CN116364990A - Membrane electrode and preparation method thereof - Google Patents
Membrane electrode and preparation method thereof Download PDFInfo
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- CN116364990A CN116364990A CN202310403789.4A CN202310403789A CN116364990A CN 116364990 A CN116364990 A CN 116364990A CN 202310403789 A CN202310403789 A CN 202310403789A CN 116364990 A CN116364990 A CN 116364990A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 60
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 229920000554 ionomer Polymers 0.000 claims abstract description 20
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 11
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003011 anion exchange membrane Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to a membrane electrode and a preparation method thereof. The preparation method of the membrane electrode provided by the invention comprises the following steps: (1) Activating the ion exchange membrane, and then depositing a conductive coating on the surface of the ion exchange membrane to obtain a pretreated ion exchange membrane; (2) Taking a pretreated ion exchange membrane as a working electrode, placing the working electrode, a counter electrode and a reference electrode in electrolyte containing a metal salt catalyst, and growing a catalyst layer on the surface of the pretreated ion exchange membrane in situ through electrochemical deposition; (3) Ionomer is coated on the surface of the catalyst layer and dried. According to the method, the ion exchange membrane is used as a substrate for in-situ growth of the catalyst, and the three-layer structure of the catalyst layer/the ion exchange membrane/the catalyst layer is directly obtained, so that the loss of catalyst raw materials in the preparation process is reduced, the bonding strength of the catalyst and the ion exchange membrane can be improved, and the electrochemical performance and the stability of a membrane electrode system are remarkably improved.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a membrane electrode and a preparation method thereof.
Background
Since the industrial revolution, human society and economy have developed at a high speed, but with the massive use of fossil energy, environmental problems have become more serious and global energy transformation is imperative. Under the background, the direct use of fossil fuels is limited, the proportion of renewable energy power generation is continuously increased, the process of're-electrification' is promoted, and the development of electrochemical devices is promoted.
The membrane electrode assembly (Membrane Electrode Assembly, MEA) is a core component of a proton exchange membrane fuel cell and a proton/anion exchange membrane electrolytic cell, plays a core role of mass transfer and energy exchange in electrochemical reaction, and plays a decisive role in the performance of an electrochemical device. Therefore, how to improve the electrochemical performance of the membrane electrode assembly is important.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems:
the membrane electrode assembly mainly comprises three key materials of a proton exchange membrane, a catalyst and a gas diffusion layer and a frame, wherein the combination condition of the catalyst layer and the ion exchange membrane plays a key role in the electrochemical performance of the membrane electrode assembly. At present, a five-in-one CCS (catalyst coated substrate) or three-in-one CCM (catalyst coated membrane) mode is mainly adopted for preparing the membrane electrode, and although the CCM method improves the bonding degree of the catalyst layer and the ion exchange membrane compared with the CCS method, the preparation process is still complex and is easily influenced by various environmental factors, the preparation process is not stable enough, and the consistency of the membrane electrode is not enough, so that the preparation mode of the membrane electrode still needs to be further explored.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a preparation method of a membrane electrode, which takes an ion exchange membrane as a substrate to grow a catalyst in situ, directly obtains a three-layer structure of a catalyst layer/the ion exchange membrane/the catalyst layer, can reduce the loss of catalyst raw materials in the preparation process, improves the bonding strength of the catalyst and the ion exchange membrane, and can prepare and control the physicochemical properties of the catalyst such as thickness, particle size and the like by changing experimental parameters, thereby avoiding the complex flow of the traditional membrane electrode preparation and remarkably improving the electrochemical performance and stability of a membrane electrode system.
The preparation method of the membrane electrode provided by the embodiment of the invention comprises the following steps:
(1) Activating the ion exchange membrane, and then depositing a conductive coating on the surface of the ion exchange membrane to obtain a pretreated ion exchange membrane;
(2) Taking the pretreated ion exchange membrane obtained in the step (1) as a working electrode, placing the working electrode, a counter electrode and a reference electrode in electrolyte containing a metal salt catalyst, and growing a catalyst layer on the surface of the pretreated ion exchange membrane in situ through electrochemical deposition;
(3) And (3) coating ionomer on the surface of the catalyst layer obtained in the step (2) and drying.
The method provided by the embodiment of the invention has the advantages and technical effects that 1, the conductive coating deposited on the surface of the ion exchange membrane can improve the conductivity of the ion exchange membrane on one hand, and can be used as a template on the ion exchange membrane to perform element replacement with the catalyst on the other hand, so that the catalyst is better deposited on the surface of the ion exchange membrane; 2. according to the method provided by the embodiment of the invention, the ion exchange membrane is taken as a substrate, and the electrochemical deposition in-situ growth catalyst is adopted, so that the bonding strength of the catalyst layer and the ion exchange membrane is improved, and the electrochemical performance and stability of the membrane electrode can be further improved; 3. the method of the embodiment of the invention simplifies the preparation process, is simple and easy to operate, and is convenient for popularization and application in industrial production.
In some embodiments, in step (1), the activating treatment comprises immersing the ion exchange membrane in a salt solution or an alkali solution.
In some embodiments, in the step (1), the conductive coating is deposited by vacuum sputtering; and/or the thickness of the conductive coating is 10-500 nm.
In some embodiments, in step (1), the conductive coating comprises at least one of platinum, palladium, nickel, iron, aluminum, copper.
In some embodiments, in step (2), the reference electrode is Ag/AgCl and the counter electrode is a platinum sheet or a graphite sheet; and/or the metal salt catalyst comprises H 2 PtCl 4 、Ni(NO 3 ) 2 、NiSO 4 、AgNO 3 、Zn(NO 3 ) 2 、Co(NO 3 ) 2 、CoCl 2 、Pb(ClO 4 ) 2 、Bi(CH 3 COO) 3 At least one of them.
In some embodiments, in the step (2), the concentration of the metal ion of the metal salt catalyst in the electrolyte is 0.01 to 0.1mol/L; and/or the electrolyte is H of 0.05-1 mol/L 2 SO 4 Or 0.1 to 2mol/L of HClO 4 。
In some embodiments, in the step (2), the scanning potential interval in the electrochemical deposition is 0.2-0.9V, the scanning speed is 1-100 mV/s, and the scanning circle number is 5-100.
In some embodiments, the step (2) further comprises, before electrochemically depositing the catalyst layer, subjecting the conductive coating on the surface of the pretreated ion-exchange membrane to a cleaning treatment; and/or, in the step (3), further comprising, before the ionomer is applied, performing a cleaning treatment on the catalyst layer.
In some embodiments, in step (3), the ionomer is present in an amount of 5 to 30wt% of the catalyst content.
The embodiment of the invention also provides a membrane electrode, which is prepared by adopting the method.
The membrane electrode prepared by the method has better bonding strength between the catalyst layer and the ion exchange membrane, so that the membrane electrode has better electrochemical performance and stability.
Drawings
FIG. 1 is a schematic illustration of the preparation of a catalyst in situ grown membrane electrode;
FIG. 2 is a scanning electron microscope image of in-situ grown platinum@copper film electrodes prepared in examples 1-3;
FIG. 3 is a graph showing comparison of electrolyzed water performance of the membrane electrodes prepared in example 1 and comparative examples 1 to 2;
FIG. 4 is a graph showing comparison of electrolytic water properties of the membrane electrodes prepared in example 1 and examples 4 to 5.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The preparation method of the membrane electrode provided by the embodiment of the invention comprises the following steps:
(1) Activating the ion exchange membrane, and then depositing a conductive coating on the surface of the ion exchange membrane to obtain a pretreated ion exchange membrane;
(2) Taking the pretreated ion exchange membrane obtained in the step (1) as a working electrode, placing the working electrode, a counter electrode and a reference electrode in electrolyte containing a metal salt catalyst, and growing a catalyst layer on the surface of the pretreated ion exchange membrane in situ through electrochemical deposition;
(3) And (3) coating ionomer on the surface of the catalyst layer obtained in the step (2) and drying.
The method provided by the embodiment of the invention has the advantages and technical effects that 1, the metal conductive coating deposited on the surface of the ion exchange membrane can improve the conductivity of the ion exchange membrane on one hand, and can be used as a template on the ion exchange membrane to perform element replacement with the catalyst on the other hand, so that the catalyst is better deposited on the surface of the ion exchange membrane; 2. according to the method provided by the embodiment of the invention, the ion exchange membrane is taken as a substrate, and the electrochemical deposition in-situ growth catalyst is adopted, so that the bonding strength of the catalyst layer and the ion exchange membrane is improved, and the electrochemical performance and stability of the membrane electrode can be further improved; 3. the method of the embodiment of the invention simplifies the preparation process, is simple and easy to operate, and is convenient for popularization and application in industrial production.
In some embodiments, preferably, in the step (1), the activation treatment is a soaking treatment of the ion exchange membrane in a salt solution or an alkali solution. Further preferably, when the ion exchange membrane is an anion exchange membrane, the salt solution is KCl, naCl, K in an amount of 0.1 to 1mol/L 2 CO 3 、Na 2 CO 3 At least one of KOH and NaOH with the concentration of 0.1-1 mol/L; when the ion exchange membrane is a cation exchange membrane, the salt solution is at least one of KCl and NaCl with the concentration of 0.1-0.5 mol/L. Still preferably, when the ion exchange membrane is a cation exchange membrane, the activation treatment further comprises the sequential use of 0.5mol/L H 2 SO 4 And 30wt% of H 2 O 2 The solution was prepared by soaking the ion exchange membranes at 80deg.C for 30min, respectively.
In the embodiment of the invention, the ion exchange membrane is soaked and activated by adopting a salt solution or an alkali solution, so that the anion exchange membrane can be converted into OH — The ions are in a conductive form, and the cation conversion membrane is converted into H + The ions are in a conductive form.
In some embodiments, preferably, in the step (1), the conductive coating is deposited by vacuum sputtering; and/or the thickness of the conductive coating is 10-500 nm. Further preferably, the conductive coating comprises at least one of platinum, palladium, nickel, iron, aluminum, copper.
In the embodiment of the invention, the thickness of the conductive coating is further optimized, so that a part of the conductive coating and the catalyst can be subjected to element replacement, the deposition of the catalyst on the ion exchange membrane is promoted, and the conductivity of the ion exchange membrane can be ensured by the rest conductive coating; if the thickness of the conductive coating is too small, for example, less than 10nm, all the replacement occurs, so that the conductivity of the ion exchange membrane is reduced; if the thickness of the conductive coating is too large, the coating is liable to fall off, resulting in deterioration of the performance of the membrane electrode.
In some embodiments, preferably, in the step (2), the reference electrode is Ag/AgCl, and the counter electrode is a platinum sheet or a graphite sheet; and/or the metal salt catalyst comprises H 2 PtCl 4 、Ni(NO 3 ) 2 、NiSO 4 、AgNO 3 、Zn(NO 3 ) 2 、Co(NO 3 ) 2 、CoCl 2 、Pb(ClO 4 ) 2 、Bi(CH 3 COO) 3 At least one of them. Further preferably, in the step (2), the concentration of the metal ion of the metal salt catalyst in the electrolyte is 0.01 to 0.1mol/L; and/or the electrolyte is H of 0.05-1 mol/L 2 SO 4 Or 0.1 to 2mol/L of HClO 4 。
In the embodiment of the invention, the components of the catalyst layer can be directly controlled by selecting the catalyst type, such as selecting H 2 PtCl 4 、CoCl 2 The PtCo catalyst layer can be prepared, so that the catalytic performance of the catalyst layer can be better regulated and controlled.
In some embodiments, preferably, in the step (2), the scanning potential interval in the electrochemical deposition is 0.2-0.9V, the scanning speed is 1-100 mV/s, and the scanning turns are 5-100.
In the embodiment of the invention, the physicochemical properties such as the thickness, the grain diameter and the like of the catalyst layer can be controlled by setting the electrochemical deposition parameters, so that the problem of catalyst loss and the complicated flow in the prior art are avoided, and the electrochemical performance and the stability of the membrane electrode are further improved.
In some embodiments, preferably, in the step (2), the step further comprises, before electrochemically depositing the catalyst layer, performing a cleaning treatment on the conductive coating layer on the surface of the pretreated ion exchange membrane; and/or, in the step (3), further comprising, before the ionomer is applied, performing a cleaning treatment on the catalyst layer. Further preferably, the cleaning treatment in the step (2) includes: the pretreatment ion exchange membrane is used as a working electrode, a platinum sheet or a graphite sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, and 0.5mol/L H is used 2 SO 4 Or 1mol/L HClO 4 Is electrolyte with 0.2-1.2V potentialCarrying out cyclic voltammetry scanning for 3-10 times at a scanning speed of 10mV/s in the interval; the cleaning treatment in the step (3) comprises the steps of keeping the constant potential for 60 seconds, keeping the potential interval of the constant potential to be 0.9-1.0V, and then flushing the catalyst layer by using deionized water.
In the embodiment of the invention, the surface metal conductive coating is cleaned before the catalyst is deposited, so that impurity particles on the surface of the metal conductive coating can be cleaned, the surface is more uniform and smooth, and the bonding strength between the catalyst layer and the ion exchange membrane is further improved; scanning is carried out at constant potential, so that surface atoms of the conductive coating can be activated, and the metal can be conveniently deposited; the catalyst layer is washed by deionized water, so that the surface of the catalyst layer can be cleaned, the influence of impurities on the membrane electrode is reduced, and the electrochemical performance and stability of the membrane electrode are further improved.
In some embodiments, preferably, in step (3), the ionomer is present in an amount of 5 to 30wt% of the catalyst content. Further preferably, the ionomer comprises at least one of Nafion, FAA3-SOLUT-10, piperion-A5, sustainion XA-9.
In the embodiment of the invention, the dosage of the ionomer is optimized, the ionomer can be used as an ion exchange membrane for transferring protons and water to a cathode, and more importantly, the ionomer plays roles of adhesion, gas transportation and proton transfer in a catalyst layer, and the dosage of the ionomer is in a proper range, so that the comprehensive performance of a membrane electrode is further improved; if the ionomer content is too small, the membrane electrode conductivity is poor, the catalyst is easy to fall off, and if the ionomer content is too large, the exposed active sites on the catalyst surface are insufficient, and the membrane electrode performance is reduced.
The embodiment of the invention also provides a membrane electrode, which is prepared by adopting the method.
The membrane electrode provided by the embodiment of the invention has better bonding strength between the catalyst layer and the ion exchange membrane, so that the membrane electrode has better electrochemical performance and stability.
The technical scheme of the present invention is described in detail below with reference to specific embodiments and drawings.
Example 1
(1) Firstly, taking an FAA3-50 type anion exchange membrane as a substrate, soaking in 1M KOH solution for 24 hours, then replacing new 1M KOH solution, soaking again for 24 hours for activation treatment, and depositing a metal copper film with the thickness of 200nm on the surface of the film by a vacuum sputtering method;
(2) The electrolytic cell was assembled as shown in FIG. 1 with 1mol/L HClO 4 The electrolyte is an anion exchange membrane side as a working electrode, and the effective working area is 10cm 2 Setting a scanning interval to be 0.2-1.2V by taking Pt as a counter electrode and Ag/AgCl as a reference electrode, and cleaning a metal copper film by cyclic voltammetry for 10 times at a scanning speed of 10 mV/s;
(3) The electrolyte is replaced by 0.05mol/L H 2 PtCl 4 /1mol/L HClO 4 The solution is provided with a scanning interval of 0.38-0.66V, the scanning speed is 10mV/s, and the cyclic voltammetry scanning times are 60 times;
(4) Maintaining at constant potential of 0.95V for 60s, taking out the anion exchange membrane, and cleaning the Pt cathode surface with deionized water;
(5) Turning over the anion exchange membrane at 11mol/L HClO 4 Repeating the step (2) in the solution;
(6) Changing the electrolyte to 0.1M Ni (NO) 3 ) 2 /1M HClO 4 The solution is provided with a scanning interval of 0.4-0.8V, the scanning speed is 10mV/s, and the cyclic voltammetry scanning times are 60 times;
(7) Keeping for 60s at a constant point of 0.9V, taking out the anion exchange membrane, and cleaning the Ni anode surface by deionized water;
(8) 100mg of FAA3-SOLUT-10 ionomer solution (10 wt%) was coated on the surface of Pt cathode/Ni anode, respectively, and dried for use.
Example 2
The preparation method of this example is the same as that of example 1, except that: the scanning speed in the step (3) is 2mV/s; the scanning speed in the step (6) is 2mV/s.
Example 3
The preparation method of this example is the same as that of example 1, except that: the scanning speed in the step (3) is 50mV/s; the scanning speed in the step (6) is 50mV/s.
Example 4
The preparation method of this example is the same as that of example 1, except that: in the step (3), the cyclic voltammetry scanning frequency is 10 times.
Example 5
The preparation method of this example is the same as that of example 1, except that: in the step (3), the cyclic voltammetry scanning frequency is 100 times.
Comparative example 1
Preparation of Pt/C and IrO at a concentration of 20mg/mL, respectively 2 Catalyst ink (solution is isopropanol water mixed solution, wherein the mass ratio of isopropanol to water is 3-1, and then 20wt% of FAA3-SOLUT-10 ionomer is added), after ultrasonic dispersion for 0.5-1 h, the negative and positive catalysts are respectively sprayed on the two sides of the anion exchange membrane by ultrasonic spraying, and drying is carried out for later use.
Comparative example 2
Preparation of Pt/C and IrO at a concentration of 20mg/mL, respectively 2 Catalyst ink (solution is isopropanol water mixed solution, wherein the mass ratio of isopropanol to water is 3-1, 20wt% of FAA3-SOLUT-10 ionomer is added), ultrasonic dispersion is carried out for 0.5-1 h, then ultrasonic spraying is used for respectively spraying the cathode and anode catalysts on the surface of foam nickel, and after drying, the catalyst ink and the anion exchange membrane are hot pressed to form a sandwich structure.
Comparative example 3
The preparation method of this example is the same as that of example 1, except that: in the step (1), a metallic copper thin film is not deposited on the surface of the anion exchange membrane.
Comparative example 4
The preparation method of this example is the same as that of example 1, except that: in the step (1), the activation treatment is not performed.
Experimental example
1. Scanning electron microscope
All samples are dried for 12 hours in a blast drying oven at 50 ℃, and gold is sprayed for 100 seconds under the current of 20mA to carry out gold plating on the samples; the surface morphology and the cross-sectional morphology of the separator were observed by electron field emission scanning electron microscopy (SEM, proglus 8100, hitachi corporation, japan).
As shown in fig. 2, SEM images of the membrane electrodes prepared in examples 1 to 3 show that the particle diameter of the middle catalyst layer of the membrane electrode prepared in example 1 is about 50nm as seen from fig. 2; the particle diameter of the middle catalyst layer of the membrane electrode prepared in example 2 was about 20 nm; the particle diameter of the middle catalyst layer of the membrane electrode obtained in example 3 was about 100 nm.
2. Hydrogen production by water electrolysis
The electrolyte was circulated at a rate of 100mL/min using 1M KOH solution as the electrolyte at a test temperature of 60 c and tested in a micro-cell test system. After activation by cyclic voltammetry and chronoamperometry, the membrane electrode current-potential profile (scan rate 10mV/s, range 1.2-2.2V) was recorded using linear cyclic voltammetry scanning.
Various membrane electrodes at 0.5A/cm 2 The corresponding potential values at the current densities of (2) are shown in Table 1. Wherein, the comparative graphs of the hydrogen production performance of the membrane electrode in example 1 and the membrane electrode in comparative examples 1 to 2 are shown in FIG. 3, and the comparative graphs of the water production performance of the membrane electrode in example 1 and the membrane electrode in examples 4 to 5 are shown in FIG. 4.
3. Electrochemical performance and durability
As in Experimental example 2, the membrane electrodes in examples 1 to 5 and comparative examples 1 to 4 were each prepared at 0.5A/cm by the constant current method 2 The current density was used for 24h stability test at the corresponding current, and the mass of the membrane electrode was compared before and after the reaction, and the catalyst loss amount was shown in table 1.
Test results:
TABLE 1
From the above test results, it is clear that example 2 uses a smaller scanning speed than example 1, and the particle size formed is smaller, resulting in a relatively low coverage; in example 3, the scanning speed was higher than that in example 1, the particle diameter was larger, the coverage was improved as compared with example 1, and the catalyst stacking phenomenon was likely to occur, and the surface layer was likely to be peeled off, so that the performance was reduced as compared with example 1.
Examples 4 to 5 differ from example 1 in that the number of turns of scanning was changed to make the coverage of the catalyst on the ion exchange membrane different, and example 4 has fewer turns of scanning and low coverage compared with example 1, and fewer active sites, and the performance of the membrane electrode was reduced; example 5 has a higher number of scanning turns than example 1, so that the coverage is higher, the catalyst stacking phenomenon occurs, a mesoporous structure is formed, and the membrane electrode performance is reduced compared with example 1.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (10)
1. The preparation method of the membrane electrode is characterized by comprising the following steps of:
(1) Activating the ion exchange membrane, and then depositing a conductive coating on the surface of the ion exchange membrane to obtain a pretreated ion exchange membrane;
(2) Taking the pretreated ion exchange membrane obtained in the step (1) as a working electrode, placing the working electrode, a counter electrode and a reference electrode in electrolyte containing a metal salt catalyst, and growing a catalyst layer on the surface of the pretreated ion exchange membrane in situ through electrochemical deposition;
(3) And (3) coating ionomer on the surface of the catalyst layer obtained in the step (2) and drying.
2. The method for producing a membrane electrode according to claim 1, wherein in the step (1), the activation treatment comprises a treatment of immersing an ion exchange membrane in a salt solution or an alkali solution.
3. The method for preparing a membrane electrode according to claim 1, wherein in the step (1), the conductive coating is deposited by vacuum sputtering; and/or the thickness of the conductive coating is 10-500 nm.
4. The method of producing a membrane electrode according to claim 1, wherein in the step (1), the conductive coating layer includes at least one of platinum, palladium, nickel, iron, aluminum, and copper.
5. The method according to claim 1, wherein in the step (2), the reference electrode is Ag/AgCl, and the counter electrode is a platinum sheet or a graphite sheet; and/or the metal salt catalyst comprises H 2 PtCl 4 、Ni(NO 3 ) 2 、NiSO 4 、AgNO 3 、Zn(NO 3 ) 2 、Co(NO 3 ) 2 、CoCl 2 、Pb(ClO 4 ) 2 、Bi(CH 3 COO) 3 At least one of them.
6. The method for producing a membrane electrode according to claim 1 or 5, wherein in the step (2), the concentration of the metal ion of the metal salt catalyst in the electrolyte is 0.01 to 0.1mol/L; and/or the electrolyte is H of 0.05-1 mol/L 2 SO 4 Or 0.1 to 2mol/L of HClO 4 。
7. The method according to claim 6, wherein in the step (2), the scanning potential interval in the electrochemical deposition is 0.2-0.9V, the scanning speed is 1-100 mV/s, and the number of scanning turns is 5-100.
8. The method according to claim 1, wherein the step (2) further comprises, before electrochemically depositing the catalyst layer, subjecting the conductive coating layer on the surface of the pretreated ion-exchange membrane to a cleaning treatment; and/or, in the step (3), further comprising, before the ionomer is applied, performing a cleaning treatment on the catalyst layer.
9. The method of producing a membrane electrode according to claim 1, wherein in the step (3), the ionomer is contained in an amount of 5 to 30wt% of the catalyst content.
10. A membrane electrode, characterized in that it is produced by the method according to any one of claims 1 to 9.
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