CN1584123A - Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode - Google Patents
Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode Download PDFInfo
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- CN1584123A CN1584123A CN 200410013296 CN200410013296A CN1584123A CN 1584123 A CN1584123 A CN 1584123A CN 200410013296 CN200410013296 CN 200410013296 CN 200410013296 A CN200410013296 A CN 200410013296A CN 1584123 A CN1584123 A CN 1584123A
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Abstract
This invention relates to a catalyst for preparing boron-hydrogen compounds in an electrolytic process and manufacture of catalytic electrodes containing it. The catalyst comprises one of hydrogen-storing alloy, carbon materials and metal borides or their mixture. It is prepared by: mixing catalyst powders 60 - 90 parts, additives 0 - 20 parts and binding agent 1 - 10 parts uniformly, adding solution to form films, and pressing the films onto current-collecting Ni or steel nets; or adding solution to form pastes, coating them onto surfaces or internal sides of Ni or steel nets in a certain thickness, and drying to obtain catalytic electrodes. The catalyst and catalytic electrodes can be used to prepare boron hydrides with high performance of electric current >50% in alkali solution by electrolysis with low cost.
Description
Technical Field
The invention relates to a catalyst for preparing borohydride by an electrolytic method and a method for preparing a catalytic electrode containing the catalyst, belonging to the field of energy materials and fuelcell hydrogen sources.
Background
The hydrogen energy economy is an energy development direction proposed by the human society for relieving resource and environmental problems, and the development core isThe hydrogen replaces the prior fossil fuel (coal and petroleum) to be used as clean, green and portable fuel. The fuel cell using hydrogen as fuel is an efficient and clean power generation device, and is gradually becoming an ideal matching power source for portable electronic products and electric vehicles. At present, the main problem limiting the development and application of fuel cells is hydrogen storage, and the existing hydrogen storage mode is low in hydrogen storage amount, such as a high-pressure hydrogen bottle (1%), a hydrogen storage alloy (1.5-3%) and the like. Borohydride is a material with a high hydrogen storage content, such as LiBH4(36.8％)、NaBH4(21.2％)、KBH4(14.8%), not only can the compounds catalyze hydrolysis to release hydrogen as a high-capacity and high-purity hydrogen source material, but also can be directly used as a high-capacity cathode material in an electrochemical mode.
Borohydride catalytic hydrolysis reaction:
borohydride direct electrochemical oxidation reaction: E0＝-12.4V
because of this, Millennium Cell company, usa, is recently developing new fuel cells using alkali metal borohydride as a direct fuel. They indicate that higher energy densities can be provided by direct electrochemical reaction of borohydrides (e.g., NaBH)4A theoretical capacity of 5673mAh/g) and a simple battery device.
At present, theconventional Schlesinger method and Bayer method are mainly used for preparing borohydride industrially. These two synthetic routes prepare 1mol of NaBH4All consume 4mol of metallic sodium, the metallic sodium used for the preparation is produced by high-temperature electrolysis, thus preparing NaBH4The cost is high and the yield is small. Considering that hydrolysis and discharge products of borohydride are both BO2 -If BO can be achieved electrochemically2 -Recovery and recycle of BH4 -The method is an attractive way for greatly reducing the cost of the borohydride, and develops the application of the borohydride into a wide market.
Electrolytic production of borohydrides has been reported in Cooper (US3437842), Hale (US4931154), but the current efficiency is low (<20%) due to the use of noble metal catalysts. The core technology of preparing borohydride by adopting an electrolytic method is to provide a catalyst with low price, low hydrogen release and high catalytic activity and establish an electrolytic device with reasonable structure.
Disclosure of Invention
In order to overcome the defects of high price and low current efficiency of the existing catalyst, the invention aims to provide a catalyst for preparing borohydride by electrolysis, namely a cheap and efficient catalyst for preparing borohydride by electrolysis and a method for preparing a catalytic electrode containing the catalyst.
The catalyst for preparing borohydride by electrolysis provided by the invention comprises three types of hydrogen storage alloy, carbon material and metal boride, which can be one of the three types of hydrogen storage alloy, carbon material and metal boride, or a mixture of any two or more of the three types of hydrogen storage alloy, carbon material and metal boride.
According to the technical scheme of the invention, the hydrogen storage alloy catalyst comprises AB5Rare earth-nickel based hydrogen storage alloy, AB2Type Laves phase alloy, AB type Ti-Ni series alloy, A2The B-type magnesium-based hydrogen storage alloy and the V-based solid solution type alloy may be one of them, or a mixture of any two or more of them. Wherein the element A comprises La, Zr, Mg, V, Ti and the like; the element B comprises Cr, Mn, Fe, Co, Ni, Cu, Zn, Al and the like,
according to the technical scheme of the invention, the carbon material catalyst comprises carbon nano tubes, activated carbon, graphite and amorphous carbon, and can be one of the carbon nano tubes or a mixture of any two or more of the carbon nano tubes, the activated carbon, the graphite and the amorphous carbon.
According to the technical scheme of the invention, the metal boride comprises cobalt boride, iron boride, vanadium boride, zinc boride, nickel boride, copper boride, titanium boride, chromium boride or silver boride, and can be one of the cobalt boride, the iron boride, the vanadium boride, the zinc boride, the nickel boride, the copper boride, the titanium boride, the chromium boride or the silver boride, or a mixture of any two or more of the cobalt boride, the iron boride, the vanadium boride, the zinc boride, the nickel.
The invention also provides a method for preparing the catalytic electrode containing the catalyst for preparing borohydride by electrolysis, which comprises a rolling method and a coating and filling method.
The specific process for preparing the catalytic electrode comprises the following steps: uniformly mixing 60-100 parts of catalyst powder, 0-20 parts of additive and 1-10 parts of binder, adding a solvent to prepare a film (repeatedly rolling on double rollers to form a film or directly casting the film), pressing the film on a current-collecting nickel net or a steel net or mixing the film into slurry with the solvent, coating or filling the slurry on the surface or the inside of the porous nickel net or the steel net, pressing to a certain thickness, and drying to obtain the catalytic electrode.
The additive is one of Hg, Pb, Cd, Zn, Ni, Co and oxides thereof, or a mixture of any two or more of the Hg, Pb, Cd, Zn, Ni and Co.
The binder is one or a mixture of any two or more of polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, potassium polyacrylate, carboxymethyl cellulose (CMC), Methyl Cellulose (MC) and polyvinyl alcohol (PVA).
The catalyst and the catalytic electrode are mainly used for preparing borohydride by electrolysis, and are characterized by low price and high efficiency, and the current efficiency can reach more than 50 percent in an alkaline solution.
Detailed Description
Example 1: 7.5g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) Mixing 2g of mercury oxide powder and 0.8g of polytetrafluoroethylene emulsion (60 wt%), adding a little isopropanol, stirring into a paste, repeatedly rolling on double rollers to form a film with the thickness of 0.3-0.5 mm, and pressing the catalytic film on a nickel net or a steel net to obtain the catalytic electrode.
Example 2: 9.9g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) And 0.15g of polytetrafluoroethylene emulsion (60 percent by weight) are stirred into slurry, then the slurry is filled on a foam nickel substrate, and after drying, the slurry is pressed into an electrode plate with the thickness of 0.5 mm.
Example 3: mixing 1g of carbon nano tube, 3.2g of activated carbon, 0.3g of cadmium oxide powder and 0.5g of polyvinylidene fluoride (PVDF), adding 2g N-methyl pyrrolidone, stirring to form slurry, casting a film with the thickness of 0.1-0.3 mm on flat glass, and pressing the catalytic film on a nickel net or a steel net to form the catalytic electrode.
Example 4: 6g of cobalt boride, 2g of lead powder, 5g of 2% CMC hydrogel and 3g of polytetrafluoroethylene emulsion (60% by weight) are stirred into slurry, then the slurry is filled on a foamed nickel matrix, and after drying, the slurry is pressed into an electrode plate with the thickness of 0.5 mm.
Example 5: 9g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) 0.6g of mercury oxide powder, 5g of 2% CMC hydrogel and 0.5g of polytetrafluoroethylene emulsion (60% by weight) are stirred into a slurry state, then the slurry is filled on a foam nickel matrix, and after drying, the foam nickel matrix is pressed into an electrode plate with the thickness of 0.5 mm.
Example 6: 4g of cobalt boride, 4.5g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) Mixing with 0.8g of polytetrafluoroethylene emulsion (60 wt%), adding a little isopropanol, stirring into a dough, repeatedly rolling on double rollers to form a film with the thickness of 0.3-0.5 mm, and pressing the catalytic film on a nickel net or a steel net to obtain the catalytic electrode.
Example 7: 4g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) Mixing 4.5g of activated carbon, 0.5g of cadmium powder and 1g of a copolymer of vinylidene fluoride and hexafluoropropylene, adding 5g of acetone, stirring to form slurry, casting a film with the thickness of 0.1-0.3 mm on flat glass, and pressing the catalytic film on a nickel net or a steel net to obtain the catalytic electrode.
Example 8: stirring 8g of nickel boride, 1g of carbon nano tube, 0.6g of lead oxide powder and 1g of polytetrafluoroethylene emulsion (60 wt.%) into slurry, filling the slurry onto a foamed nickel substrate, drying, and pressing into an electrode plate with the thickness of 0.5 mm.
Example 9: 4g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) 4g of nickel boride, 1g of carbon activated carbon and 10g of 2% polyStirring potassium acrylate hydrogel and 0.5g of polytetrafluoroethylene emulsion (60% by weight) into slurry, filling the slurry into a foam nickel substrate, drying, and pressing into an electrode plate with the thickness of 0.5 mm.
Example 10: 2g of hydrogen storage material (La)0.7Nd0.3Ni2.5Co2.4Al0.1) 5g of cobalt boride, 2g of carbon activated carbon, 1g of mercury oxide powder, 10g of 2% PVA hydrogel and 0.5g of polytetrafluoroethylene emulsion (60% by weight) are stirred into a slurry state, then the slurry is filled on a foamed nickel substrate, and after drying, the foamed nickel substrate is pressed into an electrode plate with the thickness of 0.5 mm.
Claims (8)
1. The catalyst for preparing hydroboron by electrolysis is characterized in that the catalyst is one or a mixture of any two of hydrogen storage alloy, carbon material and metal boride.
2. The catalyst for the electrolytic production of borohydride according to claim 1, characterized in that: the hydrogen storage alloy is AB5Rare earth-nickel based hydrogen storage alloy, AB2Type Laves phase alloy, AB type Ti-Ni series alloy, A2One or a mixture of any two of B-type magnesium-based hydrogen storage alloy or V-based solid solution type alloy; wherein the element A comprises La, Zr, Mg, V and Ti, and the element B comprises Cr, Mn, Fe, Co, Ni, Cu, Zn and Al.
3. The catalyst for the electrolytic production of borohydride according to claim 1, characterized in that: the carbon material is one or a mixture of any two of carbon nano tube, activated carbon, graphite or amorphous carbon.
4. The catalyst for the electrolytic production of borohydride according to claim 1, characterized in that: the metal boride is one or a mixture of any two of cobalt boride, iron boride, vanadium boride, zinc boride, nickel boride, copper boride, titanium boride, chromium boride and silver boride.
5. A method of making a catalytic electrode comprising the catalyst of claim 1, wherein: uniformly mixing 60-100 parts of catalyst powder, 0-20 parts of additive and 1-10 parts of binder, adding a solvent to prepare a membrane, pressing the membrane on a current-collecting nickel net or a steel net, or mixing the membrane into slurry with the solvent, coating or filling the membrane on the surface or inside the porous nickel net or the steel net, pressing the membrane to a certain thickness, and drying the membrane to obtain the catalytic electrode.
6. The method according to claim 5, wherein the additive is one or a mixture of any two of Hg, Pb, Cd, Zn, Ni, Co and their oxides.
7. The method according to claim 5, wherein the binder is one or a mixture of two of polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, potassium polyacrylate, carboxymethyl cellulose, methyl cellulose and polyvinyl alcohol.
8. The method according to claim 5, wherein the solvent is one or a mixture of any two of water, acetone, isopropanol, N-dimethylformamide, N-methylpyrrolidone, and tetrahydrofuran.
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| CN 200410013296 CN1284882C (en) | 2004-06-15 | 2004-06-15 | Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode |
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| CN 200410013296 CN1284882C (en) | 2004-06-15 | 2004-06-15 | Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode |
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| CN1584123A true CN1584123A (en) | 2005-02-23 |
| CN1284882C CN1284882C (en) | 2006-11-15 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659221A (en) * | 2012-05-10 | 2012-09-12 | 刘娟 | Electro-catalytic oxidation material for wastewater treatment, preparation method and application |
| CN104878268A (en) * | 2015-05-20 | 2015-09-02 | 安徽工业大学 | Multiple-principal-component Laves-base intermetallic compound with plasticity and preparation method thereof |
| CN107162125A (en) * | 2017-06-14 | 2017-09-15 | 清华大学 | A kind of method of electric Fenton system degradable organic pollutant using from oxygen supply and from acidifying |
| CN109529920A (en) * | 2018-11-12 | 2019-03-29 | 山东科技大学 | Load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and application method |
| CN111378987A (en) * | 2020-05-13 | 2020-07-07 | 西安交通大学 | Preparation method of chemical nickel-boron-plated alloy hydrogen evolution electrode |
-
2004
- 2004-06-15 CN CN 200410013296 patent/CN1284882C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659221A (en) * | 2012-05-10 | 2012-09-12 | 刘娟 | Electro-catalytic oxidation material for wastewater treatment, preparation method and application |
| CN104878268A (en) * | 2015-05-20 | 2015-09-02 | 安徽工业大学 | Multiple-principal-component Laves-base intermetallic compound with plasticity and preparation method thereof |
| CN104878268B (en) * | 2015-05-20 | 2017-09-22 | 安徽工业大学 | A kind of many pivot Laves base intermetallic compounds with plasticity and preparation method thereof |
| CN107162125A (en) * | 2017-06-14 | 2017-09-15 | 清华大学 | A kind of method of electric Fenton system degradable organic pollutant using from oxygen supply and from acidifying |
| CN109529920A (en) * | 2018-11-12 | 2019-03-29 | 山东科技大学 | Load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and application method |
| CN111378987A (en) * | 2020-05-13 | 2020-07-07 | 西安交通大学 | Preparation method of chemical nickel-boron-plated alloy hydrogen evolution electrode |
| CN111378987B (en) * | 2020-05-13 | 2021-07-06 | 西安交通大学 | Preparation method of chemical nickel-boron-plated alloy hydrogen evolution electrode |
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| Publication number | Publication date |
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| CN1284882C (en) | 2006-11-15 |
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