r/min for 60min to obtain the microporous layer slurry.
And applying the obtained microporous layer slurry on a substrate layer by using a spraying process, and drying the substrate layer in a muffle furnace at the temperature of 300 ℃ for 2 hours.
Example 3
A method of preparing a GDL for a fuel cell, the method comprising:
first, 1g of Zn (NO) is weighed3)21g of urea, 0.5g of Co (NO)3)2Dissolved in 20mL of deionized water and stirred using a glass rod until completely dissolved. 0.8g of NH4F was added to the solution and the glass rod was continued until complete dissolution. Then pouring the solution into a reaction kettle, placing the reaction kettle in an oven for reaction, setting the temperature of the oven at 140 ℃, taking the muffle out of the oven after 4 hours of reaction, leaving white powder and drying,drying to obtain ZnO/Co3O4A composite material. Then 1g of graphene oxide is taken and poured into 20g of absolute ethyl alcohol, 0.6g of adhesive is added, stirring is carried out, and then 0.9g of ZnO/Co is added3O4And (3) stirring the mixed solution in magnetic stirring at the stirring speed of 1000r/min for 60min to obtain the microporous layer slurry.
And applying the obtained microporous layer slurry on a substrate layer by using a spraying process, and drying the substrate layer in a muffle furnace at the temperature of 300 ℃ for 2 hours.
Comparative example 1
A method of preparing a GDL for a fuel cell, the method comprising:
and (2) taking 1g of graphene oxide, pouring the graphene oxide into 20g of absolute ethyl alcohol, adding 0.6g of adhesive, stirring, then adding 1g of traditional hydrophobic agent polytetrafluoroethylene, and stirring the mixed solution by using a magnetic stirrer at the stirring speed of 1000r/min for 60min to obtain the microporous layer slurry.
And applying the obtained microporous layer slurry on a substrate layer by using a spraying process, and drying the substrate layer in a muffle furnace at the temperature of 300 ℃ for 2 hours.
Comparative example 2
Commercial carbon paper 36BB from SGL corporation is commercially available.
Examples of the experiments
The GDLs provided in examples 1-3 and comparative examples 1-2 were subjected to conductivity tests, and the results are shown in the following table:
as can be seen from the above table, comparative example 1, in which no anti-ice, hydrophobic agent was added, did not differ greatly from comparative example 2, which is a commercial carbon paper, in terms of conductivity, demonstrating the feasibility of the GDL preparation schemeThe electrical conductivity of GDL is not reduced obviously after adding the anti-ice and water repellent agent, and is above 91S/cm, probably because the composition of the anti-ice and water repellent agent is ZnO/Co3O4Composite material, which also has better electrical conductivity.
The GDLs provided in examples 1-3 and comparative examples 1-2 were subjected to contact angle tests, which specifically included: testing the GDL surface with a DSA100S contact angle tester at a 5 μ L drop size, and averaging 5 times for each sample; the results are shown in the following table:
from the above table, the contact angles of the examples are all larger than those of the comparative examples, showing superior hydrophobic properties. This is because the introduction of the anti-ice and hydrophobic agent enhances the super-hydrophobic property of the GDL, so that the GDL has stronger water drainage capability. Mechanistically, this is due to the ultra-smooth surface of ZnO/Co3O4The composite material can accelerate the flow of water, so that the water is easier to be led out.
The GDLs provided in examples 1-3 and comparative examples 1-2 were subjected to a freeze time test, which is defined as the time during which 50 μ L of water droplets completely freezes on a supercooled surface. The sample is placed in a low temperature sample cell after reaching thermodynamic equilibrium. Dropping 50 μ L of water droplets on the surface will shift the transparent center during freezing of the water droplets due to the difference in reflectivity between ice and water. Recording the time required for freezing when the shape of the water drop is constant; the results are shown in the following table:
from the above table, the comparative example without addition of anti-ice, hydrophobizing agent, with ice formation after more than 20 seconds under the experimental conditions, was supplemented with ZnO/Co3O4After the composite material is compounded, the icing event of the material is prolonged to more than 140s from more than 20 s, and the ice resistance of the material is remarkably improved.
The GDLs provided in examples 1-3 and comparative examples 1-2 were subjected to ice nucleation temperature tests, which specifically included: the sample is placed in a low-temperature sample cell, the initial temperature is-5 ℃, and the cooling rate is 0.001K/s. Adding 50 mu L of deionized water drops at the initial temperature, and observing the temperature near the sample when the sample is frozen; the results are shown in the following table:
from the above table, the ice nucleation temperature of the material is higher before adding the anti-ice and hydrophobic agent, ice is generated on the surface of the sample at-5 ℃, and ZnO/Co is added3O4After the composite material is compounded, the freezing temperature of the material is obviously reduced, and when the ambient temperature is reduced to be lower than minus 20 ℃, ice is generated on the surface of the GDL.
The GDLs provided in examples 1-3 and comparative examples 1-2 were subjected to membrane electrode performance tests, which specifically included: selecting the same CCM, matching with different samples, and placing the CCM on a single cell test bench for testing a polarization curve, wherein the model of the test bench is SCRIBNER 850 e; the results are shown in FIG. 2; as can be seen from fig. 2, in the MEAs assembled by using different GDLs, the power generation performance was not greatly different, and the examples were all superior to the comparative examples, which is probably because the water-repellent performance of the examples was more excellent, and the MEA was less prone to flooding, thereby making the power generation performance more excellent.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) the method provided by the embodiment of the invention starts from the material level, and redesigns the GDL without adding matching equipment of the PEMFC to prepare the ice-resistant and super-hydrophobic GDL, so that the PEMFC cannot be damaged under the severe cold condition and can be continuously used. The redesigned GDL does not reduce the performances of conductivity, gas transmission and the like;
(2) the method provided by the embodiment of the invention designs an anti-icing and hydrophobic agent, and the composition of the anti-icing and hydrophobic agent is Zn (NO)3)2With Co (NO)3)2The composite material is microspherical and has a structure with an ultra-smooth surface, so that the GDL has the super-hydrophobic property, and meanwhile, the introduction of the composite material can obviously reduce the icing temperature of water, which can enable the GDL to have the anti-icing property. Secondly, the introduction of the material can enable the GDL to be soaked without using a traditional hydrophobic agent in the preparation process, which can improve the preparation efficiency and the preparation cost. Finally, the anti-ice and super-hydrophobic GDL designed by the method has no obvious difference in conductivity with the commercial carbon paper, and other properties of the GDL are not reduced.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for producing an anti-ice hydrophobizing agent for a fuel cell, the method comprising:
adding Zn (NO)3)2Urea and Co (NO)3)2Is dissolved inA first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
2. The method for producing an anti-icing hydrophobic agent for a fuel cell according to claim 1, wherein said Zn (NO) is3)2The mass ratio of the urea to the urea is 1: 1-5, said Zn (NO)3)2With said Co (NO)3)2The mass ratio of (A) to (B) is 1: 0.5-1; the Zn (NO)3)2And said NH4The mass ratio of F is 1: 0.2-1.
3. The method for preparing an anti-icing hydrophobic agent for a fuel cell according to claim 1, wherein the temperature of the hydrothermal reaction is 100 ℃ to 140 ℃.
4. An anti-ice hydrophobizing agent for a fuel cell, characterized in that the anti-ice hydrophobizing agent is produced by the method for producing an anti-ice hydrophobizing agent for a fuel cell according to any one of claims 1 to 3.
5. A microporous layer slurry for a fuel cell, characterized in that a raw material of the microporous layer slurry comprises: the preparation method of the anti-ice hydrophobic agent comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
6. The microporous layer slurry for a fuel cell according to claim 5, wherein the raw material of the microporous layer slurry further comprises: a conductive agent, a second solvent, and a binder;
the conductive agent comprises one of carbon nano tubes, graphene oxide and graphitized carbon;
the second solvent comprises absolute ethyl alcohol;
the binder comprises one of dopamine, KH-550, KH-540 and polyvinylidene fluoride.
7. The microporous layer slurry for a fuel cell according to claim 5, wherein the mass ratio of the conductive agent to the second solvent is 1: 8-20; the mass ratio of the conductive agent to the anti-icing hydrophobic agent is 1: 0.5-1.
8. A method of preparing a microporous layer slurry for a fuel cell, the method comprising:
dissolving a conductive agent in a second solvent to obtain a first solution;
mixing an adhesive with the first solution to obtain a second solution;
mixing an anti-icing hydrophobic agent with the second solution to obtain microporous layer slurry;
wherein the preparation method of the anti-icing hydrophobic agent comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
9. A method of manufacturing a GDL for a fuel cell, comprising:
coating the microporous layer slurry on a substrate layer, and then baking to obtain GDL; the raw materials of the microporous layer slurry comprise: a conductive agent, a second solvent, a binder and an anti-icing hydrophobic agent;
wherein the preparation method of the anti-icing hydrophobic agent comprises the following steps:
adding Zn (NO)3)2Urea and Co (NO)3)2Dissolving in a first solvent to obtain a mixed solution;
reacting NH4F is dissolved in the mixed solution, and then hydrothermal reaction is carried out to obtain white powder;
and drying the white powder to obtain the anti-icing hydrophobic agent.
10. A GDL for a fuel cell, which is manufactured by the method of claim 9.
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