CN113564633A - Water electrolysis membrane electrode, preparation method thereof and electrolytic cell - Google Patents
Water electrolysis membrane electrode, preparation method thereof and electrolytic cell Download PDFInfo
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Abstract
The invention provides a preparation method of a water electrolysis membrane electrode. The method comprises the steps of mixing, stirring and pre-adsorbing a prepared Pt-containing compound solution and conductive carbon black, then adding a Nafion solution and an isopropanol solution to mix to obtain a Pt-containing compound pre-sprayed liquid for preparing a cathode catalyst layer, mixing, stirring and pre-adsorbing an Ir compound solution and nano tin antimony oxide (ATO), then adding a Nafion solution and an isopropanol solution to mix and disperse to obtain an Ir-containing compound pre-sprayed liquid for preparing an anode catalyst layer. And respectively spraying the two pre-sprayed liquids on a proton exchange membrane, and then obtaining the membrane electrode by utilizing in-situ reduction. According to the invention, the binding force between the catalyst particles and the carrier is improved through pre-adsorption, the distribution uniformity of the catalyst particles in the membrane is improved, the growth of the noble metal nanoparticles is limited by utilizing the space blocking effect of Nafion resin on metal ions, the dispersity of the catalyst particles is improved, the noble metal loading amount of a catalyst layer in the membrane electrode is reduced, the catalyst utilization rate is improved, and thus the performance of the membrane electrode is improved.
Description
Technical Field
The invention belongs to the technical field of water electrolysis by proton exchange membranes, and particularly relates to a water electrolysis membrane electrode, a preparation method thereof and an electrolytic cell.
Background
The proton exchange membrane water electrolysis technology has the important advantages of low overpotential, high electrolysis efficiency, no equipment corrosion problem, high purity of produced hydrogen, simple equipment maintenance and the like, and is considered to be the water electrolysis technology with the greatest development prospect. The foreign proton exchange membrane water electrolysis technology accounts for about 30 percent of the specific gravity of the electrolyzed water, and in China, the specific gravity is only about 3 percent. The problems that exist at present include: the noble metal catalyst causes higher cost, the electrolysis efficiency can not meet the requirements of new energy technology, and the binding force between the catalyst layer and the proton exchange membrane is not enough, so that the stability of the electrolytic cell is reduced. Therefore, the important subjects in the field are to improve the cost performance of water electrolysis of the proton exchange membrane, reduce the consumption of the noble metal catalyst, improve the preparation technology and improve the stability of the catalyst layer.
Patent CN105742652A adopts ion exchange-reduction deposition method to sequentially reduce and deposit metal ions on the proton exchange membrane, so that the catalyst layer and the proton exchange membrane are tightly combined, and can well resist the impact of water flow and gas in the electrolysis process, and has very outstanding stability. However, the following disadvantages are present in this patent: (1) the adoption of a precursor containing chlorine ions causes residual chlorine to poison the catalyst; (2) noble metal ion adsorption and reduction are passively carried out by swelling, so that on one hand, the loading capacity of the membrane electrode is difficult to control, the process is complex and tedious, on the other hand, the catalyst is unevenly distributed, the utilization rate of the catalyst is reduced, and the performance of the membrane electrode is reduced.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a water electrolysis membrane electrode, a preparation method thereof, and an electrolytic cell, and the membrane electrode provided by the present invention has the characteristics of uniform catalyst distribution in the cathode and anode catalyst layers, low catalyst loading capacity, high electrolysis efficiency, and good electrode stability.
The invention provides a preparation method of a water electrolysis membrane electrode, which comprises the following steps:
1) mixing and stirring a Pt-containing compound solution and conductive carbon black, adding a Nafion resin solution and an isopropanol solution, and mixing to obtain a Pt-containing compound pre-spraying solution;
mixing and stirring Ir-containing compound solution and nano ATO powder, adding Nafion resin solution and isopropanol solution, and mixing to obtain Ir-containing compound pre-spraying solution;
2) spraying the Pt-containing compound pre-spraying solution on the cathode of a Nafion film, spraying the Ir-containing compound pre-spraying solution on the anode, and performing hot pressing after the spraying is finished to obtain a hot-pressed electrode film;
3) and placing the electrode membrane after hot pressing in a reducing solution for reaction, and removing metal ions to obtain the water electrolysis membrane electrode.
Preferably, the Pt-containing compound solution is a chloride ion-free Pt-containing compound solution, and the preparation method of the chloride ion-free Pt-containing compound solution includes the following steps:
adjusting the pH of the Pt precursor solution, and then dropwise adding a soluble silver salt dilute solution to form AgCl precipitate;
the Pt precursor is selected from one or more of platinum chloride, chloroplatinic acid, potassium chloroplatinite, sodium chloroplatinate and sodium chloroplatinite;
the Ir compound solution is a chloride ion-free Ir compound solution, and the preparation method of the chloride ion-free Ir compound solution comprises the following steps:
adjusting the pH of the Ir precursor solution, and then dropwise adding a soluble silver salt dilute solution to form AgCl precipitate;
the Ir precursor is selected from one or more of iridium chloride, chloroiridate, sodium chloroiridate and potassium chloroiridate;
the soluble silver salt is selected from silver nitrate or silver acetate.
Preferably, in the Pt-containing compound pre-spraying solution, the mass ratio of the solid contents of Pt and Nafion resin solution is 1: 2-10, and the mass ratio of Pt: the mass ratio of C is 1 (1-4);
in the Ir-containing compound pre-spraying solution, the solid content mass ratio of Ir to Nafion resin solution is 1: 2-10; ir: the mass ratio of ATO is 1 (1-9);
the particle size of the ATO powder is 20-80 nm.
Preferably, the solid content of the Pt-containing compound pre-spraying solution is 0.1-5%;
the solid content of the pre-spraying solution containing Ir compound is 0.1-5%.
Preferably, the hot pressing temperature is 130-160 ℃, and the hot pressing time is 60-180 s.
Preferably, the reducing agent in the reducing solution is selected from sodium borohydride and/or hydrazine hydrate, and the mass fraction of the reducing agent in the reducing solution is 0.1-1%.
Preferably, in the step 4), the reaction temperature is 25-80 ℃, and the reaction time is 0.5-24 h.
Preferably, the method for removing alkali metal ions comprises:
and (3) placing the electrode membrane subjected to the reduction reaction in a sulfuric acid solution, and treating at 60-80 ℃ for 0.5-4 h to remove metal ions through exchange.
The invention also provides a water electrolysis membrane electrode prepared by the preparation method, wherein the Pt loading amount in the membrane electrode is 0.05-0.5 mg/cm2The Ir supporting amount is 0.1-1 mg/cm2。
The invention also provides an application of the water electrolysis membrane electrode in an electrolytic cell.
Compared with the prior art, the invention provides a preparation method of a water electrolysis membrane electrode, which comprises the following steps: 1) mixing and stirring a Pt-containing compound solution and conductive carbon black, adding a Nafion resin solution and an isopropanol solution, and mixing to obtain a Pt-containing compound pre-spraying solution; mixing and stirring Ir-containing compound solution and nano ATO powder, adding Nafion resin solution and isopropanol solution, and mixing to obtain Ir-containing compound pre-spraying solution; 2) spraying the Pt-containing compound pre-spraying solution on the cathode of a Nafion film, spraying the Ir-containing compound pre-spraying solution on the anode, and performing hot pressing after the spraying is finished to obtain a hot-pressed electrode film; 3) and placing the electrode membrane after hot pressing in a reducing solution for reaction, and removing metal ions to obtain the water electrolysis membrane electrode.
The method comprises the steps of mixing, stirring and pre-adsorbing a prepared Pt-containing compound solution and conductive carbon black, then adding a Nafion solution and an isopropanol solution to mix to obtain a Pt-containing compound pre-sprayed liquid for preparing a cathode catalyst layer, mixing, stirring and pre-adsorbing an Ir compound solution and nano tin antimony oxide (ATO), then adding a Nafion solution and an isopropanol solution to mix and disperse to obtain an Ir-containing compound pre-sprayed liquid for preparing an anode catalyst layer. And respectively spraying the two pre-sprayed liquids on a proton exchange membrane, and then obtaining the membrane electrode by utilizing in-situ reduction. According to the invention, the binding force between the catalyst particles and the carrier is improved through pre-adsorption, the distribution uniformity of the catalyst particles in the membrane is improved, the growth of the noble metal nanoparticles is limited by utilizing the space blocking effect of Nafion resin on metal ions, the dispersity of the catalyst particles is improved, the noble metal loading amount of a catalyst layer in the membrane electrode is reduced, the catalyst utilization rate is improved, and thus the performance of the membrane electrode is improved.
Drawings
FIG. 1 is a graph of the I-V performance of example 1 and comparative membrane electrodes in a water electrolytic cell;
FIG. 2 is a schematic view of the structure of the water electrolytic cell provided by the present invention;
fig. 3 is a schematic structural view of a membrane electrode hollow jig prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a water electrolysis membrane electrode, which comprises the following steps:
1) mixing and stirring a Pt-containing compound solution and conductive carbon black, adding a Nafion resin solution and an isopropanol solution, and mixing to obtain a Pt-containing compound pre-spraying solution;
mixing and stirring Ir-containing compound solution and nano ATO powder, adding Nafion resin solution and isopropanol solution, and mixing to obtain Ir-containing compound pre-spraying solution;
2) spraying the Pt-containing compound pre-spraying solution on the cathode of a Nafion film, spraying the Ir-containing compound pre-spraying solution on the anode, and performing hot pressing after the spraying is finished to obtain a hot-pressed electrode film;
3) and placing the electrode membrane after hot pressing in a reducing solution for reaction, and removing metal ions to obtain the water electrolysis membrane electrode.
The method comprises the steps of firstly preparing a Pt-containing compound solution and an Ir-containing compound solution, wherein the Pt-containing compound solution and the Ir-containing compound solution are respectively a Pt-containing compound solution without chloride ions and an Ir-containing compound solution without chloride ions.
Wherein the preparation method of the Pt-containing compound solution without chloride ions comprises the following steps:
mixing a Pt precursor with ultrapure water to prepare a solution containing the Pt precursor, wherein the mass concentration of the solution is 10-20%, preferably any value between 10%, 12%, 15%, 17%, 20% or 10-20%; the Pt precursor is selected from one or more of platinum chloride, chloroplatinic acid, potassium chloroplatinite, sodium chloroplatinite and sodium chloroplatinite, and is preferably platinum chloride or chloroplatinic acid.
And adjusting the pH value of the solution containing the Pt precursor to be below 1, then dropwise adding a soluble silver salt dilute solution to form AgCl precipitate, and filtering to obtain a Pt-containing compound solution without chloride ions, wherein the soluble silver salt is selected from silver nitrate or silver acetate. The amount of the soluble silver salt dilute solution is enough to precipitate all chloride ions in the solution containing the Pt precursor.
The preparation method of the Ir compound containing solution without chloride ions comprises the following steps:
mixing an Ir precursor with ultrapure water to prepare a solution containing a Pt precursor, wherein the mass concentration of the solution is 10-20%, preferably any value between 10%, 12%, 15%, 17%, 20% or 10-20%; the Ir precursor is selected from one or more of iridium chloride, chloroiridate, sodium chloroiridate and potassium chloroiridate, and is preferably iridium chloride or chloroiridate.
And adjusting the pH value of the solution containing the Ir precursor to be less than 1, then dropwise adding a soluble silver salt dilute solution to form AgCl precipitate, and filtering to obtain an Ir-containing compound solution B without chloride ions, wherein the soluble silver salt is selected from silver nitrate or silver acetate. The amount of the soluble silver salt dilute solution is enough to precipitate all chloride ions in the solution containing the Ir precursor.
The method uses the chlorine-free Pt-containing compound solution and the chlorine-free Ir-containing compound solution, thereby avoiding the poisoning effect of chloride ions on the catalyst.
After a Pt-containing compound solution without chloride ions and an Ir-containing compound solution without chloride ions are obtained, mixing and stirring the Pt-containing compound solution and conductive carbon black, adding a Nafion resin solution and an isopropanol solution, and mixing to obtain a Pt-containing compound pre-spraying solution;
wherein in the Pt-containing compound pre-spraying solution, the mass ratio of the solid contents of Pt and Nafion resin solution is 1: 2-10, preferably 1:2, 1:4, 1:6, 1:8, 1:10, or any value between 1: 2-10; pt: the mass ratio of C is 1 (1-4), preferably any value between 1:1, 1:2, 1:3, 1:4, or 1 (1-4), and the solid content of the Pt-containing compound pre-spraying solution is 0.1-5%, preferably any value between 0.1%, 0.5%, 1%, 2%, 2.5%, 5%, or 0.1-5%.
In the invention, the mixing is mixing emulsification, and the mixing emulsification is mixing emulsification for 0.5-2 h by using a high-speed shearing machine.
Mixing and stirring the Ir-containing compound solution and the nano ATO powder, adding a Nafion resin solution and an isopropanol solution, and mixing to obtain an Ir-containing compound pre-spraying solution;
wherein the particle size of the ATO powder is preferably 20-80 nm.
In the Ir-containing compound pre-spraying solution, the solid content mass ratio of Ir to Nafion resin solution is 1: 2-10, preferably 1:2, 1:4, 1:6, 1:8, 1:10, or any value between 1: 2-10; ir: the mass ratio of ATO is 1 (1-9), preferably any value between 1:1, 1:3, 1:5, 1:7, 1:9, or 1 (1-9), and the solid content of the Ir-containing compound pre-spraying solution is 0.1-5%, preferably any value between 0.1%, 0.5%, 1%, 2%, 2.5%, 5%, or 0.1-5%.
In the invention, the mixing is mixing emulsification, and the mixing emulsification is mixing emulsification for 1-24 h by using a high-speed ball mill.
And then spraying a Pt-containing compound pre-spraying solution on the cathode of the cut and edge-sealed adsorbed Nafion membrane, spraying an Ir-containing compound pre-spraying solution on the anode, and performing hot pressing after the spraying is finished to obtain a hot-pressed electrode membrane.
The preparation method of the Nafion membrane subjected to cutting, edge sealing and adsorption comprises the following steps: and (3) placing the cut Nafion film on an ultrasonic spraying workbench, heating to 60-100 ℃, and sealing and adsorbing.
The hot pressing temperature is 130-160 ℃, preferably 130, 140, 150, 160 or any value between 130-160 ℃, and the hot pressing time is 60-180 s, preferably 60, 80, 100, 120, 140, 160 or any value between 60-180 s.
And finally, placing the electrode membrane after hot pressing in a reducing solution for reaction, and then performing ion exchange to obtain a water electrolysis membrane electrode.
The reducing agent in the reducing liquid is selected from sodium borohydride and/or hydrazine hydrate, and the mass fraction of the reducing agent in the reducing liquid is 0.1-1%, preferably 0.1%, 0.3%, 0.5%, 0.7%, 1.0%, or any value between 0.1-1%;
the reaction temperature is 25-80 ℃, preferably 25, 35, 45, 55, 65, 75, 80 or any value between 25-80 ℃, and the reaction time is 0.5-24 h, preferably 0.5, 1, 5, 10, 12, 15, 20, 24 or any value between 0.5-24 h.
In the invention, the ion exchange method comprises the following steps: and (3) placing the electrode membrane subjected to the reduction reaction in a sulfuric acid solution, treating for 0.5-4 h at 60-80 ℃ for exchange removal of metal ions, wherein the treatment temperature is preferably any value between 60, 70 and 80 or between 60 and 80 ℃, and the treatment time is any value between 0.5, 1, 2, 3 and 4 or between 0.5 and 4 h.
In the invention, the solid content of the pre-spraying liquid can be adjusted to further design a gradient distribution catalytic layer. In some embodiments of the present invention, 10%, 20%, and 30% solid catalyst is sprayed on the anode catalyst layer in sequence to form a three-layer structure. In the invention, the catalyst layer is set to be in gradient distribution, so that the catalyst loading capacity can be further reduced, and the membrane electrode performance is improved.
The invention also provides a water electrolysis membrane electrode prepared by the preparation method, wherein the Pt loading amount in the membrane electrode is 0.05-0.5 mg/cm2Preferably 0.05 to 0.3mg/cm2The Ir supporting amount is 0.1-1 mg/cm2Preferably 0.1 to 0.5mg/cm2。
The invention also provides an electrolytic cell which comprises the water electrolysis membrane electrode.
The method comprises the steps of mixing, stirring and pre-adsorbing a prepared Pt-containing compound solution and conductive carbon black, then adding a Nafion solution and an isopropanol solution to mix to obtain a Pt-containing compound pre-sprayed liquid for preparing a cathode catalyst layer, mixing, stirring and pre-adsorbing an Ir compound solution and nano tin antimony oxide (ATO), then adding a Nafion solution and an isopropanol solution to mix and disperse to obtain an Ir-containing compound pre-sprayed liquid for preparing an anode catalyst layer. And respectively spraying the two pre-sprayed liquids on a proton exchange membrane, and then obtaining the membrane electrode by utilizing in-situ reduction. According to the invention, the binding force between the catalyst particles and the carrier is improved through pre-adsorption, the distribution uniformity of the catalyst particles in the membrane is improved, the growth of the noble metal nanoparticles is limited by utilizing the space blocking effect of Nafion resin on metal ions, the dispersity of the catalyst particles is improved, the noble metal loading amount of a catalyst layer in the membrane electrode is reduced, the catalyst utilization rate is improved, and thus the performance of the membrane electrode is improved.
In order to further understand the present invention, the following describes the water electrolysis membrane electrode, the preparation method thereof and the electrolytic cell provided by the present invention with reference to the following examples, and the protection scope of the present invention is not limited by the following examples.
Example 1 cathode Pt loading 0.3mg/cm2Anode Ir supporting capacity of 0.5mg/cm2Membrane electrode preparation
(1) Respectively preparing diluted solutions with the mass ratio of 15% by using platinum chloride and iridium chloride, adjusting the pH value to be below 1, and respectively using silver acetate [ the molar ratio Ag: slowly dropwise adding (Pt + Ir) ═ 1 (1.1-1.2) dilute solution to form AgCl precipitate, and filtering to obtain Pt-containing compound solution A without chloride ions and Ir-containing compound solution B without chloride ions;
(2) mixing and stirring the solution A and quantitative conductive carbon black to ensure that the mass ratio of platinum to carbon is 3:7, then adding a Nafion resin solution (the mass ratio of the Pt to the solid content of Nafion is 1:3) and an isopropanol solution, and respectively mixing and emulsifying for 6h by using a high-speed shearing machine to obtain a Pt-containing compound pre-spraying solution, wherein the solid content of the slurry is 1%;
mixing and stirring the solution B and the nano ATO powder to ensure that Ir: adding a quantitative Nafion solution (the mass ratio of Ir to the solid content of Nafion is 1:4) and an isopropanol solution into ATO powder at a mass ratio of 1:4, and respectively mixing and emulsifying for 6h by using a high-speed ball mill to obtain a pre-spraying solution containing Ir compounds, wherein the solid content of the slurry is 1%;
(3) placing the cut Nafion membrane on an ultrasonic spraying workbench, heating to 90 ℃, carrying out edge sealing adsorption, spraying a Pt-containing compound pre-spraying solution on a cathode, and spraying an Ir-containing compound pre-spraying solution on an anode to enable the Pt loading capacity of the membrane electrode to be 0.3mg/cm2Ir supporting amount of 0.5mg/cm2Hot pressing at 130 deg.C for 180s after spraying;
(4) and (3) putting the hot-pressed membrane into sodium borohydride with the mass fraction of 0.5%, and heating to 80 ℃ for reaction for 12 hours.
(5) The membrane electrode is placed in sulfuric acid solution for treatment at 80 ℃ for 2h for exchange to remove metal ions Na+，K+And the like, so that the proton exchange membrane well recovers the proton conductivity thereof, and the membrane electrode is obtained.
(6) And assembling the obtained membrane electrode into a water electrolytic cell, wherein the structural schematic diagram of the water electrolytic cell is shown in figure 2, wherein 1 and 5 are polar plates with flow channels, 2 is carbon paper, 3 is a membrane electrode, 4 is a titanium felt, 6 is an ultrapure water inlet, 7 is an ultrapure water outlet, 8 is an oxygen outlet, and 9 is a fastening bolt.
Referring to fig. 1, fig. 1 is an I-V performance curve of example 1 and comparative membrane electrodes on a water electrolyzer test bench, under the following test conditions: the temperature of the electrolytic cell is 60 ℃, the water flow at the anode side is 15ml/min, and the area of the membrane electrode is 4cm2And the operation is carried out at normal pressure. As can be seen from FIG. 1, the membrane electrode prepared in example 1 has a test voltage of only 1.94V @2A/cm in a water electrolytic cell under the same noble metal loading2Is far lower than the membrane electrode test voltage of 2.12V @2A/cm of comparative example 12Comparative example 2 Membrane electrode test Voltage 2.91V @2A/cm2.
Comparative example 1: cathode Pt loading capacity of 0.3mg/cm2Anode Ir supporting capacity of 0.5mg/cm2Membrane electrode preparation
(1) According to the Pt loading capacity of the cathode, 0.3mg/cm2Carbon powder, chloroplatinic acid, and Nafion solution (Pt: C: Nafion solid content mass ratio 3:7:9) were quantitatively prepared. Mixing carbon powder and Nafion solution, adding isopropanol to make the solid content of the slurry be 1%, ultrasonically dispersing, spraying the slurry onto a proton exchange membrane, and drying to obtain a cathode substrate layer. Mixing chloroplatinic acid and formic acid according to the molar ratio of 1:10, and adding 40ml of ultrapure water to form cathode impregnation liquid A;
(2) according to the anode Ir loading capacity of 0.5mg/cm2ATO, chloroiridic acid, and a Nafion solution were quantitatively prepared (Ir: ATO: Nafion solid content mass ratio: 2:8: 6). Mixing ATO and Nafion solution, adding isopropanol to enable the solid content of the slurry to be 1%, ultrasonically dispersing, spraying the slurry to the other side of the proton exchange membrane, and drying to obtain an anode substrate layer. Adding chloroiridic acid into 40ml of ultrapure water to form anode impregnation liquid B;
(3) clamping the proton exchange membrane with the substrate layer with a hollow clamp, pouring the impregnation liquid A into the cathode side, and reacting at room temperature for 48h to deposit 0.3mg/cm on the cathode2And (3) pouring out the reaction solution and airing after the reaction is finished. Pouring B into the cathode side, soaking at room temperature for 48h, slowly dropwise adding 0.1mol/L sodium borohydride solution until the reaction solution is clear, pouring out the supernatant, and drying to obtain the product, namely depositing 0.5mg/cm at the anode2Ir。
(4) The resulting membrane electrode was hot pressed at 130 ℃ for 180 s.
Comparative example 2 cathode Pt loading 0.34mg/cm2Anode Ir supporting capacity of 0.54mg/cm2Membrane electrode preparation
Placing the cut proton exchange membrane in a hollow clamp (figure 3), adding 20ml of 30g/L chloroplatinic acid solution into a cavity on one side, standing at room temperature for exchange for 3h, removing the Pt-containing solution, adding 20ml of 0.05mol/L sodium borohydride solution, and reducing at room temperature for 1h to obtain the proton exchange membrane with the cathode catalyst layer; and adding 20ml of 20g/L chloroiridic acid solution into a cavity on the other side of the hollow clamp, exchanging for 3 hours at room temperature, replacing 20ml of new 20g/L chloroiridic acid solution, exchanging for 3 hours at room temperature again, removing the Ir-containing solution, adding 20ml of 0.1mol/L sodium borohydride solution, and reducing for 1 hour at normal temperature to obtain the membrane electrode. Sampling and carrying out ICP component test to obtain the Pt loading capacity of the cathode of the membrane electrode of 0.34mg/cm2Anode Ir supporting capacity of 0.54mg/cm2。
Referring to fig. 3, in fig. 3, 1 and 3 are tooling fixtures, 2 is a proton exchange membrane, and 4 is a fixing bolt.
Example 2 cathode Pt Loading 0.05mg/cm2Anode Ir supporting capacity 0.1mg/cm2Membrane electrode preparation
(1) Respectively preparing chloroplatinic acid and chloroiridic acid into dilute solutions with the mass ratio of 10%, adjusting the pH value to be below 1, respectively and slowly dropwise adding a slight excess of silver nitrate dilute solution to form AgCl precipitate, and filtering to obtain a Pt-containing compound solution A without chloride ions and an Ir-containing compound solution B without chloride ions;
(2) mixing and stirring the solution A and quantitative conductive carbon black to ensure that the mass ratio of platinum to carbon is 4:6, then adding a Nafion resin solution (the mass ratio of the Pt to the solid content of Nafion is 1:2) and an isopropanol solution, and respectively mixing and emulsifying for 0.5h by using a high-speed shearing machine to obtain a Pt-containing compound pre-spraying solution, wherein the solid content of the slurry is 0.5%;
mixing and stirring the solution B and the nano ATO powder to ensure that Ir: adding quantitative Nafion solution (the mass ratio of Ir to Nafion solid content is 1:2) and isopropanol solution into ATO powder at a mass ratio of 4:6, and respectively mixing and emulsifying for 1h by using a high-speed ball mill to obtain a pre-spraying solution containing Ir compounds, wherein the solid content of the slurry is 0.5%;
(3) placing the cut Nafion membrane on an ultrasonic spraying workbench, heating to 60 ℃, spraying a Pt-containing compound pre-spraying solution on a cathode after edge sealing and adsorption, and spraying an Ir-containing compound pre-spraying solution on an anode to ensure that the Pt loading capacity of the membrane electrode is 0.05mg/cm2Ir supporting amount of 0.1mg/cm2Hot pressing at 130 deg.C for 180s after spraying;
(4) and (3) putting the membrane electrode after hot pressing into sodium borohydride with the mass fraction of 0.1%, and heating to 80 ℃ for reaction for 0.5 h.
(5) The membrane electrode is placed in sulfuric acid solution for treatment at 80 ℃ for 0.5h to remove metal ions Na through exchange+，K+Etc., so that the proton exchange membrane well recovers its proton conductivity.
Example 3 cathode Pt Loading 0.5mg/cm2Anode Ir supporting amount of 1mg/cm2Membrane electrode preparation
(1) Preparing a dilute solution with the mass ratio of 20% by using platinum chloride or iridium chloride, adjusting the pH value to be below 1, slowly dropwise adding a slight excess of a dilute silver acetate solution to form AgCl precipitate, and filtering to obtain a Pt-containing compound solution A without chloride ions and an Ir-containing compound solution B without chloride ions;
(2) mixing and stirring the solution A and quantitative conductive carbon black to ensure that the mass ratio of platinum to carbon is 1:4, then adding a Nafion resin solution (the mass ratio of the Pt to the solid content of Nafion is 1:10) and an isopropanol solution, and respectively mixing and emulsifying for 24h by using a high-speed shearing machine to obtain a Pt-containing compound pre-spraying solution, wherein the solid content of the slurry is 5%; mixing and stirring the solution B and the nano ATO powder to ensure that Ir: adding a quantitative Nafion solution (the mass ratio of Ir to the solid content of Nafion is 1:10) and an isopropanol solution into ATO powder at a mass ratio of 1:9, and respectively mixing and emulsifying for 24h by using a high-speed ball mill to obtain a pre-spraying solution containing Ir compounds, wherein the solid content of the slurry is 5%;
(3) placing the cut Nafion membrane on an ultrasonic spraying workbench, heating to 100 ℃, spraying a Pt-containing compound pre-spraying solution on a cathode after edge sealing and adsorption, and spraying an Ir-containing compound pre-spraying solution on an anode to ensure that the Pt loading capacity of the membrane electrode is 0.5mg/cm2Ir supporting amount of 1mg/cm2Hot pressing at 130 deg.C for 180s after spraying;
(4) and (3) putting the hot-pressed film into hydrazine hydrate with the mass fraction of 1%, and heating to 80 ℃ for reaction for 24 hours.
(5) The membrane electrode is placed in sulfuric acid solution for treatment at 80 ℃ for 4h for exchange to remove metal ions Na+，K+Etc., so that the proton exchange membrane well recovers its proton conductivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the water electrolysis membrane electrode is characterized by comprising the following steps:
1) mixing and stirring a Pt-containing compound solution and conductive carbon black, adding a Nafion resin solution and an isopropanol solution, and mixing to obtain a Pt-containing compound pre-spraying solution;
mixing and stirring Ir-containing compound solution and nano ATO powder, adding Nafion resin solution and isopropanol solution, and mixing to obtain Ir-containing compound pre-spraying solution;
2) spraying the Pt-containing compound pre-spraying solution on the cathode of a Nafion film, spraying the Ir-containing compound pre-spraying solution on the anode, and performing hot pressing after the spraying is finished to obtain a hot-pressed electrode film;
3) and placing the electrode membrane after hot pressing in a reducing solution for reaction, and removing metal ions to obtain the water electrolysis membrane electrode.
2. The method according to claim 1, wherein the Pt-containing compound solution is a chloride ion-free Pt-containing compound solution, and the method for preparing the chloride ion-free Pt-containing compound solution comprises the steps of:
adjusting the pH of the Pt precursor solution, and then dropwise adding a soluble silver salt dilute solution to form AgCl precipitate;
the Pt precursor is selected from one or more of platinum chloride, chloroplatinic acid, potassium chloroplatinite, sodium chloroplatinate and sodium chloroplatinite;
the Ir compound solution is a chloride ion-free Ir compound solution, and the preparation method of the chloride ion-free Ir compound solution comprises the following steps:
adjusting the pH of the Ir precursor solution, and then dropwise adding a soluble silver salt dilute solution to form AgCl precipitate;
the Ir precursor is selected from one or more of iridium chloride, chloroiridate, sodium chloroiridate and potassium chloroiridate;
the soluble silver salt is selected from silver nitrate or silver acetate.
3. The preparation method according to claim 1, wherein in the pre-spraying solution of the Pt-containing compound, the mass ratio of the solid contents of Pt and Nafion resin solution is 1: 2-10, and the mass ratio of Pt: the mass ratio of C is 1 (1-4);
in the Ir-containing compound pre-spraying solution, the solid content mass ratio of Ir to Nafion resin solution is 1: 2-10; ir: the mass ratio of ATO is 1 (1-9);
the particle size of the ATO powder is 20-80 nm.
4. The preparation method according to claim 1, wherein the solid content of the Pt-containing compound pre-spraying solution is 0.1-5%;
the solid content of the pre-spraying solution containing Ir compound is 0.1-5%.
5. The method according to claim 1, wherein the hot-pressing temperature is 130 to 160 ℃ and the hot-pressing time is 60 to 180 seconds.
6. The preparation method according to claim 1, wherein the reducing agent in the reducing solution is selected from sodium borohydride and/or hydrazine hydrate, and the mass fraction of the reducing agent in the reducing solution is 0.1-1%.
7. The preparation method according to claim 1, wherein in the step 4), the reaction temperature is 25-80 ℃, and the reaction time is 0.5-24 h.
8. The method of claim 1, wherein the method for removing alkali metal ions comprises:
and (3) placing the electrode membrane subjected to the reduction reaction in a sulfuric acid solution, and treating at 60-80 ℃ for 0.5-4 h to remove metal ions through exchange.
9. The water electrolysis membrane electrode prepared by the preparation method according to any one of claims 1 to 8, wherein the Pt loading amount in the membrane electrode is 0.05 to 0.5mg/cm2The Ir supporting amount is 0.1-1 mg/cm2。
10. Use of a water electrolyte membrane electrode as claimed in claim 9 in an electrolytic cell.
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