CN101267035B - A nickel hydrogen cathode material and its making method - Google Patents
A nickel hydrogen cathode material and its making method Download PDFInfo
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- CN101267035B CN101267035B CN2008100240599A CN200810024059A CN101267035B CN 101267035 B CN101267035 B CN 101267035B CN 2008100240599 A CN2008100240599 A CN 2008100240599A CN 200810024059 A CN200810024059 A CN 200810024059A CN 101267035 B CN101267035 B CN 101267035B
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- nickel powder
- hydrogen
- preparation
- alloy
- bearing alloy
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000000034 method Methods 0.000 title abstract description 10
- 229910052759 nickel Inorganic materials 0.000 title description 2
- 239000010406 cathode material Substances 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- 239000001996 bearing alloy Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 9
- 230000001788 irregular Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007767 bonding agent Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 150000002910 rare earth metals Chemical group 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 8
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000002159 nanocrystal Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018007 MmNi Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910010380 TiNi Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention provides a H/Ni battery negative electrode material containing nano-crystalline nickel powder and its preparing method. The negative electrode material in MH/Ni battery is characterized in that the raw materials are hydrogen storage alloy and nano-crystalline nickel powder, the mass ratio of nano-crystalline nickel powder to hydrogen storage alloy is 3:1-1:5, negative electrode material is obtained by cold pressing preparation. The H/Ni battery negative electrode material of the preparation is added with nano-crystalline nickel powder, capable of improving charge-discharge efficiency of the hydrogen storage alloy, reducing charge platform, enhancing discharge platform, enhancing discharge capacity of the hydrogen storage alloy. In the charge-discharge cycle process, the active surface of the hydrogen storage alloy is enhanced, the electro-catalytic performance of the hydrogen storage alloy to the hydrogen is improved.
Description
Technical field
The invention belongs to energy field, relate to a kind of nickel-hydrogen battery negative pole material and preparation method thereof; Relate in particular to a kind of nickel-hydrogen battery negative pole material that comprises nanocrystalline nickel powder and preparation method thereof.
Background technology
Nickel-hydrogen secondary cell has high-energy-density, high charge-discharge ability, long-life, fail safe and reaches plurality of advantages [1-2] such as environmental protection well, in recent years, caused in relevant electric tools such as electric automobile widely and paid close attention to that this just has higher requirement to the chemical property of battery.As the hydrogen bearing alloy of nickel-hydrogen battery negative pole material chief component, the performance of battery has been played conclusive effect.So the chemical property that improves hydrogen bearing alloy becomes the key that improves battery performance.Change composition, tissue, the structure of alloy and set up the concern that new alloy system has caused numerous researchers.Emerge the alloy system of some high power capacity, but have problems such as activity cycle is long.
Nickel powder has good conductivity, is difficult for taking place advantages such as corrosion in air or in the alkaline electrolyte, is widely used in hydrogen bearing alloy, not only can be used for synthetic hydrogen bearing alloy, can also be used to prepare hydrogen-bearing alloy electrode as additive.In preparation nickel-based battery negative material, using wider additive is the crystalline state nickel powder at present.People such as nickel powder of selling as Chemical Reagent Co., Ltd., Sinopharm Group and Pan Hongge are entitled as the effect of substitution of Zr for La on the electrochemical propertiesof La at the 397 volume 1-2 phase 269-275 pages or leaves of magazine Journal of Alloys and Compounds
0.7-xZr
xMg
0.3Ni
2.45Mn
0.1Co
0.75Al
0.2The carbonyl nickel powder that the preparation negative material of mentioning in hydrogen storage electrode alloys one literary composition is adopted does not all belong to nanocrystalline nickel powder, and Kim JS is entitled as Effects of F-treatment on degradation of Mg at the 201-207 page or leaf of 104 2 phases of volume of magazine Journal of PowerSources
2Also provided same way in Nielectrode fabricated by mechanical alloying one literary composition.They consider the influence of nickel powder anticathode material aspect the electro catalytic activity of hydrogen of interpolation, and the nickel powder that is adopted has only played the effect of conductive agent or collector, almost do not have what contribution for the charge efficiency, the charging capacity that improve negative material.
Summary of the invention
The objective of the invention is provides a kind of nickel-hydrogen battery negative pole material that comprises nanocrystalline nickel powder in order to improve nickel powder in the existing cell negative electrode material to the deficiency of the electrocatalysis characteristic of hydrogen, and another object of the present invention has provided a kind of preparation method of above-mentioned material.
Technical scheme of the present invention is: when the preparation nickel-hydrogen battery negative pole material, the nickel powder that adds nanocrystalline structure, take into full account its electric catalyticing characteristic to hydrogen, nanocrystalline nickel powder can further promote the formation of hydrogen atom, increase the adsorbance of hydrogen atom on negative material, thereby can improve charge efficiency; Increase the electrochemistry capacitance of hydrogen bearing alloy; Improve the electrocatalysis characteristic of hydrogen bearing alloy.
Concrete technical scheme of the present invention is: a kind of nickel-hydrogen battery negative pole material, it is characterized in that its raw material is hydrogen bearing alloy and nanocrystalline nickel powder, and the mass ratio of nanocrystalline nickel powder and hydrogen bearing alloy is 3: 1-1: 5, preparation gets negative material by colding pressing.
The present invention also can add in preparation negative material raw material and accounts for the bonding agent that hydrogen bearing alloy weight is 2%-6%.Wherein said bonding agent is polyvinyl alcohol or polytetrafluoroethylene.
Above-mentioned hydrogen bearing alloy is rare earth based alloy, titanium-base alloy, zirconium-base alloy, magnesium base alloy or vanadium-base alloy.Hydrogen bearing alloy can be by prior art for preparing or is directly bought.
Above-mentioned nanocrystalline nickel powder is characterised in that its purity is 99%-99.9%; Average particle size particle size is 5-70 μ m; Crystallite dimension is 8-30nm; Powder shape can be irregular shape or sphere.
The invention provides the preparation method of above-mentioned nickel-hydrogen battery negative pole material, its concrete steps are as follows:
The preparation of A, nanocrystalline nickel powder: commercially available nickel powder is packed in the ball grinder, carry out ball milling, obtaining purity is 99%-99.9%; Average particle size particle size is 5-70 μ m; Crystallite dimension is 8-30nm; Powder shape can be irregular shape or spherical nanocrystalline nickel powder;
B, be 3 with hydrogen bearing alloy by mass ratio with the prepared nanocrystalline nickel powder of above-mentioned steps: 1-1: 5 mix, and preparation gets negative material by colding pressing.
In the steps A of the present invention nickel powder packed in the ball grinder, the control material ball ratio is 5: 1-50: 1, and rotating speed is 100-400 rev/min, ball milling 3-80 hour; Cold-press process described in the step B is exactly that compression moulding at normal temperatures gets final product.
The preparation of nanocrystalline nickel powder of the present invention except above-mentioned mechanical ball milling method, can also make by chemical method and smelting process.
The electrode performance test of the obtained material of the present invention is carried out under the three-electrode battery condition, and negative pole is a hydrogen-bearing alloy electrode, just very sintering Ni (OH)
2, reference electrode is the Hg/HgO electrode, electrolyte is 6M KOH.Hydrogen-bearing alloy electrode is with the current charges of 60mA/g 6 hours, leaves standstill to begin discharge after 10 minutes, and discharging current is 60mA/g, and discharge by current potential is-0.74V (Hg/HgO).The electrocatalysis characteristic of electrode pair hydrogen characterizes by linear polarization method.
Beneficial effect:
The present invention prepared nickel-hydrogen battery negative pole material added nanocrystalline nickel powder, can improve the efficiency for charge-discharge of hydrogen bearing alloy, reduce charging platform, improve discharge platform, increase the discharge capacity of hydrogen bearing alloy.In the charge and discharge cycles process, increase the active surface of hydrogen bearing alloy, improve the electrocatalysis characteristic of hydrogen bearing alloy to hydrogen.
Embodiment
Embodiment 1:
1), the preparation of nanocrystalline nickel powder: commercially available amorphous/nano crystal nickel powder is packed in the stainless steel jar mill; adopt the stainless steel ball grinding media; rotating speed is 300 rev/mins; ratio of grinding media to material is 20: 1; under argon shield, move, ball milling 50h, making purity is 99.2%; average particle size particle size is 10 μ m, and average grain size is the nanocrystalline nickel powder of 9nm.Grain shape is spherical.
2), negative material preparation: with 2: 1 proportioning of weight ratio with nanocrystalline nickel powder and commercially available MmNi
3.8Co
0.75Mn
0.4Al
0.2Rare earth based hydrogen bearing alloy mixing (Ningbo Shenjiang Technology Co., Ltd), being cold-pressed into diameter under 20MPa pressure is that 18mm, thickness are the thin slice of about 1mm.Adopt same condition that amorphous/nano crystal nickel powder and hydrogen bearing alloy are prepared into negative material, to contrast.
3), discharge and recharge experimental result and show that after discharging and recharging activation, the charging platform current potential that adds nanocrystalline nickel powder electrode has reduced 0.011V, the discharge platform current potential has improved 0.028V.The efficiency for charge-discharge of electrode be improved significantly.The discharge capacity of electrode has improved 30mAh/g.Linear polarization is the result show, the exchange current density of electrode has improved 40mA/g, and nanocrystalline nickel powder is improved significantly the electrocatalysis characteristic of electrode pair hydrogen.
Embodiment 2:
1), the preparation of nanocrystalline nickel powder: just commercially available amorphous/nano crystal nickel powder is packed in the stainless steel jar mill; adopt the stainless steel ball grinding media; rotating speed is 400 rev/mins; ratio of grinding media to material is 10: 1; under argon shield, move, ball milling 5h, making purity is 99.7%; average particle size particle size is 55 μ m, and average grain size is the nanocrystalline nickel powder of 26nm.Grain shape is irregular shape.
2), negative material preparation: with 1: 3 proportioning of weight ratio with nanocrystalline nickel powder and commercially available MmNi
3.8Co
0.75Mn
0.4Al
0.2Rare earth based hydrogen bearing alloy mixing mixing, being cold-pressed into diameter under 20MPa pressure is that 18mm, thickness are the thin slice of about 1mm.Adopt same condition that amorphous/nano crystal nickel powder and hydrogen bearing alloy are prepared into negative material, to contrast.
3), discharge and recharge experimental result and show that after discharging and recharging activation, the charging platform current potential that adds nanocrystalline nickel powder electrode has reduced 0.008V, the discharge platform current potential has improved 0.018V.The efficiency for charge-discharge of electrode is effectively improved.The discharge capacity of electrode has improved 20mAh/g.Linear polarization is the result show, the exchange current density of electrode has improved 25mA/g, and the nanocrystalline nickel powder that is added can effectively improve the electrocatalysis characteristic of electrode pair hydrogen.
Embodiment 3:
1), the preparation of nanocrystalline nickel powder: just commercially available amorphous/nano crystal nickel powder is packed in the stainless steel jar mill; adopt the stainless steel ball grinding media; rotating speed is 400 rev/mins; ratio of grinding media to material is 10: 1; under argon shield, move, ball milling 5h, making purity is 99.7%; average particle size particle size is 55 μ m, and average grain size is the nanocrystalline nickel powder of 26nm.Grain shape is irregular shape.
2), negative material preparation: with nanocrystalline nickel powder and polyvinyl alcohol mixing by homemade TiNi titanium-based hydrogen storage alloy of mechanical ball milling method and relative hydrogen bearing alloy 4% weight ratio, being cold-pressed into diameter under 20MPa pressure is that 18mm, thickness are the thin slice of about 1mm with 1: 3 proportioning of weight ratio.Adopt same condition that amorphous/nano crystal nickel powder and hydrogen bearing alloy are prepared into negative material, to contrast.
3), discharge and recharge experimental result and show that after discharging and recharging activation, the charging platform current potential that adds nanocrystalline nickel powder electrode has reduced 0.007V, the discharge platform current potential has improved 0.014V.The efficiency for charge-discharge of electrode is effectively improved.The discharge capacity of electrode has improved 16mAh/g.Linear polarization is the result show, the exchange current density of electrode has improved 22mA/g, and the nanocrystalline nickel powder that is added can effectively improve the electrocatalysis characteristic of electrode pair hydrogen.
Nickel-hydrogen battery negative pole material according to design philosophy of the present invention and design are made promptly wherein contains nanocrystalline nickel powder, can improve the efficiency for charge-discharge of hydrogen bearing alloy, reduces charging platform, improves discharge platform, increases the discharge capacity of hydrogen bearing alloy.Effectively improved the electrocatalysis characteristic of hydrogen bearing alloy to hydrogen.
Claims (6)
1. a nickel-hydrogen battery negative pole material is characterized in that its raw material is hydrogen bearing alloy and nanocrystalline nickel powder, and the mass ratio of nanocrystalline nickel powder and hydrogen bearing alloy is 3: 1-1: 5, and preparation gets negative material by colding pressing; Wherein said nanocrystalline nickel powder is characterised in that its purity is 99%-99.9%, and average particle size particle size is 5-70 μ m, and crystallite dimension is 8-30nm, and grain shape is irregular shape or sphere.
2. material according to claim 1 is characterized in that in the negative material raw material adding the bonding agent of the 2%-6% that accounts for hydrogen bearing alloy weight.
3. material according to claim 2 is characterized in that described bonding agent is polyvinyl alcohol or polytetrafluoroethylene.
4. material according to claim 1 is characterized in that hydrogen bearing alloy is rare earth based alloy, titanium-base alloy, zirconium-base alloy, magnesium base alloy or vanadium-base alloy.
5. the preparation method of a nickel-hydrogen battery negative pole material as claimed in claim 1, its concrete steps are as follows:
The preparation of A, nanocrystalline nickel powder: commercially available nickel powder packed into carry out ball milling in the ball grinder, obtaining purity is that 99%-99.9%, average particle size particle size are that 5-70 μ m, crystallite dimension are 8-30nm; Grain shape is irregular shape or spherical nanocrystalline nickel powder;
B, be 3 with hydrogen bearing alloy by mass ratio with the prepared nanocrystalline nickel powder of above-mentioned steps: 1-1: 5 mix, and preparation gets negative material by colding pressing.
6. preparation method according to claim 5 is characterized in that nickel powder packs in the ball grinder, and the control material ball ratio is 5: 1-50: 1, and rotating speed is 100-400 rev/min, the ball milling time is 3-80 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100240599A CN101267035B (en) | 2008-04-25 | 2008-04-25 | A nickel hydrogen cathode material and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100240599A CN101267035B (en) | 2008-04-25 | 2008-04-25 | A nickel hydrogen cathode material and its making method |
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| Publication Number | Publication Date |
|---|---|
| CN101267035A CN101267035A (en) | 2008-09-17 |
| CN101267035B true CN101267035B (en) | 2011-03-16 |
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|---|---|---|---|
| CN2008100240599A Expired - Fee Related CN101267035B (en) | 2008-04-25 | 2008-04-25 | A nickel hydrogen cathode material and its making method |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107968197A (en) * | 2017-11-23 | 2018-04-27 | 邓丽珍 | A kind of nickel-hydrogen battery negative pole material and its manufacture method |
| CN108281643A (en) * | 2018-01-18 | 2018-07-13 | 江西省倍特力新能源有限责任公司 | A kind of alloyed powder, slurry, negative plate manufacture craft and cell making process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696076A1 (en) * | 1994-08-04 | 1996-02-07 | Sanyo Electric Co. Ltd | Active material powder for non-sintered nickel electrode, non-sintered nickel electrode for alkaline battery and process for producing the same |
| CN1212475A (en) * | 1997-09-19 | 1999-03-31 | 中国科学院化学研究所 | Nickel-hydrogen battery negative pole material and preparing method and use |
| CN2569349Y (en) * | 2002-07-17 | 2003-08-27 | 广州市鹏辉电池有限公司 | Negative pole of nickek-hydrogen cell |
-
2008
- 2008-04-25 CN CN2008100240599A patent/CN101267035B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696076A1 (en) * | 1994-08-04 | 1996-02-07 | Sanyo Electric Co. Ltd | Active material powder for non-sintered nickel electrode, non-sintered nickel electrode for alkaline battery and process for producing the same |
| CN1212475A (en) * | 1997-09-19 | 1999-03-31 | 中国科学院化学研究所 | Nickel-hydrogen battery negative pole material and preparing method and use |
| CN2569349Y (en) * | 2002-07-17 | 2003-08-27 | 广州市鹏辉电池有限公司 | Negative pole of nickek-hydrogen cell |
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| CN101267035A (en) | 2008-09-17 |
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