CN102623757A - 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
20 beginnings of the century of 19 end of the centurys, JUNJER and the EDISON of the U.S. in Europe have invented the iron nickel oxide battery, this be a kind of with the ferroelectric utmost point as negative pole, hydroxy nickel oxide is as the storage battery of positive pole.Compare present widely used ickel-cadmium cell, lead-acid battery, Ni-H cell; This battery can bear super-charge super-discharge, and the attitude of discharging for a long time 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, and this is an ickel-cadmium cell; Lead-acid battery and Ni-H cell are incomparable, therefore, receive the society concern and greatly develop.But the negative pole of existing iron-nickel storage battery mostly adopts the ferroelectric utmost point of pouched; The manufacture craft of the ferroelectric pole plate of this pouched is multiple, equipment has high input; Cause battery cost excessive, economic benefit is lower, and because the special construction of the ferroelectric utmost point of this pouched makes active material and collector spacing too big; The influence that active material utilization is low, cause large current discharging capability a little less than; Isolate positive/negative plate with plastic spacer simultaneously; Make that the spacing of both positive and negative polarity is very big; Electrochemical polarization is big when discharging and recharging; The large current discharging capability that has caused this iron-nickel storage battery equally very a little less than, the discharge (following the current discharge of 1C multiplying power) of low range in generally only providing can not be as the power source use of electric car.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 objective 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 objective of the invention is to realize 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 the container; Described just very sintered type nickel electrode; Described negative pole is the ferroelectric utmost point of steel band type, and the ferroelectric utmost point of described steel band type comprises the burr steel belt matrix, is arranged on the active material slurry of burr steel belt matrix surface; Described active material slurry is to be processed according to following percentage by weight by 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 the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
Said 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 a in nickelous sulfate, nickel hydroxide, the rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the 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.
A kind ofly prepare the preparation method that described negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that 85～95% tri-iron tetroxide, percentage by weight are that 1～5% additive, percentage by weight are that 3～7% conductive agents evenly mix at first with percentage by weight; Adding then by percentage by weight is that the mass concentration of 1～3% binder making is 8% adhesive solution; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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 the sintered type nickel electrode and the ferroelectric utmost point of steel band type all has unique three-dimensional structure; Distance between active material and collector is shortened greatly; 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 when assembling is isolated positive/negative plate with the polyalkene diaphragm of thinner thickness; Like this electrochemical polarization when discharging and recharging very a little less than, large current discharging capability is greatly improved, the capacity of battery is bigger; Longer service life can satisfy the requirement of high-multiplying power discharge.For example 10C discharge, making Hawkins cell be used as the electric motor car electrical source of power becomes possibility, has protected environment like this, has very big social value and meaning.
Experiment by embodiment proves: battery of the present invention has improved 45～49% than conventional batteries: 10C discharge ratio, and active material utilization has improved 18.7～21%.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
Get di-iron trioxide 85 grams, additive 5 grams, conductive agent 7 grams, binding agent 3 grams.
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 the container; Described just very sintered type nickel electrode; Described negative pole is the ferroelectric utmost point of steel band type, and the ferroelectric utmost point of described steel band type comprises the burr steel belt matrix, is arranged on the active material slurry of burr steel belt matrix surface; Described active material slurry is to be processed according to following percentage by weight by each component: tri-iron tetroxide 85 grams, additive 5 grams, conductive agent 7 grams, binding agent 3 grams, described positive pole and negative pole adopt the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
Said 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 a in nickelous sulfate, nickel hydroxide, the rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the 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.
A kind ofly prepare the preparation method that described negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that tri-iron tetroxide, the weight of 85 grams is that 5 gram additives, weight are that 7 gram conductive agents evenly mix at first with weight; Adding then by weight is that mass concentration that the binder making of 3 grams becomes is 8% adhesive solution 37.5 grams; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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 the pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell respectively:
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 1.0V with 0.2C, calculated two kinds of discharge capacity of the cell.
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 0.8V with 10C, calculated two kinds of discharge capacity of the cell.
, stopped 30 minutes with the 0.1C of ferroelectric utmost point theoretical capacity charging 10 hours according to battery, be discharged to～criterion of 0.55V (zinc reference electrode relatively) with ferroelectric utmost point theoretical capacity 0.1C then, 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, like following table:
Annotate: the capacity that active material utilization is emitted with every gram tri-iron tetroxide in the mixed powder representes,
10C discharge ratio is represented with the Capacity Ratio that 10C and 0.2C emit.
By last table can find out since the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole; And the present invention isolates positive/negative plate at the laminated structure that when assembling adopts with the polyalkene diaphragm of thinner thickness, like this electrochemical polarization when discharging and recharging very a little less than, large current discharging capability is greatly improved; The capacity of battery is bigger; Wherein, 10C discharge ratio has improved 49%, and active material utilization has improved 21%.
Embodiment 2
Get di-iron trioxide 90 grams, additive 3 grams, conductive agent 5 grams, binding agent 2 grams.
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 the container; Described just very sintered type nickel electrode; Described negative pole is the ferroelectric utmost point of steel band type, and the ferroelectric utmost point of described steel band type comprises the burr steel belt matrix, is arranged on the active material slurry of burr steel belt matrix surface; Described active material slurry is to be processed according to following percentage by weight by each component: tri-iron tetroxide 90 grams, additive 3 grams, conductive agent 5 grams, binding agent 2 grams, described positive pole and negative pole adopt the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
Said 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 a in nickelous sulfate, nickel hydroxide, the rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the 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.
A kind ofly prepare the preparation method that described negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that tri-iron tetroxide, the weight of 90 grams is that 3 gram additives, weight are that 5 gram conductive agents evenly mix at first with weight; Adding then by weight is that the mass concentration of binder making of 2 grams is 8% adhesive solution 25 grams; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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 the pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell respectively:
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 1.0V with 0.2C, calculated two kinds of discharge capacity of the cell.
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 0.8V with 10C, calculated two kinds of discharge capacity of the cell.
, stopped 30 minutes with the 0.1C of ferroelectric utmost point theoretical capacity charging 10 hours according to battery, be discharged to～criterion of 0.55V (zinc reference electrode relatively) with ferroelectric utmost point theoretical capacity 0.1C then, 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, like following table:
Annotate: the capacity that active material utilization is emitted with every gram tri-iron tetroxide in the mixed powder representes,
10C discharge ratio is represented with the Capacity Ratio that 10C and 0.2C emit.
By last table can find out since the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole; And the present invention isolates positive/negative plate at the laminated structure that when assembling adopts with the polyalkene diaphragm of thinner thickness, like this electrochemical polarization when discharging and recharging very a little less than, large current discharging capability is greatly improved; The capacity of battery is bigger; Wherein, 10C discharge ratio has improved 48%, and active material utilization has improved 18.7%.
Embodiment 3
Get di-iron trioxide 95 grams, additive 1 gram, conductive agent 3 grams, binding agent 1 gram.
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 the container; Described just very sintered type nickel electrode; Described negative pole is the ferroelectric utmost point of steel band type, and the ferroelectric utmost point of described steel band type comprises the burr steel belt matrix, is arranged on the active material slurry of burr steel belt matrix surface; Described active material slurry is to be processed according to following percentage by weight by each component: tri-iron tetroxide 95 grams, additive 1 gram, conductive agent 3 grams, binding agent 1 gram, described positive pole and negative pole adopt the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
Said 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 a in nickelous sulfate, nickel hydroxide, the rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the 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.
A kind ofly prepare the preparation method that described negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that tri-iron tetroxide, the weight of 95 grams is that 1 gram additive, weight is that 3 gram conductive agents evenly mix at first with weight; Adding then by weight is that mass concentration that the binder making of 1 gram becomes is 8% adhesive solution 12.5 grams; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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 the pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell respectively:
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 1.0V with 0.2C, calculated two kinds of discharge capacity of the cell.
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 0.8V with 10C, calculated two kinds of discharge capacity of the cell.
, stopped 30 minutes with the 0.1C of ferroelectric utmost point theoretical capacity charging 10 hours according to battery, be discharged to～criterion of 0.55V (zinc reference electrode relatively) with ferroelectric utmost point theoretical capacity 0.1C then, 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, like following table:
Annotate: the capacity that active material utilization is emitted with every gram tri-iron tetroxide in the mixed powder representes,
10C discharge ratio is represented with the Capacity Ratio that 10C and 0.2C emit.
By last table can find out since the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole; And the present invention isolates positive/negative plate at the laminated structure that when assembling adopts with the polyalkene diaphragm of thinner thickness, like this electrochemical polarization when discharging and recharging very a little less than, large current discharging capability is greatly improved; The capacity of battery is bigger; Wherein, 10C discharge ratio has improved 45%, and active material utilization has improved 21%.
Embodiment 4
Get di-iron trioxide 87 grams, additive 4 grams, conductive agent 6.5 grams, binding agent 2.5 grams.
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 the container; Described just very sintered type nickel electrode; Described negative pole is the ferroelectric utmost point of steel band type, and the ferroelectric utmost point of described steel band type comprises the burr steel belt matrix, is arranged on the active material slurry of burr steel belt matrix surface; Described active material slurry is to be processed according to following percentage by weight by each component: tri-iron tetroxide 87 grams, additive 4 grams, conductive agent 6.5 grams, binding agent 2.5 grams, described positive pole and negative pole adopt the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
Said 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 a in nickelous sulfate, nickel hydroxide, the rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the 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.
A kind ofly prepare the preparation method that described negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that tri-iron tetroxide, the weight of 87 grams is that 4 gram additives, weight are that 6.5 gram conductive agents evenly mix at first with weight; Adding then by weight is that mass concentration that the binder making of 2.5 grams becomes is 8% adhesive solution 31.25 grams; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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 the pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell respectively:
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 1.0V with 0.2C, calculated two kinds of discharge capacity of the cell.
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 0.8V with 10C, calculated two kinds of discharge capacity of the cell.
, stopped 30 minutes with the 0.1C of ferroelectric utmost point theoretical capacity charging 10 hours according to battery, be discharged to～criterion of 0.55V (zinc reference electrode relatively) with ferroelectric utmost point theoretical capacity 0.1C then, 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, like following table:
Annotate: the capacity that active material utilization is emitted with every gram tri-iron tetroxide in the mixed powder representes,
10C discharge ratio is represented with the Capacity Ratio that 10C and 0.2C emit.
By last table can find out since the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole; And the present invention isolates positive/negative plate at the laminated structure that when assembling adopts with the polyalkene diaphragm of thinner thickness, like this electrochemical polarization when discharging and recharging very a little less than, large current discharging capability is greatly improved; The capacity of battery is bigger; Wherein, 10C discharge ratio has improved 46.7%, and active material utilization has improved 19.7%.
Embodiment 5
Get di-iron trioxide 92 grams, additive 2 grams, conductive agent 4.5 grams, binding agent 1.5 grams.
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 the container; Described just very sintered type nickel electrode; Described negative pole is the ferroelectric utmost point of steel band type, and the ferroelectric utmost point of described steel band type comprises the burr steel belt matrix, is arranged on the active material slurry of burr steel belt matrix surface; Described active material slurry is to be processed according to following percentage by weight by each component: tri-iron tetroxide 92 grams, additive 2 grams, conductive agent 4.5 grams, binding agent 1.5 grams, described positive pole and negative pole adopt the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
Said 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 a in nickelous sulfate, nickel hydroxide, the rare earth oxide, and conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the 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.
A kind ofly prepare the preparation method that described negative pole is the iron-nickel storage battery of the ferroelectric utmost point of steel band type, 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that tri-iron tetroxide, the weight of 92 grams is that 2 gram additives, weight are that 4.5 gram conductive agents evenly mix at first with weight; Adding then by weight is that mass concentration that the binder making of 1.5 grams becomes is 8% adhesive solution 18.75 grams; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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 the pocket type electrode as the Hawkins cell of both positive and negative polarity as reference, do control experiment.
Calculate the discharge capacity of Hawkins cell of the present invention and traditional Hawkins cell respectively:
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 1.0V with 0.2C, calculated two kinds of discharge capacity of the cell.
Battery stopped 30 minutes with 0.25C charging 8 hours, was discharged to 0.8V with 10C, calculated two kinds of discharge capacity of the cell.
, stopped 30 minutes with the 0.1C of ferroelectric utmost point theoretical capacity charging 10 hours according to battery, be discharged to～criterion of 0.55V (zinc reference electrode relatively) with ferroelectric utmost point theoretical capacity 0.1C then, 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, like following table:
Annotate: the capacity that active material utilization is emitted with every gram tri-iron tetroxide in the mixed powder representes,
10C discharge ratio is represented with the Capacity Ratio that 10C and 0.2C emit.
By last table can find out since the present invention adopt sintered type nickel electrode as anodal, the ferroelectric utmost point of steel band type as negative pole; And the present invention isolates positive/negative plate at the laminated structure that when assembling adopts with the polyalkene diaphragm of thinner thickness, like this electrochemical polarization when discharging and recharging very a little less than, large current discharging capability is greatly improved; The capacity of battery is bigger; Wherein, 10C discharge ratio has improved 45.4%, and active material utilization has improved 17.2%.
Claims (5)
1. 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 the 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 the burr steel belt matrix, be arranged on the active material slurry of burr steel belt matrix surface, described active material slurry is to be processed according to following percentage by weight by 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 the laminated structure combination and between positive pole and negative pole, are provided with polyalkene diaphragm.
2. 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: said burr steel belt matrix is to be formed by flat strip overall chemical nickel plating after mechanical punching becomes three-dimensional structure.
3. 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: described additive is at least a in nickelous sulfate, nickel hydroxide, the rare earth oxide; Conductive agent is graphite or acetylene black or carbon black, and binding agent is at least a in HPMC, CMC, the PTFE emulsion.
4. 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: 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.
One kind to prepare like the described negative pole of one of claim 1～4 be the preparation method of 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: according to the ferroelectric utmost point of the steel band type that will the prepare face steel band of making even, the flat strip of being got is become three-dimensional structure through mechanical punching, overall chemical nickel plating then makes the burr steel belt matrix; 2) preparation of active material slurry: at room temperature; Be that 85～95% tri-iron tetroxide, percentage by weight are that 1～5% additive, percentage by weight are that 3～7% conductive agents evenly mix at first with percentage by weight; Adding then by percentage by weight is that the mass concentration of 1～3% binder making is 8% adhesive solution; Stir 1 hour to evenly, make active material slurry; 3) negative pole is the moulding of the ferroelectric utmost point of steel band type: with 2) in the active material slurry that makes be coated on 1) in the surface of the burr steel belt matrix that makes; Then 60～80 ℃ of oven dry down; Through roller press roll extrusion, die-cut, the spot welding machine spot welding lug of 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 the polyalkene diaphragm folding bag around; Use again screw and nut will be just very the lug of sintered type nickel electrode be assemblied on the afflux post composition pole plate group with the lug of negative pole as the ferroelectric utmost point of steel band type;
Step 3, assembling: the pole plate that step 2 is made is assembled in the container; Cover vinyl cover; With alkaline-resisting adhesive or ultrasonic bonding container and lid are sealed, on positive and negative afflux post, put sealing ring and pad then, and the afflux post is fastened on the vinyl cover with screw;
Step 4, add electrolyte: inject the electrolyte that mixes by potassium hydroxide and lithium hydroxide in the container that after step 3 assembling, makes; 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 that injects is advisable for 15 millimeters with the pole plate group of flooding the container that is installed in step 3, places 12 hours;
Step 5, activation: step 4 is made battery 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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| 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 |
| CN103107372A (en) * | 2013-03-06 | 2013-05-15 | 佛山市南海新力电池有限公司 | Method for producing iron-nickel alkaline battery |
| 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 |
| CN104103816A (en) * | 2014-06-18 | 2014-10-15 | 河南创力新能源科技有限公司 | Cladding nickel electrode and preparation method thereof |
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| 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 |
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| 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 |
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