CN105390755B - A kind of Ni-MH battery and preparation method thereof - Google Patents

A kind of Ni-MH battery and preparation method thereof Download PDF

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CN105390755B
CN105390755B CN201510746318.9A CN201510746318A CN105390755B CN 105390755 B CN105390755 B CN 105390755B CN 201510746318 A CN201510746318 A CN 201510746318A CN 105390755 B CN105390755 B CN 105390755B
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battery
nickel
electrode
hydrogen
nickel foam
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CN105390755A (en
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马国锋
曹远麟
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HENGYANG BST POWER Co Ltd
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HENGYANG BST POWER Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

Abstract

Ni-MH battery disclosed by the invention, including iron-clad and the nickel electrode in iron-clad, hydrogen electrode, diaphragm, electrolyte, for nickel electrode by nickel foam as basis material, nickel foam inner space is filled with positive active material Ni (OH)2, conductive agent, additive and bonding agent；Hydrogen electrode is coated with negative electrode active material hydrogen-storage alloy powder, conductive agent, additive and bonding agent by porous nickel plated steel strip or copper mesh or nickel foam as basis material, porous nickel plated steel strip or copper mesh or nickel foam；Electrolyte is rich potassium type alkaline aqueous solution and sodium tungstate or the mixture of wolframic acid crystal.The invention also discloses the preparation methods of the Ni-MH battery.Ni-MH battery disclosed by the invention is under 45 DEG C of environment, and the ratio between 0.2C discharge capacities and room temperature capacity reach as high as under 70~80%, 70 DEG C of environment, and the ratio between Ni-MH battery 0.2C discharge capacities and room temperature capacity reach as high as 85~95%.And preparation method is simple, is suitble to large-scale production.

Description

A kind of Ni-MH battery and preparation method thereof
Technical field
The present invention relates to field of batteries, more particularly to a kind of Ni-MH battery and preparation method thereof.
Background technology
Ni-MH battery have high energy ratio, service life is long, operating temperature is wide, pollution-free, memory-less effect and it is extensive Using.But use environment temperature is generally within the scope of -20 DEG C~50 DEG C, and according to domestic and foreign literature, under -20 DEG C of environment, The ratio between Ni-MH battery discharge capacity and room temperature capacity reach as high as 65~75%, -40 DEG C or hereinafter, battery can not put electricity substantially； Under 50 DEG C of environment, the ratio between Ni-MH battery discharge capacity and room temperature capacity reach as high as 90~95%, but with temperature rise, battery Discharge capacity declines to a great extent, and at 70 DEG C, discharge capacity is only the 40~50% of battery room temperature discharge capacity.Make it in some spies Use under different environment is limited, such as Military Electronic Equipment power supply, communication signal terminal, field work electric tool side Face, the complicated variety of use environment had not only required under low temperature (such as -45 DEG C) environment, but also need to meet at high temperature (such as 70 DEG C) Use under environment widens the application field of Ni-MH battery to meet market needs, it is necessary to develop a kind of Ni-MH battery It can normal use under -45 DEG C~70 DEG C ultra-wide temperature environments.
Invention content
In order to solve the problems in the prior art, one of the objects of the present invention is to provide a kind of Ni-MH batteries.
The second object of the present invention is the production method for providing above-mentioned Ni-MH battery.
The technical scheme is that：Physics incorporation rare earth oxide or transition metal oxide, carry in anode formula High battery charge efficiency in a high temperauture environment；Cathode is using the AB5 types for inhaling the moderate addition special elements of hydrogen desorption plateau pressure Hydrogen storing alloy powder, and Rare-earth oxide additives are added, to improve cathode electro-chemical activity and cycle life；Diaphragm is using high-end The polyethylene or polypropylene that the alkalis suction quantity of import carboxyl grafting processing or sulfonation processing is big, good permeability and resistance to alkali ability are strong；Electricity Solution liquid selects the alkaline aqueous solution that 3 kinds of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide are configured to, and adds Enter sodium tungstate or wolframic acid crystal, controls its concentration in 0.01~0.5mol/L.Meanwhile in production method, welded using end face Technique, and by the application to current collecting plates and nickel foam heelpiece, enhance the conductive effect of positive and negative electrode, greatly reduce battery Europe Nurse internal resistance.The implementation of above scheme makes Ni-MH battery being capable of normal use under -45 DEG C~70 DEG C ultra-wide temperature environments.
Ni-MH battery as first aspect present invention comprising iron-clad and nickel electrode in iron-clad, hydrogen electrode, Diaphragm, electrolyte, it is characterised in that：
For the nickel electrode by nickel foam as basis material, the nickel foam inner space is filled with positive active material Ni (OH)2, conductive agent, additive and bonding agent；
The hydrogen electrode by porous nickel plated steel strip or copper mesh or nickel foam as basis material, the porous nickel plated steel strip or Copper mesh or nickel foam are coated with negative electrode active material hydrogen-storage alloy powder, conductive agent, additive and bonding agent；
The electrolyte is rich potassium type alkaline aqueous solution and sodium tungstate or the mixture of wolframic acid crystal.In the electrolyte by In a large amount of presence of potassium ion, the solidification point and viscosity of electrolyte are can obviously reduce, the movement velocity of ion is made to accelerate, to Improve conductivity under cryogenic.Sodium tungstate can form one layer of clad in nickel positive electrode surface, be analysed when can increase charging The polarization overpotential of oxygen reaction, and then improve high temperature compression part, moreover it is possible to the selfdecomposition process for preventing nickel positive electrode makes battery The service life for extending battery more times can be recycled.
In a preferred embodiment of the invention, the positive active material Ni (OH) in the nickel electrode2It was preparing Zinc, cobalt are co-deposited in journey.
In a preferred embodiment of the invention, the Zn content is between 3~7wt%, cobalt content 1.5~ Between 5wt%.
In a preferred embodiment of the invention, the positive active material Ni (OH) in the nickel electrode2Gram specific capacity In 210~230mAh/g, granularity is at 5~12 μm.
In a preferred embodiment of the invention, the conductive agent in the nickel electrode be cobalt protoxide, hydroxide cobalt, One or more of mixtures of cobalt carbonate, cobalt powder, nickel powder, carbon nanotube.
In a preferred embodiment of the invention, the additive in the nickel electrode is calcirm-fluoride, erbium oxide, oxidation Yttrium, titanium oxide, zirconium oxide, one or more of mixtures of thallium oxide make input to increase positive oxygen evolution reaction overpotential Energy is more used for β-Ni (OH)2It is oxidized to the charging reaction of β-NiOOH, inhibits OH-It is oxidized to O2Side reaction, to carry High battery charge efficiency in a high temperauture environment.
In a preferred embodiment of the invention, the bonding agent in the nickel electrode is sodium carboxymethylcellulose and poly- four The combination of vinyl fluoride.
In a preferred embodiment of the invention, the expression of the negative electrode active material hydrogen-storage alloy powder in the hydrogen electrode Formula is MLNi3.55Co0.75Mn0.4Al0.3X, wherein the X be meet property addition element, selected from Y, Dy, Sn, B, Si, At least one of Ti, V, Cr, the ML are the rich La mischmetals of La, Ce, Pr, Nd element composition.
In a preferred embodiment of the invention, the amount of the element X be the hydrogen-storage alloy powder 0.1~ 0.5wt%.
In a preferred embodiment of the invention, gram specific capacity of the hydrogen-storage alloy powder is in 300~320mAh/g, grain Diameter is at 35~50 μm.
In a preferred embodiment of the invention, the conductive agent in the hydrogen electrode is selected from nickel powder, superconduction carbon black, carbon and receives One or more of mixtures of mitron, are significantly greatly increased cathode electron conduction, reduce cathode in ultralow temperature and heavy-current discharge Under polarization, cathode electrochemical catalysis performance also can be improved.
In a preferred embodiment of the invention, the additive in the hydrogen electrode is terbium oxide, yttrium oxide, dysprosia One or more of mixtures of equal rare earth oxides, to improve cathode electrochemical catalysis performance and circulating battery stability.
In a preferred embodiment of the invention, the bonding agent in the hydrogen electrode be sodium carboxymethylcellulose or The combination of polyvinyl alcohol or Sodium Polyacrylate and styrene-butadiene emulsion.
In a preferred embodiment of the invention, the diaphragm is using high-end import carboxyl grafting processing or sulfonation processing Alkalis suction quantity is big, good permeability and the strength polyethylene of resistance to alkali ability or polypropylene, thickness are 0.15 ± 0.01mm.
In a preferred embodiment of the invention, a concentration of the 0.01 of the sodium tungstate in the electrolyte or wolframic acid crystal ~0.5mol/L.
In a preferred embodiment of the invention, the rich potassium type alkaline aqueous solution in the electrolyte is to use hydroxide It is 1.30~1.35g/cm that potassium, sodium hydroxide, lithium hydroxide, purified water, which are configured to density,3、OH-Molar concentration be 8.5~ The rich potassium type alkaline aqueous solution of 9.2mol/L.
The production method of Ni-MH battery as second aspect of the present invention, includes the following steps：
(1) making of nickel electrode：
(1.1) positive active material Ni (OH) is prepared2
Using complexed-precipitation method, under the conditions of existing for a certain concentration ammonium hydroxide, by certain density sodium hydroxide solution and Hybrid reaction, control ph are reacted 8~11 under stiring for certain density nickel sulfate, zinc sulfate, cobaltous sulfate mixing salt solution For temperature at 40~70 DEG C, the reaction time is 12~14h, and digestion time is 12~14h, obtains green Ni (OH)2Precipitation is poured out anti- Answer liquid, static layering to be washed with distilled water after outwelling supernatant, and be dried at 120 DEG C moisture content≤0.5% to get To positive active material Ni (OH)2；
(1.2) positive active material Ni (OH) prepared by step (1.1) is pressed288~92%, conductive agent 5~7%, addition Agent 1~2%, the weight percent of bonding agent 2~4% are simultaneously added appropriate pure water input stirrer for mixing slurry are uniformly made, Slurry material is filled into nickel foam conducting base by wet method slurry technique again, and apart from nickel foam conducting base top The part of 0.5~2.5mm is not filled with material, and roll-in after drying, above-mentioned packing material and nickel foam are collectively formed nickel electrode and control Thickness of electrode processed is 0.37 ± 0.01mm, and the nickel foam part for being not filled with material is reserved nickel foam part, cuts into institute The size needed；
(2) making of hydrogen electrode：By hydrogen-storage alloy powder 94~97%, conductive agent 1.5~2.5%, additive 1~2% glues It connects the weight percent of agent 2~4% and appropriate pure water input stirrer for mixing is added and slurry is uniformly made, then drawn by wet method Slurry is coated on the porous nickel plated steel strip of conducting base or copper mesh or nickel foam by sizing process, and apart from the porous nickel plating of conducting base The part of steel band or copper mesh or 0.5~2.5mm of nickel foam lower end are not coated by material, it is dry after roll-in, above-mentioned coating material and lead Hydrogen electrode is collectively formed in electric matrix porosity nickel plated steel strip or copper mesh or nickel foam and coordination electrode thickness is 0.26 ± 0.01mm, institute It is reserved white edge part to state and be not filled with the conducting base part of material, cuts into required size；
(3) preparation of electrolyte
It is 1.30~1.35g/cm to be configured to density with potassium hydroxide, sodium hydroxide, lithium hydroxide3、OH-Molar concentration is The aqueous solution of 8.5~9.2mol/L after being cooled to room temperature, adds sodium tungstate or wolframic acid crystal, control its concentration 0.01~ 0.5mol/L is stirred continuously, and is allowed to be completely dissolved, that is, the alkaline electrolyte containing sodium tungstate or wolframic acid is made；
(4) battery assembles：Nickel electrode, hydrogen electrode and the membrane winding of the step of prepared by step (1) (2) preparation are simultaneously implanted into In box hat, the reserved nickel foam part in nickel electrode is set to protrude diaphragm in upper end, and connect by current collecting plates and battery cap It connects, the reserved white edge part on hydrogen electrode protrudes from diaphragm lower end, and passes through a nickel foam heelpiece and the box hat bottom Connection, according to electrolyte prepared by battery capacity injection step (3), Ni-MH battery is made in sealing.
In a preferred embodiment of the invention, the current collecting plates be nickel plating steel disc, thickness 0.15~0.20mm it Between.
In a preferred embodiment of the invention, between 0.6~1.0mm, shape is the nickel foam heelpiece thickness Circle, it is consistent with box hat bottom area, and box hat bottom is previously placed in by spot welding mode.
In a preferred embodiment of the invention, the electrolyte addition of each battery is 1.5~2.4g/Ah.
In a preferred embodiment of the invention, in the step (1.1), the ammonium hydroxide a concentration of 0.5~ 5.0mol/L, a concentration of 0.5~2.0mol/L, a concentration of 0.01- of zinc ion of nickel ion in the mixing salt solution 0.2mol/L, a concentration of 0.005~0.1mol/L of cobalt ions, a concentration of 0.5~5.0mol/L of the sodium hydroxide solution.
Compared with prior art, the invention has the advantages that：
(1) use environment temperature range is wide.Under -45 DEG C~70 DEG C ultra-wide temperature environments can normal use, meet Requirement under various complicated, under -45 DEG C of environment, the ratio between Ni-MH battery 0.2C discharge capacities and room temperature capacity highest Up under 70~80%, 70 DEG C of environment, the ratio between Ni-MH battery 0.2C discharge capacities and room temperature capacity reach as high as 85~95%.
(2) internal resistance is small, output power is high.The battery afflux structure design of the present invention, using end face welding procedure, nickel electrode Upper end reserve nickel foam part and protrude diaphragm, and connect with battery cap by current collecting plates, enhancing positive conductive ability；And Box hat bottom by the strong nickel foam heelpiece of the preset conductive capability of spot welding mode, the lower end of hydrogen electrode reserve white edge part protrusion every Film paper, and connect with box hat bottom by nickel foam heelpiece, negative conductive effect is enhanced, the two combines and greatly reduces battery Electronics rapidly simultaneously can uniformly, rapidly be distributed in nickel electrode from cathode export, reduces electronic conduction resistance by ohmic internal resistance The anti-reaction speed to entire electrode makes battery have higher output power.
(3) self discharge is small, has extended cycle life.Our experiments show that ni-mh D6000mAh 1C charge the 10C discharge cycles service life More than 600 times, the self discharge after 45 DEG C of high temperature is shelved 7 days is less than 15%.
The battery integrated performance index of the present invention has been more than international IEC and country to main as defined in height temperature nickel-hydrogen battery Technical indicator is wanted, there is very strong research and economic value.
Description of the drawings
Fig. 1 is the structure sectional view of ultra-wide Ni-MH battery of the present invention.
Fig. 2 is the nickel electrode expanded schematic diagram of ultra-wide Ni-MH battery of the present invention.
Fig. 3 is the hydrogen electrode expanded schematic diagram of ultra-wide Ni-MH battery of the present invention.
Specific implementation mode
Further description is unfolded to the present invention below in conjunction with specific implementation mode.It should be understood that the following embodiments and the accompanying drawings It is only used for that the present invention is illustrated and is not limited to protection scope of the present invention.
Embodiment 1：
Positive active material Ni (OH)2Preparation use complexed-precipitation method, it is a concentration of by a concentration of 2.0mol/L ammonium hydroxide The sodium hydroxide solution and nickel sulfate of 2.0mol/L, zinc sulfate, cobaltous sulfate mixing salt solution and hybrid reaction under stiring, it is described A concentration of 0.911mol/L of nickel ion in mixing salt solution, a concentration of 0.057mol/L of zinc ion, cobalt ions it is a concentration of 0.032mol/L, for control ph 10, temperature obtains green Ni at 50 DEG C, reaction time 12h, digestion time 12h (OH)2Precipitation, pours out reaction solution, static layering is washed with distilled water after outwelling supernatant, and is dried to sample at 120 DEG C Product moisture content≤0.5% is to get to green positive active material Ni (OH)2.The positive active material Ni (OH)2Zn content exists 4.0 ± 0.3wt%, cobalt content is in 2.0 ± 0.3wt%.Its gram of specific capacity is 220mAh/g, and granularity is 8~10 μm.
By positive active material Ni (OH)290.4%, cobalt protoxide 6.0%, calcirm-fluoride 1.0%, sodium carboxymethylcellulose 0.2%, the weight percent of polytetrafluoroethylene (PTFE) 2.4% is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, Slurry material is filled into nickel foam conducting base by wet method slurry technique again, and apart from the portion of nickel foam top 1.5mm Point be not filled with material, it is dry after roll-in, above-mentioned packing material and nickel electrode is collectively formed for nickel foam and coordination electrode thickness is 0.37 ± 0.01mm, the nickel foam part for being not filled with material are reserved nickel foam part, cut into required size, that is, make At required nickel electrode.
It is MLNi that negative electrode active material, which selects expression formula,3.55Co0.75Mn0.4Al0.3The hydrogen-storage alloy powder of B, ML La, Ce, The rich La mischmetals of Pr, Nd element composition, mass percent La65%, Ce15%, Pr10%, Nd10%, element B Amount is the 0.2wt% of the hydrogen-storage alloy powder.Gram specific capacity of the hydrogen-storage alloy powder is 310mAh/g, and grain size is in 40~50 μ m。
By negative electrode active material hydrogen-storage alloy powder 94.6%, nickel powder 2.0%, yttrium oxide 1.0%, sodium carboxymethylcellulose 0.4%, the weight percent of styrene-butadiene emulsion 2.0% is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, then Slurry is coated on porous nickel plated steel strip conducting base by wet method slurry technique, and apart from the porous nickel plated steel strip of conducting base The part of lower end 0.5mm is not coated by material, roll-in, above-mentioned coating material and the common shape of the porous nickel plated steel strip of conducting base after drying It is 0.26 ± 0.01mm at hydrogen electrode and coordination electrode thickness, the conducting base part for being not coated by material is reserved white edge portion Point, required size is cut into, that is, required negative plate is made.
Diaphragm is grafted the polypropylene that the alkalis suction quantity handled is big, good permeability and resistance to alkali ability are strong using high-end import carboxyl 700/70, thickness is 0.15 ± 0.01mm.
It is 1.32 ± 0.01g/ that electrolyte potassium hydroxide, sodium hydroxide, lithium hydroxide and purified water, which are configured to density, cm3、OH-Molar concentration is the alkaline aqueous solution of 8.70 ± 0.05mol/L, and mass percent is：KOH：NaOH：LiOH· H2O：H2O=29：6.09：2.28：66.13, after being cooled to room temperature, wolframic acid sodium crystal is added, controls it in alkaline solution A concentration of 0.05mol/L.
Referring to Fig. 1, above-mentioned nickel electrode, hydrogen electrode and membrane winding at core 100 and are implanted into box hat 200, nickel electrode Nickel foam part 111 (referring to Fig. 2) protrusion diaphragm is reserved in 110 upper end, and is connect with battery cap 400 by current collecting plates 300； White edge part 121 (referring to Fig. 3) protrusion diaphragm is reserved in the lower end of hydrogen electrode 120, and passes through nickel foam heelpiece 500 and box hat 200 Bottom connects.Current collecting plates 300 are nickel plating steel disc, thickness 0.2mm；500 thickness of nickel foam heelpiece is 0.6mm, and shape is circle, It is consistent with 100 bottom area of box hat, and 100 bottom of box hat is previously placed in by spot welding mode.Above-mentioned electrolyte is injected, according to electricity The electrolyte addition of tankage, each battery is 1.5~2.6g/Ah.For raising ion diffusion flux, extend battery life, Here D6000mAh Ni-MH batteries are made in value 2.4g/Ah, sealing.
Electric performance test method is as follows：
At ambient temperature, 0.2C fills 7 hours, shelves 30min, is then discharged to 1.0V with 0.2C again, and as battery is normal Warm discharge capacity C0；
It is placed 16~24 hours at set point of temperature (- 45 ± 2) DEG C or (70 ± 2) DEG C, is then filled 7 hours, put with 0.2C 30min is set, then 1.0V is discharged to 0.2C.Battery discharge time is recorded, and discharge capacity C is calculated1, putting at a temperature of this Capacitance is battery high/low temperature discharge capability with the ratio between discharge capacity at room temperature, and calculation formula is：High/low temperature discharge capability =C1/C0* 100%.The results are shown in Table 1.
Under the conditions of room temperature (25 ± 2) DEG C, after charging by same system, shelve 30 minutes, then with different multiplying constant current Electric discharge, stopping potential when corresponding discharge-rate is 2C, 5C, 10C is respectively 0.9V, 0.8V, 0.7V, when recording battery discharge Between, and discharge capacity of the cell C is calculatedY(wherein CyDischarge capacity when for discharge-rate being yC), use Cy/C0× 100% is fixed Justice is the high-rate discharge capacity of battery.The results are shown in Table 2.
The Ni-MH battery of 1 the present embodiment 1 of table discharge time at different temperatures and high/low temperature lower the test knot of ability Fruit is shown in Table 1
Table 1
As can be seen from the above table, using Ni-MH battery made of the present invention under -45 DEG C of environment, 0.2C discharge capacities with often Under reachable 70.03~72.90%, the 70 DEG C of environment of the ratio between warm capacity, the ratio between 0.2C discharge capacities and room temperature capacity reachable 86.26~ 88.71%.
The test knot of discharge time and high magnification ability of the Ni-MH battery of 2 the present embodiment 1 of table under different discharge-rates Fruit is shown in Table 2
Table 2
As can be seen from the above table, using Ni-MH battery made of the present invention under the conditions of 2C high-multiplying power discharges, 2C electric discharges are held The ratio between amount and 0.2C discharge capacities are up to 96.52~98.42%；Under the conditions of 5C high-multiplying power discharges, 5C discharge capacities and 0.2C The ratio between discharge capacity is up to 94.44~96.52%；Under the conditions of 10C high-multiplying power discharges, 10C discharge capacities are held with 0.2C electric discharges The ratio between amount is up to 91.17~92.99%.
Embodiment 2：
Positive active material Ni (OH)2Preparation use complexed-precipitation method, it is a concentration of by a concentration of 2.0mol/L ammonium hydroxide The sodium hydroxide solution and nickel sulfate of 2.0mol/L, zinc sulfate, cobaltous sulfate mixing salt solution and hybrid reaction under stiring, it is described A concentration of 0.880mol/L of nickel ion in mixing salt solution, a concentration of 0.072mol/L of zinc ion, cobalt ions it is a concentration of 0.048mol/L, for control ph 11, temperature obtains green Ni at 55 DEG C, reaction time 12h, digestion time 12h (OH)2Precipitation, pours out reaction solution, static layering is washed with distilled water after outwelling supernatant, and is dried to sample at 120 DEG C Product moisture content≤0.5% is to get to green positive active material Ni (OH)2.The positive active material Ni (OH)2Zn content exists 5.0 ± 0.3wt%, cobalt content is in 3.0 ± 0.3wt%.Its gram of specific capacity is 215mAh/g, and granularity is 7~10 μm.
By positive active material Ni (OH)289.4%, cobalt protoxide 5.0%, cobalt powder 2.0%, yttrium oxide 0.8%, oxidation Simultaneously appropriate pure water input stirring is added in erbium 0.6%, sodium carboxymethylcellulose 0.2%, the weight percent of polytetrafluoroethylene (PTFE) 2.0% It is uniformly mixed in machine and slurry is made, then slurry material is filled into nickel foam conducting base by wet method slurry technique, and away from Part from nickel foam top 2.0mm is not filled with material, roll-in after drying, and nickel electricity is collectively formed in above-mentioned packing material and nickel foam Pole and coordination electrode thickness are 0.37 ± 0.01mm, and the nickel foam part for being not filled with material is reserved nickel foam part, is cut out It is cut into required size, that is, required nickel electrode is made.
It is MLNi that negative electrode active material, which selects expression formula,3.55Co0.75Mn0.4Al0.3The hydrogen-storage alloy powder of X, ML La, Ce, The rich La mischmetals of Pr, Nd element composition, mass percent La65%, Ce15%, Pr10%, Nd10%；Element X is The element for meeting property addition accounts for the 0.3wt% of the hydrogen-storage alloy powder including Y, Dy, B etc., and mass percent is Y30%, Dy30%, B40%.Gram specific capacity of the hydrogen-storage alloy powder is 307mAh/g, and grain size is at 38~48 μm.
By negative electrode active material hydrogen-storage alloy powder 94.6%, nickel powder 2.0%, yttrium oxide 1.0%, polyvinyl alcohol 0.4%, fourth The weight percent of benzene lotion 2.0% is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, then passes through wet method Slurry is coated on copper mesh conducting base by slurry technique, and is not coated by material apart from the part of conducting base copper mesh lower end 1.0mm Material, it is dry after roll-in, above-mentioned coating material and conducting base copper mesh be collectively formed hydrogen electrode and coordination electrode thickness be 0.26 ± 0.01mm, the conducting base part for being not coated by material are reserved white edge part, cut into required size, that is, are made required Negative plate.
Diaphragm uses the polypropylene that the alkalis suction quantity of high-end import sulfonation processing is big, good permeability and resistance to alkali ability are strong FV4365KL, thickness are 0.15 ± 0.01mm.
It is 1.33 ± 0.01g/ that electrolyte potassium hydroxide, sodium hydroxide, lithium hydroxide and purified water, which are configured to density, cm3、OH-Molar concentration is the alkaline aqueous solution of 8.80 ± 0.05mol/L, and mass percent is：KOH：NaOH：LiOH· H2O：H2O=32：4.5：2.21：67.28, after being cooled to room temperature, wolframic acid sodium crystal is added, controls it in alkaline solution A concentration of 0.08mol/L.
Referring to Fig. 1, above-mentioned nickel electrode, hydrogen electrode and membrane winding at core 100 and are implanted into box hat 200, nickel electrode Nickel foam part 111 (referring to Fig. 2) protrusion diaphragm is reserved in 110 upper end, and is connect with battery cap 400 by current collecting plates 300； White edge part 121 (referring to Fig. 3) protrusion diaphragm is reserved in the lower end of hydrogen electrode 120, and passes through nickel foam heelpiece 500 and box hat 200 Bottom connects.Current collecting plates 300 are nickel plating steel disc, thickness 0.2mm；500 thickness of nickel foam heelpiece is 0.6mm, and shape is circle, It is consistent with 100 bottom area of box hat, and 100 bottom of box hat is previously placed in by spot welding mode.Above-mentioned electrolyte is injected, according to electricity The electrolyte addition of tankage, each battery is 1.5~2.6g/Ah.For raising ion diffusion flux, extend battery life, Here D8000mAh Ni-MH batteries are made in value 2.5g/Ah, sealing.
Electric performance test method is as follows：
At ambient temperature, 0.2C fills 7 hours, shelves 30min, is then discharged to 1.0V with 0.2C again, and as battery is normal Warm discharge capacity C0；
It is placed 16~24 hours at set point of temperature (- 45 ± 2) DEG C or (70 ± 2) DEG C, is then filled 7 hours, put with 0.2C 30min is set, then 1.0V is discharged to 0.2C.Battery discharge time is recorded, and discharge capacity C is calculated1, putting at a temperature of this Capacitance is battery high/low temperature discharge capability with the ratio between discharge capacity at room temperature, and calculation formula is：High/low temperature discharge capability =C1/C0* 100%.The results are shown in Table 3.
Under the conditions of room temperature (25 ± 2) DEG C, after charging by same system, shelve 30 minutes, then with different multiplying constant current Electric discharge, stopping potential when corresponding discharge-rate is 2C, 5C, 10C is respectively 0.9V, 0.8V, 0.7V, when recording battery discharge Between, and discharge capacity of the cell C is calculatedY(wherein CyDischarge capacity when for discharge-rate being yC), use Cy/C0× 100% is fixed Justice is the high-rate discharge capacity of battery.The results are shown in Table 4.
The Ni-MH battery of 3 the present embodiment 2 of table discharge time at different temperatures and high/low temperature lower the test knot of ability Fruit is shown in Table 3
Table 3
As can be seen from the above table, using Ni-MH battery made of the present invention under -45 DEG C of environment, 0.2C discharge capacities with often Under reachable 74.36~75.24%, the 70 DEG C of environment of the ratio between warm capacity, the ratio between 0.2C discharge capacities and room temperature capacity reachable 89.17~ 90.00%.
The test knot of discharge time and high magnification ability of the Ni-MH battery of 4 the present embodiment 2 of table under different discharge-rates Fruit is shown in Table 4
Table 4
As can be seen from the above table, using Ni-MH battery made of the present invention under the conditions of 2C high-multiplying power discharges, 2C electric discharges are held The ratio between amount and 0.2C discharge capacities are up to 97.48~98.73%；Under the conditions of 5C high-multiplying power discharges, 5C discharge capacities and 0.2C The ratio between discharge capacity is up to 95.24~96.83%；Under the conditions of 10C high-multiplying power discharges, 10C discharge capacities are held with 0.2C electric discharges The ratio between amount is up to 93.53~93.83%.
Embodiment 3：
Positive active material Ni (OH)2Preparation use complexed-precipitation method, it is a concentration of by a concentration of 1.5mol/L ammonium hydroxide The sodium hydroxide solution and nickel sulfate of 1.5mol/L, zinc sulfate, cobaltous sulfate mixing salt solution and hybrid reaction under stiring, it is described A concentration of 0.6285mol/L of nickel ion in mixing salt solution, a concentration of 0.0645mol/L of zinc ion, the concentration of cobalt ions For 0.0570mol/L, for control ph 11, temperature obtains green Ni at 55 DEG C, reaction time 12h, digestion time 12h (OH)2Precipitation, pours out reaction solution, static layering is washed with distilled water after outwelling supernatant, and is dried to sample at 120 DEG C Product moisture content≤0.5% is to get to green positive active material Ni (OH)2.The positive active material Ni (OH)2Zn content exists 6.0 ± 0.3wt%, cobalt content is in 4.8 ± 0.3wt%.Its gram of specific capacity is 210mAh/g, and granularity is 5~10 μm.
By positive active material Ni (OH)289.0%, cobalt powder 3.0%, nickel powder 2.0%, carbon nanotube 2.0%, zirconium oxide 0.8, erbium oxide 0.6%, titanium oxide 0.6%, sodium carboxymethylcellulose 0.2%, the weight percent of polytetrafluoroethylene (PTFE) 1.8% is simultaneously Appropriate pure water input stirrer for mixing is added, slurry is uniformly made, then slurry material is filled by bubble by wet method slurry technique In foam nickel conducting base, and material, roll-in after drying, above-mentioned packing material are not filled with apart from the part of nickel foam top 2.0mm And it is 0.37 ± 0.01mm, the nickel foam part for being not filled with material that nickel electrode and coordination electrode thickness, which is collectively formed, in nickel foam To reserve nickel foam part, required size is cut into, that is, required nickel electrode is made.
It is MLNi that negative electrode active material, which selects expression formula,3.55Co0.75Mn0.4Al0.3The hydrogen-storage alloy powder of X, ML La, Ce, The rich La mischmetals of Pr, Nd element composition, mass percent La55%, Ce25%, Pr10%, Nd10%；Element X is The element for meeting property addition accounts for the 0.4wt% of the hydrogen-storage alloy powder, quality percentage including Dy, B, Si, Ti etc. Than for Dy30%, B30%, Si20%, Ti20%.Gram specific capacity of the hydrogen-storage alloy powder is 305mAh/g, grain size 35~ 45μm。
By negative electrode active material hydrogen-storage alloy powder 94.4%, nickel powder 1.2%, carbon nanotube 1.0%, terbium oxide 1.0% gathers Sodium acrylate 0.4%, the weight percent of styrene-butadiene emulsion 2.0% are simultaneously added appropriate pure water input stirrer for mixing and are uniformly made Slurry, then by wet method slurry technique by filled therewith on nickel foam conducting base, and apart from conducting base nickel foam lower end The part of 1.0mm is not filled with material, and roll-in after drying, hydrogen electrode is collectively formed simultaneously in above-mentioned packing material and conducting base nickel foam Coordination electrode thickness is 0.26 ± 0.01mm, and the conducting base part for being not filled with material is reserved white edge part, is cut into Required negative plate is made in required size.
Diaphragm uses the polypropylene that the alkalis suction quantity of high-end import sulfonation processing is big, good permeability and resistance to alkali ability are strong FV4365KL, thickness are 0.15 ± 0.01mm.
It is 1.34 ± 0.01g/ that electrolyte potassium hydroxide, sodium hydroxide, lithium hydroxide and purified water, which are configured to density, cm3、OH-Molar concentration is the alkaline aqueous solution of 8.90 ± 0.05mol/L, and mass percent is：KOH：NaOH：LiOH· H2O：H2O=35：4.15：2.21：66.54, after being cooled to room temperature, wolframic acid sodium crystal is added, controls it in alkaline solution A concentration of 0.1mol/L.
Referring to Fig. 1, above-mentioned nickel electrode, hydrogen electrode and membrane winding at core 100 and are implanted into box hat 200, nickel electrode Nickel foam part 111 (referring to Fig. 2) protrusion diaphragm is reserved in 110 upper end, and is connect with battery cap 400 by current collecting plates 300； White edge part 121 (referring to Fig. 3) protrusion diaphragm is reserved in the lower end of hydrogen electrode 120, and passes through nickel foam heelpiece 500 and box hat 200 Bottom connects.Current collecting plates 300 are nickel plating steel disc, thickness 0.2mm；500 thickness of nickel foam heelpiece is 0.6mm, and shape is circle, It is consistent with 100 bottom area of box hat, and 100 bottom of box hat is previously placed in by spot welding mode.Above-mentioned electrolyte is injected, according to electricity The electrolyte addition of tankage, each battery is 1.5~2.6g/Ah.For raising ion diffusion flux, extend battery life, Here F10000mAh Ni-MH batteries are made in value 2.6g/Ah, sealing.
Electric performance test method is as follows：
At ambient temperature, 0.2C fills 7 hours, shelves 30min, is then discharged to 1.0V with 0.2C again, and as battery is normal Warm discharge capacity C0；
It is placed 16~24 hours at set point of temperature (- 45 ± 2) DEG C or (70 ± 2) DEG C, is then filled 7 hours, put with 0.2C 30min is set, then 1.0V is discharged to 0.2C.Battery discharge time is recorded, and discharge capacity C is calculated1, putting at a temperature of this Capacitance is battery high/low temperature discharge capability with the ratio between discharge capacity at room temperature, and calculation formula is：High/low temperature discharge capability =C1/C0* 100%.The results are shown in Table 5.
Under the conditions of room temperature (25 ± 2) DEG C, after charging by same system, shelve 30 minutes, then with different multiplying constant current Electric discharge, stopping potential when corresponding discharge-rate is 2C, 5C, 10C is respectively 0.9V, 0.8V, 0.7V, when recording battery discharge Between, and discharge capacity of the cell C is calculatedY(wherein CyDischarge capacity when for discharge-rate being yC), use Cy/C0× 100% is fixed Justice is the high-rate discharge capacity of battery.The results are shown in Table 6.
The Ni-MH battery of 5 the present embodiment 3 of table discharge time at different temperatures and high/low temperature lower the test knot of ability Fruit is shown in Table 5
Table 5
As can be seen from the above table, using Ni-MH battery made of the present invention under -45 DEG C of environment, 0.2C discharge capacities with often Under reachable 79.23~80.51%, the 70 DEG C of environment of the ratio between warm capacity, the ratio between 0.2C discharge capacities and room temperature capacity reachable 94.25~ 95.51%.
The test knot of discharge time and high magnification ability of the Ni-MH battery of 6 the present embodiment 3 of table under different discharge-rates Fruit is shown in Table 6
Table 6
As can be seen from the above table, using Ni-MH battery made of the present invention under the conditions of 2C high-multiplying power discharges, 2C electric discharges are held The ratio between amount and 0.2C discharge capacities are up to 98.10~99.05%；Under the conditions of 5C high-multiplying power discharges, 5C discharge capacities and 0.2C The ratio between discharge capacity is up to 97.31~98.10%；Under the conditions of 10C high-multiplying power discharges, 10C discharge capacities are held with 0.2C electric discharges The ratio between amount is up to 94.30~95.06%.

Claims (30)

1. Ni-MH battery, including iron-clad and the nickel electrode in iron-clad, hydrogen electrode, diaphragm, electrolyte, it is characterised in that：
The nickel electrode is by nickel foam as basis material, and the nickel foam inner space is filled with positive active material, conduction Agent, additive and bonding agent；
The hydrogen electrode is by porous nickel plated steel strip or copper mesh or nickel foam as basis material, the porous nickel plated steel strip or copper mesh Or nickel foam is coated with negative electrode active material hydrogen-storage alloy powder, conductive agent, additive and bonding agent；
The electrolyte is rich potassium type alkaline aqueous solution and sodium tungstate or the mixture of wolframic acid crystal；
The production method of the Ni-MH battery includes the following steps：
(1) making of nickel electrode：
(1.1) positive active material is prepared
Using complexed-precipitation method, under the conditions of existing for a certain concentration ammonium hydroxide, by certain density sodium hydroxide solution and centainly The nickel sulfate of concentration, zinc sulfate, cobaltous sulfate mixing salt solution hybrid reaction under stiring, control ph is 8~11, reaction temperature At 40~70 DEG C, the reaction time is 12~14h, and digestion time is 12~14h, obtains green precipitate, pours out reaction solution, static point Layer, is washed with distilled water after outwelling supernatant, and is dried at 120 DEG C moisture content≤0.5% to get to positive electrode active material Matter；
(1.2) positive active material 88~92% prepared by step (1.1), conductive agent 5~7%, additive 1~2%, bonding are pressed The weight percent of agent 2~4% is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, then passes through wet method slurry Slurry material is filled into nickel foam conducting base by technique, and apart from the part of nickel foam conducting base 0.5~2.5mm of top Be not filled with material, it is dry after roll-in, it is 0.37 that nickel electrode and coordination electrode thickness, which is collectively formed, in above-mentioned packing material and nickel foam ± 0.01mm, the nickel foam part for being not filled with material are reserved nickel foam part, cut into required size；
(2) making of hydrogen electrode：By hydrogen-storage alloy powder 94~97%, conductive agent 1.5~2.5%, additive 1~2%, bonding agent 2~4% weight percent is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, then passes through wet method slurry work Slurry is coated on the porous nickel plated steel strip of conducting base or copper mesh or nickel foam by skill, and apart from the porous nickel plated steel strip of conducting base Or the part of 0.5~2.5mm of copper mesh or nickel foam lower end is not coated by material, roll-in, above-mentioned coating material and conductive base after drying It is 0.26 ± 0.01mm that hydrogen electrode and coordination electrode thickness, which is collectively formed, in the porous nickel plated steel strip of body or copper mesh or nickel foam, it is described not The conducting base part of packing material is reserved white edge part, cuts into required size；
(3) preparation of electrolyte
It is 1.30~1.35g/cm to be configured to density with potassium hydroxide, sodium hydroxide, lithium hydroxide3、OH-Molar concentration be 8.5~ The aqueous solution of 9.2mol/L after being cooled to room temperature, adds sodium tungstate or wolframic acid crystal, control its concentration 0.01~ 0.5mol/L is stirred continuously, and is allowed to be completely dissolved, that is, the alkaline electrolyte containing sodium tungstate or wolframic acid is made；
(4) battery assembles：Nickel electrode, hydrogen electrode and the membrane winding of the step of prepared by step (1) (2) preparation are simultaneously implanted into box hat It is interior, so that the reserved nickel foam part protrusion diaphragm in nickel electrode is connect with battery cap in upper end, and by current collecting plates, hydrogen The reserved white edge part on electrode protrudes from diaphragm lower end, and is connect with the box hat bottom by a nickel foam heelpiece, According to electrolyte prepared by battery capacity injection step (3), Ni-MH battery is made in sealing.
2. Ni-MH battery as described in claim 1, which is characterized in that prepared by the positive active material in the nickel electrode Zinc, cobalt are co-deposited in journey.
3. Ni-MH battery as claimed in claim 2, which is characterized in that between 3~7wt%, cobalt content exists the Zn content Between 1.5~5wt%.
4. Ni-MH battery as described in claim 1, which is characterized in that the positive active material gram specific capacity in the nickel electrode In 210~230mAh/g, granularity is at 5~12 μm.
5. Ni-MH battery as described in claim 1, which is characterized in that the conductive agent in the nickel electrode is cobalt protoxide, hydrogen One or more of mixtures of cobalt protoxide, cobalt carbonate, cobalt powder, nickel powder, carbon nanotube.
6. Ni-MH battery as described in claim 1, which is characterized in that the additive in the nickel electrode is calcirm-fluoride, oxidation Erbium, yttrium oxide, titanium oxide, zirconium oxide, one or more of mixtures of thallium oxide.
7. Ni-MH battery as described in claim 1, which is characterized in that the bonding agent in the nickel electrode is carboxymethyl cellulose The combination of sodium and polytetrafluoroethylene (PTFE).
8. Ni-MH battery as described in claim 1, which is characterized in that the negative electrode active material hydrogen-storage alloy in the hydrogen electrode The expression formula of powder is MLNi3.55Co0.75Mn0.4Al0.3X, wherein the X be meet property addition element, selected from Y, Dy, At least one of Sn, B, Si, Ti, V, Cr, the ML are the rich La mischmetals of La, Ce, Pr, Nd element composition.
9. Ni-MH battery as claimed in claim 8, which is characterized in that the amount of the element X is the 0.1 of the hydrogen-storage alloy powder ~0.5wt%.
10. Ni-MH battery as described in claim 1, which is characterized in that gram specific capacity of the hydrogen-storage alloy powder 300~ 320mAh/g, grain size is at 35~50 μm.
11. Ni-MH battery as described in claim 1, which is characterized in that the conductive agent in the hydrogen electrode be selected from nickel powder, One or more of mixtures of superconduction carbon black, carbon nanotube.
12. Ni-MH battery as described in claim 1, which is characterized in that the additive in the hydrogen electrode is terbium oxide, oxidation The mixture of one or more of yttrium, dysprosia.
13. Ni-MH battery as described in claim 1, which is characterized in that the bonding agent in the hydrogen electrode is carboxymethyl cellulose The combination of plain sodium or polyvinyl alcohol or Sodium Polyacrylate and styrene-butadiene emulsion.
14. Ni-MH battery as described in claim 1, which is characterized in that the diaphragm is grafted using carboxyl at processing or sulfonation The polyethylene or polypropylene of reason, thickness are 0.15 ± 0.01mm.
15. the production method of Ni-MH battery, which is characterized in that include the following steps：
(1) making of nickel electrode：
(1.1) positive active material is prepared
Using complexed-precipitation method, under the conditions of existing for a certain concentration ammonium hydroxide, by certain density sodium hydroxide solution and centainly The nickel sulfate of concentration, zinc sulfate, cobaltous sulfate mixing salt solution hybrid reaction under stiring, control ph is 8~11, reaction temperature At 40~70 DEG C, the reaction time is 12~14h, and digestion time is 12~14h, obtains green precipitate, pours out reaction solution, static point Layer, is washed with distilled water after outwelling supernatant, and is dried at 120 DEG C moisture content≤0.5% to get to positive electrode active material Matter；
(1.2) positive active material 88~92% prepared by step (1.1), conductive agent 5~7%, additive 1~2%, bonding are pressed The weight percent of agent 2~4% is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, then passes through wet method slurry Slurry material is filled into nickel foam conducting base by technique, and apart from the part of nickel foam conducting base 0.5~2.5mm of top Be not filled with material, it is dry after roll-in, it is 0.37 that nickel electrode and coordination electrode thickness, which is collectively formed, in above-mentioned packing material and nickel foam ± 0.01mm, the nickel foam part for being not filled with material are reserved nickel foam part, cut into required size；
(2) making of hydrogen electrode：By hydrogen-storage alloy powder 94~97%, conductive agent 1.5~2.5%, additive 1~2%, bonding agent 2~4% weight percent is simultaneously added appropriate pure water input stirrer for mixing slurry is uniformly made, then passes through wet method slurry work Slurry is coated on the porous nickel plated steel strip of conducting base or copper mesh or nickel foam by skill, and apart from the porous nickel plated steel strip of conducting base Or the part of 0.5~2.5mm of copper mesh or nickel foam lower end is not coated by material, roll-in, above-mentioned coating material and conductive base after drying It is 0.26 ± 0.01mm that hydrogen electrode and coordination electrode thickness, which is collectively formed, in the porous nickel plated steel strip of body or copper mesh or nickel foam, it is described not The conducting base part of packing material is reserved white edge part, cuts into required size；
(3) preparation of electrolyte
It is 1.30~1.35g/cm to be configured to density with potassium hydroxide, sodium hydroxide, lithium hydroxide3、OH-Molar concentration be 8.5~ The aqueous solution of 9.2mol/L after being cooled to room temperature, adds sodium tungstate or wolframic acid crystal, control its concentration 0.01~ 0.5mol/L is stirred continuously, and is allowed to be completely dissolved, that is, the alkaline electrolyte containing sodium tungstate or wolframic acid is made；
(4) battery assembles：Nickel electrode, hydrogen electrode and the membrane winding of the step of prepared by step (1) (2) preparation are simultaneously implanted into box hat It is interior, so that the reserved nickel foam part protrusion diaphragm in nickel electrode is connect with battery cap in upper end, and by current collecting plates, hydrogen The reserved white edge part on electrode protrudes from diaphragm lower end, and is connect with the box hat bottom by a nickel foam heelpiece, According to electrolyte prepared by battery capacity injection step (3), Ni-MH battery is made in sealing.
16. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the current collecting plates are nickel plating steel disc, Thickness is between 0.15~0.20mm.
17. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the nickel foam heelpiece thickness exists Between 0.6~1.0mm, shape is circle, consistent with box hat bottom area, and is previously placed in box hat bottom by spot welding mode.
18. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the electrolyte addition of each battery For 1.5~2.4g/Ah.
19. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the positive-active of the step (1) Substance Ni (OH)2Gram specific capacity is in 210~230mAh/g, and granularity is at 5~12 μm.
20. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that in the step (1.1), the ammonia A concentration of 0.5~5.0mol/L of water, a concentration of 0.5~2.0mol/L of nickel ion in the mixing salt solution, zinc ion A concentration of 0.01-0.2mol/L, a concentration of 0.005~0.1mol/L of cobalt ions, a concentration of the 0.5 of the sodium hydroxide solution ~5.0mol/L.
21. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the conductive agent of the step (1) is One or more of mixtures of cobalt protoxide, hydroxide cobalt, cobalt carbonate, cobalt powder, nickel powder, carbon nanotube.
22. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the additive of the step (1) is Calcirm-fluoride, erbium oxide, yttrium oxide, titanium oxide, zirconium oxide, one or more of mixtures of thallium oxide.
23. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the bonding in the nickel electrode Agent is the combination of sodium carboxymethylcellulose and polytetrafluoroethylene (PTFE).
24. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the cathode in the step (2) is lived Property substance hydrogen-storage alloy powder expression formula be MLNi3.55Co0.75Mn0.4Al0.3X, wherein the X is to meet what property was added Element, is selected from at least one of Y, Dy, Sn, B, Si, Ti, V, Cr, and the ML is the rich La mixing of La, Ce, Pr, Nd element composition Rare earth.
25. the production method of Ni-MH battery as claimed in claim 24, which is characterized in that the amount of the element X is the storage 0.1~0.5wt% of hydrogen alloyed powder.
26. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the cathode in the step (2) is lived Gram specific capacity of property substance hydrogen-storage alloy powder is in 300~320mAh/g, and grain size is at 35~50 μm.
27. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the conductive agent in the step (2) One or more of mixtures selected from nickel powder, superconduction carbon black, carbon nanotube.
28. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the additive in the step (2) For the mixture of one or more of terbium oxide, yttrium oxide, dysprosia.
29. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the bonding agent in the step (2) It is the combination of sodium carboxymethylcellulose or polyvinyl alcohol or Sodium Polyacrylate and styrene-butadiene emulsion.
30. the production method of Ni-MH battery as claimed in claim 15, which is characterized in that the diaphragm in the step (4) is adopted The polyethylene or polypropylene of processing or sulfonation processing are grafted with carboxyl, thickness is 0.15 ± 0.01mm.
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