CN114551920A - Gas diffusion layer slurry and preparation method and application thereof - Google Patents
Gas diffusion layer slurry and preparation method and application thereof Download PDFInfo
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- CN114551920A CN114551920A CN202210156725.4A CN202210156725A CN114551920A CN 114551920 A CN114551920 A CN 114551920A CN 202210156725 A CN202210156725 A CN 202210156725A CN 114551920 A CN114551920 A CN 114551920A
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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
- H01M8/02—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- 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
- H01M8/0234—Carbonaceous material
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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 provides gas diffusion layer slurry and a preparation method and application thereof, wherein the gas diffusion layer slurry comprises a conductive agent, a hydrophobic agent, a pore-forming agent and a dispersing agent in a mass ratio of (2.3-4.8) to (2.5-3.5) to (0.35-0.55) to (0.25-0.75); the pore-forming agent comprises any one of ammonium chloride, ammonium bicarbonate, polyvinyl butyral or polyvinyl alcohol or the combination of at least two of the ammonium chloride, the ammonium bicarbonate, the polyvinyl butyral or the polyvinyl alcohol; the viscosity of the gas diffusion layer slurry was 2000-4500 cps. The gas diffusion layer slurry provided by the invention has the advantages of stable performance, uniform slurry, strong conductivity, small resistance and high porosity. Through the coupling addition of various conductive agents and the slurry formula design, the conductivity of the gas diffusion layer is greatly enhanced, and the superconducting performance requirement of the next generation gas diffusion layer is met. The production preparation method of the gas diffusion layer slurry provided by the invention has the advantages of low cost and simple process, and can meet the continuous production requirement.
Description
Technical Field
The invention belongs to the field of power generation of new energy fuel cells, and particularly relates to gas diffusion layer slurry and a preparation method and application thereof.
Background
With the further promotion of the national air pollution prevention and control force, the automobile industry has higher and higher requirements on low carbonization, and the fuel cell automobile can adopt clean hydrogen production routes such as wind energy and solar energy by virtue of the excellent hydrogen energy industry route, and hydrogen energy is effectively converted into power through an interface chemical reaction, so that zero carbon emission of the automobile is realized. Compared with the traditional fuel generator, the fuel cell partially converts Gibbs free energy in fuel chemical energy into electric energy, is not limited by Carnot cycle effect, and therefore has high efficiency. The hydrogen is used as fuel, and the product has no greenhouse gas emission and is eco-friendly. With the continuous acceleration of the industrialization process of fuel cells, the fuel cells are widely used in the fields of automobiles, ships and rail traffic, and the automobile field is more characterized in that the technical route of the fuel cells and the technical route of the power cells are combined to be used as a replacement strategy of the future automobile energy. The technical routes of fuel cells are laid out by domestic vehicles and enterprises in a dispute, and the development of key technologies of the domestic vehicles and enterprises is strived to break through.
The gas diffusion layer is used as a component in a fuel cell stack and is used for providing an effective transmission channel of reaction gas, product water and electrons, and meanwhile, the gas diffusion layer optimized by the microporous layer can effectively protect a catalyst layer and a proton membrane, reduce contact resistance and effectively block transmission and conduction of electrons. The gas diffusion layer with excellent performance meets the requirements of simple production process, continuous production, good air permeability and small resistance.
CN112563516A discloses a gas diffusion layer of an environment-friendly fuel cell and a preparation method thereof, relating to the field of fuel cells; the fuel cell gas diffusion layer comprises a solvent and gas diffusion layer slurry; the gas diffusion layer slurry comprises a carbon material, a functional material, polytetrafluoroethylene hydrophobic resin dispersion liquid, a water-soluble polymer dispersant, a thickening agent and a surfactant. The preparation method comprises the following steps: A. fully dispersing the gas diffusion layer slurry into a solvent; B. coating the slurry of the gas diffusion layer on a substrate supporting layer to obtain a microporous layer coating; C. two-stage roasting heat treatment is carried out. However, the method for preparing the gas diffusion layer has high cost and is not beneficial to large-scale production and application, and the uniformity of the prepared gas diffusion layer is poor.
CN112490454A discloses a method for preparing a gas diffusion layer of a hydrogen fuel cell, comprising the steps of: weighing chopped carbon fibers with a certain mass concentration, adding the chopped carbon fibers into dispersion liquid for high-speed shearing dispersion, then adding a certain amount of bonding liquid for continuing high-speed shearing dispersion, finally preparing high-dispersion carbon fiber slurry by stirring, grinding or ball milling, weighing a certain proportion of conductive carbon black, Polytetrafluoroethylene (PTFE) emulsion, water and isopropanol for fully stirring, then ultrasonically dispersing the mixed solution for 1-3 hours to prepare microporous layer slurry A, weighing a certain proportion of acetylene black, Polytetrafluoroethylene (PTFE) emulsion, water and isopropanol for fully stirring, and then ultrasonically dispersing the mixed solution for 1-3 hours to prepare microporous layer slurry B. The gas diffusion layer prepared by the method has poor conductivity and high resistance, and can affect the performance of the lithium battery.
CN109346731A discloses a method for preparing a gas diffusion layer for a proton exchange membrane fuel cell, the gas diffusion layer is composed of a support layer and a microporous layer, the microporous layer is prepared by electrostatic spinning, and the steps are as follows: (1) mixing conductive carbon black, a water repellent, a high molecular polymer and a dispersing agent, and performing ultrasonic or mechanical stirring to form uniform spinning solution; (2) pouring the spinning solution prepared in the step (1) into an injection tube for electrostatic spinning, covering a porous supporting layer on a negative electrode receiving plate, and collecting spinning fibers; (3) and (3) placing the spinning fiber and the porous support layer into an N-filled oven, and sintering for 0.5-2h at the temperature of 150-. However, the method needs heat treatment, which causes higher requirements on process equipment using the method and larger energy consumption, and does not meet the requirements on energy conservation and emission reduction.
Because the existing preparation methods of the gas diffusion layer slurry have certain defects, the development of a gas diffusion layer product which meets the continuous production requirement, has uniform slurry, simple preparation and strong conductivity and a preparation method thereof are very important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the gas diffusion layer slurry and the preparation method and application thereof, and the gas diffusion layer slurry has the advantages of stable performance, uniform slurry, strong conductivity, small resistance and high porosity. Through the coupling addition of various conductive agents and the slurry formula design, the conductivity of the gas diffusion layer is greatly enhanced, and the superconducting performance requirement of the next-generation gas diffusion layer is met. The production and preparation method of the gas diffusion layer slurry is simple, and can meet the continuous production requirement.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a gas diffusion layer slurry, which comprises a conductive agent, a hydrophobic agent, a pore-forming agent and a dispersing agent in a mass ratio of (2.3-4.8) to (2.5-3.5) to (0.35-0.55) to (0.25-0.75);
the pore-forming agent comprises any one or the combination of at least two of ammonium chloride, ammonium bicarbonate, polyvinyl butyral ester or polyvinyl alcohol;
the viscosity of the gas diffusion layer slurry was 2000-4500 cps.
The gas diffusion layer slurry provided by the invention has the advantages of stable performance, uniform slurry, strong conductivity, small resistance and high porosity. The electric conductivity of the gas diffusion layer is greatly enhanced by coupling addition of a plurality of conductive agents, addition of pore-forming agents and slurry formula design, and the superconducting performance requirement of the next generation gas diffusion layer is met.
The mass ratio of the conductive agent, the hydrophobic agent, the pore-forming agent and the dispersant in the present invention is (2.3-4.8): (2.5-3.5): (0.35-0.55): (0.25-0.75), and examples thereof include 2.3:2.5:0.35:0.25, 4.8:3.5:0.55:0.27, 2.3:3.5:0.35:0.75, 4.8:3.5:0.35:0.75, 2.5:3.2:0.43:0.58 and 4.6:2.7:0.48:0.42, but are not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
The pore-forming agent in the invention comprises any one or a combination of at least two of ammonium chloride, ammonium bicarbonate, polyvinyl butyral ester or polyvinyl alcohol, and can be, for example, a combination of ammonium chloride and ammonium bicarbonate, a combination of ammonium bicarbonate and polyvinyl butyral ester, polyvinyl butyral ester and polyvinyl alcohol, or a combination of ammonium chloride, ammonium bicarbonate and polyvinyl butyral ester.
The pore-forming agent can increase the transmission channel and porosity of the slurry of the gas diffusion layer and accelerate the transmission rate of gas and water.
The viscosity of the slurry for the gas diffusion layer in the present invention is 2000-4500cps, for example, 2000cps, 2500cps, 3000cps, 3500cps, 4000cps or 4500cps, but not limited to the values listed, and other values not listed in the range of values are also applicable; when the viscosity of the gas diffusion layer slurry is low, poor performance of the gas diffusion layer slurry is caused, and thus, the performance of the gas diffusion layer is deteriorated; when the viscosity of the gas diffusion layer slurry is high, the preparation cost of the gas diffusion layer slurry is high.
The total mass fraction of the conductive agent, hydrophobic agent, pore-forming agent and dispersant in the present invention is 2 to 5 wt%, for example, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt% or 5 wt%, based on the mass of the gas diffusion layer slurry, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the conductive agent includes any one or a combination of at least two of conductive carbon black, conductive graphite, ketjen black, carbon nanotubes or graphene, and may be, for example, a combination of conductive carbon black and conductive graphite, a combination of conductive graphite and ketjen black, a combination of ketjen black and carbon nanotubes, a combination of carbon nanotubes and graphene, or a combination of conductive carbon black, conductive graphite and ketjen black.
The coupling of the multiple conductive agents in the gas diffusion layer slurry can improve the performance of the gas diffusion slurry, so that the conductivity of the gas diffusion layer is improved.
Preferably, the conductive agent comprises any one or a combination of at least two of Vulcan P, Vulcan XC-72R, Printex L6, ketjen black EC-600JD, Reven 14, Ensaco350G, VGCF, CNTs, or graphene, for example, can be a combination of Vulcan XC P and Vulcan-72, Vulcan XC-72R and Printex L6, Printex L6 and ketjen black EC-600JD, ketjen black EC-600JD and Reven 14, Reven 14 and Ensaco350G, Ensaco350G and VGCF, VGCF and CNTs, CNTs and graphene, or VGCF 350G, Ensaco350, CNTs.
Preferably, the hydrophobic agent comprises any one or combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, polyvinyl alcohol, polyurethane adhesives with ethyl acetate as solvent, water dispersible polyurethane, aqueous acrylic acid or isocyanate, for example, combination of polytetrafluoroethylene and polyvinylidene fluoride, combination of polyvinylidene fluoride and polychlorotrifluoroethylene, combination of polychlorotrifluoroethylene and copolymers of tetrafluoroethylene and hexafluoropropylene, combination of polyvinyl alcohol and water dispersible polyurethane, or combination of polytetrafluoroethylene, polyvinylidene fluoride and polychlorotrifluoroethylene.
Preferably, the dispersant comprises a water soluble dispersant.
The water-soluble dispersing agent is used for facilitating the dispersion of the conductive agent, the hydrophobic agent and the pore-forming agent, so that the slurry of the gas diffusion layer is more fully mixed, the uniformity is improved, and the sedimentation is not easy to occur.
Preferably, the water-soluble dispersant includes any one of or a combination of at least two of a polydimethylguanidine salt, an alkyl glycoside, an alkylphenol ethoxylate, dodecyl dimethyl betaine, or polyethylene glycol, and may be, for example, a combination of a polydimethylguanidine salt and an alkyl glycoside, a combination of an alkyl glycoside and an alkylphenol ethoxylate, a combination of an alkylphenol ethoxylate and dodecyl dimethyl betaine, a combination of dodecyl dimethyl betaine and polyethylene glycol, or a combination of a polydimethylguanidine salt, an alkyl glycoside, and an alkylphenol ethoxylate.
Preferably, the solvent used for the gas diffusion layer slurry comprises water.
In a second aspect, the present invention provides a method for preparing a slurry for a gas diffusion layer, the method comprising:
(1) mixing an aqueous dispersant and a first solvent according to the formula amount to obtain a primary mixed solution;
(2) mixing a conductive agent, a pore-forming agent, a second solvent and the primary mixed liquid obtained in the step (1) according to the formula amount, and carrying out first stirring to obtain a secondary mixed liquid;
(3) mixing a hydrophobizing agent, a third solvent and the remixed liquid obtained in the step (2) according to the formula amount, and carrying out second stirring to obtain the gas diffusion layer slurry;
and based on the total mass M of the first solvent, the second solvent and the third solvent as 100%, the mass of the first solvent is 35-45% of the mass of M, the mass of the second solvent is 45-55% of M, and the balance is the third solvent.
The mass of the first solvent is 35 to 45% of the mass M, for example, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44% or 45% based on 100% of the total mass M of the first solvent, the second solvent and the third solvent, but is not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable; the second solvent has a mass of 45-55% of M, for example 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or 55%, but is not limited to the recited values, and other values not recited in the range of values are also applicable; the balance being the third solvent.
Preferably, the mixing of step (1) is performed under vacuum.
Preferably, the mixing of step (2) is performed under vacuum.
Preferably, the first stirring in step (2) has a shear rate of 800-.
The first stirring shear rate in step (2) of the present invention is 800-.
The stirring speed of the first stirring in step (2) of the present invention is 45 to 60r/min, and may be, for example, 45r/min, 47r/min, 49r/min, 50r/min, 52r/min, 54r/min, 56r/min, 58r/min or 60r/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The first stirring is carried out in a vacuum constant-speed stirring device, a stirring tool bit and a shearing tool bit are arranged in the vacuum constant-speed stirrer, the stirring tool bit provides stirring, and the shearing tool bit provides shearing.
The first stirring time in step (2) of the present invention is 8 to 12 hours, for example, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the viscosity of the remixed liquid in the step (2) is 1000-.
The invention limits the viscosity of the remixed liquid to be 1000-3200cps, when the viscosity of the remixed liquid is higher, the preparation cost of the gas diffusion layer slurry is too high, and the requirement of practical production practice is not met, and when the viscosity of the remixed liquid is lower, the viscosity of the gas diffusion layer slurry is too low, and the performance of the gas diffusion layer slurry is poor, so that the performance of the gas diffusion layer is poor.
Preferably, the mixing of step (3) is performed under vacuum.
Preferably, the shearing speed of the second stirring in the step (3) is 400-1500r/min, the stirring speed is 30-45r/min, and the time is 2-6 h.
The second stirring shear rate in step (3) of the present invention is 400-1500r/min, such as 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, 1100r/min, 1200r/min, 1400r/min or 1500r/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The stirring speed of the second stirring in step (3) of the present invention is 30 to 45r/min, and may be, for example, 30r/min, 32r/min, 34r/min, 36r/min, 38r/min, 40r/min, 42r/min, 44r/min or 45r/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The second stirring time in step (3) of the present invention is 2 to 6 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the preparation method further comprises the following steps:
(a) mixing a dispersant, a fourth solvent and gas diffusion layer slurry in vacuum to obtain a first solution supplement;
(b) mixing a conductive agent, a pore-forming agent, a fifth solvent and the first liquid supplement obtained in the step (a) in vacuum, and carrying out third stirring to obtain a second liquid supplement;
(c) mixing a hydrophobizing agent, a sixth solvent and the second replenishing liquid obtained in the step (b) in vacuum, and carrying out fourth stirring to complete the replenishment of the gas diffusion layer slurry;
the mass ratio of the conductive agent, the hydrophobic agent, the pore-forming agent and the dispersing agent is (2.3-4.8): (2.5-3.5): (0.35-0.55): (0.25-0.75), and may be, for example, 2.3:2.5:0.35:0.25, 4.8:3.5:0.55:0.27, 2.3:3.5:0.35:0.75, 4.8:3.5:0.35:0.75, 2.5:3.2:0.43:0.58 or 4.6:2.7:0.48:0.42, but not limited to the above-mentioned values, and other values in the above-mentioned range are also applicable.
And based on the total mass M of the fourth solvent, the fifth solvent and the sixth solvent as 100%, the mass of the fourth solvent is 35-45% of the mass of M, the mass of the fifth solvent is 45-55% of the mass of M, and the balance is the third solvent.
The mass of the fourth solvent is 35 to 45% of the total mass M of the fourth solvent, the fifth solvent and the sixth solvent, based on 100%, and may be, for example, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44% or 45%, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable. The mass of the fifth solvent is 45 to 55% of the mass of M, and may be, for example, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or 55%, but is not limited to the values listed, and other values not listed in the range of the values are also applicable. The balance being the third solvent.
Preferably, the third stirring in step (b) has a shear rate of 1200-3000r/min, a stirring rate of 5-20r/min, and a stirring time of 50-70 min.
The third stirring shear rate in step (b) of the present invention is 1200-3000r/min, such as 1200r/min, 1400r/min, 1600r/min, 1800r/min, 2000r/min, 2200r/min, 2400r/min, 2600r/min, 2800r/min, 3000r/min, but is not limited to the values listed, and other values not listed in this range are equally applicable.
The stirring speed of the third stirring in step (b) of the present invention is 5 to 20r/min, and may be, for example, 5r/min, 7r/min, 9r/min, 11r/min, 13r/min, 15r/min, 17r/min, 20r/min, but is not limited to the values listed, and other values not listed in the numerical range may be applied.
The third stirring time in step (b) of the present invention is 50-70min, such as 50min, 52min, 55min, 57min, 60min, 62min, 65min, 67min, 70min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the viscosity of the second fluid of step (b) is 1000-.
Preferably, the shear rate of the fourth stirring in the step (c) is 400-1500r/min, the stirring speed is 30-45r/min, and the time is 0.5-1 h.
The fourth stirring in step (c) of the present invention has a shear rate of 400-1500r/min, such as 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, 1100r/min, 1200r/min, 1400r/min or 1500r/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The stirring speed of the fourth stirring in step (c) of the present invention is 30 to 45r/min, and may be, for example, 30r/min, 32r/min, 34r/min, 36r/min, 38r/min, 40r/min, 42r/min, 44r/min or 45r/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The fourth stirring time in step (c) of the present invention is 0.5 to 1 hour, and may be, for example, 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour or 1 hour, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a third aspect, the present invention provides a gas diffusion layer prepared from the gas diffusion layer slurry of the first aspect.
Compared with the prior art, the invention has the beneficial effects that:
(1) the slurry of the gas diffusion layer slurry has stable performance, uniform slurry, strong conductivity, small resistance and high porosity. Through the coupling addition of various conductive carbon blacks and the slurry formula design, the conductivity of the gas diffusion layer is greatly enhanced, the resistivity in the plane direction reaches 4-9m omega cm, and the superconducting performance requirement of the next-generation gas diffusion layer is met.
(2) The production and preparation method has low cost and simple process, and can meet the continuous production requirement.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In order to facilitate the technical scheme provided by the invention to be understood by those skilled in the art, the invention exemplarily provides an apparatus system for preparing a gas diffusion layer paddle, wherein the preparation system comprises a reaction apparatus and a storage apparatus, and the reaction apparatus is connected with the storage apparatus;
the volume of the storage device is not less than 20% of the volume of the reaction device;
a vacuum constant-speed stirring device is respectively and independently arranged in the reaction device and the material storage device; the vacuum constant-speed stirring device is used for stirring materials in the reaction device and the material storage device in vacuum.
The reaction device is used for preparing gas diffusion layer slurry, and the storage device is used for storing the prepared gas diffusion layer slurry; the vacuum constant-speed stirring device in the material storage device maintains the stability of the slurry of the gas diffusion layer in the material storage device through vacuum stirring.
The prepared slurry of the gas diffusion layer in the reaction device is used for coating, the slurry of the gas diffusion layer needs to be prepared in a supplementing way after being consumed, the slurry of the residual gas diffusion layer is not less than 50% of the volume of the reaction device, and the volume of the slurry of the gas diffusion layer prepared in the supplementing way is less than 20% of the slurry of the residual gas diffusion layer.
Example 1
This example provides a gas diffusion layer slurry, which includes conductive carbon black Vulcan P, polytetrafluoroethylene, polyvinyl butyral ester, and polydiglyguanidine salt in a mass ratio of 2.5:2.9:0.38:0.35, the viscosity of the gas diffusion layer is 2000cps, the solvent used in the gas diffusion layer slurry is water, and the mass fraction of the water is 5 wt% based on the mass of the gas diffusion layer slurry.
The preparation method of the gas diffusion layer slurry comprises the following steps:
(1) mixing the polydimethylguanidine salt and 35% of water by mass of the solvent M under the vacuum condition according to the formula amount, wherein the total mass M of the solvent is 100%, so as to obtain a primary mixed solution;
(2) mixing conductive carbon black Vulcan P, polyvinyl butyral, 50% water with the mass M and the primary mixed liquid obtained in the step (1) according to the formula amount under the vacuum condition, and stirring for 8 hours at a shearing speed of 3000r/min and a stirring speed of 48r/min to obtain a remixed liquid with the viscosity of 2000 cps;
(3) and (3) mixing polytetrafluoroethylene, 15% of water with the mass of M and the remixed liquid obtained in the step (2) according to the formula amount under the vacuum condition, and stirring for 3 hours at a shearing speed of 800r/min and a stirring speed of 42r/min to obtain the gas diffusion layer slurry.
Example 2
The embodiment provides a gas diffusion layer slurry, which comprises conductive graphite, polyvinylidene fluoride, ammonium bicarbonate and polyethylene glycol in a mass ratio of 4.8:3.5:0.55:0.27, wherein the viscosity of a gas diffusion layer is 4500cps, a solvent used by the gas diffusion layer slurry is water, and the mass fraction of the water is 2 wt% based on the mass of the gas diffusion layer slurry.
The preparation method of the gas diffusion layer slurry comprises the following steps:
(1) mixing polyethylene glycol and water with the mass of 40% of M according to the formula amount under the vacuum condition to obtain a primary mixed solution, wherein the total mass M of the solvent is 100%;
(2) mixing conductive graphite, ammonium bicarbonate and 45% water with the mass of M with the primary mixed liquid obtained in the step (1) according to the formula amount under the vacuum condition, and stirring for 10 hours at a shearing speed of 2500r/min and a stirring speed of 50r/min to obtain a remixed liquid with the viscosity of 2600 cps;
(3) and (3) mixing polyvinylidene fluoride, 15% of water with the mass being M and the remixed liquid obtained in the step (2) according to the formula amount under the vacuum condition, and stirring for 2 hours at a shearing speed of 400r/min and a stirring speed of 34r/min to obtain the gas diffusion layer slurry.
Example 3
The embodiment provides a gas diffusion layer slurry, which comprises CNTs, polychlorotrifluoroethylene, polyvinyl alcohol and alkyl glycoside in a mass ratio of 2.3:3.5:0.35:0.75, wherein the viscosity of the gas diffusion layer is 3000cps, the solvent used by the gas diffusion layer slurry is water, and the mass fraction of the water is 4.3 wt% based on the mass of the gas diffusion layer slurry.
The preparation method of the gas diffusion layer slurry comprises the following steps:
(1) mixing alkyl sugar and 45% of water by mass of M under a vacuum condition to obtain a primary mixed solution, wherein the total mass M of the solvent is 100%;
(2) mixing CNTs, polyvinyl alcohol, 48% water with the mass being M and the primary mixed liquid obtained in the step (1) according to the formula amount under the vacuum condition, and stirring for 9 hours at a shearing speed of 800r/min and a stirring speed of 55r/min to obtain a remixed liquid with the viscosity being 1500 cps;
(3) and (3) mixing polychlorotrifluoroethylene, 7% by mass of water of M and the remixed liquid obtained in the step (2) according to the formula amount under a vacuum condition, and stirring for 5 hours at a shear speed of 1200r/min and a stirring speed of 45r/min to obtain the gas diffusion layer slurry.
Example 4
The embodiment provides a gas diffusion layer slurry, which comprises graphene, hexafluoropropylene, polyvinyl butyral and alkylphenol ethoxylate in a mass ratio of 4.8:3.5:0.35:0.75, wherein the viscosity of the gas diffusion layer is 3500cps, a solvent used by the gas diffusion layer slurry is water, and the mass fraction of the water is 3.8 wt% based on the mass of the gas diffusion layer slurry.
The preparation method of the gas diffusion layer slurry comprises the following steps:
(1) mixing alkylphenol polyoxyethylene ether with 42% of water by mass M under the vacuum condition according to the formula amount by taking the total mass M of the solvent as 100% to obtain a primary mixed liquid;
(2) mixing graphene, polyvinyl butyral, 55% water with the mass of M and the primary mixed liquid obtained in the step (1) according to the formula amount under a vacuum condition, and stirring for 12 hours at a shearing speed of 2000r/min and a stirring speed of 45r/min to obtain a remixed liquid with the viscosity of 1000 cps;
(3) mixing hexafluoropropylene, 3% of water with the mass of M and the remixed liquid obtained in the step (2) according to the formula amount under the vacuum condition, and stirring for 6 hours at a shear speed of 1000r/min and a stirring speed of 38r/min to obtain the gas diffusion layer slurry.
Example 5
This example provides a gas diffusion layer slurry, which includes ketjen black, aqueous acrylic acid, polyvinyl alcohol, and dodecyl dimethyl betaine in a mass ratio of 2.5:3.2:0.43:0.58, and the viscosity of the gas diffusion layer is 4000cps, the solvent used in the gas diffusion layer slurry is water, and the mass fraction of the water is 3 wt% based on the mass of the gas diffusion layer slurry.
The preparation method of the gas diffusion layer slurry comprises the following steps:
(1) mixing dodecyl dimethyl betaine and 38% water by mass of the solvent M under a vacuum condition according to the formula amount, wherein the total mass M of the solvent is 100%, so as to obtain a primary mixed solution;
(2) mixing Ketjen black, polyvinyl alcohol, 52% water with the mass of M and the primary mixed liquid obtained in the step (1) according to the formula amount under the vacuum condition, and stirring for 11 hours at a shearing speed of 1500r/min and a stirring speed of 60r/min to obtain a remixed liquid with the viscosity of 3200 cps;
(3) and (3) mixing the water-based acrylic acid, 10% of water with the mass M and the remixed liquid obtained in the step (2) according to the formula amount under the vacuum condition, and stirring for 4 hours at a shear speed of 1500r/min and a stirring speed of 30r/min to obtain the gas diffusion layer slurry.
Example 6
The procedure was as in example 1 except that the conductive carbon black Vulcan P was replaced with a mixture of same mass of Vulcan P and Vulcan XC-72 in which the mass ratio of Vulcan P to Vulcan XC-72 was 1: 1.
Example 7
The procedure of example 1 was repeated, except that 50% by mass of water based on M in step (2) was replaced with 60% by mass of water based on M and 15% by mass of water based on M in step (3) was replaced with 5% by mass of water based on M, thereby giving a remixed liquid having a viscosity of 800cps in step (2).
Example 8
The procedure of example 1 was repeated, except that 50% by mass of water based on M in step (2) was replaced with 36% by mass of water based on M and 15% by mass of water based on M in step (3) was replaced with 29% by mass of water based on M, to thereby give a remixed liquid having a viscosity of 3400cps in step (2).
Example 9
This example also provides a method of complementary preparation of the gas diffusion layer slurry of example 4, the method comprising the steps of:
(a) mixing alkylphenol polyoxyethylene ether, 43% of water by mass M and gas diffusion layer slurry in vacuum to obtain a first solution supplement, wherein the total mass M of the solvent is 100%;
(b) mixing graphene, polyvinyl butyral, 52% water with the mass being M and the first replenishing liquid obtained in the step (a) in vacuum, and stirring for 60min at a shearing speed of 1600r/min and a stirring speed of 15r/min to obtain a second replenishing liquid with the viscosity being 2500 cps;
(c) mixing hexafluoropropylene, 5% of water with the mass being M and the second replenishing liquid obtained in the step (b) in vacuum, and stirring for 0.7h at the shearing speed of 800r/min and the stirring speed of 40r/min to complete the replenishment of the gas diffusion layer slurry;
the mass ratio of the graphene to the hexafluoropropylene to the polyvinyl butyral to the alkylphenol polyoxyethylene is 4.8:3.5:0.35: 0.75;
the amount of make-up gas diffusion layer slurry in this example was 20% of the remaining gas diffusion layer slurry.
Example 10
This example also provides a method of complementary preparation of the gas diffusion layer slurry of example 5, the method comprising the steps of:
(a) mixing dodecyl dimethyl betaine, water with the mass of 36% of M and gas diffusion layer slurry in vacuum to obtain a first fluid replacement with the viscosity, wherein the total mass M of the solvent is 100%;
(b) mixing Ketjen black, polyvinyl alcohol, 48% water by mass M and the first fluid infusion obtained in the step (a) in vacuum, and stirring at a shearing speed of 2000r/min and a stirring speed of 10r/min for 55min to obtain a second fluid infusion with a viscosity of 1800 cps;
(c) mixing water-based acrylic acid, 16% water by mass of M and the second replenishing liquid obtained in the step (b) in vacuum, and stirring for 1h at a shear speed of 1200r/min and a stirring speed of 35r/min to complete replenishment of gas diffusion layer slurry;
the mass ratio of the conductive agent to the hydrophobic agent to the pore-forming agent to the dispersing agent is 2.5:3.2:0.43: 0.58;
the amount of make-up gas diffusion layer slurry in this example was 15% of the remaining gas diffusion layer slurry.
Comparative example 1
In this comparative example, a gas diffusion layer slurry comprising conductive carbon black Vulcan P, polytetrafluoroethylene, polyvinyl butyral, and polydiglybiguanide salt in a mass ratio of 2.1:2.2:0.57:0.78 was provided, the remainder being the same as in example 1.
Comparative example 2
In this comparative example, a gas diffusion layer slurry is provided which does not include polyvinyl butyral and which includes conductive carbon black Vulcan P, polytetrafluoroethylene and polydimethylguanidine salt in a mass ratio of 2.3:2.5:0.25, with the remainder being the same as in example 1.
Comparative example 3
A gas diffusion layer slurry was provided in this comparative example, which was the same as example 1 except that polyvinyl butyral ester in the gas diffusion layer slurry was replaced with equal mass of isopropyl alcohol.
Comparative example 4
A gas diffusion layer slurry was provided in this comparative example, which was the same as example 1 except that polyvinyl butyral ester in the gas diffusion layer slurry was replaced with ethylene glycol of an equal mass.
Comparative example 5
A gas diffusion layer slurry was provided in this comparative example, which was the same as in example 1 except that polyvinyl butyral ester in the gas diffusion layer slurry was replaced with ammonium oxalate of an equal mass.
Comparative example 6
In this comparative example, a gas diffusion layer slurry was provided having a mass fraction of 5.4 wt% water removal, resulting in a gas diffusion layer slurry viscosity of 1800cps, with the remainder being the same as in example 1.
Comparative example 7
In this comparative example, a gas diffusion layer slurry was provided having a mass fraction of 1.7 wt% water removal, resulting in a gas diffusion layer slurry viscosity of 4700cps, the remainder being the same as in example 1.
The slurry for gas diffusion layers obtained in examples 1 to 10 and comparative examples 1 to 7 was sprayed on hydrophobized carbon paper using carbon fibers as a substrate, dried, and then calcined in a muffle furnace at 350 ℃ for 60min to obtain a gas diffusion layer.
The performance of the gas diffusion layer was tested as follows:
(1) porosity: GB/T20042.7 proton exchange membrane fuel cell part 7: a carbon paper characteristic test method;
(2) resistivity in the plane direction: GB/T20042.7 proton exchange membrane fuel cell part 7: a carbon paper characteristic test method;
(3) air permeability: seventh 7 part of GB/T20042.7 proton exchange membrane fuel cell: a carbon paper characteristic test method;
the results obtained are shown in table 1.
TABLE 1
From the data of table 1, one can see:
(1) the gas diffusion layers prepared from the gas diffusion layer slurries of examples 1 to 5 had higher porosity and smaller in-plane resistivity, indicating that the gas diffusion layer slurries provided by the present invention were excellent in performance.
(2) As can be seen from the comparison between example 1 and example 6, the coupling of multiple conductive agents in the slurry of the gas diffusion layer in the present invention affects the performance of the gas diffusion layer, and the coupling of multiple conductive agents can improve the electrical conductivity of the gas diffusion layer.
(3) As can be seen from a comparison of example 1 with examples 7-8, the viscosity of the re-mixture in the present invention affects the performance of the gas diffusion layer; when the re-mixing fluid viscosity is too high, the preparation cost of the gas diffusion layer slurry is too high, and the requirements of actual production practice are not met, and when the re-mixing fluid viscosity is too low, the viscosity of the gas diffusion layer slurry is too low, and the performance of the gas diffusion layer slurry is poor, so that the performance of the gas diffusion layer is poor.
(4) The comparison between the example 1 and the examples 9 to 10 shows that the gas diffusion layer still has better performance after the slurry is supplemented in the invention, and the slurry of the gas diffusion layer can be continuously supplemented in the invention, so that the requirement of continuous production can be realized.
(5) As can be seen from the comparison between example 1 and comparative example 1, the mass ratio of the conductive agent, the hydrophobic agent, the pore-forming agent and the dispersing agent in the slurry of the gas diffusion layer in the invention affects the performance of the gas diffusion layer; the gas diffusion layer slurry prepared under the mass ratio of the conductive agent, the hydrophobic agent, the pore-forming agent and the dispersing agent has better performance.
(6) As can be seen from the comparison of example 1 with comparative examples 2 to 5, when the pore-forming agent is absent in the gas diffusion layer slurry of the present invention, the performance of the gas diffusion layer is deteriorated, and the addition of the pore-forming agent contributes to the increase of the porosity of the gas diffusion layer; further, when a gas diffusion layer slurry is prepared using a pore-forming agent other than the present invention, the performance of the gas diffusion layer is deteriorated.
(7) As can be seen from a comparison of example 1 with comparative examples 6 to 7, the viscosity of the slurry for the gas diffusion layer in the present invention affects the performance of the gas diffusion layer; when the viscosity of the gas diffusion layer slurry is low, poor performance of the gas diffusion layer slurry is caused, thereby causing poor performance of the gas diffusion layer; when the viscosity of the gas diffusion layer slurry is high, the preparation cost of the gas diffusion layer slurry is high.
In conclusion, the slurry of the gas diffusion layer provided by the invention has the advantages of stable slurry performance, uniform slurry, strong conductivity, small resistance and high porosity. By the coupling addition of multiple conductive agents and the slurry formula design, the conductivity of the gas diffusion layer is greatly enhanced, and the superconducting performance requirement of the next generation gas diffusion layer is met; the production and preparation method has low cost and simple process, and can meet the continuous production requirement.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (10)
1. The gas diffusion layer slurry is characterized by comprising a conductive agent, a hydrophobic agent, a pore-forming agent and a dispersing agent in a mass ratio of (2.3-4.8) - (2.5-3.5) - (0.35-0.55) - (0.25-0.75);
the pore-forming agent comprises any one or the combination of at least two of ammonium chloride, ammonium bicarbonate, polyvinyl butyral ester or polyvinyl alcohol;
the viscosity of the gas diffusion layer slurry was 2000-4500 cps.
2. The gas diffusion layer slurry of claim 1, wherein the conductive agent comprises any one of or a combination of at least two of conductive carbon black, conductive graphite, ketjen black, carbon nanotubes, or graphene;
preferably, the conductive agent comprises any one of or a combination of at least two of Vulcan P, Vulcan XC-72R, Printex L6, ketjen black EC-600JD, Reven 14, Ensaco350G, VGCF, CNTs, or graphene.
3. The slurry for a gas diffusion layer according to claim 1 or 2, wherein the hydrophobic agent comprises any one of or a combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropylene, a copolymer of tetrafluoroethylene and a perfluoroalkyl vinyl ether, polyvinyl alcohol, a polyurethane adhesive with ethyl acetate as a solvent, a water-dispersible polyurethane, an aqueous acrylic or an isocyanate.
4. The gas diffusion layer slurry according to any one of claims 1 to 3, wherein the dispersant comprises a water-soluble dispersant;
preferably, the water-soluble dispersant comprises any one or a combination of at least two of polydimethylguanidine salt, alkyl glycoside, alkylphenol ethoxylates, dodecyl dimethyl betaine or polyethylene glycol;
preferably, the solvent used for the gas diffusion layer slurry comprises water.
5. A method of preparing a slurry for a gas diffusion layer according to any one of claims 1 to 4, comprising:
(1) mixing a dispersant and a first solvent according to the formula amount to obtain a primary mixed solution;
(2) mixing a conductive agent, a pore-forming agent, a second solvent and the primary mixed liquid obtained in the step (1) according to the formula amount, and carrying out first stirring to obtain a secondary mixed liquid;
(3) mixing a hydrophobizing agent, a third solvent and the remixed liquid obtained in the step (2) according to the formula amount, and carrying out second stirring to obtain the gas diffusion layer slurry;
and the mass of the first solvent is 35-45% of the mass of the first solvent, the mass of the second solvent is 45-55% of the mass of the second solvent, and the balance is the third solvent, wherein the total mass M of the first solvent, the second solvent and the third solvent is 100%.
6. The method according to claim 5, wherein the mixing of step (1) is performed under vacuum;
preferably, the mixing of step (2) is performed under vacuum;
preferably, the first stirring in the step (2) has a shear speed of 800-;
preferably, the viscosity of the remixing solution in the step (2) is 1000-.
7. The production method according to claim 5 or 6, wherein the mixing of step (3) is performed under vacuum conditions;
preferably, the shearing speed of the second stirring in the step (3) is 400-1500r/min, the stirring speed is 30-45r/min, and the time is 2-6 h.
8. The method of any one of claims 5 to 7, further comprising the steps of:
(a) mixing a dispersant, a fourth solvent and gas diffusion layer slurry in vacuum to obtain a first solution supplement;
(b) mixing a conductive agent, a pore-forming agent, a fifth solvent and the first liquid supplement obtained in the step (a) in vacuum, and carrying out third stirring to obtain a second liquid supplement;
(c) mixing a hydrophobizing agent, a sixth solvent and the second replenishing liquid obtained in the step (b) in vacuum, and carrying out fourth stirring to complete the replenishment of the gas diffusion layer slurry;
the mass ratio of the conductive agent, the hydrophobic agent, the pore-forming agent and the dispersing agent is (2.3-4.8): (2.5-3.5): 0.35-0.55): 0.25-0.75);
and based on the total mass M of the fourth solvent, the fifth solvent and the sixth solvent as 100%, the mass of the fourth solvent is 35-45% of the mass of M, the mass of the fifth solvent is 45-55% of the mass of M, and the balance is the sixth solvent.
9. The method as claimed in claim 8, wherein the third stirring step (b) has a shear rate of 1200-3000r/min, a stirring rate of 5-20r/min, and a stirring time of 50-70 min;
preferably, the viscosity of the second fluid supplement in the step (b) is 1000-;
preferably, the shear rate of the fourth stirring in the step (c) is 400-1500r/min, the stirring speed is 30-45r/min, and the time is 0.5-1 h.
10. A gas diffusion layer prepared from the gas diffusion layer slurry of any of claims 1-4.
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