CN108682901B - High-capacity double-bag type iron-nickel battery - Google Patents
High-capacity double-bag type iron-nickel battery Download PDFInfo
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Abstract
The invention discloses a high-capacity double-bag type iron-nickel battery, wherein a battery plate group consists of a bag type nickel positive plate, a bag type iron negative plate and a multilayer composite diaphragm or a grid separator positioned between the bag type nickel positive plate and the bag type iron negative plate, the electrode material of the bag type nickel positive plate consists of a positive active material, a conductive agent, an additive and a binder, the electrode material of the bag type iron negative plate consists of iron-based oxide powder, a conductive agent, an additive and a binder, and the electrolyte is an alkaline solution containing the additive in a liquid-rich state. According to the invention, through optimization of the anode and cathode formulas and the electrolyte formula and adjustment of the battery structure, the charge-discharge performance and the cycle performance of the novel iron-nickel battery are improved, and the novel iron-nickel battery also has the advantages of high discharge voltage platform, good overcharge and overdischarge resistance, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of iron-nickel batteries, and particularly relates to a large-capacity double-bag iron-nickel battery for industrial application.
Background
As is well known, the high-capacity bag-type battery has bag-type positive and negative plates with high mechanical strength and redundant electrolyte, so that the high-capacity bag-type battery can be ensured to have better circulation stability. The high-capacity cadmium-nickel bag type battery has the characteristics of safety, durability, long cycle life and the like, and is widely used in the industrial fields of starting or emergency power supplies of railway locomotives, mines, armored vehicles, aircraft engines and the like at present. However, the development of cadmium-nickel secondary batteries is greatly restricted due to the problem of contamination of the cadmium electrode. The larger the battery capacity, the more potential safety hazards will be. The prepared large-capacity lithium ion battery has great potential safety hazard when being used in important social fields such as rail transit and the like. Therefore, development of a new green battery having a large capacity for industrial use has been very slow.
The traditional bag-type iron-nickel battery has the advantages of safety, environmental friendliness, no pollution, environmental friendliness and the like, and is developed rapidly in a plurality of application fields. However, the positive electrode used for the conventional pouch-type batterythe material is common non-spherical β type nickel hydroxide with low tap density of only 1.5g/cm3Much lower than spherical nickel hydroxide (2.1 g/cm)3) the conventional bag-type iron-nickel battery adopts a thicker insulating plastic grid plate, so that the overall volumetric specific energy of the battery is lower, the internal resistance is larger, the discharge rate is low, and in addition, the battery has higher cost and poor cycle performance and hardly meets the requirements of the energy storage field.
Disclosure of Invention
The invention provides a high-capacity double-bag type iron-nickel battery which is used for meeting the requirements of the field of energy storage, aiming at the problems of low specific energy, poor rate capability, short cycle life, high cost and the like of the conventional iron-nickel battery.
the invention adopts the following technical scheme that the high-capacity double-bag type iron-nickel battery comprises a battery shell, a battery cover, a battery polar plate group, electrolyte, an electrode column and an exhaust valve, wherein the battery polar plate group and the electrolyte are mutually sealed and buckled, the battery polar plate group is positioned in the battery shell, the electrode column and the exhaust valve are arranged on the battery cover and are connected with a positive electrode and a negative electrode, the high-capacity double-bag type iron-nickel battery is characterized in that the battery polar plate group consists of a bag type nickel positive plate, a bag type iron negative plate and a multilayer composite diaphragm or a polar grid positioned between the bag type nickel positive plate and the bag type iron negative plate, the electrode material of the bag type nickel positive plate consists of at least two of spherical β type nickel hydroxide, cobalt-coated spherical β type nickel hydroxide, common non-spherical β type nickel hydroxide or Ni-Al-M ternary layered hydroxide, M is Co, Zn, Ca, Y or Mg, the electrode material of the bag type iron negative plate consists of iron-based oxide powder, the conductive agent, the additive and the binder, and the.
More preferably, the composite membrane is composed of at least two of sulfonated polypropylene membrane, fluorinated polypropylene membrane, grafted polypropylene membrane, polyethylene membrane, nylon membrane or polypropylene needle-punched non-woven fabric, and the number of the layers is more than 2.
Further preferably, the electrode material of the pouch type nickel positive plate consists of 55-94.9wt.% of positive active material, 3-30wt.% of conductive agent, 2-10wt.% of additive and 0.1-5wt.% of binder, wherein the conductive agent is at least two of conductive carbon material, nickel powder, cobalt powder, cobaltous oxide or cobalt hydroxide, the additive is at least one of yttrium oxide, erbium oxide, calcium hydroxide, calcium carbonate, zinc oxide, calcium fluoride or calcium tungstate, and the binder is at least one of sodium carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate, carboxyethyl cellulose, polytetrafluoroethylene or hydroxypropyl methyl cellulose; the electrode material of the bag-type iron negative plate consists of 55-91.9wt.% of iron-based oxide powder, 5-20wt.% of conductive agent, 3-20wt.% of additive and 0.1-5wt.% of binder, the iron-based oxide powder is at least one of ferroferric oxide, ferric oxide or ferrous oxide, the conductive agent is at least one of conductive graphite, acetylene black, conductive carbon black, carbon nano tubes, graphene, carbon fibers, titanium protoxide, copper powder, nickel powder, cobalt powder, tin powder or iron powder, the additive is at least two of bismuth sulfide, cerium oxide, ferrous sulfide, ytterbium hydroxide, zirconium hydroxide, cobaltous sulfide, copper hydroxide, copper sulfide, nickel hydroxide or nickel sulfate, and the binder is at least one of sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene, hydroxypropyl methyl cellulose, sodium polyacrylate, polyethylene oxide or styrene butadiene rubber.
preferably, at least one of spherical β -type nickel hydroxide, cobalt-coated spherical β -type nickel hydroxide, common non-spherical β -type nickel hydroxide and Ni-Al-M ternary layered hydroxide in the positive electrode active material is subjected to pre-oxidation treatment in a chemical oxidation or electrochemical oxidation mode.
More preferably, the molecular formula of the Ni-Al-M ternary layered hydroxide in the positive active material is [ Ni [ ]xAl(1-x)My(OH)2]·[(Aa-)z·mH2O]Wherein M is Co, Zn, Ca, Y or Mg, Aa-Is OH-、Cl-、CO3 2-、NO3 -、BO2 -、MoO4 2-Or WO4 2-0.9. gtoreq.x.gtoreq.0.6, y>0，z>0，m>0。
Further preferably, the electrolyte is a mixed solution composed of KOH and LiOH and having a total molar concentration of 4-7mol/L, and the electrolyte further contains 0.5-2wt.% of sodium tungstate, 0.5-5wt.% of sodium metaborate, 0.5-2wt.% of sodium fluoride, and 0.5-8wt.% of sodium sulfide or potassium sulfide.
The preparation method of the high-capacity double-bag type iron-nickel battery is characterized in that the specific preparation process of the bag type nickel positive plate comprises the following steps:
uniformly mixing the positive active material, the conductive agent, the additive and the binder, spraying alkali liquor or distilled water for mixing powder, and granulating; wrapping active substance particles into a steel strip pole box through a powder wrapping machine, and performing the working procedures of strip splicing, embossing, cutting and welding to obtain a bag-type nickel positive plate;
or uniformly mixing the positive active material, the conductive agent, the additive and the binder aqueous solution to prepare positive slurry; coating a layer of positive slurry layer on the surface of the porous nickel-plated steel strip with burrs by adopting a single-side sizing mode, and drying at 50-150 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing transverse grains to be pressed into a blank; and spot-welding the blank with the edge-wrapped ribs and the current collecting plate to form the conductive tabs to obtain the bag-type nickel positive plate.
The preparation method of the high-capacity double-bag type iron-nickel battery is characterized in that the specific preparation process of the bag type iron negative plate comprises the following steps: uniformly mixing iron-based oxide powder, a conductive agent, an additive and a binder aqueous solution to prepare negative electrode slurry; coating a layer of negative slurry layer on the surface with burrs of the perforated nickel-plated steel strip by adopting a single-side sizing mode, and drying at 50-150 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing cross striations to form the blank; and spot-welding the blank with a wrapping rib and a current collecting plate to form the conductive tab to obtain the bag-type iron negative plate.
In conclusion, the beneficial effects of the invention are as follows: the invention improves the problems of the original iron-nickel battery through the optimization of the anode and cathode formula, the optimization of the electrolyte formula, the electrode preparation method and the like. The main improvements are represented in the following aspects: (1) by introducing beneficial additives (such as calcium tungstate) into the cathode material of the iron-nickel battery, the high-temperature performance and the overcharge resistance of the cathode material can be effectively improved. Through the mixed doping treatment of the spherical and non-spherical materials of the positive electrode active substance, the accumulation state of the active substance in the substrate box is adjusted, and the utilization rate of the active substance of the electrode plate is improved. The addition of a proper amount of Ni-Al-M ternary layered hydroxide can inhibit the expansion of the plate, increase the structural stability of the positive plate in the circulating process and improve the overcharge resistance and rate capability of the battery. (2) The invention also provides a novel preparation method of the slurry-pulling combined coating powder, which is beneficial to uniformly distributing various beneficial additives and conductive agents in the electrode and solves the problem of nonuniform mixing of the traditional bag-type nickel electrode additives. The hardening resistance of the negative electrode is improved through improving the formula of the negative electrode (for example, novel additives such as ytterbium hydroxide, zirconium hydroxide and cobaltous sulfide are adopted), and the charging efficiency of the negative electrode is improved. (3) Through the improvement of the electrolyte formula and the combined use of various additives, the high and low temperature and cycle performance of the battery can be effectively improved. The bag-type positive electrode active material prepared by the technical scheme has the advantages of high utilization rate, excellent bag-type iron negative electrode capacity performance and rate capability, low internal resistance, good rate performance, long cycle life and the like.
Drawings
FIG. 1 is a schematic structural diagram of a bag-type iron-nickel battery prepared by the invention;
in the figure: 1-battery case, 2-bag type iron negative plate, 3-composite diaphragm or grid, 4-bag type nickel positive plate, 5-battery cover, 6-electrode column, 7-exhaust valve and 8-nut.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter is limited to the examples. All the technologies implemented based on the above-mentioned contents of the present invention belong to the scope of the present invention.
as shown in fig. 1, the high-capacity double-bag iron-nickel battery comprises a battery case 1, a battery cover 5, a battery polar plate group and electrolyte, which are hermetically fastened with each other, and an electrode column 6 and an exhaust valve 7, which are arranged on the battery cover 5 and connected with a positive electrode and a negative electrode, wherein the electrode column 6 is fixed on the battery cover 5 through a nut 8, the battery polar plate group comprises a bag-type nickel positive plate 4, a bag-type iron negative plate 2, and a multilayer composite diaphragm or a separator grid 3, which is arranged between the bag-type nickel positive plate 4 and the bag-type iron negative plate 2, the electrode material of the bag-type nickel positive plate 4 comprises a positive electrode active material, a conductive agent, an additive and a binder, wherein the positive electrode active material mainly comprises spherical β type nickel hydroxide, cobalt-coated spherical β type nickel hydroxide, common non-spherical β type nickel hydroxide or a Ni-Al-M ternary layered hydroxide, M is Co, Zn, Ca, Y or Mg, the electrode material of the bag-type iron 2 comprises iron-based oxide powder, the conductive agent, the additive-containing alkaline solution in a rich state, the composite solution 3, the sulfonated polypropylene diaphragm or polypropylene grafted polypropylene diaphragm, and at least two or polypropylene grafted polypropylene diaphragms.
Example 1
[Ni0.8Al0.2Co0.05(OH)2]·[(BO2 -)z·mH2O]Preparation of positive electrode active material:
firstly, preparing a nickel chloride compound into a nickel salt solution with the molar concentration of 1.8mol/L by using deionized water without carbon dioxide, dissolving aluminum sulfate and cobalt sulfate into a sodium hydroxide solution with the molar concentration of 4mol/L according to the molar ratio of nickel, aluminum and cobalt elements of 0.8:0.2:0.05, and preserving in inert gas nitrogenUnder protection, slowly dropwise adding a nickel salt solution into a reaction kettle filled with a composite alkaline solution, controlling the reaction temperature to be 55 ℃, controlling the pH of the final reaction mixture to be 10.5, aging the mother solution at 55 ℃ for 36 hours after the reaction is finished, and then filtering; drying the filter cake at 125 ℃ for 2h, grinding into powder, sieving with a 200-mesh sieve for later use, transferring 8g of the obtained powder into a prepared sodium metaborate solution with the molar concentration of 0.5mol/L, performing hydrothermal treatment at 160 ℃ for 1h under the protection of inert gas nitrogen, filtering, washing, drying, and grinding again to obtain Ni0.8Al0.2Co0.05(OH)2]·[(BO2 -)z·mH2O]Powder samples.
spherical β type nickel hydroxide, cobalt-coated spherical nickel hydroxide, ordinary non-spherical β type nickel hydroxide and Ni as positive electrode active material0.8Al0.2Co0.05(OH)2]·[(BO2 -)z·mH2O]The pre-oxidation treatment of (2) in this example employs a chemical oxidation method: adding a certain amount of active substances into 1M alkaline solution, adding a certain proportion of sodium persulfate or potassium persulfate or sodium hypochlorite for oxidation, and controlling the oxidation state of nickel to be about 3.2.
Preparing a bag type nickel positive plate:
pre-oxidized common non-spherical nickel hydroxide 20g, [ Ni ]0.8Al0.2Co0.05(OH)2]·[(Cl-)z·mH2O]20g of spherical nickel hydroxide, 40g of spherical nickel hydroxide, 5g of cobaltous oxide, 12g of conductive graphite, 1g of calcium tungstate, 1g of zinc oxide and 1g of PTFE dry powder are uniformly mixed, a sodium hydroxide solution is sprayed, rolling granulation is carried out, active substance particles are wrapped in a steel strip pole box through a powder wrapping machine, and the bag-type nickel positive plate is prepared through the working procedures of strip splicing, embossing, cutting, welding and the like.
Preparing a bag type iron negative plate:
uniformly mixing 65g of ferroferric oxide powder, 5g of nickel powder, 10g of conductive graphite, 5g of bismuth sulfide, 1g of ytterbium hydroxide, 1g of cerium oxide, 1g of nickel hydroxide, 10g of PVA solution with the mass concentration of 2.5% and 2g of SBR aqueous solution with the mass concentration of 2% to prepare negative electrode slurry; coating a slurry layer on the surface with burrs of the perforated nickel-plated steel strip by adopting a single-side sizing mode, and drying at the temperature of 100 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing transverse grains to form the blank; and spot-welding the blank with a wrapping rib and a current collecting plate to form the conductive tab to obtain the bag-type iron negative plate.
Preparing an electrolyte: dissolving 1g of potassium hydroxide and 3g of lithium hydroxide in deionized water to prepare a mixed solution with the total molar concentration of 6M, and taking 1000mL of the mixed solution, and adding 10g of sodium tungstate, 10g of sodium metaborate, 5g of potassium fluoride and 2g of sodium sulfide.
The positive and negative plates of the battery are isolated by adopting an isolating grid with the thickness of about 2 mm. And adding the prepared bag-type nickel positive plate and bag-type iron negative plate into a grid through the conventional bag-type battery assembly process, then putting the grid into a square battery case, injecting alkaline electrolyte for activation, sealing, and assembling the 200AH battery. The designed capacity of the negative electrode is 1.5 times that of the positive electrode. The cell structure is shown in figure 1.
Example 2
[Ni0.9Al0.1Ca0.05(OH)2]·[(CO3 2-)z·mH2O]Preparation of positive electrode active material:
firstly, preparing nickel sulfate into a nickel salt solution with the molar concentration of 2.0mol/L by using deionized water, dissolving aluminum sulfate and calcium chloride into a sodium hydroxide solution with the molar concentration of 5mol/L according to the molar ratio of nickel, aluminum and calcium elements of 0.9:0.1:0.05, slowly dropwise adding the nickel salt solution into a reaction kettle filled with a composite alkaline solution, wherein the reaction temperature is 55 ℃, the pH value of a mixture after the final reaction is 10.5, aging a mother solution for 36 hours at the temperature of 55 ℃ after the reaction is finished, and then filtering; drying the filter cake at 125 ℃ for 1h, grinding the filter cake into powder, and sieving the powder with a 200-mesh sieve to obtain Ni0.9Al0.1Ca0.05(OH)2]·[(CO3 2-)z·mH2And O powder sample.
Mixing Ni0.9Al0.1Ca0.05(OH)2]·[(CO3 2-)z·mH2O was subjected to the pre-oxidation treatment in the same manner as in example 1, and the oxidation state of nickel was controlled to about 3.15.
Preparing a bag type nickel positive plate:
40g of ordinary non-spherical nickel hydroxide, [ Ni ]0.9Al0.1Ca0.05(OH)2]·[(CO3 2-)z·mH2O]20g of pre-oxidized spherical nickel hydroxide, 15g of cobalt powder, 5g of conductive graphite, 5g of nickel powder, 1g of calcium fluoride, 1g of yttrium oxide, 1g of zinc oxide, 6g of CMC with the mass concentration of 2.5% and 1g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry; coating a layer of anode slurry on the surface of the porous nickel-plated steel strip with burrs by adopting a single-side sizing mode, and drying at the temperature of 120 ℃ for later use; oppositely wrapping the hole surfaces of every two coated cured layers of the dried coated steel strips together to prepare strip-shaped electrode plate boxes, and splicing a plurality of electrode plate boxes into a blank with a certain width and transversely pressing transverse grains to press the blank; and spot-welding the blank with the edge-wrapped ribs and the current collecting plate to form the conductive tabs to obtain the bag-type nickel positive plate.
Preparing a bag type iron negative plate:
uniformly mixing 60g of ferroferric oxide powder, 10g of ferrous oxide powder, 5g of iron powder, 5g of conductive carbon black, 5g of copper hydroxide, 1g of zirconium hydroxide, 1g of nickel sulfate, 10g of HPMC solution with the mass concentration of 2.5%, 1g of PTFE aqueous solution with the mass concentration of 60% and 2g of SBR aqueous solution with the mass concentration of 2% to prepare negative electrode slurry; coating a slurry layer on the surface with burrs of the perforated nickel-plated steel strip by adopting a single-side sizing mode, and drying at the temperature of 100 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing transverse grains to form the blank; and spot-welding the blank with a wrapping rib and a current collecting plate to form the conductive tab to obtain the bag-type iron negative plate.
Preparing an electrolyte: dissolving 1000g of potassium hydroxide and 30g of lithium hydroxide in deionized water to prepare a mixed solution with the total molar concentration of 6M, and taking 1000mL of the mixed solution, adding 10g of sodium tungstate, 10g of sodium metaborate, 5g of potassium fluoride and 5g of potassium sulfide.
The positive and negative plates of the battery are isolated by adopting an isolating grid with the thickness of about 2 mm. And adding the prepared bag-type nickel positive plate and bag-type iron negative plate into a grid through the conventional bag-type battery assembly process, then putting the grid into a square battery case, injecting alkaline electrolyte for activation, sealing, and assembling the 200AH battery. The designed capacity of the negative electrode is 1.5 times that of the positive electrode. The cell structure is shown in figure 1.
Example 3
[Ni0.7Al0.3Y0.05(OH)2]·[(Cl-)z·mH2O]Preparation of positive electrode active material:
firstly, preparing a nickel chloride compound into a nickel salt solution with the molar concentration of 2.0mol/L by using deionized water without carbon dioxide, dissolving aluminum chloride and yttrium chloride into a sodium hydroxide solution with the molar concentration of 3mol/L according to the molar ratio of nickel-aluminum-yttrium elements of 0.7:0.3:0.05, slowly dropwise adding the nickel salt solution into a reaction kettle filled with a composite alkaline solution under the protection of inert gas nitrogen, wherein the reaction temperature is 60 ℃, the pH value of a mixture after the final reaction is 11, after the reaction is finished, aging a mother solution for 48 hours at 70 ℃, and then filtering; drying the filter cake at 125 deg.C for 2h, and grinding into powder to obtain [ Ni ]0.7Al0.3Y0.05(OH)2]·[(Cl-)z·mH2O]Powder samples.
Preparing a bag type nickel positive plate:
pre-oxidized spherical nickel hydroxide 40g, [ Ni ]0.7Al0.3Y0.05(OH)2]·[(Cl-)z·mH2O]40g of nickel powder, 5g of conductive carbon fiber, 1g of calcium hydroxide, 1g of yttrium oxide, 1g of PTFE dry powder, 6g of HPMC with the mass concentration of 2.5% and 1g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry; coating a layer of anode slurry on the surface of the porous nickel-plated steel strip with burrs by adopting a single-side sizing mode, and drying at the temperature of 120 ℃ for later use; oppositely wrapping the hole surfaces of every two coated cured layers of the dried coated steel strips together to prepare strip-shaped electrode plate boxes, and splicing a plurality of electrode plate boxes into a blank with a certain width and transversely pressing transverse grains to press the blank; passing the blank throughAnd spot-welding the edge-covering ribs and the current collecting plates with the conductive tabs to obtain the bag-type nickel positive plate.
Preparing a bag type iron negative plate:
60g of ferroferric oxide, 5g of ferric oxide, 5g of conductive graphite, 2g of titanium dioxide, 5g of nickel powder, 6g of copper sulfide, 5g of cobaltous sulfide, 2g of nickel sulfide, 8g of CMC solution with the mass concentration of 2.5% and 2g of SBR aqueous solution with the mass concentration of 2% are uniformly mixed to prepare negative electrode slurry; coating a slurry layer on the surface with burrs of the perforated nickel-plated steel strip by adopting a single-side sizing mode, and drying at the temperature of 100 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing transverse grains to form the blank; and spot-welding the blank with a wrapping rib and a current collecting plate to form the conductive tab to obtain the bag-type iron negative plate.
Preparing an electrolyte: dissolving 1000g of potassium hydroxide and 50g of lithium hydroxide in deionized water to prepare a mixed solution with the total molar concentration of 6M, and taking 1000mL of the mixed solution, and adding 20g of sodium tungstate, 5g of sodium metaborate, 20g of potassium fluoride and 10g of sodium sulfide.
The separators of the positive plate and the negative plate of the battery adopt a separator grid with the thickness of about 1.5 mm. And adding the prepared bag-type nickel positive plate and bag-type iron negative plate into a grid through the conventional bag-type battery assembly process, then putting the grid into a square battery case, injecting alkaline electrolyte for activation, sealing, and assembling the 200AH battery. The designed capacity of the negative electrode is 1.5 times that of the positive electrode. The cell structure is shown in figure 1.
Example 4
Preparing a bag type nickel positive plate:
pre-oxidized common non-spherical nickel hydroxide 20g, [ Ni ]0.8Al0.2Co0.05(OH)2]·[(Cl-)z·mH2O]20g of spherical nickel hydroxide, 30g of spherical nickel hydroxide, 10g of cobaltous oxide, 16g of conductive graphite, 2g of calcium tungstate, 1g of yttrium oxide and 1g of PTFE dry powder are uniformly mixed, and sodium hydroxide solution is sprayed for grinding and granulation. Active material particles are packed into a steel strip pole box through a powder packing machine, and the bag-type nickel positive electrode is prepared through the working procedures of strip splicing, embossing, cutting, welding and the likeAnd (4) a polar plate.
Preparing a bag type iron negative plate:
uniformly mixing 60g of ferroferric oxide powder, 5g of ferrous oxide, 5g of conductive carbon black, 5g of carbon fiber, 1g of tin powder, 5g of cobaltous sulfide, 5g of copper hydroxide, 2g of ytterbium hydroxide, 2g of nickel hydroxide, 8g of PVA solution with the mass concentration of 2.5% and 2g of SBR aqueous solution with the mass concentration of 2% to prepare cathode slurry; coating a slurry layer on the surface with burrs of the perforated nickel-plated steel strip by adopting a single-side sizing mode, and drying at the temperature of 100 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing transverse grains to form the blank; and spot-welding the blank with a wrapping rib and a current collecting plate to form the conductive tab to obtain the bag-type iron negative plate.
Preparing an electrolyte: dissolving 1000g of potassium hydroxide and 100g of lithium hydroxide in deionized water to prepare a mixed solution with the total molar concentration of 6M, and taking 1000mL of the mixed solution, and adding 10g of sodium tungstate, 20g of sodium metaborate, 10g of potassium fluoride and 8g of sodium sulfide.
The positive and negative plates of the battery are isolated by a composite diaphragm of sulfonated polypropylene and polyethylene with the thickness of about 0.4 mm. And adding the prepared bag-type nickel positive plate and bag-type iron negative plate into a grid through the conventional bag-type battery assembly process, then putting the grid into a square battery shell, injecting alkali liquor for activation, sealing, and assembling the 200AH battery. The designed capacity of the negative electrode is 1.5 times that of the positive electrode. The cell structure is shown in figure 1.
Example 5
The battery separator prepared in example 1 was replaced with a sulfonated polypropylene and fluorinated polypropylene composite separator having a thickness of about 0.8 mm from a separator grid, and a 200AH battery was assembled in the same manner as in example 1, using a bag-type nickel positive electrode plate, a bag-type iron negative electrode plate, a positive-negative electrode ratio and an electrolyte.
Example 6
The battery separator prepared in example 2 was replaced with a sulfonated polypropylene and nylon composite separator having a thickness of about 1.0 mm from a separator grid, and a 200AH battery was assembled in the same manner as in example 2, using a bag-type nickel positive electrode plate, a bag-type iron negative electrode plate, a positive-negative electrode ratio and an electrolyte.
Comparative example 1
Preparing a bag type nickel positive plate:
uniformly mixing 75g of common non-spherical nickel hydroxide, 5g of cobaltous oxide, 19g of conductive graphite and 1g of PTFE dry powder, spraying a sodium hydroxide solution, and carrying out rolling granulation; and (3) wrapping active substance particles into the steel strip pole box through a powder wrapping machine, and performing the working procedures of strip splicing, embossing, cutting, welding and the like to prepare the bag-type nickel positive plate.
Preparing a bag type iron negative plate:
uniformly mixing 84g of ferroferric oxide powder, 10g of conductive graphite and 2g of nickel sulfate, spraying a sodium hydroxide solution, rolling, drying and granulating; and (3) wrapping active substance particles into the steel strip pole box through a powder wrapping machine, and performing the working procedures of strip splicing, embossing, cutting, welding and the like to prepare the bag-type iron negative plate.
Preparing an electrolyte: potassium hydroxide was dissolved in deionized water to make a 6M solution.
The positive and negative plates of the battery are isolated by adopting an isolating grid with the thickness of about 2 mm. And adding the prepared bag-type nickel positive plate and the prepared bag-type iron negative electrode into a grid through the conventional bag-type battery equipment process, then putting the grid into a square battery case, injecting alkaline electrolyte for activation, sealing, and assembling the 200AH battery. The designed capacity of the negative electrode is 1.5 times that of the positive electrode.
And (3) testing gram capacity of the bag electrode and capacity performance of the battery: the batteries prepared by using specific examples 1 to 6 and comparative example 1 were activated at 0.2C, charged at 0.2C for 6 hours, and then left to stand for 10 minutes, and then discharged at 0.2C to a voltage of 1.0, respectively, to obtain room-temperature discharge capacities. And the unipolar plates were evaluated for active gram capacity.
Testing the high and low temperature performance of the battery: the battery is charged and discharged at 0.2C under the environment temperature of 25 ℃ to obtain the capacity of 0.2C at normal temperature. Then carrying out 0.2C charge-discharge at the temperature of 45 ℃ to obtain high-temperature discharge capacity; and then carrying out 0.2C charge and discharge at the temperature of-20 ℃ to obtain low-temperature discharge capacity. And respectively calculating the ratio of discharge capacity under the high and low temperature conditions to the capacity under the normal temperature, and evaluating the high and low temperature performance of the capacitor.
And (3) testing the cycle performance of the battery: the batteries prepared in examples 1 to 6 and comparative example 1 were subjected to 1C charge-discharge cycles at an ambient temperature of 25C, respectively, and the capacity retention rate was calculated after 1000 cycles.
TABLE 1 Battery and plate Performance test
From the test results, the high-capacity long-life double-bag battery prepared by the method has the advantages of high utilization rate of positive and negative active substances, excellent rate capability and cycle stability, and can meet the requirements of commercial batteries, particularly high-capacity high-power long-life batteries. The improvement in these properties is mainly attributed to: by introducing beneficial additives (such as calcium tungstate) into the positive electrode material of the nickel-metal hydride battery, the high-temperature performance and the overcharge resistance of the positive electrode material can be effectively improved. Through the mixed doping treatment of the spherical and non-spherical materials of the positive electrode active substance, the accumulation state of the active substance in the substrate box is adjusted, and the utilization rate of the active substance of the electrode plate is improved. The addition of a proper amount of Ni-Al-M ternary layered hydroxide can inhibit the expansion of the plate, increase the structural stability of the positive plate in the circulating process and improve the overcharge resistance and rate capability of the battery. The preparation method of the anode slurry combined with the coating powder is beneficial to the uniform distribution of various beneficial additives and conductive agents in the electrode, and solves the problem of uneven mixing of the traditional bag-type nickel electrode additives. The hardening resistance of the negative electrode is improved through improving the formula (for example, novel additives such as ytterbium hydroxide, zirconium hydroxide and cobaltous sulfide) and the preparation mode of the negative electrode, and the charging efficiency and the utilization rate of active substances of the negative electrode are improved. Through the improvement of the electrolyte formula and the combined use of various additives, the high and low temperature and cycle performance of the battery can be effectively improved. The bag-type positive active material prepared by the technical scheme has high utilization rate, and the bag-type iron negative capacity performance and rate capability are excellent, and the prepared double-bag-type iron-nickel battery has the advantages of low internal resistance, good rate capability, long cycle life and the like.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (1)
1. A high-capacity double-bag type iron-nickel battery comprises a battery case, a battery cover, a battery polar plate group, electrolyte, an electrode column and an exhaust valve, wherein the battery polar plate group and the electrolyte are mutually sealed and buckled, the electrode column and the exhaust valve are arranged on the battery cover and are connected with a positive electrode and a negative electrode, the battery polar plate group is positioned in the battery case and is composed of a bag type nickel positive plate, a bag type iron negative plate and a multilayer composite diaphragm or a polar separation grid positioned between the bag type nickel positive plate and the bag type iron negative plate, the electrode material of the bag type nickel positive plate is composed of a positive electrode active material, a conductive agent, an additive and a binder, wherein the positive electrode active material is mainly composed of at least one of spherical β type nickel hydroxide, cobalt-coated spherical β type nickel hydroxide and common non-spherical β type nickel hydroxide and Ni-Al-M ternary layered hydroxide, the pre-oxidation treatment mode is chemical oxidation, and the molecular formula of the Ni-Al-M ternary layered hydroxide in the positive electrode active material is [ Ni-Al-Ni ternary layered Ni-M ternary layered hydroxidexAl（1-x）My(OH)2]·[(Aa-)z·mH2O]Wherein M is Co, Ca, or Y, Aa-Is OH−、Cl-、CO3 2−、NO3 −、BO2 -、MoO4 2-Or WO4 2-0.9. gtoreq.x.gtoreq.0.6, y>0，z>0，m>0；
The electrode material of the bag-type nickel positive plate comprises 55-94.9wt.% of positive active material, 3-30wt.% of conductive agent, 2-10wt.% of additive and 0.1-5wt.% of binder, wherein the conductive agent is at least two of conductive carbon material, nickel powder, cobalt powder, cobaltous oxide or cobalt hydroxide, the additive is at least one of yttrium oxide, erbium oxide, calcium hydroxide, calcium carbonate, zinc oxide, calcium fluoride or calcium tungstate, and the binder is at least one of sodium carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate, carboxyethyl cellulose, polytetrafluoroethylene or hydroxypropyl methyl cellulose; the specific preparation process of the bag type nickel positive plate comprises the following steps:
uniformly mixing the positive active material, the conductive agent, the additive and the binder, spraying alkali liquor or distilled water for mixing powder, and granulating; wrapping active substance particles into a steel strip pole box through a powder wrapping machine, and performing the working procedures of strip splicing, embossing, cutting and welding to obtain a bag-type nickel positive plate;
or uniformly mixing the positive active material, the conductive agent, the additive and the binder aqueous solution to prepare positive slurry; coating a layer of positive slurry layer on the surface of the porous nickel-plated steel strip with burrs by adopting a single-side sizing mode, and drying at 50-150 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing transverse grains to be pressed into a blank; spot welding conductive tabs on the blank through edge-wrapping ribs and a current collecting plate to obtain a bag-type nickel positive plate;
the electrode material of the bag-type iron negative plate consists of 55-91.9wt.% of iron-based oxide powder, 5-20wt.% of conductive agent, 3-20wt.% of additive and 0.1-5wt.% of binder, the iron-based oxide powder is at least one of ferroferric oxide, ferric oxide or ferrous oxide, the conductive agent is at least one of conductive graphite, conductive carbon black, carbon nano tubes, graphene, carbon fibers, titanium monoxide, copper powder, nickel powder, cobalt powder, tin powder or iron powder, the additive is at least two of bismuth sulfide, cerium oxide, ferrous sulfide, ytterbium hydroxide, zirconium hydroxide, cobaltous sulfide, copper hydroxide, copper sulfide, nickel hydroxide or nickel sulfate, and the binder is at least one of sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene, hydroxypropyl methyl cellulose, sodium polyacrylate, polyethylene oxide or styrene butadiene rubber; the specific preparation process of the bag type iron negative plate comprises the following steps: uniformly mixing iron-based oxide powder, a conductive agent, an additive and a binder aqueous solution to prepare negative electrode slurry; coating a layer of negative slurry layer on the surface with burrs of the perforated nickel-plated steel strip by adopting a single-side sizing mode, and drying at 50-150 ℃ for later use; oppositely wrapping the hole surfaces of every two dried coating curing layers of the coated steel strips together to manufacture a strip-shaped electrode plate box; then a plurality of electrode plate boxes are spliced into a blank with a certain width and are connected with transverse pressing cross striations to form the blank; spot welding conductive tabs on the blank through edge-covered ribs and a current collecting plate to obtain a bag-type iron negative plate;
the electrolyte is an alkaline solution containing additives in a rich liquid state, is a mixed solution consisting of KOH and LiOH and having a total molar concentration of 4-7mol/L, and also comprises 0.5-2wt.% of sodium tungstate, 0.5-5wt.% of sodium metaborate, 0.5-2wt.% of sodium fluoride and 0.5-8wt.% of sodium sulfide or potassium sulfide;
the composite diaphragm is composed of at least two of sulfonated polypropylene diaphragm, fluorinated polypropylene diaphragm, grafted polypropylene diaphragm, polyethylene diaphragm, nylon diaphragm or polypropylene needle-punched non-woven fabric, and the number of the layers is more than 2.
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| CN110931269B (en) * | 2019-12-09 | 2021-12-17 | 河南创力新能源科技股份有限公司 | Capacitive iron-nickel battery iron electrode |
| CN110931786B (en) * | 2019-12-11 | 2022-10-28 | 河南创力新能源科技股份有限公司 | Preparation method of iron-nickel battery cathode silicate crystal material |
| CN111477846B (en) * | 2020-03-27 | 2022-03-29 | 深圳市量能科技有限公司 | High-rate nickel-metal hydride battery positive electrode and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894948A (en) * | 2010-07-15 | 2010-11-24 | 河南省恒明风云电源有限公司 | Method for preparing bag type metal hydride cathode of alkaline storage battery |
| CN102956893A (en) * | 2012-11-01 | 2013-03-06 | 浙江天能能源科技有限公司 | Low-temperature nickel-hydrogen battery and preparation method thereof |
| CN104037406A (en) * | 2014-06-12 | 2014-09-10 | 河南师范大学 | Positive active material for nickel-based secondary battery and preparation method thereof |
| CN105390755A (en) * | 2015-11-05 | 2016-03-09 | 衡阳电科电源有限公司 | Super-wide-temperature-range nickel-hydrogen battery and manufacturing method therefor |
| CN107681118A (en) * | 2017-09-03 | 2018-02-09 | 河南师范大学 | Iron nickel secondary batteries negative plate and preparation method thereof and the iron nickel secondary batteries using the negative plate |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300114A (en) * | 1999-12-16 | 2001-06-20 | 厦门大学 | Electrolyte solution for rechargeable Ni-H2 battery |
| JP3976482B2 (en) * | 2000-08-08 | 2007-09-19 | 三洋電機株式会社 | Method for producing positive electrode active material for alkaline storage battery, nickel electrode using this positive electrode active material, and alkaline storage battery using this nickel electrode |
| CN100359722C (en) * | 2003-01-20 | 2008-01-02 | 株式会社汤浅开发 | Closed nickel-hydrogen storage battery and its production method |
| CN100487969C (en) * | 2003-01-31 | 2009-05-13 | 株式会社汤浅开发 | Sealed alkaline storage battery, electrode structure thereof, charging method and charger for sealed alkaline storage battery |
| CN100347886C (en) * | 2006-01-20 | 2007-11-07 | 东南大学 | Positive electrode material and positive electrode for secondary alkaline cell and their preparation method |
| CN101262051B (en) * | 2008-03-27 | 2010-07-28 | 东莞市迈科科技有限公司 | A nickel-hydrogen high-temperature battery and its making method |
| CN102376987B (en) * | 2010-08-19 | 2015-09-30 | 比亚迪股份有限公司 | A kind of Ni-MH battery electrolyte and Ni-MH battery |
| JP6293686B2 (en) * | 2015-02-16 | 2018-03-14 | プライムアースＥｖエナジー株式会社 | Method for producing alkaline storage battery and alkaline storage battery |
| CN107181009B (en) * | 2017-06-12 | 2019-07-05 | 高新峰 | A kind of iron-nickel storage battery and preparation method thereof |
-
2018
- 2018-06-01 CN CN201810557701.3A patent/CN108682901B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894948A (en) * | 2010-07-15 | 2010-11-24 | 河南省恒明风云电源有限公司 | Method for preparing bag type metal hydride cathode of alkaline storage battery |
| CN102956893A (en) * | 2012-11-01 | 2013-03-06 | 浙江天能能源科技有限公司 | Low-temperature nickel-hydrogen battery and preparation method thereof |
| CN104037406A (en) * | 2014-06-12 | 2014-09-10 | 河南师范大学 | Positive active material for nickel-based secondary battery and preparation method thereof |
| CN105390755A (en) * | 2015-11-05 | 2016-03-09 | 衡阳电科电源有限公司 | Super-wide-temperature-range nickel-hydrogen battery and manufacturing method therefor |
| CN107681118A (en) * | 2017-09-03 | 2018-02-09 | 河南师范大学 | Iron nickel secondary batteries negative plate and preparation method thereof and the iron nickel secondary batteries using the negative plate |
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