CN102593437B - Disposable nickel hydrogen battery negative electrode material, negative electrode piece, battery and preparation methods thereof - Google Patents

Disposable nickel hydrogen battery negative electrode material, negative electrode piece, battery and preparation methods thereof Download PDF

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Publication number
CN102593437B
CN102593437B CN201210050409.5A CN201210050409A CN102593437B CN 102593437 B CN102593437 B CN 102593437B CN 201210050409 A CN201210050409 A CN 201210050409A CN 102593437 B CN102593437 B CN 102593437B
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battery
powder
negative electrode
nickel
negative plate
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CN102593437A (en
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邹建新
谭剑波
曾小勤
丁文江
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Shanghai Jiaotong University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to a negative electrode material of a nickel hydrogen battery, and specifically relates to a disposable high-capacity replaceable nickel hydrogen battery negative electrode material. The invention also relates to a negative electrode piece, a nickel hydrogen electrode and preparation methods of the negative electrode piece and the nickel hydrogen electrode. The disposable nickel hydrogen battery negative electrode material comprises the following components in percentage by mass based on the total mass of the components: 35.56%-68.51% of LaNi5, 3.36%-8.03% of MgH2, 24.21%-56.10% of a bonding agent and 1.25%-3.08% of foam nickel. The negative electrode piece is made of the disposable nickel hydrogen battery negative electrode material, and the nickel hydrogen battery comprises the negative electrode piece. The method for preparing the negative electrode piece or the nickel hydrogen battery comprises the steps of mixing, piece pressing, welding and the like. According to the invention, the technical problems of the existing nickel hydrogen battery that the discharge specific capacity is low and the alloy is atomized easily are solved.

Description

Disposable nickel-hydrogen battery negative pole material, negative plate, battery and preparation method thereof
Technical field
The present invention relates to a kind of negative material of Ni-MH battery, be specifically related to the replaceable nickel-hydrogen battery negative pole material of a kind of disposable high power capacity; The invention still further relates to a kind of negative plate, NiH electrode and preparation method thereof.
Background technology
MH-Ni battery is the high-energy battery of new generation after Cd-Ni battery, compares with Cd-Ni battery, and the capacity of MH-Ni battery improves more than 50%, has also eliminated the pollution of Cd to environment simultaneously.MH-Ni battery is to develop on the basis with high pressure Ni-MH battery in space flight, because high pressure Ni-MH battery pressure is high, but also needs noble metal to make catalyst, so be difficult to civilian acceptance.Therefore, research work since civilian Ni-MH battery in 20 century 70 mid-terms, to the eighties, Holland, Japan, the U.S. are all devoted to research and develop hydrogen-bearing alloy electrode, the Battery Company such as PANASONIC Sanyo Toshiba are successively successfully developed MH-Ni battery, the exploitation that enters the MH-Ni battery nineties has formed industrialization, and China also successfully develops battery hydrogen bearing alloy.Because it has the favor that high power capacity, the feature such as high-power, pollution-free enjoy people, be one of important direction of current battery development field, and LaNi 5wherein to study to obtain also more ripe negative material early.
LaNi 5alloy is CaCu 5type hexagonal structure, inhales hydrogen and forms LaNi 5h 6, hydrogen storage content is about 1.4%.Its theoretical specific discharge capacity is about 370mAh/g, but in actual discharge process, is subject to the impact aspect dynamics, often lower than theoretical value, and LaNi 5inhale after hydrogen, because hydrogen atom enters interstitial void, the lattice of metal is expanded, and after putting hydrogen, metal lattice shrinks again.Therefore, suction is repeatedly put hydrogen and can be caused alloy to form even efflorescence of crackle.So, have in actual applications many restrictions.
Summary of the invention
A first aspect of the present invention object is for above-mentioned the deficiencies in the prior art, at LaNi 5on basis, provide a kind of MgH of containing 2and LaNi 5the negative material of Ni-MH battery, this negative material is a kind of disposable high power capacity replaceable battery negative material, operation is used very convenient; The discharge capacity of this negative material is than only having merely LaNi 5the discharge capacity of negative material greatly improve; Owing to being disposable electric discharge, also avoided the pulverizing problem of alloy in discharge process simultaneously.
The present invention solves the problems of the technologies described above by the following technical programs, reaches object of the present invention.
A disposable nickel-hydrogen battery negative pole material, the quality percentage composition by accounting for component gross mass, comprises following component:
LaNi 535.56％～68.51％；
MgH 23.36％～8.03％；
Binding agent 24.21%～56.10%;
Nickel foam 1.25%～3.08%.
Further, described binding agent is hydroxyl nickel powder.
A second aspect of the present invention object is to provide a kind of negative plate.Described negative plate is the negative plate being prepared from foregoing disposable nickel-hydrogen battery negative pole material.
A third aspect of the present invention object is to provide a kind of Ni-MH battery, and the negative material of described Ni-MH battery is a kind of disposable high power capacity replaceable battery negative material, and operation is used very convenient; The discharge capacity of this negative material is than only having merely LaNi 5the discharge capacity of negative material greatly improve; Owing to being disposable electric discharge, also avoided the pulverizing problem of alloy in discharge process simultaneously.
The present invention solves the problems of the technologies described above by the following technical programs, reaches object of the present invention.
A Ni-MH battery, comprises negative plate, and described negative plate is the negative plate being prepared from aforesaid disposable nickel-hydrogen battery negative pole material.
A fourth aspect of the present invention object is to provide the method for preparation negative plate as previously described.
A method of preparing negative plate as previously described, comprises the following steps:
(1) take respectively described LaNi 5, described MgH 2with described binding agent, described LaNi 5, described MgH 2with described binding agent be powder; Further, described LaNi 5, described MgH 2with described binding agent be through screening 200 order powder;
(2) described powder is mixed;
(3) the described powder of a part is packed in the filling tank of battery stamping system, then put into a slice nickel foam, and then pack a part of described powder into, carry out compressing tablet, obtain disk; Further, the test force that described battery stamping system is chosen is 12～15KN, and pressure keeps 2～3min;
(4) take out described disk, then weld the preceding paragraph nickel bar, make required negative plate; Further, adopt spot welding machine to carry out described weldering the preceding paragraph nickel bar.
A fifth aspect of the present invention object is to provide a kind of method of preparing foregoing Ni-MH battery.
A method of preparing foregoing Ni-MH battery, comprises following operation:
(a) by the foregoing method of preparing negative plate, prepare described negative plate;
(b) with diaphragm paper, described negative plate is encased, and put into positive plate in two outsides of described diaphragm paper, obtain electrode, described electrode forms the layer structure of described positive plate, described diaphragm paper, described negative plate from outside to inside;
(c) described electrode is put into box, then add the electrolyte configuring, obtain described Ni-MH battery.
Further, in described operation (c), the KOH solution that described electrolyte is 2～3mol/L.
Further, wherein said positive plate is Ni (OH) 2positive plate.
Compared with prior art, advantage of the present invention is:
(1) the present invention has improved the specific discharge capacity as the hydrogen bearing alloy of negative material, adds MgH 2after the nickel-hydrogen battery negative pole material that makes than in the past simple LaNi 5it is high 2～5 times that the specific discharge capacity of negative material is wanted.
(2) due to the convertibility of whole battery, in use with changing with use, convenient and swift.
(3) owing to being disposable electric discharge, avoided the pulverizing problem in charge and discharge process repeatedly as the hydrogen bearing alloy of negative material, and discharge time is long, the efficiency of battery is brought into play better.
(4) manufacture craft is simple, easy for operation.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, so that those skilled in the art understands object of the present invention, feature and effect fully.
Accompanying drawing explanation
Fig. 1 is the discharge time-voltage curve of the Ni-MH battery in embodiment 1;
Fig. 2 is the discharge time-voltage curve of the Ni-MH battery in embodiment 2;
Fig. 3 is the discharge time-voltage curve of the Ni-MH battery in embodiment 3;
Fig. 4 is the discharge time-voltage curve of the Ni-MH battery in embodiment 4.
Embodiment
A disposable nickel-hydrogen battery negative pole material, the quality percentage composition by accounting for component gross mass, comprises following component:
LaNi 535.56％～68.51％；
MgH 23.36％～8.03％；
Binding agent 24.21%～56.10%;
Nickel foam 1.25%～3.08%.
Wherein binding agent is hydroxyl nickel powder.
A Ni-MH battery, comprises negative plate.Negative plate is the negative plate being prepared from aforesaid disposable nickel-hydrogen battery negative pole material.
A method of preparing aforementioned Ni-MH battery, comprises the following steps:
(1) by the amount of a Ni-MH battery of preparation, take respectively LaNi 5, MgH 2with hydroxyl nickel powder, LaNi 5, MgH 2with hydroxyl nickel powder be through screening 200 order powder;
(2) powder is mixed;
(3) powder is packed in the filling tank of battery stamping system, charge weight is half of total amount of above-mentioned powder, then putting into diameter is a slice nickel foam of 10～11mm, and then pack half remaining powder into, carry out compressing tablet, obtaining diameter is 10～11mm disk, and the test force of choosing in compressing tablet process is 12～15KN, and pressure keeps 2～3min;
(4) compressing tablet complete after taking-up disk, with the ac spot welding machine segment length that burn-ons, be then the nickel bar of 8～10cm, the wide 4～5mm of being, make required negative plate; Nickel bar is the conventional nickel bar in this area;
(5) with the diaphragm paper that length is 7～8cm, the wide 4～5cm of being, the disk that is welded with nickel bar is encased, and put into Ni (OH) in two outsides of diaphragm paper 2positive plate, obtains electrode, and electrode forms Ni (OH) from outside to inside 2the layer structure of positive plate, diaphragm paper, negative plate; Diaphragm paper is the conventional diaphragm paper in this area;
(6) electrode is put into the box that specification is 6cm * 2.5cm * 10cm～7cm * 3cm * 11cm (box can be selected the conventional plastics box in this area), adding the concentration that 100～120ml configures is 2～3mol/L electrolyte (KOH solution) again, obtains Ni-MH battery.
Embodiment 1
(1) take respectively 1.4142gLaNi 5, 0.0867gMgH 2, 0.0635g nickel foam, 0.4998g hydroxyl nickel powder, LaNi 5, MgH 2, hydroxyl nickel powder be through screening 200 order powder;
(2) powder is mixed;
(3) powder is packed in the filling tank of battery stamping system, charge weight is half of total amount of above-mentioned powder, so putting into diameter is a slice nickel foam of 10mm, and then pack half remaining powder into and carry out compressing tablet, obtain the disk that diameter is 10mm, the test force of choosing in compressing tablet process is 15KN, and pressure keeps 2min;
(4) compressing tablet complete after the above-mentioned disk of taking-up, then with ac spot welding machine burn-on a segment length be 10cm, wide be the nickel bar of 5mm, make required negative plate;
(5) by length, be that 7.7cm, the wide diaphragm paper for 5cm encase the disk that is welded with nickel bar, and put into Ni (OH) in two outsides of diaphragm paper 2positive plate, obtains electrode, and electrode forms the layer structure of positive plate, diaphragm paper, negative plate from outside to inside;
(6) electrode is put into the plastics etui that specification is 6.2cm * 2.8cm * 11cm, then added the electrolyte (KOH solution) that concentration that 100ml configures is 2mol/L, obtain Ni-MH battery.
The above-mentioned Ni-MH battery making is through the test of LAND battery test system, and the electric current of choosing in test process is 10mA, and cut-ff voltage is 0.8V, and recording Ni-MH battery specific discharge capacity of the present invention is 747.2mAh/g, is about 11h discharge time.Time m-voltage curve as Fig. 1.Result shows that its specific discharge capacity is much higher than negative pole merely by LaNi 5(negative pole is merely by LaNi for the battery of making 5the theoretical specific discharge capacity of the battery of making is about 370mAh/g).
Embodiment 2
(1) take respectively 1.4146gLaNi 5, 0.0863gMgH 2, 0.0650g nickel foam, 1.0008g hydroxyl nickel powder, LaNi 5, MgH 2, hydroxyl nickel powder be through screening 200 order powder;
(2) then powder is mixed;
(3) powder is packed in the filling tank of battery stamping system, charge weight is half of total amount of above-mentioned powder, then putting into diameter is a slice nickel foam of 10mm, and then pack half remaining powder into and carry out compressing tablet, obtaining diameter is 10mm disk, the test force of choosing in compressing tablet process is 15KN, and pressure keeps 2min;
(4) compressing tablet complete after taking-up disk, then with ac spot welding machine burn-on a segment length be 10cm, wide be the nickel bar of 5mm, make required negative plate;
(5) by length, be that 7.5cm, the wide diaphragm paper for 4cm encase the disk that is welded with nickel bar, and put into Ni (OH) in two outsides of diaphragm paper 2positive plate, obtains electrode, and electrode forms the layer structure of positive plate, diaphragm paper, negative plate from outside to inside;
(6) electrode is put into the plastics etui that specification is 6.4cm * 2.5cm * 10.2cm, then to add the concentration that 100ml configures be 2mol/L electrolyte (KOH solution), obtain Ni-MH battery.
To the above-mentioned Ni-MH battery making, through the test of LAND battery test system, the electric current of choosing in test process is 10mA, and cut-ff voltage is 0.8V.The Ni-MH battery specific discharge capacity that records the present embodiment is 814.0mAh/g, is about 14h discharge time.Time m-voltage curve as Fig. 2.Result shows that its specific discharge capacity is much higher than negative pole merely by LaNi 5(negative pole is merely by LaNi for the battery of making 5the theoretical specific discharge capacity of the battery of making is about 370mAh/g).
Embodiment 3
(1) take respectively 1.2679gLaNi 5, 0.2316gMgH 2, 0.0656g nickel foam, 2.0004g hydroxyl nickel powder, LaNi 5, MgH 2, hydroxyl nickel powder be through screening 200 order powder;
(2) then powder is mixed;
(3) powder is packed in the filling tank of battery stamping system, charge weight is half of total amount of above-mentioned powder, then putting into diameter is a slice nickel foam of 10mm, and then pack half remaining powder into and carry out compressing tablet, obtaining diameter is 10mm disk, the test force of choosing in compressing tablet process is 15KN, and pressure keeps 2min;
(4) compressing tablet complete after taking-up disk, then with A.C. welder burn-on a segment length be 10cm, wide be the nickel bar of 5mm, make required negative plate;
(5) by length, be that 7.2cm, the wide diaphragm paper for 4.8cm encase the disk that is welded with nickel bar, and put into Ni (OH) in two outsides of diaphragm paper 2positive plate, obtains electrode, and electrode forms the layer structure of positive plate, diaphragm paper, negative plate from outside to inside;
(6) electrode is put into the plastics etui that specification is 6.5cm * 3cm * 10.5cm, then to add the concentration that 100～120ml configures be 2mol/L electrolyte (KOH solution), obtain Ni-MH battery.
The above-mentioned Ni-MH battery making is through the test of LAND battery test system, and the electric current of choosing in test process is 10mA, and cut-ff voltage is 0.8V, and the Ni-MH battery specific discharge capacity that records the present embodiment is 1062.6mAh/g, is about 24h discharge time.Time m-voltage curve as Fig. 3.Result shows that its specific discharge capacity is much higher than negative pole merely by LaNi 5(negative pole is merely by LaNi for the battery of making 5the theoretical specific discharge capacity of the battery of making is about 370mAh/g).
Embodiment 4
(1) take respectively 2.6747gLaNi 5, 0.3253gMgH 2, 0.0505g nickel foam, 0.9989g hydroxyl nickel powder, LaNi 5, MgH 2, hydroxyl nickel powder be through screening 200 order powder;
(2) then powder is mixed.
(3) powder is packed in the filling tank of stamping system, charge weight is half of total amount of above-mentioned powder, then putting into diameter is a slice nickel foam of 10mm, and then pack half remaining powder into and carry out compressing tablet, obtaining diameter is 10mm disk, the test force of choosing in compressing tablet process is 15KN, and pressure keeps 2min;
(4) compressing tablet complete after taking-up disk, then with A.C. welder burn-on a segment length be 10cm, wide be the nickel bar of 5mm, make required negative plate;
(5) by length, be that 7.6cm, the wide diaphragm paper for 5cm encase the disk that is welded with nickel bar, and put into Ni (OH) in two outsides of diaphragm paper 2positive plate, obtains electrode, and electrode forms the layer structure of positive plate, diaphragm paper, negative plate from outside to inside;
(6) electrode is put into the plastics etui that specification is 6cm * 3cm * 11cm, then to add the concentration that 100～120ml configures be 2mol/L electrolyte (KOH solution), obtain Ni-MH battery.
The above-mentioned Ni-MH battery making is through the test of LAND battery test system, and the electric current of choosing in test process is 10mA, and cut-ff voltage is 0.8V, and the Ni-MH battery specific discharge capacity that records the present embodiment is 1809.5mAh/g, is about 55h discharge time.Time m-voltage curve as Fig. 4.Result shows that its specific discharge capacity is much higher than negative pole merely by LaNi 5(negative pole is merely by LaNi for the battery of making 5the theoretical specific discharge capacity of the battery of making is about 370mAh/g).
Fig. 1～4 are the time m-voltage curve after the test of LAND battery test system.Through above-mentioned example, find, the specific discharge capacity of battery is relevant with the powder quality of making cell negative electrode material, and along with the increase of quality, specific discharge capacity increases, and corresponding discharge time is also longer.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technical staff in the art, all should be in the determined protection range by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (6)

1. a preparation method for negative plate, described negative plate is the negative plate being prepared from disposable nickel-hydrogen battery negative pole material; Described negative material, by the quality percentage composition that accounts for component gross mass, comprises following component:
It is characterized in that, the preparation method of described negative plate comprises the following steps:
(1) take respectively described LaNi 5, described MgH 2with described hydroxyl nickel powder, described LaNi 5, described MgH 2with described hydroxyl nickel powder be powder;
(2) described powder is mixed;
(3) the described powder of a part is packed in the filling tank of battery stamping system, then put into a slice nickel foam, and then pack a part of described powder into, carry out compressing tablet, obtain disk;
(4) take out described disk, then weld the preceding paragraph nickel bar, make required negative plate.
2. a preparation method for Ni-MH battery, is characterized in that, comprises following operation:
(a) by method claimed in claim 1, prepare described negative plate;
(b) with diaphragm paper, described negative plate is encased, and put into positive plate in two outsides of described diaphragm paper, obtain electrode, described electrode forms the layer structure of described positive plate, described diaphragm paper, described negative plate from outside to inside;
(c) described electrode is put into box, then add the electrolyte configuring, obtain described Ni-MH battery.
3. the preparation method of Ni-MH battery as claimed in claim 2, wherein, in described step (3), the test force that described battery stamping system is chosen is 12～15KN, pressure keeps 2～3min.
4. the preparation method of Ni-MH battery as claimed in claim 2, wherein, in described operation (c), the KOH solution that described electrolyte is 2～3mol/L.
5. the preparation method of Ni-MH battery as claimed in claim 2, wherein, in described step (1), described LaNi 5, described MgH 2with described hydroxyl nickel powder be through screening 200 object powder.
6. the preparation method of Ni-MH battery as claimed in claim 2, wherein said positive plate is Ni (OH) 2positive plate.
CN201210050409.5A 2012-02-29 2012-02-29 Disposable nickel hydrogen battery negative electrode material, negative electrode piece, battery and preparation methods thereof Expired - Fee Related CN102593437B (en)

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CN102800853A (en) * 2012-08-30 2012-11-28 上海锦众信息科技有限公司 Preparation method of negative electrode material of nickel-based alkaline secondary battery
CN102899681A (en) * 2012-10-26 2013-01-30 华侨大学 Porous nickel composite electrode, electroplating solution and preparation method of porous nickel composite electrode

Citations (3)

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Publication number Priority date Publication date Assignee Title
US7201789B1 (en) * 1997-10-22 2007-04-10 Hydro-Quebec Nanocomposites with activated interfaces prepared by mechanical grinding of magnesium hydrides and use for storing hydrogen
CN101165947A (en) * 2007-09-17 2008-04-23 广东工业大学 Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses
CN101304087A (en) * 2008-06-12 2008-11-12 中国科学院上海微系统与信息技术研究所 Method for preparing nickel-hydrogen battery cathode

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GB0317894D0 (en) * 2003-07-31 2003-09-03 Johnson Matthey Plc Hydrogen supply system

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US7201789B1 (en) * 1997-10-22 2007-04-10 Hydro-Quebec Nanocomposites with activated interfaces prepared by mechanical grinding of magnesium hydrides and use for storing hydrogen
CN101165947A (en) * 2007-09-17 2008-04-23 广东工业大学 Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses
CN101304087A (en) * 2008-06-12 2008-11-12 中国科学院上海微系统与信息技术研究所 Method for preparing nickel-hydrogen battery cathode

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