CN104894595A - High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof - Google Patents
High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof Download PDFInfo
- Publication number
- CN104894595A CN104894595A CN201510257124.2A CN201510257124A CN104894595A CN 104894595 A CN104894595 A CN 104894595A CN 201510257124 A CN201510257124 A CN 201510257124A CN 104894595 A CN104894595 A CN 104894595A
- Authority
- CN
- China
- Prior art keywords
- amorphous
- nickel
- oxide
- metal oxide
- preparation
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-catalytic-activity amorphous metal oxide hydrogen evolution electrode and a preparation method thereof. The electrode comprises an active coating made from an amorphous metal oxide, which is selected from any one or more of amorphous nickel oxide, amorphous ruthenium oxide, amorphous molybdenum oxide, amorphous cerium oxide, and amorphous strontium oxide. The preparation method comprises: step1, pre-treating a nickel screen to form a porous transition nickel oxide layer; step2, preparing an active coating precursor solution and coating the nickel screen with the precursor solution; and step3, performing thermal decomposition and laser-cladding assisted solidification to obtain the hydrogen evolution electrode. The preparation method is simple and is low in thermal decomposition temperature. The prepared hydrogen evolution electrode is high in catalytic activity and is not prone to polarize in a high current density. A catalyst firmly combines with a matrix and is not prone to fall off. The hydrogen evolution electrode has excellent anti-reverse-current performance. Compared with a conventional nickel screen, in a high current density of 4000A/m<2>, the electrode can reduce the hydrogen evolution overpotential by 250 mV. In a situation of frequent startup and shutdown, the voltage of an electrolytic bath is stable, and the fluctuation amplitude is small.
Description
Technical field
The present invention relates to a kind of electrode, particularly, amorphous metal oxide hydrogen-precipitating electrode (hereinafter referred to as " catalysis electrode ") relating to a kind of high catalytic activity and preparation method thereof, it is mainly used in the negative electrode of water electrolysis hydrogen producing.
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 one of industrial most important hydrogen production process, but its higher cathode overpotential causes, and electrolytic process efficiency is lower, brine electrolysis energy consumption is larger, therefore research and development has the cathode material of high catalytic performance, and reducing overpotential of hydrogen evolution is the effective way reducing brine electrolysis energy consumption.
There is high corrosion resistance under nickel cathodic polarization condition in the alkaline electrolyte and liberation of hydrogen efficiency is higher, in traditional industry is produced, be widely used as water electrolysis cathode material.But nickel electrode specific surface area is less, need to improve its hydrogen evolution activity through surface treatment, as thermal treatment decomposes the nickel powder obtained or the polycrystalline nickel generated by the chemical vapour deposition of hydroxyl nickel palpus by hydroxyl nickel, see " ECS's magazine " (" Journal of the electrochemistry society "), 1981,128 (9): 1877-1880, but its complicated process of preparation and catalytic activity increase limited.The tunnel-like pore structure that Raney's nickel (Raney Ni) is special and meticulous crackle make it have high specific surface area, and there is high electrochemical activity and good stability, see " electrochemical applications magazine " (" Journal of applied electrochemistry "), 1992,22 (8): 71 1-7 16, but it easily polarizes at higher current densities.
By the reduction overpotential that employing noble metal platinum really can be larger as catalyzer, realize less energy-consumption hydrogen manufacturing.But platinum is expensive, cannot really suitability for industrialized production application.Develop new cheapness, high-efficient electrode catalyzer realizes important channel that is clean, less energy-consumption hydrogen manufacturing.1980, Smith (Smith) propose first in the 7th international catalysis meeting non-crystaline amorphous metal can as catalytic material after, arouse widespread concern.Compared with traditional catalyst, amorphous catalysts surface has the higher unsaturated center of concentration, and the ligancy at unsaturated center has certain limit, makes its catalytic activity and selectivity obviously be better than corresponding crystalline-state catalyst.Make amorphous alloy in heterogeneous catalyst, have great magnetism, be considered to 2l century the most promising high-efficiency cleaning new catalytic material.
The preparation method of current amorphous alloy mainly contains quenching method, chemical reduction method.Quenching method refers to the metal or alloy of melting by all means with at least 10
5-10
6the speed Fast Cooling of K/s, makes the atom in melt have little time to carry out regularly arranged just completing and solidifies, thus make the disordered structure of liquid metal be kept thus form non-crystalline state.Can prepare amorphous alloy on a large scale by this method, but obtained amorphous alloy specific surface area is less, usually only has 0.1-0.2 m
2/ g, catalytic activity is extremely low, if be used as catalyzer, also need through strict, complicated reactivation process, see " advanced catalysis (Adv. catal.) ", " amorphous metallic alloy catalytic material (New Catalytic Materials from Amorphous Metal Alloys) ", More receives .A(Molnar .A), Smith .G .V(Smim.G .V), Ba Ertuoke .M(Bartok.M), 1989,36:329-383.The eighties in 20th century, people have been developed chemical preparation amorphous alloy and have been used it for catalyticing research.The method at room temperature uses reducing substances (as KBH
4or NaH
2pO
2) reducing metal ion, while metal deposition, metalloid B or P also deposits together along with metal (M), thus forms M-B (P) amorphous alloy.The amorphous alloy that chemical reduction method obtains has the specific surface area more much bigger than quenching method gained amorphous alloy, but the standby amorphous alloy component of this legal system is unstable, size distribution is uneven, easily reunite.And it stores difficulty, very easily oxidized in atmosphere, industrial applications (see " the preparation and modification progress of amorphous alloy catalyst ", " application chemical industry ", 2010,29 (4): 592-595) cannot be realized.
Therefore, the novel method of exploitation preparation amorphous catalysts, prepares the amorphous catalysts having stability and catalyst activity concurrently significant for the industrial application realizing amorphous catalysts.
Summary of the invention
The object of the present invention is to provide a kind of liberation of hydrogen catalytic electrolysis for water electrolysis hydrogen producing and preparation method thereof, solve that existing water electrolysis liberation of hydrogen catalysis electrode catalytic efficiency is low, easily polarize under high current density, catalyzer easily comes off, the problem of degeneration-resistant current capacity difference.
For achieving the above object, the invention provides a kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity, this electrode package containing amorphous metal oxide activated coating, this amorphous metal oxide select in amorphous nickel oxide, amorphous oxide ruthenium, amorphous oxide molybdenum, amorphous oxide cerium, amorphous oxide strontium any one or multiple.
The amorphous metal oxide hydrogen-precipitating electrode of above-mentioned high catalytic activity, wherein, described amorphous metal oxide activated coating is that activated coating precursor liquid prepares through thermolysis, laser assisted method, described activated coating precursor liquid is nickel acetate, in acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate any one or multiplely to mix.
The amorphous metal oxide hydrogen-precipitating electrode of above-mentioned high catalytic activity, wherein, the thickness of described amorphous metal oxide activated coating is at 0.1-20 μm.
Present invention also offers a kind of preparation method of amorphous metal oxide hydrogen-precipitating electrode of above-mentioned high catalytic activity, the method includes the steps of:
Step 1, pre-treatment nickel screen: carry out texturing and oxide treatment, forms Porous transition nickel oxide layer;
Step 2, configuration activated coating precursor liquid, and be coated on above-mentioned pretreated nickel screen, form coating; Described activated coating precursor liquid is nickel acetate, in acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate any one or multiplely to mix;
Step 3, through thermolysis, laser melting coating auxiliary formation amorphous metal oxide activated coating, thus obtains catalysis electrode.
Above-mentioned preparation method, wherein, in described step 1, pre-treatment nickel screen also comprises in advance by substrate nickel screen dipping by lye a few hours, then thoroughly cleans nickel screen, to remove the impurity such as greasy dirt on nickel screen.
Above-mentioned preparation method, wherein, in described step 1, utilizes laser to carry out pre-treatment to nickel screen.
Above-mentioned preparation method, wherein, the concentration of described activated coating precursor liquid is 30-300 grams per liter.In described activated coating precursor liquid, in acetic acid ruthenium, the consumption of nickel acetate is 0 ~ 10; The consumption of cerous acetate is 0 ~ 0.3; The consumption of acetic acid molybdenum is 0 ~ 3; The consumption of strontium acetate is 0 ~ 0.5.Preferably, in described activated coating precursor liquid, each activeconstituents selects the mixture of acetic acid ruthenium, nickel acetate and strontium acetate, and wherein, acetic acid ruthenium, nickel acetate and strontium acetate mass ratio are between 1:(2 ~ 3): between (0.2 ~ 0.5).
Above-mentioned preparation method, wherein, in step 2, activated coating precursor liquid is coated on nickel screen surface through Best-Effort request technique, makes to apply more even, and efficiency improves.
Above-mentioned preparation method, wherein, in step 3, the Best-Effort request that go back several times after laser melting coating assists consolidation hockets coating, thermal decomposition steps.
Above-mentioned preparation method, wherein, in step 3, described heat decomposition temperature is less than 400 DEG C, is decomposed by activated coating precursor liquid and generates corresponding amorphous metal oxide.
Above-mentioned preparation method, wherein, the thickness of described amorphous metal oxide activated coating is at 0.1-20 μm.
Catalysis electrode prepared by the present invention at substrate surface adhere firmly, evenly.There is excellent catalytic activity, hypopolarization rate and good degeneration-resistant current capability.Compared with traditional nickel screen, at 4000A/m
2high current density under, it can reduce overpotential of hydrogen evolution 250mv.Under the condition of frequent switching on and shutting down, electrolytic bath flattens steady, and fluctuating range is little.
Accompanying drawing explanation
The 200 times of electronic digital microscope photos in catalysis electrode local prepared by Fig. 1 embodiments of the invention two.
The partial sweep electromicroscopic photograph of catalysis electrode prepared by Fig. 2 embodiments of the invention two.
The overpotential curve that catalysis electrode prepared by Fig. 3 embodiments of the invention one to three contrasts with pure nickel net.
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.
Embodiment one
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.Utilize laser to carry out texturing and oxide treatment, form Porous transition nickel oxide layer, to increase the specific surface area of nickel screen, be conducive to the catalytic activity improving hydrogen-precipitating electrode.The nickel acetate of the acetic acid ruthenium of 80 grams per liters, 150 grams per liters, the cerous acetate ethanolic soln of 40 grams per liters are mixed by ethanolic soln weight ratio 1:1:0.2, is made into activated coating precursor liquid.Be coated on substrate nickel screen through Best-Effort request technique by this precursor liquid, the baking oven being placed in 250 degree carries out thermolysis in 40 minutes, makes above-mentioned precursor liquid be decomposed into amorphous oxides, then utilizes laser melting coating to carry out auxiliary consolidation, obtains catalysis electrode 1.The processing condition of above-mentioned laser melting coating are: the laser apparatus of described laser is 5 kW Constant Electric Current excitation CO
2laser apparatus, laser melting coating power is 3.2 kW, and sweep velocity is 450 mm/min, and spot diameter is 3 mm.
Embodiment two
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.Utilize laser to carry out texturing and oxide treatment, form Porous transition nickel oxide layer.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.This precursor liquid is coated on substrate nickel screen through Best-Effort request technique, is placed in the baking oven 40 minutes of 300 degree, then utilizes laser melting coating (processing condition are with embodiment one) to carry out auxiliary consolidation.Repeated impregnations lift and thermolysis 5 times, obtain catalysis electrode 2.
Embodiment three
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.Utilize laser to carry out texturing and oxide treatment, form Porous transition nickel oxide layer.The cerous acetate ethanolic soln of the acetic acid molybdenum of the acetic acid ruthenium of 70 grams per liters, 50 grams per liters, the strontium acetate of 75 grams per liters and 90 grams per liters is mixed by ethanolic soln weight ratio 1:1:0.2:0.2, is made into activated coating precursor liquid.This precursor liquid is coated on through Best-Effort request technique on the substrate nickel screen processed, is placed in the baking oven 45 minutes of 350 degree, then utilizes laser melting coating (processing condition are with embodiment one) to carry out auxiliary consolidation.Repeated impregnations lift and thermolysis 6 times, obtain catalysis electrode 3.
Embodiment four
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.Utilize laser to carry out texturing and oxide treatment, form Porous transition nickel oxide layer.The ethanolic soln of the nickel acetate of the acetic acid ruthenium of 40 grams per liters, 120 grams per liters, the strontium acetate of 60 grams per liters is mixed by ethanolic soln weight ratio 1:1:0.2, is made into activated coating precursor liquid.This precursor liquid is coated on through Best-Effort request technique on the substrate nickel screen processed, is placed in the baking oven 30 minutes of 400 degree, then utilizes laser melting coating (processing condition are with embodiment one) to carry out auxiliary consolidation.Repeated impregnations lift and thermolysis 3 times, obtain catalysis electrode 4.
Embodiment five
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then clean by washed with de-ionized water.Utilize laser to carry out texturing and oxide treatment, form Porous transition nickel oxide layer.The cerous acetate ethanolic soln of the acetic acid molybdenum of the acetic acid ruthenium of 70 grams per liters, 50 grams per liters, the strontium acetate of 75 grams per liters and 90 grams per liters is mixed by ethanolic soln weight ratio 1:1:0.2:0.2, is made into activated coating precursor liquid.This precursor liquid is coated on through Best-Effort request technique on the substrate nickel screen processed, is placed in the baking oven 45 minutes of 350 degree, then utilizes laser melting coating (processing condition are with embodiment one) to carry out auxiliary consolidation.Repeated impregnations lift and thermolysis 6 times, obtain catalysis electrode 5.
Catalysis electrode prepared by the present invention, through characterizing with the activated coating of the laboratory facilities such as electronic digital microscope and scanning electron microscope to embodiment two, as shown in figure 1 and 2.The coating of this catalysis electrode activated coating evenly as seen from the figure, and coat-thickness can accurately control.
Carry out electrolytic weight loss test to the catalysis electrode of above-described embodiment, result is as shown in table 1 below.
Table 1: catalysis electrode electrolytic weight loss test data prepared by embodiment one ~ five
Activated coating and substrate have excellent bonding force as can be seen from Table 1, and electrolysis is substantially without coming off at higher current densities, meets the standard of the industrial electrode of water electrolysis.
Carried out experiment test to the catalytic activity of hydrogen evolution of above-described embodiment, adopt constant current electrolysis to survey the electropotential of catalysis electrode, its result is as table 2.
Table 2: catalysis electrode hydrogen-evolution overpotential test data prepared by embodiment one ~ five
As can be seen from Table 2, the hydrogen-evolution overpotential of the catalysis electrode of embodiment one ~ five preparation is all lower than the hydrogen-evolution overpotential of pure nickel net.
Linear scanning method is adopted to test overpotential of hydrogen evolution to embodiment one, embodiment two and embodiment three.Result as shown in Figure 3.As seen from Figure 3 compared with pure nickel net, catalysis electrode has lower overpotential at higher current densities, illustrates that catalysis electrode has higher catalytic activity and good resistance to polarizability at higher current densities.
The performance of degeneration-resistant electric current is the important indicator of a measurement negative electrode, carries out degeneration-resistant current testing to catalysis electrode prepared by present method on electrolyzer, and electrolyzer hydrogen output is 0.5m
3/ h, has 18 unit cell.(temperature 85 DEG C, the KOH solution of massfraction 30%, current density 2000A/m under the condition of industrial electrolysis
2) discontinuous electrolysis 30 days, electrolysis every day 12h, record the change of average groove pressure, result is as shown in table 3.
Table 3: catalysis electrode discontinuous electrolytic chamber groove pressure change (current density 2000A/m prepared by embodiment one ~ five
2)
As can be seen from upper table 3, electrolysis after 30 days the average groove pressure of electrolyzer cell substantially there is no wide variation, more steadily, illustrate that electrode prepared by present method has the performance of good degeneration-resistant electric current.
Substrate nickel screen is first used dipping by lye a few hours by the present invention, then cleans up.Utilize laser to carry out texturing and oxide treatment, form Porous transition nickel oxide layer.One or more in nickel acetate, acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate are measured than being configured to ethanolic soln, as activated coating precursor liquid by setting.Then the activated coating precursor liquid configured is coated on nickel screen surface, then through thermolysis, laser assisted consolidation activated coating, thus obtains catalysis electrode.(thickness of coating and firmness) selects the number of times of coating and thermolysis according to actual needs, can be once also can be repeatedly.
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 (10)
1. the amorphous metal oxide hydrogen-precipitating electrode of a high catalytic activity, it is characterized in that, this electrode package containing amorphous metal oxide activated coating, this amorphous metal oxide select in amorphous nickel oxide, amorphous oxide ruthenium, amorphous oxide molybdenum, amorphous oxide cerium, amorphous oxide strontium any one or multiple.
2. the amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity as claimed in claim 1, it is characterized in that, described amorphous metal oxide activated coating is that activated coating precursor liquid prepares through thermolysis, laser assisted method, described activated coating precursor liquid is nickel acetate, in acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate any one or multiplely to mix.
3. the amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity as claimed in claim 1, it is characterized in that, the thickness of described amorphous metal oxide activated coating is at 0.1-20 μm.
4. a preparation method for the amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity as claimed in claim 1, it is characterized in that, the method includes the steps of:
Step 1, pre-treatment nickel screen: carry out texturing and oxide treatment, forms Porous transition nickel oxide layer;
Step 2, configuration activated coating precursor liquid, and be coated on above-mentioned pretreated nickel screen, form coating; Described activated coating precursor liquid is nickel acetate, in acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate any one or multiplely to mix; The concentration of described activated coating precursor liquid is 30-300 grams per liter;
Step 3, assists consolidation to form amorphous metal oxide activated coating through thermolysis, laser melting coating, thus obtains the amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity.
5. preparation method as claimed in claim 4, it is characterized in that, in described step 1, pre-treatment nickel screen also comprises in advance by substrate nickel screen dipping by lye a few hours, then thoroughly cleans nickel screen; Described texturing and oxide treatment are carried out nickel screen by laser.
6. preparation method as claimed in claim 4, it is characterized in that, in described activated coating precursor liquid, in acetic acid ruthenium, the consumption of nickel acetate is 0 ~ 10; The consumption of cerous acetate is 0 ~ 0.3; The consumption of acetic acid molybdenum is 0 ~ 3; The consumption of strontium acetate is 0 ~ 0.5.
7. preparation method as claimed in claim 6, it is characterized in that, in described activated coating precursor liquid, each activeconstituents selects the mixture of acetic acid ruthenium, nickel acetate and strontium acetate, and wherein, acetic acid ruthenium, nickel acetate and strontium acetate mass ratio are between 1:(2 ~ 3): between (0.2 ~ 0.5).
8. preparation method as claimed in claim 4, it is characterized in that, in step 2, activated coating precursor liquid is coated on nickel screen surface through Best-Effort request technique.
9. preparation method as claimed in claim 8, is characterized in that, in step 3, and the Best-Effort request that go back several times after laser melting coating assists consolidation hockets coating, thermal decomposition steps.
10. preparation method as claimed in claim 4, it is characterized in that, in step 3, described heat decomposition temperature is less than 400 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510257124.2A CN104894595B (en) | 2015-05-19 | 2015-05-19 | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510257124.2A CN104894595B (en) | 2015-05-19 | 2015-05-19 | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104894595A true CN104894595A (en) | 2015-09-09 |
| CN104894595B CN104894595B (en) | 2017-09-12 |
Family
ID=54027538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510257124.2A Expired - Fee Related CN104894595B (en) | 2015-05-19 | 2015-05-19 | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104894595B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105350015A (en) * | 2015-10-28 | 2016-02-24 | 派新（上海）能源技术有限公司 | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole |
| CN106934188A (en) * | 2015-12-24 | 2017-07-07 | 北京有色金属研究总院 | A kind of screening technique of hydrogen evolution electrode material alloying component |
| CN107492633A (en) * | 2017-07-04 | 2017-12-19 | 上海空间电源研究所 | A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof |
| CN107723735A (en) * | 2017-09-27 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of nano metal simple substance and its modified oxide transient metal sulfide array catalyst and its preparation method and application |
| CN107815703A (en) * | 2016-09-14 | 2018-03-20 | 蓝星(北京)化工机械有限公司 | Hydrogen evolution activity negative electrode and preparation method thereof and the electrolytic cell for including the hydrogen evolution activity negative electrode |
| CN110721720A (en) * | 2019-10-25 | 2020-01-24 | 山东大学 | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof |
| CN111118539A (en) * | 2019-06-06 | 2020-05-08 | 天津大学 | Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method |
| CN111715233A (en) * | 2020-06-11 | 2020-09-29 | 江苏大学 | Preparation method of iron-doped molybdenum oxide nano material and application of iron-doped molybdenum oxide nano material in bifunctional electrocatalytic water decomposition |
| CN113416980A (en) * | 2021-06-09 | 2021-09-21 | 江西理工大学 | Efficient full-hydrolysis water catalyst MoO2-CeOx/NF and preparation method thereof |
| CN114616358A (en) * | 2019-10-30 | 2022-06-10 | 德诺拉工业有限公司 | Electrode for electrochemical hydrogen evolution |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798063A (en) * | 1971-11-29 | 1974-03-19 | Diamond Shamrock Corp | FINELY DIVIDED RuO{11 {11 PLASTIC MATRIX ELECTRODE |
| JPH10273791A (en) * | 1997-03-28 | 1998-10-13 | Japan Energy Corp | Water electrolyzing cell |
| US20110045209A1 (en) * | 2008-05-01 | 2011-02-24 | Maxim Seleznev | Continuous or discrete metallization layer on a ceramic substrate |
| CN102115882A (en) * | 2010-01-05 | 2011-07-06 | 上海工程技术大学 | Method for cladding alloy on surface of metallic matrix |
| CN102127776A (en) * | 2010-01-15 | 2011-07-20 | 北京有色金属研究总院 | Amorphous plating layer with high hydrogen evolution catalytic activity and preparation method thereof |
| CN102216496A (en) * | 2008-12-02 | 2011-10-12 | 德诺拉工业有限公司 | Electrode suitable as hydrogen-evolving cathode |
| CN103924263A (en) * | 2014-04-03 | 2014-07-16 | 重庆大学 | Preparation method of high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode |
| CN104022023A (en) * | 2014-06-24 | 2014-09-03 | 上海大学 | Method for metal induced crystallization of amorphous silicon membrane from excimer laser-assisted nickel acetate solution |
| CN104087866A (en) * | 2014-07-31 | 2014-10-08 | 宁国市宁武耐磨材料有限公司 | High-heat-resistant and wear-resistant ball for ball mill |
-
2015
- 2015-05-19 CN CN201510257124.2A patent/CN104894595B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798063A (en) * | 1971-11-29 | 1974-03-19 | Diamond Shamrock Corp | FINELY DIVIDED RuO{11 {11 PLASTIC MATRIX ELECTRODE |
| JPH10273791A (en) * | 1997-03-28 | 1998-10-13 | Japan Energy Corp | Water electrolyzing cell |
| US20110045209A1 (en) * | 2008-05-01 | 2011-02-24 | Maxim Seleznev | Continuous or discrete metallization layer on a ceramic substrate |
| CN102216496A (en) * | 2008-12-02 | 2011-10-12 | 德诺拉工业有限公司 | Electrode suitable as hydrogen-evolving cathode |
| CN102115882A (en) * | 2010-01-05 | 2011-07-06 | 上海工程技术大学 | Method for cladding alloy on surface of metallic matrix |
| CN102127776A (en) * | 2010-01-15 | 2011-07-20 | 北京有色金属研究总院 | Amorphous plating layer with high hydrogen evolution catalytic activity and preparation method thereof |
| CN103924263A (en) * | 2014-04-03 | 2014-07-16 | 重庆大学 | Preparation method of high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode |
| CN104022023A (en) * | 2014-06-24 | 2014-09-03 | 上海大学 | Method for metal induced crystallization of amorphous silicon membrane from excimer laser-assisted nickel acetate solution |
| CN104087866A (en) * | 2014-07-31 | 2014-10-08 | 宁国市宁武耐磨材料有限公司 | High-heat-resistant and wear-resistant ball for ball mill |
Non-Patent Citations (1)
| Title |
|---|
| 付银辉 等，: ""Ni-Ru-Ir氧化物阴极涂层的析氢活性"", 《电化学》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105350015A (en) * | 2015-10-28 | 2016-02-24 | 派新（上海）能源技术有限公司 | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole |
| CN106934188B (en) * | 2015-12-24 | 2019-06-25 | 北京有色金属研究总院 | A kind of screening technique of hydrogen evolution electrode material alloying component |
| CN106934188A (en) * | 2015-12-24 | 2017-07-07 | 北京有色金属研究总院 | A kind of screening technique of hydrogen evolution electrode material alloying component |
| CN107815703B (en) * | 2016-09-14 | 2019-09-10 | 蓝星(北京)化工机械有限公司 | Hydrogen evolution activity cathode and preparation method thereof and electrolytic cell comprising the hydrogen evolution activity cathode |
| CN107815703A (en) * | 2016-09-14 | 2018-03-20 | 蓝星(北京)化工机械有限公司 | Hydrogen evolution activity negative electrode and preparation method thereof and the electrolytic cell for including the hydrogen evolution activity negative electrode |
| CN107492633B (en) * | 2017-07-04 | 2019-12-03 | 上海空间电源研究所 | A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof |
| CN107492633A (en) * | 2017-07-04 | 2017-12-19 | 上海空间电源研究所 | A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof |
| CN107723735B (en) * | 2017-09-27 | 2019-05-07 | 中国科学院长春应用化学研究所 | A kind of nano metal nickel and nickel oxide modification tungsten disulfide array catalyst and its preparation method and application |
| CN107723735A (en) * | 2017-09-27 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of nano metal simple substance and its modified oxide transient metal sulfide array catalyst and its preparation method and application |
| CN111118539A (en) * | 2019-06-06 | 2020-05-08 | 天津大学 | Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method |
| CN111118539B (en) * | 2019-06-06 | 2022-03-22 | 天津大学 | Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method |
| CN110721720A (en) * | 2019-10-25 | 2020-01-24 | 山东大学 | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof |
| CN110721720B (en) * | 2019-10-25 | 2020-09-08 | 山东大学 | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof |
| CN114616358A (en) * | 2019-10-30 | 2022-06-10 | 德诺拉工业有限公司 | Electrode for electrochemical hydrogen evolution |
| CN111715233A (en) * | 2020-06-11 | 2020-09-29 | 江苏大学 | Preparation method of iron-doped molybdenum oxide nano material and application of iron-doped molybdenum oxide nano material in bifunctional electrocatalytic water decomposition |
| CN113416980A (en) * | 2021-06-09 | 2021-09-21 | 江西理工大学 | Efficient full-hydrolysis water catalyst MoO2-CeOx/NF and preparation method thereof |
| CN113416980B (en) * | 2021-06-09 | 2023-03-21 | 江西理工大学 | Efficient full-hydrolysis water catalyst MoO 2 -CeO x /NF and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104894595B (en) | 2017-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104894595A (en) | High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof | |
| US9255335B2 (en) | Catalysts for low temperature electrolytic CO2 reduction | |
| Wang et al. | Fabrication and evaluation of platinum/diamond composite electrodes for electrocatalysis: Preliminary studies of the oxygen-reduction reaction | |
| US10738387B2 (en) | Electrochemical cell containing a graphene coated electrode | |
| CN108796535A (en) | One kind having three metallic coppers-cobalt-molybdenum/nickel foam porous electrode material and the preparation method and application thereof | |
| CN107904614A (en) | A kind of Ni3S2@Ni Fe LDH analysis oxygen electro catalytic electrodes and preparation method and application | |
| WO2016076277A1 (en) | Oxygen-generating anode | |
| CN108767277B (en) | Fe-Pd-based nano-porous material and preparation method thereof | |
| CN108611655B (en) | Electrode unit and electrode composed of same | |
| CN105214685A (en) | A kind of platinum cobalt alloy structured catalysis material for brine electrolysis and preparation method thereof | |
| US20150136613A1 (en) | Catalysts for low temperature electrolytic co reduction | |
| Pierozynski | Hydrogen evolution reaction at Pd-modified carbon fibre and nickel-coated carbon fibre materials | |
| Hu et al. | Tunable selectivity and high efficiency of CO2 electroreduction via borate-enhanced molten salt electrolysis | |
| WO2004061163A1 (en) | Metal-coated carbon surfaces for use in fuel cells | |
| Bhardwaj et al. | Nanostructured Cu foam and its derivatives: emerging materials for the heterogeneous conversion of CO 2 to fuels | |
| Hassan et al. | The electrocatalytic behavior of electrodeposited Ni–Mo–P alloy films towards ethanol electrooxidation | |
| Kheirmand et al. | Electrodeposition of platinum nanoparticles on reduced graphene oxide as an efficient catalyst for oxygen reduction reaction | |
| Floner et al. | Homogeneous coating of graphite felt by nickel electrodeposition to achieve light nickel felts with high surface area | |
| Cheng et al. | Dynamic hydrogen bubble template electrodeposited Bi on graphite felt and the effect of its post-processing in vanadium redox flow batteries | |
| Yang et al. | Preparation of nanoporous Cu/Cu2O composites by anodic oxidation and their electrocatalytic performance towards methanol oxidation | |
| KR101263177B1 (en) | electrolytic cell for a monolithic photovoltaic-electrolytic hydrogen generation system | |
| CN115491691A (en) | Preparation method and application of self-supporting nano porous layer sheet FeCo/Ce-O-N composite electrode material | |
| JP2008138282A (en) | Anode for alkaline electrolysis | |
| CN112981442A (en) | FeCoMoPC amorphous alloy for alkaline full-hydrolysis and preparation method thereof | |
| Pierozynski et al. | Hydrogen evolution reaction at Pd-modified nickel-coated carbon fibre in 0.1 M NaOH solution |
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: 20170912 Termination date: 20180519 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |