CN102623757B - Iron-nickel storage battery adopting steel-strip iron electrode as cathode and preparation method of iron-nickel storage battery - Google Patents
Iron-nickel storage battery adopting steel-strip iron electrode as cathode and preparation method of iron-nickel storage battery Download PDFInfo
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Abstract
The invention relates to an iron-nickel storage battery adopting a steel-strip iron electrode as a cathode and a preparation method of the iron-nickel storage battery. The iron-nickel storage battery comprises a vessel with electrolyte, a cathode and an anode, wherein the cathode and the anode are arranged inside the vessel, the anode is a sintered nickel electrode, the cathode is a steel-strip iron electrode, the steel-strip iron electrode comprises a burr steel-strip base body and active substance slurry which is arranged on the surface of the burr steel-strip base body, the active substance slurry is prepared from the following ingredients by weight percent: 85 to 95 percent of ferroferric oxide, 1 to 5 percent of additive, 3 to 7 percent of conductive agent and 1 to 3 percent of binder, the anode and the cathode are assembled in a lamination-type structure, and a polyolefin diaphragm is arranged between the anode and the cathode; and since the sintered nickel electrode is adopted as the anode, the steel-strip iron electrode is adopted as the cathode, and a positive plate and a negative plate are isolated by the thin polyolefin diaphragm in a lamination-type structure when in assembling, the iron-nickel storage battery has the advantages of large capacity, strong large-current discharging capacity and long service life.
Description
Technical field
The present invention relates to the technical field of secondary cell, relate in particular to that a kind of capacity is high, large current discharging capability is strong, the negative pole of long service life is iron-nickel storage battery of the ferroelectric utmost point of steel band type and preparation method thereof.
Background technology
19 20 beginnings of the century of the end of the century, the JUNJER in Europe and the EDISON of the U.S. have invented iron nickel oxide battery, and this is a kind of using the ferroelectric utmost point as negative pole, and hydroxy nickel oxide is as anodal storage battery.Compare now widely used ickel-cadmium cell, lead-acid battery, Ni-H cell, this battery can bear super-charge super-discharge, long-term electric discharge state such as shelves at the abuse of electrical property, and the life-span of this iron-nickel storage battery is long, cycle life can reach more than 2000 times, and be more than 20 years service life, this is ickel-cadmium cell, lead-acid battery and Ni-H cell are incomparable, therefore, receive social concern and greatly develop.But the negative pole of existing iron-nickel storage battery mostly adopts the ferroelectric utmost point of pocket type structure, the manufacture craft of the ferroelectric pole plate of this pocket type structure is multiple, equipment investment is large, cause the cost of battery excessive, economic benefit is lower, and due to the special construction of the ferroelectric utmost point of this pocket type structure make active material and collector spacing too large, the impact that active material utilization is low, a little less than causing large current discharging capability; Simultaneously with plastic spacer isolation positive/negative plate, make the spacing of both positive and negative polarity very large, while discharging and recharging, electrochemical polarization is large, cause equally the large current discharging capability of this iron-nickel storage battery very weak, the general electric discharge (the following current discharge of 1C multiplying power) that middle low range only can be provided, the power source that can not serve as electric car uses.Therefore develop that a kind of capacity is high, large current discharging capability is strong, the iron-nickel storage battery of long service life has very high social effect and value.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art and provide that a kind of capacity is high, large current discharging capability is strong, the negative pole of long service life is iron-nickel storage battery of the ferroelectric utmost point of steel band type and preparation method thereof.
The object of the present invention is achieved like this:
A kind of negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: tri-iron tetroxide 85～95%, additive 1～5%, conductive agent 3～7%, binding agent 1～3%, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole.
Described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
Described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion.
Described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
Preparing described negative pole is a preparation method for the iron-nickel storage battery of the ferroelectric utmost point of steel band type, and its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first the tri-iron tetroxide that is 85～95% by percentage by weight, percentage by weight are that 1～5% additive, percentage by weight are that 3～7% conductive agents evenly mix, the adhesive solution that the mass concentration of the binder making that then to add by percentage by weight be 1～3% is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting is advisable with 15 millimeters of the pole plate groups of flooding the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
The present invention compared with prior art has following advantage:
The present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole, because the matrix of sintered type nickel electrode and the ferroelectric utmost point of steel band type all has unique three-dimensional structure, make like this distance between active material and collector greatly shorten, the utilance of active material is greatly improved, and then large current discharging capability is obviously strengthened; In addition, the laminated structure that the present invention adopts in the time of assembling is with the polyalkene diaphragm isolation positive/negative plate of thinner thickness, electrochemical polarization in the time discharging and recharging is very weak like this, large current discharging capability is greatly improved, the capacity of battery is larger, longer service life, can meet the requirement of high-multiplying power discharge.For example 10C electric discharge, making Hawkins cell be used as electric motor car electrical source of power becomes possibility, has protected like this environment, has very large social value and meaning.
By experimental results show that of embodiment: battery of the present invention has improved 45～49% than conventional batteries: 10C electric discharge ratio, and active material utilization has improved 18.7～21%.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
Get 85 grams of di-iron trioxides, 5 grams of additives, 7 grams of conductive agents, 3 grams of binding agents.
A kind of negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: 85 grams of tri-iron tetroxides, 5 grams of additives, 7 grams of conductive agents, 3 grams of binding agents, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole.
Described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
Described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion.
Described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
Preparing described negative pole is a preparation method for the iron-nickel storage battery of the ferroelectric utmost point of steel band type, and its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first tri-iron tetroxide, the weight that by weight is 85 grams is that 5 grams of additives, weight are that 7 grams of conductive agents evenly mix, then 37.5 grams of the mass concentration that the binder making that to add by weight be 3 grams the becomes adhesive solutions that is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting is advisable with 15 millimeters of the pole plate groups of flooding the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
The configuration of described electrolyte is in water, to mix potassium hydroxide and lithium hydroxide, and the concentration that wherein guarantees potassium hydroxide is that the concentration of 5～6mol/L, lithium hydroxide is 0.3～0.5 mol/L.
Get traditional by pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate respectively the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell:
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 1.0V with 0.2C, calculates two kinds of discharge capacity of the cell.
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 0.8V with 10C, calculates two kinds of discharge capacity of the cell.
, stop 30 minutes, then with ferroelectric be discharged to～0.55V(of utmost point theoretical capacity 0.1C relative zinc reference electrode with the 0.1C charging of ferroelectric utmost point theoretical capacity 10 hours according to battery) criterion, calculate ferroelectric extremely in the gram volume of active material.
The active material utilization of the battery of the present invention that embodiment 1 makes and traditional battery and the comparison of discharge capability, as following table:
Note: the capacity that active material utilization is emitted with every gram of tri-iron tetroxide in mixed powder represents,
The Capacity Ratio that 10C electric discharge ratio is emitted with 10C and 0.2C represents.
As can be seen from the above table due to the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole, and the laminated structure that the present invention adopts in the time of assembling is with the polyalkene diaphragm isolation positive/negative plate of thinner thickness, electrochemical polarization in the time discharging and recharging is very weak like this, large current discharging capability is greatly improved, the capacity of battery is larger, wherein, 10C electric discharge ratio has improved 49%, and active material utilization has improved 21%.
Embodiment 2
Get 90 grams of di-iron trioxides, 3 grams of additives, 5 grams of conductive agents, 2 grams of binding agents.
A kind of negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: 90 grams of tri-iron tetroxides, 3 grams of additives, 5 grams of conductive agents, 2 grams of binding agents, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole.
Described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
Described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion.
Described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
Preparing described negative pole is a preparation method for the iron-nickel storage battery of the ferroelectric utmost point of steel band type, and its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first tri-iron tetroxide, the weight that by weight is 90 grams is that 3 grams of additives, weight are that 5 grams of conductive agents evenly mix, then 25 grams of the adhesive solutions that the mass concentration that to add by weight be the binder making of 2 grams is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting is advisable with 15 millimeters of the pole plate groups of flooding the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
The configuration of described electrolyte is in water, to mix potassium hydroxide and lithium hydroxide, and the concentration that wherein guarantees potassium hydroxide is that the concentration of 5～6mol/L, lithium hydroxide is 0.3～0.5 mol/L.
Get traditional by pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate respectively the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell:
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 1.0V with 0.2C, calculates two kinds of discharge capacity of the cell.
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 0.8V with 10C, calculates two kinds of discharge capacity of the cell.
, stop 30 minutes, then with ferroelectric be discharged to～0.55V(of utmost point theoretical capacity 0.1C relative zinc reference electrode with the 0.1C charging of ferroelectric utmost point theoretical capacity 10 hours according to battery) criterion, calculate ferroelectric extremely in the gram volume of active material.
The active material utilization of the battery of the present invention that embodiment 2 makes and traditional battery and the comparison of discharge capability, as following table:
Note: the capacity that active material utilization is emitted with every gram of tri-iron tetroxide in mixed powder represents,
The Capacity Ratio that 10C electric discharge ratio is emitted with 10C and 0.2C represents.
As can be seen from the above table due to the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole, and the laminated structure that the present invention adopts in the time of assembling is with the polyalkene diaphragm isolation positive/negative plate of thinner thickness, electrochemical polarization in the time discharging and recharging is very weak like this, large current discharging capability is greatly improved, the capacity of battery is larger, wherein, 10C electric discharge ratio has improved 48%, and active material utilization has improved 18.7%.
Embodiment 3
Get 95 grams of di-iron trioxides, 1 gram of additive, 3 grams of conductive agents, 1 gram of binding agent.
A kind of negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: 95 grams of tri-iron tetroxides, 1 gram of additive, 3 grams of conductive agents, 1 gram of binding agent, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole.
Described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
Described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion.
Described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
Preparing described negative pole is a preparation method for the iron-nickel storage battery of the ferroelectric utmost point of steel band type, and its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first tri-iron tetroxide, the weight that by weight is 95 grams is that 1 gram of additive, weight are that 3 grams of conductive agents evenly mix, then 12.5 grams of the mass concentration that the binder making that to add by weight be 1 gram the becomes adhesive solutions that is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting is advisable with 15 millimeters of the pole plate groups of flooding the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
The configuration of described electrolyte is in water, to mix potassium hydroxide and lithium hydroxide, and the concentration that wherein guarantees potassium hydroxide is that the concentration of 5～6mol/L, lithium hydroxide is 0.3～0.5 mol/L.
Get traditional by pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate respectively the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell:
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 1.0V with 0.2C, calculates two kinds of discharge capacity of the cell.
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 0.8V with 10C, calculates two kinds of discharge capacity of the cell.
, stop 30 minutes, then with ferroelectric be discharged to～0.55V(of utmost point theoretical capacity 0.1C relative zinc reference electrode with the 0.1C charging of ferroelectric utmost point theoretical capacity 10 hours according to battery) criterion, calculate ferroelectric extremely in the gram volume of active material.
The active material utilization of the battery of the present invention that embodiment 3 makes and traditional battery and the comparison of discharge capability, as following table:
Note: the capacity that active material utilization is emitted with every gram of tri-iron tetroxide in mixed powder represents,
The Capacity Ratio that 10C electric discharge ratio is emitted with 10C and 0.2C represents.
As can be seen from the above table due to the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole, and the laminated structure that the present invention adopts in the time of assembling is with the polyalkene diaphragm isolation positive/negative plate of thinner thickness, electrochemical polarization in the time discharging and recharging is very weak like this, large current discharging capability is greatly improved, the capacity of battery is larger, wherein, 10C electric discharge ratio has improved 45%, and active material utilization has improved 21%.
Embodiment 4
Get 87 grams of di-iron trioxides, 4 grams of additives, 6.5 grams of conductive agents, 2.5 grams of binding agents.
A kind of negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: 87 grams of tri-iron tetroxides, 4 grams of additives, 6.5 grams of conductive agents, 2.5 grams of binding agents, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole.
Described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
Described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion.
Described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
Preparing described negative pole is a preparation method for the iron-nickel storage battery of the ferroelectric utmost point of steel band type, and its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first tri-iron tetroxide, the weight that by weight is 87 grams is that 4 grams of additives, weight are that 6.5 grams of conductive agents evenly mix, then 31.25 grams of the mass concentration that the binder making that to add by weight be 2.5 grams the becomes adhesive solutions that is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting is advisable with 15 millimeters of the pole plate groups of flooding the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
The configuration of described electrolyte is in water, to mix potassium hydroxide and lithium hydroxide, and the concentration that wherein guarantees potassium hydroxide is that the concentration of 5～6mol/L, lithium hydroxide is 0.3～0.5 mol/L.
Get traditional by pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate respectively the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell:
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 1.0V with 0.2C, calculates two kinds of discharge capacity of the cell.
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 0.8V with 10C, calculates two kinds of discharge capacity of the cell.
, stop 30 minutes, then with ferroelectric be discharged to～0.55V(of utmost point theoretical capacity 0.1C relative zinc reference electrode with the 0.1C charging of ferroelectric utmost point theoretical capacity 10 hours according to battery) criterion, calculate ferroelectric extremely in the gram volume of active material.
The active material utilization of the battery of the present invention that embodiment 4 makes and traditional battery and the comparison of discharge capability, as following table:
Note: the capacity that active material utilization is emitted with every gram of tri-iron tetroxide in mixed powder represents,
The Capacity Ratio that 10C electric discharge ratio is emitted with 10C and 0.2C represents.
As can be seen from the above table due to the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole, and the laminated structure that the present invention adopts in the time of assembling is with the polyalkene diaphragm isolation positive/negative plate of thinner thickness, electrochemical polarization in the time discharging and recharging is very weak like this, large current discharging capability is greatly improved, the capacity of battery is larger, wherein, 10C electric discharge ratio has improved 46.7%, and active material utilization has improved 19.7%.
Embodiment 5
Get 92 grams of di-iron trioxides, 2 grams of additives, 4.5 grams of conductive agents, 1.5 grams of binding agents.
A kind of negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: 92 grams of tri-iron tetroxides, 2 grams of additives, 4.5 grams of conductive agents, 1.5 grams of binding agents, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole.
Described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
Described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion.
Described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
Preparing described negative pole is a preparation method for the iron-nickel storage battery of the ferroelectric utmost point of steel band type, and its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first tri-iron tetroxide, the weight that by weight is 92 grams is that 2 grams of additives, weight are that 4.5 grams of conductive agents evenly mix, then 18.75 grams of the mass concentration that the binder making that to add by weight be 1.5 grams the becomes adhesive solutions that is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting is advisable with 15 millimeters of the pole plate groups of flooding the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
The configuration of described electrolyte is in water, to mix potassium hydroxide and lithium hydroxide, and the concentration that wherein guarantees potassium hydroxide is that the concentration of 5～6mol/L, lithium hydroxide is 0.3～0.5 mol/L.
Get traditional by pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate respectively the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell:
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 1.0V with 0.2C, calculates two kinds of discharge capacity of the cell.
Battery, with 0.25C charging 8 hours, stops 30 minutes, is discharged to 0.8V with 10C, calculates two kinds of discharge capacity of the cell.
, stop 30 minutes, then with ferroelectric be discharged to～0.55V(of utmost point theoretical capacity 0.1C relative zinc reference electrode with the 0.1C charging of ferroelectric utmost point theoretical capacity 10 hours according to battery) criterion, calculate ferroelectric extremely in the gram volume of active material.
The active material utilization of the battery of the present invention that embodiment 5 makes and traditional battery and the comparison of discharge capability, as following table:
Note: the capacity that active material utilization is emitted with every gram of tri-iron tetroxide in mixed powder represents,
The Capacity Ratio that 10C electric discharge ratio is emitted with 10C and 0.2C represents.
As can be seen from the above table due to the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole, and the laminated structure that the present invention adopts in the time of assembling is with the polyalkene diaphragm isolation positive/negative plate of thinner thickness, electrochemical polarization in the time discharging and recharging is very weak like this, large current discharging capability is greatly improved, the capacity of battery is larger, wherein, 10C electric discharge ratio has improved 45.4%, and active material utilization has improved 17.2%.
Claims (2)
1. the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type, comprise the container that fills electrolyte, be arranged on negative pole and positive pole in container, described just very sintered type nickel electrode, it is characterized in that: described negative pole is the ferroelectric utmost point of steel band type, the ferroelectric utmost point of described steel band type, comprise burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be made up according to following percentage by weight of each component: tri-iron tetroxide 85～95%, additive 1～5%, conductive agent 3～7%, binding agent 1～3%, described positive pole and negative pole adopt laminated structure combination, and be provided with polyalkene diaphragm between positive pole and negative pole, described burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure, described additive is at least one in nickelous sulfate, nickel hydroxide, rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least one in HPMC, CMC, PTFE emulsion, described electrolyte is the mixed solution of potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, described polyalkene diaphragm is one deck polypropylene non-woven fabric lining one deck radiation grafted polyethylene film, and described container is the housing of nylon or polyolefin material.
2. prepare the preparation method that negative pole as claimed in claim 1 is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, it is characterized in that: its preparation method comprises the steps:
Step 1, negative pole are the preparation of the ferroelectric utmost point of steel band type: the 1) preparation of matrix: get flat strip according to the ferroelectric utmost point of the steel band type that will prepare, got flat strip is become to three-dimensional structure through mechanical punching, then overall chemical nickel plating, makes burr steel belt matrix; 2) preparation of active material slurry: at room temperature, first the tri-iron tetroxide that is 85～95% by percentage by weight, percentage by weight are that 1～5% additive, percentage by weight are that 3～7% conductive agents evenly mix, the adhesive solution that the mass concentration of the binder making that then to add by percentage by weight be 1～3% is 8%, stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: by 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes, then at 60～80 ℃, dry,, spot welding machine spot welding lug die-cut through roller press roll extrusion, slicing machine, making negative pole is the ferroelectric utmost point of steel band type;
The preparation of step 2, pole plate group: get the ferroelectric utmost point of steel band type that existing sintered type nickel electrode makes as anodal, step 1 as negative pole, with polyalkene diaphragm folding bag around, be assemblied on current-collecting pole again composition pole plate group with the lug that screw and nut are the ferroelectric utmost point of steel band type by the lug of sintered type nickel electrode just very and negative pole;
Step 3, assembling: the pole plate that step 2 is made is assembled in container, cover vinyl cover, make container together with sealing of lid with alkaline-resisting adhesive or ultrasonic bonding, then on positive and negative current-collecting pole, put sealing ring and pad, and current-collecting pole is fastened on vinyl cover with screw;
Step 4, add electrolyte: in the container making after step 3 assembling, inject the electrolyte being mixed by potassium hydroxide and lithium hydroxide, wherein concentration of potassium hydroxide is that 5～6mol/L, lithium hydroxide concentration are 0.3～0.5 mol/L, the liquid level of electrolyte height injecting floods 15 millimeters of the pole plate groups of the container that is arranged on step 3, places 12 hours;
Step 5, activation: step 4 is made to battery and pass through: with 0.25C charging 8 hours, stop 30 minutes, be discharged to 1.0V with 0.2C, repeat 3 times discharge and recharge and carry out activation processing, obtain the iron-nickel storage battery that negative pole is the ferroelectric utmost point of steel band type.
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| EP2721688B1 (en) | 2011-06-15 | 2018-02-28 | University of Southern California | High efficiency iron electrode and additives for use in rechargeable iron-based batteries |
| CN103022574A (en) * | 2012-12-18 | 2013-04-03 | 河南创力新能源科技有限公司 | Integrated iron-nickel storage battery |
| CN103107372B (en) * | 2013-03-06 | 2015-12-02 | 佛山市南海新力电池有限公司 | A kind of manufacture method of fe-Ni alkaline cell |
| CN104103816B (en) * | 2014-06-18 | 2016-08-24 | 河南创力新能源科技股份有限公司 | A kind of clad type nickel electrode and preparation method thereof |
| CN104103858B (en) * | 2014-06-18 | 2016-08-24 | 河南创力新能源科技股份有限公司 | A kind of clad type iron electrode and preparation method thereof |
| CN104064823A (en) * | 2014-06-19 | 2014-09-24 | 杭州纽普新能源有限公司 | Gel-electrolyte iron-nickel storage battery and manufacturing method thereof |
| CN105280965A (en) * | 2015-11-17 | 2016-01-27 | 四川宝生实业发展有限公司 | Single-bag type high-power high-capacity Fe-Ni battery |
| CN107181009B (en) * | 2017-06-12 | 2019-07-05 | 高新峰 | A kind of iron-nickel storage battery and preparation method thereof |
| CN109301094A (en) * | 2017-07-25 | 2019-02-01 | 宁波堇山新材料有限公司 | A kind of plating Ni steel band uses the preparation method of the battery steel shell of the steel band and the steel shell |
| US11611115B2 (en) | 2017-12-29 | 2023-03-21 | Form Energy, Inc. | Long life sealed alkaline secondary batteries |
| CN112805851A (en) | 2018-07-27 | 2021-05-14 | 福恩能源公司 | Negative electrode for electrochemical cell |
| CN109742331B (en) * | 2018-12-18 | 2021-03-30 | 深圳市量能科技有限公司 | Negative plate of secondary nickel-metal hydride battery and manufacturing method thereof |
| CN111146408B (en) * | 2020-02-11 | 2022-11-29 | 河南创力新能源科技股份有限公司 | Preparation method of iron-nickel battery cathode |
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