CN1283022C - Zinc-nickel secondary cell and preparation method thereof - Google Patents

Zinc-nickel secondary cell and preparation method thereof Download PDF

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CN1283022C
CN1283022C CNB031138829A CN03113882A CN1283022C CN 1283022 C CN1283022 C CN 1283022C CN B031138829 A CNB031138829 A CN B031138829A CN 03113882 A CN03113882 A CN 03113882A CN 1283022 C CN1283022 C CN 1283022C
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nickel
zinc
hydroxide
battery
electrode
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CN1434534A (en
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周震涛
刘澧蒲
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South China University of Technology SCUT
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South China University of Technology SCUT
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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

Abstract

The present invention relates to a preparation method for a secondary zinc-nickel battery, and a secondary zinc-nickel battery made by the preparation method, which belongs to the field of a chemical electric power source. In the preparation method, a positive plate and a negative plate are partitioned by membrane paper to be laminated to be wound into a barrel which is sheathed in a battery case, an electrolyte is filled into the barrel, the positive plate is in contact with the battery case used as a positive electrode current collector, the negative plate is connected with a negative electrode cap in a welding mode through an electrical conductive terminal, and a battery is sealed, packaged and stored finally. The obtained secondary zinc-nickel battery has the advantages of high voltage, large discharge capacity, long cycle life, small internal resistance, heavy current, good discharge performance, no environmental pollution, etc.

Description

Zinc-nickel secondary batteries and preparation method thereof
(1) technical field under
The present invention relates to field of chemical power source, in more detail the preparation method of zinc-nickel secondary batteries.
The invention still further relates to the zinc-nickel secondary batteries of described method preparation.
(2) background technology
In recent years, along with developing rapidly of human social economy, high-tech products such as laptop computer, portable communications apparatus, cordless power tool, digital camera, video camera have obtained fast development.Develop supporting with it removable chemical power source and just become a urgent problem.Generally, these portable electronic electric equipment products all require supporting with it chemical power source to possess higher operating voltage, higher specific energy, bigger operating current, long cycle life, smaller volume, safe and cheap advantages such as price.
People are to the existing history that goes up a century of the research of zinc-nickel cell system.It is found that in research process zinc dendrite growth, zinc electrode distortion can appear in zinc-nickel secondary batteries in recycling process, nickel electrode expands and oxidized zinc poisons, barrier film is oxidized and by problems such as zinc dendrite penetrate.These a series of reasons have caused the useful life of this battery short, make this battery string fail to realize extensive practicability and industrialization so far.
People such as the M.Tokuda of SANYO GS Electric Applicance Co., Ltd are U.S.'s patent of invention " hermetically sealed alkaline battery " [M.Tokuda of application recently, M.Yano, M.Nogami, S.Fujitani, K.Nishio, US Pat.6,265,105B1,2001], adopt clorox (NaClO) solution oxide nickel hydroxide [Ni (OH) 2] method prepare γ type hydroxy nickel oxide (γ-NiOOH) as the positive active material of zinc-nickel secondary batteries, adopt the negative electrode active material of calamine cream as zinc-nickel secondary batteries, and the copper pin is inserted in the calamine cream as negative current collector.The electric conductivity of γ type hydroxy nickel oxide is relatively poor, electric conducting materials such as itself and graphite powder must be carried out mechanical mixture and are pressed into the powder ring, then with three powder rings compacted together and tightly be close to battery case could be as the positive pole of zinc-nickel secondary batteries.The cylindrical diaphragm of making of the vinylon nonwoven fabrics loads negative zinc cream and plays a part both positive and negative polarity is isolated.But also there is following problem in these background technologies:
(1) production process of anode is complicated, the difficult control of the quality of γ type hydroxy nickel oxide;
(2) density of γ type hydroxy nickel oxide is less, causes the useful load of positive active material unit volume little, and battery capacity is lower;
(3) because the density of γ type hydroxy nickel oxide is less, also cause electric conductivity relatively poor, the internal resistance of battery is bigger, and heavy-current discharge performance is relatively poor;
(4) γ type hydroxy nickel oxide and electric conducting material graphite powder are carried out mechanical mixture and make the powder ring as positive pole, the electric conductivity of this positive pole is also relatively poor;
(5) calamine cream is as battery cathode, and the copper pin is as negative current collector, and the contact area of copper pin and calamine cream is little, and contact resistance is big, and it is bigger to polarize, and causes the resistance of negative pole bigger, and the operating voltage of battery is lower, and it is bigger to generate heat.
(3) summary of the invention
The objective of the invention is to problem at the prior art existence, a kind of preparation method of zinc-nickel secondary batteries is provided, the gained zinc-nickel secondary batteries have voltage height, discharge capacity big, have extended cycle life, internal resistance is little, heavy-current discharge performance is excellent, fail safe is good, and advantage such as non-environmental-pollution.
The zinc-nickel secondary batteries that provides described method prepared is provided.
The preparation method of zinc-nickel secondary batteries of the present invention comprises: adopt the coiled battery structure, with diaphragm paper positive plate and negative plate are separated, the cylindrical shape that is rolled into stacked together packs in the battery case, inject electrolyte, positive plate contacts with battery case as plus plate current-collecting body, negative plate is weldingly connected by conducting terminal and negative pole cap, at last battery is sealed, packs, stores.
Described electrolyte solution is the potassium hydroxide or the sodium hydrate aqueous solution of saturated zinc oxide, and concentration is 1-14M.
Described cadmium film is that thickness is vinylon, polypropylene, polyethylene nonwoven fabrics, polyethylene or the polypropylene grafted film of 0.15-0.30mm.
Described positive plate prepares by following method:
(1) conducting base is drawn one or more conducting terminals; Described conducting base thickness is 0.1-3.0mm, and conducting base is foaming nickel, nickel screen or a nickel strap;
(2) the hydroxide nickel powder is mixed with additives for battery, wherein the consumption of hydroxide nickel powder accounts for 70%-98%, and surplus is an additive; Described hydroxide nickel powder is ball-type nickel hydroxide and/or ordinary hydrogen nickel oxide; Described additive is one or more the mixture in graphite powder, acetylene black, conductive carbon black, metal nickel powder, cadmium metal powder, copper powder, metal zinc, cobalt compound, manganese compound, aluminium compound, zinc compound, cadmium compound, the lithium compound etc.;
(3) use the dissolution with solvents binding agent, the weight ratio of solvent and binding agent is 1: 10-99; Described solvent can be water miscible, as water, ethanol etc., also can be non-water-soluble, as N-methyl pyrrolidone, dimethylacetylamide etc.;
Described binding agent can be water-soluble or water dispersible, as carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE) emulsion, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO) one or more mixtures wherein; Also can be non-water-soluble, as Kynoar (PVDF) and/or hexafluoropropylene etc.;
(4) mixture that (2) are obtained mixes with binder solution that (3) obtain and is made into slurry, be coated on the conducting base, 60-120 ℃ of oven dry down, after the moulding the nickel hydroxide positive plate sheet;
Two rolling mills that described forming method can adopt diameter 100-400mm are rolled to the thickness moulding of 0.20-0.90mm with positive plate, or adopt the hydraulic press of 100-500 ton positive plate to be depressed into the thickness moulding of 0.20-0.90mm.
The moulding of nickel hydroxide positive plate sheet also can be adopted dry process preparation: with the nickel hydroxide that mixes and additives for battery powder is that two rolling mills of 100-400mm are rolled to the thickness moulding of 0.20-0.90mm with pole piece by diameter with conducting base directly, or the hydraulic press of employing 100-500 ton is depressed into the thickness moulding of 0.20-0.90mm with the nickel hydroxide that mixes and additives for battery powder with conducting base;
(5) with the electrolysis chemical synthesizing method nickel hydroxide in the above-mentioned positive plate is transformed into β type hydroxy nickel oxide, what adopted when electrolysis changes into can be Titanium electrode or graphite electrode or cadmium oxide electrode to electrode;
The cadmium oxide electrode is to adopt two of nickel plated steel strips, and cadmium oxide powder, binding agent, water are made into slurry, is coated in steel strip surface, dries moulding under 60-150 ℃ condition.
Can pole piece be rolled to the thick moulding of 0.30-0.90mm with two rolling mills of diameter 50-400mm.
Above-mentioned nickel hydroxide positive plate sheet is immersed in the electrolysis tank that fills alkaline electrolyte electrode metal titanium electrode or graphite electrode or cadmium oxide electrode with two.Two the positive terminal in rectification source links to each other with the nickel hydroxide positive plate sheet to the be placed in two sides of nickel hydroxide positive plate sheet of electrode, and negative pole end links to each other to electrode with two.The current density of electrolysis tank is controlled at 0.1-50mA/cm 2, voltage control is at 1.4-3.0V, and electrolysis time is 0.5-24 hour.
Described alkaline electrolyte is dissolved in deionized water, distilled water or the running water preparation by in potassium hydroxide, NaOH, the lithium hydroxide one or more and gets.Wherein, potassium hydroxide or concentration sodium hydroxide are 1-12M, and the concentration of lithium hydroxide is 10-40g/l.
The nickel hydroxide that electrolysis finishes in the positive plate of back is converted into β type hydroxy nickel oxide.
To take out with the positive plate of β type hydroxy nickel oxide, promptly can be used as the anodal standby of zinc-nickel secondary batteries after cleaning with deionized water, distilled water or running water, then can stay repeatedly electrode metal titanium electrode, graphite electrode or cadmium oxide electrode and use.
The preparation method of described negative plate is as follows:
(1) the negative pole conducting base is drawn one or more conducting terminals.Conducting base can be any in foam copper, copper mesh or the copper strips, and thickness is 0.1-3.0mm.Negative pole conducting base surface can be plated indium as required and be handled.
(2) metal zinc is mixed mutually with cathode additive agent.This metal zinc is that to select particle diameter for use be 70-300 purpose metallic zinc alloyed powder, has wherein added micro-indium, bismuth or lead and compound thereof as corrosion inhibiter; This cathode additive agent can be one or more the mixture in zinc oxide, calcium oxide, magnesium oxide, cadmium oxide, alundum (Al, indium compound, bismuth compound, the lead compound etc.The percentage by weight of metal zinc in mixture is 60%-95%, and the percentage by weight of cathode additive agent in mixture is 5%-40%.
(3) in (2) described mixture, add binding agent.Described binding agent can be one or more the mixture in carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE) emulsion, polyvinyl alcohol (PVA), polyacrylic acid (PAA), the polyethylene glycol oxide (PEO) etc.The weight percent content of binding agent in mixture is 1%-30%.
(4) (3) described negative pole mixture is coated on the conducting base of negative pole, under 60-120 ℃ condition, dries, on the surface of this negative pole conducting base, apply one deck then again and prevent that the zinc dendrite growth from penetrating the composite coating of barrier film.This composite coating is made up of one or more the mixture in calcium oxide, calcium hydroxide, magnesium oxide, cadmium oxide, the alundum (Al etc.The weight percent content of this mixture in composite coating is 99%-70%.Simultaneously, also add one or more mixture in carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE) emulsion, polyvinyl alcohol (PVA), polyacrylic acid (PAA), the polyethylene glycol oxide (PEO) etc. therein as binding agent.The weight percent content of this binding agent in composite coating is 1%-30%.
(5) 60-120 ℃ of oven dry down, moulding gets negative plate.
The moulding of described negative plate can be adopted two rolling mills of diameter 100-400mm or adopt the hydraulic press of 100-500 ton pressure that negative plate is depressed into the moulding of 0.30-0.75mm thickness.
The electrolysis den process prepare zinc-nickel secondary batteries positive active material β type hydroxy nickel oxide (principle of β-NiOOH) is as follows:
β-NiOOH overcharges and can form γ-NiOOH, but by adding suitable additive and controlling the generation that reaction condition can suppress γ-NiOOH.
The principle that zinc-nickel secondary batteries discharges and recharges reaction is as follows:
Anodal reaction
Negative reaction
The battery overall reaction:
The standard free energy Δ G of cell reaction 0Be-80694 cards, standard heat of formation Δ H 0Be-85534 cards, Entropy Changes Δ S 0Be-16.239 card/degree.By Δ G 0=-nE 0F can calculate the thermodynamics electromotive force E of cell reaction 0Be 1.854V.N represents the equivalents of reactant in the formula; F is a Faraday constant.Battery can be emitted heat at discharge process, causes the battery heating, and wherein the battery heating that is caused by Entropy Changes accounts for more than 40% of total amount of heat.The theoretical specific energy of cell reaction is 326wh/kg.
The present invention compared with prior art has following advantage:
(1) the present invention is simple with the technology that the electrolysis forming technology prepares the anodal β type of zinc-nickel secondary batteries hydroxy nickel oxide, and quality is controlled easily;
(2) density of this β type hydroxyl oxidize nickel hydroxide active material is big, the specific capacity height, and electric conductivity is good;
(3) adopt calamine cream to make negative electrode active material with respect to prior art, and the copper pin inserted in the calamine cream as negative current collector, the present invention is coated on negative pole zinc powder activity material on the negative pole conducting bases such as foam copper, copper mesh or copper strips, help to increase the contact area of zinc powder activity material and negative pole conducting base, increase the response area of electrode, reduce the internal resistance of battery, improve the heavy-current discharge performance of battery;
(4) the present invention applies one deck again and prevents that the zinc dendrite growth from penetrating the composite coating of barrier film on the surface of the negative pole conducting base that applies mixture such as negative electrode active material, can prevent effectively that zinc dendrite from penetrating barrier film and causing battery short circuit and scrap;
(5) adopt specific area very big foaming nickel, nickel screen or nickel strap and metallic matrixes such as foam copper, copper mesh or copper strips as the conducting base of battery positive and negative electrode, improved the utilance of battery positive and negative electrode active material and the area of electrode reaction;
(6) the present invention adopts the coiled battery structure to prepare zinc-nickel secondary batteries, have voltage height, specific discharge capacity big, have extended cycle life, characteristics such as internal resistance is little, heavy-current discharge performance excellence;
(7) the prepared positive and negative electrode of the present invention has that density is big, specific area is big, good conductivity, specific capacity height, specific power are big, electric performance stablity, operating procedure are simple, quality advantage such as control easily, is specially adapted to the positive and negative electrode as zinc-nickel secondary batteries.The zinc-nickel secondary batteries of the present invention preparation have voltage height, specific discharge capacity big, have extended cycle life, characteristics such as internal resistance is little, heavy-current discharge performance is excellent, safety and non-environmental-pollution.
(4) description of drawings
Fig. 1 is the AA type zinc-nickel secondary batteries charging and discharging curve figure that the present invention prepares.
(5) embodiment
As shown in Figure 1, the condition that discharges and recharges of this battery is as follows:
(1) with 200mA electric current constant current charge 240 minutes, the upper voltage limit of charging was 2.05V;
(2) constant voltage was 2.05V charging 150 minutes, and the upper limit current of charging is 400mA;
(3) shelve 10 minutes;
(4) reduce to 1.0V with 200mA electric current constant-current discharge to cell voltage;
(1) work step to the (4) work step is a charge and discharge cycles of battery.
Embodiment 1
Cutting is of a size of 40 * 100mm, and thickness is the conducting base of nickel strap a slice of 0.25mm as positive pole, conducting terminal of spot welding therein.With percentage by weight is that 70% ordinary hydrogen nickel oxide powder and percentage by weight are that 27% conductive additive graphite powder mixes.With percentage by weight is the water dissolving of 3% PVA binding agent elder generation, adding water with said mixture again is mixed together and evenly is made into anode sizing agent, be coated on the nickel strap, in 100 ℃ baking oven, dry, the clean dried gain in weight of anode sizing agent is controlled at 8 ± 0.1g, it is thick with two rolling mills of diameter 400mm the nickel strap positive plate to be rolled to 0.50mm, immerses to fill in the sodium hydrate aqueous solution that concentration the is 14M electrolysis tank of (wherein also containing lithium hydroxide 40g/l).
With the electrolysis forming technology nickel hydroxide in the above-mentioned molded positive plate is transformed into β type hydroxy nickel oxide.Is the Titanium electrode in order to what positive pole is carried out cell reaction to electrode.The Titanium electrode is of a size of 40 * 100mm.The Titanium electrode is immersed in the same electrolysis tank with positive plate, and two Titaniums are to the be placed in two sides of nickel hydroxide positive plate sheet of electrode.The positive terminal in rectification source and nickel hydroxide positive plate sheet link, and negative pole end then links with two Titanium electrodes.The current density of electrolysis tank is controlled to be 0.1mA/cm 2, voltage control is at 1.4V, and electrolysis time is 24 hours.
After electrolysis finishes electrode active material is changed into the positive plate taking-up of hydroxy nickel oxide by nickel hydroxide, promptly can be used as the anodal standby of zinc-nickel secondary batteries after cleaning with distilled water.The Titanium electrode then can stay repeatedly and use.
Cutting is of a size of copper strips a slice of 38 * 95mm, and thickness is 0.15mm, draws a conducting terminal therein, as the conducting base of negative pole.With percentage by weight is that 60% particle diameter is that 70 purpose Zinc alloy powders, 18% zinc oxide, 18.9% calcium oxide, 0.1% indium metal mix, be made into slurry with 3% PVA binding agent, an amount of water, be coated on the copper strip surface, dry in 120 ℃ baking oven, the clean dried gain in weight of monolithic electrode slurry is 4.5g.On the surface of this negative pole conducting base, apply one deck then again and prevent that the zinc dendrite growth from penetrating the composite coating of barrier film.Pole piece is reentered in 120 ℃ the baking oven and dries.The clean dried gain in weight of composite coating is 0.5g, and the calcium oxide by 30%, 28% cadmium oxide, 2% PVA and 40% water are formed.Hydraulic press with 200 tons of pressure is depressed into the moulding of 0.75mm thickness with negative plate.
Separate stacked together being rolled in the battery case that cylindrical shape packs into the AA type with the positive plate and the negative plate of diaphragm paper with the above-mentioned zinc-nickel secondary batteries that has prepared.The composite diaphragm that diaphragm paper is made up of polyethylene nonwoven fabrics and polycthylene grafted film, thickness are 0.15mm.Inject the saturated NaOH electrolyte 3g that has dissolved zinc oxide then.The concentration of NaOH electrolyte is 14M.Positive plate contacts with battery case as plus plate current-collecting body, and negative plate is weldingly connected by conducting terminal and negative pole cap, at last battery is sealed, packs, stores.
The AA type zinc-nickel secondary batteries that assembles is carried out at normal temperatures the electric performance test of battery.The condition of test is as follows:
1. with 200mA electric current constant current charge 240 minutes, the upper voltage limit of charging was 2.05V;
2. constant voltage was 2.05V charging 150 minutes, and the upper limit current of charging is 400mA;
3. shelved 10 minutes;
4. with 200mA electric current constant-current discharge to 1.0V;
5. according to 1. work step to the 4. work step carry out charge and discharge cycles 10 times.The open circuit voltage that records battery is 1.815V, and discharge capacity is 856mAh first.The discharge capacity of each time charge and discharge cycles sees Table 1:
Table 1
Cycle-index 1 2 3 4 5 6 7 8 9 10
Discharge capacity (mAh) 856 852 845 825 803 780 768 757 736 725
Embodiment 2
Cutting is of a size of 40 * 100mm, and thickness is the conducting base of nickel screen a slice of 0.25mm as positive pole, conducting terminal of spot welding therein.With percentage by weight is that 98% ball-type hydroxide nickel powder and percentage by weight are that 2% conductive additive cadmium metal powder mixes.Is that two rolling mills of 100-400mm are rolled to the moulding of 0.50mm thickness with pole piece by diameter with the nickel screen conducting base with the nickel hydroxide that mixes directly with the conductive additive powder.The clean dried gain in weight of positive mix is controlled at 8 ± 0.1g, or adopts the hydraulic press of 100-500 ton pressure directly nickel hydroxide and the conductive additive that mixes to be depressed into the moulding of 0.50mm thickness with the nickel screen conducting base.The positive plate immersion is filled in the 1M sodium hydrate aqueous solution electrolysis tank of (wherein also containing lithium hydroxide 10g/l).
With the electrolysis forming technology nickel hydroxide in the above-mentioned molded positive plate is transformed into β type hydroxy nickel oxide.Is graphite electrode in order to what positive pole is carried out cell reaction to electrode.Graphite electrode is the graphite cake that is of a size of 40 * 100mm.Graphite electrode is immersed in the same electrolysis tank the be placed in two sides of nickel hydroxide electrode of two graphite electrodes with positive plate.The positive terminal and the nickel hydroxide electrode in rectification source link, and negative pole end then links with two graphite electrodes.The current density of electrolysis tank is controlled to be 50mA/cm 2, voltage control is at 3.0V, and electrolysis time is 0.5 hour.
After electrolysis finishes electrode active material is changed into the positive plate taking-up of hydroxy nickel oxide by nickel hydroxide, promptly can be used as the anodal standby of zinc-nickel secondary batteries after cleaning with running water.Graphite electrode then can stay repeatedly and use.
Cutting is of a size of copper mesh a slice of 38 * 95mm, and thickness is 0.1mm, draws the conducting base of a conducting terminal as negative pole therein.With percentage by weight is that 95% particle diameter is that 300 purpose Zinc alloy powders, percentage by weight are that 2.5% zinc oxide, 1.9% calcium oxide, 0.1% indium oxide mix, with percentage by weight be that 0.5% PPA binding agent, an amount of water are made into slurry, be coated on the copper mesh surface, in 80 ℃ baking oven, dry.The clean dried gain in weight of monolithic electrode slurry is 4.8g.On the surface of this negative pole conducting base, apply one deck then again and prevent that the zinc dendrite growth from penetrating the composite coating of barrier film.Pole piece is reentered in 80 ℃ the baking oven and dries.The clean dried gain in weight of composite coating is 0.5g, is that 30% calcium hydroxide, 28% magnesium oxide, 2% CMC and 40% water are formed by percentage by weight.Two rolling mills with diameter 200mm are rolled to the thick moulding of 0.30mm with cathode pole piece.
Separate with the positive plate and the negative plate of diaphragm paper with the above-mentioned zinc-nickel secondary batteries that has prepared, the cylindrical shape that is rolled into stacked together packs in the AA type battery case.The composite diaphragm that diaphragm paper is made up of polypropylene non-woven fabric and polypropylene grafted film, thickness are 0.30mm.Inject the saturated potassium hydroxide electrolyte 4g that has dissolved zinc oxide then.The concentration of potassium hydroxide electrolyte is 1M.Positive plate contacts with battery case as plus plate current-collecting body, and negative plate is weldingly connected by conducting terminal and negative pole cap, at last battery is sealed, packs, stores.
The AA type zinc-nickel secondary batteries that assembles is carried out at normal temperatures the electric performance test of battery.The condition of test is as follows:
1. with 200mA electric current constant current charge 240 minutes, the charging upper voltage limit was 2.05V;
2. constant voltage was 2.05V charging 150 minutes, and the charging upper limit current is 400mA;
3. shelved 10 minutes;
4. with 200mA electric current constant-current discharge to 1.0V;
5. according to 1. work step to the 4. work step carry out charge and discharge cycles 10 times.The open circuit voltage that records battery is 1.785V, and discharge capacity is 1056mAh first.The discharge capacity of each time charge and discharge cycles sees Table 2:
Table 2
Cycle-index 1 2 3 4 5 6 7 8 9 10
Discharge capacity (mAh) 1056 1058 1058 1055 1053 1045 1040 1037 1036 1025
Embodiment 3
The cutting surface density is 450g/m 2, being of a size of 40 * 100mm, thickness is the conducting base of foaming nickel sheet a slice of 2.0mm as positive pole.Metallic nickel content＞99.5% of foaming nickel sheet, other impurity content is: carbon≤200ppm, iron≤100ppm, sulphur≤80ppm, copper≤100ppm, silicon≤50ppm.Its porosity 〉=95%, hole count 80～110ppi.Tensile strength: vertically 〉=1.25N/mm 2, laterally 〉=1.00N/mm 2Elongation: vertically 〉=5%, laterally 〉=12%.
Conducting terminal of spot welding on foaming nickel sheet is that 93% ball-type hydroxide nickel powder and percentage by weight are that 6% conductive additive metal nickel powder mixes with percentage by weight.With percentage by weight is the water dissolving of 1% CMC binding agent elder generation, adding water with positive mix again is mixed together and evenly is made into slurry, be coated in foaming nickel the inside, in 80 ℃ baking oven, dry, the clean dried gain in weight of positive powder is controlled at 8 ± 0.1g, with diameter is that two rolling mills of 300mm will foam that to be rolled to 0.55mm thick for the nickel pole piece, immerses to fill in the potassium hydroxide aqueous solution that concentration the is 7M electrolysis tank of (wherein also containing lithium hydroxide 20g/1).
With the electrolysis forming technology nickel hydroxide in the above-mentioned molded positive plate is transformed into β type hydroxy nickel oxide.Is the cadmium oxide electrode in order to what positive pole is carried out cell reaction to electrode.This cadmium oxide electrode is to adopt two chip sizes to be all the nickel plated steel strip of 40 * 100mm, is that 95% cadmium oxide powder, 5% PVA, an amount of water are made into slurry with percentage by weight, is coated on the nickel plated steel strip surface, dries in 80 ℃ baking oven.The clean dried gain in weight of monolithic electrode active material is 8.0g.It is thick with diameter to be that two rolling mills of 100mm are rolled to 0.50mm with the nickel plated steel strip pole piece, immerses in the same electrolysis tank with positive plate.The be placed in two sides of nickel hydroxide electrode of two cadmium oxide electrodes.The positive terminal and the nickel hydroxide electrode in rectification source link, and negative pole end and two cadmium oxide electrodes link.The current density of electrolysis tank is controlled to be 2.5mA/cm 2, voltage control is at 1.60V, and electrolysis time is 12 hours.
After electrolysis finishes electrode active material is changed into the positive plate taking-up of hydroxy nickel oxide by nickel hydroxide, promptly can be used as the anodal standby of zinc-nickel secondary batteries after cleaning with deionized water.The cadmium oxide electrode then can stay repeatedly and use.
Cutting is of a size of foam copper a slice of 38 * 95mm, and thickness is 3.0mm, draws the conducting base of a conducting terminal as negative pole therein.With percentage by weight is that 85% particle diameter is that 200 purpose Zinc alloy powders, 5% zinc oxide, 2% magnesium oxide, 4.9% calcium oxide, 0.1% indium hydroxide mix, with percentage by weight be that 3% PTFE emulsion is made into slurry, brush in the foam copper the inside.The clean dried gain in weight of monolithic electrode slurry is 5g.On the surface of this negative pole conducting base, apply one deck then again and prevent that the zinc dendrite growth from penetrating the composite coating of barrier film.The baking oven of pole piece being put into 80 ℃ is dried.The clean dried gain in weight of composite coating is 0.5g, is that 28% calcium hydroxide, 30% cadmium oxide, 2% PTFE and 40% water are formed by percentage by weight.The two rolling mills that with diameter are 300mm are rolled to the thick moulding of 0.35mm with cathode pole piece.
Separate stacked together being rolled in the battery case that cylindrical shape packs into the AA type with the positive plate and the negative plate of diaphragm paper with the above-mentioned zinc-nickel secondary batteries that has prepared.The composite diaphragm that diaphragm paper is made up of vinylon nonwoven fabrics and polypropylene grafted film.Inject the saturated potassium hydroxide electrolyte 3g that has dissolved zinc oxide then.The concentration of potassium hydroxide electrolyte is 10M.Positive plate contacts with battery case as plus plate current-collecting body, and negative plate is weldingly connected by conducting terminal and negative pole cap, at last battery is sealed, packs, stores.
The AA type zinc-nickel secondary batteries that assembles is carried out at normal temperatures the electric performance test of battery.Test condition is as follows:
1. with 200mA electric current constant current charge 240 minutes, the charging upper voltage limit was 2.05V;
2. constant voltage was 2.05V charging 150 minutes, and the charging upper limit current is 400mA;
3. shelved 10 minutes;
4. with 200mA electric current constant-current discharge to 1.0V;
5. according to 1. work step to the 4. work step carry out charge and discharge cycles 10 times.The open circuit voltage that records battery is 1.825V, and discharge capacity is 1856mAh first.The discharge capacity of each time charge and discharge cycles sees Table 3:
Table 3
Cycle-index 1 2 3 4 5 6 7 8 9 10
Discharge capacity (mAh) 1856 1866 1865 1865 1863 1860 1861 1858 1856 1855

Claims (4)

1, a kind of preparation method of zinc-nickel secondary batteries, it is characterized in that adopting the coiled battery structure, with diaphragm paper positive plate and negative plate are separated, the garden tubular that is rolled into stacked together packs in the battery case, inject electrolyte, positive plate contacts with battery case as plus plate current-collecting body, and negative plate is weldingly connected by conducting terminal and negative pole cap, at last battery is sealed, packs, stores; Described positive plate adopts following method to prepare:
(1) conducting base is drawn one or more conducting terminals; Described conducting base thickness is 0.1-3.0mm, and conducting base is foaming nickel, nickel screen or a nickel strap;
(2) the hydroxide nickel powder mixes with additives for battery, and wherein the consumption of hydroxide nickel powder accounts for 70%-98%, and surplus is an additive; Described hydroxide nickel powder is ball-type nickel hydroxide and/or nickel hydroxide; Described additive is wherein one or more mixtures of graphite powder, acetylene black, conductive carbon black, metal nickel powder, cadmium metal powder, copper powder, metal zinc, cobalt compound, manganese compound, aluminium compound, zinc compound, cadmium compound, lithium compound;
(3) use the dissolution with solvents binding agent, the weight ratio of solvent and binding agent is 1: 10-99; Described solvent is water miscible water or ethanol, or non-water-soluble N-methyl pyrrolidone or dimethylacetylamide; Described binding agent is water miscible or the carboxymethyl cellulose of water dispersible (CMC), polytetrafluoroethylene (PTFE) emulsion, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO) one or more mixtures wherein; Or non-water-soluble Kynoar (PVDF) and/or hexafluoropropylene;
(4) mixture that (2) are obtained mixes with binder solution that (3) obtain and is made into slurry, be coated on the conducting base, 60-120 ℃ of oven dry down, after the moulding the nickel hydroxide positive plate sheet;
(5) with the electrolysis chemical synthesizing method nickel hydroxide in the positive plate in (4) step is transformed into β type hydroxy nickel oxide, what adopt when electrolysis changes into is Titanium electrode, graphite electrode or cadmium oxide electrode to electrode.
2, the preparation method of zinc-nickel secondary batteries according to claim 1 is characterized in that described electrolyte is the potassium hydroxide or the sodium hydrate aqueous solution of saturated zinc oxide, and concentration is 1-14M.
3, the preparation method of zinc-nickel secondary batteries according to claim 1 and 2 is characterized in that described cadmium film paper is that thickness is vinylon, polypropylene, polyethylene nonwoven fabrics, polyethylene or the polypropylene grafted film of 0.15-0.30mm.
4, the zinc-nickel secondary batteries of the described method preparation of claim 1.
CNB031138829A 2003-03-10 2003-03-10 Zinc-nickel secondary cell and preparation method thereof Expired - Fee Related CN1283022C (en)

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