CN1434534A - Zinc-nickel secondary cell and preparation method thereof - Google Patents
Zinc-nickel secondary cell and preparation method thereof Download PDFInfo
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- Y02E60/10—Energy storage using batteries
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Abstract
This invention relates to a preparation method for ZnNi secondary cell and the cell prepared by the said method which is to isolate the positive and negative plates by diaphragm paper to be put into cell shell after being laminated and winded and fill in electrolyte, the positive plate contacts with the shell of positive collector, the negative is connected with the negative cap in weld via conductive terminal, finally go on with sealing, packing and storage, with the advantags of high voltage, large discharge capacitance, long circulation life, small internal resistance, excellent large current discharging performance.
Description
(I) in the field of technology
The invention relates to the field of chemical power sources, in particular to a preparation method of a zinc-nickel secondary battery.
The invention also relates to a zinc-nickel secondary battery prepared by the method.
(II) background of the invention
In recent years, high-tech products such as portable computers, portable communication devices, cordless electric tools, digital cameras, video cameras, and the like have been rapidly developed with rapid development of human socioeconomic performance. The development of a mobile chemical power supply matched with the device becomes a problem to be solved urgently. Generally, the portable electronic and electrical products require a chemical power source to have the advantages of higher operating voltage, higher specific energy, higher operating current, longer cycle life, smaller volume, safety, and low price.
The research on zinc-nickel battery systems has been carried out for hundreds of years. In the research process, the zinc-nickel secondary battery has the problems of zinc dendrite growth, zinc electrode deformation, nickel electrode expansion, zinc oxide poisoning, diaphragm oxidation, zinc dendrite penetration and the like in the recycling process. The series of reasons cause the short service life of the battery, so that the battery series cannot realize large-scale practical application and industrialization.
U.S. patent application "fully sealed alkaline storage battery" recently filed by sanyo electric limited, m.tokuda, m.yano, m.nogami, s.fujitani, k.nishio, US Pat. No. 6, 265, 105B 1, 2001]Oxidizing nickel hydroxide [ Ni (OH)]with sodium hypochlorite (NaClO) solution2]The gamma-NiOOH is prepared by the method, the gamma-NiOOH is used as a positive electrode active substance of the zinc-nickel secondary battery, the calamine cream is used as a negative electrode active substance of the zinc-nickel secondary battery, and the copper needle is inserted into the calamine cream to be used as the anode active substance ofthe zinc-nickel secondary batteryAnd a negative current collector. The gamma-type nickel oxyhydroxide has poor conductivity, and can be used as the anode of a zinc-nickel secondary battery only by mechanically mixing the gamma-type nickel oxyhydroxide with conductive materials such as graphite powder and the like, pressing the gamma-type nickel oxyhydroxide into powder rings, and then pressing the three powder rings together and tightly attaching the three powder rings to a battery shell. The cathode zinc paste is loaded by a diaphragm cylinder made of vinylon non-woven fabric and plays a role in isolating the anode and the cathode. However, these background arts also have the following problems:
(1) the production process of the battery anode is complex, and the quality of the gamma-type nickel oxyhydroxide is difficult to control;
(2) the density of the gamma-type nickel oxyhydroxide is low, so that the loading capacity of the unit volume of the positive active material is low, and the battery capacity is low;
(3) because the density of the gamma-type hydroxyl nickel oxide is low, the conductivity is poor, the internal resistance of the battery is high, and the large-current discharge performance is poor;
(4) the gamma-type hydroxyl nickel oxide and the conductive material graphite powder are mechanically mixed to form a powder ring as a positive electrode, and the conductivity of the positive electrode is poor;
(5) the calamine cream is as the battery negative pole, and the copper needle is as negative pole mass flow body, and the area of contact of copper needle and calamine cream is little, and contact resistance is big, and polarization is great, causes the resistance of negative pole great, and the operating voltage of battery is lower, and it is great to generate heat.
Disclosure of the invention
The invention aims to provide a preparation method of a zinc-nickel secondary battery aiming at the problems in the prior art, and the obtained zinc-nickel secondary battery has the advantages of high voltage, large discharge capacity, long cycle life, small internal resistance, excellent large-current discharge performance, good safety, no environmental pollution and the like.
The invention also aims to provide the zinc-nickel secondary battery prepared by the method.
The preparation method of the zinc-nickel secondary battery comprises the following steps: the winding type battery structure is adopted, the positive plate and the negative plate are separated by the diaphragm paper, the positive plate and the negative plate are laminated together and rolled into a cylinder shape to be sleeved in a battery shell, electrolyte is injected, the positive plate is in contact with the battery shell serving as a positive current collector, the negative plate is connected with a negative cap in a welding mode through a conductive terminal, and finally the battery is sealed, packaged and stored.
The electrolyte solution is potassium hydroxide or sodium hydroxide aqueous solution of saturated zinc oxide, and the concentration is 1-14M.
The cadmium film is a vinylon, polypropylene, polyethylene non-woven fabric, polyethylene or polypropylene graft film with the thickness of 0.15-0.30 mm.
The positive plate is prepared by the following method:
(1) one or more conductive terminals are led out of the conductive base body; the thickness of the conductive substrate is 0.1-3.0mm, and the conductive substrate is foamed nickel, a nickel net or a nickel belt;
(2) mixing nickel hydroxide powder with a battery additive, wherein the nickel hydroxide powder accounts for 70-98% of the total weight of the battery additive, and the balance is the additive; the nickel hydroxide powder is spherical nickel hydroxide and/or common nickel hydroxide; the additive is one or a mixture of more than one of graphite powder, acetylene black, conductive carbon black, metallic nickel powder, metallic cadmium powder, metallic copper powder, metallic zinc powder, a cobalt compound, a manganese compound, an aluminum compound, a zinc compound, a cadmium compound, a lithium compound and the like;
(3) dissolving the binder by using a solvent, wherein the weight ratio of the solvent to the binder is 1: 10-99; the solvent may be water-soluble, such as water, ethanol, etc., or water-insoluble, such as N-methylpyrrolidone, dimethylacetamide, etc.;
the binder may be water soluble or water dispersible, such as one or a mixture of more than one of carboxymethyl cellulose (CMC), Polytetrafluoroethylene (PTFE) emulsion, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyethylene oxide (PEO), and the like; or may be water insoluble, such as polyvinylidene fluoride (PVDF) and/or hexafluoropropylene, and the like;
(4) mixing the mixture obtained in the step (2) and the binder solution obtained in the step (3) to prepare slurry, coating the slurry on a conductive substrate, drying the conductive substrate at 60-120 ℃, and forming to obtain a nickel hydroxide positive plate;
the forming method can adopt a double-roller rolling machine with the diameter of 100-.
The nickel hydroxide positive plate can be formed by adopting a dry process: directly rolling the uniformly mixed nickel hydroxide and battery additive powder together with the conductive substrate to the thickness of 0.20-0.90mm through a double-rolling mill with the diameter of 100-400mm, and molding, or pressing the uniformly mixed nickel hydroxide and battery additive powder together with the conductive substrate to the thickness of 0.20-0.90mm by adopting an oil press with the weight of 100-500 tons;
(5) converting the nickel hydroxide in the positive plate into β type nickel oxyhydroxide by an electrolytic formation method, wherein the counter electrode used in the electrolytic formation can be a metallic titanium electrode, a graphite electrode or a cadmium oxide electrode;
the cadmium oxide electrode is made up by using two pieces of nickel-plated steel band, mixing cadmium oxide powder, adhesive and water into slurry, coating it on the surface of steel band, drying at 60-150 deg.C and forming.
The pole pieces can be rolled to a thickness of 0.30-0.90mm by a double-rolling machine with a diameter of 50-400mm for molding.
The nickel hydroxide positive plate and two counter electrode metal titanium electrodes, or graphite electrodes or cadmium oxide electrodes are immersed into an electrolytic bath containing alkaline electrolyte. The two counter electrodes are respectively arranged on two sides of the nickel hydroxide positive plate, the positive end of the rectifying source is connected with the nickel hydroxide positive plate, and the negative end of the rectifying source is connected with the two counter electrodes. The current density of the electrolytic cell is controlled between 0.1 and 50mA/cm2The voltage is controlled to be 1.4-3.0V, and the electrolysis time is 0.5-24 hours.
The alkaline electrolyte is prepared by dissolving one or more of potassium hydroxide, sodium hydroxide and lithium hydroxide in deionized water, distilled water or tap water. Wherein, the concentration of potassium hydroxide or sodium hydroxide is 1-12M, and the concentration of lithium hydroxide is 10-40 g/l.
After the electrolysis is finished, the nickel hydroxide in the positive plate is converted into β type nickel oxyhydroxide.
The positive plate with β type nickel oxyhydroxide is taken out and washed by deionized water, distilled water or tap water to be used as the positive electrode of the zinc-nickel secondary battery for standby, and the counter electrode metal titanium electrode, graphite electrode or cadmium oxide electrode can be left for repeated use.
The preparation method of the negative plate comprises the following steps:
(1) one or more conductive terminals are led out from the negative conductive matrix. The conductive substrate can be any one of foamed copper, copper mesh or copper strip, and the thickness of the conductive substrate is 0.1-3.0 mm. The surface of the negative electrode conductive substrate can be plated with indium as required.
(2) Mixing metal zinc powder with a negative electrode additive. The metal zinc powder is metal zinc alloy powder with the grain diameter of 70-300 meshes, wherein a trace amount of indium, bismuth or lead and compounds thereof are added as corrosion inhibitors; the negative electrode additive can be one or more of zinc oxide, calcium oxide, magnesium oxide, cadmium oxide, aluminum oxide, indium compound, bismuth compound, lead compound and the like. The weight percentage of the metal zinc powder in the mixture is 60-95%, and the weight percentage of the negative electrode additive in the mixture is 5-40%.
(3) Adding a binder into the mixture in the step (2). The binder may be one or more of carboxymethyl cellulose (CMC), Polytetrafluoroethylene (PTFE) emulsion, polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyethylene oxide (PE0), etc. The content of the binder in the mixture is 1 to 30 percent by weight.
(4) And (3) coating the negative electrode mixture on a conductive substrate of a negative electrode, drying at 60-120 ℃, and then coating a composite coating for preventing the growth of zinc dendrites from penetrating through a diaphragm on the surface of the conductive substrate of the negative electrode. The composite coating is composed of one or more of calcium oxide, calcium hydroxide, magnesium oxide, cadmium oxide, aluminum oxide and the like. The weight percentage content of the mixture in the composite coating is 99-70%. At the same time, one or more than one mixture of carboxymethyl cellulose (CMC), Polytetrafluoroethylene (PTFE) emulsion, polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyethylene oxide (PEO) and the like is added as a binder. The weight percentage content of the binder in the composite coating is 1-30%.
(5) Drying at 60-120 deg.C, and forming to obtain negative plate.
The negative plate can be formed by adopting a double-rolling mill with the diameter of 100-400mm or an oil press with the pressure of 100-500 tons to press the negative plate to the thickness of 0.30-0.75 mm.
The principle of preparing β type nickel oxyhydroxide (β -NiOOH) as the positive electrode active material of the zinc-nickel secondary battery by an electrolytic synthesis method is as follows:
β -NiOOH will form gamma-NiOOH when overcharged, but the formation of gamma-NiOOH can be suppressed by adding appropriate additives and controlling the reaction conditions.
The principle of the charge-discharge reaction of the zinc-nickel secondary battery is as follows:
the total reaction of the battery:
the standard free energy G DEG of the battery reaction is-80694 calories, the standard heat of formation H DEG is-85534 calories, and the entropy change S DEG is-16.239 calories/degree. The thermodynamic electromotive force E ° of the cell reaction was calculated from G ° -nE ° F to be 1.854V. Wherein n represents the equivalent number of reactants; f is the Faraday constant. The battery emits heat during the discharge process, resulting in battery heating, wherein the battery heating caused by entropy change accounts for more than 40% of the total heat. The theoretical specific energy of the cell reaction was 326 wh/kg.
Compared with the prior art, the invention has the following advantages:
(1) the method for preparing β type nickel oxyhydroxide of the positive electrode of the zinc-nickel secondary battery by using the electrolytic formation technology has simple process and easy quality control;
(2) the β type hydroxyl nickel oxide active substance has high density, high specific capacity and excellent conductivity;
(3) compared with the prior art that the zinc paste is used as a negative active substance, and the copper needle is inserted into the zinc paste to be used as a negative current collector, the invention coats the negative zinc powder active substance on a negative conductive substrate such as foamed copper, a copper net or a copper strip, and the like, which is beneficial to increasing the contact area of the zinc powder active substance and the negative conductive substrate, increasing the reaction area of an electrode, reducing the internal resistance of the battery and improving the high-current discharge performance of the battery;
(4) according to the invention, the surface of the negative conductive substrate coated with the mixture of the negative active material and the like is coated with a composite coating for preventing the zinc dendrite from growing and penetrating through the diaphragm, so that the situation that the zinc dendrite penetrates through the diaphragm to cause short circuit and scrap of the battery can be effectively prevented;
(5) the foamed nickel, nickel net or nickel belt with large specific surface area and the metal matrixes such as the foamed copper, copper net or copper belt are used as the conductive matrixes of the positive electrode and the negative electrode of the battery, so that the utilization rate of active substances of the positive electrode and the negative electrode of the battery and the area of electrode reaction are improved;
(6) the zinc-nickel secondary battery prepared by adopting the winding battery structure has the characteristics of high voltage, large specific discharge capacity, long cycle life, small internal resistance, excellent heavy-current discharge performance and the like;
(7) the positive and negative electrodes prepared by the invention have the advantages of large density, large specific surface area, good conductivity, high specific capacity, large specific power, stable electrical property, simple and easy operation process, easy quality control and the like, and are particularly suitable for being used as the positive and negative electrodes of the zinc-nickel secondary battery. The zinc-nickel secondary battery prepared by the invention has the characteristics of high voltage, large specific discharge capacity, long cycle life, small internal resistance, excellent large-current discharge performance, safety, no environmental pollution and the like.
The invention has great promotion effect on the practicability and industrialization of the zinc-nickel secondary battery.
(IV) description of the drawings
FIG. 1 is a charge-discharge curve diagram of AA type zinc-nickel secondary battery prepared by the present invention.
(V) detailed description of the preferred embodiments
As shown in fig. 1, the charge and discharge conditions of the battery were as follows:
(1) charging at a constant current of 200mA for 240 minutes, wherein the upper limit voltage of the charging is 2.05V;
(2) charging for 150 minutes at a constant voltage of 2.05V, wherein the upper limit current of the charging is 400 mA;
(3) standing for 10 minutes;
(4) discharging with a constant current of 200mA until the voltage of the battery is reduced to 1.0V; the steps from (1) to (4) are a charge-discharge cycle of the battery.
Example 1
A nickel strip with the size of 40 multiplied by 100mm and the thickness of 0.25mm is cut to be used as a conductive matrix of the anode, and a conductive terminal is spot-welded in the nickel strip. The common nickel hydroxide powder with the weight percentage of 70 percent and the conductive additive graphite powder with the weight percentage of 27 percent are evenly mixed. Dissolving 3% PVA binder by weight percentage with water, adding water into the mixture, uniformly mixing the mixture and the water to prepare anode slurry, coating the anode slurry on a nickel strip, drying the nickel strip in a drying oven at 100 ℃, controlling the net dry weight gain of the anode slurry to be 8 +/-0.1 g, rolling the nickel strip anode plate to be 0.50mm thick by using a double-roller mill with the diameter of 400mm, and immersing the nickel strip anode plate into an electrolytic tank containing 14M sodium hydroxide aqueous solution (wherein the lithium hydroxide also contains 40 g/l).
The nickel hydroxide in the formed positive plate is converted into β type nickel oxyhydroxide by electrolysis technology, the counter electrode for electrolysis reaction of the positive electrode is a metallic titanium electrode with the size of 40 x 100mm, the metallic titanium electrode and the positive plate are immersed into the same electrolytic tank, the two metallic titanium counter electrodes are respectively arranged on two sides of the positive plate of nickel hydroxide, the positive end of a rectifying source is connected with the positive plate of nickel hydroxide, the negative end is connected with the two metallic titanium electrodes, and the current density of the electrolytic tank is controlled to be 0.1mA/cm2The voltage was controlled at 1.4V and the electrolysis time was 24 hours.
After the electrolysis is finished, the positive plate of which the electrode active material is converted into the nickel oxyhydroxide by the nickel hydroxide is taken out and washed by distilled water to be used as the positive electrode of the zinc-nickel secondary battery for standby. The titanium metal electrode can be used repeatedly.
And cutting a 38 x 95mm copper strip into one piece with the thickness of 0.15mm, and leading out a conductive terminal serving as a conductive substrate of the cathode. The method comprises the steps of uniformly mixing 60 wt% of zinc alloy powder with the grain size of 70 meshes, 18 wt% of zinc oxide, 18.9 wt% of calcium oxide and 0.1 wt% of metal indium, preparing slurry with 3 wt% of PVA binder and a proper amount of water, coating the slurry on the surface of a copper strip, and drying in a 120 ℃ oven, wherein the net dry weight gain of thesingle-piece electrode slurry is 4.5 g. And then coating a composite coating layer for preventing the zinc dendrite from growing and penetrating through the diaphragm on the surface of the negative electrode conductive substrate. And putting the pole piece into the oven at 120 ℃ again for drying. The dry weight gain of the composite coating was 0.5g, consisting of 30% calcium oxide, 28% cadmium oxide, 2% PVA and 40% water. The negative plate was pressed to a thickness of 0.75mm by an oil press of 200 tons pressure.
The positive plate and the negative plate of the prepared zinc-nickel secondary battery are separated by using diaphragm paper, and are laminated together and rolled into a cylinder shape to be sleeved in an AA type battery shell. The diaphragm paper is a composite diaphragm consisting of polyethylene non-woven fabrics and polyethylene grafted films, and the thickness of the diaphragm paper is 0.15 mm. Then, 3g of a sodium hydroxide electrolyte solution saturated with and dissolving zinc oxide was injected. The concentration of the sodium hydroxide electrolyte was 14M. The positive plate is contacted with a battery case as a positive current collector, the negative plate is welded and connected with a negative cap through a conductive terminal, and finally, the battery is sealed, packaged and stored.
And (3) carrying out electrical property test on the assembled AA type zinc-nickel secondary battery at normal temperature. The conditions tested were as follows:
① charging at 200mA current for 240 min with upper limit voltage of 2.05V;
② constant voltage is charged for 150 minutes at 2.05V, and the upper limit current of the charging is 400 mA;
③ left for 10 minutes;
④ constant current discharging to 1.0V at 200mA current;
⑤ the chargeand discharge cycles were carried out for 10 times according to the steps ① to ④, the open circuit voltage of the cell was measured to be 1.815V, the first discharge capacity was 856mah, the discharge capacity of each charge and discharge cycle is shown in table 1:
TABLE 1
Example 2
| Circulation of Number of times | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Discharge of electricity Capacity of (mAh) | 856 | 852 | 845 | 825 | 803 | 780 | 768 | 757 | 736 | 725 |
A nickel mesh sheet with the size of 40 multiplied by 100mm and the thickness of 0.25mm is cut to be used as a conductive matrix of the anode, and a conductive terminal is spot-welded in the nickel mesh sheet. The spherical nickel hydroxide powder with the weight percentage of 98 percent and the conductive additive metal cadmium powder with the weight percentage of 2 percent areevenly mixed. And directly rolling the uniformly mixed nickel hydroxide and conductive additive powder together with the nickel mesh conductive substrate to the thickness of 0.50mm by a double-rolling mill with the diameter of 100-400mm, and molding. The net dry weight gain of the anode powder is controlled at 8 +/-0.1 g, or the nickel hydroxide and the conductive additive which are uniformly mixed and the nickel mesh conductive matrix are directly pressed to the thickness of 0.50mm by adopting an oil press with the pressure of 100-ton and 500-ton for molding. The positive electrode sheet was immersed in an electrolytic bath containing 1M aqueous sodium hydroxide solution (which also contained 10g/l lithium hydroxide).
The nickel hydroxide in the formed positive plate is converted into β type nickel oxyhydroxide by electrolysis technology, the counter electrode for carrying out electrolysis reaction on the positive electrode is a graphite electrode, the graphite electrode is a graphite plate with the size of 40 multiplied by 100mm, the graphite electrode and the positive plate are immersed into the same electrolytic tank, the two graphite electrodes are respectively arranged on two sides of the nickel hydroxide electrode, the positive end of a rectification source is connected with the nickel hydroxide electrode,the negative end is connected with two graphite electrodes. The current density of the electrolytic cell is controlled to be 50mA/cm2The voltage was controlled at 3.0V and the electrolysis time was 0.5 hour.
After the electrolysis is finished, the positive plate with the electrode active material converted into the nickel oxyhydroxide by the nickel hydroxide is taken out and washed by tap water to be used as the positive electrode of the zinc-nickel secondary battery for standby. The graphite electrode can be left for repeated use.
A copper net piece with the size of 38multiplied by 95mm is cut, the thickness is 0.1mm, and a conductive terminal is led out to be used as a conductive base body of a negative electrode. Uniformly mixing 95 wt% of zinc alloy powder with the grain diameter of 300 meshes, 2.5 wt% of zinc oxide, 1.9 wt% of calcium oxide and 0.1 wt% of indium oxide, preparing a slurry with 0.5 wt% of PPA binder and a proper amount of water, coating the slurry on the surface of a copper mesh, and drying in an oven at 80 ℃. The net dry weight gain of the monolithic electrode paste was 4.8 g. And then coating a composite coating layer for preventing the zinc dendrite from growing and penetrating through the diaphragm on the surface of the negative electrode conductive substrate. And putting the pole piece into an oven at 80 ℃ again for drying. The net dry weight gain of the composite coating is 0.5g, and the composite coating consists of 30 weight percent of calcium hydroxide, 28 weight percent of magnesium oxide, 2 weight percent of CMC and 40 weight percent of water. And rolling the negative pole piece to the thickness of 0.30mm by using a double-rolling machine with the diameter of 200mm, and molding.
The positive plate and the negative plate of the prepared zinc-nickel secondary battery are separated by diaphragm paper, and are laminated together to be rolled into a cylinder shape to be sleeved in an AA type battery shell. The membrane paper is a composite membrane consisting of polypropylene non-woven fabrics and polypropylene graft membranes, and the thickness of the membrane paper is 0.30 mm. Then, 4g of potassium hydroxide electrolyte solution in which zinc oxide was dissolved in a saturated state was injected. The concentration of the potassium hydroxide electrolyte was 1M. The positive plate is contacted with a battery case as a positive current collector, the negative plate is welded and connected with a negative cap through a conductive terminal, and finally, the battery is sealed, packaged and stored.
And (3) carrying out electrical property test on the assembled AA type zinc-nickel secondary battery at normal temperature. The conditions tested were as follows:
① charging at constant current of 200mA for 240 min, with upper limit voltage of 2.05V;
② constant voltage is charged for 150 minutes at 2.05V, the upper limit current of charging is 400 mA;
③ left for 10 minutes;
④ constant current discharging to 1.0V at 200mA current;
⑤ the charge and discharge cycles were carried out for 10 times according to the steps ① to ④, the open-circuit voltage of the cell was measured to be 1.785V, the first discharge capacity was 1056mah, and the discharge capacity of each charge and discharge cycle is shown in table 2:
TABLE 2
Example 3
| Circulation of Number of times | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Discharge of electricity Capacity of (mAh) | 1056 | 1058 | 1058 | 1055 | 1053 | 1045 | 1040 | 1037 | 1036 | 1025 |
The cut surface density is 450g/m2One piece of foamed nickel sheet with the size of 40 multiplied by 100mm and the thickness of 2.0mm is used as the conductive substrate of the anode. The metallic nickel content of the foaming nickel sheet is more than 99.5 percent, and the other impurity contents are as follows: less than or equal to 200ppm of carbon, less than or equal to 100ppm of iron, less than or equal to 80ppm of sulfur, less than or equal to 100ppm of copper and less than or equal to 50ppm of silicon. The porosity is more than or equal to 95 percent, and the number of pores is 80-110 ppi. Tensile strength: longitudinal direction is more than or equal to 1.25N/mm2Transverse direction is more than or equal to 1.00N/mm2. Elongation percentage: longitudinal direction is 55%, and transverse direction is more than or equal to 12%.
Welding a conductive terminal on the foamed nickel sheet, and uniformly mixing the spherical nickel hydroxide powder with the weight percentage of 93 percent and the conductive additive metallic nickel powder with the weight percentage of 6 percent. Dissolving 1% CMC binder by weight with water, then adding water into the CMC binder and the anode powder, uniformly mixing the CMC binder and the anode powder to prepare slurry, coating the slurry in foamed nickel, drying the foamed nickel in a drying oven at 80 ℃, controlling the net dry weight gain of the anode powder to be 8 +/-0.1 g, rolling the foamed nickel pole piece to be 0.55mm thick by a double-roller mill with the diameter of 300mm, and immersing the foamed nickel pole piece in an electrolytic bath containing 7M potassium hydroxide aqueous solution (wherein 20g/l of lithium hydroxide is also contained).
Converting nickel hydroxide in the formed positive plate into β type hydroxyl nickel oxide by electrolysis technology, using the counter electrode for carrying out electrolysis reaction on the positive electrode as a cadmium oxide electrode, wherein the cadmium oxide electrode is a nickel-plated steel belt with the same size of 40 x 100mm, preparing slurry by 95% of cadmium oxide powder, 5% of PVA and a proper amount of water according to the weight percentage, coating the slurry on the surface of the nickel-plated steel belt, drying the nickel-plated steel belt in an oven at 80 ℃, rolling the net dry weight gain of a single electrode active substance to be 8.0g, rolling the nickel-plated steel belt pole piece to be 0.50mm thick by a double-rolling mill with the diameter of 100mm, immersing the nickel-plated steel belt pole piece and the positive plate into the same electrolytic tank, arranging the two cadmium oxide electrodes on two sides of the nickel hydroxide electrode, connecting the positive end of a rectification source with the nickel hydroxide electrode, connecting the negative end with the two cadmium oxide electrodes, and controlling the current density of the electrolytic tank to be 2.5mA/cm2The voltage was controlled at 1.60V and the electrolysis time was 12 hours.
And after the electrolysis is finished, taking out the positive plate of which the electrode active substance is converted into the nickel oxyhydroxide by the nickel hydroxide, and cleaning the positive plate by deionized water to be used as the positive electrode of the zinc-nickel secondary battery for standby. The cadmium oxide electrode can be left for repeated use.
Cutting a piece of foamed copper with the size of 38 multiplied by 95mm, wherein the thickness is 3.0mm, and leading out a conductive terminal as a conductive base body of a negative electrode. The preparation method comprises the steps of uniformly mixing 85 wt% of zinc alloy powder with the particle size of 200 meshes, 5 wt% of zinc oxide, 2 wt% of magnesium oxide, 4.9 wt% of calcium oxide and 0.1 wt% of indium hydroxide, preparing a slurry with 3 wt% of PTFE emulsion, and brushing the slurry in the foaming copper. The net dry weight gain of the monolithic electrode paste was 5 g. And then coating a composite coating layer for preventing the zinc dendrite from growing and penetrating through the diaphragm on the surface of the negative electrode conductive substrate. And (3) putting the pole piece into an oven at 80 ℃ for drying. The net dry weight gain of the composite coating is 0.5g, and the composite coating consists of 28 weight percent of calcium hydroxide, 30 weight percent of cadmium oxide, 2 weight percent of PTFE and 40 weight percent of water. And rolling the negative pole piece to the thickness of 0.35mm by using a double-rolling machine with the diameter of 300mm, and molding.
The positive plate and the negative plate of the prepared zinc-nickel secondary battery are separated by using diaphragm paper, and are laminated together and rolled into a cylinder shape to be sleeved in an AA type battery shell. The diaphragm paper is a composite diaphragm consisting of a vinylon non-woven fabric and a polypropylene grafted film. Then, 3g of potassium hydroxide electrolyte saturated with zinc oxide dissolved therein was injected. The concentration of the potassium hydroxide electrolyte was 10M. The positive plate is contacted with a battery case as a positive current collector, the negative plate is welded and connected with a negative cap through a conductive terminal, and finally, the battery is sealed, packaged and stored.
And (3) carrying out electrical property test on the assembled AA type zinc-nickel secondary battery at normal temperature. The test conditions were as follows:
① charging at constant current of 200mA for 240 min, with upper limit voltage of 2.05V;
② constant voltage is charged for 150 minutes at 2.05V, the upper limit current of charging is 400 mA;
③ left for 10 minutes;
④ constant current discharging to 1.0V at 200mA current;
⑤ the charge and discharge cycles were carried out for 10 times according to the steps ① to ④, the open-circuit voltage of the cell was measured to be 1.825V, the first discharge capacity was 1856mah, the discharge capacity of each charge and discharge cycle is shown in table 3:
TABLE 3
| Circulation of Number of times | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Discharge of electricity Capacity of mAh) | 1856 | 1866 | 1865 | 1865 | 1863 | 1860 | 1861 | 1858 | 1856 | 1855 |
Claims (7)
1. A process for preparing secondary Zn-Ni battery features that a coiled battery structure is used, which is prepared through separating positive plate from negative plate by diaphragm paper, laminating them together, rolling to become cylindrical shape, inserting it in battery case, filling electrolyte, welding the negative plate to negative cap via conducting terminal, and sealing, packing and storing.
2. The method of claim 1, wherein the electrolyte solution is an aqueous solution of potassium hydroxide or sodium hydroxide saturated with zinc oxide, and has a concentration of 1 to 14M.
3. The method of manufacturing a zinc-nickel secondary battery according to claim 1 or 2, wherein the cadmium film is a vinylon, polypropylene, polyethylene non-woven fabric, polyethylene, or polypropylene graft film having a thickness of 0.15 to 0.30 mm.
4. The method for producing a zinc-nickel secondary battery according to claim 1, 2 or 3, characterized in that the positive electrode sheet is produced by:
(1) one or more conductive terminals are led out of the conductive base body; the thickness of the conductive substrate is 0.1-3.0mm, and the conductive substrate is foamed nickel, a nickel net or a nickel belt;
(2) mixing nickel hydroxide powder with a battery additive, wherein the nickel hydroxide powder accounts for 70-98% of the total weight of the battery additive, and the balance is the additive; the nickel hydroxide powder is spherical nickel hydroxide and/or nickel hydroxide; the additive is one or more of graphite powder, acetylene black, conductive carbon black, metallic nickel powder, metallic cadmium powder, metallic copper powder, metallic zinc powder, a cobalt compound, a manganese compound, an aluminum compound, a zinc compound, a cadmium compound and a lithium compound;
(3) dissolving the binder by using a solvent, wherein the weight ratio of the solvent to the binder is 1: 10-99; the solvent is water soluble or ethanol or water insoluble N-methyl pyrrolidone or dimethyl acetamide; the binder is one or more of water-soluble or water-dispersible carboxymethyl cellulose (CMC), Polytetrafluoroethylene (PTFE) emulsion, polyacrylic acid (PAA), polyvinyl alcohol (PVA) and polyethylene oxide (PEO); or non-water soluble polyvinylidene fluoride (PVDF) and/or hexafluoropropylene;
(4) mixing the mixture obtained in the step (2) and the binder solution obtained in the step (3) to prepare slurry, coating the slurry on a conductive substrate, drying the conductive substrate at 60-120 ℃, and forming to obtain a nickel hydroxide positive plate;
(5) converting the nickel hydroxide in the positive plate in the step (4) into β type nickel oxyhydroxide by an electrolytic formation method, wherein a counter electrode used in the electrolytic formation is a metallic titanium electrode, a graphite electrode or a cadmium oxide electrode.
5. The method according to claim 4, wherein the step (5) comprises immersing the nickel hydroxide positive electrode sheet of the step (4) in an electrolytic bath containing an alkaline electrolyte together with two counter metal titanium electrodes, graphite electrodes, or cadmium oxide electrodes, the two counter electrodes being disposed on both sides of the nickel hydroxide positive electrode sheet, the positive terminal of the rectifyingsource being connected to the nickel hydroxide positive electrode sheet, and the negative terminal being connected to the two counter electrodes; the current density of the electrolytic cell is controlled between 0.1 and 50mA/cm2The voltage is controlled to be 1.4-3.0V, and the electrolysis time is 0.5-24 hours; the alkaline electrolyte is prepared by dissolving one or more of potassium hydroxide, sodium hydroxide and lithium hydroxide in deionized water, distilled water or tap water; wherein, the concentration of potassium hydroxide or sodium hydroxide is 1-12M, and the concentration of lithium hydroxide is 10-40 g/l.
6. The method of manufacturing a zinc-nickel secondary battery according to claim 1, 2 or 3, characterized in that the negative electrode sheet is manufactured by:
(1) one or more conductive terminals are led out of the negative conductive substrate, the negative conductive substrate is any one of foamed copper, a copper mesh or a copper strip, and the thickness of the negative conductive substrate is 0.1-3.0 mm;
(2) mixing metal zinc powder with a negative electrode additive, wherein the metal zinc powder is metal zinc alloy powder with the particle size of 70-300 meshes, and trace indium, bismuth or lead and compounds thereof are added as corrosion inhibitors; the negative electrode additive is a mixture of one or more of zinc oxide, calcium oxide, magnesium oxide, cadmium oxide, aluminum oxide, indium compound, bismuth compound and lead compound, the weight percentage of the metal zinc powder in the mixture is 60-95%, and the weight percentage of the negative electrode additive in the mixture is 5-40%;
(3) adding a binder into the mixture in the step (2), wherein the binder is one or more of carboxymethyl cellulose (CMC), Polytetrafluoroethylene (PTFE) emulsion, polyvinyl alcohol (PVA),polyacrylic acid (PAA) and polyethylene oxide (PEO), and the weight percentage of the binder in the mixture is 1-30%;
(4) coating the negative electrode mixture obtained in the step (3) on a negative electrode conductive substrate, drying at 60-120 ℃, then coating a composite coating layer for preventing zinc dendrite from growing and penetrating through a diaphragm on the surface of the negative electrode conductive substrate, wherein the composite coating layer is composed of one or more than one of calcium oxide, calcium hydroxide, magnesium oxide, cadmium oxide and aluminum oxide, the weight percentage content of the mixture in the composite coating layer is 99-70%, and meanwhile, one or more than one of carboxymethyl cellulose (CMC), Polytetrafluoroethylene (PTFE) emulsion, polyvinyl alcohol (PVA), polyacrylic acid (PAA) and polyethylene oxide (PEO) is/are added as a binder, and the weight percentage content of the binder in the composite coating layer is 1-30%;
(4) drying at 60-120 deg.C, and forming to obtain negative plate.
7. A zinc-nickel secondary battery produced by the method of claim 1.
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