CN1050450C - Hydrogen-storage alloy material for hydrogen electrode - Google Patents

Hydrogen-storage alloy material for hydrogen electrode Download PDF

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Publication number
CN1050450C
CN1050450C CN95112291A CN95112291A CN1050450C CN 1050450 C CN1050450 C CN 1050450C CN 95112291 A CN95112291 A CN 95112291A CN 95112291 A CN95112291 A CN 95112291A CN 1050450 C CN1050450 C CN 1050450C
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China
Prior art keywords
hydrogen
battery
storage alloy
alloy material
hydrogen storage
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Expired - Fee Related
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CN95112291A
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Chinese (zh)
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CN1128413A (en
Inventor
陈文博
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WEIHAI WENLONG BATTERY CO Ltd
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WEIHAI WENLONG BATTERY CO Ltd
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Priority to CN95112291A priority Critical patent/CN1050450C/en
Publication of CN1128413A publication Critical patent/CN1128413A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a hydrogen storage alloy material which is used for hydrogen electrodes of alkaline secondary batteries. The chemical formula of the hydrogen storage alloy material is Mm<1-x>Ca<x>Ni<5-y-z-u-v>Co<y>Mn<z>Al<u>B<v>, wherein 0.05<=x<=0.2, 0.2<=y<=0.4, 0.2<=z<=0.4, 0.1<=u<=0.3 and 0.05<=v<=0.15. Under a condition of 30 to 50 DEG C, after the surface of the hydrogen storage alloy is plated with nickel, the hydrogen storage alloy is made into a hydrogen storage electrode. The performance, such as activating performance, initial capacity, the discharge performance of high multiplying power, cycle life, safe seal, etc., of a battery which is made by using the present invention is superior to that of the battery which is made of the existing alloy materials, and the battery is suitable for large-scale production.

Description

Hydrogen-storage alloy material for hydrogen electrode
The present invention relates to a kind of alloy material, specifically a kind of nickel/hydrogen battery hydrogen-storage alloy material for hydrogen electrode.
We know that nickel/hydrogen battery is a kind of high-tech product of Recent study, exploitation, and its key is the selection and the making of hydrogen electrode storage alloy material for hydrogen.Improve electrochemistry capacitance, prolong the useful life in the hydrogen-storage alloy repeated charge-discharge cycles process, suppress the decay of its discharge capacity, this is the important subject of hydrogen storage electrode.At present, on rare earth-Ni-base hydrogen bearing electrode basis, the scientific worker researchs and develops out many alloy materials, makes bianry alloy form a series of multielement rare earth-Ni-base hydrogen bearing electrode metal, as LaNi 2.5Co 2.4Al 0.1, La 0.7Nd 0.2Ti 0.1Ni 2.5Co 2.4Al 0.1, that in the recent period representative is the NaNi that Japan Patent JP63-264869 provides 3.8Co 0.5Mn 0.4Al 0.3Yet the useful life of nickel/hydrogen battery of making of above-mentioned alloy, performances such as high current charge-discharge, self discharge, sealing are still undesirable, in order to improve combination property, J.Less-CommonMet., 172.P1175.1991, introduced on the alloyed powder surface and carried out chemical nickel plating, but before chemical plating, needed to add Pdcl 2Make sensitization, activation processing Deng precious metal solution, and at high temperature (80-90 ℃) carries out, this is the conditional request strictness on the one hand, is difficult for carrying out, and cost increases greatly.
Purpose of the present invention is exactly the deficiency that has various alloys now in order to overcome, and a kind of have high electrochemistry capacitance and catalytic activity are provided, and the repeated charge-discharge cycles life-span is long, the hydrogen-storage alloy material for hydrogen electrode that self-discharge rate is low.
The object of the present invention is achieved like this, partly replaces norium Na with the Ca element, partly replaces Ni in the norium with elements such as CO, Mn, Al, B, makes storage alloy material for hydrogen, and its alloy formula is:
Na 1-xCa xNi 5-y-z-u-vCo yMn zAl uB v
X=0.1 y=0.3 0.2≤2≤0.3 0.2≤u in the formula≤0.3 v=0.1
Na is commercially available norium, and its rare earth element total content is not less than 95wt%.Above-mentioned alloy material becomes the particle of 30-70 μ m through the Mechanical Crushing ball milling, then at its surface chemical plating Ni-P alloy, coating is thick between 0.4-0.8 μ m, become hydrogen-storage alloy powder, make electrode, then can be used to make nickel/hydrogen battery by common preparation electrode process.
The preferred chemical formula of alloy of the present invention is:
Na 0.9Ca 0.1Ni 4.1Co 0.3Mn 0.2Al 0.3B 0.1
The present invention has added elements such as Ca, Co, Mn, Al, B in Mn-Ni, partly replace Na with Ca, partly replaces Ni with Co, Mn, Al, B, and compared to existing technology, the present invention has following outstanding advantage:
1, Ca has occupied lattice position in the alloy, and it at first is oxidized to Ca (OH) in continuous charge and discharge process 2Thereby, protected the oxidized of norium Na in the inner alloy effectively, make to have the NaNi that inhales the hydrogen lattice 5Structure does not go to pot; Added B on the other hand, the hydride that forms behind the absorption hydrogen has the bridged ring network structure of part, and this has hindered the outdiffusion of inner hydrogen effectively, has avoided hydrogen to be diffused into anodal and the NiOOH reaction, makes nickel/hydrogen battery of making that lower self discharge be arranged.
2, added two kinds of elements of Mn, B in the alloy of the present invention, the particle that makes the hydrogen-storage alloy microparticle surfaces have catalytic activity, thus chemical plating Mi-P alloy can directly be carried out on the alloyed powder surface under temperate condition.Drip the reducing agent inferior sodium phosphate, the nickel ion in the solution is reduced the catalysis particle place at particulate, progressively forms nucleus then, and diffusion is grown up, and makes coating very even.Because the coating overwhelming majority is Ni, this just makes hydrogen-storage alloy that an excellent protection cover is arranged, and has prevented that effectively lattice from putting expansion and contraction in the hydrogen process in suction, also causes the battery short circuit or the lost of life with regard to the micronize that has prevented alloy electrode; Because coating has favorable conductive, heat conductivility, make nickel/hydrogen battery of making that the characteristic of good fast charging and discharging be arranged; Because coating is made up of the thick metal Ni-P of 0.4～0.8 μ m, and good catalytic activity is arranged, there is not absorbed H in the time of can making charging 2, O 2Be combined to water mutually, make inner pressure of battery reduce, can security seal, be convenient to large-scale industrial production.
Thereby, use the battery that storage alloy material for hydrogen of the present invention is made, its electrochemistry capacitance and activity function height, item technical indicators such as high-rate discharge ability, cycle life, sealing property all are better than prior art significantly.
Provide embodiment below:
Embodiment 1: press Na 0.9Ca 0.1Ni 4.1Co 0.3Mn 0.3Al 0.2B 0.1The proportioning of chemical formula is weighed, and wherein Na is a norium, is the commercially available prod, and Ca, Ni, Co, Mn, Al, B purity are 99%.Batching is dry to be placed in the water-cooled copper pincers pot of vaccum sensitive stove, the induction furnace exhaust of finding time, and melting under the argon gas atmosphere protection, and pour into alloy cast ingot.The Mechanical Method powder process of gained alloy is worn into the alloyed powder of 30～70 μ m with the roller milling machine, carries out chemical plating nickel-phosphorus alloy on its surface then, and bath concentration and process conditions that it is selected for use are:
NiCl 26H 2O 9g/l
NaH 2PO 2H 2O 11.5g/l
Na 3C 6H 5O 72B 2O 16g/l
NH 4Cl 8g/l
PH 8.2-8.8
Temperature (℃) 35～50 chemical plating gained thickness of coating reach 0.6 μ m.The present invention is owing to added elements such as Ca, B, can successfully carry out chemical plating at cryogenic conditions with less material, obtain well behaved coating, get this alloyed powder, add furnishing pastel such as PTFE, water, as base material, making metal-hydride negative through slurry, roll extrusion, section with perforation nickel plating stainless steel band, is anodal with the nickel hydroxide, 5NKOH+1NLiOH solution is electrolyte, nylon nonwoven fabrics is a barrier film, is assembled into AA type sealed cell A, simultaneously consisting of NaNi 4.0Co 0.4Mn 0.3Al 0.3Alloy dress up the battery B of same model by same process, battery A can reach nominal capacity 1000mAh through twice activation, battery B then needs 7 times, shows that the activity function of battery A is good; Compress into the row test in to A, B battery latter stage in charging in addition, the interior pressure of A battery will be starkly lower than B battery, shows that the new material that the A battery adopts can reduce interior pressure, makes cell sealing safety, is suitable for suitability for industrialized production.See attached list 1:
Subordinate list 1 AA type A, two kinds of cell activation number of times of B and interior the pressure contrast
Discharge time 1 2 3 4 5 6 7
Discharge capacity (MAh) A 920 1020 1100 1180 1210 1240 1240
B 560 710 820 890 940 980 1010
Inner pressure of battery (MPa) A 0.04 0.06 0.08 0.09 0.10 0.11 0.12
B 0.05 0.08 0.10 0.13 0.15 0.19 0.22
Embodiment 2
Melting must consist of in vaccum sensitive stove
Na 0.9Ca 0.1Ni 4.1Co 0.3Mn 0.2Al 0.3B 0.1Hydrogen-storage alloy, and make AA type sealed cell C by embodiment 1 technology, by the IEC relative standard of Ni/cd battery the battery B of embodiment 1 and the battery C of present embodiment are carried out cycle life, the self discharge test, through 500 circulations, the C battery capacity only descends 7%, and the B battery capacity descends 15%; 28 days self-discharge rates of C battery are 21%, and B battery then is 31%; C high-rate battery discharge and specific energy performance are also significantly better than B battery (seeing attached list 2) in addition.
The heavy-current discharge of subordinate list 2 B, C two batteries and specific energy contrast
Discharge-rate 0.2C 1C 3C 5C
Discharge capacity (MAh) B 1160 1040 960 910
C 1240 1120 1010 930
Volume energy density (Mh/l) B 168.6 151.2 139.4 132.3
C 180.2 162.8 146.8 135.2
Weight energy density (Mh/kg) B 55.7 50.0 46.1 42.7
C 59.5 53.8 48.5 44.7

Claims (2)

1, a kind of hydrogen-storage alloy material for hydrogen electrode contains the norium element, it is characterized in that the chemical formula of alloy is:
Na 1-xCa xNi 5-y-z-u-vCo yMn zAl uB v
X=0.1 y=0.3 0.2≤z≤0.3 0.2≤u≤0.3 v=0.1 in the formula
2, hydrogen-storage alloy material for hydrogen electrode as claimed in claim 1 is characterized in that said alloy formula is:
Na 0.9Ca 0.1Ni 4.1Co 0.3Mn 0.2Al 0.3B 0.1
CN95112291A 1995-12-22 1995-12-22 Hydrogen-storage alloy material for hydrogen electrode Expired - Fee Related CN1050450C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN95112291A CN1050450C (en) 1995-12-22 1995-12-22 Hydrogen-storage alloy material for hydrogen electrode

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Application Number Priority Date Filing Date Title
CN95112291A CN1050450C (en) 1995-12-22 1995-12-22 Hydrogen-storage alloy material for hydrogen electrode

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CN1128413A CN1128413A (en) 1996-08-07
CN1050450C true CN1050450C (en) 2000-03-15

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1057405C (en) * 1997-08-04 2000-10-11 南开大学 Hydrogen-adsorped alloy electrode material
CN1297021C (en) * 2005-05-31 2007-01-24 钢铁研究总院 Cathode material in use for nickel-hydrogen battery in high capacity

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078827A (en) * 1992-05-16 1993-11-24 上海工业大学 A kind of hydrogen-storing alloy as electrode
CN1107815A (en) * 1994-03-04 1995-09-06 徐虎林 Composite, insulating, light organosilicon wall material and its production process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078827A (en) * 1992-05-16 1993-11-24 上海工业大学 A kind of hydrogen-storing alloy as electrode
CN1107815A (en) * 1994-03-04 1995-09-06 徐虎林 Composite, insulating, light organosilicon wall material and its production process

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