CN114481185A - Corrosion-resistant current collector and preparation method and application thereof - Google Patents
Corrosion-resistant current collector and preparation method and application thereof Download PDFInfo
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- CN114481185A CN114481185A CN202111588843.4A CN202111588843A CN114481185A CN 114481185 A CN114481185 A CN 114481185A CN 202111588843 A CN202111588843 A CN 202111588843A CN 114481185 A CN114481185 A CN 114481185A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 47
- 238000005260 corrosion Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 86
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000001257 hydrogen Substances 0.000 claims abstract description 72
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 claims abstract description 63
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 44
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 39
- 238000004070 electrodeposition Methods 0.000 claims abstract description 30
- 239000011241 protective layer Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 15
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 67
- 229910052759 nickel Inorganic materials 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 229910052719 titanium Inorganic materials 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000003792 electrolyte Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000012528 membrane Substances 0.000 claims description 32
- 229910001220 stainless steel Inorganic materials 0.000 claims description 32
- 239000010935 stainless steel Substances 0.000 claims description 32
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 32
- 239000012498 ultrapure water Substances 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000005238 degreasing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 150000000703 Cerium Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000010970 precious metal Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 107
- 239000010936 titanium Substances 0.000 description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000007664 blowing Methods 0.000 description 12
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 238000000840 electrochemical analysis Methods 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 235000010344 sodium nitrate Nutrition 0.000 description 7
- 239000004317 sodium nitrate Substances 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 ceria modified nickel Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
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- 239000011888 foil Substances 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/036—Bipolar electrodes
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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
- 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
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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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention is suitable for the electrochemical protection technology of a current collector, and provides a corrosion-resistant current collector and a preparation method and application thereof, wherein the current collector comprises a substrate and a protective layer coated on the surface of the substrate, the protective layer is cerium oxide, and the thickness of the protective layer is 8-200 nm; the preparation method of the cerium oxide is constant current electrochemical deposition. The invention also provides a preparation method and an application method of the corrosion-resistant current collector. Therefore, the oxidation speed of the current collector is reduced through the surface protection technology, after the current collector protected by cerium oxide is applied to the hydrogen production device by the alkaline polymer membrane electrolysis water, the device can realize stable and efficient hydrogen production, the stability is good, meanwhile, the current collector is prevented from being modified by precious metal Au, the cost of the hydrogen production device by the alkaline polymer membrane electrolysis water is reduced, and the device has a good industrial application prospect.
Description
Technical Field
The invention relates to an electrochemical protection technology of a current collector, in particular to a corrosion-resistant current collector and a preparation method and application thereof.
Background
Under the large background of carbon neutralization, hydrogen energy with the characteristics of 'cleanness, low carbon, safety, high efficiency' and the like is developing at a high speed. Hydrogen production is the source of all in the whole industrial chain of hydrogen energy. The hydrogen production method mainly comprises five technical routes of coal hydrogen production, natural gas hydrogen production, petroleum hydrogen production, industrial byproduct hydrogen production, water electrolysis hydrogen production and the like. Wherein, the method for preparing the green hydrogen by electrolyzing water in large scale by utilizing renewable energy is an ideal hydrogen preparation route. The method for preparing the green hydrogen by electrolyzing water on a large scale by utilizing renewable energy sources such as wind energy, solar energy and the like can effectively eliminate the problem of carbon emission in the hydrogen production process and realize continuous and stable energy supply.
At present, in the water electrolysis hydrogen production technology, the proton exchange membrane has high current density (>1A/cm2) High overall operating efficiency (74-87%) and high hydrogen purity (>99.99%), and the like, and is demonstrated and applied by application scenes such as hydrogen stations and the like and gradually popularized. Although the cost of the proton exchange membrane electrolytic cell has been reduced by 40% in the last five years, practical application in the field still faces problems to be solved such as high catalyst cost, high energy consumption, and incomplete technology.
In order to reduce the cost, the alkaline polymer membrane electrolytic water with the advantages of available non-noble metal catalyst, wider material selection of bipolar plates and the like is receiving more and more attention. Mainstream research work on hydrogen production by water electrolysis is dedicated to the development of a non-noble metal catalyst with low cost, high activity and high stability, so that the hydrogen production efficiency is improved and the hydrogen production cost is reduced. However, in general, the catalyst in the polymer electrolytic water electrolyzer cell usually accounts for only about 24% of the cost, and the electrolyzer materials such as the bipolar plate and the current collector account for more than 40% of the cost of the whole electrolyzer cell. In an alkaline polymer membrane electrolytic cell, a current collector and the like are easy to generate electrochemical corrosion in preference to a catalyst in an oxygen evolution reaction, and the application of a high-end electrochemical hydrogen production device can be greatly limited due to the problems of energy consumption increase caused by corrosion and the like. In order to ensure the performance and the service life of the electrolytic cell, the current collector is protected, and the protection method has important significance for the wide application of the whole alkaline polymer membrane electrolytic cell.
Acid corrosion resistant non-noble metal ZrO is selected for traditional proton type polymer electrolytic cell2Or metal Au modification and the like, so that the corrosion of the current collector in an electrochemical oxidation environment is relieved. In which the metal Au is expensive and ZrO2Can not stably exist in a strong alkaline system. In view of this, the development of a non-noble metal protective layer with corrosion resistance in an alkaline environment has very important scientific significance and practical value for the application of the current collector in an alkaline oxidation environment.
Disclosure of Invention
Aiming at the defects, the invention aims to provide the corrosion-resistant current collector and the preparation method and application thereof, the oxidation speed of the current collector is reduced by a surface protection technology, and after the current collector protected by cerium oxide is applied to an alkaline polymer membrane water electrolysis hydrogen production device, the device can realize stable and efficient hydrogen production, has good stability and has better industrial application prospect.
In order to achieve the above purpose, the present invention provides a corrosion-resistant current collector, which includes a substrate and a protective layer coated on the surface of the substrate, wherein the protective layer is cerium oxide and has a thickness of 8-200 nm; the preparation method of the cerium oxide is constant current electrochemical deposition.
According to the corrosion-resistant current collector, the substrate is at least one of Ni, Ti, stainless steel and carbon.
According to the corrosion-resistant current collector disclosed by the invention, the current of constant-current electrochemical deposition is 0.8-1.2mA/cm2。
According to the corrosion-resistant current collector, the thickness of the protective layer is 15-40 nm.
According to the corrosion-resistant current collector, the protective layer is of a cubic fluorite structure, and Ce on the surface of the protective layer4+And Ce3+In a molar ratio of 1.6-2.0: 1.
According to the corrosion-resistant current collector of the present invention, the present invention also provides a method for preparing the corrosion-resistant current collector, comprising the steps of:
s1, ultrasonically degreasing and deoiling the current collector in acetone or absolute ethyl alcohol, then washing with ultrapure water, ultrasonically removing surface oxides of the current collector in hydrochloric acid after washing, and then washing with ultrapure water to obtain a pretreated current collector material;
s2, preparing cerium salt with the molar concentration of 0.2-2mM and the molar concentration of 0.1M, and preparing cerium salt electrolyte by using ultrapure water as a solvent;
s3, taking the pretreated current collector material as a working electrode, the cerium salt electrolyte as an electrolyte and a platinum net as a counter electrode; at room temperatureControlling the electrochemical deposition current to be 0.8-1.2mA/cm2And taking out the current collector, cleaning and drying in vacuum to obtain the current collector protected by cerium oxide.
According to the preparation method of the present invention, in step S2, the cerium salt is at least one of cerium nitrate or cerium sulfate.
The invention also provides an application method of the corrosion-resistant current collector in a hydrogen production device by electrolyzing water with an alkaline polymer film, which comprises the following steps:
a1, ultrasonically dispersing a platinum-carbon catalyst, a conductive adhesive and an n-propanol solution to form catalyst slurry, spraying the catalyst slurry on two sides of an alkaline polymer membrane to form a membrane electrode, and soaking and activating the membrane electrode;
a2 hot-pressing the corrosion-resistant current collector and the membrane electrode to form an integral electrode, and assembling the integral electrode and the bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device.
According to the application method of the invention, the sustainable operation time of the alkaline polymer membrane water electrolysis hydrogen production device is more than 500 hours.
The invention aims to provide a corrosion-resistant current collector and a preparation method thereof, wherein cerium oxide is prepared by a constant current electrochemical deposition method, and the surface of the current collector is coated with the cerium oxide, so that the current collector can be prevented from being in direct contact with electrolyte; ce in cerium oxide4+/Ce3+The concentration of free oxygen electrons generated in the oxygen evolution reaction of the catalyst reaching the conductive substrate is reduced, so that the oxidation corrosion speed of the current collector is slowed down; the corrosion speed of the current collector after protection is obviously reduced, and the method provides help for ensuring the performance of the electrolytic cell and prolonging the service life. In conclusion, the beneficial effects of the invention are as follows: the oxidation speed of the current collector is reduced by the cerium oxide surface protection technology, after the corrosion-resistant current collector protected by cerium oxide is applied to the alkaline polymer film electrolytic water hydrogen production device, the device has good stability in strong alkaline and strong oxidation environments, can realize stable and efficient hydrogen production, avoids using a noble metal Au to modify the current collector, reduces the cost of the alkaline polymer film electrolytic water hydrogen production device, and has better industrial performanceAnd the application prospect is good.
Drawings
Fig. 1 is a schematic structural view of the current collector of the present invention. Wherein, 1-conductive substrate, 2-cerium oxide protective layer.
Fig. 2 is a transmission electron micrograph and an environmental scanning electron micrograph of the ceria protected nickel current collector of example 1.
Fig. 3 is an X-ray diffraction pattern of the cerium oxide protected nickel current collector of example 1.
Fig. 4 is an X-ray photoelectron spectrum of cerium in the cerium oxide protected nickel current collector of example 1.
Fig. 5 is an interface element analysis diagram of the cerium oxide protected nickel current collector in example 1.
Fig. 6 is an ac impedance plot of ceria modified nickel current collectors with different thicknesses.
Fig. 7 is a comparison of the corrosion rates of ceria protected nickel current collectors and unprotected current collectors.
Fig. 8 is a graph of the ac impedance of the ceria protected nickel current collector as a function of electrolysis time.
Fig. 9 is a performance diagram of cerium oxide protected nickel current collector applied to an alkaline polymer membrane hydrogen production device by water electrolysis.
Fig. 10 is a graph of the stability of the cerium oxide protected nickel current collector applied to an alkaline polymer membrane hydrogen production apparatus by water electrolysis.
Fig. 11 is a stability comparison graph of cerium oxide protected titanium current collector and unprotected titanium current collector applied to an alkaline polymer membrane water electrolysis hydrogen production device.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more 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 intended to limit the invention.
The invention provides a corrosion-resistant current collector which comprises a substrate and a protective layer coated on the surface of the substrate, wherein the protective layer of the current collector is cerium oxide, the coating thickness of the cerium oxide on the surface of the current collector is 8-200nm, and the coating thickness is smaller than 8nm, and the cerium oxide is too thin to play a good roleProtection, the coating thickness is more than 200nm, and the conductivity is reduced if the coating thickness is too thick; the preparation method of the cerium oxide is constant current electrochemical deposition. The cerium oxide protective layer is of a cubic fluorite structure, and Ce on the surface of the cerium oxide protective layer4+And Ce3+In a molar ratio of 1.6-2.0: 1. The coating thickness of the cerium oxide on the surface of the current collector is preferably 20-25 nm. The structural schematic of the current collector of the present invention is shown in figure 1.
The preparation method of the corrosion-resistant current collector comprises the following steps:
step one, pretreating a current collector material
Ultrasonically degreasing and deoiling a current collector in acetone or absolute ethyl alcohol, washing with ultrapure water, ultrasonically removing surface oxides in a hydrochloric acid solution, and then cleaning with ultrapure water to obtain the pretreated current collector material.
In order to prevent corrosion of the current collector, the surface of the current collector is coated with an oily substance, and the oily substance influences the uniformity of subsequent cerium oxide electrodeposition. The oxide on the surface of the current collector also has an effect on the subsequent electrodeposition of cerium oxide.
The substrate of the current collector is at least one of Ni, Ti, stainless steel and carbon. For example, it may be any one of Ni, Ti, stainless steel, and carbon; it may also be a mixture of Ni and Ti, a mixture of Ni and stainless steel, a mixture of Ni and carbon; a mixture of three materials of Ni, Ti, and stainless steel, a mixture of three materials of Ni, Ti, and carbon, and so on are also possible, and of course, the selection of the current collector is not limited to the above-listed combinations, and other combinations of Ni, Ti, stainless steel, and carbon are also included.
The structure of the current collector comprises at least one of a foil, a woven mesh, a punched mesh, a grid, a felt, or a foam. The volume concentration of the hydrochloric acid solution is 0.8-1.5 mol/L.
Step two cerium salt electrolyte
Cerium salt electrolyte with the molar concentration of 0.5-8mM and the molar concentration of 0.1M is prepared by using ultrapure water as a solvent.
The cerium salt is at least one of cerium nitrate and cerium sulfate; any one of sodium nitrate and cerium nitrate is selected.
Step three
The pretreated current collector material is used as a working electrode, the cerium salt electrolyte is used as electrolyte, and the platinum mesh is used as a counter electrode. Controlling the electrochemical deposition current to be 0.5-1.5mA/cm at room temperature2And the electrolysis time is 2-15 minutes, and the current collector is taken out, cleaned and dried in vacuum to obtain the cerium oxide protected current collector.
In the invention, the electrochemical deposition current is less than 0.5mA/cm2When the current is too small, the speed of forming the cerium oxide layer is too slow; the electrochemical deposition current is more than 1.5mA/cm2And the current is too large, so that a cerium oxide film with uneven thickness is easily formed, and the effect of protecting the nickel current collector by cerium oxide is influenced.
Oxidizing cerium salt into cerium oxide by electrochemical deposition, wherein the electrochemical deposition current is 0.8-1.2mA/cm2The electrolysis time is 4-6 minutes. The coating thickness of the cerium oxide on the current collector is 15-40 nm.
The electrochemical protection method of the current collector in the invention is to use constant current electrochemical deposition cerium oxide protective layer, and compare the corrosion speed of the nickel current collector protected by cerium oxide in the invention with that of the unprotected current collector, see fig. 7. The current collector protected by the cerium oxide prepared by the invention can effectively slow down the corrosion speed of the current collector.
After the current collector protected by cerium oxide is applied to the alkaline polymer membrane water electrolysis hydrogen production device, the device can realize stable and efficient hydrogen production, and the purity of hydrogen is as high as 99.99%. The anode electrode can realize large hydrogen output, high energy efficiency, high stability and continuous operation for more than 500 hours.
In order to verify the method of cerium oxide for protecting the current collector in the present invention, the present invention provides the following several examples. And performing a transmission electron microscope image, an environmental scanning electron microscope image, an X-ray diffraction image, an X-ray photoelectron energy spectrum and an interface element analysis image on the current collector obtained in each embodiment. Because a plurality of analysis graphs are obtained in a plurality of examples, only the relevant graphs in examples 1 to 3 are listed in the invention. A transmission electron micrograph and an environmental scanning electron micrograph of the cerium oxide protected current collector of example 1 are shown in fig. 2; the X-ray diffraction pattern of the cerium oxide protected current collector of example 1 is shown in fig. 3; an X-ray photoelectron plot of cerium in the cerium oxide protected current collector of example 1 is shown in fig. 4; the elemental analysis plot of the interface of the ceria protected nickel current collector in example 1 is shown in fig. 5; the ac impedance data for nickel current collectors with different ceria thicknesses for examples 1-3 are shown in fig. 6; a comparison of the corrosion rates of the cerium oxide protected and unprotected current collectors of example 1 is shown in fig. 7. The graph of the ac impedance of the ceria protected current collector of example 1 as a function of electrolysis time is shown in fig. 8.
Example 1
Ultrasonically degreasing and deoiling a nickel current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically treating in 1mol/L hydrochloric acid for 10min to remove surface oxides, and then washing with ultrapure water for 3 times to obtain a pretreated nickel current collector; dissolving 0.5mmol of cerium nitrate and 10mmol of ammonium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a nickel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm by using the nickel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the nickel current collector, alternately cleaning the nickel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain the current collector 1.
Example 2
Ultrasonically degreasing and deoiling a nickel current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically treating in 1mol/L hydrochloric acid for 10min to remove surface oxides, and then washing with ultrapure water for 3 times to obtain a pretreated nickel current collector; dissolving 0.5mmol of cerium nitrate and 10mmol of sodium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a nickel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm by using the nickel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 2min to obtain cerium oxide with the thickness of about 8-10 nm; and taking out the nickel current collector, alternately cleaning the nickel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain a current collector 2.
Example 3
Ultrasonic degreasing nickel current collector in acetone for 10min, rinsing with ultrapure water for 3 times, ultrasonic treating in 1mol/L hydrochloric acid for 10min to remove surface oxide, and ultrasonic cleaning with ultrapure waterWashing with water for 3 times to obtain a pretreated nickel current collector; dissolving 0.5mmol of cerous sulfate and 10mmol of sodium nitrate in 100ml of water to obtain cerous nitrate electrolyte; mixing cerium nitrate electrolyte and a nickel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm by using the nickel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 15min, wherein the thickness of the obtained cerium oxide is about 80-100 nm; and taking out the nickel current collector, alternately cleaning the nickel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain the current collector 3.
Example 4
Ultrasonically degreasing and deoiling a nickel current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated nickel current collector; dissolving 0.5mmol of cerium sulfate and 10mmol of ammonium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a nickel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm by using the nickel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the nickel current collector, alternately cleaning the nickel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain a current collector 4.
Example 5
Ultrasonically degreasing and deoiling a stainless steel current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated stainless steel current collector; dissolving 0.5mmol of cerium nitrate and 10mmol of ammonium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a stainless steel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the stainless steel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the stainless steel current collector, alternately cleaning the stainless steel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain a current collector 5.
Example 6
Ultrasonic degreasing of stainless steel current collector in acetoneRemoving oil for 10min, rinsing with ultrapure water for 3 times, putting into 1mol/L hydrochloric acid, ultrasonically treating for 10min to remove surface oxides, and cleaning with ultrapure water for 3 times to obtain a pretreated stainless steel current collector; dissolving 0.5mmol of cerium nitrate and 10mmol of sodium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a stainless steel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the stainless steel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the stainless steel current collector, alternately cleaning the stainless steel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain a current collector 6.
Example 7
Ultrasonically degreasing and deoiling a stainless steel current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated stainless steel current collector; dissolving 0.5mmol of cerium sulfate and 10mmol of sodium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a stainless steel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the stainless steel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2The constant current electrochemical deposition is carried out for 5min, and the thickness of the obtained cerium oxide is about 20-25 nm; and taking out the stainless steel current collector, alternately cleaning the stainless steel current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain a current collector 7.
Example 8
Ultrasonically degreasing and deoiling a stainless steel current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated stainless steel current collector; dissolving 0.5mmol of cerium sulfate and 10mmol of ammonium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a stainless steel current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the stainless steel current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; taking out the stainless steel current collector, alternately cleaning with water and ethanol for 3 times, and blowing nitrogen gasAnd (5) sweeping and drying to obtain a current collector 8.
Example 9
Ultrasonically degreasing and deoiling the titanium current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated titanium current collector; dissolving 0.5mmol of cerium nitrate and 10mmol of ammonium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a titanium current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the titanium current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the titanium current collector, alternately cleaning the titanium current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain a current collector 9.
Example 10
Ultrasonically degreasing and deoiling the titanium current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated titanium current collector; dissolving 0.5mmol of cerium nitrate and 10mmol of sodium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a titanium current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the titanium current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the titanium current collector, alternately cleaning the titanium current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain the current collector 10.
Example 11
Ultrasonically degreasing and deoiling the titanium current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated titanium current collector; dissolving 0.5mmol of cerium sulfate and 10mmol of sodium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a titanium current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the titanium current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2The obtained cerium oxide has a thickness of about 20-25nm by constant current electrochemical deposition for 5minRight; and taking out the titanium current collector, alternately cleaning the titanium current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain the current collector 11.
Example 12
Ultrasonically degreasing and deoiling the titanium current collector in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then washing with ultrapure water for 3 times to obtain a pretreated titanium current collector; dissolving 0.5mmol of cerium sulfate and 10mmol of ammonium nitrate in 100ml of water to obtain cerium nitrate electrolyte; mixing cerium nitrate electrolyte and a titanium current collector, performing ultrasonic treatment for 15min, applying 1mA/cm to the mixture by using the titanium current collector as a working electrode, a Pt net as a counter electrode and a saturated calomel electrode as a reference electrode2Carrying out constant current electrochemical deposition for 5min to obtain cerium oxide with the thickness of about 20-25 nm; and taking out the titanium current collector, alternately cleaning the titanium current collector with water and ethanol for 3 times, and blowing and drying by nitrogen flow to obtain the current collector 12.
As can be seen from FIG. 4, Ce exists mainly in the valence state of 3+/4+ in the cerium oxide protective layer, and Ce in the cerium oxide4+/Ce3 +The concentration of free oxygen electrons generated in the oxygen evolution reaction of the catalyst reaching the conductive substrate can be reduced, so that the oxidation corrosion speed of the current collector is reduced. Fig. 6 shows the ac impedance values of nickel current collectors of different cerium oxide thicknesses, it can be seen that the ac impedance values of the nickel current collectors increase with increasing thickness of cerium oxide; the thickness of cerium oxide is too large, the resistance value of the nickel current collector is large, and the conductivity is poor; the thickness of cerium oxide is too small, and the corrosion resistance of the current collector is poor; when the thickness of the cerium oxide is 20-25nm, the resistance value of the current collector is optimal, and the conductivity is good. As can be seen from fig. 7, the nickel current collector with ceria protection can effectively reduce the corrosion rate of the current collector relative to the unprotected nickel current collector.
In order to verify the properties of hydrogen production stability and the like of the device after the cerium oxide protected current collector is applied to the alkaline polymer membrane water electrolysis hydrogen production device, the invention is provided with the following application examples. And the electrochemical properties of the alkaline polymer membrane water electrolysis hydrogen production device in each application example are tested, and the test results are shown in table 1. Meanwhile, when the collector protected by cerium oxide is applied to the alkaline polymer membrane water electrolysis hydrogen production device, an alternating current impedance diagram of the nickel collector protected by cerium oxide along with the change of electrolysis time is measured, and the diagram is shown in fig. 8; a performance graph of applying the nickel current collector protected by cerium oxide to an alkaline polymer membrane water electrolysis hydrogen production device is determined, and the performance graph is shown in fig. 9; the stability of applying the ceria protected nickel current collector to an alkaline polymer membrane hydrogen production plant from water electrolysis was determined, see fig. 10. And comparing the stability of the device for producing hydrogen by electrolyzing water by using the titanium current collector protected by cerium oxide and the unprotected titanium current collector as alkaline polymer films, and referring to fig. 11.
Application example 1
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; and soaking and activating the membrane electrode in a 1mol/L KOH solution. Then, any one of the cerium oxide protection nickel current collectors obtained in the embodiment 1 or 4-7 is selected to be hot-pressed with a membrane electrode to form an integral electrode, and the integral electrode is assembled with a bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography is selected for on-line analysis.
Application example 2
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; and soaking and activating the membrane electrode in a 1mol/L KOH solution. Then, any one of the cerium oxide protection nickel current collectors obtained in the embodiment 2 is selected to be hot-pressed with a membrane electrode to form an integral electrode, and the integral electrode is assembled with a bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography is selected for on-line analysis.
Application example 3
The content of active metal is 0.4mg/cm2Commercial platinum carbon catalystUltrasonically dispersing 20% of conductive adhesive and n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of an alkaline polymer membrane to form a membrane electrode; and soaking and activating the membrane electrode in a 1mol/L KOH solution. Then, any one of the cerium oxide protection nickel current collectors obtained in the embodiment 3 is selected to be hot-pressed with a membrane electrode to form an integral electrode, and the integral electrode is assembled with a bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography is selected for on-line analysis.
Application example 4
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; and soaking and activating the membrane electrode in a 1mol/L KOH solution. Then, any one of the cerium oxide protective stainless steel current collectors obtained in the embodiments 5 to 8 is selected to be hot-pressed with a membrane electrode to form an integral electrode, and the integral electrode is assembled with a bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography is selected for on-line analysis.
Application example 5
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; and soaking and activating the membrane electrode in a 1mol/L KOH solution. Then any one of the cerium oxide protective titanium current collectors obtained in the implementation examples 9-12 is selected to be hot-pressed with a membrane electrode to form an integral electrode, and the integral electrode is assembled with a bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography is selected for on-line analysis. In order to separate the cerium oxide protected current collector from the unprotected current collector in the present inventionAfter the method is applied to the hydrogen production device by electrolyzing water with the alkaline polymer membrane, the properties of the hydrogen production device are compared, and the method is provided with the following comparison examples. And the electrochemical properties of the alkaline polymer membrane water electrolysis hydrogen production device in each comparative example are tested, and the specific test results are shown in table 1.
Comparative example 1
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; the membrane electrode is soaked and activated in 1mol/L KOH solution. Then selecting an unprotected nickel current collector to be hot-pressed with the membrane electrode to form an integral electrode, and assembling the integral electrode with the bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography was selected for on-line analysis and the specific reaction properties are listed in table 1.
Comparative example 2
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; and soaking and activating the membrane electrode in a 1mol/L KOH solution. Then selecting an unprotected stainless steel current collector to be hot-pressed with a membrane electrode to form an integral electrode, and assembling the integral electrode with a bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography was selected for on-line analysis and the specific reaction properties are listed in table 1.
Comparative example 3
The content of active metal is 0.4mg/cm2Carrying out ultrasonic dispersion on a commercial platinum-carbon catalyst, a 20% conductive adhesive and an n-propanol solution for 30min to form catalyst slurry, and spraying the catalyst slurry on two sides of a basic polymer membrane to form a membrane electrode; the membrane electrode is soaked and activated in 1mol/L KOH solution. Subsequent selection for unprotectedThe titanium current collector and the membrane electrode are hot-pressed to form an integral electrode, and the integral electrode and the bipolar plate are assembled to form the alkaline polymer membrane water electrolysis hydrogen production device; introducing water vapor with the humidity of 100% into two ends of the electrode, reacting at 80 deg.C, and performing electrochemical test by using two-electrode system to obtain H2Gas chromatography was selected for on-line analysis and the specific reaction properties are listed in table 1.
TABLE 1 electrochemical test results of the respective application examples and comparative examples
From the above data, it is understood that the current collector corrosion rate is significantly reduced in application example 1 as compared with application example 2 and application example 3, and that the cerium oxide protective layer of 20 to 25nm can reduce the current collector corrosion rate. Application example 1 compared with comparative example 1, application example 4 compared with comparative example 2, and application example 5 compared with comparative example 3, the deterioration degree of the alkaline polymer membrane water electrolysis hydrogen production device with the cerium oxide-protected current collector is greatly reduced.
As can be seen from FIG. 8, the nickel current collector protected by cerium oxide in the alkaline polymer membrane electrolytic water hydrogen production device has almost unchanged resistance value and stable performance along with the increase of the electrolysis time. Fig. 10 also shows that the application of the cerium oxide protective current collector to the alkaline polymer membrane water electrolysis hydrogen production device can stabilize the output current under constant voltage. Fig. 11 illustrates that the stability of the hydrogen production device obtained by applying the cerium oxide-protected titanium current collector to the alkaline polymer film water electrolysis hydrogen production device is superior to that of the hydrogen production device obtained by applying the unprotected titanium current collector to the alkaline polymer film water electrolysis hydrogen production device, the cerium oxide-protected current collector can effectively slow down the corrosion rate of the current collector, and the stability of the obtained hydrogen production device is good. Therefore, after the current collector protected by cerium oxide is applied to the alkaline polymer membrane water electrolysis hydrogen production device, the device can realize stable and efficient hydrogen production, has high stability, can continuously run for more than 500 hours, and has long service life.
In conclusion, the cerium oxide is prepared by the constant current electrochemical deposition method, and the surface of the current collector is coated with the cerium oxide, so that the problem that the cerium oxide is not dissolved in the current collector can be avoidedAvoiding direct contact between a current collector and electrolyte; ce in cerium oxide4+/Ce3+The concentration of free oxygen electrons generated in the oxygen evolution reaction of the catalyst reaching the conductive substrate is reduced, so that the oxidation corrosion speed of the current collector is slowed down; the corrosion speed of the current collector after protection is obviously reduced, and the method provides help for ensuring the performance of the electrolytic cell and prolonging the service life. In conclusion, the beneficial effects of the invention are as follows: the oxidation speed of the current collector is reduced by the cerium oxide surface protection technology, after the corrosion-resistant current collector protected by cerium oxide is applied to the alkaline polymer film electrolytic water hydrogen production device, the device has good stability in strong alkaline and strong oxidation environments, can realize stable and efficient hydrogen production, avoids using noble metal Au to modify the current collector, reduces the cost of the alkaline polymer film electrolytic water hydrogen production device, and has good industrial application prospect.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The corrosion-resistant current collector is characterized by comprising a substrate and a protective layer coated on the surface of the substrate, wherein the protective layer is cerium oxide and the thickness of the protective layer is 8-200 nm; the preparation method of the cerium oxide is constant current electrochemical deposition.
2. The corrosion resistant current collector of claim 1, wherein the substrate is at least one of Ni, Ti, stainless steel, carbon.
3. The corrosion resistant current collector of claim 1, wherein the galvanostatic electrochemical deposition has a current of 0.8-1.2mA/cm2。
4. The corrosion resistant current collector of claim 1, wherein the protective layer has a thickness of 15-40 nm.
5. The corrosion-resistant current collector of claim 1, wherein the protective layer is of a cubic fluorite structure, and the Ce on the surface of the protective layer4+And Ce3+In a molar ratio of 1.6-2.0: 1.
6. A method of making the corrosion resistant current collector of any one of claims 1-5, comprising the steps of:
s1, ultrasonically degreasing and deoiling the current collector in acetone or absolute ethyl alcohol, then washing with ultrapure water, ultrasonically removing surface oxides of the current collector in a hydrochloric acid solution after washing, and then washing with ultrapure water to obtain a pretreated current collector material;
s2, preparing cerium salt with the molar concentration of 0.2-2mM and the molar concentration of 0.1M, and preparing cerium salt electrolyte by using ultrapure water as a solvent;
s3, taking the pretreated current collector material as a working electrode, the cerium salt electrolyte as an electrolyte and a platinum net as a counter electrode; controlling the electrochemical deposition current to be 0.8-1.2mA/cm at room temperature2And taking out the current collector, cleaning and drying in vacuum to obtain the cerium oxide protected current collector.
7. The method according to claim 6, wherein in step S2, the cerium salt is at least one of cerium nitrate or cerium sulfate.
8. A method for applying the corrosion-resistant current collector as claimed in any one of claims 1 to 5 in a hydrogen production device by electrolyzing water through an alkaline polymer membrane, which is characterized by comprising the following steps:
a1, ultrasonically dispersing a platinum-carbon catalyst, a conductive adhesive and an n-propanol solution to form a catalyst slurry, spraying the catalyst slurry on two sides of an alkaline polymer membrane to form a membrane electrode, and soaking and activating the membrane electrode;
a2 hot-pressing the corrosion-resistant current collector and the membrane electrode to form an integral electrode, and assembling the integral electrode and the bipolar plate to form the alkaline polymer membrane water electrolysis hydrogen production device.
9. The application method of claim 8, wherein the alkaline polymer membrane water electrolysis hydrogen production device has a sustainable operation time of more than 500 hours.
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