CN1284882C - 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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- CN1284882C CN1284882C CN 200410013296 CN200410013296A CN1284882C CN 1284882 C CN1284882 C CN 1284882C CN 200410013296 CN200410013296 CN 200410013296 CN 200410013296 A CN200410013296 A CN 200410013296A CN 1284882 C CN1284882 C CN 1284882C
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Abstract
The present invention discloses a catalyst for preparing borohydride by an electrolysis method and a method for preparing a catalytic electrode containing the catalyst. The catalyst is one kind or mixtures of two or multiple kinds of hydrogen storing alloys, carbon materials and metal boride. 60 to 100 parts of catalyst powder, 0 to 20 parts of additive and 1 to 10 parts of adhesive are uniformly mixed, a membrane is firstly prepared by adding a solvent, and then, the membrane is pressed on a current collecting nickel screen or steel screen; or mixtures are prepared to be pulp by the solvent and are coated or filled to the surface or the inner part of the porous nickel screen or steel screen, and the porous nickel screen or steel screen is pressed to be with certain thickness and is dried to obtain the catalytic electrode. The catalyst and the catalytic electrode of the present invention are used for preparing the borohydride and have low price and highly efficient properties, and the current efficiency can reach more than 50% in alkali solutions.
Description
Technical field
The present invention relates to a kind of method for preparing catalysis electrode, belong to energy and material, fuel cell hydrogen source field.
Background technology
Hydrogen Energy economy is that human society is to alleviate a kind of energy development direction that resource and environmental problem propose, and the core content of this development is to substitute existing fossil oil (coal, oil) as cleaning, green, the fuel that is easy to carry and transports with hydrogen.The fuel cell that with hydrogen is fuel then is a kind of power generation assembly efficient, cleaning, and becomes the desirable supporting power supply of portable type electronic product and electromobile gradually.At present, fuel cell development and the subject matter of using are the storages of hydrogen, and the existing storage hydrogen mode that adopts, hydrogen-storage amount is all lower, as High Pressure Hydrogen bottle (1%), hydrogen-storage alloy (1.5～3%) etc.Hydroborate is a kind of material of high storage hydrogen richness, as LiBH
4(36.8%), NaBH
4(21.2%), KBH
4(14.8%), moreover, these compounds can the catalytic hydrolysis release hydrogen as heavy body, High Purity Hydrogen source material, again can be directly by electrochemical means as the heavy body negative material.
The hydroborate catalytic hydrolysis reaction:
Hydroborate Direct Electrochemistry oxidizing reaction:
E
0＝-12.4V
Just because of this, recently, it is the new fuel cell of direct fuel that U.S. Millennium Cell company is developing with alkali metal borohydride.They point out by hydroborate Direct Electrochemistry reaction, can provide more high-energy-density (as NaBH
4Theoretical capacity is 5673mAh/g) and easy cell apparatus.
At present, industrial preparation hydroborate is mainly continued to use traditional Schlesinger method and Bayer method.These two kinds of synthetic routes prepare 1mol NaBH
4All to consume the 4mol sodium Metal 99.5, prepare used sodium Metal 99.5 and adopt high-temperature electrolysis to produce, therefore prepare NaBH
4The cost height, output is little.Hydrolysis and the discharging product of considering hydroborate are BO
2 -If can realize BO with electrochemical method
2 -Reclaim and cycles prepare BH
4 -, this is the tempting approach that the hydroborate cost descends significantly, and vast market is opened up in the application of hydroborate.
Cooper (US3437842) once reported preparing boron hydride by electrolytic method among the Hale (US4931154), but owing to use noble metal catalyst, made current efficiency low (＜20%).We think that employing preparing boron hydride by electrolytic method, its core technology provide cheapness, hang down and release hydrogen, high catalytic activity catalyst and set up electrolyzer rational in infrastructure.
Summary of the invention
In order to overcome above-mentioned existing catalyzer, the shortcoming that cost an arm and a leg, current efficiency is low, the purpose of this invention is to provide a kind of inexpensive, prepare the method for catalysis electrode efficiently.
The invention provides a kind of preparation method who is used for the catalysis electrode of electrolytic preparation hydroborate, comprise rolled-on method and apply completion method preparing catalysis electrode.
Preparation catalysis electrode detailed process is: with catalyst fines (60～100 parts), additive (0～20 part) and binding agent (1～10 part) mixing, solubilizing agent is made film (rolling film forming or direct casting film forming repeatedly two rolling on) earlier, then with mould on afflux nickel screen or steel mesh, perhaps use solvent furnishing pulpous state, apply or be filled into the surperficial or inner of porous nickel screen or steel mesh then, be depressed into certain thickness, oven dry promptly gets catalysis electrode.
According to technical scheme of the present invention, described catalyzer comprises hydrogen storage alloy, carbon material, metal boride three classes, can be wherein a kind of, also can be two or more mixture arbitrarily wherein.
According to technical scheme of the present invention, described hydrogen storage alloy catalyzer comprises AB
5Type rare earth nickel base hydrogen storage alloy, AB
2Type Laves phase alloy, AB type Ti-Ni are alloy, A
2Type B Mg base hydrogen bearing alloy and V base Solid solution type alloy can be wherein a kind of, also can be two or more mixture arbitrarily wherein.Wherein elements A comprises La, Zr, Mg, V, Ti etc.; Element B comprises Cr, Mn, Fe, Co, Ni, Cu, Zn, Al etc.,
According to technical scheme of the present invention, described carbon material catalyzer comprises carbon nanotube, activated carbon, graphite, indefiniteness carbon, can be wherein a kind of, also can be two or more mixture arbitrarily wherein.
According to technical scheme of the present invention, described metal boride comprises boronation cobalt, FeB, vanadium boride, boronation zinc, nickel borides, boron copper, titanium boride, chromium boride or boronation silver, can be wherein a kind of, also can be two or more mixture arbitrarily wherein.
Described additive is a kind of in Hg, Pb, Cd, Zn, Ni, Co and the oxide compound thereof, or two or more mixture arbitrarily wherein.
Described binding agent is a kind of in the multipolymer, polyacrylic acid potassium, carboxymethyl cellulose (CMC), methylcellulose gum (MC), polyvinyl alcohol (PVA) of tetrafluoroethylene, polyvinylidene difluoride (PVDF), vinylidene and R 1216 or two or more mixture arbitrarily wherein.
Catalyzer of the present invention and catalysis electrode are mainly used in electrolysis system hydroborate, are characterized in having cheap price and performance efficiently, and it is in basic solution, and current efficiency can reach more than 50%.
Embodiment
Embodiment 1: with 7.5g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1), 2g red precipitate powder and 0.8g ptfe emulsion (60%wt.) mix, add a little Virahol, stir into dough, be rolled into the film that thickness is 0.3～0.5mm repeatedly two rolling on then, again catalytic film is pressed on nickel screen or the steel mesh, catalysis electrode.
Embodiment 2: with 9.9g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1), 0.15g ptfe emulsion (60%wt.) stirs into pulpous state, then slurries is filled on the nickel foam substrate, after the oven dry, is pressed into the electrode slice that thickness is 0.5mm again.
Embodiment 3: 1g carbon nanotube, 3.2g activated carbon, 0.3g Cadmium oxide powder and 0.5g polyvinylidene difluoride (PVDF) (PVDF) are mixed, add the 2g N-Methyl pyrrolidone, stir into soup compound, then at the smooth film that thickness is 0.1～0.3mm of casting on glass, again catalytic film is pressed on nickel screen or the steel mesh, catalysis electrode.
Embodiment 4: CMC hydrogel and the 3g ptfe emulsion (60%wt.) of 6g boronation cobalt, 2g lead powder end, 5g 2% are stirred into pulpous state, then slurries are filled on the nickel foam substrate, after the oven dry, be pressed into the electrode slice that thickness is 0.5mm again.
Embodiment 5: with 9g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1), CMC hydrogel and the 0.5g ptfe emulsion (60%wt.) of 0.6g red precipitate powder, 5g 2% stir into pulpous state, then slurries is filled on the nickel foam substrate, after the oven dry, is pressed into the electrode slice that thickness is 0.5mm again.
Embodiment 6: with 4g boronation cobalt, 4.5g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1) and 0.8g ptfe emulsion (60%wt.) mix, add a little Virahol, stir into dough, be rolled into the film that thickness is 0.3～0.5mm repeatedly two rolling on then, again catalytic film is pressed on nickel screen or the steel mesh, catalysis electrode.
Embodiment 7: with 4g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1), the multipolymer of 4.5g activated carbon, 0.5g cadmium dust and 1g vinylidene and R 1216 mixes, add 5g acetone, stir into soup compound, then at the smooth film that thickness is 0.1～0.3mm of casting on glass, again catalytic film is pressed on nickel screen or the steel mesh, catalysis electrode.
Embodiment 8: 8g nickel borides, 1g carbon nanotube, 0.6g lead oxide powder and 1g ptfe emulsion (60%wt.) are stirred into pulpous state, then slurries are filled on the nickel foam substrate, after the oven dry, be pressed into the electrode slice that thickness is 0.5mm again.
Embodiment 9: with 4g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1), 4g nickel borides, 1g carbon gac, 10g 2% polyacrylic acid potassium hydrogel and 0.5g ptfe emulsion (60%wt.) stir into pulpous state, then slurries is filled on the nickel foam substrate, after the oven dry, is pressed into the electrode slice that thickness is 0.5mm again.
Embodiment 10: with 2g hydrogen storage material (La
0.7Nd
0.3Ni
2.5Co
2.4Al
0.1), 5g boronation cobalt, 2g carbon gac,, 1g red precipitate powder 10g 2%PVA hydrogel and 0.5g ptfe emulsion (60%wt.) stir into pulpous state, then slurries is filled on the nickel foam substrate, after the oven dry, is pressed into the electrode slice that thickness is 0.5mm again.
Claims (7)
1. the preparation method of a catalysis electrode, it is characterized in that: with 60～100 parts of catalyst fineses, 0～20 part of additive and 1～10 part of mixing of binding agent, solubilizing agent is made film earlier, then with mould on afflux nickel screen or steel mesh, perhaps use solvent furnishing pulpous state, apply or be filled into the surperficial or inner of porous nickel screen or steel mesh then, be depressed into the thickness of 0.1-0.5mm, oven dry promptly gets catalysis electrode; Described catalyzer is a kind of or wherein any two kinds mixture in hydrogen storage alloy, carbon material, the metal boride.
2. preparation method according to claim 1 is characterized in that described additive is a kind of or wherein any two kinds mixture in Hg, Pb, Cd, Zn, Ni, Co and the oxide compound thereof.
3. preparation method according to claim 1 is characterized in that described binding agent is a kind of or wherein any two kinds mixture in the multipolymer, polyacrylic acid potassium, carboxymethyl cellulose, methylcellulose gum, polyvinyl alcohol of tetrafluoroethylene, polyvinylidene difluoride (PVDF), vinylidene and R 1216.
4. preparation method according to claim 1 is characterized in that described solvent is water, acetone, Virahol, N, a kind of or wherein any two kinds mixture in dinethylformamide, N-Methyl pyrrolidone, the tetrahydrofuran (THF).
5. preparation method according to claim 1 is characterized in that: described hydrogen storage alloy is AB
5Type rare earth nickel base hydrogen storage alloy, AB
2Type Laves phase alloy, AB type Ti-Ni are alloy, A
2A kind of or wherein any two kinds mixture in Type B Mg base hydrogen bearing alloy or the V base Solid solution type alloy; Wherein elements A is La, Zr, Mg, V, Ti, and element B is Cr, Mn, Fe, Co, Ni, Cu, Zn, Al.
6. preparation method according to claim 1 is characterized in that: described carbon material is a kind of or wherein any two kinds mixture in carbon nanotube, activated carbon, graphite or the indefiniteness carbon.
7. preparation method according to claim 1 is characterized in that: described metal boride is a kind of or wherein any two kinds mixture in boronation cobalt, FeB, vanadium boride, boronation zinc, nickel borides, boron copper, titanium boride, chromium boride, the boronation silver.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013296 CN1284882C (en) | 2004-06-15 | 2004-06-15 | Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 CN1584123A (en) | 2005-02-23 |
| CN1284882C true CN1284882C (en) | 2006-11-15 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659221B (en) * | 2012-05-10 | 2013-08-28 | 深圳市地大东江环境研究院 | Electro-catalytic oxidation material for wastewater treatment, preparation method and application |
| 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 |
| CN109529920B (en) * | 2018-11-12 | 2021-11-02 | 山东科技大学 | Supported titanium boride catalyst for light alkane isomerization and preparation method and using method thereof |
| 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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