CN100383285C - Electrode for water electrolysis and its making process - Google Patents
Electrode for water electrolysis and its making process Download PDFInfo
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- CN100383285C CN100383285C CNB2005100156595A CN200510015659A CN100383285C CN 100383285 C CN100383285 C CN 100383285C CN B2005100156595 A CNB2005100156595 A CN B2005100156595A CN 200510015659 A CN200510015659 A CN 200510015659A CN 100383285 C CN100383285 C CN 100383285C
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- electrode
- nickel
- water electrolysis
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- mixed solution
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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
Abstract
The present invention relates to an electrode for water electrolysis and a preparing method thereof. The weight percentage of nickel element in a depositional layer on the electrode is from 30 to 99%, the weight percentage of sulfur element in the depositional layer on the electrode is from 1 to 40%, the weight percentage of manganese content in the depositional layer on the electrode is from 0.01 to 30%, and alloy on the electrode is in the structure of non crystalline state or nanometer crystal. The preparing method of the electrode for water electrolysis comprises that: the mixed solution of nickel ion, manganese ion and a containing sulfur elemental compound is prepared, wherein the concentration of the nickel ion in the mixed solution is from 0.006 to 1.3 mol/l, the concentration of the manganese ion in the mixed solution is from 0.006 to 1.3 mol/l, and the mol concentration of the sulfur element of the sulfur compound in the mixed solution is from 0.006 to 2.5 mol/l; pretreated metal nickel is soaked in the prepared solution, the complexing agent of 1-100 gram/l is added, the temperature of the solution is from 5 to 80 DEG C, a metal net or a metal band is used as a cathode, the metal nickel is used as an anode, the cathode and the anode are energized for 10 min to 10 hours, and current density is 1 to 100 mA/cm2. The present invention can effectively lower the hydrogen separating and the oxygen separating over-potential of the water electrolysis.
Description
Technical field
The invention belongs to the water electrolysis technical field, particularly electrode for electrolysis and preparation method thereof.
Background technology
The Ni-S alloy electrode is the cathode for hydrogen evolution that a class relatively has application prospect, studies more thoroughly.The Ni-S alloy electrode has higher evolving hydrogen reaction activity, can reduce liberation of hydrogen (HER) reaction potential, and the HER overpotential of Ni-S alloy is than the low 250～350mV of Fe cathode overpotential.
The making of Ni-S alloy layer can be divided into two classes by the composition of plating bath: (1) thiosulfate solution system has direct current electrode position and pulse plating dual mode; (2) watt bath system.The thiosulfate solution system is divided into two kinds by its bath composition: 1. sulfate system, plating bath major ingredient NiSO
4, (NH
4)
2SO
46H
2O, Na
2S
2O
35H
2O, Na
3C
6H
5O
72H
2O; 2. chloride system, plating bath major ingredient NiCl
2, Na
2S
2O
35H
2O, NH
4Cl, Na
2SO
3, the adherence of coating of two kinds of plating bath acquisitions is similar.The former conductive capability is lower, and anode dissolution is poor, and wherein sulphur content reduces along with the increase of current density, PH, Trisodium Citrate, increases along with the increase of Sulfothiorine; The latter is because there is the existence of chlorine to make brittle coating.The main preparation methods of Ni-S alloy is to bathe in the system solution at traditional watt to add CS (NH
2)
2, KSCN or Na
2S
2O
3Be prepared from Deng as the sulphur source, forming NiS
xThe electrochemical catalysis activity of (sulphur content is about 17%～20%, massfraction) electrode pair evolving hydrogen reaction reaches the highest when non-crystalline state or microlitic structure.(bath element is: NiSO in basic watt bath
46H
2O, NiCl
26H
2O and H
3BO
4) the middle KSCN that adds, NaSCN, thiocarbamide, electroplate in different sulphur source such as sodium hyposulfate, obtains the Ni-S alloy layer of different sulphur contents.Current density, thiourea concentration, temperature, the pH value all exerts an influence to sulphur content in the coating, and obtaining thiourea concentration and current density after deliberation is the principal element of decision sulphur content.
Summary of the invention
The present invention has proposed employing electrode for water electrolysis and preparation method thereof in order to solve the deficiencies in the prior art, has been that the sedimentary method of matrix electricity consumption prepares electrode for water electrolysis with wire netting or metal strip both.By the enforcement of above-mentioned technology, the liberation of hydrogen of water electrolysis process, overpotential for oxygen evolution are effectively reduced.
Electrode for water electrolysis of the present invention is achieved by following technical proposals:
Electrode for water electrolysis of the present invention is: nickel element weight percent in the settled layer on electrode is 30～95%, element sulphur weight percent in the settled layer on electrode is 1～40%, and manganese element weight percent in the settled layer on electrode is 0.01～30%; Alloy is non-crystalline state or nanocrystalline structure on the electrode.
The mol ratio of nickel sulphur is 0.4～54 in the alloy electrode, and the mol ratio of nickel manganese is 0.9～9300.
The preparation method of electrode for water electrolysis of the present invention is to realize by following steps:
(1) preparation nickel ion, mn ion and contain the mixing solutions of the compound of element sulphur, wherein nickel ion concentration is 0.006～1.3 mol in the mixing solutions, manganese ion concentration is 0.006～1.3 mol, and the concentration of element sulphur is 0.006～2.5 mol in the compound of sulphur;
(2) will be immersed in the solution of step (1) preparation through pretreated metallic nickel, and add 1～100 grams per liter complexing agent, solution temperature is 5～80 ℃, with wire netting or metal strip as negative electrode, metallic nickel was switched on 10 minutes～10 hours as anode, and current density is 1～100mA/cm
2, at the settled layer of electrode surface deposition nickeliferous sulphur manganese alloy of one deck and sulfide.
Described wire netting or metal strip adopt following treatment process:
(1) wire netting or metal strip are made the electrode desired shape, utilize hot alkaline solution that grease is carried out on its surface then and remove processing; Mainly be to utilize hot alkaline solution that electrochemical deoiling is carried out in greasy saponification and emulsifying effect, the process that the grease of electrode surface is removed.Basic solution contains alkaline matters such as sodium hydroxide, yellow soda ash.
(2) with wire netting or metal strip at 5～15% hydrochloric acid soln, temperature activates under 15～30 ℃ of conditions.In order effectively to remove the metallic substrate surface passive film, guarantee coating and matrix energy good combination, wire netting will activate before plating.
The direct current electric plating method is adopted in energising of the present invention, and galvanized anode is large-area metallic nickel, and negative electrode is to want galvanized electrode slice, and temperature is controlled at 15～80 ℃.
The described compound that contains element sulphur adopts any one of Sulfothiorine, thiocarbamide, sodium hyposulfate, sodium sulfocynanate or potassium thiocyanate;
Described nickel ion adopts one or more of single nickel salt, nickelous chloride, nickel sulfamic acid, nickel pyrophosphate, nickel fluoborate or nickel acetate:
Described mn ion adopts one or both mixing of manganous sulfate or Manganous chloride tetrahydrate;
Described complexing agent is one or more of Trisodium Citrate, trisodium phosphate, ammonium sulfate, ammonium chloride, Repone K, sal epsom, ammonium citrate or boric acid;
Described wire netting or metal strip body material are nickel, iron or copper.
The water electrolysis electrode of making according to technique scheme is as negative electrode, and the big area nickel screen is as anode, and mercuric oxide electrode is as reference electrode, and 30% potassium hydroxide is compared with the nickel screen of not plating, at 100mA/cm as ionogen
2Overpotential of hydrogen evolution can reduce more than 10 millivolts under the electric current.The water electrolysis electrode of making according to technique scheme is as anode, at 400mA/cm
2Overpotential for oxygen evolution also reduces more than 10 millivolts under the electric current.
Description of drawings
Fig. 1: the XRD test result of alloy electrode.
Embodiment
Embodiment 1:
With single nickel salt 60 grams per liters, Sulfothiorine 14 grams per liters, manganous sulfate 40 grams per liters, Trisodium Citrate 12 grams per liters, ammonium sulfate 28 grams per liter wiring solution-formings are done anode with the big area nickel screen, and electroplating current density is 18mA/cm
2Electroplating time is 6 hours, electroplating temperature is 25 ℃, on nickel screen, electroplate the Ni-S-Mn alloy electrode, the electric current nickel screen electrode that the Ni-S-Mn electrode more plate during for-200mA is shuffled 170 millivolts, and the usefulness roughness of choppy sea potential sweep method test electrode by a small margin is 183, and the XRD test result shows that the Ni-S-Mn alloy is an amorphous structure, as shown in Figure 1,100 hours rear electrodes of brine electrolysis still have good electrocatalysis characteristic and in 30% potassium hydroxide.
Embodiment 2:
With nickelous chloride 200 grams per liters, Sulfothiorine 200 grams per liters, Manganous chloride tetrahydrate 200 grams per liters, Trisodium Citrate 100 grams per liters, ammonium chloride 100 grams per liter wiring solution-formings are done anode with the big area nickel screen, and electroplating current density is 1mA/cm
2Electroplating time is 10 minutes, electroplating temperature is 25 ℃, on nickel screen, electroplate the Ni-S-Mn alloy electrode, the electric current nickel screen electrode that the Ni-S-Mn electrode does not more plate during for-200mA is shuffled 10 millivolts, with the roughness of choppy sea potential sweep method test electrode by a small margin is 20, and the XRD test result shows that the Ni-S-Mn alloy is an amorphous structure, and 100 hours rear electrodes of brine electrolysis still have good electrocatalysis characteristic in 30% potassium hydroxide.
Embodiment 3:
With nickelous chloride 5 grams per liters, Sulfothiorine 5 grams per liters, Manganous chloride tetrahydrate 5 grams per liters, Trisodium Citrate 2 grams per liters, ammonium chloride 2 grams per liter wiring solution-formings are done anode with the big area nickel screen, and electroplating current density is 100mA/cm
2Electroplating time is 10 hours, electroplating temperature is 25 ℃, on nickel screen, electroplate the Ni-S-Mn alloy electrode, the electric current nickel screen electrode that the Ni-S-Mn electrode does not more plate during for-200mA is shuffled 10 millivolts, with the roughness of choppy sea potential sweep method test electrode by a small margin is 20, and the XRD test result shows that the Ni-S-Mn alloy is an amorphous structure, and 100 hours rear electrodes of brine electrolysis still have good electrocatalysis characteristic in 30% potassium hydroxide.
Embodiment 4:
With nickelous chloride 5 grams per liters, single nickel salt 5 grams per liters, Sulfothiorine 5 grams per liters, Manganous chloride tetrahydrate 5 grams per liters, Trisodium Citrate 2 grams per liters, sal epsom 2 grams per liters, Repone K 2 grams per liter wiring solution-formings are done anode with the big area nickel screen, and electroplating current density is 100mA/cm
2Electroplating time is 10 hours, electroplating temperature is 25 ℃, on nickel screen, electroplate the Ni-S-Mn alloy electrode, the electric current nickel screen electrode that the Ni-S-Mn electrode does not more plate during for-200mA is shuffled 10 millivolts, with the roughness of choppy sea potential sweep method test electrode by a small margin is 20, and the XRD test result shows that the Ni-S-Mn alloy is an amorphous structure, and 100 hours rear electrodes of brine electrolysis still have good electrocatalysis characteristic in 30% potassium hydroxide.
Open and electrode for water electrolysis of proposing of the present invention and preparation method thereof, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, processing parameter realize.Product of the present invention and method are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (1)
1. electrode for water electrolysis, it is characterized in that: nickel element weight percent in the settled layer on electrode is 30～95%, element sulphur weight percent in the settled layer on electrode is 1～40%, and manganese element weight percent in the settled layer on electrode is 0.01～30%; Alloy is non-crystalline state or nanocrystalline structure on the electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100156595A CN100383285C (en) | 2005-10-27 | 2005-10-27 | Electrode for water electrolysis and its making process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100156595A CN100383285C (en) | 2005-10-27 | 2005-10-27 | Electrode for water electrolysis and its making process |
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| Publication Number | Publication Date |
|---|---|
| CN1772954A CN1772954A (en) | 2006-05-17 |
| CN100383285C true CN100383285C (en) | 2008-04-23 |
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|---|---|---|---|
| CNB2005100156595A Expired - Fee Related CN100383285C (en) | 2005-10-27 | 2005-10-27 | Electrode for water electrolysis and its making process |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534653B (en) * | 2012-03-05 | 2014-12-17 | 广州华秦机械设备有限公司 | Manufacturing method for anode plate of water electrolyte device |
| CN103397339B (en) * | 2013-07-26 | 2016-06-22 | 华南理工大学 | A kind of electrolysis Aquatic product oxygen composite catalyzing electrode and preparation method thereof and application |
| CN108220993A (en) * | 2016-12-09 | 2018-06-29 | 广州华秦机械设备有限公司 | A kind of water electrolysis antioxidant activity anode plate prescription and preparation method thereof |
| CN106894045B (en) * | 2017-01-06 | 2019-02-01 | 燕山大学 | A kind of preparation method of the Fe2O3 doping nickel-base composite material for Electrochemical oxygen evolution |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5438277A (en) * | 1977-09-01 | 1979-03-22 | Osaka Soda Co Ltd | Cathode with low hydrogen overvoltage |
| JPS5741390A (en) * | 1980-08-25 | 1982-03-08 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| JPS5747884A (en) * | 1980-09-01 | 1982-03-18 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| JPS57177984A (en) * | 1981-04-24 | 1982-11-01 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| US4421626A (en) * | 1979-12-17 | 1983-12-20 | Occidental Chemical Corporation | Binding layer for low overvoltage hydrogen cathodes |
| US4422920A (en) * | 1981-07-20 | 1983-12-27 | Occidental Chemical Corporation | Hydrogen cathode |
| JPS6017096A (en) * | 1983-07-06 | 1985-01-28 | Toyo Soda Mfg Co Ltd | Production of electrode |
-
2005
- 2005-10-27 CN CNB2005100156595A patent/CN100383285C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5438277A (en) * | 1977-09-01 | 1979-03-22 | Osaka Soda Co Ltd | Cathode with low hydrogen overvoltage |
| US4421626A (en) * | 1979-12-17 | 1983-12-20 | Occidental Chemical Corporation | Binding layer for low overvoltage hydrogen cathodes |
| JPS5741390A (en) * | 1980-08-25 | 1982-03-08 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| JPS5747884A (en) * | 1980-09-01 | 1982-03-18 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| JPS57177984A (en) * | 1981-04-24 | 1982-11-01 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| US4422920A (en) * | 1981-07-20 | 1983-12-27 | Occidental Chemical Corporation | Hydrogen cathode |
| JPS6017096A (en) * | 1983-07-06 | 1985-01-28 | Toyo Soda Mfg Co Ltd | Production of electrode |
Non-Patent Citations (1)
| Title |
|---|
| 电镀原理与工艺. 覃奇贤等，95、158，天津科学技术出版社. 1995 * |
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|---|---|
| CN1772954A (en) | 2006-05-17 |
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Granted publication date: 20080423 Termination date: 20111027 |