CN1283015C - Multi-layer film electrode for nickle-hydrogen cell and preparation method thereof - Google Patents
Multi-layer film electrode for nickle-hydrogen cell and preparation method thereof Download PDFInfo
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- CN1283015C CN1283015C CNB2004100775270A CN200410077527A CN1283015C CN 1283015 C CN1283015 C CN 1283015C CN B2004100775270 A CNB2004100775270 A CN B2004100775270A CN 200410077527 A CN200410077527 A CN 200410077527A CN 1283015 C CN1283015 C CN 1283015C
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Abstract
The present invention relates to a multilayer thin membrane electrode for a nickel-hydrogen battery and a preparing method of a multilayer thin membrane electrode for a nickel-hydrogen battery. The thin membrane electrode is composed of a basal body thin membrane and a protective membrane, wherein the main component of the basal body thin membrane comprises magnesium and nickel, and a chemical composition comprises Mg<p-x> A<x> Ni<1-y> B<y>; the protective membrane which is a catalytic protective membrane is one of Pd, Pt, Ag, Au, Co and C<1-r> Mg<r> Ni<t-q> D<q> or a two-component alloy or a multicomponent alloy of Pd, Pt, Ag, Au, Co and C<1-r> Mg<r> Ni<t-q> D<q>. The preparing method comprises the following procedures: firstly, an alloy target is prefabricated in an induction melting method or a powder metallurgy method; secondly, the basal body thin membrane is prepared on a basal sheet in a physical vapor deposition method to deposit the catalytic protective membrane on the surface of the basal body thin membrane; the procedures are repeated to obtain a multilayer thin membrane. The thin membrane which can be used for a negative electrode of a nickel-hydrogen battery has the characteristics of small thin membrane crystal particle size, large specific surface area, great current, good discharge performance, and long electrode service life. Nanometer multilayer combination has the combination reinforcement effect and performs the multiple catalytic action. The multilayer thin membrane electrode can be integrated into a micro mechanical device to provide power support for the development of the micro device.
Description
Technical field
The present invention relates to physical vapour deposition (PVD) built up membrane material technology field, specifically be meant a kind of multi-layer film electrode for nickle-hydrogen cell and preparation method thereof.
Background technology
At present, the global annual production of Ni-MH battery has reached more than 1,000,000,000, but the specific energy density of Ni-MH battery and high-rate discharge capacity still remain to be improved.For this reason, the exploitation of nickel-hydrogen battery negative pole material is a key technology.In several classes of current research use for nickel-hydrogen battery hydrogen storage electrode alloy, Mg was that alloy has superior prospect, wherein Mg
2Ni theoretical electrochemistry capacity reaches 1000mAh/g, and far above other a few class hydrogen bearing alloys, and price is well below other alloy system.Therefore, Mg is that the exploitation of alloy has very tempting prospect.But the suction of Mg base hydrogen storage alloy/release the hydrogen dynamic performance is poor, and the chemical property of Mg is very active, easily reacts with electrolyte, causes performance degradation.Therefore improve the suction that Mg is an alloy/release dynamic performance and electrode performance is the problem that attracts people's attention always.The present main method that adopts, as element substitution, acid, alkali, fluorine liquid surface modification treatment and surface coat,, mechanical alloying method compound and be to form method such as nano-crystalline and amorphous structure in the alloy at Mg with other hydrogen bearing alloy.These methods are improved the electrode performance of Mg-Ni alloy to a certain extent, but the result is still unsatisfactory.Discharge capacity decay as amorphous alloy electrode is very fast, and cycle life has only tens times.Therefore, further improving Mg is the stability of alloy electrode, and promptly cycle life just becomes the key of development Mg-Ni alloy electrode material.Moreover, with the film of magnesium target and nickel target co-sputtering or co-deposition method preparation, composition is difficult to control, poor repeatability, is not suitable for producing in enormous quantities at present.The Chinese ZL02115117.2 patent of invention that the applicant obtains discloses a kind of film electrode for nickel-hydrogen battery and preparation method thereof, this method can be controlled film thickness, distributed components, good reproducibility, be fit to produce in enormous quantities, and the cycle life of membrane electrode also improves.But this technology just covers single protective layer at electrode surface; very little to the membrane electrode catalytic action; the high power discharge ability; be difficult to adapt to the startup load of electrical micro-machine; and in a single day superficial layer is destroyed; electrode performance still can sharply descend, and is showing particularly outstandingly aspect the cycle life of electrode.
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part; a kind of multi-layer film electrode for nickle-hydrogen cell and preparation method thereof is provided; cover multi-protective layer at electrode surface; this plural layers have the effect of compound enhancement effect and nano-catalytic; solved the high power discharge ability with the damaged easily shortcoming of single film, this membrane electrode cycle life is further prolonged.
The present invention is achieved through the following technical solutions: described a kind of multi-layer film electrode for nickle-hydrogen cell is made up of matrix film and catalysis diaphragm, and the main component of matrix film is magnesium and nickel, and chemical composition is Mg[
P-x] A[
x] Ni[
1-y] B[
y], A is Ti, Al, Mn, Y, mishmetal, B is Cu, Zr, V, and 1.0≤p≤2.5,0≤x≤1.5,0≤y≤0.8 wherein, described matrix film and diaphragm alternately cover, and described catalysis diaphragm is Pd, Pt, Ag, Au, Co, C
[1-r]Mg
[r]Ni
[t-q]D
[q]In a kind of or binary or multicomponent alloy, C comprises mishmetal, D comprises a kind of or binary or the multicomponent alloy among Cu, Zr, V, Al, Mn, the Co, wherein 0≤r≤0.5,0≤q≤2.5,3≤t≤5.5.
In order to realize the present invention better, the thickness of every layer of matrix film is 10～1000nm, and every layer of catalysis diaphragm thickness is 10～1000nm, and the integral thickness of matrix film and catalysis diaphragm is 50～100000nm.
The preparation method of described a kind of multi-layer film electrode for nickle-hydrogen cell; at first with induction melting or powder metallurgy process prealloy target; on substrate, make the matrix film with physical gas-phase deposite method then; then cover one deck catalysis diaphragm at the matrix film surface with physical gas-phase deposite method; repeatedly repeat above step at last, on the catalysis diaphragm, further make the matrix film and cover the catalysis diaphragm.
In order to realize the present invention better, preparation matrix film is magnesium and nickel with the main component of alloys target, and chemical composition is that chemical composition is Mg
[p-x]A
[x]Ni
[1-y]B
[y], A is Ti, Al, Mn, Y, mishmetal, B is Cu, Zr, V, wherein 1.0≤p≤2.5,0≤x≤1.5,0≤y≤0.8; Preparation catalysis protective film is mishmetal and nickel with the main component of alloys target, and chemical composition is C
[1-r]Mg
[r]Ni
[t-q]D
[q]In a kind of or binary or multicomponent alloy, C comprises mishmetal, D comprises a kind of or binary or the multicomponent alloy among Cu, Zr, V, Al, Mn, the Co, wherein 0≤r≤0.5,0≤q≤2.5,3≤t≤5.5; Substrate comprises metal, semiconductor, insulator; Physical gas-phase deposite method comprises sputter, electron beam evaporation or the laser ablation method of adopting.
Principle of the present invention: studies show that; non-crystaline amorphous metal has good corrosion resistance; the surface texture of alloy and composition have significant effects to the cycle performance of electrode; the hydrogen-bearing alloy powder surface treatment that routine is used is relatively difficult, has the film of protective effect concurrently then than being easier to and both had catalytic action in the covering of hydrogen bearing alloy thin-film material surface.Therefore, the present invention prepares amorphous and/or nano-crystal film by physical gas-phase deposite method, and at alloy film material surface coverage catalysis diaphragm.The present invention uses alloys target when physical vapour deposition (PVD), overcome the shortcoming of uneven components, and can directly prepare Mg
2The film of Ni structure, good reproducibility, and also alloy target material size and composition can be controlled flexibly, be fit to industrial production, inherited the advantage of ZL02115117.2 Chinese invention patent, simultaneously, this plural layers have compound enhancement effect, and electrochemistry capacitance effectively improves; This plural layers also have the nano-catalytic effect, and charge-discharge velocity is further enhanced.The operation principle of multi-layer film electrode for nickle-hydrogen cell and operational environment require film that good cycle characteristics and non-oxidizability are arranged; The present invention covers alternately on the alloy firm surface that multilayer hydrogen can freely pass through but not the then intransitable catalysis diaphragm of protium; this multilayer protective film can play better catalytic action and prevent because of surface local damages rapid reduction and even the inefficacy that causes electrochemistry capacitance, further prevents to store up hydrogen film and pernicious gas or electrolyte reaction and the cycle characteristics and the capacity of reduction Ni-MH battery.
The present invention compared with prior art, have following advantage and beneficial effect: this alloy firm is (no matter be the matrix film, or catalysis diaphragm) adopts the physical gas-phase deposite method preparation, tissue is by amorphous and nanocrystalline the composition, response speed to hydrogen is fast, avoided the harm of heavy metal powder in the conventional production process, this preparation method is a kind of environment protection method of producing nickel-hydrogen battery negative pole; Plural layers are made nickel-hydrogen battery negative pole can make micro cell, also can be integrated on the micromechanics, has solved the dependence problem of micromechanics to externally fed; Multi-layer thin-film electrode has the effect of multilayer protection and multilayer catalysis, and can adjust composition, structure and the thickness of each layer film easily, prevents to damage rapid reduction and even the inefficacy that causes electrochemistry capacitance because of surface local; Each laminated gold thin film thickness of the present invention preparation and the integral thickness of film can be controlled arbitrarily, distributed components is adjustable, good reproducibility, specific capacity height (900mAh/g), have extended cycle life; Multi-layer thin-film electrode is because the alternately covering of matrix film and diaphragm; form multi-protective layer; effectively prevented to cause the sharply problem of decline of electrode performance because of protective layer is damaged; further improve the reliability and the useful life of electrode, overcome the shortcoming of general thin electrode large current discharging capability difference.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment one
With the induction melting method with block 44% magnesium, 55% nickel and 1% zirconium (percentage by weight; be smelted into alloy-steel casting down together), behind the high annealing, be processed into target with wire cutting method; by laser ablation on silicon chip; the Pt layer of evaporation 10nm at first, evaporation matrix film then, thickness is 100nm; change the Pt target; the Pt layer of evaporation 10nm repeats above step on the matrix film, obtains 10 layers of Mg-Ni-Zr matrix film and 11 layers of plural layers that Pt catalysis protective film is alternately arranged.
Embodiment two
With the induction melting method with block 45% magnesium; 54% nickel and 1% aluminium are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by magnetron sputtering on sheet glass; at first; the Pd layer of evaporation 10nm; each layer matrix film thickness is 50nm; change the Pd target, the Pd layer of evaporation 10nm repeats above step on this film; obtain 10 layers of Mg-Ni-Al matrix film and 11 layers of plural layers that Pd catalysis protective film is alternately arranged; follow evaporation matrix film, thickness is 100nm, changes the Pt target; the Pt layer of evaporation 10nm on the matrix film; repeat above step, obtain 10 layers of Mg-Ni-A1 matrix film and 10 layers of plural layers that Pt catalysis protective film is alternately arranged, film integral is 20 layers of matrix film and 21 layers of protection catalytic film.
Embodiment three
With the induction melting method block 54% magnesium, 44% nickel, 1% vanadium and 1% manganese are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, by magnetron sputtering on the thick nickel sheet of 2.5mm.At first; the Pd layer of evaporation 20nm; evaporation matrix film then, thickness is 20nm, changes the Pd target; the Pd layer of evaporation 20nm on this film; repeat above step, obtain 20 layers of Mg-Ni-V-Mn matrix film and 21 layers of plural layers that Pd catalysis protective film is alternately arranged, then evaporation matrix film; thickness is 20nm, changes MmNi
3.5Co
1.2Al
0.2Mn
0.1Target, the MmNi of evaporation 50nm on this film
3.5Co
1.2Al
0.2Mn
0.1Layer repeats above step, obtains 20 layers of Mg-Ni-V-Mn matrix film and 20 layers of MmNi
3.5Co
1.2Al
0.2Mn
0.1The plural layers that the catalysis protective film is alternately arranged, film add up to by 40 layers of matrix film and 41 layers of protection catalytic film and form.
Embodiment four
With powder metallurgy process with 55% magnesium, 45% nickel by powder 650 ℃ of sintering 20 hours, behind the high annealing, be processed into target with wire cutting method, by electron beam evaporation plating on the thick nickel sheet of 0.5mm, at first, the MmNi of evaporation 20nm
3.3Layer, then, evaporation matrix film, thickness is 50nm, changes MmNi
3.3Target, the MmNi of evaporation 50nm on this film
3.3Layer repeats above step, obtains 39 layers of Mg-Ni matrix film and 40 layers of MmNi
3.3The plural layers that the catalysis protective film is alternately arranged.
Embodiment five
With the induction melting method block 53% magnesium, 42% nickel and 5% aluminium are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, on the thick aluminium flake of 0.5mm, film thickness is 100nm, changes MmNi by magnetron sputtering
3.5Co
1.2Al
0.2Mn
0.1Target, the MmNi of evaporation 50nm on this film
3.5Co
1.2Al
0.2Mn
0.1Layer repeats above step, obtains 20 layers of Mg-Ni-Al matrix film and 21 layers of MmNi
3.5Co
1.2Al
0.2Mn
0.1The plural layers that the catalysis protective film is alternately arranged.
Embodiment six
With the induction melting method block 53% magnesium, 42% nickel and 5% aluminium are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, on the thick nickel sheet of 1.5mm, film thickness is 200nm, changes MmNi by magnetron sputtering
3.5Co
1.2Al
0.2Mn
0.1Target, the MmNi of evaporation 200nm on this film
3.5Co
1.2Al
0.2Mn
0.1Layer repeats above step, obtains 20 layers of Mg-Ni-Al matrix film and 21 layers of MmNi
3.5Co
1.2Al
0.2Mn
0.1The plural layers that the catalysis protective film is alternately arranged.
Embodiment seven
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, on the thick nickel sheet of 1.5mm, film thickness is 200nm, changes MmNi by magnetron sputtering
3.5Co
1.3Al
0.2Mn
0.1Target, the MmNi of evaporation 50nm on this film
3.5Co
1.3Al
0.2Mn
0.1Layer repeats above step, obtains 30 layers of Mg-Ni-Al-Cu matrix film and 31 layers of MmNi
3.5Co
1.3Al
0.2Mn
0.1The plural layers that the catalysis protective film is alternately arranged.
Embodiment eight
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, on the thick aluminium flake of 0.5mm, film thickness is 150nm, changes MmNi by magnetron sputtering
3.3Target, the MmNi of evaporation 50nm on this film
3.3Layer repeats above step, obtains 20 layers of Mg-Ni-Al-Cu matrix film and 21 layers of MmNi
3.3The plural layers that the catalysis protective film is alternately arranged.
Embodiment nine
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by electron beam evaporation plating on the thick nickel sheet of 1.5mm; film thickness is 40nm, changes the Pd target, the Pd layer of evaporation 10nm on this film; repeat above step, obtain 60 layers of Mg-Ni-Al-Cu matrix film and 61 layers of plural layers that Pd catalysis protective film is alternately arranged.
Embodiment ten
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by the laser beam evaporation on the thick nickel sheet of 1.5mm; film thickness is 400nm, changes the Pd target, the Pd layer of evaporation 10nm on this film; repeat above step, obtain 35 layers of Mg-Ni-Al-Cu matrix film and 36 layers of plural layers that Pd catalysis protective film is alternately arranged.
Embodiment 11
With the induction melting method block 29% magnesium, 70% nickel, 1% zirconium are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by laser ablation on silicon chip; film thickness is 20nm, changes the Au target, the Au layer of evaporation 10nm on this film; repeat above step, obtain 20 layers of Mg-Ni-Zr matrix film and 21 layers of plural layers that Au catalysis protective film is alternately arranged.
Embodiment 12
With the induction melting method block 30% magnesium, 70% nickel are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by magnetron sputtering on sheet glass; film thickness is 300nm, changes the Au target, the Au layer of evaporation 10nm on this film; repeat above step, obtain 50 layers of Mg-Ni matrix film and 51 layers of plural layers that Au catalysis protective film is alternately arranged.
Embodiment 13
With the induction melting method block 55% magnesium, 45% nickel are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, on the thick silicon chip of 2.5mm, film thickness is 200nm, changes MmNi by magnetron sputtering
3.5Co
1.2Al
0.2Mn
0.1Target, the MmNi of evaporation 5nm on this film
3.5Co
1.2Al
0.2Mn
0.1Layer repeats above step, obtains 20 layers of Mg-Ni matrix film and 21 layers of MmNi
3.5Co
1.2Al
0.2Mn
0.1The plural layers that the catalysis protective film is alternately arranged.
Embodiment 14
With powder metallurgy process with 55% magnesium, 45% nickel by powder 650 ℃ of sintering 20 hours; behind the high annealing; be processed into target with wire cutting method; by electron beam evaporation plating on the thick sheet glass of 0.5mm; film thickness is 500nm, changes the Pt target, the Pt layer of evaporation 5nm on this film; repeat above step, obtain 10 layers of Mg-Ni matrix film and 11 layers of plural layers that Pt catalysis protective film is alternately arranged.
Embodiment 15
With the induction melting method block 53% magnesium, 42% nickel and 5% aluminium are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by magnetron sputtering on the thick palladium sheet of 0.5mm; film thickness is 1 μ m, changes the Pd target, the Pd layer of evaporation 5nm on this film; repeat above step, obtain 20 layers of Mg-Ni-Al matrix film and 20 layers of plural layers that Pd catalysis protective film is alternately arranged.
Embodiment 16
With the induction melting method block 53% magnesium, 42% nickel and 5% aluminium are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by magnetron sputtering on the thick nickel sheet of 1.5mm; film thickness is 100nm, changes the Ag target, the Ag layer of evaporation 20nm on this film; repeat above step, obtain 60 layers of Mg-Ni-Al matrix film and 61 layers of plural layers that Ag catalysis protective film is alternately arranged.
Embodiment 17
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by magnetron sputtering on the thick nickel sheet of 1.5mm; film thickness is 150 μ m, changes the Ag target, the Ag layer of evaporation 300nm on this film; repeat above step, obtain 20 layers of Mg-Ni-Al-Cu matrix film and 21 layers of plural layers that Ag catalysis protective film is alternately arranged.
Embodiment 18
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting, behind the high annealing, are processed into target with wire cutting method, on the thick aluminium flake of 0.5mm, film thickness is 1 μ m, changes MmNi by magnetron sputtering
3.5Co
1.2Al
0.2Mn
0.1Target, the MmNi of evaporation 100nm on this film
3.5Co
1.2Al
0.2Mn
0.1Layer repeats above step, obtains 49 layers of Mg-Ni-Al-Cu matrix film and 50 layers of MmNi
3.5Co
1.2Al
0.2Mn
0.1The plural layers that the catalysis protective film is alternately arranged.
Embodiment 19
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by electron beam evaporation plating on the thick nickel sheet of 1.5mm; film thickness is 1000nm, changes the Ni target, the Ni layer of evaporation 200nm on this film; repeat above step, obtain 50 layers of Mg-Ni-Al-Cu matrix film and 51 layers of plural layers that Ni catalysis protective film is alternately arranged.
Embodiment 20
With the induction melting method block 50% magnesium, 41% nickel, 3% aluminium and 6% bronze medal are smelted into alloy-steel casting; behind the high annealing; be processed into target with wire cutting method; by the laser beam evaporation on the thick copper sheet of 1.5mm; each layer matrix film thickness is 500nm, changes the Au target, the Au layer of evaporation 50nm on this film; repeat above step, obtain 10 layers of Mg-Ni-Al-Cu matrix film and 11 layers of plural layers that Au catalysis protective film is alternately arranged.
Claims (7)
1. a multi-layer film electrode for nickle-hydrogen cell is made up of matrix film and diaphragm, and the main component of matrix film is magnesium and nickel, and chemical composition is Mg
[p-x]A
[x]Ni
[1-y]B
[y], A is Al, Mn, Y or mishmetal, B is Cu, Zr or V, wherein 1.0≤p≤2.5; 0≤x≤1.5,0≤y≤0.8 is characterized in that, described matrix film and diaphragm alternately cover; described diaphragm is Pd, Pt, Ag or Au, or any binary of above-mentioned element or multicomponent alloy, or alloy C
[1-r]M
G[r]Ni
[t-q]D
[q]The catalysis diaphragm that constitutes, C comprises mishmetal, D comprises Al, Mn or Co, or any binary of above-mentioned element or multicomponent alloy, r=0 wherein, 0≤q≤2.5,3≤t≤5.5.
2. a kind of multi-layer film electrode for nickle-hydrogen cell according to claim 1 is characterized in that, the thickness that described matrix film is every layer is 10～1000nm.
3. a kind of multi-layer film electrode for nickle-hydrogen cell according to claim 1 is characterized in that, the thickness that described catalysis diaphragm is every layer is 10～1000nm.
4. a kind of multi-layer film electrode for nickle-hydrogen cell according to claim 1 is characterized in that, the integral thickness of described matrix film and catalysis diaphragm is 50～100000nm.
5. the preparation method of a multi-layer film electrode for nickle-hydrogen cell, it is characterized in that, at first with induction melting or powder metallurgy process prealloy target, on substrate, make the matrix film with physical gas-phase deposite method then, then cover one deck catalysis diaphragm at the matrix film surface with physical gas-phase deposite method, repeatedly repeat above step at last, on the catalysis diaphragm, further make the matrix film and cover the catalysis diaphragm; Described preparation matrix film is magnesium and nickel with the main component of alloys target, and chemical composition is Mg
[p-x]A
[x]Ni
[1-y]B
[y], A is Al, Mn, Y or mishmetal, B is Cu, Zr or V, wherein 1.0≤p≤2.5,0≤x≤1.5,0≤y≤0.8; Described preparation catalysis protective film is mishmetal and nickel with the main component of alloys target, and chemical composition is C
[1-r]Mg
[r]Ni
[t-q]D
[q], C comprises mishmetal, D comprises Al, Mn or Co, or any binary of above-mentioned element or multicomponent alloy, r=0 wherein, 0≤q≤2.5,3≤t≤5.5.
6. the preparation method of a kind of multi-layer film electrode for nickle-hydrogen cell according to claim 5 is characterized in that, described substrate comprises metal, semiconductor or insulator.
7. the preparation method of a kind of multi-layer film electrode for nickle-hydrogen cell according to claim 5 is characterized in that, described physical gas-phase deposite method comprises the method that adopts sputter, electron beam evaporation or laser ablation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100775270A CN1283015C (en) | 2004-12-22 | 2004-12-22 | Multi-layer film electrode for nickle-hydrogen cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100775270A CN1283015C (en) | 2004-12-22 | 2004-12-22 | Multi-layer film electrode for nickle-hydrogen cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1624958A CN1624958A (en) | 2005-06-08 |
| CN1283015C true CN1283015C (en) | 2006-11-01 |
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ID=34765444
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100775270A Expired - Fee Related CN1283015C (en) | 2004-12-22 | 2004-12-22 | Multi-layer film electrode for nickle-hydrogen cell and preparation method thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831619A (en) * | 2010-05-28 | 2010-09-15 | 浙江大学 | Nano-crystalline Mg-Ni multilayer composite film and preparation method thereof |
| CN103985849A (en) * | 2013-02-07 | 2014-08-13 | 北京大学 | Magnesium-based thin film structure and preparation method thereof |
| CN105428607B (en) * | 2014-09-05 | 2023-05-02 | 松下能源(无锡)有限公司 | Nickel-hydrogen secondary battery and method for manufacturing same |
| CN108649212B (en) * | 2018-04-13 | 2020-08-04 | 清华大学 | Preparation method and device of magnesium alloy anode material |
| CN116240494A (en) * | 2023-03-20 | 2023-06-09 | 华南理工大学 | Magnesium-based ternary hydrogen storage alloy film and preparation method thereof |
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