CN100470893C - High power nickel-hydrogen accumulator negative electrode active substance and its preparation method and nickel-hydrogen accumulator - Google Patents
High power nickel-hydrogen accumulator negative electrode active substance and its preparation method and nickel-hydrogen accumulator Download PDFInfo
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- CN100470893C CN100470893C CNB2005100353150A CN200510035315A CN100470893C CN 100470893 C CN100470893 C CN 100470893C CN B2005100353150 A CNB2005100353150 A CN B2005100353150A CN 200510035315 A CN200510035315 A CN 200510035315A CN 100470893 C CN100470893 C CN 100470893C
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Abstract
The invention relates to a high-power nickel hydrogen accumulator negative active material, relative preparation and nickel hydrogen accumulator, wherein it deposits one layer of alloy film on the surface of hydrogen storage alloy powder which comprises one or the combination of nickel, palladium, platinum, gold, and rhodium which can not be oxidized by oxygen, and the combination between one or two of metal aluminum and zinc which can be dissolved in alkali solution, to form porous structure that contains one or more of nickel, palladium, platinum, gold and rhodium on the surface of hydrogen storage alloy. The preparation comprises: depositing one layer of alloy film on the surface of hydrogen storage alloy powder; arranging the powder in high-temperature alkali to be treated to form said porous structure on its surface; the negative surface of accumulator is coated with said negative active material. The invention can improve the anti-oxidization property of cathode of nickel hydrogen accumulator.
Description
Technical field
The present invention relates to the negative electrode active material that nickel-hydrogen accumulator is used, particularly relate to negative electrode active material that a kind of high-capacity nickel-hydrogen battery uses and preparation method thereof and nickel-hydrogen accumulator.
Background technology
The alkali secondary Ni-MH battery negative electrode active material generally adopts AB
5(LaNi
5) hydrogen-storage alloy, in battery charge and discharge process,, make positive pole reach oxygen evolution potential, thereby produce oxygen owing to seriously polarize or overcharge in the part of anode.The oxygen that produces sees through barrier film and arrives negative pole, and part of oxygen is at the compound generation water of negative pole, and always some oxygen because can't be compound and with the hydrogen-storage alloy oxidation.Behind the alloyed powder surface oxidation, the electrically contacting property of powder and electro-chemical activity reduce, and this is the main cause that causes battery capacity attenuation in cyclic process.
Nickel-hydrogen high-power battery such as H-SC class, be mainly used in electric tool and toy, the charging or discharging current of this battery all requires than the conventional batteries height, cause battery to discharge and recharge temperature higher, and temperature is high more, and the oxidation rate of hydrogen-storage alloy is just fast more, makes oxidation or the hydroxide film that forms one deck electrochemistry inertia on the surface of alloyed powder, the inert membrane makes contact resistance increase between the alloyed powder, and hydrogen atom is obstructed in alloy surface electrochemical reaction process; In addition, because the specific surface of conventional hydrogen-storage alloy is less, be generally 0.01～0.1m
2/ g, battery are when heavy-current discharge, and the real current density of negative pole is very high, serious polarization.Cause the reduction of the heavy-current discharge platform (discharge power) of battery, and finally caused the inefficacy in advance of battery.
In order to slow down the oxidation of negative pole, one of conventional method is to adopt the high temperature alkali treatment, and alloy surface Mn, the dissolving of Al element enter solution, make the relative enrichment on the surface of Ni element, thereby improve the antioxygenic property of alloyed powder, but the effect of improving of this method is very limited.Be exactly that hydrogen-storage alloy is adopted chemical plating in addition, reducing agent is sodium hypophosphite or sodium borohydride, still, is example with the chemical nickel plating, and chemical plating can reduce alloy surface conductivity and electro-chemical activity at NI-P or NI-B alloy that the alloyed powder surface forms.In addition, adopt the method for chemical plating can't form alloy film that the present invention mentions and the loose structure that can enlarge markedly the alloyed powder specific area.
Summary of the invention
The present invention is intended to address the above problem, and provide a kind of specific surface that can effectively improve the antioxygenic property of battery cathode and significantly improve battery cathode, and make battery prepared therefrom after initial and some circulations, still can keep good electrical contact and electro-chemical activity, with the heavy-current discharge power of raising battery and the negative electrode active material of cycle life; The nickel-hydrogen accumulator that the present invention also aims to provide the preparation method of this negative electrode active material and contain described negative electrode active material.
For achieving the above object, the invention provides a kind of negative electrode active material, it is at hydrogen-storage alloy powder surface deposition one deck alloy firm, this alloy firm comprise be difficult for by in the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the rhodium one or more composition and in alkaline aqueous solution the composition of one or more in the metallic element aluminium of dissolving, the zinc etc. easily, and the surface of hydrogen-storage alloy is formed be rich in one or more loose structure in metallic nickel, palladium, platinum, gold, the rhodium.
Preferred alloy firm is nickel-aluminium or nickel-kirsite film, and wherein the atomic ratio ratio of aluminium or zinc is 1～50%, and the atomic ratio ratio of preferred aluminium or zinc is 10～40%, and the thickness of alloy firm is 0.01～1.0 μ m, and preferred thickness is 0.1～0.3 μ m.
The present invention also provides the preparation method of described negative electrode active material, this method is at hydrogen-storage alloy powder surface deposition one deck alloy firm, this alloy firm comprises and is difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkaline aqueous solution, dissolves easily, the composition of one or both in the zinc etc., place the high-temperature alkaline aqueous solution to handle the hydrogen-storage alloy powder behind the deposit alloy film, make the aluminium in the alloy film, element generation point-like corrosion dissolutions such as zinc enter in the alkaline aqueous solution, make the surface formation of hydrogen-storage alloy be rich in metallic nickel, palladium, platinum, gold, the loose structure of one or more in the rhodium.
The deposition of described metal composites on the hydrogen-storage alloy powder surface is pending hydrogen-storage alloy powder to be placed in the magnetron sputtering coater that adopts plane magnetic controlled sputtering target, target is to comprise to be difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkaline aqueous solution, dissolves easily, the alloy of the composition of one or both in the zinc etc., alloy powder freely falls by deadweight and passes through sputtering target, perhaps make alloyed powder pass through ultrasonic wave being parallel on the plane of target, methods such as mechanical oscillation are thrown moving, finish sputter deposition process simultaneously.Hydrogen-storage alloy powder adopts repeatedly sputter process.
The hydrogen-storage alloy powder that deposits alloy firm is placed alkaline aqueous solution, and after stir process, it is neutral being washed till pH value with deionized water, and vacuumize.
The present invention also provides the nickel-hydrogen accumulator that contains described negative electrode active material, this nickel-hydrogen accumulator comprises positive pole, barrier film, negative pole and electrolyte, they are sealed in the battery case, it is characterized in that, described negative terminal surface is coated with described negative electrode active material, this negative electrode active material is at hydrogen-storage alloy powder surface deposition one deck alloy firm, this alloy firm comprises and is difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkaline aqueous solution, dissolves easily, the composition of one or more in the zinc, and make the surface formation of hydrogen-storage alloy be rich in metallic nickel, palladium, platinum, gold, the loose structure of one or more in the rhodium.
Contribution of the present invention is that it efficiently solves the surface oxidation problem of cathode hydrogen storing alloy powder and has significantly improved the specific surface of electrode.Since the surface deposition of hydrogen-storage alloy one deck alloy firm, and the surface is formed be rich in one or more the composition loose structure that is difficult for by in the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the rhodium by alkali treatment, make this film have good oxidative resistance, form high specific surface simultaneously.Make hydrogen-storage alloy powder after initial and some circulations of battery, still can keep good electrical contact and electro-chemical activity, thereby having guaranteed that negative pole discharges and recharges is reflected at carrying out smoothly of alloyed powder surface.The heavy-current discharge performance of battery and the cycle performance of battery have been improved.
Description of drawings
Fig. 1 is battery and the Comparative Examples 10C discharge cycles intermediate value voltage-contrast curve that adopts negative electrode active material preparation of the present invention.
Fig. 2 is battery and the Comparative Examples 10C discharge cycles capacity comparison curve that adopts negative electrode active material preparation of the present invention.
Embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Embodiment 1:
With the female powder MmNi of pending hydrogen-storage alloy
3.55Co
0.75Mn
0.4Al
0.3(Mm represents by one or more mishmetals formed among La, Ce, Pr, the Nd) places in the special magnetron sputtering coater, and the female powder of hydrogen-storage alloy can be made with known method.It is that nickel, palladium, platinum, gold, rhodium etc. are difficult for by one or more and the alloy of the composition formation of one or both in the metal of dissolving easily in alkaline aqueous solution such as aluminium, zinc in the metal of oxygen complete oxidation that coating machine adopts plane magnetic controlled sputtering target, target.In this example, preferred nickel-aluminium alloy, wherein the preferred proportion of aluminium is 30% (atomic ratio), the target vertical level is provided with, the high about 3m of target, coating machine single treatment amount is 200kG.Pending powder utilizes the powder deadweight freely to fall from the coating machine top and by sputtering target, finishes sputter deposition process simultaneously.Powder is taked repeatedly sputter process.Finish that powder falls into the coating machine bottom after the sputter, by a conveying device powder is promoted to the coating machine top, and begins sputter next time, finish after the sputter to sputter procedure required time next time and be about 5 minutes.Because powder is in the process of free fall, be at random over against the face of target surface, by repeatedly sputter, can make the alloy powder all surface form coating layer relatively uniformly.
Step 1, setting vacuum degree are 8.5 * 10
-3Handkerchief after reaching setting vacuum degree, feeds argon gas to vacuum degree 3 * 10
-1Handkerchief is set at 8mA/cm with sputtering current
2, energized, argon gas ion high-speed impact nickel alumin(i)um alloy target, the atom of target is ejected, and is deposited on the surface of alloyed powder, and deposition rate is 0.5 μ m/min, and hydrogen-storage alloy powder is carried out 6 sputters.Get alloyed powder argon-ion gun etching after the sputter, adopt AES to analyze surface composition (adopting U.S. PHI company model is the PHI5800 Auger electron spectrometer) again, when the characteristic peak of La appearred in the AES spectrogram, the degree of depth of etching was approximately 0.2 μ m.But, preliminary judgement is about 0.2 μ m so forming film thickness at alloy surface.
Step 2, the hydrogen-storage alloy powder behind the plating is placed 80 ℃, in the 30%KOH aqueous solution, about 1 hour of stir process, it is neutral being washed till PH with deionized water, and vacuumize, like this, has just made negative electrode active material A of the present invention.Do carrier gas with helium, nitrogen is done adsorbed gas, records that alloyed powder BET specific surface is 0.5m after the sputter
2/ g (adopting Beijing Bi Aode company model is SSA3500 specific surface analyzer).
Identical with above-mentioned steps, only, make negative electrode active material A1, A2, A3 respectively with adopting the nickel alumin(i)um alloy target of different aluminum content (10%, 20%, 40%) in the step 1 respectively.The contrast situation that records its BET specific surface and related data and A is atomic ratio as table 1:(content)
Table 1
| Contrast project/processing classification | A | A1 | A2 | A3 |
| Alloys target aluminium content (%) | 30 | 10 | 20 | 40 |
| Handle back specific surface area (m 2/g) | 0.5 | 0.2 | 0.3 | 0.5 |
| Nickel content (%) after the plated film alkali treatment (plating amount before the alkali treatment relatively) | 70 | 90 | 80 | 60 |
The content maximum of nickel aluminium/nickel zinc alloy target aluminium or zinc is no more than 50% among the present invention, otherwise under the situation of same sputter plated thickness, can not obtain best rich nickel effect (rich nickel amount) on the surface of hydrogen-storage alloy, thus among the present invention the content range of nickel aluminium/nickel zinc alloy target aluminium or zinc 1～50%.
By table 1 data as can be known, along with the increase of aluminium content, the specific surface of handling the back powder also increases gradually, when aluminium content about 30%, specific surface reaches maximum, increases aluminium content again, specific surface is not significantly improved, but rich nickel effect (nickel content) has reduced.
Aluminium content is 30% in the alloys target so work as among the present invention, is obtaining to have guaranteed best rich nickel effect (nickel content) simultaneously under the prerequisite on high specific surface after the processing.
Step 3, get and make negative electrode active material A100 part, 0.5 part of conductive black, 2 parts of nickel powders, 10 parts of bonding agent HPMC (3% concentration), 2 parts of PTFE (60% concentration), 20 parts of deionized waters fully stir, and are mixed with cathode size.Adopt the mode of slurry that cathode size evenly is overlying on perforation nickel plated steel strip both sides, and it is thick to be rolled into 0.34～0.35mm by roller mill, cuts into the 35mm*320mm specification, makes the SC3000mAh battery cathode sheet, with the supporting ni-mh SC3000mAh capacity battery of making of corresponding positive pole, be designated as category-A;
Embodiment 2: different with the step 1 of embodiment 1 is that hydrogen-storage alloy powder is carried out sputter process 2 times in the vacuum sputtering coating machine.The film thickness of measuring alloy surface is about 0.05 μ m, carries out step 2 then and handles, and handles the back specific surface and is about 0.15m
2/ g makes battery by step 3, is designated as category-B;
Embodiment 3:
Different with the step 1 of embodiment 1 is that hydrogen-storage alloy powder is carried out sputter process 15 times in the vacuum sputtering coating machine.The film thickness of measuring alloy surface is about 0.5 μ m, carries out step 2 then and handles, and handles the back specific surface and is about 0.8m
2/ g makes battery by step 3, is designated as the C class;
Embodiment 4:
Different with the step 1 of embodiment 1 is, target is nickel-kirsite, and the content of zinc is 30% (atomic ratio), and hydrogen-storage alloy powder is carried out sputter process 6 times in the vacuum sputtering coating machine.The film thickness of measuring alloy surface is about 0.2 μ m, carries out step 2 then and handles, and handles the back specific surface and is about 0.5m
2/ g.Make battery by step 3, be designated as the D class;
Comparative Examples 1:
The female powder of pending alloy is placed an amount of 80 ℃, after the 30% KOH aqueous solution fully stirs 1 hour, add 3% (bronze weight is involutory) inferior sodium phosphate reducing agent and abundant the stirring 20 minutes, after reacting completely, clean to PH=7 with deionized water, vacuumize is standby. and testing its BET absorption specific surface simultaneously is 0.03m
2/ g.Make battery by step 3, be designated as the E class.
Comparative Examples 2:
Place 1 part of plating bath to mix in 1 part of female powder of pending alloy, fully stir.Solution composition is: nickelous sulfate (NiSO
47H
2O) 30g/L, sodium hypophosphite (NaH
2PO
2H
2O) 20g/L, ammonium citrate ((NH
4)
3C
6H
5O
7) 50g/L, bath temperature is controlled to be 90 ℃, and pH value is controlled to be 8～10, and the processing time is 15min.To handle the back alloyed powder and clean to PH=7 with deionized water, vacuumize is standby. and testing its BET absorption specific surface simultaneously is 0.04m
2/ g.Make battery by step 3, be designated as the F class.
With battery A～F contrast test of being correlated with.
Method of testing:
Battery was shelved 5 minutes with 1C charging 65 minutes, propped up discharge capacity, the middle threshold voltage of record battery to 0.8V/ with 10C (30A) current discharge.Loop test 200 times.
Test result sees Table threshold voltage and capacity comparison and Fig. 1, Fig. 2 in 2:10C (30A) discharge.
Table 2
| The battery classification | A | B | C | D | E | F |
| Threshold voltage (V) in initial | 1.131 | 1.118 | 1.115 | 1.125 | 1.070 | 1.074 |
| Threshold voltage in after 200 times (V) | 1.110 | 1.078 | 1.080 | 1.100 | 1.000 | 0.999 |
| Intermediate value voltage drop (mV) | 21 | 40 | 35 | 25 | 70 | 75 |
| Initial discharge capacity (mAh) | 3020 | 3012 | 3005 | 3009 | 2940 | 2933 |
| Discharge capacity after 200 times (mAh) | 2849 | 2632 | 2741 | 2816 | 2332 | 2322 |
| Capability retention (%) | 94.3 | 87.4 | 91.2 | 93.6 | 79.3 | 79.2 |
Remarks: all fully activation before the A-F battery testing.
As shown in table 2, adopt negative electrode active material of the present invention to make the initial middle threshold voltage of battery category-A (embodiment 1) 10C (30A) discharge and can reach 1.131V, illustrate that embodiment 1 battery cathode active substance has excellent initial performance.After 200 circulations, middle threshold voltage still can keep 1.110V, the intermediate value voltage drop only is 21mV, and discharge capacity can keep initial more than 94%, illustrates after embodiment 1 battery cathode active substance is through 200 circulations still to keep electrically contacting property and higher electro-chemical activity preferably.
And the initial middle threshold voltage of category-B battery (embodiment 2) 10C (30A) discharge is 1.118V, intermediate value voltage drop after 200 circulations reaches 40mV, it only is 87.4% that capacity keeps, and estimation is because sputtering time is too short, and the film that forms on the surface of hydrogen-storage alloy powder exists local imperfect institute to cause.
Threshold voltage can reach 1.115V during C class battery (embodiment 3) 10C (30A) discharge was initial, intermediate value voltage drop after 200 circulations reaches 35mV, capacity remains 91.2%, initial analysis is because sputtering time is longer, the film that the hydrogen-storage alloy surface forms is thicker, though can keep good electrical contact, influence know clearly hydrogen atom by the alloyed powder surface to the diffusion of alloyed powder inside and alloy powder mutually in hydrogen atom spread desorption rate to alloy surface, promptly reduced the electro-chemical activity of alloyed powder.
Threshold voltage can reach 1.125V during D class battery (embodiment 4) 10C (30A) discharge was initial, and the intermediate value voltage after 200 circulations is reduced to 25mV, and capacity remains 93.6%, illustrated that plated nickel-kirsite film can be obtained and the similar result of nickel-aluminum alloy films.
Threshold voltage was 1.070V during E class battery (Comparative Examples 1) 10C (30A) discharge was initial, and the intermediate value voltage drop after 200 circulations reaches 70mV, and capacity remains 79.3%; Threshold voltage was 1.074V during F class battery (Comparative Examples 2) 10C (30A) discharge was initial, and the intermediate value voltage drop after 200 circulations reaches 75mV, and capacity remains 79.2%.Because the structure that the present invention mentions is failed to form in the hydrogen-storage alloy powder surface after Comparative Examples 1 and Comparative Examples 2 methods are handled, can not obtain initial and some circulation back good electrical contact and electro-chemical activity.
In sum, the present invention can significantly improve the high-rate battery discharge ability and can obviously improve the cycle life of battery.
Claims (7)
1, a kind of high power nickel-hydrogen accumulator negative electrode active substance, it is characterized in that, at hydrogen-storage alloy powder surface deposition one deck alloy firm, this alloy firm comprises and is difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkaline aqueous solution, dissolves easily, the composition of one or more in the zinc, place the high-temperature alkaline aqueous solution to handle the hydrogen-bearing alloy powder behind the deposit alloy film, make the aluminium in the alloy firm, the zinc element dissolving enters in the alkaline aqueous solution, thereby forming, the surface that makes hydrogen-storage alloy is rich in metallic nickel, palladium, platinum, gold, the loose structure of one or more in the rhodium, the thickness of described alloy firm are 0.01～1 μ m.
2, high power nickel-hydrogen accumulator negative electrode active substance as claimed in claim 1 is characterized in that, preferred alloy firm is nickel-aluminum alloy films, and wherein the atomic ratio ratio of aluminium is 1～50%.
3, high power nickel-hydrogen accumulator negative electrode active substance as claimed in claim 1 is characterized in that, the thickness of described alloy firm is 0.1～0.3 μ m.
4, a kind of preparation method of negative electrode active material according to claim 1, it is characterized in that, at hydrogen-storage alloy powder surface deposition one deck alloy firm, this alloy firm is by being difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkali, dissolves easily, the composition of one or both in the zinc is formed, place the high-temperature alkaline aqueous solution to handle the hydrogen-storage alloy powder behind the deposit alloy film, make the aluminium in the alloy film, the zinc element dissolving enters in the alkaline aqueous solution, make the surface formation of hydrogen-storage alloy be rich in metallic nickel, palladium, platinum, gold, the loose structure of one or more in the rhodium, the thickness of described alloy firm are 0.01～1 μ m.
5, preparation method as claimed in claim 4, it is characterized in that, the deposition of described metal composites on the hydrogen-storage alloy powder surface is pending hydrogen-storage alloy powder to be placed in the magnetron sputtering coater that adopts plane magnetic controlled sputtering target, target is by being difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkali, dissolves easily, the alloy that the composition of one or both in the zinc is formed, alloy powder freely falls by deadweight or passes through ultrasonic wave, mechanical vibration method is thrown moving, and, finish sputter deposition process simultaneously by sputtering target.
6, preparation method as claimed in claim 5 is characterized in that, hydrogen-storage alloy powder adopts repeatedly sputter process.
7, a kind of nickel-hydrogen accumulator that contains the described negative electrode active material of claim 1, comprise positive pole, barrier film, negative pole and electrolyte, they are sealed in the battery case, it is characterized in that, described negative terminal surface is coated with described negative electrode active material, this negative electrode active material is at hydrogen-storage alloy powder surface deposition one deck alloy firm, this alloy firm comprises and is difficult for by the metallic nickel of oxygen complete oxidation, palladium, platinum, gold, the composition of one or more in the rhodium and the metallic element aluminium that in alkaline aqueous solution, dissolves easily, the composition of one or more in the zinc, place the high-temperature alkaline aqueous solution to handle the hydrogen-bearing alloy powder behind the deposit alloy film, make the aluminium in the alloy firm, the zinc element dissolving enters in the alkaline aqueous solution, thereby forming, the surface that makes hydrogen-storage alloy is rich in metallic nickel, palladium, platinum, gold, the loose structure of one or more in the rhodium, the thickness of described alloy firm are 0.01～1 μ m.
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| CN101580955B (en) * | 2008-05-16 | 2011-04-20 | 比亚迪股份有限公司 | Surface processing method for hydrogen storage alloy powder |
| CN104347871A (en) * | 2013-07-26 | 2015-02-11 | 比亚迪股份有限公司 | Nickel-hydrogen battery anode active material, preparation method thereof, anode containing anode active material and nickel-hydrogen battery |
| WO2019093125A1 (en) * | 2017-11-08 | 2019-05-16 | シャープ株式会社 | Negative electrode for batteries, battery and method for producing battery |
| CN111224115B (en) * | 2018-11-27 | 2021-06-11 | 中国科学院大连化学物理研究所 | Zinc-based battery negative electrode and preparation and application thereof |
| JP7354989B2 (en) * | 2020-10-30 | 2023-10-03 | トヨタ自動車株式会社 | Composite alloy manufacturing method and electrode manufacturing method |
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| CN1234620A (en) * | 1998-02-19 | 1999-11-10 | 松下电器产业株式会社 | Hydrogen-absorbing alloy, its production method and alkaline accumulator using same |
| JP2982199B2 (en) * | 1990-02-21 | 1999-11-22 | 松下電器産業株式会社 | Hydrogen storage alloy electrode, method for producing the same, and sealed alkaline storage battery using the electrode |
| CN1248071A (en) * | 1998-09-11 | 2000-03-22 | 松下电器产业株式会社 | Alkaline accumulator, hydrogen alloy electrode and production method thereof |
| CN1577916A (en) * | 2003-07-02 | 2005-02-09 | 三星Sdi株式会社 | Microporous film containing nano particles and its forming method, and fuel cell containing the same |
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|---|---|---|---|---|
| JP2982199B2 (en) * | 1990-02-21 | 1999-11-22 | 松下電器産業株式会社 | Hydrogen storage alloy electrode, method for producing the same, and sealed alkaline storage battery using the electrode |
| CN1234620A (en) * | 1998-02-19 | 1999-11-10 | 松下电器产业株式会社 | Hydrogen-absorbing alloy, its production method and alkaline accumulator using same |
| CN1248071A (en) * | 1998-09-11 | 2000-03-22 | 松下电器产业株式会社 | Alkaline accumulator, hydrogen alloy electrode and production method thereof |
| CN1577916A (en) * | 2003-07-02 | 2005-02-09 | 三星Sdi株式会社 | Microporous film containing nano particles and its forming method, and fuel cell containing the same |
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Addressee: Zhao Jie Document name: patent for invention |
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Granted publication date: 20090318 Termination date: 20190613 |