CN116252538A - Preparation method and application of electrolytic water diaphragm - Google Patents

Preparation method and application of electrolytic water diaphragm Download PDF

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Publication number
CN116252538A
CN116252538A CN202310533664.3A CN202310533664A CN116252538A CN 116252538 A CN116252538 A CN 116252538A CN 202310533664 A CN202310533664 A CN 202310533664A CN 116252538 A CN116252538 A CN 116252538A
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dispersion liquid
electrolytic water
coating
semi
finished product
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薛晓武
张瀚文
黄金强
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Shenzhen General Hydrogen Energy Technology Co ltd
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Shenzhen General Hydrogen Energy Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries

Abstract

The invention relates to a preparation method and application of an electrolytic water diaphragm. According to the invention, the PFSA resin stock solution is prepared into dispersion solutions with different formulas, and then the dispersion solutions are coated for multiple times to prepare the electrolytic water diaphragm with high mechanical strength, and the electrolytic water diaphragm is prepared by using a multi-layer sandwich structure method, so that the electrolytic water diaphragm has longer service life and extremely low gas permeability. The electrolytic water membrane prepared by the invention can be used for an electrolytic water proton exchange membrane, a hydrogen fuel cell proton exchange membrane, a flow battery membrane or a chlor-alkali membrane.

Description

Preparation method and application of electrolytic water diaphragm
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a preparation method and application of an electrolytic water diaphragm.
Background
The membranes used in current commercial electrolyzed water are mainly perfluorosulfonic acid proton membranes, and short side chain PFSA membranes. The perfluorinated sulfonic acid resin (PFSA resin) needs to bear high pressure of more than or equal to 3Mpa for a long time, and has low-load operation, frequent start-stop and low gas permeability.
At present, most of domestic and foreign electrolytic water diaphragms are homogeneous diaphragms, and a small amount of diaphragms comprise single reinforced layers, so that the diaphragms are generally poor in mechanical performance, high in cost and short in service life.
Disclosure of Invention
Based on this, it is necessary to provide a method for preparing an electrolytic water membrane with high mechanical strength and low gas permeation and application thereof.
In order to achieve the above object, the present invention provides a technical solution:
a preparation method of an electrolytic water diaphragm comprises the following steps:
s100, preparing a dispersion liquid, wherein the dispersion liquid comprises at least one of a dispersion liquid 1, a dispersion liquid 2 and a dispersion liquid 3, and the specific steps comprise:
preparing a first dispersing agent and a first solvent into a first dispersing agent solution, and mixing a PFSA resin stock solution with the first dispersing agent solution to obtain a dispersing liquid 1;
preparing a second dispersant solution from a second dispersant and a second solvent, and mixing the second dispersant solution with the dispersion liquid 1 to obtain a dispersion liquid 2;
preparing Pt/C and a third solvent into a third dispersing agent solution, and mixing the third dispersing agent solution with the dispersing liquid 1 to obtain a dispersing liquid 3;
s200, coating for the 1 st time, coating the dispersion liquid on a base film, bonding by using a reinforcing layer, carrying out step heating to 60-80 ℃ and preserving heat for 25-35min to obtain a semi-finished product 1;
s300, coating for the 2 nd time, coating the dispersion liquid on the semi-finished product 1 after the semi-finished product 1 is cooled, bonding by using a reinforcing layer, heating to 60-80 ℃ in a step manner, and preserving heat for 25-35min to obtain a semi-finished product 2;
s400, repeating coating, coating for the nth time, coating the dispersion liquid on the semi-finished product n-1 after the semi-finished product n-1 is cooled, and bonding by using a reinforcing layer to obtain a semi-finished product n, wherein n is an integer, and the value range of n is more than or equal to 3 and less than or equal to 33;
s500, coating the topmost layer after the semi-finished product n is cooled, coating the topmost layer by using a dispersion liquid, heating to 100-180 ℃ in a step mode, and preserving heat for 35-40min to obtain the electrolytic water diaphragm.
Wherein the choice of the dispersion during coating depends on the material of the reinforcing layer.
Preferably, the reinforcing layer comprises at least one of expanded polytetrafluoroethylene, a fiber woven porous polyimide and polyetheretherketone, the dispersion 1 is used for bonding the expanded polytetrafluoroethylene, the dispersion 2 is used for bonding the polyetheretherketone, and the dispersion 3 is used for bonding the fiber woven porous polyimide.
Preferably, the specific steps for preparing the dispersion 3 comprise:
and wetting the Pt/C with water, performing ultrasonic dispersion in a third solvent for 1-2h to obtain a third dispersing agent solution, and mixing with the dispersing liquid 1 to obtain a dispersing liquid 3, wherein the Pt content in the Pt/C is 15-35%.
Preferably, the first dispersant includes an alkylphenol ethoxylate dispersant or a fatty alcohol ethoxylate dispersant.
Preferably, the second dispersant includes at least one of nano cerium oxide or nano silicon dioxide, nano titanium dioxide and phosphotungstic acid.
Preferably, the first solvent includes at least one of isopropyl alcohol, n-propyl alcohol, ethanol, and water; the second solvent comprises at least one of isopropanol, n-propanol, ethanol and water; the third solvent includes at least one of isopropyl alcohol, n-propyl alcohol, ethanol, and water.
Preferably, in the dispersion liquid 1, the mass ratio of the PFSA resin stock solution to the first dispersant solution is (90-100): 1, a step of; in the dispersion liquid 2, the mass ratio of the dispersion liquid 1 to the second dispersant solution is (90-100): 1, a step of; in the dispersion 3, the mass ratio of the dispersion 1 to the third dispersant solution is (90 to 100): 1.
preferably, the PFSA resin stock solution is 10% -25%.
Preferably, the thickness of each coating is in the range of 150 μm to 300 μm.
The invention also provides an application of the electrolytic water membrane prepared by the preparation method according to any one of the above, and the electrolytic water membrane is applied to an electrolytic water proton exchange membrane, a hydrogen fuel cell proton exchange membrane, a flow battery membrane or a chlor-alkali membrane.
The invention has the beneficial effects that:
according to the invention, the PFSA resin stock solution is prepared into dispersion solutions with different formulas, and then the dispersion solutions are coated for multiple times to prepare the electrolytic water diaphragm with high mechanical strength, and the electrolytic water diaphragm is prepared by using a multi-layer sandwich structure method, so that the electrolytic water diaphragm has longer service life and extremely low gas permeability.
Drawings
FIG. 1 is a flow chart of the preparation of an electrolyzed water proton exchange membrane;
FIG. 2 is a schematic diagram of the structure of an electrolytic water proton exchange membrane.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available.
A method for preparing an electrolytic water membrane, as shown in figure 1, comprises the steps of:
s100, preparing a dispersion liquid, wherein the dispersion liquid comprises at least one of a dispersion liquid 1, a dispersion liquid 2 and a dispersion liquid 3, and the specific steps comprise:
preparing a first dispersant and a first solvent into a first dispersant solution, wherein the mass ratio of the first dispersant to the first solvent is 1: (60-100), and mixing the PFSA resin stock solution with a first dispersing agent solution to obtain a dispersing liquid 1;
the PFSA resin stock solution comprises Solvay D79 resin and/or D2020CS resin.
The PFSA resin stock solution is 10% -25%.
Specifically, the first dispersant includes an alkylphenol ethoxylate dispersant or a fatty alcohol ethoxylate dispersant, more specifically, the first dispersant includes at least one of Nereid dispersant (Ninal, also called coconut fatty acid diethanolamide), polyethylene glycol octylphenyl ether, polyethylene glycol hexadecyl ether, tributyl phosphate, polysorbate-20, nonylphenol ethoxylate (NPEO), octylphenol ethoxylate (OPEO), dodecylpolyoxyethylene ether (DPEO), and dinonylphenol ethoxylate (DNPEO); the first solvent includes at least one of isopropyl alcohol, n-propyl alcohol, ethanol, and water; in the dispersion liquid 1, the mass ratio of the PFSA resin stock solution to the first dispersant solution is (90-100): 1.
the second dispersant and the second solvent are prepared into a second dispersant solution, and the dispersion 1 is mixed with the second dispersant solution to obtain a dispersion 2.
In the second dispersing agent solution, the mass ratio of the second dispersing agent to the second solvent is (90-100): (1-20).
Specifically, the second dispersant comprises at least one of nano cerium oxide or nano silicon dioxide, nano titanium dioxide and phosphotungstic acid; the second solvent includes at least one of isopropyl alcohol, n-propyl alcohol, ethanol, and water; in the dispersion liquid 2, the mass ratio of the dispersion liquid 1 to the second dispersing agent solution is (90-100): 1.
more specifically, the phosphotungstic acid (PWA) is used for enhancing the conductivity of the membrane at high temperature, so that the proton conductivity of the membrane is improved, on the other hand, the added nano silicon dioxide (SiO 2) and nano titanium dioxide (TiO 2) have water retention effects, so that the water absorption rate of the membrane can be improved, and the stability of the phosphotungstic acid is ensured.
The nano silicon dioxide (SiO 2) and the nano titanium dioxide (TiO 2) are mainly used for keeping the water retention performance of the membrane, and are mainly positioned in the middle layer in the sandwich structure of the membrane, so that the water retention performance of the membrane is enhanced, and the membrane is not easy to curl when being coated with the catalytic layer. The nano cerium dioxide ion is used for a free radical quencher, so that the performance degradation of the membrane caused by free radical attack in the use process of the membrane is reduced.
Wetting Pt/C with water, firstly performing ultrasonic dispersion in a third solvent for 1-2h to obtain a third dispersant solution, and then mixing with the PFSA dispersion to obtain a dispersion 3, wherein the Pt content in the Pt/C is 15-35% (mass), and the mass ratio of the Pt/C to the third solvent in the third dispersant solution is 1: (90-100).
Specifically, the third solvent comprises at least one of isopropanol, n-propanol, ethanol and water, and in the dispersion liquid 3, the mass ratio of the dispersion liquid 1 to the third dispersant solution is (90-100): 1.
the viscosity of the dispersion liquid 1, the dispersion liquid 2 and the dispersion liquid 3 ranges from 70 to 300cps.
S200, coating for the 1 st time, coating dispersion liquid on a base film, simultaneously bonding by using a reinforcing layer, and then carrying out step heating to 60-80 ℃ and preserving heat for 25-35min to obtain a semi-finished product 1.
S300, coating for the 2 nd time, coating dispersion liquid on the semi-finished product 1 after the semi-finished product 1 is cooled, bonding by using a reinforcing layer, heating to 60-80 ℃ in a step manner, and preserving heat for 25-35min to obtain the semi-finished product 2.
S400, repeating coating, coating for the nth time, coating the dispersion liquid on the semi-finished product n-1 after the semi-finished product n-1 is cooled, and bonding by using a reinforcing layer to obtain a semi-finished product n, wherein n is an integer, and the value range of n is more than or equal to 3 and less than or equal to 33.
S500, coating the topmost layer after the semi-finished product n is cooled, coating the topmost layer by using a dispersion liquid, heating to 100-180 ℃ in a step mode, and preserving heat for 35-40min to obtain the electrolytic water diaphragm.
Wherein, during the coating process, the choice of dispersion depends on the material of the reinforcing layer.
The reinforcing layer comprises at least one of expanded polytetrafluoroethylene (ePTFE), fiber woven porous polyimide (polyimide) and polyether-ether-ketone (modified PI), wherein the dispersion liquid 1 is used for bonding expanded polytetrafluoroethylene, the dispersion liquid 2 is used for bonding polyether-ether-ketone, and the dispersion liquid 3 is used for bonding fiber woven porous polyimide, so that the delamination phenomenon of the electrolytic water diaphragm after long-time use is prevented.
The use of the reinforcing layer can increase the mechanical properties of the membrane, so that the membrane works under higher pressure and has lower swelling rate, the coating of the catalytic layer is convenient, the fatigue resistance and mechanical fatigue resistance are improved, and the service life is prolonged; the service life is long, so that the electrolytic water diaphragm is not easy to fail.
It should be noted that, as shown in fig. 2, when the reinforcing layer 1 is polyetheretherketone and the reinforcing layer 2 is a porous polyimide woven with fibers, a mixture of the dispersion 2 and the dispersion 3 may be used as the dispersion between the reinforcing layer 1 and the reinforcing layer 2.
The low-temperature coating wet of the previous steps S200 and S300 is to dry the solvent, and the last heating up of 100-180 ℃ is to crystallize/cure the PFSA resin while drying out the solvent.
Specifically, the thickness of each coating is in the range of 150 μm to 300 μm.
The invention also provides an application of the electrolytic water membrane prepared by the preparation method according to any one of the above, and the electrolytic water membrane is applied to an electrolytic water proton exchange membrane, a hydrogen fuel cell proton exchange membrane, a flow battery membrane or a chlor-alkali membrane.
Example 1
S100, preparing a dispersion liquid 1:
1 part of TritonX-100 (polyethylene glycol octyl phenyl ether), 60 parts of n-propanol and 30 parts of isopropanol are subjected to ultrasonic treatment for 30min to prepare a first dispersing agent solution, and Solvay D79 resin with the solid content of 15% is mixed with the first dispersing agent solution to obtain a dispersing liquid 1, wherein the mass ratio of the Solvay D79 resin to the first dispersing agent solution is 90:1, a step of;
s200, coating for the 1 st time, coating a layer of dispersion liquid 1 on a flat Polyimide (PI) film, bonding by using an enhancement layer 1 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 25min to obtain a semi-finished product 1;
s300, coating for the 2 nd time, coating the semi-finished product 1 by using the dispersion liquid 1 after the semi-finished product 1 is cooled, bonding by using the enhancement layer 2 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain a semi-finished product 2;
s400, coating for the 3 rd time, coating the semi-finished product 1 by using the dispersion liquid 1 after the semi-finished product 2 is cooled, bonding by using the enhancement layer 3 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain a semi-finished product 3;
s500, coating for the 4 th time, coating by using the dispersion liquid 1 after the semi-finished product 3 is cooled, bonding by using the enhancement layer 4 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain the semi-finished product 4;
s600, coating for the 5 th time, coating the topmost layer by using the dispersion liquid 1 after the semi-finished product 4 is cooled, heating to 150 ℃ in a step manner, and preserving heat for 40min to obtain the electrolytic water diaphragm.
Example 2
S100, preparing a dispersion liquid 1:
1 part of Nereid dispersion liquid, 50 parts of n-propanol and 20 parts of isopropanol are subjected to ultrasonic treatment for 30min to prepare a first dispersing agent solution, and Solvay D79 resin with the solid content of 25% is mixed with the first dispersing agent solution to obtain a dispersing liquid 1, wherein the mass ratio of the Solvay D79 resin to the first dispersing agent solution is 90:1, a step of;
coating and drying:
s200, coating for the 1 st time, coating a layer of dispersion liquid 1 on a flat Polyimide (PI) film, immediately bonding by using an enhancement layer 1 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 25min to obtain a semi-finished product 1;
s300, coating for the 2 nd time, coating the semi-finished product 1 with the dispersion liquid 1 after the semi-finished product 1 is cooled, immediately bonding with the reinforcing layer 2 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain a semi-finished product 2;
s400, coating for the 3 rd time, coating the semi-finished product 2 with the dispersion liquid 1 after the semi-finished product 2 is cooled, immediately bonding with the reinforcing layer 3 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain a semi-finished product 3;
s500, coating for the 4 th time, coating the semi-finished product 2 by using the dispersion liquid 1 after the semi-finished product 3 is cooled, immediately bonding by using the enhancement layer 4 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain a semi-finished product 4;
s600, coating for the 5 th time, coating the topmost layer by using the dispersion liquid 1 after the semi-finished product 4 is cooled, heating to 150 ℃ in a step manner, and preserving heat for 40min to obtain the electrolytic water diaphragm.
Example 3
S100, preparing a dispersion liquid 1 and a dispersion liquid 3:
s110, dispersing 5 parts of BrijC10 (polyethylene glycol cetyl ether), 1 part of TNBP (tributyl phosphate), 4 parts of Polysorbate20 (Polysorbate-20), 60 parts of n-propanol and 30 parts of isopropanol under an ultrasonic cell grinder for 24 hours in parts by weight to prepare a first dispersing agent solution; mixing Solvay D79 resin with solid content of 15% with a first dispersant solution to obtain a dispersion liquid 1, wherein the mass ratio of the Solvay D79 resin to the first dispersant solution is 90:1, a step of;
s120, soaking 1 part of 30% Pt/C in deionized water, then performing ultrasonic dispersion in 100 parts of propanol/isopropanol mixed solution for 1-2 hours to obtain a third dispersing agent solution, mixing with the dispersing solution 1 to obtain a third dispersing agent solution, and stirring for 2 hours to obtain a dispersing solution 3, wherein the mass ratio of the dispersing solution 1 to the third dispersing agent solution is 90:1, a step of;
coating and drying:
s200, coating a layer of dispersion liquid 3 on a flat polyethylene terephthalate (PET) film, immediately bonding by using an enhancement layer 1 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 25min to obtain a semi-finished product 1;
s300, after the semi-finished product 1 is cooled, performing secondary coating, coating on the semi-finished product 1 by using the dispersion liquid 3, immediately bonding by using the reinforcing layer 2 (porous polyimide woven by fibers), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain the semi-finished product 2;
s400, after the semi-finished product 2 is cooled, coating for three times, coating the semi-finished product 1 by using the dispersion liquid 3, immediately bonding by using the reinforcing layer 3 (porous polyimide woven by fibers), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain the semi-finished product 3;
s500, after the semi-finished product 3 is cooled, coating four times, coating the semi-finished product 1 with the dispersion liquid 3, immediately bonding with the reinforcing layer 4 (porous polyimide woven by fibers), heating to 60-80 ℃ in a step manner, preserving heat for 25-35min to obtain a semi-finished product 4,
s600, coating a semi-finished product 4 film by using a dispersion liquid 3, and immediately bonding by using a reinforcing layer 5 (ePTFE) to obtain a semi-finished product 5;
s700, coating the topmost layer by using the dispersion liquid 1 after the semi-finished product 5 is cooled, heating to 150 ℃ in a step mode, and preserving heat for 40min to obtain the electrolytic water diaphragm.
Example 4
S100, preparing a dispersion liquid 1, a dispersion liquid 2 and a dispersion liquid 3:
s110, dispersing 5 parts of BrijC10 (polyethylene glycol cetyl ether), 1 part of TNBP (tributyl phosphate), 4 parts of Polysorbate20 (Polysorbate-20), 60 parts of n-propanol and 30 parts of isopropanol under an ultrasonic cell grinder for 24 hours in parts by weight to prepare a first dispersing agent solution; mixing Solvay D79 resin with solid content of 15% with a first dispersant solution to obtain a dispersion liquid 1, wherein the mass ratio of the Solvay D79 resin to the first dispersant solution is 90:1, a step of;
s120, preparing a second dispersing agent with the mass concentration of 20% by using nano cerium oxide and water, mixing the second dispersing agent with the mass concentration of 20% with the dispersing liquid 1, and stirring for 2 hours to obtain a dispersing liquid 2, wherein the mass ratio of the dispersing liquid 1 to the second dispersing agent solution is 100:1, a step of;
s130, soaking 1 part of 30% Pt/C in deionized water, then ultrasonically dispersing in 100 parts of propanol/isopropanol mixed solution for 1-2 hours to prepare a third dispersing agent solution, mixing with the dispersing solution 1, and stirring for 2 hours to obtain a dispersing solution 3, wherein the mass ratio of the dispersing solution 1 to the third dispersing agent solution is 100:1, a step of;
coating and drying:
s200, coating a layer of dispersion liquid 1 on a flat polyethylene terephthalate (PET) film, immediately bonding by using an enhancement layer 1 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 25min to obtain a semi-finished product 1;
s300, after the semi-finished product 1 is cooled, performing secondary coating, coating the semi-finished product 1 by using the dispersion liquid 2, immediately bonding by using the reinforcing layer 2 (polyether-ether-ketone), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain the semi-finished product 2;
s400, after the semi-finished product 2 is cooled, coating for three times, coating the semi-finished product 1 with a mixed solution of the dispersion liquid 2 and the dispersion liquid 3, immediately bonding the semi-finished product 1 with a reinforcing layer 3 (porous polyimide woven by fibers), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain the semi-finished product 3, wherein the mass ratio of the dispersion liquid 2 to the dispersion liquid 3 in the mixed solution is 1:1;
s500, coating a semi-finished product 4 film by using a dispersion liquid 3, immediately bonding by using a reinforcing layer 5 (ePTFE), heating to 60 ℃ in a step manner, and preserving heat for 30min to obtain a semi-finished product 4;
s600, coating the topmost layer by using the dispersion liquid 1 after the semi-finished product 4 is cooled, heating to 150 ℃ in a step mode, and preserving heat for 40min to obtain the electrolytic water diaphragm.
The performance of the electrolytic water separators and films (Nafion 117, nafion 115) commonly used in the market obtained in examples 1 to 4 was tested, and the results are shown in table 1.
TABLE 1 Performance test results
Figure SMS_1
The films commonly used in the market are homogeneous films, and the inside of the films is not provided with a filling layer, namely a reinforcing layer, so that in order to meet the use requirement, the films can reach better mechanical properties through a certain thickness, and the cost is correspondingly higher.
As can be seen from Table 1, the same mechanical properties as Nafion115 and 117 can be achieved at 60 μm thickness in the examples. The maximum pressure difference performance of the catalyst is higher than that of Nafion115 and Nafion117 while the physical performance is met by the thinner thickness, the lower swelling rate is favorable for coating the catalytic layer, and the service life of the catalyst can be prolonged by the higher water absorption rate.
In terms of proton conductivity, the proton conductivity was also enhanced correspondingly due to the reduction in thickness, and in the embodiment, the proton conductivity tested was in the planar direction, and the proton conductivities in Nafion117, nafion115, and examples 1-4 were all 0.1S/cm.
It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.

Claims (10)

1. The preparation method of the electrolytic water diaphragm is characterized by comprising the following steps:
s100, preparing a dispersion liquid, wherein the dispersion liquid comprises at least one of a dispersion liquid 1, a dispersion liquid 2 and a dispersion liquid 3, and the specific steps comprise:
preparing a first dispersing agent and a first solvent into a first dispersing agent solution, and mixing a PFSA resin stock solution with the first dispersing agent solution to obtain a dispersing liquid 1;
preparing a second dispersant solution from a second dispersant and a second solvent, and mixing the second dispersant solution with the dispersion liquid 1 to obtain a dispersion liquid 2;
preparing Pt/C and a third solvent into a third dispersing agent solution, and mixing the third dispersing agent solution with the dispersing liquid 1 to obtain a dispersing liquid 3;
s200, coating for the 1 st time, coating the dispersion liquid on a base film, bonding by using a reinforcing layer, carrying out step heating to 60-80 ℃ and preserving heat for 25-35min to obtain a semi-finished product 1;
s300, coating for the 2 nd time, coating the dispersion liquid on the semi-finished product 1 after the semi-finished product 1 is cooled, bonding by using a reinforcing layer, heating to 60-80 ℃ in a step manner, and preserving heat for 25-35min to obtain a semi-finished product 2;
s400, repeating coating, coating for the nth time, coating the dispersion liquid on the semi-finished product n-1 after the semi-finished product n-1 is cooled, and bonding by using a reinforcing layer to obtain a semi-finished product n, wherein n is an integer, and the value range of n is more than or equal to 3 and less than or equal to 33;
s500, coating the topmost layer by using a dispersion liquid after the semi-finished product n is cooled, heating to 100-180 ℃ in a step manner, and preserving heat for 35-40min to obtain the electrolytic water diaphragm;
wherein the choice of the dispersion during coating depends on the material of the reinforcing layer.
2. The method of producing an electrolytic water separator according to claim 1, wherein the reinforcing layer comprises at least one of expanded polytetrafluoroethylene, a fiber woven porous polyimide, and a polyether ether ketone, the dispersion 1 is used for bonding the expanded polytetrafluoroethylene, the dispersion 2 is used for bonding the polyether ether ketone, and the dispersion 3 is used for bonding the fiber woven porous polyimide.
3. The method for producing an electrolytic water membrane according to claim 1, wherein the specific step of producing the dispersion 3 comprises:
the Pt/C is wetted by water, is firstly dispersed in a third solvent for 1 to 2 hours by ultrasonic, and is then mixed with the dispersion liquid 1 to obtain a dispersion liquid 3.
4. The method for producing an electrolytic water separator according to claim 1, wherein the first dispersant comprises an alkylphenol ethoxylate dispersant or a fatty alcohol ethoxylate dispersant.
5. The method of preparing an electrolytic water membrane according to claim 1, wherein the second dispersant comprises at least one of nano cerium oxide, nano silicon dioxide, nano titanium dioxide and phosphotungstic acid.
6. The method for producing an electrolytic water membrane according to claim 1, wherein the first solvent comprises at least one of isopropyl alcohol, n-propyl alcohol, ethanol, and water; the second solvent comprises at least one of isopropanol, n-propanol, ethanol and water; the third solvent includes at least one of isopropyl alcohol, n-propyl alcohol, ethanol, and water.
7. The method for producing an electrolytic water membrane according to claim 1, wherein in the dispersion liquid 1, the mass ratio of the PFSA resin stock solution to the first dispersant solution is (90 to 100): 1, a step of; in the dispersion liquid 2, the mass ratio of the dispersion liquid 1 to the second dispersant solution is (90-100): 1, a step of; in the dispersion 3, the mass ratio of the dispersion 1 to the third dispersant solution is (90 to 100): 1.
8. the method for preparing an electrolytic water membrane according to claim 1, wherein the PFSA resin stock solution is 10% -25%.
9. The method of producing an electrolytic water separator according to claim 1, wherein the thickness of each coating is in the range of 150 μm to 300 μm.
10. The application of the electrolytic water membrane prepared by the preparation method according to any one of claims 1 to 9, which is characterized in that the electrolytic water membrane is applied to an electrolytic water proton exchange membrane, a hydrogen fuel cell proton exchange membrane, a flow battery membrane or a chlor-alkali membrane.
CN202310533664.3A 2023-05-12 2023-05-12 Preparation method and application of electrolytic water diaphragm Pending CN116252538A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1694290A (en) * 2005-05-20 2005-11-09 武汉理工大学 Composite proton exchange membrane for high-temp proton exchange membrane fuel cell and preparation method
CN111041524A (en) * 2019-12-31 2020-04-21 山东东岳未来氢能材料有限公司 Ultrathin low-resistance chlor-alkali electrolytic cell diaphragm and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1694290A (en) * 2005-05-20 2005-11-09 武汉理工大学 Composite proton exchange membrane for high-temp proton exchange membrane fuel cell and preparation method
CN111041524A (en) * 2019-12-31 2020-04-21 山东东岳未来氢能材料有限公司 Ultrathin low-resistance chlor-alkali electrolytic cell diaphragm and preparation method thereof

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