CN104894595B - A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof - Google Patents
A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof Download PDFInfo
- Publication number
- CN104894595B CN104894595B CN201510257124.2A CN201510257124A CN104894595B CN 104894595 B CN104894595 B CN 104894595B CN 201510257124 A CN201510257124 A CN 201510257124A CN 104894595 B CN104894595 B CN 104894595B
- Authority
- CN
- China
- Prior art keywords
- amorphous
- nickel
- preparation
- metal oxide
- acetate
- 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.)
- Expired - Fee Related
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
Abstract
The invention discloses amorphous metal oxide hydrogen-precipitating electrode of a kind of high catalytic activity and preparation method thereof.The electrode includes any one or more in amorphous metal oxide active coating, amorphous metal oxide selection amorphous nickel oxide, amorphous oxide ruthenium, amorphous oxide molybdenum, amorphous oxide cerium, amorphous oxide strontium.Its preparation method is included：Step 1, nickel screen is pre-processed, Porous transition nickel oxide layer is formed；Step 2, active coating precursor liquid is configured, and is coated on nickel screen；Step 3, consolidated through thermal decomposition, laser melting coating auxiliary, obtain the hydrogen-precipitating electrode.The preparation technology is simple, and heat decomposition temperature is low, and the hydrogen-precipitating electrode catalytic activity of preparation is high, polarization is difficult under high current density, catalyst is firmly combined with substrate, difficult for drop-off, and degeneration-resistant current capability is excellent.Compared with traditional nickel screen, in 4000A/m2High current density under, it can reduce overpotential of hydrogen evolution 250mv.Under conditions of machine is frequently switched on, electrolytic bath is flattened surely, and fluctuating range is small.
Description
Technical field
The present invention relates to a kind of electrode, in particular it relates to a kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity
（Hereinafter referred to as " catalysis electrode "）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 resource, and it is just more and more closed as low-carbon and the zero carbon energy by people
Note.Water electrolysis hydrogen producing is one of industrial most important hydrogen production process, but its higher cathode overpotential causes electrolytic process to be imitated
Rate is relatively low, electrolysis water consumption is larger, therefore cathode material of the research and development with high catalytic performance, and reduction overpotential of hydrogen evolution is
Reduce the effective way of electrolysis water consumption.
Nickel has high corrosion resistance under the conditions of cathodic polarization in the alkaline electrolyte and liberation of hydrogen efficiency is higher, in traditional industry
It is widely used as water electrolysis cathode material in production.But nickel electrode specific surface area is smaller, it is necessary to which surface treated improves its liberation of hydrogen
Activity, such as heat treatment are decomposed obtained nickel powder or the polycrystalline nickel palpus generated by hydroxyl nickel chemical vapor deposition, ginseng by hydroxyl nickel
See《Electrochemical Society magazine》（《Journal of the electrochemistry society》）, 1981,128 (9)：
1877-1880, but its preparation technology is complicated and catalytic activity increase is limited.Raney's nickel（Raney Ni）Special tunnel-like hole
Structure and fine crackle make it have high specific surface area, and have high electro-chemical activity and good stability, referring to《Electricity
Chemical activator magazine》（《Journal of applied electrochemistry》）, 1992,22 (8)：71 1-7 16,
But its easily polarization at higher current densities.
Low energy consumption hydrogen manufacturing can be realized with larger reduction overpotential really as catalyst by using noble metal platinum.But
Platinum is expensive, it is impossible to real industrialized production and application.Exploitation new cheap, high-efficient electrode catalyst are to realize cleaning, low energy
Consume the important channel of hydrogen manufacturing., Smith in 1980（Smith）Propose that non-crystaline amorphous metal can first in the 7th international catalysis meeting
As after catalysis material, to arouse widespread concern.Compared with traditional catalyst, amorphous catalysts surface has concentration
Higher unsaturated center, and the ligancy at unsaturated center has certain limit, makes its catalytic activity and selectivity substantially excellent
In corresponding crystalline-state catalyst.So that amorphous alloy has great attraction in heterogeneous catalysis, it is considered to be 2l centuries
Most promising high-efficiency cleaning new catalytic material.
The preparation method of current amorphous alloy mainly has quenching method, chemical reduction method.Quenching method refers to the gold of melting
Category or alloy are by all means with least 105—106K/s speed Fast Cooling, makes the atom in melt have little time progress
It is regularly arranged just to complete solidification, so that the disordered structure of liquid metal is maintained forming amorphous state.By this
Method can prepare amorphous alloy on a large scale, but obtained amorphous alloy specific surface area is smaller, and generally only 0.1-0.2
m2/ g, catalytic activity is extremely low, if being used as catalyst, in addition it is also necessary to pass through strict, complicated activation process, referring to《Advanced catalysis
（Adv. catal.）》, " amorphous metallic alloy catalysis 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.In the 1980s, people, which have developed chemical reduction method, prepares amorphous alloy
And use it for catalyticing research.This method is to use reducing substances (such as KBH at room temperature4Or NaH2PO2) reducing metal ion,
While metal deposit, metalloid B or P is deposited together also with metal (M), so as to form the conjunction of M-B (P) amorphous state
Gold.Amorphous alloy made from chemical reduction method has the specific surface area more much bigger than amorphous alloy obtained by quenching method, but should
Method prepare amorphous alloy component it is unstable, particle diameter distribution is uneven, it is easy reunite.And its storage is difficult, in atmosphere easily by
Oxidation, it is impossible to realize industrial applications（Referring to " preparation of amorphous alloy catalyst and Progress in Modification ",《Application
Work》,2010,29(4):592-595).
Therefore, exploitation prepares the new method of amorphous catalysts, prepares and has the amorphous of stability and catalyst activity concurrently and urge
Agent is significant for the commercial Application for realizing amorphous catalysts.
The content of the invention
It is an object of the invention to provide a kind of for liberation of hydrogen catalytic electrolysis of water electrolysis hydrogen producing and preparation method thereof, solve
Existing water electrolysis liberation of hydrogen catalysis electrode catalytic efficiency is low, easily polarization, catalyst be easy to fall off under high current density, degeneration-resistant current capacity
Poor the problem of.
, should the invention provides a kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity to reach above-mentioned purpose
Electrode includes amorphous metal oxide active coating, amorphous metal oxide selection amorphous nickel oxide, amorphous oxide ruthenium, amorphous
Any one or more in molybdenum oxide, amorphous oxide cerium, amorphous oxide strontium.
The amorphous metal oxide hydrogen-precipitating electrode of above-mentioned high catalytic activity, wherein, described amorphous metal oxide is lived
Property coating to be active coating precursor liquid prepare through thermal decomposition, laser assisted method, described active coating precursor liquid is acetic acid
Any one or more in nickel, acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate is mixed.
The amorphous metal oxide hydrogen-precipitating electrode of above-mentioned high catalytic activity, wherein, described amorphous metal oxide is lived
The thickness of property coating is at 0.1-20 μm.
Present invention also offers a kind of preparation method of the amorphous metal oxide hydrogen-precipitating electrode of above-mentioned high catalytic activity,
The method includes the steps of：
Step 1, nickel screen is pre-processed：Texturing and oxidation processes are carried out, Porous transition nickel oxide layer is formed；
Step 2, active coating precursor liquid is configured, and is coated on above-mentioned pretreated nickel screen, coating is formed；Described
Active coating precursor liquid is any one or more mixing in nickel acetate, acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate
Into；
Step 3, aid in forming amorphous metal oxide active coating through thermal decomposition, laser melting coating, so as to obtain catalysis electricity
Pole.
Above-mentioned preparation method, wherein, in described step 1, pretreatment nickel screen is also included substrate nickel screen alkali in advance
Immersion steeps a few hours, then thoroughly cleaning is carried out to nickel screen, to remove the impurity such as the greasy dirt on nickel screen.
Above-mentioned preparation method, wherein, in described step 1, nickel screen is pre-processed using laser.
Above-mentioned preparation method, wherein, the concentration of described active coating precursor liquid is 30-300 g/l.Described work
Property coating precursor liquid in, in terms of 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
For 0 ~ 3；The consumption of strontium acetate is 0 ~ 0.5.Preferably, each active component selection acetic acid ruthenium in described active coating precursor liquid,
The mixture of nickel acetate and strontium acetate, wherein, acetic acid ruthenium, nickel acetate and strontium acetate mass ratio are between 1:（2~3）:（0.2
~0.5）Between.
Above-mentioned preparation method, wherein, in step 2, the impregnated czochralski process of active coating precursor liquid is coated on nickel screen table
Face so that coating to be more uniformly distributed, efficiency is improved.
Above-mentioned preparation method, wherein, in step 3, also alternately soaked several times after laser melting coating auxiliary consolidation
Stain lifting coating, thermal decomposition steps.
Above-mentioned preparation method, wherein, in step 3, described heat decomposition temperature is less than 400 DEG C, by active coating forerunner
Liquid decomposes the corresponding amorphous metal oxide of generation.
Above-mentioned preparation method, wherein, the thickness of described amorphous metal oxide active coating is at 0.1-20 μm.
Catalysis electrode prepared by the present invention is in substrate surface adhesion-tight, uniform.With excellent catalytic activity, hypopolarization
Rate and good degeneration-resistant current capability.Compared with traditional nickel screen, in 4000A/m2High current density under, it can reduce liberation of hydrogen mistake
Current potential 250mv.Under conditions of machine is frequently switched on, electrolytic bath is flattened surely, and fluctuating range is small.
Brief description of the drawings
The local 200 times of electronic digital microscope photos of catalysis electrode 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 is compareed with pure nickel net.
Embodiment
Below in conjunction with accompanying drawing, by specific embodiment, the invention will be further described, and these embodiments are merely to illustrate
The present invention, is not limiting the scope of the invention.
Embodiment one
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then cleaned up with deionized water.Using swash
Light carries out texturing and oxidation processes, forms Porous transition nickel oxide layer, to increase the specific surface area of nickel screen, is conducive to improving liberation of hydrogen
The catalytic activity of electrode.80 g/l of acetic acid ruthenium, 150 g/l of nickel acetate, 40 g/l of cerous acetate ethanol solution are pressed into second
Alcoholic solution weight compares 1:1:0.2 is well mixed, and is made into active coating precursor liquid.The impregnated czochralski process of the precursor liquid is coated on
On substrate nickel screen, it is placed in 40 minutes in 250 degree of baking oven and is thermally decomposed so that above-mentioned precursor liquid is decomposed into amorphous oxides,
Then auxiliary consolidation is carried out using laser melting coating, obtains catalysis electrode 1.The process conditions of above-mentioned laser melting coating are：Described laser
Laser be 5 kW constant current electric excitations CO2Laser, laser melting coating power is 3.2 kW, and sweep speed is 450 mm/min,
Spot diameter is 3 mm.
Embodiment two
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then cleaned up with deionized water.Using swash
Light carries out texturing and oxidation processes, forms Porous transition nickel oxide layer.By 30 g/l of acetic acid ruthenium, 300 g/l of nickel acetate,
70 g/l of acetic acid molybdenum ethanol solution compares 1 by ethanol solution weight:1:1 is well mixed, and is made into active coating precursor liquid.Should
The impregnated czochralski process of precursor liquid is coated on substrate nickel screen, is placed in 300 degree of baking oven 40 minutes, is then utilized laser melting coating
（Process conditions be the same as Example one）Carry out auxiliary consolidation.Repeated impregnations are lifted and thermally decomposed 5 times, obtain catalysis electrode 2.
Embodiment three
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then cleaned up with deionized water.Using swash
Light carries out texturing and oxidation processes, forms Porous transition nickel oxide layer.By 70 g/l of acetic acid ruthenium, 50 g/l of acetic acid molybdenum,
75 g/l of strontium acetate and 90 g/l of cerous acetate ethanol solution press ethanol solution weight ratio 1:1:0.2:0.2 is well mixed,
It is made into active coating precursor liquid.The impregnated czochralski process of the precursor liquid is coated on treated substrate nickel screen, is placed in 350 degree
Baking oven in 45 minutes, then utilize laser melting coating（Process conditions be the same as Example one）Carry out auxiliary consolidation.Repeated impregnations are lifted
With thermal decomposition 6 times, catalysis electrode 3 is obtained.
Example IV
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then cleaned up with deionized water.Using swash
Light carries out texturing and oxidation processes, forms Porous transition nickel oxide layer.By 40 g/l of acetic acid ruthenium, 120 g/l of nickel acetate,
The ethanol solution of 60 g/l of strontium acetate compares 1 by ethanol solution weight:1:0.2 is well mixed, and is made into active coating precursor liquid.
The impregnated czochralski process of the precursor liquid is coated on treated substrate nickel screen, is placed in 400 degree of baking oven 30 minutes, then
Utilize laser melting coating（Process conditions be the same as Example one）Carry out auxiliary consolidation.Repeated impregnations are lifted and thermally decomposed 3 times, must be catalyzed electricity
Pole 4.
Embodiment five
Substrate nickel screen is soaked 4 hours in 20% sodium hydroxide solution, then cleaned up with deionized water.Using swash
Light carries out texturing and oxidation processes, forms Porous transition nickel oxide layer.By 70 g/l of acetic acid ruthenium, 50 g/l of acetic acid molybdenum,
75 g/l of strontium acetate and 90 g/l of cerous acetate ethanol solution press ethanol solution weight ratio 1:1:0.2:0.2 is well mixed,
It is made into active coating precursor liquid.The impregnated czochralski process of the precursor liquid is coated on treated substrate nickel screen, is placed in 350 degree
Baking oven in 45 minutes, then utilize laser melting coating（Process conditions be the same as Example one）Carry out auxiliary consolidation.Repeated impregnations are lifted
With thermal decomposition 6 times, catalysis electrode 5 is obtained.
Catalysis electrode prepared by the present invention, through with laboratory facilities such as electronic digital microscope and ESEMs to embodiment
Two active coating is characterized, as shown in figure 1 and 2.Catalysis electrode active coating coating is uniform as seen from the figure, applies
Thickness degree is accurately controlled.
Electrolytic weight loss test is carried out to the catalysis electrode of above-described embodiment, it is as a result as shown in table 1 below.
Table 1：Catalysis electrode electrolytic weight loss test data prepared by embodiment one ~ five
Active coating has excellent adhesion with substrate as can be seen from Table 1, is electrolysed at higher current densities basic
Without coming off, meet the standard of the industrial electrode of water electrolysis.
Experiment test has been carried out to the catalytic activity of hydrogen evolution of above-described embodiment, catalysis electrode is surveyed using constant current electrolysis
Electrode potential, its result such as table 2.
Table 2：Catalysis electrode hydrogen-evolution overpotential test data prepared by embodiment one ~ five
From Table 2, it can be seen that the hydrogen-evolution overpotential of catalysis electrode prepared by embodiment one ~ five is below the liberation of hydrogen of pure nickel net
Current potential.
Overpotential of hydrogen evolution is tested using linear scanning method to embodiment one, embodiment two and embodiment three.As a result such as Fig. 3
It is shown.As seen from Figure 3 compared with pure nickel net, catalysis electrode has relatively low overpotential at higher current densities, and explanation is urged
Polarizing electrode has higher catalytic activity and preferable resistance to polarizability at higher current densities.
The performance of degeneration-resistant electric current is to weigh the important indicator of a negative electrode, and the catalysis electrode prepared to this method is in electrolytic cell
Upper to carry out degeneration-resistant current testing, electrolytic cell hydrogen output is 0.5m3/ h, has 18 unit cells.Under conditions of industrial electrolysis
（85 DEG C of temperature, the KOH solution of mass fraction 30%, current density 2000A/m2）Discontinuous electrolysis 30 days, is electrolysed 12h daily, remembers
The change of the average groove pressure of record, as a result as shown in table 3.
Table 3：The discontinuous electrolytic chamber's groove buckling of catalysis electrode prepared by embodiment one ~ five（Current density 2000A/m2）
The average groove pressure in electrolytic cell cell is relatively more flat substantially without great changes after being electrolysed 30 days it can be seen from upper table 3
Surely, performance of the electrode with preferable degeneration-resistant electric current prepared by this method is illustrated.
Substrate nickel screen is first used dipping by lye a few hours by the present invention, is then cleaned up.Texturing and oxygen are carried out using laser
Change is handled, and forms Porous transition nickel oxide layer.By one kind or many in nickel acetate, acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate
Plant and be configured to ethanol solution by setting metering ratio, be used as active coating precursor liquid.Then by the active coating precursor liquid configured
Nickel screen surface is coated on, then active coating is consolidated through thermal decomposition, laser assisted, so as to obtain catalysis electrode.According to actual need
Will（The thickness and firmness of coating）Selection coating and the number of times of thermal decomposition, can be once or repeatedly.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. the amorphous metal oxide hydrogen-precipitating electrode of a kind of high catalytic activity, it is characterised in that the electrode includes amorphous metal oxygen
Compound active coating, the amorphous metal oxide selection amorphous nickel oxide, amorphous oxide ruthenium, amorphous oxide molybdenum, amorphous oxide cerium,
Any one or more in amorphous oxide strontium;Described amorphous metal oxide active coating is active coating precursor liquid warp
Thermal decomposition, laser assisted method are prepared, described active coating precursor liquid is nickel acetate, acetic acid ruthenium, acetic acid molybdenum, cerous acetate and
Any one or more in strontium acetate is mixed.
2. the amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity as claimed in claim 1, it is characterised in that the amorphous
The thickness of metal oxide active coating is at 0.1-20 μm.
3. a kind of preparation method of the amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity as claimed in claim 1, it is special
Levy and be, the method includes the steps of：
Step 1, nickel screen is pre-processed：Texturing and oxidation processes are carried out, Porous transition nickel oxide layer is formed；
Step 2, active coating precursor liquid is configured, and is coated on above-mentioned pretreated nickel screen, coating is formed；Described activity
Coating precursor liquid mixes for any one or more in nickel acetate, acetic acid ruthenium, acetic acid molybdenum, cerous acetate and strontium acetate；Institute
The concentration for the active coating precursor liquid stated is 30-300 g/l；
Step 3, amorphous metal oxide active coating is formed through thermal decomposition, laser melting coating auxiliary consolidation, so as to obtain high catalysis
The amorphous metal oxide hydrogen-precipitating electrode of activity.
4. preparation method as claimed in claim 3, it is characterised in that in described step 1, pretreatment nickel screen also includes advance
Substrate nickel screen is used into dipping by lye a few hours, thoroughly cleaning then is carried out to nickel screen；The texturing and oxidation processes are by swashing
Light is carried out to nickel screen.
5. preparation method as claimed in claim 3, it is characterised in that in described active coating precursor liquid, in terms of 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.
6. preparation method as claimed in claim 5, it is characterised in that each active component choosing in described active coating precursor liquid
The mixture of acetic acid ruthenium, nickel acetate and strontium acetate is selected, wherein, acetic acid ruthenium, nickel acetate and strontium acetate mass ratio are between 1:（2
~3）:（0.2~0.5）Between.
7. preparation method as claimed in claim 3, it is characterised in that in step 2, the impregnated lifting work of active coating precursor liquid
Skill is coated on nickel screen surface.
8. preparation method as claimed in claim 7, it is characterised in that in step 3, also some after laser melting coating auxiliary consolidation
Secondaryly alternately Best-Effort request coating, thermal decomposition steps.
9. preparation method as claimed in claim 3, it is characterised 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 CN104894595A (en) | 2015-09-09 |
| CN104894595B true 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) |
Families Citing this family (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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN110721720B (en) * | 2019-10-25 | 2020-09-08 | 山东大学 | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof |
| IT201900020026A1 (en) * | 2019-10-30 | 2021-04-30 | Industrie De Nora Spa | ELECTRODE FOR THE ELECTROLYTIC EVOLUTION OF HYDROGEN |
| 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 |
| 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 |
Citations (4)
| 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 |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10273791A (en) * | 1997-03-28 | 1998-10-13 | Japan Energy Corp | Water electrolyzing cell |
| EP2285752A1 (en) * | 2008-05-01 | 2011-02-23 | 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 |
| 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 |
| CN104087866B (en) * | 2014-07-31 | 2016-04-06 | 宁国市宁武耐磨材料有限公司 | A kind of ball mill high heat-resistant and wear-resistant ball |
-
2015
- 2015-05-19 CN CN201510257124.2A patent/CN104894595B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| CN102216496A (en) * | 2008-12-02 | 2011-10-12 | 德诺拉工业有限公司 | Electrode suitable as hydrogen-evolving cathode |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| "Ni-Ru-Ir氧化物阴极涂层的析氢活性";付银辉 等，;《电化学》;20100515;第16卷(第2期);第202页摘要、第1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104894595A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104894595B (en) | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof | |
| Wang et al. | Fabrication and evaluation of platinum/diamond composite electrodes for electrocatalysis: Preliminary studies of the oxygen-reduction reaction | |
| CN105355926B (en) | Air cathode, air cathode preparation method and microbiological fuel cell | |
| EP3060701A2 (en) | Electrochemical cell containing a graphene coated electrode | |
| CN111224113B (en) | Ni-N4 monoatomic catalyst anchored by multistage carbon nanostructure and preparation method and application thereof | |
| CN103422116A (en) | Method for producing porous nickel-based ruthenium oxide composite hydrogen evolution electrode | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN103331172B (en) | Preparation method for non-Pt non-H anode catalyst of proton exchange membrane fuel cell (PEMFC) | |
| CN107863539B (en) | Preparation method of biomass alkaline fuel cell anode | |
| Mo et al. | Experimental studies on the effects of sheet resistance and wettability of catalyst layer on electro-catalytic activities for oxygen evolution reaction in proton exchange membrane electrolysis cells | |
| CN105200421B (en) | A kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode hydrogen storage layer | |
| CN110592616A (en) | Method for preparing platinum/titanium dioxide nanotube composite electrode by electroplating method | |
| CN106683896A (en) | Preparation method and application of core-shell-structured nickel molybdate/manganese dioxide composite material | |
| CN114045505A (en) | High-activity large-size electrolytic water hydrogen evolution electrode and pulse laser preparation method thereof | |
| Hassan et al. | The electrocatalytic behavior of electrodeposited Ni–Mo–P alloy films towards ethanol electrooxidation | |
| CN105161319A (en) | Method for preparing amorphous carbon coated and oxygen vacancy modified titanium dioxide nanotube array supported nickel-cobalt oxide electrode material | |
| CN110112423B (en) | Microchannel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst and application method thereof | |
| CN110265681B (en) | Composite electrode for catalyzing oxidation of sodium formate and preparation method and application thereof | |
| CN101195091B (en) | Process for producing high entropy metal catalyst | |
| CN105289591A (en) | Preparation method of nano carbon based loaded two-dimensional noble metal cluster composite material | |
| CN110010912A (en) | A kind of catalyst of fuel cell and its preparation method and application | |
| CN101425581B (en) | Method for preparing double effect oxygen electrode catalyst | |
| CN111276703B (en) | Surface fuel cell electrode with high electrochemical activity ratio and preparation and application thereof | |
| CN110112424B (en) | Anode of ethanol fuel cell and preparation method thereof | |
| CN112981442A (en) | FeCoMoPC amorphous alloy for alkaline full-hydrolysis and preparation method thereof |
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 |