CN1149633A - Preparation for new evolving hydrogen reaction electrode - Google Patents
Preparation for new evolving hydrogen reaction electrode Download PDFInfo
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- CN1149633A CN1149633A CN95116198A CN95116198A CN1149633A CN 1149633 A CN1149633 A CN 1149633A CN 95116198 A CN95116198 A CN 95116198A CN 95116198 A CN95116198 A CN 95116198A CN 1149633 A CN1149633 A CN 1149633A
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- alloy
- electrode
- preparation
- hydrogen reaction
- evolving hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to a new type electrode with high evolving hydrogen reaction and strong resistance of outage short circuit. The composition of the electrode consists of at least alloy A with good electro catalytic property and alloy B with good hydrogen-storage capability. Said electrode not only possesses of the good catalytic property for evolving hydrogen reaction and chemical stability of long term continuous electrolysis, but also possesses of strong capability for resisting outage short circuit and oxidizing corrosion resistance.
Description
The invention belongs to the electrochemistry category.
The preparation of evolving hydrogen reaction electrode the most widely of research at present both at home and abroad is based on Raney's nickel and nickel-molybdenum alloy, because of the Raney's nickel alloy have specific surface area big, decide crack degree advantages of higher.Recently report has Raney's nickel alloy that compound coating technology the produces NaOH at 35% weight part, at 90 ℃ and 200mA/cm
2During electrolysis, the evolving hydrogen reaction overpotential is 80mV, and electrochemical stability is preferably arranged under the continuous electrolysis condition under the current density.And nickel-molybdenum alloy is the most active electrocatalysis alloy of Recent study, and it does not resemble the Raney's nickel alloy and is characteristics such as cellular structure, but owing to have d electronics synergistic effect, this alloy shows very high evolving hydrogen reaction activity.People such as D.E.Brown report decomposes the Ni of hydrogen reduction method preparation with elevated temperature heat
60Mo
40Alloy electrode is at the KOH of 30% weight part, at 70 ℃ and 500mA/cm
2(geometric area relatively), continuous electrolysis is after 11000 hours, and the reaction overpotential is 60mV.At present above two alloy electrodes are considered to most possible negative active core-shell material as chlorine industry., in the industrial electrolysis process of border, left alone without help electrification can often take place, this discontinuous or intermittently under the electrolytic condition (especially left alone without help electric two week the back), Raney's nickel and nickel-molybdenum alloy evolving hydrogen reaction catalytic activity almost completely disappear.Therefore, mainly there is anti-left alone without help electrical short ability in existing evolving hydrogen reaction electrode material, and electrode materials is defective such as perishable oxidation in intermittent process.
Purpose of the present invention solves present Raney's nickel and nickel-molybdenum alloy electrode exactly under the intermittence electrolytic condition, defectives such as its catalytic activity and electrochemical stability difference when especially left alone without help electric two weeks are above, a kind of novel to prepare, have good anti-left alone without help electrical short, long lifetime, highly active evolving hydrogen reaction electrode.
Technology contents of the present invention comprises novel electrode structure and composition Design, the making of novel electrode.
This novel electrode structure mainly is made of following 3 parts: i.e. electrode skeleton, alloy A and alloy B.The function of alloy A mainly plays electrocatalysis characteristic, in electrode evolving hydrogen reaction process, guarantees that electrode has good evolving hydrogen reaction activity.The function of alloy B is the effect of playing electrochemistry absorption portion hydrogen and storage is arranged in electrolytic process; Another function of alloy B is to play the effect that electrochemistry discharges hydrogen in left alone without help electric intermittent process, with guarantee electrode at intermittent process interalloy A not by severe oxidation and corrosion.According to the design with upper electrode arrangement, alloy A can be made of arbitrary alloy in Raney's nickel alloy, nickel-molybdenum alloy, the dynamax.Alloy B can be by LaNi
5Type, Ti-Ni system and polynary misch metal alloy MnNi
5Arbitrary alloy constitutes in the hydrogen storage materials such as type.The main program that electrode is made is as follows: the alloy B powder crossing 200 mesh sieves, be adhered on the porousness nickel electrode skeleton with the PVA latax, and after waiting to do, plate one deck alloy A with the continuous current electrodip process.
The concrete steps that carry out an invention are: use earlier the smelting method for preparing alloy B.Bulk alloy B selects 300～400 purpose alloy powders after mechanical process is pulverized, be adhered on the porousness nickel electrode skeleton with the PVA latax, behind the airing, modifies with continuous current electrodip process counter electrode surface; Select the alloy A of amorphous nickel molybdenum alloy, because of it has very high electrocatalysis characteristic as novel electrode.Its preparation method is to use electrodip process, makes alloy A be deposited in the alloy B surface.The composition and the condition of galvanic deposit are as follows: NiSO
46H
2O is 50～80 grams per liters; Na
2MoO
42H
2O8～11 grams per liters; Trisodium Citrate (Na
3Cit) 30～50 grams per liters, the pH value of solution transfers to 8.5～9.5 with anhydrous sodium sulphate, and its cathode current density is 20～60mA/cm
2, bath temperature is 25 ± 5 ℃.
This novel electrode not only has the electrochemical stability of good long-term continuous electrolysis, and has very strong anti-left alone without help electrical short ability.The electrocatalysis characteristic of electrode evolving hydrogen reaction depends primarily on the character of surface amorphous nickel-molybdenum alloy; when left alone without help electrical short takes place; the hydrogen storage alloy B of electrode interior reversibly discharges the hydrogen of storing by diffusion, and to support the consumption reversible circulation, guard electrode surface alloy A exempts from oxidation and corrosion:
This novel electrode can reduce electrolysis energy consumption significantly as substituting the iron cathode material (the evolving hydrogen reaction overpotential is greater than 300mV) of present chlorine industry, increases economic efficiency, and reduces cathode hydrogen evolution overpotential 200mV, and 1 ton of caustic soda of every production can be saved 140 degree.
Example 1 is by rare earth alloy LaNi
4.9Si
0.1The electrode that constitutes with the amorphous nickel molybdenum alloy film of the about 12 μ m of thickness is as the evolving hydrogen reaction negative electrode, and anode adopts the big area nickel strap.At the NaOH of 30% weight part, at 70 ℃ with mA/cm
2Behind the continuous electrolysis 4 months, after 2 weeks, cathode hydrogen evolution reaction overpotential is about 88mV at left alone without help electrical short for the about 85mV of electrode evolving hydrogen reaction overpotential, electrode.
Example 2 is with misch metal alloy MnNi
3.6Co
0.75Mn
0.42Al
0.27The electrode that constitutes with the about 12 μ m amorphous nickel molybdenum alloy films of thickness is as the evolving hydrogen reaction negative electrode, and anode adopts big area Pt silk screen, at the KOH of 30% weight part, at 70 ℃ and 200mA/cm
2Behind the continuous electrolysis 6 months, the evolving hydrogen reaction overpotential is between 80～85mV.After 3 weeks, electrode evolving hydrogen reaction overpotential increases about 3～5mV to electrode at left alone without help electrical short.
Claims (1)
1. the preparation method of an evolving hydrogen reaction electrode, it is characterized in that it is by electrode skeleton, three parts of alloy A and alloy B constitute, its preparation method is to use earlier the smelting method for preparing alloy B, bulk alloy B is after mechanical process is pulverized, select 300～400 purpose alloy powders, be adhered on the porousness nickel electrode skeleton with the PVA latax, behind the airing, modify with continuous current electrodip process counter electrode surface, select the alloy A of amorphous nickel molybdenum alloy then as electrode, its preparation method is to use electrodip process, makes alloy A be deposited in the alloy B surface, and the composition and the condition of galvanic deposit are as follows: NiSO
46H
2O concentration is 50～80 grams per liters, Na
2MoO
42H
2O is 8～11 grams per liters, Trisodium Citrate (Na
3Cit) 30～50 grams per liters, the pH value of solution transfers to 8.5～9.5 with anhydrous sodium sulphate, and its cathode current density is 20～60mA/cm
2, bath temperature is 25 ± 5 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116198A CN1048295C (en) | 1995-11-03 | 1995-11-03 | Preparation for new evolving hydrogen reaction electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116198A CN1048295C (en) | 1995-11-03 | 1995-11-03 | Preparation for new evolving hydrogen reaction electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149633A true CN1149633A (en) | 1997-05-14 |
| CN1048295C CN1048295C (en) | 2000-01-12 |
Family
ID=5080800
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95116198A Expired - Fee Related CN1048295C (en) | 1995-11-03 | 1995-11-03 | Preparation for new evolving hydrogen reaction electrode |
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| CN (1) | CN1048295C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120440A (en) * | 2014-08-01 | 2014-10-29 | 太原理工大学 | Application of photoelectric catalytic membrane in preparation and storage of hydrogen by decomposing water |
| CN104562076A (en) * | 2015-01-23 | 2015-04-29 | 上海大学 | Method for preparing cathode catalysis electrode in coal electrolysis hydrogenation liquefaction |
| CN105200421A (en) * | 2015-10-28 | 2015-12-30 | 派新（上海）能源技术有限公司 | Method for laser micro cladding preparation of hydrogen storage layer of hydrogen evolution electrode |
| 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 |
| CN109072461A (en) * | 2016-03-31 | 2018-12-21 | 西门子股份公司 | The technology of anode activation in situ is carried out by the cathode in alkaline water electrolytic pond |
| CN110373682A (en) * | 2019-07-17 | 2019-10-25 | 西安建筑科技大学 | A kind of Quito Ti-Mn hole cathode material for hydrogen evolution, preparation method and application |
| CN110373683A (en) * | 2019-07-17 | 2019-10-25 | 西安建筑科技大学 | A kind of Quito Ti-Fe hole cathode material for hydrogen evolution, preparation method and application |
| CN110373684A (en) * | 2019-07-17 | 2019-10-25 | 西安建筑科技大学 | A kind of Quito V-Ti-Ni hole cathode material for hydrogen evolution, preparation method and application |
| CN111705332A (en) * | 2020-05-20 | 2020-09-25 | 上海应用技术大学 | Simple electrodeposited Co-Ce/NF electrode material and preparation and application thereof |
| CN111871427A (en) * | 2020-07-16 | 2020-11-03 | 清华-伯克利深圳学院筹备办公室 | Precious metal/molybdenum-nickel composite material and preparation method and application thereof |
| CN114351187A (en) * | 2021-11-23 | 2022-04-15 | 中国华能集团清洁能源技术研究院有限公司 | HER electrode overpotential test method for simulating industrial alkaline electrolyzed water test conditions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4357227A (en) * | 1979-03-29 | 1982-11-02 | Olin Corporation | Cathode for chlor-alkali cells |
| US4405434A (en) * | 1980-08-18 | 1983-09-20 | Olin Corporation | Raney alloy coated cathode for chlor-alkali cells |
| DE3587430T2 (en) * | 1985-04-10 | 1994-02-17 | Asahi Glass Co Ltd | LONG-LASTING OVERVOLTAGE CATHODE WITH LOW HYDROGEN CONTENT AND THEIR PRODUCTION. |
| CN1034874C (en) * | 1990-12-24 | 1997-05-14 | 南开大学 | Production method of hydrogen storage alloy electrode |
-
1995
- 1995-11-03 CN CN95116198A patent/CN1048295C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104120440A (en) * | 2014-08-01 | 2014-10-29 | 太原理工大学 | Application of photoelectric catalytic membrane in preparation and storage of hydrogen by decomposing water |
| CN104120440B (en) * | 2014-08-01 | 2016-05-04 | 太原理工大学 | The application of a kind of photoelectrocatalysis film in hydrogen production by water decomposition storage hydrogen |
| CN104562076A (en) * | 2015-01-23 | 2015-04-29 | 上海大学 | Method for preparing cathode catalysis electrode in coal electrolysis hydrogenation liquefaction |
| CN104562076B (en) * | 2015-01-23 | 2018-05-01 | 上海大学 | Preparation method for the cathode catalysis electrode in coal electrolyzing hydrogenation liquefaction |
| CN105200421A (en) * | 2015-10-28 | 2015-12-30 | 派新（上海）能源技术有限公司 | Method for laser micro cladding preparation of hydrogen storage layer of hydrogen evolution electrode |
| 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 |
| CN105200421B (en) * | 2015-10-28 | 2018-10-02 | 派新（上海）能源技术有限公司 | A kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode hydrogen storage layer |
| CN109072461A (en) * | 2016-03-31 | 2018-12-21 | 西门子股份公司 | The technology of anode activation in situ is carried out by the cathode in alkaline water electrolytic pond |
| CN110373684A (en) * | 2019-07-17 | 2019-10-25 | 西安建筑科技大学 | A kind of Quito V-Ti-Ni hole cathode material for hydrogen evolution, preparation method and application |
| CN110373683A (en) * | 2019-07-17 | 2019-10-25 | 西安建筑科技大学 | A kind of Quito Ti-Fe hole cathode material for hydrogen evolution, preparation method and application |
| CN110373682A (en) * | 2019-07-17 | 2019-10-25 | 西安建筑科技大学 | A kind of Quito Ti-Mn hole cathode material for hydrogen evolution, preparation method and application |
| CN110373684B (en) * | 2019-07-17 | 2021-06-11 | 西安建筑科技大学 | V-Ti-Ni-based porous hydrogen evolution cathode material, preparation method and application |
| CN110373683B (en) * | 2019-07-17 | 2021-06-15 | 西安建筑科技大学 | Ti-Fe-based porous hydrogen evolution cathode material, preparation method and application |
| CN110373682B (en) * | 2019-07-17 | 2021-06-22 | 西安建筑科技大学 | Ti-Mn-based porous hydrogen evolution cathode material, preparation method and application |
| CN111705332A (en) * | 2020-05-20 | 2020-09-25 | 上海应用技术大学 | Simple electrodeposited Co-Ce/NF electrode material and preparation and application thereof |
| CN111705332B (en) * | 2020-05-20 | 2021-07-20 | 上海应用技术大学 | Simple electrodeposited Co-Ce/NF electrode material and preparation and application thereof |
| CN111871427A (en) * | 2020-07-16 | 2020-11-03 | 清华-伯克利深圳学院筹备办公室 | Precious metal/molybdenum-nickel composite material and preparation method and application thereof |
| CN111871427B (en) * | 2020-07-16 | 2023-04-07 | 清华-伯克利深圳学院筹备办公室 | Precious metal/molybdenum-nickel composite material and preparation method and application thereof |
| CN114351187A (en) * | 2021-11-23 | 2022-04-15 | 中国华能集团清洁能源技术研究院有限公司 | HER electrode overpotential test method for simulating industrial alkaline electrolyzed water test conditions |
| CN114351187B (en) * | 2021-11-23 | 2023-11-07 | 中国华能集团清洁能源技术研究院有限公司 | HER electrode overpotential test method for simulating industrial alkaline electrolyzed water test conditions |
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| Publication number | Publication date |
|---|---|
| CN1048295C (en) | 2000-01-12 |
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