CN1320681C - Long time stored nickel-hydrogen battery and mfg. method thereof - Google Patents

Long time stored nickel-hydrogen battery and mfg. method thereof Download PDF

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CN1320681C
CN1320681C CNB2005100348472A CN200510034847A CN1320681C CN 1320681 C CN1320681 C CN 1320681C CN B2005100348472 A CNB2005100348472 A CN B2005100348472A CN 200510034847 A CN200510034847 A CN 200510034847A CN 1320681 C CN1320681 C CN 1320681C
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battery
aqueous solution
coooh
concentration
coating layer
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CN1688062A (en
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李文良
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Shenzhen Highpower Technology Co Ltd
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Shenzhen Highpower Technology Co Ltd
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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 present invention discloses a long stored Ni-H battery which uses Ni (OH) 2 coated with beta-coooh as an active material of an anode sheet, a nonwoven membrane through sulphonation treatment and an alkaline electrolyte containing soluble bromide R<n>Br<m>. The present invention also discloses a making method of the Ni-H battery, which comprises the steps of making the anode and cathode sheets, assembling the battery and forming the battery, wherein in the step of making the anode sheet, the Ni (OH) 2 coated with beta-coooh is prepared firstly, then a current collector is used as a skeleton and a binder is added in for manufacture. Except that the capacity, the internal resistance and the cyclic life performance of the Ni-H battery exceed those of the existing Ni-H battery, the present invention has the obvious characteristics of favorable storage character, over discharge resistance and charge retention. When stored for a year at a normal temperature of 20 (+/-) 5 DEG C, the battery still has voltage of over 1.2V and capacity recovery ratio of 100%. After long-time of short circuit at temperature of 45 DEG C, battery capacity almost has no loss. In addition, the battery enhances the charge retention by 5% to 10% than that of the general Ni-H battery.

Description

A kind of Ni-H cell that can be long time stored and preparation method thereof
Technical field
The battery that the present invention relates to be used for directly to change chemical energy and be electric energy deposit active material manufacturing alkaline battery nickel hydroxide electrode with electrochemical method on carrier, especially relate to a kind of Ni-H cell that can be long time stored and preparation method thereof.
Background technology
Ni-H cell is the high energy alkaline secondary cell of new generation after ickel-cadmium cell, has high power capacity, characteristics such as high-power, pollution-free, is one of important developing direction of current secondary cell.But because the positive and negative electrode material that is adopted is different with ickel-cadmium cell, the mechanism of electrochemical reaction is also different, and Ni-H cell is compared with ickel-cadmium cell, its long time stored poor-performing, and self discharge is obviously greater than ickel-cadmium cell.In long storage process, hydrogen in the hydrogen electrode in the Ni-H cell is easily constantly overflowed from hydrogen-storage alloy and is formed hydrogen, and after these hydrogen were moved to anodal surface, reduction was coated on the conductive layer on NiOOH surface, make to form conductive network and be reduced, cause that electric weight reduces.Simultaneously, conductive network is caused the Ni-H cell capacitance loss by expendable destruction.The positive electrode active materials of existing Ni-H cell generally is with ordinary hydrogen oxidation nickel (OH) 2Be mixed and made into conductive agents such as cobalt powder, cobalt protoxides, anodal is matrix with foaming nickel.Cobalt protoxide is the best conductive agent of present effect, and it can progressively dissolve in alkaline electrolyte, separate out, and is formed with β-Co (OH) 2The Ni of coating layer (OH) 2, again through the oxidation of overcharging at Ni (OH) 2The surface form hydroxy cobalt oxide β-CoOOH coating layer, but in oxidizing process, β-Co (OH) 2Major part change into β-CoOOH, also have fraction to change into Co (OH) 3, because the current density of inside battery each point is inhomogeneous, the thickness and the density of β-CoOOH coating layer are also inequality, cause the conductive network skewness, and Co (OH) 3Anti-reducing power not as β-CoOOH, battery is being deposited in the process for a long time, Co (OH) 3Constantly be reduced into β-Co (OH) 2, can cause that also electric weight reduces, cause that conductive network is destroyed, reduce the recoverable capacity ratio of battery.
Summary of the invention
The technical problem to be solved in the present invention is the defective that overcomes prior art, propose a kind of higher retention of charge is arranged, have that good anti-mistake puts that performance and capacity can not lose can be long time stored Ni-H cell.
Another technical problem that the present invention will solve is the defective that overcomes prior art, proposes a kind of manufacture method of Ni-H cell that can be long time stored.
For Ni-H cell that can be long time stored of the present invention, above-mentioned technical problem is solved like this:
This Ni-H cell that can be long time stored comprises positive plate, negative plate, is in the electrolyte of barrier film, housing and injection housing between the positive/negative plate.
The characteristics of this Ni-H cell that can be long time stored are:
The active material of positive plate is the hydroxide nickel (OH) of cladding hydroxy cobalt oxide β-CoOOH 2Use the cladding hydroxy cobalt oxide (Ni (OH) of β-CoOOH) 2As the active material of positive plate, no longer add other conductive agents and make Ni-H cell, this battery has improved retention of charge, Ni in storage process (OH) 2Coating layer β-CoOOH the conductive network on surface can be not destroyed, has long time storedly, and the characteristics that good anti-mistake is put performance can not lost, be had to battery capacity.
For Ni-H cell that can be long time stored of the present invention, above-mentioned technical problem can be solved so according to qualifications:
Described barrier film is the non-weaving cloth barrier film of handling through oversulfonate, to reach long time stored effect.It is a kind of hydrophilic treated that sulfonation is handled, the barrier film possess hydrophilic property of handling through oversulfonate is good, the advantage that self discharge is little, the good hydrophilic property of barrier film helps battery in the long-term storage or the course of work, the conservation rate of diaphragm electrolyte, help keeping the utilance of active material, Ni-H cell deposit or the course of work in, the impurity NH in the barrier film 2Meeting of-ion and Ni (OH) 2React, cause the Ni (OH) that reacts 2Lost efficacy, caused that battery reduced recoverable capacity ratio, and the impurity NH in the barrier film that oversulfonate is handled 2-ion concentration is lower than the barrier film that adopts other processing methods, helps improving the self-discharge performance of battery.
Described electrolyte is to comprise soluble bromide R nBr mAlkaline electrolyte, with the long time stored performance that improves battery with recycle performance.Bromide ion can effectively stop hydrogen-storage alloy powder excessively oxidated, the hydrogen storage capacity of protection hydrogen-storage alloy powder.
For Ni-H cell that can be long time stored of the present invention, above-mentioned technical problem can further be solved like this:
It is that oleum is handled, chlorosulfonic acid is handled that described sulfonation is handled, or anhydrous slufuric acid is handled.
Described non-weaving cloth is the non-weaving cloth that the polyalkenes fiber is made.
Described polyalkenes fiber is a polypropylene fibre, or polyethylene fibre.
The soluble bromide R that described electrolyte comprises nBr mBe KBr, NaBr, NiBr 2, or CoBr 2
Described electrolyte is proportioning according to the ratio of mole is KOH: LiOH: NaOH: R nBr m=(5～8): (0.1～1.0): (0.1～3.0): the aqueous solution of (0.001～0.100).
For the manufacture method of Ni-H cell that can be long time stored of the present invention, above-mentioned technical problem is solved like this:
The characteristics of the manufacture method of this Ni-H cell that can be long time stored are that following steps are arranged successively:
(1) make positive and negative plate:
The Ni (OH) for preparing coating beta-CoOOH earlier 2, adopt the Ni (OH) of coating beta-CoOOH again 2, be that skeleton adds binding agent making positive plate with the collector;
With the collector is that skeleton adds binding agent making negative plate;
(2) assembled battery: the collocation of moulding positive and negative plate and barrier film is packed into behind the battery case, through annotating electrolyte, sealing;
(3) battery changes into: the battery after will sealing, the time that ageing is set under the temperature of setting.
For the manufacture method of Ni-H cell that can be long time stored of the present invention, above-mentioned technical problem can be solved so according to qualifications:
The Ni of described preparation coating beta-CoOOH (OH) 2Following steps are arranged successively:
(1) under 45 ℃～50 ℃ of temperature, ratio according to mole is Ni: Co: Zn=1: (0.02～0.05): (0.04～0.08), the cobalt sulfate solution of the zinc sulfate solution of the nickel sulfate solution of concentration 2.8mol/L～3.0mol/L, concentration 2.8mol/L～3.0mol/L and concentration 2.8mol/L～3.0mol/L is injected reactor respectively to be mixed, little by little drip the sodium hydrate aqueous solution of concentration 3mol/L～5mol/L then, with pH value stabilization to 13～14, under constantly stirring, make nickel, zinc, the whole crystallizations of cobalt ions;
(2) cobalt sulfate solution with concentration 2.8mol/L～3.0mol/L adds in the reactor gradually, the cobalt addition be nickel mole 4.6%～5.4%, with pH value stabilization to 9～10, make the cobalt ions crystallization coat Ni (OH) 2The surface with deionized water wash hydroxide repeatedly, makes the pH value change into 7～8 again, dewaters then, dries and made β-Co (OH) 2The zincification Ni (OH) of coating layer 2
(3) be that the NaOH aqueous solution of 68wt～72wt% drops to the above-mentioned β of having-Co (OH) with concentration 2The zincification Ni (OH) of coating layer 2In, after complete haptoreaction took place for both under constantly stirring, the consumption that makes the NaOH aqueous solution was above-mentioned prepared β-Co (OH) 2The zincification Ni (OH) of coating layer 2Weight 8%～12%, in the heat baking 1.2 hours～1.8 hours down of 90 ℃～110 ℃ of temperature, make β-Co (OH) 2Coating layer is oxidized to β-CoOOH coating layer, at last with deionized water wash and to adjust the pH value be 7～8, dewaters, dries the Ni (OH) that makes coating beta-CoOOH again 2
The assembling of described battery is that the collocation of the positive and negative plate that will make and barrier film is packed into behind the battery case, and through annotating electrolyte, sealing and make Ni-H cell, electrolyte is to comprise soluble bromide R nBr mAlkaline electrolyte, with the long time stored performance that improves battery with recycle performance.
Changing into of described battery is with the battery after sealing, and ageing is 1～10 day under the temperature of setting.
Described barrier film is the non-weaving cloth barrier film of handling through oversulfonate.To reach long time stored effect.
For the manufacture method of Ni-H cell that can be long time stored of the present invention, above-mentioned technical problem can further be solved like this:
It is that oleum is handled, chlorosulfonic acid is handled that described sulfonation is handled, or anhydrous slufuric acid is handled.
Described non-weaving cloth is the non-weaving cloth that the polyalkenes fiber is made.
Described polyalkenes fiber is a polypropylene fibre, or polyethylene fibre.
Described electrolyte is proportioning according to the ratio of mole is KOH: LiOH: NaOH: R nBr m=(5～8): (0.1～1.0): (0.1～3.0): the aqueous solution of (0.001～0.100).
Described binding agent is a kind of or any two or more mixture of the polytetrafluoroethylene PTFE aqueous solution, the CMC CMC aqueous solution, the hydroxypropyl methylcellulose HPMC aqueous solution, the PVAC polyvinylalcohol L aqueous solution, the Sodium Polyacrylate PAAS aqueous solution, the styrene butadiene rubber sbr aqueous solution.
The present invention adopts the Ni (OH) of coating beta-CoOOH 2The Ni-H cell of making has good comprehensive performances.Except that capacity, internal resistance, cycle life performance surpassed existing Ni-H cell, its outstanding feature was that battery has good storage, good anti-over-discharge property and retention of charge.Stored 1 year down 20 ± 5 ℃ of normal temperature, cell voltage is still more than 1.2V, and the capacity restoration rate reaches 100%; After 45 ℃ of following long-time short circuits of temperature, battery capacity is not loss almost; In addition, this battery charge hold facility improves 5%～10% than general Ni-H cell.
Embodiment
A kind of capacity be 2000mAh can be long time stored AA type Ni-H cell, comprise that adopting copper mesh is that skeleton carries out soaking moments later the negative pole of oven dry, cutting moulding again after dry powder filling, the roll-in in binding agent, the non-weaving cloth barrier film that moulding positive and negative plate and the polypropylene fibre of handling through oversulfonate are made is rolled into tubular and packs into behind the battery case, through annotating electrolyte, sealing and make, the active material of its positive plate is the Ni of coating beta-CoOOH (OH) 2
The manufacture method of this Ni-H cell that can be long time stored comprises making, the assembling of battery and the changing into of battery of positive and negative plate.
The making of described positive plate is the Ni (OH) for preparing coating beta-CoOOH earlier 2, take following steps successively:
Under 48 ℃ of temperature, ratio according to mole is Ni: Co: Zn=1: 0.04: 0.06, the cobalt sulfate solution of the zinc sulfate solution of the nickel sulfate solution of concentration 2.9mol/L, concentration 2.9mol/L and concentration 2.9mol/L is injected reactor respectively to be mixed, little by little drip the sodium hydrate aqueous solution of concentration 4mol/L then, with pH value stabilization to 13～14, under constantly stirring, make nickel, zinc, the whole crystallizations of cobalt ions;
Cobalt sulfate solution with concentration 2.9mol/L adds in the reactor gradually then, the cobalt addition be nickel mole 5.0%, with pH value stabilization to 9～10, make the cobalt ions crystallization coat Ni (OH) 2The surface with deionized water wash hydroxide repeatedly, makes the pH value change into 7～8 again, dewaters then, dries and made β-Co (OH) 2The zincification Ni (OH) of coating layer 2
With concentration is that the NaOH aqueous solution of 70wt% drops to the above-mentioned β of having-Co (OH) 2The zincification Ni (OH) of coating layer 2In, after complete haptoreaction took place for both under constantly stirring, the consumption that makes the NaOH aqueous solution was above-mentioned prepared β-Co (OH) 2The zincification Ni (OH) of coating layer 2Weight 10%, in the heat baking 1.5 hours down of 100 ℃ of temperature, make β-Co (OH) 2Coating layer is oxidized to β-CoOOH coating layer, at last with deionized water wash and to adjust the pH value be 7～8, dewaters, dries the Ni (OH) that makes coating beta-CoOOH again 2
Adopt the Ni (OH) of coating beta-CoOOH again 2, be that skeleton carries out the dry powder embedding and oozes with foaming nickel collector, be rolled into pole piece after, in the polytetrafluoroethylene PTFE aqueous solution, soak moments later oven dry again, be cut into positive plate at last.
The making of described negative plate is to be that skeleton carries out dry powder and fills with the copper mesh collector, be rolled into pole piece after, in the polytetrafluoroethylene PTFE aqueous solution, soak moments later oven dry again, be cut into negative plate at last.
The assembling of described battery, be that positive and negative plate and the barrier film that will make is rolled into tubular, pack into behind the battery case, through annotating electrolyte, sealing and make Ni-H cell, it is KOH: LiOH: NaOH: KBr=6 according to the ratio of mole that electrolyte adopts proportioning: 0.5: 2: 0.05 the aqueous solution.
Changing into of described battery was with the battery after sealing, 45 ℃ of following ageings of temperature 24 hours.
And with existing Ni (OH) 2The making capacity is the method for the common AA type Ni-H cell of 2000mAh, it is that positive electrode active materials adopts common zincification nickel hydroxide that its positive plate is made, with foaming nickel is skeleton, add the cobalt protoxide of 5wt%, adopt dry powder embedding infiltration method, after being rolled into pole piece again, be dried into positive plate once again in the polytetrafluoroethylene PTFE aqueous solution soaking.The making of negative plate is identical with the specific embodiment of the present invention with the assembling of battery, but the barrier film that uses is the non-weaving cloth of making through the polypropylene fibre of fluorination treatment, and changing into of battery is with behind the battery seal, deposited at normal temperatures 24 hours, (C is the charge-discharge magnification of battery to battery with 0.1C, as follows) charged 3 hours, under 45 ℃ of temperature, deposited 24 hours then, battery with 0.1C charging 15 hours, is discharged to 1.0V with 0.5C again, changes with 0.2C to be discharged to 1.0V, again with 0.5C charging 2.5 hours, be discharged to 1.0V with 0.5C, change with 0.2C again and be discharged to 1.0V, finish changing into of battery.
Below with experimental data explanation battery of the present invention and existing Ni (OH) 2The making capacity is the performance difference of the common AA type Ni-H cell of 2000mAh.
Experiment requires the test battery capacity according to IEC61951-2, GB/T15100-2003's.After battery has been put electricity, adopt AC impedence method to require the test battery internal resistance according to IEC61951-2GB, T15100-2003.
Adopt 1C to charge and discharge the acceleration cycle test battery life-span, the termination capacity is 80% of an initial capacity, and the battery life test result sees Table 1:
Table 1
Storage at normal temperature is test capacity recovery ratio after 1 year: battery was charged 16 hours with 0.1C, be discharged to 1.0V with 0.2C, 0.1C charge 16 hours, after 20 ± 5 ℃ of normal temperature are stored 1 year down, battery is charged with 0.1C, be discharged to 1.0V with 0.2C, storage at normal temperature after 1 year capacity restoration ratio test result see Table 2:
Table 2
The invention scheme The contrast scheme
The battery sequence number 1A 2A 3A 1B 2B 3B
Final cell voltage 1.221 1.227 1.224 1.154 1.148 1.151
Capacity (mAh) before storing 2031.5 2054.3 2014.7 2028.4 2017.3 2047.5
Store back capacity (mAh) 2023.4 2050.2 2002.6 1738.4 1736.9 1750.6
The capacity restoration rate 99.6％ 99.8％ 99.4％ 85.7％ 86.1％ 85.5％
Average recovery rate 99.6％ 85.8％
Short-circuit test capacity restoration ratio: battery was charged 16 hours with 0.1C, be discharged to 1.0V with 0.2C, again with 0.1C charging 16 hours, battery connects 2 Ω resistance, in 45 ℃ of following short circuits of temperature after 7 days, battery with 0.1C charging 16 hours, is discharged to 1.0V with 0.2C, and capacity of short circuit is recovered the ratio test result and is seen Table 3:
Table 3
The invention scheme The contrast scheme
The battery sequence number 1A 2A 3A 1B 2B 3B
Initial capacity (mAh) 2042.6 2061.2 2038.4 2031.3 2018.2 2026.4
First week after the short circuit Capacity (mAh) 2020.1 2011.7 2018.0 1661.6 1638.8 1639.4
The capacity restoration rate 98.9％ 97.6％ 99.0％ 81.8％ 81.2％ 80.9％
Second week after the short circuit Capacity (mAh) 2034.4 2036.5 2030.2 1647.4 1640.8 1653.5
The capacity restoration rate 99.6％ 98.8％ 99.6％ 81.1％ 81.3％ 81.6％
The 3rd week after the short circuit Capacity (mAh) 2058.9 2055.0 2052.7 1655.5 1644.8 1645.4
The capacity restoration rate 99.8％ 99.7％ 99.7％ 81.5％ 81.5％ 81.2％
The test retention of charge: battery with 0.1C charging 16 hours, is discharged to 1.0V with 0.2C, again with 0.1C charging 16 hours, after 20 ± 5 ℃ of normal temperature are stored 28 days down battery is discharged to 1.0V with 0.2C, the battery remaining power test result sees Table 4:
Table 4
The invention scheme The contrast scheme
The battery sequence number 1A 2A 3A 1B 2B 3B
Initial capacity (mAh) 2049.1 2071.6 2064.3 2035.4 2026.5 2041.2
Residual capacity (mAh) 1749.9 1783.6 1771.2 1540.8 1517.8 1539.1
The residual capacity ratio 85.4％ 86.1％ 85.8％ 15.7％ 74.9％ 75.4％
Average proportions 84.53％ 75.33％
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of being submitted to.

Claims (5)

  1. One kind can be long time stored Ni-H cell, comprise positive plate, negative plate, be in the electrolyte of barrier film, housing and injection housing between the positive/negative plate, it is characterized in that:
    The active material of positive plate is the hydroxide nickel (OH) of cladding hydroxy cobalt oxide β-CoOOH 2, the Ni of described coating beta-CoOOH (OH) 2Adopt the following steps preparation successively:
    1) under 45 ℃～50 ℃ of temperature, ratio according to mole is Ni: Co: Zn=1: (0.02～0.05): (0.04～0.08), the cobalt sulfate solution of the zinc sulfate solution of the nickel sulfate solution of concentration 2.8mol/L～3.0mol/L, concentration 2.8mol/L～3.0mol/L and concentration 2.8mol/L～3.0mol/L is injected reactor respectively to be mixed, little by little drip the sodium hydrate aqueous solution of concentration 3mol/L～5mol/L then, with pH value stabilization to 13～14, under constantly stirring, make nickel, zinc, the whole crystallizations of cobalt ions;
    2) cobalt sulfate solution with concentration 2.8mol/L～3.0mol/L adds in the reactor gradually, the cobalt addition be nickel mole 4.6%～5.4%, with pH value stabilization to 9～10, make the cobalt ions crystallization coat Ni (OH) 2The surface with deionized water wash hydroxide repeatedly, makes the pH value change into 7～8 again, dewaters then, dries and made β-Co (OH) 2The zincification Ni (OH) of coating layer 2
    3) be that the NaOH aqueous solution of 68wt～72wt% drops to the above-mentioned β of having-Co (OH) with concentration 2The zincification Ni (OH) of coating layer 2In, after complete haptoreaction took place for both under constantly stirring, the consumption that makes the NaOH aqueous solution was above-mentioned prepared β-Co (OH) 2The zincification Ni (OH) of coating layer 2Weight 8%～12%, in the heat baking 1.2 hours～1.8 hours down of 90 ℃～110 ℃ of temperature, make β-Co (OH) 2Coating layer is oxidized to β-CoOOH coating layer, at last with deionized water wash and to adjust the pH value be 7～8, dewaters, dries the Ni (OH) that makes coating beta-CoOOH again 2
  2. 2. according to the described Ni-H cell that can be long time stored of claim 1, it is characterized in that:
    Described electrolyte is to comprise soluble bromide KBr, NaBr, NiBr 2Or CoBr 2Alkaline electrolyte.
  3. One kind can be long time stored the manufacture method of Ni-H cell, it is characterized in that: following steps are arranged successively:
    (1) make positive and negative plate:
    The Ni (OH) for preparing coating beta-CoOOH earlier 2, adopt the Ni (OH) of coating beta-CoOOH again 2, be that skeleton adds binding agent making positive plate, the Ni of described preparation coating beta-CoOOH (OH) with the collector 2Following steps are arranged successively:
    1) under 45 ℃～50 ℃ of temperature, ratio according to mole is Ni: Co: Zn=1: (0.02～0.05): (0.04～0.08), the cobalt sulfate solution of the zinc sulfate solution of the nickel sulfate solution of concentration 2.8mol/L～3.0mol/L, concentration 2.8mol/L～3.0mol/L and concentration 2.8mol/L～3.0mol/L is injected reactor respectively to be mixed, little by little drip the sodium hydrate aqueous solution of concentration 3mol/L～5mol/L then, with pH value stabilization to 13～14, under constantly stirring, make nickel, zinc, the whole crystallizations of cobalt ions;
    2) cobalt sulfate solution with concentration 2.8mol/L～3.0mol/L adds in the reactor gradually, the cobalt addition be nickel mole 4.6%～5.4%, with pH value stabilization to 9～10, make the cobalt ions crystallization coat Ni (OH) 2The surface with deionized water wash hydroxide repeatedly, makes the pH value change into 7～8 again, dewaters then, dries and made β-Co (OH) 2The zincification Ni (OH) of coating layer 2
    3) be that the NaOH aqueous solution of 68wt～72wt% drops to the above-mentioned β of having-Co (OH) with concentration 2The zincification Ni (OH) of coating layer 2In, after complete haptoreaction took place for both under constantly stirring, the consumption that makes the NaOH aqueous solution was above-mentioned prepared β-Co (OH) 2The zincification Ni (OH) of coating layer 2Weight 8%～12%, in the heat baking 1.2 hours～1.8 hours down of 90 ℃～110 ℃ of temperature, make β-Co (OH) 2Coating layer is oxidized to β-CoOOH coating layer, at last with deionized water wash and to adjust the pH value be 7～8, dewaters, dries the Ni (OH) that makes coating beta-CoOOH again 2
    With the collector is that skeleton adds binding agent making negative plate;
    (2) assembled battery: the collocation of moulding positive and negative plate and barrier film is packed into behind the battery case, through annotating electrolyte, sealing;
    (3) battery changes into: the battery after will sealing, the time that ageing is set under the temperature of setting.
  4. 4. according to the manufacture method of the described Ni-H cell that can be long time stored of claim 3, it is characterized in that:
    Described electrolyte is proportioning according to the ratio of mole is KOH: LiOH: NaOH: (KBr, NaBr, NiBr 2Or CoBr 2)=(5～8): (0.1～1.0): (0.1～3.0): the aqueous solution of (0.001～0.100).
  5. 5. according to the manufacture method of the described Ni-H cell that can be long time stored of claim 4, it is characterized in that:
    Described binding agent is a kind of or any two or more mixture of the polytetrafluoroethylene PTFE aqueous solution, the CMC CMC aqueous solution, the hydroxypropyl methylcellulose HPMC aqueous solution, the PVAC polyvinylalcohol L aqueous solution, the Sodium Polyacrylate PAAS aqueous solution, the styrene butadiene rubber sbr aqueous solution.
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CN101794913A (en) * 2010-03-23 2010-08-04 欧阳宁 Maintenance-free nickel/metal hydride (MH-Ni) battery and manufacturing method thereof
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