CN105200421A - Method for laser micro cladding preparation of hydrogen storage layer of hydrogen evolution electrode - Google Patents
Method for laser micro cladding preparation of hydrogen storage layer of hydrogen evolution electrode Download PDFInfo
- Publication number
- CN105200421A CN105200421A CN201510712391.4A CN201510712391A CN105200421A CN 105200421 A CN105200421 A CN 105200421A CN 201510712391 A CN201510712391 A CN 201510712391A CN 105200421 A CN105200421 A CN 105200421A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- hydrogen storage
- laser
- rare earth
- alloy powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000003860 storage Methods 0.000 title claims abstract description 36
- 238000005253 cladding Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 12
- 229910018007 MmNi Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000007581 slurry coating method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 230000007850 degeneration Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000004372 laser cladding Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020191 CeNi Inorganic materials 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- PGDDJXSLIWMIRI-UHFFFAOYSA-N acetic acid;molybdenum Chemical compound [Mo].CC(O)=O PGDDJXSLIWMIRI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- -1 hydride form Chemical group 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- 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
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for laser micro cladding preparation of a hydrogen storage layer of a hydrogen evolution electrode. The method comprises that a mixed rare earth hydrogen storage alloy powder is micro-cladded on a nickel substrate via laser to prepare the hydrogen storage layer; the mixed rare earth hydrogen storage alloy powder includes MmNi[5-x](Co, Mn, Al)[x], wherein Mm represents one or more of La, Ce, Pr or Nd, and x is 0-1.2. Compared with the prior art, the prepared hydrogen storage layer has the advantages of dense microstructure, refined grains, firm binding force with the nickel substrate, and small contact resistance, has a hole structure, and allows the hydrogen storage performance to be improved substantially. In intermittent electrolytic conditions, the hydrogen evolution electrode including the prepared hydrogen storage layer not only has relatively high electrocatalytic activity of hydrogen evolution reaction and the electrochemical stability of continuous electrolysis, but also has relatively strong countercurrent resistant performance. The method is simple in preparation technology, prone to realization of automation, less in material loss, and strong in economic feasibility, and has quite good market application prospects.
Description
Technical field
The invention belongs to Laser Surface Treatment and electrochemical field, relate to a kind of hydrogen-precipitating electrode, particularly relate to a kind of method that laser fine fusion covering prepares Ni-based hydrogen-precipitating electrode storage hydrogen layer.
Background technology
Hydrogen Energy is universally acknowledged clean energy, and it is just being subject to people as low-carbon (LC) and the zero carbon energy and is more and more paying close attention to.Water electrolysis hydrogen producing is then one of industrial most important hydrogen production process.Specific surface area is large, porosity advantages of higher because having simultaneously for RaneyNi alloy, study hydrogen-precipitating electrode the most widely both at home and abroad, see " electrochemical applications magazine " (" Journalofappliedelectrochemistry "), 1992,22 (8): 711-716.Ni-Mo alloy, because having d electronics synergistic effect, makes it have very high electrocatalytic properties of hydrogen evolution, becomes the evolving hydrogen reaction catalytic material that Recent study is enlivened the most, see " functional materials ", and 1995,26 (5): 456-458.
But in actual industrial electrolytic process, the unexpected power failure of electrolyzer or out of service be recurrent.Under interval electrolytic condition, after especially having a power failure 2 weeks, the electrochemical stability of above two kinds of hydrogen-precipitating electrodes is all not ideal enough, and electro catalytic activity declines obviously.
MmNi
5alloy powder has electrochemical reversible and inhales the characteristic of putting hydrogen.Its electrochemical reversible is inhaled the reaction of putting hydrogen and is shown below:
When electrolysis, MmNi
5alloy has adsorbed a large amount of hydrogen existed with hydride form, and when short circuit, first hydrogen ion adsorption originally discharges to consume counter current, avoids the oxidation of active cathode surface coating.By at electrode matrix area load one deck hydrogen storage alloy, can ensure electrode in interval electrolytic process Catalytic Layer not by severe oxidation and corrosion, see " Materials Science and Engineering ", 1990,8:1.
The preparation of current hydrogen-precipitating electrode storage hydrogen layer mainly contains compound plating method and latax method.Patent CN102899681A adopts Composite Coatings legal system standby a kind of containing LaNi
5porous composite electrode, but because the influence factor of Composite Coatings is many, energy consumption is high, thus be not a kind of clean, less energy-consumption prepare approach.Powdered alloy latax is bonded in electrode matrix surface by patent CN1149633A, after dry, and galvanic deposit Catalytic Layer from the teeth outwards.The shortcoming of this method: one is that storage hydrogen layer is combined loosely with matrix, and in brine electrolysis process, powder very easily comes off, and causes the catalytic activity of electrode to decline; Two is that electrode materials and substrate contact are abundant not, indirectly adds contact resistance, adds the overpotential of hydrogen-precipitating electrode.
Summary of the invention
The object of the invention is to provide a kind of laser fine fusion covering to prepare the method for Ni-based hydrogen-precipitating electrode storage hydrogen layer for the deficiencies in the prior art, solve the existing water electrolysis liberation of hydrogen catalysis electrode problems such as catalyzer easily comes off at higher current densities, degeneration-resistant current capacity is poor, thus improve catalytic performance and the work-ing life of electrode.
For achieving the above object, the invention provides a kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode storage hydrogen layer, the method is, through laser, mixed rare earth hydrogen storage alloy powder fine fusion covering is stored up hydrogen layer to prepare on Ni substrate, and described mixed rare earth hydrogen storage alloy powder comprises: MmNi
5-x(Co, Mn, Al)
x, wherein Mm refers to one or more in La, Ce, Pr, Nd, x=0 ~ 1.2.
Above-mentioned method, wherein, the method comprises following steps:
Step 1, carries out oil removing, rust cleaning by described Ni substrate surface;
Step 2, makes slurry by mixed rare earth hydrogen storage alloy powder and binder solution with certain proportion uniform stirring, brushes on Ni substrate surface, dries, obtain slurry coating;
Step 3, utilizes pulse laser beam to carry out continuous sweep to above-mentioned slurry coating, makes the adhesive cures in slurry, forms cladding coating.
Above-mentioned method, wherein, step 1 also comprises preheat treatment step, and preheating temperature is 700 ~ 1000 DEG C.
Above-mentioned method, wherein, the method also comprises: step 4, cleans the additional size without laser irradiation (namely without laser beam flying).
Above-mentioned method, wherein, described cladding coating thickness is between 5um ~ 20um.
Above-mentioned method, wherein, in step 2, described binder solution selects one or more in sodium silicate solution, methylcellulose gum spirituous solution, epoxy resin acetone soln.
Above-mentioned method, wherein, in step 3; described pulse laser beam is produced by pulsed laser, and this pulsed laser power is 10W ~ 120W, and pulsewidth is 1 ~ 20ms; laser scanning speed is 120 ~ 300mm/min, and laser facula is the round spot of 20um ~ 100um diameter, and shielding gas is argon gas.
Above-mentioned method, wherein, the granularity of described mixed rare earth hydrogen storage alloy powder is 15 ~ 100um.
Above-mentioned method, wherein, described Ni substrate is the one worked out nickel screen, draw in the net in nickel or nickel foam.
Laser melting coating (LaserCladding), also known as laser cladding or laser cladding, is a kind of new process for modifying surface.It by adding cladding material at substrate surface, and utilizes the laser beam of high-energy-density to make it the method for consolidation together with substrate surface thin layer, is the filling cladding layer of metallurgical binding at substrate surface formation and its.Laser melting and coating technique and laser micro-(carefully) melting and coating technique are all laser technologies, are all to utilize laser to produce high temperature melt object, and just the latter is miniaturization.
The invention provides a kind of method that laser fine fusion covering prepares Ni-based hydrogen-precipitating electrode storage hydrogen layer, mixed rare earth hydrogen storage alloy powder and binder solution are made slurry with certain proportion uniform stirring, be preset at Ni substrate surface, utilize laser fine fusion to overlay on Ni substrate and prepare hydrogen-precipitating electrode storage hydrogen layer.Compared with prior art, the storage hydrogen layer tissue densification prepared by the present invention, grain refining, with Ni substrate bonding force jail, contact resistance is little; It has " hole " structure simultaneously, can further improve hydrogen storage property.This preparation technology is simple, and easily be automated, spillage of material is few, and economic feasibility is strong.Under interval electrolytic condition, hydrogen-precipitating electrode not only has the electro catalytic activity of higher evolving hydrogen reaction and the electrochemical stability of continuous electrolysis, and has stronger degeneration-resistant current capability.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph that the embodiment of the present invention two stores up hydrogen layer pattern.
Embodiment
Below in conjunction with accompanying drawing, by specific embodiment, the invention will be further described, and these embodiments, only for illustration of the present invention, are not limiting the scope of the invention.
Comparative example one
Nickel screen matrix is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.The acetic acid molybdenum ethanolic soln of the nickel acetate of the acetic acid ruthenium of 30 grams per liters, 300 grams per liters, 70 grams per liters is mixed by ethanolic soln weight ratio 1:1:1, is made into activated coating precursor liquid.Be coated on substrate nickel screen through Best-Effort request technique by this precursor liquid, be placed in the baking oven 30 minutes of 470 degree, repeated impregnations lift and thermolysis 5 times, obtain comparison electrode 1.
Comparative example two
Nickel screen matrix is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.Blank braiding nickel screen electrode 2 as a comparison.
Embodiment one
Nickel screen matrix is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.By LaNi
5powdered alloy and water glass solution stir with 5:1 weight ratio, are made into pasty slurry, slurry are brushed the surface in Ni substrate.The baking oven described Ni substrate being placed in 110 degree carries out drying and processing in 300 minutes, and the organic solvent in slurry is volatilized.Utilize pulse laser beam to carry out continuous sweep according to planned orbit to above-mentioned slurry coating surface, the Binder Phase in slurry is solidified; Optical fiber laser average output power 50W, laser spot diameter 0.02mm, pulsewidth 5ms, laser scanning speed 150mm/min.After laser irradiation, employing organic solvent (acetone, ethanol etc.) washes the additional size without laser irradiation, obtains storage hydrogen layer 1.
Embodiment two
Nickel screen matrix is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.By LaNi
4co powdered alloy and methocel solution stir with 4:1 weight ratio, are made into pasty slurry, slurry are brushed the surface in Ni substrate.The baking oven described Ni substrate being placed in 110 degree carries out drying and processing in 30 minutes, and the organic solvent in slurry is volatilized.Utilize pulse laser beam to carry out continuous sweep according to planned orbit to above-mentioned slurry coating surface, the Binder Phase in slurry is solidified; Optical fiber laser average output power 70W, laser spot diameter 0.05mm, pulsewidth 10ms, laser scanning speed 200mm/min.After laser irradiation, employing organic solvent washes the additional size without laser irradiation, obtains storage hydrogen layer 2.
Characterize through storing up hydrogen layer by scanning electron microscope laboratory facilities to embodiment two, as shown in Figure 1.The coating of this storage hydrogen layer evenly as seen from Figure 1, and coat-thickness can accurately control (realizing by regulating the concentration of mixed rare earth hydrogen storage alloy powder in slurry), and " hole " structure is obvious.
Embodiment three
Nickel screen matrix is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.By CeNi
5powdered alloy and water glass solution stir with 5:1 weight ratio, are made into pasty slurry, slurry are brushed the surface in Ni substrate.The baking oven described Ni substrate being placed in 110 degree carries out drying and processing in 30 minutes, and the organic solvent in slurry is volatilized.Utilize pulse laser beam to carry out continuous sweep according to planned orbit to above-mentioned slurry coating surface, the Binder Phase in slurry is solidified; Optical fiber laser average output power 90W, laser spot diameter 0.08mm, pulsewidth 15ms, laser scanning speed 250mm/min.After laser irradiation, employing organic solvent washes the additional size without laser irradiation, obtains storage hydrogen layer 3.
Embodiment four
Nickel screen matrix is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.By LaNi
5powdered alloy and epoxy resin solution stir with 4:1 weight ratio, are made into pasty slurry, slurry are brushed the surface in Ni substrate.The baking oven described Ni substrate being placed in 110 degree carries out drying and processing in 30 minutes, and the organic solvent in slurry is volatilized.Utilize pulse laser beam to carry out continuous sweep according to planned orbit to above-mentioned slurry coating surface, the Binder Phase in slurry is solidified; Optical fiber laser average output power 110W, laser spot diameter 0.10mm, pulsewidth 5ms, laser scanning speed 120mm/min.After laser irradiation, employing organic solvent washes the additional size without laser irradiation, obtains storage hydrogen layer 4.
The performance of degeneration-resistant electric current is the important indicator of a measurement negative electrode, prepare layer of Ni-Mo alloy layer in the surperficial method of using comparative example one of the storage hydrogen layer of the embodiment of the present invention 1 ~ 4 preparation and obtain hydrogen-precipitating electrode, this hydrogen-precipitating electrode carries out degeneration-resistant current testing on electrolyzer, and electrolyzer hydrogen output is 0.5m
3/ h, has 18 unit cell.The comparison electrode that the hydrogen-precipitating electrode obtained by the embodiment of the present invention 1 ~ 4 and comparative example 1 ~ 2 obtain, (temperature 85 DEG C, the KOH solution of massfraction 30%, current density 2000A/m under the condition of industrial electrolysis
2) interval electrolysis 60 days, electrolysis every day 12h, record the change of average groove pressure, result is as shown in table 1.
The interval electrolytic curve of the hydrogen-precipitating electrode that table 1 obtains for the embodiment of the present invention 1 ~ 4 and comparative example 1 ~ 2.
As shown in Table 1, (in order to simulate power-off condition after repeatedly repeatedly disconnecting and connecting, intentional disconnection and connection circuit), the electrolyzer cell groove pressure increase of embodiment one, two, three, four and comparative example one, two is respectively 30mV, 30mV, 40mV, 50mV, 130mV and 160mV.The groove pressure of embodiment one, two, three, four is known compared with comparative example one, two, and stability has had and has improved significantly, illustrates that electrode prepared by present method has good degeneration-resistant current capability.
Laser fine fusion covering disclosed by the invention is the process for treating surface of a kind of advanced person, utilizes high energy laser beam that load is melted at the powdered alloy of substrate surface, is formed and has " hole " structure and coating of combining closely metallurgical with base material.This coating have dense structure, grain refining, pore and crackle few, with the advantage such as Ni substrate contact resistance is little.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. laser fine fusion covering prepares a method for hydrogen-precipitating electrode storage hydrogen layer, it is characterized in that, the method is, through laser, mixed rare earth hydrogen storage alloy powder fine fusion covering is stored up hydrogen layer to prepare on Ni substrate, and described mixed rare earth hydrogen storage alloy powder comprises: MmNi
5-x(Co, Mn, Al)
x, wherein Mm refers to one or more in La, Ce, Pr, Nd, x=0 ~ 1.2.
2. the method for claim 1, is characterized in that, the method comprises following steps:
Step 1, carries out oil removing, rust cleaning by described Ni substrate surface;
Step 2, makes slurry by mixed rare earth hydrogen storage alloy powder and binder solution uniform stirring, brushes on Ni substrate surface, dries, obtain slurry coating;
Step 3, utilizes pulse laser beam to carry out continuous sweep to above-mentioned slurry coating, makes the adhesive cures in slurry, forms cladding coating.
3. method as claimed in claim 2, it is characterized in that, step 1 also comprises preheat treatment step, and preheating temperature is 700 ~ 1000 DEG C.
4. method as claimed in claim 2, it is characterized in that, the method also comprises: step 4, cleans the additional size without laser beam flying.
5. method as claimed in claim 2, it is characterized in that, described cladding coating thickness is between 5um ~ 20um.
6. method as claimed in claim 2, is characterized in that, in step 2, described binder solution selects one or more in sodium silicate solution, methylcellulose gum spirituous solution, epoxy resin acetone soln.
7. method as claimed in claim 2; it is characterized in that; in step 3; described pulse laser beam is produced by pulsed laser; this pulsed laser power is 10W ~ 120W, and pulsewidth is 1 ~ 20ms, and laser scanning speed is 120 ~ 300mm/min; laser facula is the round spot of 20um ~ 100um diameter, and shielding gas is argon gas.
8. the method for claim 1, is characterized in that, the granularity of described mixed rare earth hydrogen storage alloy powder is 15 ~ 100um.
9. the method for claim 1, is characterized in that, described Ni substrate is the one worked out nickel screen, draw in the net in nickel or nickel foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510712391.4A CN105200421B (en) | 2015-10-28 | 2015-10-28 | A kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode hydrogen storage layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510712391.4A CN105200421B (en) | 2015-10-28 | 2015-10-28 | A kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode hydrogen storage layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105200421A true CN105200421A (en) | 2015-12-30 |
| CN105200421B CN105200421B (en) | 2018-10-02 |
Family
ID=54948371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510712391.4A Expired - Fee Related CN105200421B (en) | 2015-10-28 | 2015-10-28 | A kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode hydrogen storage layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105200421B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986427A (en) * | 2017-04-28 | 2017-07-28 | 南京大学连云港高新技术研究院 | A kind of preparation method for simplifying energy-saving catalysis pole plate |
| CN107151805A (en) * | 2017-04-10 | 2017-09-12 | 中国科学院高能物理研究所 | Foam rare earth-nickel alloys and preparation method thereof, purposes |
| JP2019522729A (en) * | 2016-06-29 | 2019-08-15 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ | electrode |
| CN115341233A (en) * | 2022-10-18 | 2022-11-15 | 山东华特环保科技有限公司 | High-catalysis-stability electrolytic sodium hypochlorite composite cathode and preparation method thereof |
| CN118422193A (en) * | 2024-07-03 | 2024-08-02 | 英利能源发展有限公司 | A method for preparing a solar cell electrode |
| JP2025039384A (en) * | 2023-09-08 | 2025-03-21 | トヨタ自動車株式会社 | Method for manufacturing active material layer for battery, active material layer for battery, and battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149633A (en) * | 1995-11-03 | 1997-05-14 | 南开大学 | Preparation for new evolving hydrogen reaction electrode |
| CN1295355A (en) * | 2000-12-19 | 2001-05-16 | 南开大学 | Regeneration method of deactivated negative alloy powder of secondary nickel-hydrogen battery |
| CN1831195A (en) * | 2006-04-14 | 2006-09-13 | 清华大学 | Distribution type laser spot alloying method |
| CN101125366A (en) * | 2007-07-02 | 2008-02-20 | 北京浩运工贸有限公司 | Method for preparing AB5 type mixed rare-earth hydrogen-bearing alloy powder |
| CN101775525A (en) * | 2010-01-19 | 2010-07-14 | 秦皇岛首钢长白结晶器有限责任公司 | Laser cladding cobalt-based alloy coating material for copper plate of continuous casting crystallizer and process |
-
2015
- 2015-10-28 CN CN201510712391.4A patent/CN105200421B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149633A (en) * | 1995-11-03 | 1997-05-14 | 南开大学 | Preparation for new evolving hydrogen reaction electrode |
| CN1295355A (en) * | 2000-12-19 | 2001-05-16 | 南开大学 | Regeneration method of deactivated negative alloy powder of secondary nickel-hydrogen battery |
| CN1831195A (en) * | 2006-04-14 | 2006-09-13 | 清华大学 | Distribution type laser spot alloying method |
| CN101125366A (en) * | 2007-07-02 | 2008-02-20 | 北京浩运工贸有限公司 | Method for preparing AB5 type mixed rare-earth hydrogen-bearing alloy powder |
| CN101775525A (en) * | 2010-01-19 | 2010-07-14 | 秦皇岛首钢长白结晶器有限责任公司 | Laser cladding cobalt-based alloy coating material for copper plate of continuous casting crystallizer and process |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019522729A (en) * | 2016-06-29 | 2019-08-15 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ | electrode |
| CN107151805A (en) * | 2017-04-10 | 2017-09-12 | 中国科学院高能物理研究所 | Foam rare earth-nickel alloys and preparation method thereof, purposes |
| CN107151805B (en) * | 2017-04-10 | 2019-01-29 | 中国科学院高能物理研究所 | Foam rare earth-nickel alloys and preparation method thereof, purposes |
| CN106986427A (en) * | 2017-04-28 | 2017-07-28 | 南京大学连云港高新技术研究院 | A kind of preparation method for simplifying energy-saving catalysis pole plate |
| CN106986427B (en) * | 2017-04-28 | 2020-09-15 | 南京大学连云港高新技术研究院 | Preparation method of simplified energy-saving catalytic polar plate |
| CN115341233A (en) * | 2022-10-18 | 2022-11-15 | 山东华特环保科技有限公司 | High-catalysis-stability electrolytic sodium hypochlorite composite cathode and preparation method thereof |
| JP2025039384A (en) * | 2023-09-08 | 2025-03-21 | トヨタ自動車株式会社 | Method for manufacturing active material layer for battery, active material layer for battery, and battery |
| CN118422193A (en) * | 2024-07-03 | 2024-08-02 | 英利能源发展有限公司 | A method for preparing a solar cell electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105200421B (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105200421A (en) | Method for laser micro cladding preparation of hydrogen storage layer of hydrogen evolution electrode | |
| JP6698629B2 (en) | Catalyst assembly | |
| CN104894595B (en) | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof | |
| CN105350015A (en) | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole | |
| EP3060701A2 (en) | Electrochemical cell containing a graphene coated electrode | |
| CN101717951B (en) | Cathode-catalyzed electrode producing method in coal electrolyzing, hydrogenizing and liquefying process | |
| Prataap et al. | Electrodeposited-hydroxide surface-covered porous nickel–cobalt alloy electrodes for efficient oxygen evolution reaction | |
| Wendt et al. | Materials research and development of electrocatalysts for alkaline water electrolysis | |
| CN102899681A (en) | Porous nickel composite electrode, electroplating solution and preparation method of porous nickel composite electrode | |
| CN108247060A (en) | A kind of preparation method of nickel-base alloy electrolysis cathode for hydrogen evolution porous material | |
| CN103825011B (en) | The tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film | |
| CN121241167A (en) | Methods for manufacturing electrolyzer systems and electrodes | |
| CN110323077B (en) | A kind of composite electrode material based on Zr-Cu-based amorphous alloy and preparation method thereof | |
| CN101783406A (en) | Cathode, membrane electrode comprising the same, and preparation method thereof | |
| JP4378202B2 (en) | Composite sheet for hydrogen storage and method for producing the same | |
| JPH07282860A (en) | Manufacture of alkaline secondary battery and catalytic electrode body | |
| Wang et al. | A facile preparation of novel Pt-decorated Ti electrode for methanol electro-oxidation by high-energy micro-arc cladding technique | |
| CN119852098A (en) | High-flexibility nano-porous bimetal copper-nickel alloy-copper-nickel oxide material and preparation method and application thereof | |
| CN114808041B (en) | Preparation and activation and regeneration method of Pb-based pseudo-stable anode for manganese electrowinning | |
| CN112599784A (en) | Porous aluminum alloy current collector and preparation method thereof, and porous aluminum alloy composite sodium negative electrode and preparation method thereof | |
| Videa et al. | Electrodeposition of nickel-molybdenum nanoparticles for their use as electrocatalyst for the hydrogen evolution reaction | |
| CN121511328A (en) | Electrode for electrochemical cell used in alkaline decomposition of water into hydrogen and oxygen and its manufacturing method | |
| EP3294932B1 (en) | Method for producing a metallic coating with macro-pores, coated substrate with such a coating and use of such a substrate | |
| CN110373682B (en) | A Ti-Mn-based porous hydrogen evolution cathode material, preparation method and application | |
| EP0048284A1 (en) | Improved raney alloy coated cathode for chlor-alkali cells and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181002 Termination date: 20191028 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |