CN100416896C - Cathode hydrogen-stored material used for low-temperature Ni-H battery and battery thereof - Google Patents

Cathode hydrogen-stored material used for low-temperature Ni-H battery and battery thereof Download PDF

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CN100416896C
CN100416896C CNB2005101237477A CN200510123747A CN100416896C CN 100416896 C CN100416896 C CN 100416896C CN B2005101237477 A CNB2005101237477 A CN B2005101237477A CN 200510123747 A CN200510123747 A CN 200510123747A CN 100416896 C CN100416896 C CN 100416896C
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battery
hydrogen
low temperature
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alloy
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CN1971979A (en
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朱磊
吴伯荣
董桂霞
陈晖�
刘明义
简旭宇
杜军
蒋利军
毛昌辉
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GRIMN Engineering Technology Research Institute Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
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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
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Abstract

This invention relates to one alloy materials of nickel and hydrogen battery in low temperature and its battery, which comprises the following components: LaxCeyPrzNimConMnuAlv,wherein, x=0.16- 0.5,y=0.12-0.81,z=0.03-0.59,m=3.7-3.8,n=0.55-0.6,u=0.25- 0.45,v=0.1-0.25.

Description

The cathode hydrogen-stored material and the battery thereof that can be used for the low temperature nickel hydrogen battery
Technical field
The invention belongs to field of functional materials.Be specifically related to be used to prepare the cathode hydrogen-stored material of the Ni-MH battery that the cryogenic property requirement is arranged.
Background technology
The low temperature nickel hydrogen battery can be widely used in military affairs, Aero-Space, navigation, oil, coal, geological prospecting and operation, reach mountain-climbing sports items, antarctic investigation on ice, be the secondary portable power source that the wide cold district in the Northern Hemisphere uses simultaneously, have very strong strategic importance, scientific value and economic worth.Ni-MH battery product under the prior art, particularly present business-like Ni-MH battery product, its serviceability temperature only in-20～50 ℃ of scopes, and when the subzero temperature reduces battery performance descend very fast, under low temperature more even can not emit electric energy.For under low temperature more (being low to moderate-35～-40 ℃) still have the occasion of sufficient electric power output demand, as fields such as military affairs, Aero-Space, this type of Ni-MH battery product all can't satisfy instructions for use.Ni-MH battery is made up of nickel hydroxide positive plate, hydrogen-storage alloy negative pole, barrier film and potassium hydroxide electrolyte, the main cause of Ni-MH battery decreased performance is that the capacity of hydrogen-storage alloy negative material under the low temperature descends very fast under the low temperature, so it is more crucial, also more urgent to improving the ni-mh cryogenic property to develop under the low temperature well behaved storage alloy material for hydrogen.
Summary of the invention
The purpose of this invention is to provide a kind of low temperature (35～-40 ℃) down discharge capacity than the high a lot of Hydrogen storage alloy materials for negative electrodes in present commercially available prod.
Another object of the present invention provides a kind of Ni-MH battery with cryogenic property.
To achieve these goals, the present invention takes following technical proposals:
A kind of cathode hydrogen-stored material that can be used for the low temperature nickel hydrogen battery, its chemical expression is: La xCe yPr zNi mCo nMn uAl r, x=0.16～0.5 wherein, y=0.12～0.81, z=0.03～0.59, m=3.7～3.8, n=0.55～0.6, u=0.25～0.45, r=0.1～0.25.This material belongs to AB 5The type hydrogen-storage alloy, during this hydrogen-storage alloy was formed, A was La, Ce, Pr element, the B side is Ni, Co, Mn, Al element.
Adopting hydrogen storage material of the present invention to satisfy has the Ni-MH battery product needed of cryogenic property requirement.
In cathode hydrogen-stored material of the present invention, x, y, z, m, n, u, v is preferably: x=0.5, y=0.27, z=0.19, m=3.8, n=0.6, u=0.4, v=0.1.
A kind of Ni-MH battery is the battery that comprises that cathode hydrogen-stored material of the present invention is made.
For present Ni-MH battery, used negative material mainly is mishmetal AB 5Type alloy, capacity be generally at 300～340mAh/g, is to improve capacity of negative plates, and it is alloy that the system of developing at present mainly contains zirconium system, titanium system and magnesium, but except that the part zirconium alloy, all because combination property is relatively poor etc. former thereby do not obtain practical application.
AB 5The type alloy mainly easily forms hydride element (as rare earth element etc.) by the A side and B side (Ni, Co, Mn, Al etc.) is formed, and is to belong to CaCu 5The intermetallic compound of structure.Its charge/discharge capacity is mainly put the hydrogen process from the suction of alloy.In Ni-MH battery, the reaction that takes place in the charge and discharge process is:
Anodal:
Figure C20051012374700041
Negative pole:
Figure C20051012374700042
M is a hydrogen-storage alloy
The hydrogen-storage alloy that uses for nickel-hydrogen battery at present mainly is made up of mishmetal (Mm), Ni, Co, Mn, Al, and typical composition is MmNi 3.55Co 0.75Mn 0.4Al 0.3, the mishmetal mainly formed of Mm wherein by La, Ce, Pr, Nd.When temperature was lower than zero degree, along with the reduction of temperature, the alloy capacity descended very big, and by alloy compositions optimization, the applicant has invented and can satisfy the storage alloy material for hydrogen that the low temperature nickel hydrogen battery uses.The low temperature that the present invention the proposes storage alloy material for hydrogen composition that uses for nickel-hydrogen battery consists of: La xCe yPr zNi mCo nMn uAl v, x=0.16～0.5 wherein, y=0.12～0.81, z=0.03～0.59, m=3.7～3.8, n=0.55～0.6, u=0.25～0.45, v=0.1～0.25.
Use storage alloy material for hydrogen of the present invention, under the low temperature (30～-40 ℃) discharge capacity be improved significantly, best result is that-40 ℃ of following discharge capacities reach 260mAh/g ,-30 ℃ of following discharge capacities reach 280mAh/g, cryogenic property is with the obvious advantage.
Embodiment
Percentage composition batching according to each element in the alloying component proportioning; confected materials (is vacuumized at induction furnace; vacuum degree 0.1Pa; logical then argon shield pressure 0.05MPa) melting (power 15KW in; 2 minutes) and cast alloy pig; with alloy pig mechanical lapping powdered, powder is standby with 200 mesh sieves screening back afterwards.After alloyed powder and carbonyl nickel powder evenly mixed with 1: 3 weight proportion, cold pressing plate is as negative pole on the nickel foam substrate at 20 * 20mm under the 20MPa pressure, just very anodal with the nickel that uses for nickel-hydrogen battery, positive electrode capacity is excessive far away than capacity of negative plates, adopts sandwich simulated battery structure to carry out the negative pole performance test.During test, at first at room temperature anticathode fully activates, and is specific as follows: pressed the 125mAh/g current charges 3.5 hours, shelve 15 minutes after, to voltage 0.9V, shelve the charge-discharge test that carries out next circulation after 15 minutes with the 60mAh/g current discharge again.The discharge capacity of alloy material will reach maximum along with the carrying out of charge and discharge cycles and relatively stablely get off, and this moment, activation promptly came to an end.After finishing, activation can carry out the discharge capacity test under the low temperature, the test system is: adopt sandwich simulated battery structure that negative pole was at room temperature pressed the 125mAh/g current charges 3.5 hours, placed at low temperatures afterwards 8 hours, again with the 60mAh/g current discharge to voltage 0.3V, this moment, capacity was the discharge capacity of negative material under the low temperature (35～-40 ℃).
By the above-mentioned preparation cathode hydrogen-stored material method that can be used for the low temperature nickel hydrogen battery of the present invention, 6 kinds of cathode hydrogen-stored materials of the present invention have been prepared, be embodiment 1-6, and adopt above-mentioned method of testing, the alloy composition of embodiment 1-6 and room temperature, low temperature (35～-40 ℃) discharge capacity of negative material down see the following form Comparative Examples Mm Ni 3.55Co 0.75Mn 0.4Al 0.3Test in the condition of equal test with the alloy of embodiment 1-6, that tests and compare sees the following form.The result shows, storage alloy material for hydrogen of the present invention, at low temperatures (30～-40 ℃) discharge capacity be improved significantly, best result is that-40 ℃ of following discharge capacities reach 260mAh/g,-30 ℃ of following discharge capacities reach 280mAh/g, and the cryogenic property of storage alloy material for hydrogen of the present invention obviously is better than Comparative Examples Mm Ni 3.55Co 0.75Mn 0.4Al 0.3Cryogenic property.
Discharge capacity under the composition of alloy of the present invention and present commercial alloy and the different temperatures (mAh/g) relatively

Claims (3)

1. a cathode hydrogen-stored material that can be used for the low temperature nickel hydrogen battery is characterized in that its chemical expression is: La xCe yPr zNi mCo nMn uAl v, x=0.16～0.5 wherein, y=0.12～0.81, z=0.03～0.59, m=3.7～3.8, n=0.55～0.6, u=0.25～0.45, v=0.1～0.25.
2. according to the described cathode hydrogen-stored material of claim 1, it is characterized in that: x=0.5, y=0.27, z=0.19, m=3.8, n=0.6, u=0.4, v=0.1.
3. a Ni-MH battery is characterized in that: be the battery that comprises that the described cathode hydrogen-stored material of claim 1 is made.
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CN105463256B (en) * 2015-12-03 2017-08-25 内蒙古稀奥科贮氢合金有限公司 A kind of Hydrogen storage alloy for nickel-metal hydride battery and preparation method thereof
CN111180718A (en) * 2019-12-31 2020-05-19 深圳拓量技术有限公司 Hydrogen storage alloy powder of nickel-hydrogen battery for ultralow temperature environment and preparation method thereof
CN113881872B (en) * 2021-10-27 2022-05-20 厦门钨业股份有限公司 Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0855618A (en) * 1994-08-11 1996-02-27 Japan Storage Battery Co Ltd Sealed alkaline storage battery
CN1153404A (en) * 1996-10-11 1997-07-02 天津莫比士电池有限公司 Nickel-hydrogen cell cathode alloy material and method for making Ni-H cell using same
JPH09270255A (en) * 1996-03-30 1997-10-14 Toshiba Corp Hydrogen storage alloy for battery and nickel hydrogen secondary battery
CN1251472A (en) * 1999-09-28 2000-04-26 四川大学 Hydrogen-storage alloy electrode material of low-Co lanthanum-praseodymium-cerium-nickel series
CN1424782A (en) * 2002-12-27 2003-06-18 四川大学 Hydrogen storing rare earth alloy without neodymium for nickle-hydrogen power batteries
CN1560937A (en) * 2004-03-08 2005-01-05 江阴润华电池制造有限公司 High-power nickel storage alloy electrode and its preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0855618A (en) * 1994-08-11 1996-02-27 Japan Storage Battery Co Ltd Sealed alkaline storage battery
JPH09270255A (en) * 1996-03-30 1997-10-14 Toshiba Corp Hydrogen storage alloy for battery and nickel hydrogen secondary battery
CN1153404A (en) * 1996-10-11 1997-07-02 天津莫比士电池有限公司 Nickel-hydrogen cell cathode alloy material and method for making Ni-H cell using same
CN1251472A (en) * 1999-09-28 2000-04-26 四川大学 Hydrogen-storage alloy electrode material of low-Co lanthanum-praseodymium-cerium-nickel series
CN1424782A (en) * 2002-12-27 2003-06-18 四川大学 Hydrogen storing rare earth alloy without neodymium for nickle-hydrogen power batteries
CN1560937A (en) * 2004-03-08 2005-01-05 江阴润华电池制造有限公司 High-power nickel storage alloy electrode and its preparation method

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