CN1794496A - Hydrogen storage alloy powder surface cladded with nickel boron alloy and its preparation method - Google Patents
Hydrogen storage alloy powder surface cladded with nickel boron alloy and its preparation method Download PDFInfo
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- CN1794496A CN1794496A CNA2005100156608A CN200510015660A CN1794496A CN 1794496 A CN1794496 A CN 1794496A CN A2005100156608 A CNA2005100156608 A CN A2005100156608A CN 200510015660 A CN200510015660 A CN 200510015660A CN 1794496 A CN1794496 A CN 1794496A
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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
- Y02E60/10—Energy storage using batteries
Abstract
This invention puts forward a method for covering the NiB alloy on the surface of an alloy powder storing hydrogen and its preparation method including: first of all preparing a mixed solution of 0.3-1.5mol/L Ni ions, 10-140g/L Seignette salt, 5-90g/LNaOH and 1-30mg/L PbNO3, then preparing a B ionic solution of 0.015-0.45mol/L, then immerging the alloy powder into said mixed solution to be mixed by a mixer in the rotation speed of 50-300t/m and adding B ionic solution steadily in the solution for 20-160minutes in 1-10 times, the solution temperature is 20-100deg.C and the PH value is 5-14 and the alloy powder surface is covered with a NiB alloy layer.
Description
Technical field
The present invention relates to technical field of nickel, proposed a kind of at hydrogen storage alloy powder surface cladded with nickel boron alloy and preparation method thereof.
Background technology
Metal-hydrogen nickel battery (MH/Ni) is a kind of novel green battery that grows up the nineties in 20th century, and it and ickel-cadmium cell have good interchangeability, but does not have cadmium pollution and specific energy height.Extensive use and portable information device.In the electric automobile field, also has quite optimistic application prospect.The performance of metal-hydrogen nickel battery negative pole hydrogen-bearing alloy electrode is main relevant with the body phase character such as kind, composition and institutional framework of alloy, but the modification of the surface treatment of hydrogen bearing alloy and electrode can significantly improve the chemical property of negative pole.Aspect the finishing of alloyed powder and electrode, people have carried out a large amount of research. and the document that has shows: the acid of alloy surface, alkali treatment, reduction and fluorination treatment etc. can form rich nickel dam on the surface of alloy, make electrode have higher some catalytic activity, therefore improved the performance of electrode.The compound that is coated with one deck Pd powder or Pd at electrode surface can reduce the oxygen partial pressure of electrode interior effectively.Electroplate Co and Pd not only plays the effect of little collector at electrode surface, and the electricity that improves negative terminal surface urges words active.Method with replacement copper plating coats the discharge performance that copper can improve hydrogen bearing alloy on the hydrogen storing alloy powder surface, passes through Passivation Treatment again, can improve the aerial stability of copper layer, and discharge is had no adverse effect.The patent of application was once introduced the method at hydrogen-bearing alloy electrode surface cladded with nickel sulphur alloy-layer before me, and the method can improve the discharge performance of electrode and the life-span of improving electrode.This patent is mainly introduced another kind of with the method for chemical method at hydrogen storage alloy powder surface cladded with nickel boron alloy, the heavy-current discharge performance and the life-span that are used to improve electrode.
Summary of the invention
The present invention proposes a kind ofly at hydrogen storage alloy powder surface cladded with nickel boron alloy and preparation method thereof, by the enforcement of above-mentioned technology, is that hydrogen-bearing alloy electrode discharge performance and circulation discharge performance are significantly improved.
The present invention promptly contains the 0.001-20% boron element at hydrogen storage alloy powder surface cladded with nickel boron alloy in the sedimentary deposit on alloyed powder, boron element in sedimentary deposit with NiB
2Or Ni
2B
5The boron compound form exist.
The preparation method of hydrogen storage alloy powder surface cladded with nickel boron alloy of the present invention, step is as follows:
(1) configuration 0.3-1.5 mol nickel ion, 10-140 grams per liter sodium potassium tartrate tetrahydrate, the plumbi nitras mixed solution of 5-90 grams per liter NaOH and 1-30 mg/litre;
(2) the boron ion solution of configuration 0.015-0.45 mol;
(3) alloyed powder is immersed in the solution of (1) being joined, stir with blender, rotating speed is 50-300 rev/min, and in solution, dose the solution that (2) are configured to gradually, processing time is 20-160 minute, repeats this process 1-10 time, and solution temperature is 20-100 ℃, the solution pH value is 5-14, coats one deck ni-b alloy layer on the alloyed powder surface.
Described nickel ion comprises materials such as nickelous sulfate, nickel chloride, nickel acetate, nickel sulfamic acid or nickelous hypophosphite.
Described boron ion comprises materials such as sodium borohydride, potassium borohydride, dimethyamine borane or diethylamine borane.
Form battery according to above-mentioned technology side by electrode and nickel hydroxide electrode that the alloyed powder of handling and a certain proportion of nickel powder are mixed and made into, mercuric oxide electrode is as reference electrode, and the 6N potassium hydroxide solution is as electrolyte.The normal temperature low discharging current ability of electrode can not impact, but the large current discharging capability that helps electrode, along with the increase of discharging current, the effect of improvement is more and more obvious, under the 2C discharge, the electrode after process the method is handled has improved 18% than the discharge capacity of electrode before handling.Aspect the life-span, after the 1C circulation 250 times, handle rear electrode and can keep 79.26% of capacity, and before handling electrode only to keep 13.86% of capacity.It is apparent in view to improve effect.
Embodiment
Embodiment 1:
Nickel chloride 5g/L, potassium borohydride 0.3g/L, NaOH 10g/L are made into mixed solution.Complexing agent is a sodium potassium tartrate tetrahydrate, and concentration is 20g/L.Stabilizer is a plumbi nitras, and concentration is 2.5mg/L.The solution pH value is 13, and temperature is 90 ℃.Stir with blender, the time is 35 minutes, can make the alloyed powder surface coat one deck and contain NiB
2And Ni
5B
2Alloy-layer, the content of B element is more than 0.1%.The electrode that alloyed powder is after treatment made, discharge capacity under 0.5C, 1C, 1.5C, 2C electric current is all big than the electrode capacity under the same conditions that is untreated, especially under the 2C discharging condition, its Capacity Ratio electrode capacity that is untreated has improved 8.6%.And cycle life also can improve.After 250 circulations, the electrode that is untreated can only keep 13.57% of its capacity, and the capacity of handling rear electrode can keep its original 61.23%.
Embodiment 2:
Nickelous sulfate 10g/L, sodium borohydride 0.6g/L, NaOH 30g/L are made into mixed solution.Complexing agent is a sodium potassium tartrate tetrahydrate, and concentration is 60g/L.Temperature is 90 ℃.Stir with blender, the chemical plating time is 80 minutes, can make the alloyed powder surface coat one deck and contain NiB
2And Ni
5B
2Alloy-layer, the content of B element is more than 0.2%.The discharge capacity of electrode under 0.5C, 1C, 1.5C, 2C electric current that alloyed powder is after treatment made is all big than the electrode capacity under the same conditions that is untreated, and especially under the 2C discharging condition, its Capacity Ratio electrode capacity that is untreated has improved 16%.And cycle life also can improve.After 250 circulations, the electrode that is untreated can only keep 13.57% of its capacity, and the capacity of handling rear electrode can keep its original 77.14%.
Embodiment 3:
Nickel chloride 130g/L, sodium borohydride 2.6g/L, NaOH 90g/L are made into mixed solution.Complexing agent is a sodium potassium tartrate tetrahydrate, and concentration is 130g/L.Temperature is 90 ℃.Stir with blender, the chemical plating time is 120 minutes, can make the alloyed powder surface coat one deck and contain NiB
2And Ni
5B
2Alloy-layer, the content of B element is more than 0.5%.The discharge capacity of electrode under 0.5C, 1C, 1.5C, 2C electric current that alloyed powder is after treatment made is all big than the electrode capacity under the same conditions that is untreated, and especially under the 2C discharging condition, its Capacity Ratio electrode capacity that is untreated has improved 6.3%.And cycle life also can improve.After 250 circulations, the electrode that is untreated can only keep 13.57% of its capacity, and the capacity of handling rear electrode can keep its original 42.78%.
The present invention is open and propose at hydrogen storage alloy powder surface cladded with nickel boron alloy and preparation method thereof, and those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, technological parameter, structural design 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 (4)
1. at hydrogen storage alloy powder surface cladded with nickel boron alloy, it is characterized in that on alloyed powder, containing in the sedimentary deposit 0.001-20% boron element, boron element in sedimentary deposit with NiB
2Or Ni
2B
5The boron compound form exist.
2. the preparation method of the hydrogen storage alloy powder surface cladded with nickel boron alloy of a claim 1 is characterized in that:
(1) configuration 0.3-1.5 mol nickel ion, 10-140 grams per liter sodium potassium tartrate tetrahydrate, the plumbi nitras mixed solution of 5-90 grams per liter NaOH and 1-30 mg/litre;
(2) the boron ion solution of configuration 0.015-0.45 mol;
(3) alloyed powder is immersed in the solution of (1) being joined, stir with blender, rotating speed is 50-300 rev/min, and in solution, dose the solution that (2) are configured to gradually, processing time is 20-160 minute, repeats this process 1-10 time, and solution temperature is 20-100 ℃, the solution pH value is 5-14, coats one deck ni-b alloy layer on the alloyed powder surface.
3. the preparation method of a kind of hydrogen storage alloy powder surface cladded with nickel boron alloy as claimed in claim 2 is characterized in that described nickel ion adopts nickelous sulfate, nickel chloride, nickel acetate, nickel sulfamic acid or nickelous hypophosphite.
4. the preparation method of a kind of hydrogen storage alloy powder surface cladded with nickel boron alloy as claimed in claim 2 is characterized in that described boron ion adopts sodium borohydride, potassium borohydride, dimethyamine borane or diethylamine borane.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100156608A CN100346509C (en) | 2005-10-27 | 2005-10-27 | Hydrogen storage alloy powder surface cladded with nickel boron alloy and its preparation method |
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| CNB2005100156608A CN100346509C (en) | 2005-10-27 | 2005-10-27 | Hydrogen storage alloy powder surface cladded with nickel boron alloy and its preparation method |
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|---|---|
| CN1794496A true CN1794496A (en) | 2006-06-28 |
| CN100346509C CN100346509C (en) | 2007-10-31 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899639A (en) * | 2010-08-24 | 2010-12-01 | 浙江大学 | Method for improving corrosion resistance of hydrogen storage alloy by surface boronising method |
| CN101229515B (en) * | 2008-01-17 | 2012-08-29 | 南开大学 | Method of preparing highly effective hydrogenation amorphous alloy catalyst |
| CN105958024A (en) * | 2016-06-09 | 2016-09-21 | 桂林理工大学 | Method for improving electrochemical performance of AB3-type hydrogen storage alloy by using Co-B-C alloy |
| CN106001543A (en) * | 2016-06-09 | 2016-10-12 | 桂林理工大学 | Method for modifying La-Mg-Ni based hydrogen storage alloy by utilizing Ni-B-C alloy |
| CN108059126A (en) * | 2017-12-04 | 2018-05-22 | 上海交通大学 | One kind contains NiB12Reversible composite hydrogen storage material and preparation method thereof |
| CN109722667A (en) * | 2019-01-29 | 2019-05-07 | 西南科技大学 | A kind of high temperature resistant anti-ablation alloy |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279637C (en) * | 1996-01-22 | 2006-10-11 | 东芝株式会社 | Hydrogen-absorbing alloy, method of surface modification of the alloy, negative electrode for battery and alkaline secondary battery |
| JP2982805B1 (en) * | 1998-02-19 | 1999-11-29 | 松下電器産業株式会社 | Hydrogen storage alloy for battery, method for producing the same, and alkaline storage battery using the same |
| MX241166B (en) * | 2001-06-29 | 2006-10-16 | Ovonic Battery Co | Hydrogen storage battery; positive nickel electrode; positive electrode active material and methods for making. |
| JP4030381B2 (en) * | 2002-08-09 | 2008-01-09 | 三洋電機株式会社 | Nickel metal hydride storage battery |
-
2005
- 2005-10-27 CN CNB2005100156608A patent/CN100346509C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229515B (en) * | 2008-01-17 | 2012-08-29 | 南开大学 | Method of preparing highly effective hydrogenation amorphous alloy catalyst |
| CN101899639A (en) * | 2010-08-24 | 2010-12-01 | 浙江大学 | Method for improving corrosion resistance of hydrogen storage alloy by surface boronising method |
| CN101899639B (en) * | 2010-08-24 | 2012-09-19 | 浙江大学 | Method for improving corrosion resistance of hydrogen storage alloy by surface boronising method |
| CN105958024A (en) * | 2016-06-09 | 2016-09-21 | 桂林理工大学 | Method for improving electrochemical performance of AB3-type hydrogen storage alloy by using Co-B-C alloy |
| CN106001543A (en) * | 2016-06-09 | 2016-10-12 | 桂林理工大学 | Method for modifying La-Mg-Ni based hydrogen storage alloy by utilizing Ni-B-C alloy |
| CN108059126A (en) * | 2017-12-04 | 2018-05-22 | 上海交通大学 | One kind contains NiB12Reversible composite hydrogen storage material and preparation method thereof |
| CN109722667A (en) * | 2019-01-29 | 2019-05-07 | 西南科技大学 | A kind of high temperature resistant anti-ablation alloy |
| CN109722667B (en) * | 2019-01-29 | 2020-08-18 | 西南科技大学 | High-temperature-resistant ablation-resistant alloy |
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|---|---|
| CN100346509C (en) | 2007-10-31 |
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