CN100459246C - Steel strip, cell cathode using same and cell and their manufacture methods - Google Patents
Steel strip, cell cathode using same and cell and their manufacture methods Download PDFInfo
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- CN100459246C CN100459246C CNB2005101176810A CN200510117681A CN100459246C CN 100459246 C CN100459246 C CN 100459246C CN B2005101176810 A CNB2005101176810 A CN B2005101176810A CN 200510117681 A CN200510117681 A CN 200510117681A CN 100459246 C CN100459246 C CN 100459246C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The provided porous steel strip contains Ni powder on surface. Wherein, the Ni particle size is over the Ni layer thickness. This invention can improve the performance of basic secondary cell while reduces cell internal resistance.
Description
Technical field
The invention relates to a kind of steel band, use battery cathode and the battery and their preparation method of this steel band, more specifically say so about a kind of steel band, the alkaline secondary cell negative electrode that uses this steel band and battery and their preparation method.
Background technology
Alkaline secondary cell as nickel-cadmium secondary cell or nickel-hydrogen secondary cell, generally comprises the electrode group and the alkaline electrolyte that are sealed in the battery container.Described electrode group comprises positive pole, negative pole and dividing plate.Positive pole contains a kind of conducting base that is loaded with positive electrode, and described positive electrode contains as the nickel hydroxide powder of major constituent and adhesive.Negative pole contains a kind of conducting base that is loaded with negative material, and described negative material contains major constituent and adhesive, is selected from simple substance, oxide and/or hydroxide or the hydrogen bearing alloy of cadmium as major constituent as described in nickel-cadmium secondary cell or the nickel-hydrogen secondary cell.Described dividing plate is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy, and described electrode group and alkaline electrolyte are contained in the battery case together.Described battery container can also the double as cathode terminal.
In the prior art, generally use the conducting base of common nickel plating Punching steel strip material as alkaline secondary cell negative electrode.The production technology of common nickel plating Punching steel strip material is first with the steel band punching, again electric deposition nickel on Punching steel strip.The surface of the common nickel plating Punching steel strip material that makes like this is smooth shape, and roughness is not enough.When using common nickel plating Punching steel strip material as the conducting base of negative pole, the surface combination power of negative material and nickel plating Punching steel strip is poor, along with the volume that carries out negative material of charge and discharge process also constantly expands and shrinks, thereby after repeatedly discharging and recharging, negative material comes off from nickel plating Punching steel strip substrate surface, thereby makes the cycle performance of alkaline secondary cell relatively poor.And the real contact area of negative material and nickel plating Punching steel strip is little, makes the internal resistance of cell higher, and capacity is lower.
Summary of the invention
The objective of the invention is provides a kind of alkaline secondary cell negative electrode and battery that can improve the cycle performance and the capacity of battery and reduce the steel band of the internal resistance of cell and use this steel band in order to overcome the shortcoming that prior art neutral and alkali secondary cell cycle performance is poor, internal resistance is higher and capacity is lower.
Another object of the present invention provides their preparation method.
The invention provides a kind of steel band, this steel band is a steel band with holes, and this steel strip surface contains nickel dam, and wherein, the surface distributed of described steel band has the nickel powder particle, and the granularity of nickel powder particle is greater than the thickness of nickel dam.
The invention provides a kind of preparation method of steel band, this method comprise with steel band punching and in electrodeposit liquid electric deposition nickel, wherein, also contain nickel powder in the described electrodeposit liquid.
The invention provides a kind of alkaline secondary cell negative electrode, this negative pole contains negative material and conducting base, described conducting base is a steel band, this steel band is a steel band with holes, this steel strip surface contains nickel dam, wherein, the surface distributed of described steel band has the nickel powder particle, and the granularity of nickel powder particle is greater than the thickness of nickel dam.
The invention provides a kind of preparation method of alkaline secondary cell negative electrode, this method comprises the preparation steel band and negative material is coated on the described steel band, the preparation method of described steel band comprise with steel band punching and in electrodeposit liquid electric deposition nickel, wherein, also contain nickel powder in the described electrodeposit liquid.
The invention provides a kind of alkaline secondary cell, this battery comprises electrode group and alkaline electrolyte, described electrode group and alkaline electrolyte are sealed in the battery container, and described electrode group comprises positive pole, negative pole and dividing plate, and negative pole contains negative material and conducting base, described conducting base is a steel band, this steel band is a steel band with holes, and this steel strip surface contains nickel dam, wherein, the surface distributed of described steel band has the nickel powder particle, and the granularity of nickel powder particle is greater than the thickness of nickel dam.
The invention provides a kind of preparation method of alkaline secondary cell, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and dividing plate are prepared into an electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, the preparation method of described negative pole comprises negative material is coated on the steel band, the preparation method of described steel band comprise with steel band punching and in electrodeposit liquid electric deposition nickel, wherein, also contain nickel powder in the described electrodeposit liquid.
The steel strip surface of the present invention preparation is coarse, and having increased negative material and steel band is the surface combination power and the real contact area of conducting base, so has improved the cycle performance and the capacity of alkaline secondary cell and reduced the internal resistance of battery.
Description of drawings
The common nickel plating Punching steel strip SEM figure that Fig. 1 adopts prior art to make for Comparative Examples 1;
The nickel plating Punching steel strip SEM figure that Fig. 2 makes for embodiment 1.
Embodiment
According to steel band provided by the invention, be benchmark with the total weight of steel band, the surface distributed of described steel band has the nickel powder particle of 0.1-3 weight %, is preferably 0.3-2 weight %.Described nickel powder particle is uneven distribution in steel strip surface.The granularity of described nickel powder particle is the 0.6-150 micron, is preferably the 1-100 micron.Here granularity is meant the equivalent grain size of nickel powder particle, i.e. the equivalent particle diameter.
The thickness of the pore size in the material of described steel band and size, hole and density and nickel dam has been as well known to those skilled in the art, and the present invention does not limit this.For example, can use SPCC steel band (cold rolling carbon element steel band); The aperture in hole is preferably the 1-5 millimeter, and density is 1000-4000/square decimeter; The thickness of nickel dam is preferably the 0.5-10 micron; Steel band is of a size of conventional size, and the requirement of satisfying battery gets final product.
The preparation method of steel band provided by the invention, this method comprise with steel band punching and in electrodeposit liquid electric deposition nickel, wherein, also contain nickel powder in the described electrodeposit liquid.
Wherein, the content of nickel powder in electrodeposit liquid is the 5-50 grams per liter, is preferably the 10-40 grams per liter; The granularity of nickel powder is the 0.6-150 micron, is preferably the 1-100 micron.Preferably carry out electro-deposition under stirring condition, wherein mixing speed is preferably 25-600 rev/min, more preferably 50-500 rev/min.Can be before electro-deposition begins, also can be in electrodeposition process, to add nickel powder, nickel powder is adsorbed on the Punching steel strip under high-speed stirred equably or has deposited on the Punching steel strip of a certain amount of nickel, nickel is also in electro-deposition in the time of absorption, so just improved the roughness of steel band, and the nickel of electro-deposition with nickel powder parcel or with the nickel powder codeposition together, so nickel powder firmly is being distributed on the steel band.
The purpose of punching is in order to make steel band have the hole, thereby helps filling on steel band electrode slurry.The method of described punching has been as well known to those skilled in the art, uses the punching die punching in embodiments of the invention.
The purpose of electric deposition nickel is to plate nickel dam in steel strip surface, to prevent the reaction of steel band and electrode slurry.The method of electric deposition nickel has been conventionally known to one of skill in the art.In general, the method for described electric deposition nickel comprises puts into electrodeposit liquid with steel band, connects DC power supply and gets final product.Contain nickel salt and buffer in the described electrodeposit liquid; The pH value of electrodeposit liquid is 3-5, is preferably 3.8-4.4; As long as the least concentration of described nickel salt make nickel can electro-deposition to steel band, maximum concentration is the saturated concentration of nickel salt, is preferably the 0.5-3 mol; Nickel salt can be selected from one or more in the hydrochloride, sulfate, carbonate, acetate, nitrate, borate, phosphate, oxide, organic salt of nickel; The concentration of described buffer is the 0.25-1 mol, and described buffer is selected from one or more in acetic acid, boric acid, the citric acid; The temperature of electro-deposition is 30-80 ℃, is preferably 40-60 ℃; Current strength is 1-5A/dm
2
According to the negative pole of alkaline secondary cell provided by the invention, consisting of of described negative material is conventionally known to one of skill in the art.In general, described negative material contains major constituent and adhesive, is selected from simple substance, oxide and/or the hydroxide of cadmium, perhaps hydrogen bearing alloy as major constituent as described in nickel-cadmium secondary cell or the nickel-hydrogen secondary cell.
Described hydrogen bearing alloy can be selected from can be as any hydrogen bearing alloy of alkaline secondary cell negative electrode key component, and this hydrogen bearing alloy can produce alkaline electrolyte in electrochemical reaction hydrogen absorbs, and, the reversible hydrogen ground of absorption is resolved.
The kind of described adhesive and content are conventionally known to one of skill in the art, and for example, described adhesive can be selected from carboxymethyl cellulose, hydroxypropyl methylcellulose, methylcellulose, Sodium Polyacrylate, the polytetrafluoroethylene one or more; In general, according to the difference of adhesive therefor kind, the content of adhesive is the 0.01-5 weight % of major constituent, is preferably 0.02-3 weight %.
Described negative material can also contain additive, and the kind of additive and content are conventionally known to one of skill in the art.For example, described additive is selected from one or more in graphite, carbon black, nickel powder, the cobalt powder etc.In general, described content of additive is the 0.1-15 weight % of major constituent, is preferably 0.5-10 weight %.
According to the preparation method of alkaline secondary cell negative electrode provided by the invention, except described steel band prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.For example, can adopt conventional method that negative material is coated in described conducting base (nickel plating Punching steel strip).For example, negative material is mixed into pasty state, applies and/or be filled on the described conducting base, drying, pressing mold or pressing mold not can obtain described negative pole.Wherein, described solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.In general, the content of described solvent is the 10-30 weight % of major constituent, is preferably 15-25 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
According to alkaline secondary cell provided by the present invention, described dividing plate is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described electrode group and alkaline electrolyte are contained in the battery case together.Described dividing plate can be selected from various dividing plates used in the alkaline secondary cell, as polyolefine fiber nonwoven fabrics and the surperficial chip component of introducing hydrophilic fibre or handling through sulfonation.The position of described dividing plate, character and kind are conventionally known to one of skill in the art.
Anode can be selected from the used positive pole of various alkaline secondary cells, and it can be commercially available, and also can adopt existing method preparation.Described conducting base is an alkaline secondary cell conducting base commonly used, as matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
Contain nickel hydroxide and adhesive as positive electrode as described in nickel-cadmium secondary cell or the nickel-hydrogen secondary cell, described adhesive can adopt adhesive used in the negative pole.The content of adhesive is conventionally known to one of skill in the art, is generally the 0.01-5 weight % of nickel hydroxide, is preferably 0.02-3 weight %.
Can also contain additive in the described positive electrode, the kind of described additive and content are conventionally known to one of skill in the art.For example, described additive can be selected from the metal of cobalt, described cobalt, zinc, cadmium, manganese and in the compound one or more.In general, in element, described content of additive is the 0-15 weight % of nickel hydroxide, is preferably 2-10 weight %.In positive electrode, add cobalt additive and can improve the conductivity that reaches between the positive active material between positive active material and the conducting base.In positive electrode, introduce additives such as zinc, cadmium, manganese and can improve battery stability of structure in charge and discharge process, thus the cycle life of raising battery.
The preparation method of described anode plate can adopt conventional preparation method.For example,, also have additive to be blended into pasty state sometimes, apply and/or be filled on the described conducting base described nickel hydroxide, adhesive and solvent, drying, pressing mold or pressing mold not can obtain described anode plate.Wherein, described solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described pastel have viscosity, can be coated on the described conducting base to get final product.In general, the content of described solvent is the 15-40 weight % of nickel hydroxide, is preferably 20-35 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
Described electrolyte is the used electrolyte of alkaline secondary cell, as in potassium hydroxide aqueous solution, sodium hydrate aqueous solution, the lithium hydroxide aqueous solution one or more.The injection rate of electrolyte is generally 0.9-1.6g/Ah, the concentration of electrolyte be generally 6-8 rub/liter.
According to the preparation method of alkaline secondary cell provided by the invention, except described steel band prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.In general, between described positive pole for preparing and negative pole, dividing plate is set, constitutes an electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, can obtain alkaline secondary cell provided by the invention.
To the present invention be described in more detail by embodiment below.
Embodiment 1
This example illustrates steel band provided by the invention, uses battery cathode and the battery and their preparation method of this steel band.
(1) preparation of negative pole
Get and be of a size of 5000 millimeters * 210 millimeters * 0.08 millimeter SPCC steel band, with the punching of SPCC steel band, the aperture of punching is 3.6 millimeters with punching die (punch press, model J123-16 are forged in Shanghai two), and density is 1900/dm
2Put it into (nickelous sulfate (NiSO in the electrodeposit liquid of the present invention then
4.7H
2O) 0.75 mol, nickel chloride (NiCl
2.6H
2O) 0.13 mol, boric acid (H
3BO
3) 0.5 mol, nickel powder (granularity is 10 microns) 10 grams per liters, the pH value is 4.0), be 1A/dm in current strength
2, temperature is that 50 ℃, mixing speed are under 100 rev/mins the condition, to carry out electro-deposition, makes nickel plating Punching steel strip of the present invention.Wherein, utilizing the multi-functional electrolysis liquid of the ZNS-1B type microcomputer calibrator of Shanghai Daily Use Hardware Industry Inst to measure nickel layer thickness is 2 microns, is 0.35 weight % with the content of the nickel powder particle of atomic absorption detecting steel strip surface.The JSM-5610LV type scanning electron microscopy of employing Jeol Ltd. obtains the SEM figure (as shown in Figure 2) of this nickel plating Punching steel strip.
The CdO of 100 weight portions, the carboxymethyl cellulose binder and 20 parts by weight of deionized water of 0.5 weight portion are fully stirred, be mixed into pasty slurry.This slurry is coated on the above-mentioned nickel plating Punching steel strip that obtains equably, oven dry, roll-in then, cuts to make and be of a size of 270 millimeters * 33 millimeters * 0.5 millimeter negative pole, wherein, the content of CdO is about 11 grams.
(2) Zheng Ji preparation
The nickel hydroxide of 95 weight portions, the CoO (cobalt protoxide) of 5 weight portions, the carboxymethyl cellulose binder and 20 parts by weight of deionized water of 0.2 weight portion are fully stirred, be mixed into pasty slurry.Get regular-type foam nickel, be made into 220 millimeters * 63 millimeters * 1.4 millimeters nickel foam substrate after pressure, the cut-parts, nickel strap 220 millimeters * 4 millimeters * 0.1 millimeter of the centre position of nickel foam substrate roller weldering, fill the above-mentioned slurry that obtains, oven dry, roll-in then, cut to make and be of a size of 220 millimeters * 33 millimeters * 0.5 millimeter positive pole.Wherein, the content of nickel hydroxide is about 9 grams.
(3) assembling of battery
The positive pole that negative pole, dividing plate grafted polypropylene diaphragm, the step (2) that step (1) is obtained obtains stacks gradually the electrode group that is wound into scroll, the electrode group that obtains is put into the cylindrical cell external case of an end opening, (electrolyte is KOH and LiOH mixed aqueous solution to add electrolyte 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make nickel-cadmium cell B1 (SC-1900mAh) after the sealing.
Comparative Examples 1
Adopt condition and the material identical with embodiment 1, make reference cell CB1, different is not have nickel powder in the electrodeposit liquid.Adopt the JSM-5610LV type scanning electron microscopy of Jeol Ltd. to obtain the SEM figure (as shown in Figure 1) of the steel band that Comparative Examples 1 makes.
By Fig. 2 and Fig. 1 as can be seen, the nickel plating Punching steel strip surface ratio ordinary steel belt surface made of the present invention is coarse.
Embodiment 2
This example illustrates steel band provided by the invention, uses battery cathode and the battery and their preparation method of this steel band.
(1) preparation of negative pole
Get and be of a size of 5000 millimeters * 180 millimeters * 0.035 millimeter SPCC steel band, with the punching of SPCC steel band, the aperture of punching is 1.8 millimeters with punching die, and density is 2700/dm
2Put it into (nickelous sulfate (NiSO in the electrodeposit liquid of the present invention then
4.7H
2O) 2.5 mol, nickel chloride (NiCl
2.6H
2O) 0.13 mol, boric acid (H
3BO
3) 0.75 mol, the pH value is 4.2), be 3A/dm in current strength
2, temperature is that 55 ℃, mixing speed are under 400 rev/mins the condition, to carry out electro-deposition, adding granularity in the electrodeposit liquid and be 80 microns nickel powders in the process of electro-deposition and making its concentration is 18 grams per liters, makes nickel plating Punching steel strip of the present invention.Wherein, wherein utilizing the multi-functional electrolysis liquid of the ZNS-1B type microcomputer calibrator of Shanghai Daily Use Hardware Industry Inst to measure nickel layer thickness is 8 microns, is 0.85 weight % with the content of the nickel powder particle of atomic absorption detecting steel strip surface.
LaNi with 100 parts of weight
5Hydrogen bearing alloy, the carboxymethyl cellulose binder of 0.5 part of weight, 5 parts of weight Ni reach 20 parts of weight deionized waters and fully stir, and are mixed into pasty slurry.This slurry is coated on the above-mentioned nickel plating Punching steel strip that obtains equably, oven dry, roll-in then, cuts to make and be of a size of 130 millimeters * 44 millimeters * 0.4 millimeter negative pole, wherein, LaNi
5Content be about 11 the gram.
(2) Zheng Ji preparation
With the nickel hydroxide of 95 parts of weight, the CoO of 5 parts of weight (cobalt protoxide), the carboxymethyl cellulose binder of 0.2 part of weight reaches 30 parts of weight deionized waters and fully stirs, and is mixed into pasty slurry.Get regular-type foam nickel, be made into 98 millimeters * 44 millimeters * 0.8 millimeter nickel foam substrate after pressure, the cut-parts, nickel strap 20 millimeters * 1.5 millimeters * 0.2 millimeter of the centre position of nickel foam substrate spot welding, nickel strap exposes 10 millimeters of nickel screens, fill the above-mentioned slurry that obtains, oven dry, roll-in make and are of a size of 98 millimeters * 44 millimeters * 0.8 millimeter positive pole then.Wherein, the content of nickel hydroxide is about 10 grams.
(3) assembling of battery
The positive pole that negative pole, dividing plate grafted polypropylene diaphragm, (2) that (1) is obtained obtain stacks gradually the electrode group that is wound into scroll, the electrode group that obtains is put into the cylindrical cell external case of an end opening, (electrolyte is KOH and LiOH mixed aqueous solution to add electrolyte 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make nickel-hydrogen cell B2 (AA-2200mAh) after the sealing.
Comparative Examples 2
Adopt condition and the material identical with embodiment 2, make reference cell CB2, different is not have nickel powder in the electrodeposit liquid.
Embodiment 3
This example illustrates steel band provided by the invention, uses battery cathode and the battery and their preparation method of this steel band.
(1) preparation of negative pole
Get and be of a size of 5000 millimeters * 210 millimeters * 0.08 millimeter SPCC steel band, with the punching of SPCC steel band, the aperture of punching is 4.2 millimeters with punching die (punch press, model J123-16 are forged in Shanghai two), and density is 3500/dm
2Put it into (nickelous sulfate (NiSO in the electrodeposit liquid of the present invention then
4.7H
2O) 0.75 mol, nickel chloride (NiCl
2.6H
2O) 1.25 mol, boric acid (H
3BO
3) 0.65 mol, nickel powder (granularity is 50 microns) 35 grams per liters, the pH value is 4.0), be 1A/dm in current strength
2, temperature is that 50 ℃, mixing speed are under 200 rev/mins the condition, to carry out electro-deposition, makes nickel plating Punching steel strip of the present invention.Wherein, utilizing the multi-functional electrolysis liquid of the ZNS-1B type microcomputer calibrator of Shanghai Daily Use Hardware Industry Inst to measure nickel layer thickness is 4.5 microns, is 1.8 weight % with the content of the nickel powder particle of atomic absorption detecting steel strip surface.
With the CdO of 100 weight portions, the carboxymethyl cellulose binder of 0.5 weight portion reaches 20 parts by weight of deionized water and fully stirs, and is mixed into pasty slurry.This slurry is coated on the above-mentioned nickel plating Punching steel strip that obtains equably, oven dry, roll-in then, cuts to make and be of a size of 270 millimeters * 33 millimeters * 0.5 millimeter negative pole, wherein, the content of CdO is about 11 grams.
(2) Zheng Ji preparation
With the nickel hydroxide of 95 weight portions, the CoO of 5 weight portions (cobalt protoxide), the carboxymethyl cellulose binder of 0.2 weight portion reaches 20 parts by weight of deionized water and fully stirs, and is mixed into pasty slurry.Get regular-type foam nickel, be made into 220 millimeters * 63 millimeters * 1.4 millimeters nickel foam substrate after pressure, the cut-parts, nickel strap 220 millimeters * 4 millimeters * 0.1 millimeter of the centre position of nickel foam substrate roller weldering, fill the above-mentioned slurry that obtains, oven dry, roll-in then, cut to make and be of a size of 220 millimeters * 33 millimeters * 0.5 millimeter positive pole.Wherein, the content of nickel hydroxide is about 9 grams.
(3) assembling of battery
The positive pole that negative pole, dividing plate grafted polypropylene diaphragm, (2) that (1) is obtained obtain stacks gradually the electrode group that is wound into scroll, the electrode group that obtains is put into the cylindrical cell external case of an end opening, (electrolyte is KOH and LiOH mixed aqueous solution to add electrolyte 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make nickel-cadmium cell B3 (SC-1900mAh) after the sealing.
Comparative Examples 3
Adopt condition and the material identical with embodiment 3, make reference cell CB3, different is not have nickel powder in the electrodeposit liquid.
Embodiment 4
This example illustrates steel band provided by the invention, uses battery cathode and the battery and their preparation method of this steel band.
(1) preparation of negative pole
Get and be of a size of 5000 millimeters * 180 millimeters * 0.035 millimeter SPCC steel band, with the punching of SPCC steel band, the aperture of punching is 2.5 millimeters with punching die, and density is 2700/dm
2Put it into (nickelous sulfate (NiSO in the electrodeposit liquid of the present invention then
4.7H
2O) 0.5 mol, boric acid (H
3BO
3) 0.75 mol, the pH value is 4.1), be 1A/dm in current strength
2, temperature is that 55 ℃, mixing speed are under 400 rev/mins the condition, to carry out electro-deposition, adding granularity in the electrodeposit liquid and be 2 microns nickel powder in the process of electro-deposition and making its concentration is 25 grams per liters, makes nickel plating Punching steel strip of the present invention.Wherein, wherein utilizing the multi-functional electrolysis liquid of the ZNS-1B type microcomputer calibrator of Shanghai Daily Use Hardware Industry Inst to measure nickel layer thickness is 0.75 micron, is 1.2 weight % with the content of the nickel powder particle of atomic absorption detecting steel strip surface.
LaNi with 100 parts of weight
5Hydrogen bearing alloy, the carboxymethyl cellulose binder of 0.5 part of weight, 5 parts of weight Ni reach 20 parts of weight deionized waters and fully stir, and are mixed into pasty slurry.This slurry is coated on the above-mentioned nickel plating Punching steel strip that obtains equably, oven dry, roll-in then, cuts to make and be of a size of 130 millimeters * 44 millimeters * 0.4 millimeter negative pole, wherein, LaNi
5Content be about 11 the gram.
(2) Zheng Ji preparation
With the nickel hydroxide of 95 parts of weight, the CoO of 5 parts of weight (cobalt protoxide), the carboxymethyl cellulose binder of 0.2 part of weight reaches 30 parts of weight deionized waters and fully stirs, and is mixed into pasty slurry.Get regular-type foam nickel, be made into 98 millimeters * 44 millimeters * 0.8 millimeter nickel foam substrate after pressure, the cut-parts, nickel strap 20 millimeters * 1.5 millimeters * 0.2 millimeter of the centre position of nickel foam substrate spot welding, nickel strap exposes 10 millimeters of nickel screens, fill the above-mentioned slurry that obtains, oven dry, roll-in make and are of a size of 98 millimeters * 44 millimeters * 0.8 millimeter positive pole then.Wherein, the content of nickel hydroxide is about 10 grams.
(3) assembling of battery
The positive pole that negative pole, dividing plate grafted polypropylene diaphragm, (2) that (1) is obtained obtain stacks gradually the electrode group that is wound into scroll, the electrode group that obtains is put into the cylindrical cell external case of an end opening, (electrolyte is KOH and LiOH mixed aqueous solution to add electrolyte 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make nickel-hydrogen cell B4 (AA-2200mAh) after the sealing.
Comparative Examples 4
Adopt condition and the material identical with embodiment 4, make reference cell CB4, different is not have nickel powder in the electrodeposit liquid.
Embodiment 5-8
Embodiment 5-8 measures capacity, internal resistance and the cycle performance of battery B1-B4 respectively.
Measure by the IEC285:1993 standard.
Measurement result is as shown in table 1.
Comparative Examples 5-8
Comparative Examples 5-8 measures capacity, internal resistance and the cycle performance of reference cell CB1-CB4 respectively.
Adopt the method identical to measure with embodiment 5-8.
Measurement result is as shown in table 1.
Table 1
| The embodiment numbering | The battery numbering | Capacity (mAh) | Internal resistance (m Ω) | Capability retention (%) |
| Embodiment 5 | B1 | 1950 | 5.4 | After 400 10C that circulate discharge is 90 |
| Comparative Examples 5 | CB1 | 1900 | 6.2 | After 400 10C that circulate discharge is 78 |
| Embodiment 6 | B2 | 2210 | 6.3 | After 300 1C that circulate discharge is 88 |
| Comparative Examples 6 | CB2 | 2150 | 7.8 | After 300 1C that circulate discharge is 75 |
| Embodiment 7 | B3 | 1945 | 5.5 | After 400 10C that circulate discharge is 89 |
| Comparative Examples 7 | CB3 | 1890 | 6.2 | After 400 10C that circulate discharge is 76 |
| Embodiment 8 | B4 | 2215 | 6.2 | After 300 1C that circulate discharge is 90 |
| Comparative Examples 8 | CB4 | 2150 | 7.7 | After 300 1C that circulate discharge is 75 |
From the result shown in the table 1 as can be seen, compare with the alkaline secondary cell that obtains with prior art, the cycle performance and the capacity of alkaline secondary cell provided by the invention are significantly improved, and internal resistance obviously reduces.
Claims (9)
1, a kind of steel band, this steel band are steel band with holes, and this steel strip surface contains nickel dam, it is characterized in that, the surface distributed of described steel band has the nickel powder particle, and the granularity of nickel powder particle is greater than the thickness of nickel dam.
2, steel band according to claim 1, wherein, described nickel powder particle is uneven distribution in steel strip surface.
3, steel band according to claim 1 wherein, is a benchmark with the total weight of steel band, and the surface distributed of described steel band has the nickel powder particle of 0.1-3 weight %.
4, steel band according to claim 3 wherein, is a benchmark with the total weight of steel band, and the surface distributed of described steel band has the nickel powder particle of 0.3-2 weight %.
5, steel band according to claim 1, wherein, the thickness of described nickel dam is the 0.5-10 micron, the granularity of described nickel powder particle is the 0.6-150 micron.
6, steel band according to claim 5, wherein, the granularity of described nickel powder particle is the 1-100 micron.
7, steel band according to claim 1, wherein, described steel band is the SPCC steel band; The bore dia in described hole is the 1-5 millimeter, and density is 1000-4000/square decimeter; The thickness of described nickel dam is the 0.5-10 micron.
8, a kind of alkaline secondary cell negative electrode, this negative pole contains negative material and conducting base, and described conducting base is a steel band, it is characterized in that, and described steel band is any described steel band among the claim 1-7.
9, a kind of alkaline secondary cell, this battery comprises electrode group and alkaline electrolyte, described electrode group and alkaline electrolyte are sealed in the battery container, described electrode group comprises positive pole, negative pole and dividing plate, negative pole contains negative material and conducting base, described conducting base is a steel band, it is characterized in that, described steel band is any described steel band among the claim 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101176810A CN100459246C (en) | 2005-11-08 | 2005-11-08 | Steel strip, cell cathode using same and cell and their manufacture methods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101176810A CN100459246C (en) | 2005-11-08 | 2005-11-08 | Steel strip, cell cathode using same and cell and their manufacture methods |
Publications (2)
| Publication Number | Publication Date |
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| CN1964110A CN1964110A (en) | 2007-05-16 |
| CN100459246C true CN100459246C (en) | 2009-02-04 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2342471Y (en) * | 1998-10-23 | 1999-10-06 | 许开华 | Punch steel belt for battery pole plate |
| CN1361311A (en) * | 2000-12-28 | 2002-07-31 | 长沙力元新材料股份有限公司 | Foamed nickel material with superhigh binding force and its prepn |
| CN1558462A (en) * | 2004-01-16 | 2004-12-29 | 武汉大学 | Sealed basic Ni-Cd secondary cell |
| US20050123782A1 (en) * | 2001-02-15 | 2005-06-09 | Chen Szuchain F. | Copper foil with low profile bond enhancement |
| CN2715355Y (en) * | 2004-07-15 | 2005-08-03 | 常德力元新材料有限责任公司 | Secondary battery pole piece backing with nickel-base composite plating |
-
2005
- 2005-11-08 CN CNB2005101176810A patent/CN100459246C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2342471Y (en) * | 1998-10-23 | 1999-10-06 | 许开华 | Punch steel belt for battery pole plate |
| CN1361311A (en) * | 2000-12-28 | 2002-07-31 | 长沙力元新材料股份有限公司 | Foamed nickel material with superhigh binding force and its prepn |
| US20050123782A1 (en) * | 2001-02-15 | 2005-06-09 | Chen Szuchain F. | Copper foil with low profile bond enhancement |
| CN1558462A (en) * | 2004-01-16 | 2004-12-29 | 武汉大学 | Sealed basic Ni-Cd secondary cell |
| CN2715355Y (en) * | 2004-07-15 | 2005-08-03 | 常德力元新材料有限责任公司 | Secondary battery pole piece backing with nickel-base composite plating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1964110A (en) | 2007-05-16 |
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