CN114959765A - Adhesive for membrane electrode, preparation method of membrane electrode slurry, membrane electrode and proton exchange membrane water electrolyzer - Google Patents
Adhesive for membrane electrode, preparation method of membrane electrode slurry, membrane electrode and proton exchange membrane water electrolyzer Download PDFInfo
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 62
- 239000000853 adhesive Substances 0.000 title claims abstract description 50
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 33
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 10
- 239000011268 mixed slurry Substances 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 25
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 238000010008 shearing Methods 0.000 claims description 15
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- -1 polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer Polymers 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002077 nanosphere Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses an adhesive for a membrane electrode, a preparation method of membrane electrode slurry, a membrane electrode and a proton exchange membrane water electrolyzer, wherein the adhesive is a nano microspherical fluorocarbon polymer, and can be mixed with a catalyst and perfluorinated sulfonic acid resin under certain conditions to prepare slurry so as to form a more reasonable gas-solid-liquid three-phase electrode structure and avoid shielding reaction sites of the catalyst. Meanwhile, the adhesive and the membrane electrode pulping process can obviously improve the structural stability of the electrode, resist the damage of the bubble effect in the electrolytic water to the membrane electrode and further improve the service life of the electrolytic bath.
Description
Technical Field
The invention belongs to the technical field of water electrolysis of proton exchange membranes, and particularly relates to an adhesive for a membrane electrode, a preparation method of membrane electrode slurry, a membrane electrode and a water electrolyzer of a proton exchange membrane.
Background
Accelerating the development of hydrogen energy and promoting the energy supply in China. And the proton exchange membrane electrolytic hydrogen Production (PEM) has better flexibility and responsiveness, excellent response speed and wide power working range, and is particularly suitable for the fluctuation and intermittence of the power generation of renewable energy sources. The membrane electrode assembly is the core part of a PEM electrolyser and plays a crucial role in the performance of the electrolyser. In the process of preparing the membrane electrode, establishing a reasonable gas-solid-liquid three-phase interface and a membrane electrode structure is one of the keys for improving the performance of the electrode.
In the prior art, research on the nano structure development and the dispersion method of the catalyst is mostly focused, for example, CN 114150343 discloses a nano antler-shaped NiMoCu catalyst and a preparation method thereof, and CN 110721717 discloses a porous sheet tungsten nitride/carbon composite material and a preparation method thereof, which both improve the reaction surface area and catalytic sites of the catalyst, and further improve the activity of the catalyst; but the stability of the membrane electrode and the degradation problem of the proton exchange membrane cannot be improved.
In a fuel cell system, CN106159284B discloses a technical scheme of using polytetrafluoroethylene and nano carbon powder as slurry, realizing a nano array by a complex electroplating process, and the removal and washing processes of electroplating solution and adhesive have environmental protection problems, and the membrane electrode preparation process is complicated. CN102088092B discloses that a catalyst layer is made into a three-dimensional network structure, the number of active sites exposed by the catalyst is increased to provide a channel for gas-liquid transmission, the problems of uneven electrode surface, non-uniform pore size and the like exist in ultrasonic spraying, and polarization is increased when the catalyst layer works at high current density.
The fuel cell is greatly different from an electrolytic water system, the fuel cell mainly inputs gas, the gas in the electrolytic water is output outwards, and a large amount of bubbles are generated at the interface of hydrogen evolution and oxygen evolution of the electrolytic water, so mass transfer polarization also occurs in gas diffusion, and a reasonable gas conveying channel needs to be constructed. The operation pressure of the electrolytic water system is more than 3MPa, while the working pressure of the fuel cell is 1-3bar, which is one order of magnitude smaller than that of the electrolytic water system, and the difference of the stability and the pressure difference resistance of the membrane electrode is huge. The operating current density in the electrolyzed water can typically reach several amperes per square centimeter, much higher than in fuel cell systems, and therefore the precious metal loading varies widely. In the membrane electrode preparation process in the fuel cell, the perfluorinated sulfonic acid resin can have the functions of an ion conductor and an adhesive, and the bonding strength of the perfluorinated sulfonic acid resin in an electrolyzed water system hardly meets the service life requirement of the membrane electrode, so that the adhesive with higher bonding strength is required to be added, and the large-area coverage of the active sites of the catalyst is avoided.
Therefore, in combination with the market demand for large-scale long-life water electrolysis equipment, development of a membrane electrode core assembly with simple preparation process and long service life is urgently needed.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide the adhesive for the membrane electrode and the preparation method of the slurry containing the adhesive, which have the advantages of simple and convenient process, uniform dispersion, stable structure and long service life, can ensure the transmission requirement of gas diffusion on the electrode structure and increase the stability of the electrode structure.
The invention also aims to provide a membrane electrode prepared by the slurry prepared by the membrane electrode slurry preparation method and a proton exchange membrane water electrolyzer.
In order to realize the effect of the invention, the invention adopts the following technical scheme:
an adhesive for a membrane electrode is a nano microspherical fluorocarbon polymer.
In a particular embodiment, the fluorocarbon polymer is selected from one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and aqueous dispersion emulsions thereof, preferably one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, and polytetrafluoroethylene, and aqueous dispersion emulsions thereof.
In a specific embodiment, the viscosity average molecular weight of the fluorocarbon polymer is 1 to 700000, preferably 5000 to 500000.
In a specific embodiment, the fluorocarbon polymer nanospheres have dimension D 50 0.01-5 μm, preferably 50-400 nm, and spherical.
On the other hand, the preparation method of the membrane electrode slurry for the proton exchange membrane water electrolyzer comprises the following steps:
a) mixing a catalyst, perfluorinated sulfonic acid resin, deionized water and an organic solvent, placing the mixture in a high-speed shearing emulsifying machine for pulping to obtain mixed slurry 1, preferably pulping at 40-80 ℃ at the rotation speed of 1000-5000 rpm for 30-120 min;
b) and adding the adhesive powder or the aqueous dispersion emulsion thereof into the mixed slurry 1, putting the mixture into a sand mill to submerge and disperse, preferably dispersing for 30-90 min at the rotating speed of 300-3000 rpm until the viscosity of the slurry reaches 50-800 mPa & s, and discharging to obtain the membrane electrode slurry.
In a preferred embodiment, in the step a), the catalyst, the organic solvent and the deionized water are placed in a high-speed shearing emulsifying machine, the mixture is stirred at the rotating speed of 2000-5000 rpm for 15-60 min at the temperature of 40-80 ℃, then the rotating speed is reduced to 300-2000 rpm, the perfluorosulfonic acid resin solution is dropwise added while stirring, the rotating speed is increased to 2000-5000 rpm after the dropwise addition is finished, and the dispersion is continued for 30-60 min, so that the mixed slurry 1 is obtained.
In a specific embodiment, the catalyst accounts for 3-35 wt% of the mass fraction of the membrane electrode slurry, the perfluorinated sulfonic acid resin accounts for 0.3-30 wt% of the membrane electrode slurry, and the dry weight of the adhesive accounts for 0.1-10 wt% of the membrane electrode slurry.
In a particular embodiment, the catalyst is selected from IrO 2 、RuO 2 、SnO 2 One or more of Pt/C, PtIr/C, WC and WN; preferably, the organic solvent is one or more of ethanol, N-propanol, isopropanol, ethylene glycol, tetrahydrofuran, acetone or N-methylpyrrolidone.
In still another aspect, a membrane electrode of a water electrolyzer with proton exchange membrane is prepared by the membrane electrode slurry prepared by the preparation method.
In another aspect, a proton exchange membrane water electrolyzer comprises the membrane electrode.
Compared with the prior art, the invention has the beneficial effects that:
the nano spherical adhesive adopted by the invention is based on the high temperature resistance, chemical corrosion resistance, hydrophobicity and the like of the fluorocarbon polymer, so that the influence of the adhesive on the utilization rate of the catalyst can be avoided, the transmission requirement of gas diffusion on an electrode structure is ensured, and the stability and the service life of the electrode structure are improved.
The preparation method of the membrane electrode slurry has the advantages of simple and convenient process and uniform dispersion, and combines the adhesive for the membrane electrode with specific morphology and material quality, so that the finally prepared membrane electrode has stable structure, long service life and good corrosion resistance.
Drawings
FIG. 1 is a SEM image schematic diagram of the adhesive for membrane electrode of the present invention.
FIG. 2 is a graph showing polarization properties of membrane electrodes prepared in examples of the present invention and comparative examples.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting.
An adhesive for membrane electrode is a nano microspherical fluorocarbon polymer, and an SEM spectrogram of the adhesive is shown in figure 1; specifically, the viscosity average molecular weight of the fluorocarbon polymer may be 1 to 700000, including, but not limited to, 10, 100, 1000, 10000, 50000, 100000, 200000, 300000, 400000, 500000, 600000, preferably 5000 to 500000; the size range of the nano microspheres is D 50 0.01 to 5 μm, for example, including but not limited to 15nm, 30nm, 50nm, 60nm, 80nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 600nm, 800nm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, preferably 50 to 400nm, the shape of the nanospheres is spherical. The fluorocarbon polymer is one or more of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), Polytetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and aqueous dispersion emulsion thereof. The fluorine-containing resin has the characteristics of both fluororesin and general resin, has good chemical corrosion resistance, high temperature resistance, oxidation resistance and the like, and can be suitable forA PEM electrolyzer should have a long-term high temperature and humidity electrochemical environment. In addition, the compatibility of the C-F bond in the molecular chain and the main chain of the perfluorinated sulfonic acid resin is good, and more stable winding can be formed; the long-chain C-F structure of the adhesive can also generate larger binding force with the catalyst carrier, and powder falling and cracks are not easy to occur. The adhesive provided by the invention is in a nano spherical structure, has hydrophobicity, and can form a reasonable gas-solid-liquid three-phase interface with a catalyst and perfluorinated sulfonic acid resin under the condition of uniform dispersion, so that the adhesive is prevented from covering reaction sites of the catalyst, a gas diffusion transmission channel is provided, and the electrochemical activity of a membrane electrode is further improved.
The preparation method of the membrane electrode slurry for the proton exchange membrane water electrolyzer is characterized by comprising the following steps:
a) premixing a catalyst, perfluorinated sulfonic acid resin, deionized water and an organic solvent according to a weight ratio, placing the premixed material in a high-speed shearing emulsifying machine, and pulping at the rotating speed of 1000-5000 rpm (such as but not limited to 1500rpm, 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm and 4500rpm) at the temperature of 40-80 ℃ (such as but not limited to 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ and 75 ℃) to obtain mixed slurry 1, wherein the pulping time is 30-120 min (such as but not limited to 40min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 90min, 100min and 110 min);
b) adding the adhesive into the mixed slurry 1 according to the weight ratio, then placing the mixed slurry into a sand mill, dispersing the mixed slurry at the rotating speed of 300-3000 rpm (including but not limited to 400rpm, 500rpm, 600rpm, 700 rpm, 800rpm, 900rpm, 1000rpm, 1500rpm, 2000rpm, 2500rpm and 2800rpm for 30-90 min, and discharging the mixed slurry until the viscosity of the slurry meets the requirement to obtain the membrane electrode slurry.
Alternatively, mixed slurry 1 can also be prepared as follows:
putting a mixed solution of a catalyst, a part of organic solvent and water in a high-speed shearing emulsifying machine according to a weight ratio, stirring at the rotating speed of 2000-5000 rpm at the temperature of 40-80 ℃ for 15-60 min, then beginning to reduce the rotating speed to 300-2000 rpm, dropwise adding a perfluorinated sulfonic acid resin solution while stirring, increasing the rotating speed to 2000-5000 rpm after dropwise adding is finished, and continuously dispersing for 30-60 min to obtain a mixed slurry 1.
In the preparation method of the membrane electrode slurry, the membrane electrode slurry consists of a catalyst, perfluorinated sulfonic acid resin, an adhesive, water and an organic solvent; the catalyst accounts for 3-35 wt% of the mass fraction of the membrane electrode slurry, the perfluorinated sulfonic acid resin accounts for 0.3-30 wt% of the membrane electrode slurry, and the dry weight of the adhesive accounts for 0.1-10 wt% of the membrane electrode slurry. The viscosity range of the finally prepared membrane electrode slurry is 50-800 mPas.
Wherein the organic solvent is one or more of ethanol, N-propanol, isopropanol, ethylene glycol, tetrahydrofuran, acetone and N-methylpyrrolidone.
In the present invention, the kind of the catalyst is not particularly limited, and may be any conventional catalyst in the field of electrolysis of water, for example, the catalyst may be selected from IrO 2 、RuO 2 、SnO 2 One or more of Pt/C, PtIr/C, WC and WN.
The method for forming the membrane electrode slurry into the membrane electrode in the present invention can be fully referred to the prior art, for example, gravure coating method, spray coating method, slit extrusion method, etc., and is not particularly limited.
The invention is further illustrated by the following more specific examples, which are not to be construed as limiting in any way.
Example 1
The adhesive is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) water-based dispersion emulsion with the viscosity average molecular weight of 40 ten thousand, and the nano microspheres D thereof 50 150nm, solid content 30 wt%. In this embodiment, a membrane electrode slurry is prepared according to the following steps:
a) according to the proportion of deionized water to isopropanol being 1: 1 preparing water-alcohol mixed liquor and catalyst IrO 2 Accounting for 30 wt% of the total amount of the membrane electrode slurry; the perfluorinated sulfonic acid resin solution is prepared according to the concentration of 5 wt%, and the amount of the perfluorinated sulfonic acid resin accounts for 2.33 wt% of the total amount of the membrane electrode slurry; the solid content of the PVDF-HFP emulsion is 30 wt%, and the dosage is 3.33 wt% of the total amount of the membrane electrode slurry.
b) Premixing the catalyst, the perfluorinated sulfonic acid resin, 96 wt% of deionized water and isopropanol according to the weight ratio, placing the premixed material in a high-speed shearing emulsifying machine, and pulping at 55 ℃ at the rotating speed of 5000rpm for 45min to obtain mixed slurry 1.
c) Adding the PVDF-HFP aqueous dispersion emulsion into the mixed slurry 1 according to the weight ratio, then placing the mixed slurry into a sand mill, dispersing at the rotating speed of 500rpm for 40min until the viscosity of the slurry reaches 400mPa & s, and discharging to obtain the membrane electrode slurry 1.
Example 2
PVDF aqueous dispersion emulsion with the viscosity average molecular weight of 20 ten thousand is adopted as an adhesive, and the nano-microsphere D is 50 50nm, solid content 27 wt%. In this embodiment, a membrane electrode slurry is prepared according to the following steps:
a) according to the proportion of deionized water to isopropanol being 1: 1 preparing water-alcohol mixed liquor and catalyst IrO 2 Accounting for 30 wt% of the total amount of the membrane electrode slurry; the perfluorinated sulfonic acid resin solution is prepared according to the concentration of 5 wt%, and the amount of the perfluorinated sulfonic acid resin accounts for 2.33 wt% of the total amount of the membrane electrode slurry; the solid content of the PVDF emulsion is 27 wt%, and the dosage is 3.7 wt% of the total amount of the membrane electrode slurry.
b) Adding IrO into 25.5 wt% of the total amount of the aqueous alcohol mixed solution 2 And placing the mixture into a high-speed shearing emulsifying machine, and stirring the mixture for 15min at the rotating speed of 2000rpm at the temperature of 60 ℃.
c) And (3) reducing the rotating speed of the high-speed shearing emulsifying machine to 500rpm, dropwise adding the perfluorinated sulfonic acid resin solution while stirring, increasing the rotating speed to 2500rpm after the dropwise adding is finished, and continuously dispersing for 30min to obtain the mixed slurry 1.
d) Adding the PVDF aqueous dispersion emulsion into the mixed slurry 1 according to the weight ratio, then placing the mixed slurry into a sand mill, dispersing the mixed slurry at the rotating speed of 1500rpm for 30min until the viscosity of the slurry reaches 610mPa & s, and discharging the slurry to obtain membrane electrode slurry 2.
Example 3
Adopting PVDF aqueous dispersion emulsion (nanometer microsphere D) with viscosity average molecular weight of 20 ten thousand 50 50 nm), and an aqueous dispersion emulsion of PTFE (nanosphere D) having a viscosity average molecular weight of 37 ten thousand 50 80 nm), as 1: 3 to obtain a mixed adhesive having a total solid content of 45 wt%.
In this embodiment, a membrane electrode slurry is prepared according to the following steps:
a) according to the proportion of deionized water: ethanol: isopropanol ratio ═ 1: 0.5: 0.5, preparing a water-alcohol mixed solution, wherein the catalyst WC accounts for 15 wt% of the total amount of the membrane electrode slurry; the perfluorinated sulfonic acid resin solution is prepared according to the concentration of 5 wt%, and the amount of the perfluorinated sulfonic acid resin accounts for 3.46 wt% of the total amount of the membrane electrode slurry; the solid content of the mixed adhesive emulsion is 45 wt%, and the dosage of the mixed adhesive emulsion is 10 wt% of the total amount of the membrane electrode slurry.
b) Adding WC into 7.2 wt% of the total amount of the aqueous alcohol mixed solution, placing in a high-speed shearing emulsifying machine, and stirring at 2000rpm for 15min at 50 ℃.
c) And (3) reducing the rotating speed of the high-speed shearing emulsifying machine to 1000rpm, dropwise adding the perfluorinated sulfonic acid resin solution while stirring, increasing the rotating speed to 3500rpm after the dropwise adding is finished, and continuously dispersing for 45min to obtain the mixed slurry 1.
d) Adding the mixed adhesive emulsion into the mixed slurry 1 according to the weight ratio, then placing the mixed adhesive emulsion into a sand mill, dispersing at the rotating speed of 2500rpm for 45min until the viscosity of the slurry reaches 320mPa & s, and discharging to obtain membrane electrode slurry 3.
Example 4
PTFE solid micro powder with the viscosity average molecular weight of 37 ten thousand is adopted as an adhesive, and the nano microsphere D is 50 This example prepared membrane electrode slurry at 2.7 μm, as follows:
a) according to the proportion of deionized water to isopropanol being 1: 1 preparing water-alcohol mixed liquor and catalyst IrO 2 Accounting for 35 wt% of the total amount of the membrane electrode slurry; the perfluorinated sulfonic acid resin solution is prepared according to the concentration of 5 wt%, and the amount of the perfluorinated sulfonic acid resin accounts for 2.75 wt% of the total amount of the membrane electrode slurry; the amount of the PTFE adhesive is 10 wt% of the total amount of the membrane electrode slurry.
b) Premixing the catalyst and the perfluorinated sulfonic acid resin solution according to the weight ratio, placing the premixed catalyst and the perfluorinated sulfonic acid resin solution into a high-speed shearing emulsifying machine, and pulping at the rotating speed of 5000rpm at the temperature of 55 ℃ for 60min to obtain mixed slurry 1.
c) Adding PTFE solid micro powder into the mixed slurry 1 according to the weight ratio, then placing the mixed slurry into a sand mill, dispersing the mixed slurry at the rotating speed of 3000rpm for 90min until the viscosity of the slurry reaches 300mPa & s, and discharging the slurry to obtain membrane electrode slurry 4.
Example 5
PTFE solid micro powder (nano microsphere D) with viscosity average molecular weight of 37 ten thousand is adopted 50 2.7 μm), and PVDF-HFP aqueous dispersion emulsion (nanosphere D) having a viscosity average molecular weight of 50 ten thousand 50 400nm), as per 1: 1 proportion, and the total solid content of the mixed adhesive is 55 wt%. Membrane electrode slurry 5 was obtained according to the catalyst/perfluorosulfonic acid resin/adhesive ratio of example 3, with the other preparation steps unchanged.
Example 6
Adopting PVDF aqueous dispersion emulsion with the viscosity average molecular weight of 5000 and nano microspheres D thereof 50 30nm, solid content 35 wt%, as adhesive. Membrane electrode slurry 6 was obtained according to the catalyst/perfluorosulfonic acid resin/adhesive ratio of example 2, with the other preparation steps unchanged.
Comparative example 1
Membrane electrode slurry was prepared according to the catalyst/perfluorosulfonic acid resin ratio of example 3 without the use of an adhesive, comprising the steps of:
a) according to the proportion of deionized water to isopropanol being 1: 1, preparing a water-alcohol mixed solution, wherein a catalyst WC accounts for 15 wt% of the total amount of membrane electrode slurry; the perfluorinated sulfonic acid resin solution is prepared according to the concentration of 5 wt%, and the amount of the perfluorinated sulfonic acid resin accounts for 3.5 wt% of the total amount of the membrane electrode slurry;
b) adding 15.1 wt% of water-alcohol mixed solution into WC, placing in a high-speed shearing emulsifying machine, and stirring at 60 deg.C and 2000rpm for 15 min;
c) and (3) reducing the rotating speed of the high-speed shearing emulsifying machine to 500rpm, dropwise adding the perfluorinated sulfonic acid resin solution while stirring, increasing the rotating speed to 2500rpm after the dropwise adding is finished, and continuously dispersing for 50min to obtain membrane electrode slurry 7.
Comparative example 2
PVDF aqueous dispersion emulsion with the viscosity average molecular weight of 20 ten thousand is selected as an adhesive according to the mixture ratio and the raw materials of the embodiment 2, and the nano-microspheres D of the PVDF aqueous dispersion emulsion 50 50nm, solid content 27 wt%. The traditional process for preparing membrane electrode slurry comprises the following steps:
a) according to the proportion of deionized water to isopropanol being 1: 1 preparing water-alcohol mixed liquorCatalyst IrO 2 Accounting for 30 wt% of the total amount of the membrane electrode slurry; the perfluorinated sulfonic acid resin solution is prepared according to the concentration of 5 wt%, and the amount of the perfluorinated sulfonic acid resin accounts for 2.33 wt% of the total amount of the membrane electrode slurry; the solid content of the PVDF emulsion is 27 wt%, and the dosage is 3.7 wt% of the total amount of the membrane electrode slurry;
b) IrO catalyst 2 Placing the perfluorinated sulfonic acid resin solution, the PVDF emulsion and the water-alcohol mixed solution into a high-speed shearing emulsifying machine, and stirring at the rotating speed of 5000rpm for 120min at the temperature of 60 ℃; membrane electrode slurry 8 is obtained.
Comparative example 3
Replacement of the polyvinylidene fluoride-hexafluoropropylene copolymer of example 1 with D 50 The membrane electrode slurry 9 was obtained as a micron-sized powder of 10 μm under the same conditions.
Comparative example 4
The polyvinylidene fluoride-hexafluoropropylene copolymer of example 1 was replaced with amorphous particle powder, and other conditions were completely the same, to obtain membrane electrode slurry 10.
The membrane electrode slurries prepared in the examples and the comparative examples are prepared into membrane electrodes according to the method of CN114050277A, and various performance indexes of the membrane electrodes are detected by the following method:
porosity: testing by a mercury porosimeter according to GB/T21650.1-2008;
total pore area: testing by a mercury porosimeter according to GB/T21650.1-2008;
tortuosity: the test is carried out according to GB/T21650.1-2008 by a mercury porosimeter.
TABLE 1 pore size analysis results of the electrodes
The data in table 1 clearly show that the porosity of the membrane electrode is obviously increased and the pore area is increased along with the increase of the addition amount of the adhesive; the reduction of the particle size and the broadening of the particle size distribution of the adhesive can also cause the increase of the porosity and the increase of the tortuosity of the membrane electrode; however, if the formula is the same, the membrane electrode obtained by the traditional pulping method instead of the preparation method provided by the patent is not well dispersed, so that the stacking among particles is not uniform, the local stacking is tight, and the total pore area is reduced.
Fig. 2 shows a polarization performance graph of the membrane electrodes prepared in examples and comparative examples, and it can be seen that in the electrode prepared according to the present invention, the porosity and pore area of the electrode are increased due to the introduction of the stacked structure of multi-scale particles, more reaction sites are exposed, and the gas mass transfer channels are increased, so that the voltage is reduced and the electrochemical performance of the membrane electrode is more excellent under the same current density. The proton channel is mainly born by the perfluorinated sulfonic acid resin, the preparation method provided by the patent improves the dispersion uniformity of the adhesive in the proton exchange resin solution, can ensure that the contact between the catalyst in the electrode and the membrane is more compact and uniform, can easily obtain a better proton transfer path, and improves the electrochemical performance of the membrane electrode.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The adhesive for the membrane electrode is characterized by being a nano micro-spherical fluorocarbon polymer.
2. The adhesive for a membrane electrode according to claim 1, wherein the fluorocarbon polymer is one or more selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer and aqueous dispersion emulsion thereof, preferably one or more selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer and polytetrafluoroethylene and aqueous dispersion emulsion thereof.
3. The adhesive for a membrane electrode according to claim 1 or 2, wherein the fluorocarbon polymer has a viscosity average molecular weight of 1 to 700000, preferably 5000 to 500000.
4. The adhesive for membrane electrode according to claim 1, wherein the fluorocarbon polymer nanospheres have a dimension D 50 0.01-5 μm, preferably 50-400 nm, and spherical.
5. A preparation method of membrane electrode slurry for a proton exchange membrane water electrolyzer is characterized by comprising the following steps:
a) mixing a catalyst, perfluorinated sulfonic acid resin, deionized water and an organic solvent, placing the mixture in a high-speed shearing emulsifying machine for pulping to obtain mixed slurry 1, preferably pulping at 40-80 ℃ at the rotating speed of 1000-5000 rpm for 30-120 min;
b) and adding the adhesive powder or the aqueous dispersion emulsion thereof into the mixed slurry 1, putting the mixture into a sand mill to submerge and disperse, preferably dispersing for 30-90 min at the rotating speed of 300-3000 rpm until the viscosity of the slurry reaches 50-800 mPa & s, and discharging to obtain the membrane electrode slurry.
6. The preparation method of claim 5, wherein in the step a), the catalyst, the organic solvent and deionized water are placed in a high-speed shearing emulsifying machine, the mixture is stirred at the rotating speed of 2000-5000 rpm for 15-60 min at 40-80 ℃, then the rotating speed is reduced to 300-2000 rpm, the perfluorinated sulfonic acid resin solution is dropwise added while stirring, the rotating speed is increased to 2000-5000 rpm after the dropwise addition is finished, and the dispersion is continued for 30-60 min, so that the mixed slurry 1 is obtained.
7. The preparation method according to claim 5 or 6, wherein the catalyst accounts for 3-35 wt% of the membrane electrode slurry, the perfluorosulfonic acid resin accounts for 0.3-30 wt% of the membrane electrode slurry, and the dry weight of the adhesive accounts for 0.1-10 wt% of the membrane electrode slurry.
8. A method of preparing a membrane electrode slurry according to claim 5 or 6, wherein the catalyst is selected from IrO 2 、RuO 2 、SnO 2 One or more of Pt/C, PtIr/C, WC and WN; preferably, the organic solvent is one or more of ethanol, N-propanol, isopropanol, ethylene glycol, tetrahydrofuran, acetone or N-methylpyrrolidone.
9. A membrane electrode for a water electrolyzer with proton exchange membrane, characterized in that it is made from the membrane electrode slurry prepared by the preparation method of any one of claims 5 to 8.
10. A proton exchange membrane water electrolyser comprising the membrane electrode of claim 9.
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