CN1794499A - Positive electrode material of metal hydride-nickel battery and its preparation method - Google Patents

Positive electrode material of metal hydride-nickel battery and its preparation method Download PDF

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CN1794499A
CN1794499A CNA2005100612808A CN200510061280A CN1794499A CN 1794499 A CN1794499 A CN 1794499A CN A2005100612808 A CNA2005100612808 A CN A2005100612808A CN 200510061280 A CN200510061280 A CN 200510061280A CN 1794499 A CN1794499 A CN 1794499A
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metal hydride
nickel
positive electrode
battery
slurry
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CN1333480C (en
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张文魁
涂江平
黄辉
甘永平
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

This invention relates to a positive pole material of a metallic hydride-Ni battery and its preparation method, in which, said positive pole material is composed of a foam Ni matrix and positive pole filling materials including an active substance spherical beta-Ni(OH)<SUB>2</SUB> bonder and a conduction additive CoSO<SUB>4</SUB>7H<SUB>2</SUB>O to reduce the cost of raw materials and increase the usability of positive active substance.

Description

Positive electrode of a kind of metal hydride-nickel cell and preparation method thereof
(1) technical field
The present invention relates to positive electrode of a kind of metal hydride-nickel cell and preparation method thereof, this positive electrode especially is fit to make cheap low capacity power-type Ni/metal hydride-nickel-based battery.
(2) background technology
Metal hydride-nickel cell (Ni-MH battery) is that the employing metal hydride is a negative material, nickel hydroxide is the novel secondary cell of a class of positive electrode, compare with traditional nickel-cadmium cell, have the energy density height, non-environmental-pollution, memory-less effect, advantages such as have extended cycle life, low-temperature characteristics is good, and overcharging resisting electricity and overdischarge characteristic are good, therefore after Ni-MH battery realizes that in the phase earlier 1990s industrialization is produced, develop very fast.
Produce metal hydride-nickel cell at present both at home and abroad, positive active material adopts spherical β-Ni (OH) usually 2, wherein need to add high-purity CoO about 10% as conductive additive.Because the various raw materials for production prices of Ni-MH battery rise steadily in recent years, the price of nickel and cobalt skyrockets especially in the world, causes the production cost of Ni-MH battery constantly to increase, and has brought serious cost pressure to manufacturer.According to measuring and calculating, in the plain edition metal hydride-nickel cell, CoO conductive additive occupied cost in anodal cost generally can reach about 20%, and in power-type Ni/metal hydride-nickel-based battery, this ratio is taller, even can be reached about 30%.Therefore, develop a kind of low-cost anodal conductive additive,, have very important significance reducing the cost of metal hydride-nickel cell.Analyze the production technology of all kinds of cobalt salts, because high-purity CoO need adopt high-purity Co powder as raw materials for production, so its cost is expensive and influenced greatly by the market factor, and CoSO 47H 2During producing, O can utilize the cobalt-containing alloy of all kinds of useless cobalts and recovery, cheap for manufacturing cost, its market price (being converted to identical cobalt content) has only 1/3~1/5 of CoO, therefore as the anode additive of metal hydride-nickel cell, can reduce the anodal cost of raw material significantly, the production of metal hydride-nickel cell is had the obvious practical meaning.
(3) summary of the invention
In order to reduce the production cost of metal hydride-nickel cell, the invention provides positive electrode of a kind of metal hydride-nickel cell and preparation method thereof, this positive electrode especially is fit to cheap low capacity type power nickel-hydrogen cell.
For reaching goal of the invention, the technical solution used in the present invention is as follows:
A kind of positive electrode of metal hydride-nickel cell is made of nickel foam substrate and anodal packing material, and described anodal packing material comprises the spherical β-Ni (OH) of active material 2, adhesive, described anodal packing material also comprises conductive additive CoSO 47H 2O.Described anodal packing material is made up of the component of following quality proportioning: β-Ni (OH) 2: CoSO 47H 2O: adhesive is 1: 0.05~0.3: 0.012~0.045.Preferred proportioning is β-Ni (OH) 2: CoSO 47H 2O: adhesive is 1: 0.15~0.25: 0.015~0.042.Here the amount of said adhesive refers to not contain the amount of dissolve medium, needs when preparing usually earlier with dissolve medium adhesive melt into slurry, and described adhesive also can be mixed by multiple material.
When the anodal packing material of preparation, also adopt the commercially available adhesive that is mixed with slurry in advance often, the present invention recommends the slurry that uses for being that 60% ptfe emulsion and mass concentration are the mixture that 3% sodium carboxymethylcellulose makes with solid content.The mass ratio of preferred 60% ptfe emulsion and 3% sodium carboxymethylcellulose is: 1~5: 20~50.More preferably the mass ratio of 60% ptfe emulsion and 3% sodium carboxymethylcellulose is: 1~5: 30~40.
The present invention also provides the method for the positive electrode of the above-mentioned metal hydride-nickel cell of preparation, comprises the steps:
1) the preparation adhesive becomes slurry earlier;
2) with CoSO 47H 2O is dissolved in the water, and adds slurry, spherical β-Ni (OH) again 2Mix, get slurry, the amount of described water is spherical β-Ni (OH) 210~40% of amount;
The above-mentioned slurry that obtains is filled in the nickel foam substrate oven dry.Described bake out temperature is recommended as 120~150 ℃; More preferably bake out temperature is 130 ℃.
The method of the positive electrode of preparation metal hydride-nickel cell of the present invention, preparing anodal packing material adhesive therefor, to recommend to select for use solid content be that 60% the ptfe emulsion and the sodium carboxymethylcellulose of mass concentration 3% are mixed with slurry, described 60% ptfe emulsion in advance: 3% sodium carboxymethylcellulose mass ratio 1~5: 20~50.
Narration particularly, the method for the above-mentioned positive electrode of preparation that the present invention is more excellent is:
(1) with CoSO 47H 2O is dissolved in the water, and the amount of water is spherical β-Ni (OH) 210~40% of amount adds solid content and is 60% ptfe emulsion and 3% (mass concentration) sodium carboxymethylcellulose and stirs, and adds spherical β-Ni (OH) then 2Mix pulp.
(2) the pulpous state packing material is adopted nickel foam slurry method be filled in the nickel foam substrate, the foam nickel electrode that slurry is good must be through oven dry, and bake out temperature is 130 ℃.
In the said method step (1), the ratio of each component is: β-Ni (OH) 2: CoSO 47H 2O: 60% ptfe emulsion: 3% sodium carboxymethylcellulose is: 1: 0.05~0.3: 0.01~0.05: 0.2~0.5, be preferably β-Ni (OH) 2: CoSO 47H 2O: 60% ptfe emulsion: 3% sodium carboxymethylcellulose is 1: 0.15~0.25: 0.01~0.05: 0.3~0.4.
After the oven dry, to electrode cut, behind roll-in and the soldering polar ear, obtain the metal hydride-nickel battery positive pole, when adopting this positive pole to prepare battery, the technological process of its technology and present conventional Ni-MH battery is basic identical, the positive pole and the negative pole centre that make are served as a contrast with polypropylene every the nonwoven fabrics barrier film, pack into behind the coiling in the battery case, inject quantitative electrolyte then, with positive pole ear and top cover welding, slot rolling seals, through changing into sorting after promptly can be made into the battery finished product.
A kind of manufacturing metal hydride-nickel cell positive electrode of the present invention is compared as the method for anodal conductive agent with the employing CoO of routine, and its advantage is mainly reflected in: (1) adopts CoSO 47H 2O can reduce anodal manufacturing cost significantly as conductive additive, helps reducing the cost of metal hydride-nickel cell; (2) adopt CoSO 47H 2O is as anode additive, in the battery formation process, and CoSO 47H 2But the crystallization water slow release that O carries is come out, and can increase the electrolyte content in the battery gradually, increases substantially the utilance and the cyclical stability of active material.Therefore, the method for metal hydride-nickel cell positive electrode provided by the invention and preparation thereof can reduce anodal manufacturing cost significantly, is particularly suitable for making cheap low capacity type power nickel-hydrogen cell.
(4) description of drawings
Fig. 1, Fig. 3, Fig. 5 are with the β-Ni (OH) in the positive pole of this method preparation 2The specific capacity curve chart, Fig. 2, Fig. 4, Fig. 6 are the cyclic curves of battery that adopts the positive pole assembling of this method preparation.
(5) embodiment
The invention will be further described below in conjunction with specific embodiments and the drawings, but protection of the present invention is not limited thereto:
Embodiment 1:
The commercially available solid content of adhesive employing is 60% ptfe emulsion and existing 3% sodium carboxymethylcellulose of preparing in the anodal packing material.The quality proportioning of anodal packing material is: β-Ni (OH) 2: CoSO 47H 2O: 60% ptfe emulsion: 3% sodium carboxymethylcellulose is 1: 0.1: 0.01: 0.2.Take by weighing 10gCoSO 47H 2O, 100g β-Ni (OH) 2, by proportioning 60% ptfe emulsion and 3% sodium carboxymethylcellulose are mixed with slurry earlier during preparation, again with 10gCoSO 47H 2O is dissolved in the water of 25g, adds slurry and stirs, and adds spherical β-Ni (OH) again 2Mix pulp, adopt the slurry method to be filled in the nickel foam substrate then, discard unnecessary anodal packing material.The good foam nickel electrode of slurry is 120 ℃ of oven dry down, cuts then, roll-in and spot welding lug, makes positive plate, and pole piece is of a size of: (80 ± 1) * (40 ± 0.05) * (0.72 ± 0.01) (mm), sheet heavily is 6.8 ± 0.1g, wherein β-Ni (OH) 2The about 5.1g of net weight, negative pole adopts the cold rolling hydrogen-occlussion alloy electrode of copper mesh matrix, be of a size of (100 ± 1) * (40.0 ± 0.05) * (0.28 ± 0.01) (mm), sheet heavily is 9.0 ± 0.1g.Reservoir quantity is a 2.8g electrolyte, after slot rolling seals, shelves under the normal temperature 5 hours, changes into then and sorting process.The technology that changes into sorting is: (1) battery is earlier with 0.1C charging 4 hours; (2) battery after the preliminary charging was shelved in baking oven 24 hours, and temperature is 50 ℃; (3) battery is taken out in baking oven, after waiting to be chilled to normal temperature, to battery charge 6 hours, 0.4C was discharged to 1.0V then with the 0.2C multiplying power; (4) with 0.5C multiplying power charging 3 hours, be discharged to 1.0V with 0.5C then; (5) with 1.0C multiplying power charging 72 minutes, be discharged to 1.0V with 1.0C then.The results are shown in accompanying drawing 1 and Fig. 2.
Fig. 1 is the β-Ni (OH) in the positive pole for preparing 2The specific capacity curve, along with the increase of cycle-index, β-Ni in the positive pole (OH) 2Specific capacity increase gradually, through 100 times the circulation after, β-Ni (OH) 2Specific capacity surpass 280mAh/g (near theoretical capacity 289mAh/g).Fig. 2 is the cyclic curve that adopts the battery of the positive pole assembling for preparing, and after 100 circulations, the capacity of battery still is in ascendant trend, and the peak capacity of battery shows and adopts the anodal battery of assembling of the present invention to have good cyclical stability near 1430mAh.
Embodiment 2:
The commercially available solid content of adhesive employing is 60% ptfe emulsion and existing 3% sodium carboxymethylcellulose of preparing in the anodal packing material.The quality proportioning of anodal packing material is: β-Ni (OH) 2: CoSO 47H 2O: 60% ptfe emulsion: 3% sodium carboxymethylcellulose is 1: 0.18: 0.01: 0.2, take by weighing 18gCoSO 47H 2O, 100g β-Ni (OH) 2, by proportioning 60% ptfe emulsion and 3% sodium carboxymethylcellulose are mixed with slurry earlier during preparation, again with 18gCoSO 47H 2O is dissolved in the water of 25g, adds slurry and stirs, and adds spherical β-Ni (OH) again 2Mix pulp, adopt the slurry method to be filled in the nickel foam substrate then, discard unnecessary anodal packing material.The good foam nickel electrode of slurry is 130 ℃ of oven dry down, cuts then, roll-in and spot welding lug, makes positive plate, and pole piece is of a size of: (80 ± 1) * (40 ± 0.05) * (0.72 ± 0.01) (mm), sheet heavily is 7.0 ± 0.1g, wherein β-Ni (OH) 2The about 5.0g of net weight, negative pole adopts the cold rolling hydrogen-occlussion alloy electrode of copper mesh matrix, be of a size of (100 ± 1) * (40.0 ± 0.05) * (0.28 ± 0.01) (mm), sheet heavily is 9.0 ± 0.1g.Reservoir quantity is a 2.8g electrolyte, after slot rolling seals, shelves under the normal temperature 5 hours, changes into then and sorting process.The technology that changes into sorting is: (1) battery is earlier with 0.1C charging 4 hours; (2) battery after the preliminary charging was shelved in baking oven 24 hours, and temperature is 50 ℃; (3) battery is taken out in baking oven, after waiting to be chilled to normal temperature, to battery charge 6 hours, 0.4C was discharged to 1.0V then with the 0.2C multiplying power; (4) with 0.5C multiplying power charging 3 hours, be discharged to 1.0V with 0.5C then; (5) with 1.0C multiplying power charging 72 minutes, be discharged to 1.0V with 1.0C then.Result such as accompanying drawing 3 and Fig. 4.
Fig. 3 is the β-Ni (OH) in the preparation positive pole 2The specific capacity curve, along with the increase of cycle-index, β-Ni in the positive pole (OH) 2Specific capacity increase gradually, through 100 times the circulation after, β-Ni (OH) 2Specific capacity near 290mAh/g (near theoretical capacity 289mAh/g).Fig. 4 is the cyclic curve that adopts the battery of the positive pole assembling for preparing, and after 100 circulations, the capacity of battery still is in ascendant trend, and the about 1410mAh of the peak capacity of battery shows and adopts the anodal battery of assembling of the present invention to have good cyclical stability.
Embodiment 3:
The commercially available solid content of adhesive employing is 60% ptfe emulsion and existing 3% sodium carboxymethylcellulose of preparing in the anodal packing material.The quality proportioning of anodal packing material is: β-Ni (OH) 2: CoSO 47H 2O: 60% ptfe emulsion: 3% sodium carboxymethylcellulose is 1: 0.3: 0.02: 0.2, take by weighing 30gCoSO 47H 2O, 100g β-Ni (OH) 2, by proportioning 60% ptfe emulsion and 3% sodium carboxymethylcellulose are mixed with slurry earlier during preparation, again with 30gCoSO 47H 2O is dissolved in the water of 25g, adds slurry and stirs, and adds spherical β-Ni (OH) again 2Mix pulp, adopt the slurry method to be filled in the nickel foam substrate then, discard unnecessary anodal packing material.The foam nickel electrode that slurry is good is dried down at 130 ℃, cut then, roll-in and spot welding lug, make positive plate, pole piece is of a size of: (80 ± 1) * (40 ± 0.05) * (0.70 ± 0.01) (mm), sheet heavily is 6.9 ± 0.1g, and negative pole adopts the cold rolling hydrogen-occlussion alloy electrode of copper mesh matrix, be of a size of (100 ± 1) * (4.0 ± 0.05) * (0.29 ± 0.01) is (mm), sheet heavily is 9.0 ± 0.1g, wherein β-Ni (OH) 2The about 4.5g of net weight.Reservoir quantity is a 2.8g electrolyte, after slot rolling seals, shelves under the normal temperature 5 hours, changes into then and sorting process.The technology that changes into sorting is: (1) battery is earlier with 0.1C charging 4 hours; (2) battery after the preliminary charging was shelved in baking oven 24 hours, and temperature is 50 ℃; (3) battery is taken out in baking oven, after waiting to be chilled to normal temperature, to battery charge 6 hours, 0.4C was discharged to 1.0V then with the 0.2C multiplying power; (4) with 0.5C multiplying power charging 3 hours, be discharged to 1.0V with 0.5C then; (5) with 1.0C multiplying power charging 72 minutes, be discharged to 1.0V with 1.0C then.Result such as accompanying drawing 5 and Fig. 6.
Fig. 5 is the β-Ni (OH) in the preparation positive pole 2The specific capacity curve, along with the increase of cycle-index, β-Ni in the positive pole (OH) 2Specific capacity increase gradually, through 100 times the circulation after, β-Ni (OH) 2Specific capacity surpass 270mAh/g.Fig. 6 is the cyclic curve that adopts the battery of the positive pole assembling for preparing, and after 100 circulations, the capacity of battery still is in ascendant trend, and the about 1230mAh/g of battery peak capacity shows and adopts the anodal battery of assembling of the present invention to have good cyclical stability.

Claims (10)

1. the positive electrode of metal hydride one nickel-based battery is made of nickel foam substrate and anodal packing material, and described anodal packing material comprises the spherical β-Ni (OH) of active material 2, adhesive, it is characterized in that described anodal packing material also comprises conductive additive CoSO 47H 2O.
2. the positive electrode of metal hydride-nickel battery as claimed in claim 1 is characterized in that described anodal packing material is made up of the component of following quality proportioning: β-Ni (OH) 2: CoSO 47H 2O: adhesive is 1: 0.05~0.3: 0.012~0.045.
3. the positive electrode of metal hydride-nickel battery as claimed in claim 2 is characterized in that described anodal packing material is made up of the component of following quality proportioning: β-Ni (OH) 2: CoSO 47H 2O: adhesive is 1: 0.15~0.25: 0.015~0.042.
4. as the positive electrode of claim 1 or 2 or 3 described metal hydride-nickel batteries, it is characterized in that described adhesive is mixed with slurry in advance, described slurry is that solid content is that 60% ptfe emulsion and mass concentration are the mixture of 3% sodium carboxymethylcellulose.
5. the positive electrode of metal hydride-nickel battery as claimed in claim 4 is characterized in that described 60% the ptfe emulsion and the mass ratio of 3% sodium carboxymethylcellulose are: 1~5: 20~50.
6. the positive electrode of metal hydride-nickel battery as claimed in claim 5 is characterized in that described 60% the ptfe emulsion and the mass ratio of 3% sodium carboxymethylcellulose are: 1~5: 30~40.
7. a method for preparing the positive electrode of metal hydride-nickel battery as claimed in claim 1 is characterized in that comprising the steps:
1) the preparation adhesive becomes slurry earlier;
2) with CoSO 47H 2O is dissolved in the water, and adds slurry, spherical β-Ni (OH) again 2Mix, get slurry, the amount of described water is spherical β-Ni (OH) 21O~40% of amount;
3) the above-mentioned slurry that obtains is filled in the nickel foam substrate oven dry.
8. the method for the positive electrode of preparation metal hydride-nickel battery as claimed in claim 7 is characterized in that the bake out temperature described in the step (2) is 120~150 ℃.
9. the method for the positive electrode of preparation metal hydride one nickel-based battery as claimed in claim 8 is characterized in that the bake out temperature described in the step (2) is 130 ℃.
10. the method for the positive electrode of preparation metal hydride-nickel battery as claimed in claim 7, it is characterized in that the slurry described in the step (1) is that solid content is 60% the ptfe emulsion and the sodium carboxymethylcellulose mixture of mass concentration 3%, described 60% ptfe emulsion: 3% sodium carboxymethylcellulose 1~5: 20~50.
CNB2005100612808A 2005-10-26 2005-10-26 Positive electrode material of metal hydride-nickel battery and its preparation method Expired - Fee Related CN1333480C (en)

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JP3287165B2 (en) * 1995-02-28 2002-05-27 松下電器産業株式会社 Manufacturing method of nickel positive electrode for alkaline storage battery
JP4454052B2 (en) * 1998-02-23 2010-04-21 パナソニック株式会社 Method for producing nickel electrode active material for alkaline storage battery, and method for producing nickel positive electrode
JP4496704B2 (en) * 2001-03-05 2010-07-07 株式会社ジーエス・ユアサコーポレーション Manufacturing method of nickel metal hydride battery
CN1237633C (en) * 2002-12-16 2006-01-18 深圳市格林美高新技术有限公司 Additive of electrode material for nickel-hydrogen cell and preparing method thereof
CN1553530A (en) * 2003-05-30 2004-12-08 沈阳浩普科技发展有限公司 Manufacture of cobalt coated spheric nickle hydroxide for power nickle-hydrogen battery

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