CN101609889B - Cadmium negative pole, preparation method thereof and secondary nickel-cadmium battery containing same - Google Patents
Cadmium negative pole, preparation method thereof and secondary nickel-cadmium battery containing same Download PDFInfo
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- CN101609889B CN101609889B CN2008101266967A CN200810126696A CN101609889B CN 101609889 B CN101609889 B CN 101609889B CN 2008101266967 A CN2008101266967 A CN 2008101266967A CN 200810126696 A CN200810126696 A CN 200810126696A CN 101609889 B CN101609889 B CN 101609889B
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Abstract
The invention relates to a cadmium negative pole used for a secondary nickel-cadmium battery. The cadmium negative pole comprises a current collector and a negative pole material covered on the current collector, and the negative pole material contains a negative pole active substance and negative pole adhesive, wherein the negative pole material also contains a conductive metallic oxide which contains at least two metallic elements. The growth of cadmium dendritic crystals of a battery prepared by adopting the cadmium negative pole is effectively restrained in a charging process, thereby better meeting the requirements on the low-current charge and the high-current discharge of the battery.
Description
Technical field
The present invention relates to a kind of negative pole and preparation method thereof, and the battery that uses this negative pole, relate to a kind of cadmium cathode and preparation method thereof in particular, and the secondary nickel-cadmium cell that uses this cadmium cathode.
Background technology
Nickel-based battery has obtained development fast since 1901 are invented, from 1976 to 1986 during the decade, the sales volume of global nickel-cadmium cell has enlarged 3 times, promptly is increased to 1,500,000,000 dollars by 500,000,000 dollars of less thaies.In recent years, nickel-cadmium cell market has developed into one of the most important component in secondary cell market.
Compare with other battery, nickel-cadmium cell all has bigger advantage at aspects such as overcharging resisting, heavy-current discharge, quick charge, fail safe and low costs, and still, its trickle charge performance (little electric current, long-time continuing are charged) but fails to improve always.Nickel-cadmium cell is when low current charge, because the growing up gradually of cadmium dendrite, long, part cadmium electro-chemical activity in the cadmium electrode is reduced and discharging efficiency is descended, and the growth of dendrite also causes barrier film to be punctured easily, causes micro-short circuit, even short circuit.Nickel-cadmium cell the battery micro-short circuit occurs when circulation discharges into 150 left and right sides, cause battery capacity sharply to descend, even short circuit, and therefore, the charge and discharge circulation life of its low current charge, heavy-current discharge is greatly limited.
The trickle charge cycle performance of nickel-cadmium cell (low current charge class cycle performance) is one and troubles the problem that battery circle is resolved for many years and not.That is, in the slow process of charging of the little electric current of battery,, barrier film has been produced very big influence, to such an extent as to make the degradation of battery because the existence that principle is separated out in the dissolving of cadmium cathode causes the growth of cadmium dendrite.In addition, this class battery often all is low current charge and requires heavy-current discharge, though can suppress the growth of cadmium cathode dendrite in the low current charge process to a certain extent by some modes, but the heavy-current discharge performance of battery is still undesirable, therefore, this improves low current charge with regard to the heavy-current discharge performance that has determined impossible sacrifice battery, therefore, can't accomplish to make battery to take into account good low current charge performance and heavy-current discharge performance simultaneously.
CN1487616A discloses a kind of nickel-cadmium accumulator, this battery comprises cadmium oxide negative electrode, nickel hydroxide positive plate, described cadmium oxide negative electrode is bonded electrode, its electrode substance dry powder is made up of active material cadmium oxide, conductive agent, other additives, it is characterized in that described conductive agent comprises Kocide SD.Because the conductivity of Kocide SD is relatively poor, the polarization of intensifier electrode easily in charging process hinders moving of electronics and ion, and therefore, the discharge performance of battery is relatively poor.In addition, though the adding of Kocide SD can be played the effect that suppresses dendritic growth to a certain extent, but still can't dissolve cadmium dendrite, therefore, still not ideal enough to the effect that suppresses cadmium cathode cadmium dendritic growth.
Summary of the invention
The objective of the invention is to overcome the secondary ickel-cadmium cell of prior art when low current charge, easily cause the growth of cadmium cathode cadmium dendrite, and make the defective of battery performance variation, provide a kind of and can effectively suppress the growth of secondary nickel-cadmium cell cadmium cathode cadmium dendrite when low current charge and make battery have the cadmium cathode that is used for the secondary ickel-cadmium cell of good electrochemical and contain the secondary ickel-cadmium cell of this cadmium cathode.
The invention provides a kind of cadmium cathode that is used for the secondary nickel-cadmium cell, described cadmium cathode comprises collector and the negative material that is coated on this collector, described negative material contains negative electrode active material and negative pole adhesive, wherein, described negative material also contains the metal oxide of conduction, and burning 7 things of described conduction are the metal oxide that contains at least two kinds of metallic elements.
The present invention also provides the preparation method of this cadmium cathode, this method comprises and will contain the slurry coating of negative material and solvent and/or be filled on the collector, dry, roll or do not roll, described negative material contains negative electrode active material and negative pole adhesive, wherein, described negative material also contains the metal oxide of conduction, and the metal oxide of described conduction is the metal oxide that contains at least two kinds of metallic elements.
The present invention also provides a kind of secondary ickel-cadmium cell, and this battery comprises pole piece and alkaline electrolyte, and described pole piece and alkaline electrolyte are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, and wherein, described negative pole is a cadmium cathode provided by the invention.
The metal oxide of the conduction that contains in the cadmium cathode of secondary nickel-cadmium cell provided by the invention has certain solubility in alkaline electrolyte, when battery charge, because the variation of this metal oxide valence state causes its solubility change, and can cover equably on cadmium oxide, battery charge is when latter stage, cell voltage rose to certain value, it can further reduce again, this process is an electronics of having captured cadmium, destroyed the growth interface of cadmium crystal, metal ion in the alkali lye in the metal oxide of free conduction then can direct oxidation cadmium particle surface cadmium, the reduzate of the metal oxide of conduction is then covering equably at the cadmium particle surface, stoped the further growth of cadmium dendrite, made the growth of cadmium dendrite be subjected to effective inhibition.And the metal oxide of this conduction also can provide electronics when battery discharge, emits certain capacity, plays the effect of conduction in negative pole effectively, and high-rate battery discharge is had certain benefit.This material of discharge attitude can be dissolved in the alkaline electrolyte, and the material of this discharge attitude can or not be reduced by further oxidation at positive pole yet, that is, its attitude material that discharges aligns stabilizer pole, even or respond and also do not influence its dissolving in alkali lye.Because the metal oxide of this conduction is gradual slow dissolving in circulation overcharges, so can in negative pole, play the effect of conduction effectively, the initial capacity performance of battery and the consistency of battery have also been obtained improving greatly, guaranteed that promptly low current charge has satisfied the requirement of heavy-current discharge again.
Especially contain the manganese metal oxide for conduction of the present invention, charging latter stage, when cell voltage raises, manganic can be captured the electronics of the cadmium of particle surface, destroyed the growth interface of cadmium crystal, the reduzate of the manganese that produces is attached to its surface, thereby can stop the growth of cadmium dendrite effectively, the two-way interaction makes growing up of cadmium dendrite become very difficult, the liberation of hydrogen overpotential on manganese surface is high more a lot of than nickel, raising to battery charge efficient has very big benefit, and manganese the time can lose electronics in discharge and is dissolved in the alkali lye, can not have a negative impact to heavy-current discharge.In addition, it improves a lot to the little electric current overcharging resisting of nickel-cadmium cell ability, can improve the speed that negative pole absorbs oxygen, can stop the growth of cadmium dendrite effectively, suppress further growing up of cadmium crystal, liberation of hydrogen overpotential on the bivalent manganese that charging produces can improve the charge efficiency in charging later stage far above nickel; And some conductivity also can be provided when heavy-current discharge, and after discharging, himself promptly promptly returns in the alkali lye, can not reduce the increase that cause polarization because of the conductivity of self.Such material also is in cyclic process in the battery cyclic process, the effect longer duration that it is good can increase substantially nickel-cadmium cell trickle charge cycle performance, and such additive environmentally safe, meets the ROHS standard, and with low cost.
Embodiment
According to the present invention, the described cadmium cathode that is used for the secondary nickel-cadmium cell comprises collector and the negative material that is coated on this collector, described negative material contains negative electrode active material and negative pole adhesive, it is characterized in that, described negative material also contains the metal oxide of conduction, and the metal oxide of described conduction is the metal oxide that contains at least two kinds of metallic elements.
Under the preferable case, the metal oxide of described conduction has the composition shown in the following formula:
A
aM
bMn
cO
4, wherein, a represents the atoms of elements quantity of A representative, 0≤a≤1.2, and b represents the atoms of elements quantity of M representative, 0≤b≤1.0, and a, b are not zero simultaneously; C represents the quantity of manganese atom, 0.1≤c≤2.2, and A is lithium, sodium or potassium element, M is a kind of in alkali metal, alkali earth metal and the thulium, and A and M are not with a kind of element.Described rare earth element refers to lanthanide series in the periodic table of elements, comprise lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu), and with closely-related two elements of 15 elements of group of the lanthanides, scandium (Sc) and yttrium (Y), totally 17 elements.Under the preferable case, the metal oxide of conduction of the present invention can be selected from LiMn
2O
4, NaMn
2O
4, KMn
2O
4, La
1/3MnO
4, Ce
1/3MnO
4, Pr
1/3MnO
4, Nd
1/3MnO
4, Pm
1/3MnO
4, Sm
1/3MnO
4, Eu
1/3MnO
4, Gd
1/3MnO
4, Tb
1/3MnO
4, Dy
1/3MnO
4, Er
1/3MnO
4, Tm
1/3MnO
4, Y
1/3MnO
4, Yb
1/3MnO
4, Lu
1/3MnO
4And Ho
1/3MnO
4In one or more.
More preferably under the situation, the metal oxide of conduction of the present invention is selected from LiMn
2O
4, NaMn
2O
4And KMn
2O
4In one or more.
Weight with described negative electrode active material is benchmark, and the content of the metal oxide of described conduction is 0.01-25 weight %, is preferably 0.05-12 weight %.
The kind of described negative electrode active material is conventionally known to one of skill in the art, as, can be selected from cadmium, cadmium oxide and the cadmium hydroxide one or more.
Can also contain conductive agent in the described negative material, described conductive agent can be selected from one or more in nickel powder, conductive black, cadmium powder and the graphite, weight with described negative electrode active material is benchmark, and the content of described conductive agent can be 0-5 weight %, is preferably 0.1-2 weight %.The content of cathode conductive agent is more among the secondary nickel-cadmium cell preparation technology of prior art, be generally the 2-12 weight % of negative electrode active material, because the adding of the metal oxide that conducts electricity in the NI-G secondary battery cathode material of the present invention, can be good at playing the effect of conductive agent, therefore, general only the needs adds more a spot of conductive agent, in most cases, can add conductive agent again.
Negative pole adhesive in the described negative material can adopt known in the art all can be used for the adhesive of cadmium cathode.For example, described negative pole adhesive can be selected from one or more in polytetrafluoroethylene, butadiene-styrene rubber, polyvinyl alcohol and the cellulose-based polymer, the kind that can be used for the cellulose-based polymer of negative pole adhesive is conventionally known to one of skill in the art, for example, can be selected from and to be selected from methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose and the hydroxyethylcellulose one or more; Weight with described negative electrode active material is benchmark, and the content of described negative pole adhesive can be 1-10 weight %, is preferably 2-6 weight %.
Under the preferable case, the negative pole adhesive in the described negative material is the mixture of hydrophobicity adhesive and hydrophilic adhesive.The ratio of described hydrophobicity adhesive and hydrophilic adhesive can determine according to actual needs that for example, the part by weight of hydrophilic adhesive and hydrophobicity adhesive can be (0.1-1): 1.Described hydrophobicity adhesive can for, for example, polytetrafluoroethylene and/or butadiene-styrene rubber.Described hydrophilic adhesive can for, for example, cellulose-based polymer and/or polyvinyl alcohol.
Collector can adopt the collector of all available cadmium cathodes known in the art, for example can be the Punching steel strip that steel band makes through punching press, and one deck nickel or nickel alloy can be electroplated in the surface of described Punching steel strip.Described negative material is coated in the both sides of collector Punching steel strip respectively.
According to the present invention, the preparation method of described cadmium cathode comprises and will contain the slurry coating of negative material and solvent and/or be filled on the collector, dry, roll or do not roll, described negative material contains negative electrode active material and negative pole adhesive, wherein, described negative material also contains the metal oxide of conduction, and the metal oxide of described conduction is the metal oxide that contains at least two kinds of metallic elements.
It is benchmark that the consumption of the metal oxide of described conduction makes the weight with described negative electrode active material, and the content of the metal oxide of conduction is 0.01-25 weight %, is preferably 0.05-12 weight %.
In the preparation method according to cadmium cathode of the present invention, the above-mentioned definition to cadmium cathode of employed each raw material such as the present invention is not described in detail in this.
Solvent, negative electrode active material and negative pole adhesive consumption are conventionally known to one of skill in the art in the described slurry.In general, be benchmark with the weight of negative electrode active material, the content of described solvent can be 15-60 weight %, is preferably 15-50 weight %.Described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols; The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
When preparation contains the slurry of negative material and solvent, described the metal oxide of negative electrode active material, negative pole adhesive, conduction and the mixing of solvent can be carried out also can carrying out step by step simultaneously, under the preferable case, in order to make the slurry that makes can and more easily evenly be coated on the collector, the described preparation method who contains the slurry of negative material and solvent comprises elder generation with negative pole adhesive, negative electrode active material and solvent, and then mixes with the metal oxide of conduction.
More even for what the negative pole adhesive was mixed with other component, described negative pole adhesive normally adds with the form of adhesive agent emulsion, and described adhesive agent emulsion is meant adhesive and water or alcohols, as the emulsion of ethanol, glycerol, isopropyl alcohol formation.The solid content of adhesive is generally 1-20 weight % in the hydrophilic adhesive emulsion; The solid content of adhesive is generally 10-60 weight % in the hydrophobic adhesive emulsion.
If also contain conductive agent in the described negative pole, method provided by the invention also is included in and makes before the cathode size, in the mixture of metal oxide that contains negative electrode active material, negative pole adhesive, conduction that obtains and solvent, add conductive agent, and the step that mixes.Described conductive agent can add simultaneously also and can add step by step, and the performance of the order anticathode slurry of adding does not have remarkable influence.
Secondary nickel-cadmium cell provided by the invention comprises pole piece and alkaline electrolyte, and described pole piece and alkaline electrolyte are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, and described negative pole is a cadmium cathode provided by the invention.
Because improvements of the present invention only relate to the cadmium cathode of secondary nickel-cadmium cell, therefore in secondary nickel-cadmium cell provided by the invention, described nickel positive pole, barrier film and alkaline electrolyte solution are had no particular limits, can use all types of nickel positive poles, barrier film and the alkaline electrolyte solution that can in the secondary nickel-cadmium cell, use.Those of ordinary skill in the art can be according to the instruction of prior art, can select and prepare described nickel positive pole, barrier film and the alkaline electrolyte solution of secondary nickel-cadmium cell of the present invention easily, and make secondary nickel-cadmium cell of the present invention by described nickel positive pole, cadmium cathode, barrier film and alkaline electrolyte solution.
For example, described nickel positive pole can be by with the aqueous solution and the deionized water and stirring pulp thing of ball-type nickel hydroxide, cobalt protoxide, conductive black and ptfe emulsion, hydroxypropyl methylcellulose and be coated onto on the foaming nickel that is welded with the drainage band, the nickel electrode that makes through oven dry, roll-in, cut-parts.
Described barrier film can be through welding or the bonding composite diaphragm that forms by modified polypropene felt, vinylon felt or nylon felt and wettability microporous polyolefin film.
Described alkaline electrolyte solution can be at least a aqueous solution that is selected among KOH, NaOH and the LiOH.
The following examples will the present invention is described further, but can not be interpreted as it is qualification to protection range of the present invention.
Embodiment 1
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 4 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company) and the 10 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add polytetrafluoroethylene suspension-turbid liquid and the 1.6 kilograms of butadiene-styrene rubber aqueous solution and 1.8 kilograms of PVA solution mixing and stirring that concentration is 4 weight % that concentration is 60 weight % that 1.2 kilograms of solid contents are 60 weight % then, add the metal oxide LiMn of 0.5 kilogram of conduction at last
2O
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, after 220 ℃ of oven dry, roll-in, on cutting machine, cut then and obtain some long 240 millimeters * wide 33.6 millimeters * thick 580 microns nickel negative poles that are of a size of, wherein, contain 10 gram negative electrode active materials.
(2) Zheng Ji preparation
92 kilograms of ball-type nickel hydroxides, 7 kilograms of cobalt protoxides, 11 kilograms of carbon blacks mixed to stir with the binder solution of being made up of 4 kilograms of polytetrafluoroethylene, 0.2 kilogram of hydroxypropyl methylcellulose and 40 kilograms of deionized waters form uniform anode sizing agent.
This slurry is coated onto on wide 60 millimeters, the thick 1.2 millimeters foaming nickel that is welded with the drainage band equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 184 millimeters * wide 32.5 millimeters * thick 600 microns nickel positive poles that are of a size of afterwards then, wherein, contain 7.5 gram positive active materials.
With above-mentioned cadmium cathode, nickel positive pole across by forming pole piece with up-coiler coiling multi-turn and receive and keep in battery steel shell through welding or the bonding composite diaphragm that forms by modified polypropene felt and wettability microporous polyolefin film, contain through spot welding, jet-bedding, injection 25% KOH and 1.5% LiOH electrolyte and to seal the nominal capacity of making the SC type be that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 2
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 3 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company) and 0.5 kilogram of graphite, the 16 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add polytetrafluoroethylene suspension-turbid liquid and the 1.5 kilograms of butadiene-styrene rubber aqueous solution and 1 kilogram of PVA mixing and stirring that concentration is 10 weight % that concentration is 60 weight % that 1 kilogram of solid content is 60 weight % then, add the metal oxide LiMn of 1.8 kilograms of conductions at last
2O
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.63 millimeters * thick 580 microns nickel negative poles that are of a size of afterwards then, wherein, contain 10.5 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 3
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 3 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company), 0.8 kilogram of cadmium powder and the 11 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add 1.5 kilograms of solid contents then and be polytetrafluoroethylene suspension-turbid liquid and the 1.2 kilograms of butadiene-styrene rubber aqueous solution and 2 kilograms of PVA mixing and stirring that concentration is 8 weight % that concentration is 60 weight % of 60%, add the metal oxide LiMn of 2.4 kilograms of conductions at last
2O
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.6 millimeters * thick 580 microns nickel negative poles that are of a size of afterwards then, wherein, contain 11.5 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 4
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
Is the aqueous solution and 4 kg water of the hydroxypropyl methylcellulose of 3 weight %s with 8 kilograms with concentration with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company), fully stir evenly, add 1.5 kilograms of solid contents then and be polytetrafluoroethylene suspension-turbid liquid and the 1 kilogram of butadiene-styrene rubber aqueous solution and 1.6 kilograms of PVA mixing and stirring that concentration is 9 weight % that concentration is 60 weight % of 60%, add the metal oxide LiMn of 1.45 kilograms of conductions at last
2O
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.6 millimeters * thick 580 microns nickel negative poles that are of a size of afterwards then, wherein, contain 10.5 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 5
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 0.5 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company) and the 20 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add polytetrafluoroethylene suspension-turbid liquid and the 1.8 kilograms of butadiene-styrene rubber aqueous solution and 1 kilogram of PVA solution mixing and stirring that concentration is 15 weight % that concentration is 60 weight % that 1 kilogram of solid content is 60 weight % then, add the metal oxide KMn of 4 kilograms of conductions at last
2O
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.63 millimeters * thick 600 microns nickel negative poles that are of a size of afterwards then, wherein, contain 10.8 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 6
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 3 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company) and the 12 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add polytetrafluoroethylene suspension-turbid liquid and the 2 kilograms of butadiene-styrene rubber aqueous solution and 1.6 kilograms of PVA solution mixing and stirring that concentration is 10 weight % that concentration is 60 weight % that 0.8 kilogram of solid content is 60 weight % then, add the metal oxide NaMn of 3 kilograms of conductions at last
2O
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.63 millimeters * thick 600 microns nickel negative poles that are of a size of afterwards then, wherein, contain 11 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 7
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 2 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company) and the 15 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add polytetrafluoroethylene suspension-turbid liquid and the 1 kilogram of butadiene-styrene rubber aqueous solution and 1.5 kilograms of PVA solution solvent mixing and stirring that concentration is 6 weight % that concentration is 60 weight % that 1.6 kilograms of solid contents are 60 weight % then, add the metal oxide lanthanum manganate La of 5 kilograms of conductions at last
1/3MnO
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.63 millimeters * thick 580 microns nickel negative poles that are of a size of afterwards then, wherein, contain 10 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 8
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
(1) preparation of negative pole
The aqueous solution and 3 kg water with 75 kilograms of negative electrode active material cadmium oxides, 5 kilograms of Spongy Cadmiums (big city, Hebei company) and the 10 kilograms of concentration hydroxypropyl methylcellulose that is 3 weight %, fully stir evenly, add polytetrafluoroethylene suspension-turbid liquid and the 1.8 kilograms of butadiene-styrene rubber aqueous solution and 2 kilograms of PVA solution solvent mixing and stirring that concentration is 12 weight % that concentration is 60 weight % that 1.6 kilograms of solid contents are 60 weight % then, add the metal oxide mangaic acid cerium Ce of 8 kilograms of conductions at last
1/3MnO
4, mix to stir forming uniform cathode size.
This slurry is coated on wide 220 millimeters, the thick 80 microns nickel plating Punching steel strip equably, 220 ℃ of oven dry, roll-ins are cut on cutting machine and obtain some long 240 millimeters * wide 33.6 millimeters * thick 60 microns nickel negative poles that are of a size of afterwards then, wherein, contain 10.5 gram negative electrode active materials.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 9
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
Method according to embodiment 8 prepares the secondary nickel-cadmium cell, and different is that when the preparation negative pole, the metal oxide of the conduction of adding is 4 kilograms of mangaic acid cerium Ce
1/3MnO
4With 4 kilograms of LiMn
2O
4Mixture.
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Embodiment 10
Present embodiment is used to illustrate secondary nickel-cadmium cell provided by the invention
Method according to embodiment 1 prepares the NI-G secondary cell, and different is that when the preparation negative pole, the metal oxide of described conduction is 0.5 kilogram of mangaic acid yttrium Y
1/3MnO
4
The nominal capacity that above-mentioned cadmium cathode is prepared into the SC type according to the method identical with embodiment 1 is that the secondary nickel-cadmium cell of 1500 MAHs is some.
Comparative Examples 1
This Comparative Examples is used to illustrate the preparation of reference secondary nickel-cadmium cell
Method according to embodiment 1 prepares the secondary nickel-cadmium cell, and different is, does not contain the metal oxide of conduction in the described cadmium cathode, adds 5 kilograms of nickel powders, prepares some reference cells.
Comparative Examples 2
This Comparative Examples is used to illustrate the preparation of reference secondary nickel-cadmium cell
Method according to embodiment 5 prepares the secondary nickel-cadmium cell, and different is, does not contain the metal oxide of conduction in the described cadmium cathode, adds 4 kilograms of carbon blacks, prepares some reference cells.
Comparative Examples 3
This Comparative Examples is used to illustrate the preparation of reference secondary nickel-cadmium cell
Method according to embodiment 1 prepares the secondary nickel-cadmium cell, and different is that in described cadmium cathode, the metal oxide with Kocide SD replacement conduction prepares some reference cells.
Embodiment 11-20
Present embodiment is used to illustrate the performance test of battery
(1) cycle performance test (low current charge, heavy-current discharge)
Extract 2 respectively from each Battery pack of embodiment 1-10 preparation, note is A1, A2 respectively; B1, B2; C1, C2; D1, D2; E1, E2; F1, F2; G1, G2; H1, H2; I1, I2; J1, J2, the above-mentioned secondary nickel-cadmium cell that makes was charged 11 hours with 210mA respectively first, shelved 0.15 hour, being discharged to voltage with 10A then is 0.8V, the initial discharge capacity of record battery, and repeat above-mentioned circulation, the discharge capacity of battery after the record circulation 50 times, 100 times, 150 times, 200 times and 250 times respectively, and the capacity sustainment rate of counting cell according to the following equation;
Capacity sustainment rate=(discharge capacity first of the discharge capacity/battery of N back of circulation battery) * 100%
The result is as shown in table 1.
(2) self-discharge performance test
From every Battery pack of embodiment 1-10 preparation, extract 20 batteries more respectively once more, the secondary nickel-cadmium cell of above-mentioned extraction was charged 11 hours with 210mA respectively first, shelved 15 minutes, being discharged to voltage with 10A then is 0.8V, shelved 20 minutes, the initial discharge capacity of record battery, and the average initial discharge capacity of counting cell, repeat above-mentioned circulation 150 times then, at the 20th time, 40 times, 60 times, 80 times, 100 times, 120 times, after 140 charging processes, battery is shelved discharge again after 24 hours, and the discharge capacity of record battery after circulation 150 times, and calculate the average discharge capacity of every group of 20 batteries respectively.The result is as shown in table 2.
(3) high temperature self-discharge performance test
From each Battery pack of embodiment 1-10 preparation, extract 198 more respectively once more, earlier the above-mentioned secondary nickel-cadmium cell that makes is discharged to 1.0V with 1500mA respectively first, then, with 1500mA charging 75 minutes, shelved 15 minutes, 1500mA is discharged to 1.0V, the discharge capacity first of record battery, be initial capacity, and calculate the mean value of the initial capacity of every group of 198 batteries respectively; And then with 1500mA charging 75 minutes:
Self-discharge rate %=((battery is discharge capacity-discharge capacity of battery after shelving first)/battery is discharge capacity first) * 100%
1, from above-mentioned every Battery pack, extracts 66, descend placement after 30 days at 60 ℃ on battery, after the taking-up, under room temperature (25 ℃), shelved 30 minutes, test voltage is discharged to 1.0V with 1500mA again, the discharge capacity of record battery, and calculating the mean value of the discharge capacity of every group of 66 batteries respectively, the result is as shown in table 3.
2, from above-mentioned every Battery pack, extract 66, battery was shelved 28 days under normal temperature (25 ℃), take out and shelved 30 minutes, test voltage is discharged to 1.0V with 1500mA again, the discharge capacity of record battery, and calculating the mean value of the discharge capacity of every group of 66 batteries respectively, the result is as shown in table 4.
3, extract 66 from above-mentioned every Battery pack, battery was shelved under 60 ℃ 7 days, take out and shelved 30 minutes, test voltage is discharged to 1.0V with 1500mA again, writes down its discharge capacity.Write down the discharge capacity of battery, and calculate the mean value of the discharge capacity of every group of 66 batteries respectively, the result is as shown in table 5.
Comparative Examples 4-6
Present embodiment is used to illustrate the performance test of reference cell
Extract 2 respectively from each Battery pack of Comparative Examples 1-3 preparation, note is AC1, AC2 respectively; BC1, BC2, CC1, CC2, and according to the initial capacity and the cycle performance of the method test battery of embodiment 11-20, the result is as shown in table 1.From each Battery pack of Comparative Examples 1-3 preparation, extract 20 respectively once more, and according to the self-discharge performance of the method test battery of embodiment 11-20, the result is as shown in table 2.
From each Battery pack of Comparative Examples 1-3 preparation, extract 198 respectively once more, and according to the high temperature self-discharge performance of the method test battery of embodiment 11-20, the result is respectively shown in table 3-table 5.
Table 1
From the result of table 1 as can be seen, the low current charge of secondary nickel-cadmium cell of the present invention, the cycle performance of battery of heavy-current discharge are good, and after charge and discharge cycles 250 times, the capacity sustainment rate of battery is significantly higher than reference cell still up to more than 80%.
Table 2
| The embodiment numbering | The average initial capacity (mAh) of 20 batteries | The average size (mAh) of 150 back 20 batteries of circulation |
| Embodiment 1 | 1447 | 1345 |
| Embodiment 2 | 1481 | 1347 |
| Embodiment 3 | 1515 | 1485 |
| Embodiment 4 | 1468 | 1355 |
| Embodiment 5 | 1459 | 1349 |
| Embodiment 6 | 1444 | 1406 |
| Embodiment 7 | 1459 | 1366 |
| Embodiment 8 | 1466 | 1335 |
| Embodiment 9 | 1458 | 1359 |
| Embodiment 10 | 1450 | 1344 |
| Comparative Examples 1 | 1455 | 1151 |
| Comparative Examples 2 | 1348 | 1124 |
| Comparative Examples 3 | 1367 | 1008 |
From the result of table 2 as can be seen, battery illustrates that at more than 75% of discharge capacity first that still can reach battery through the capacity after 150 times after repeatedly the shelving circulations this secondary nickel-cadmium cell has long cycle life.
Table 3
| The embodiment numbering | The average initial capacity (mAh) of 66 batteries | The average size (mAh) of battery after placing 3 days under 60 ℃ | Place 3 days self-discharge rate % down at 60 ℃ |
| Embodiment 1 | 1468 | 1165 | 20.64 |
| Embodiment 2 | 1465 | 1167 | 20.34 |
| Embodiment 3 | 1514 | 1219 | 21.48 |
| Embodiment 4 | 1479 | 1172 | 20.76 |
| Embodiment 5 | 1463 | 1159 | 20.78 |
| Embodiment 6 | 1452 | 1161 | 20.05 |
| Embodiment 7 | 1464 | 1161 | 20.70 |
| Embodiment 8 | 1463 | 1165 | 20.37 |
| Embodiment 9 | 1466 | 1168 | 20.29 |
| Embodiment 10 | 1456 | 1160 | 20.31 |
| Comparative Examples 1 | 1463 | 1175 | 19.69 |
| Comparative Examples 2 | 1365 | 1022 | 25.13 |
| Comparative Examples 3 | 1367 | 1014 | 25.82 |
Table 4
| The embodiment numbering | The average initial capacity (mAh) of 66 batteries | Shelve the average size (mAh) of battery after 28 days at normal temperatures | Shelve 28 days self-discharge rate % at normal temperatures |
| Embodiment 1 | 1461 | 1178 | 19.37 |
| Embodiment 2 | 1458 | 1167 | 19.96 |
| Embodiment 3 | 1527 | 1209 | 20.83 |
| Embodiment 4 | 1468 | 1174 | 20.03 |
| Embodiment 5 | 1464 | 1166 | 20.36 |
| Embodiment 6 | 1453 | 1161 | 20.10 |
| Embodiment 7 | 1467 | 1172 | 20.11 |
| Embodiment 8 | 1457 | 1166 | 19.97 |
| Embodiment 9 | 1462 | 1169 | 20.01 |
| Embodiment 10 | 1460 | 1166 | 20.14 |
| Comparative Examples 1 | 1471 | 1093 | 25.69 |
| Comparative Examples 2 | 1355 | 1039 | 23.32 |
| Comparative Examples 3 | 1368 | 1033 | 24.49 |
Table 5
| The embodiment numbering | The average initial capacity (mAh) of 66 batteries | The average size (mAh) of battery after shelving 7 days under 60 ℃ | Under 60 ℃, shelve 7 days self-discharge rate % |
| Embodiment 1 | 1475 | ?1024 | 30.61 |
| Embodiment 2 | 1461 | ?1011 | 30.83 |
| Embodiment 3 | 1518 | ?1047 | 31.04 |
| Embodiment 4 | 1459 | ?1008 | 30.92 |
| Embodiment 5 | 1463 | ?1008 | 31.11 |
| Embodiment 6 | 1456 | ?1007 | 30.85 |
| Embodiment 7 | 1459 | ?1011 | 30.71 |
| Embodiment 8 | 1460 | ?1007 | 31.02 |
| Embodiment 9 | 1465 | ?1012 | 30.94 |
| Embodiment 10 | 1459 | ?1021 | 30.05 |
| Comparative Examples 1 | 1465 | ?924 | 36.95 |
| Comparative Examples 2 | 1358 | ?798 | 41.25 |
| Comparative Examples 3 | 1366 | ?618 | 54.77 |
From the result of table 3-table 5 as can be seen, the self-discharge rate of secondary nickel-cadmium cell of the present invention after normal temperature and hot conditions are placed all is starkly lower than reference cell, therefore, illustrates that battery of the present invention has good security performance.
In sum, the secondary nickel-cadmium cell that adopts the negative pole that contains the metal oxide of conduction of the present invention to prepare has good trickle charge cycle performance, be the performance of low current charge, heavy-current discharge, the self-discharge rate of battery can reach requirement, and has good security performance.
Claims (9)
1. cadmium cathode that is used for the secondary nickel-cadmium cell, described cadmium cathode comprises collector and the negative material that is coated on this collector, described negative material contains negative electrode active material and negative pole adhesive, it is characterized in that, described negative material also contains the metal oxide of conduction, and the metal oxide of described conduction has the composition shown in the following formula:
A
aM
bMn
cO
4, wherein, a represents the atoms of elements quantity of A representative, 0≤a≤1.2, and b represents the atoms of elements quantity of M representative, 0≤b≤1.0, and a, b are not zero simultaneously; C represents the quantity of manganese atom, 0.1≤c≤2.2, and A is lithium, sodium or potassium element, M is a kind of in alkali metal, alkali earth metal and the thulium, and A and M are not with a kind of element.
2. negative pole according to claim 1 wherein, is a benchmark with the weight of described negative electrode active material, and the content of the metal oxide of described conduction is 0.01-25 weight %, and the content of described negative pole adhesive is 1-10 weight %.
3. negative pole according to claim 1, wherein, the metal oxide of described conduction is selected from LiMn
2O
4, NaMn
2O
4, KMn
2O
4, La
1/3MnO
4, Ce
1/3MnO
4, Pr
1/3MnO
4, Nd
1/3MnO
4, Pm
1/3MnO
4, Sm
1/3MnO
4, Eu
1/3MnO
4, Gd
1/3MnO
4, Tb
1/3MnO
4, Dy
1/3MnO
4, Er
1/3MnO
4, Tm
1/3MnO
4, Y
1/3MnO
4, Yb
1/3MnO
4, Lu
1/3MnO
4And Ho
1/3MnO
4In one or more.
4. negative pole according to claim 1 and 2, wherein, described negative electrode active material is selected from one or more in cadmium, cadmium oxide and the cadmium hydroxide; Described negative pole adhesive is selected from one or more in polytetrafluoroethylene, butadiene-styrene rubber, polyvinyl alcohol and the cellulose-based polymer.
5. the preparation method of the described cadmium cathode of claim 1, wherein, this method comprises and will contain the slurry coating of negative material and solvent and/or be filled on the collector, dry, roll or do not roll, described negative material contains negative electrode active material and negative pole adhesive, it is characterized in that, described negative material also contains the metal oxide of conduction, and the metal oxide of described conduction has the composition shown in the following formula:
A
aM
bMn
cO
4, wherein, a represents the atoms of elements quantity of A representative, 0≤a≤1.2, and b represents the atoms of elements quantity of M representative, 0≤b≤1.0, and a, b are not zero simultaneously; C represents the quantity of manganese atom, 0.1≤c≤2.2, and A is lithium, sodium or potassium element, M is a kind of in alkali metal, alkali earth metal and the thulium, and A and M are not with a kind of element.
6. method according to claim 5, wherein, it is benchmark that the consumption of each material makes the weight with described negative electrode active material, and the content of the metal oxide of conduction is 0.01-25 weight %, and the content of negative pole adhesive is 1-10 weight %.
7. method according to claim 5, wherein, the described preparation method who contains the slurry of negative material and solvent comprises elder generation with negative pole adhesive, negative electrode active material and solvent, and then mixes with the metal oxide of conduction.
8. method according to claim 5, wherein, the metal oxide of described conduction is selected from LiMn
2O
4, NaMn
2O
4, KMn
2O
4, La
1/3MnO
4, Ce
1/3MnO
4, Pr
1/3MnO
4, Nd
1/3MnO
4, Pm
1/3MnO
4, Sm
1/3MnO
4, Eu
1/3MnO
4, Gd
1/3MnO
4, Tb
1/3MnO
4, Dy
1/3MnO
4, Er
1/3MnO
4, Tm
1/3MnO
4, Y
1/3MnO
4, Yb
1/3MnO
4, Lu
1/3MnO
4And Ho
1/3MnO
4In one or more.
9. secondary nickel-cadmium cell, this battery comprises pole piece and alkaline electrolyte, and described pole piece and alkaline electrolyte are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, it is characterized in that described negative pole is any described cadmium cathode among the claim 1-4.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420575A (en) * | 2001-11-21 | 2003-05-28 | 松下电器产业株式会社 | Cadmium cathode and Ni-Cd accumulator comprising same |
| CN1487616A (en) * | 2002-09-30 | 2004-04-07 | 比亚迪股份有限公司 | Nickel-cadmium accumulator |
| CN1767249A (en) * | 2004-07-23 | 2006-05-03 | 日本无公害电池研究所 | Nickel electrode and alkali storage battery using the same |
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2008
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420575A (en) * | 2001-11-21 | 2003-05-28 | 松下电器产业株式会社 | Cadmium cathode and Ni-Cd accumulator comprising same |
| CN1487616A (en) * | 2002-09-30 | 2004-04-07 | 比亚迪股份有限公司 | Nickel-cadmium accumulator |
| CN1767249A (en) * | 2004-07-23 | 2006-05-03 | 日本无公害电池研究所 | Nickel electrode and alkali storage battery using the same |
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