CN101645501A - Sintering method of hydrogen storage alloy electrode - Google Patents
Sintering method of hydrogen storage alloy electrode Download PDFInfo
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- CN101645501A CN101645501A CN200910306667A CN200910306667A CN101645501A CN 101645501 A CN101645501 A CN 101645501A CN 200910306667 A CN200910306667 A CN 200910306667A CN 200910306667 A CN200910306667 A CN 200910306667A CN 101645501 A CN101645501 A CN 101645501A
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- sintering
- argon gas
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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
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Abstract
The invention relates to a sintering method of hydrogen storage alloy electrode which is characterized in that hydrogen storage alloy powder is used as active electrode material, nickel-coated steel mesh is used as skeleton material; hydrogen storage alloy powder and nickel-coated steel mesh are used to perform electrode-forming through direct rolling; hydrogen absorption treatment of the formed electrode is perform before sintering process, then sintering process is performed, and finally the dehydrogenation of the electrode is performed. The electrode plate prepared by the method of the invention has high strength and moderate flexibility; the electrode has high capacity, good high rate of charge-discharge performance, high discharge plateau, much higher activation property and less production cost.
Description
Technical field
The present invention relates to a kind of sintering method of nickel-hydrogen battery negative pole electrode slice, be specifically related to adopt suction hydrogen-dehydriding that hydrogen-occlussion alloy electrode is carried out sintering, thereby obtain the better electrode of performance.
Background technology
Negative plate is the critical component of Ni-MH battery, and its performance is the key that key, especially the electrokinetic cell performance of decision Ni-MH battery performance further improves.In order to improve the performance of electrode, mainly be originally by adjusting prescription, alloy powder or electrode are carried out surface coating, chemical surface treatment, greatly, also having environmental problem but these methods have increased material use amount, Working Procedure Controlling difficulty; Though these processing methods part has been improved electrode performance, certain gap is still arranged with the requirement of electrokinetic cell.
Summary of the invention
The objective of the invention is provides a kind of sintering method of nickel-hydrogen battery negative pole sheet in order to optimize the hydrogen storage electrode preparation method, thereby obtains the better electrode slice of performance, satisfies requirements such as the low-heat of Ni-MH power cell, low internal resistance and high power characteristic.
Adopt the inventive method to prepare electrode slice and existing surface treatment and prepare electrode slice to compare cost suitable, but the inventive method has surface treatment and sintering double action concurrently, the electrode slice internal resistance of preparing is low, the electro catalytic activity height.The Ni-MH battery that electrode slice assembled by the inventive method preparation has characteristics such as activity function is good, high rate capability is excellent, discharge voltage plateau is high, have extended cycle life, and is applicable to fields such as electric tool, electric bicycle, battery-operated motor cycle, electric automobile; And the raising greatly of activity function also can reduce the production cost of battery.
Purpose of the present invention can reach by following measure:
A kind of sintering method of hydrogen-occlussion alloy electrode: adopt hydrogen-storage alloy as electrode active material, nickel plating steel mesh as framework material; Hydrogen-storage alloy powder and nickel plating steel mesh are carried out electrode moulding with direct rolling mode; Shaped electrode is inhaled the hydrogen processing before sintering, carry out sintering then, behind the sintering electrode is carried out dehydrogenation and handles.
In the electrode roll forming process, draught pressure is 400-500MPa.
Sintering temperature is 400 ℃-700 ℃; Heating rate is preferably 10 ℃ of per minutes; The sintered heat insulating time is 0.5-5 hour, naturally cools to room temperature then.
It is after shaped electrode is put into vacuum furnace that described suction hydrogen is handled preferred process, first extracting vacuum and use high-purity argon gas prepurging, extracting vacuum to 1 again
0-3-10
-5Pa, charge into purity greater than 99.999% hydrogen to 0.01-0.02MPa or charge into purity greater than 99.999% hydrogen and argon gas gaseous mixture to 0.1-0.15MPa, the temperature remains within the normal range 30-60 minute.
Behind the described sintering electrode being carried out dehydrogenation, to handle preferred process be after electrode is cooled to room temperature, is warming up to 80-100 ℃ again and carries out dehydrogenation, and dehydrogenation is promptly to vacuum furnace extracting vacuum to 10
-3-10
-5Pa; Charge into high-purity argon gas then, naturally cool to room temperature and can take out electrode slice.
Concrete steps of the present invention comprise:
(1) adopt hydrogen-storage alloy powder as electrode active material (can also add nickel powder), nickel plating steel mesh according to the 0.5-1% of active material quality as framework material; Adopt the direct rolling of powder to carry out the electrode slice moulding; Draught pressure is 400-500MPa;
(2) require to carry out cut-parts and sabot according to battery design after the electrode slice moulding;
(3) electrode slice that will cut out good and sabot is put into vacuum heat treatment furnace, shuts fire door;
(4) inhaling the hydrogen processing before the sintering is extracting vacuum 10
-1Below the Pa, charge into high-purity argon gas to 0.05-0.1MPa, again extracting vacuum to 10
-1Below the Pa, prepurging is 3 times repeatedly;
(5) extracting vacuum to 10
-3-10
-5Below the Pa, charge into purity greater than 99.999% hydrogen to 0.01-0.02MPa or charge into purity greater than 99.999% hydrogen and argon gas gaseous mixture (hydrogen: the argon gas volume ratio is 10: 90) to 0.1-0.15MPa, kept 30-60 minute;
(6) be warming up to 400-700 ℃ with the programming rate of 10 ℃ of per minutes and carry out sintering, be incubated 0.5-5 hour;
(7) naturally cool to room temperature then;
(8) it is to be warming up to 80-100 ℃, extracting vacuum to 10 that the dehydrogenation of then carrying out is handled
-2Below the Pa;
(9) charge into high-purity argon gas (to 0.1MPa), cooling reaches room temperature and can take out electrode slice.
Adopt the main feature of the electrode slice of the present invention's preparation to be: electrode of the present invention is in sintering process, oxide on surface can reduce, greatly reduce the oxygen content of electrode active material, produce micro-crack at alloy surface simultaneously, improved the electro catalytic activity and the kinetics performance of electrode surface; Composition is more even behind the electrode sintering, has eliminated the crystal lattice stress and the distortion that produce in preparation process at hydrogen-storage alloy powder; Bond in sintering process between the alloy powder particle, former contact-making surface becomes crystal boundary and connects, and combines closelyr between alloy powder particle and the framework material, has increased electrode and has effectively conducted electricity specific area, thereby reduced the resistance of electrode.
Advantage of the present invention is:
1, electrode is in sintering process, because having carried out suction hydrogen-dehydrogenation, handles at electrode, and be in hydrogen reduction atmosphere in the stove, the alloy surface oxide is removed, greatly reduce the oxygen content of electrode active material, produce micro-crack at alloy surface simultaneously, improved the electro catalytic activity and the kinetics performance of electrode surface greatly, this helps to improve activity function, discharge capacity and the high power charging-discharging ability of electrode;
2, owing to alloy surface oxide in the sintering process is removed, reduced the resistance of sintering, alloying component is more even behind the electrode sintering; The crystal lattice stress and the distortion that in preparation process, produce at hydrogen-storage alloy powder have been eliminated; Between the alloy powder particle in sintering process easier formation adhesive surface, former contact-making surface becomes crystal boundary and connects; Combine between alloy powder particle and the framework material tightr, thereby reduced electrode resistance, improved anti-efflorescence ability, this helps to improve capacity, cycle life, discharge platform, the high-rate discharge ability of electrode.
3, in the methods of the invention, electrode has experienced dehydrogenation processing of suction hydrogen and high temperature hydrogenation treatment in preparation process, electrode has in fact experienced an activation process, adopts by the Ni-MH battery activation of the prepared electrode assembling of the inventive method and accelerates greatly, has reduced the production cost of battery.
Embodiment:
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:
With-150 order hydrogen-storage alloy powders is that electrode active material, nickel plating steel mesh are framework material, adopts twin rollers to carry out powder direct rolling and forming electrode slice, and electrode slice is according to the designing requirement processing of D type 6.5Ah battery; The electrode slice that processes is put into vacuum heat treatment furnace, shut fire door, extracting vacuum 10
-1Below the Pa, charge into high-purity argon gas to 0.05-0.1MPa, again extracting vacuum to 10
-1Below the Pa, prepurging is 3 times repeatedly; Extracting vacuum to 10
-3-10
-5Pa, charge into purity greater than 99.999% hydrogen to 0.01-0.02MPa; Programming rate with 10 ℃ of per minutes is warming up to 400 ℃, is incubated 3 hours; Naturally cool to room temperature then; Be warming up to 80-100 ℃, extracting vacuum to 10
-2Below the Pa; Charge into high-purity argon gas, be cooled to room temperature and take out electrode slice.
Embodiment 2:
With-150 order hydrogen-storage alloy powders is that electrode active material, nickel plating steel mesh are framework material, adopts twin rollers to carry out powder direct rolling and forming electrode slice, and electrode slice is according to the designing requirement processing of D type 6.5Ah battery; The electrode slice that processes is put into vacuum heat treatment furnace, shut fire door, extracting vacuum 10
-1Below the Pa, charge into high-purity argon gas to 0.05-0.1MPa, again extracting vacuum to 10
-1Below the Pa, prepurging is 3 times repeatedly; Extracting vacuum to 10
-3-10
-5Pa, charge into purity greater than 99.999% the gaseous mixture that contains 90% hydrogen and 10% argon gas to 0.1-0.15MPa; Programming rate with 10 ℃ of per minutes is warming up to 500 ℃, is incubated 2 hours; Naturally cool to room temperature then; Be warming up to 80-100 ℃, extracting vacuum to 10
-2Below the Pa; Charge into high-purity argon gas, be cooled to room temperature and take out electrode slice.
Adopt simulated battery and cell tester to testing with the embodiment of the invention 1 and example 2 prepared electrode slices, discharge and recharge with 0.2C, the electrode initial capacity reaches more than the 290mAH/g, and electrode promptly reaches high discharge capacity 316mAH/g the 2nd circulation; Discharge and recharge with 1C, electrode capacity reaches more than the 308mAH/g; Fill 5C with 1C and put, electrode capacity reaches more than the 280mAH/g; Fill 10C with 1C and put, electrode capacity reaches more than the 250mAH/g; Compare comparison electrode, it is high that capacity is all wanted, and the activation number of times has reduced 7 times, and discharge platform and cycle performance also will be got well, and along with the raising of discharge-rate, gap is big more.
With the embodiment of the invention 1 and example 2 prepared electrode slices is negative plate, with the spherical hickelous nydroxide is that positive active material and nickel foam are that the electrode slice that framework material prepares is a positive plate, with 6mol potassium hydroxide+0.5mol lithium hydroxide/L solution is electrolyte, is that barrier film is assembled into D type 6.5Ah battery with the polypropylene.After changing into, the electric current that adopts 6.5A was to battery charge 72 minutes, and with the current discharge of 65A, final voltage is set at 0.8, and discharge time, discharge platform was greater than 90% greater than 5.8 minutes.According to the relevant national standard charge and discharge cycles, battery cycle life is greater than 1200 times.
Claims (7)
1. the sintering method of a hydrogen-occlussion alloy electrode is characterized in that: adopting hydrogen-storage alloy powder is framework material as electrode active material, nickel plating steel mesh; Hydrogen-storage alloy powder and nickel plating steel mesh are carried out electrode moulding with direct rolling mode; Shaped electrode is inhaled the hydrogen processing before sintering, carry out sintering then, behind the sintering electrode is carried out dehydrogenation and handles.
2. method according to claim 1 is characterized in that: in the electrode roll forming process, draught pressure is 400-500MPa.
3. method according to claim 1 is characterized in that: sintering temperature is 400 ℃-700 ℃; Heating rate is 10 ℃ of per minutes; The sintered heat insulating time is 0.5-5 hour, naturally cools to room temperature then.
4. method according to claim 1, it is characterized in that: it is after shaped electrode is put into vacuum furnace that described suction hydrogen is handled, elder generation's extracting vacuum and use the high-purity argon gas prepurging, extracting vacuum is to 10-3-10-5Pa again, charge into purity greater than 99.999% hydrogen to 0.01-0.02MPa or charge into purity greater than 99.999% hydrogen and argon gas gaseous mixture to 0.1-0.15MPa, the temperature remains within the normal range 30-60 minute.
5. method according to claim 4 is characterized in that: hydrogen in hydrogen and the argon gas gaseous mixture: the volume ratio of argon gas is 10: 90.
6. according to each described method of claim 1-5, it is characterized in that: behind the described sintering electrode being carried out that dehydrogenation handles is after electrode is cooled to room temperature, be warming up to 80-100 ℃ again and carry out dehydrogenation, dehydrogenation promptly to the vacuum furnace extracting vacuum to 10-3-10-5Pa; Charge into high-purity argon gas then, naturally cool to room temperature and can take out electrode slice.
7. according to each described method of claim 6, it is characterized in that: in the certain embodiments, charge into high-purity argon gas to 0.1MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103066673A CN101645501B (en) | 2009-09-07 | 2009-09-07 | Sintering method of hydrogen storage alloy electrode |
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|---|---|---|---|
| CN2009103066673A CN101645501B (en) | 2009-09-07 | 2009-09-07 | Sintering method of hydrogen storage alloy electrode |
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| CN101645501A true CN101645501A (en) | 2010-02-10 |
| CN101645501B CN101645501B (en) | 2011-10-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039765A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing V-Ti-Cr-Fe hydrogen storage alloy |
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2009
- 2009-09-07 CN CN2009103066673A patent/CN101645501B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039765A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing V-Ti-Cr-Fe hydrogen storage alloy |
| CN105039765B (en) * | 2015-07-31 | 2017-03-08 | 四川大学 | A kind of preparation method of V Ti Cr Fe hydrogen-storage alloy |
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| CN101645501B (en) | 2011-10-05 |
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