CN107732162A - A kind of lead-carbon battery negative electrode material and preparation method of high circulation number - Google Patents
A kind of lead-carbon battery negative electrode material and preparation method of high circulation number Download PDFInfo
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- CN107732162A CN107732162A CN201711107204.5A CN201711107204A CN107732162A CN 107732162 A CN107732162 A CN 107732162A CN 201711107204 A CN201711107204 A CN 201711107204A CN 107732162 A CN107732162 A CN 107732162A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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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
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- 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 present invention relates to a kind of lead-carbon battery negative electrode material and preparation method of high circulation number, belong to cell manufacturing techniques field.Following component by weight is included as raw material：5~10 parts of sulfuric acid, 0.5~2 part of barium sulfate, 0.5~2 part of silicon carbide powder, 0.1~0.15 part of white carbon, 0.2~0.4 part of graphene modacrylic fibers, 0.05~0.1 part of titanate coupling agent, 0.1~0.15 part of nonionic surfactant, 7~12 parts of pure water, 50~60 parts of lead powder.There is lead carbon battery made of negative material used in lead carbon battery provided by the invention capacitance to lose the advantages of electricity is small greatly, after circulation electric discharge.
Description
Technical field
The present invention relates to a kind of lead-carbon battery negative electrode material and preparation method of high circulation number, belong to cell manufacturing techniques
Field.
Background technology
At present, Lead-acid Battery Technology technique is very ripe, with capacity is big, security is good, cost is low, recyclable
The features such as, future will be the mainstream technology of weak mixed technology, but traditional lead acid batteries high current charge-discharge short life the problems such as system
The about popularization of the technology, the novel battery technology of lead carbon battery can solve this deficiency.Lead carbon battery by Carbon Materials with tradition
Negative material lead is mixed to form composite negative pole, after negative pole introduces Carbon Materials, the sulfation phenomenon that can be effectively improved under PSoC,
Improve charge acceptance and high rate performance.After improvement, the product charging interval is 1/8th of lead-acid battery, and cycle life is
More than four times of lead-acid battery, compared with lithium battery, it may have low temperature performance well, cost be low, production and recovery process maturation etc.
Advantage.
CN104577058A discloses a kind of lead carbon battery negative electrode active material preparation method, belongs to lead-acid accumulator making
Technical field.It is dry-mixed, wet by the proportion optimizing and control each stage of each composition using special lead carbon battery and cream equipment
Mixed, acid is done time, and then the quality of production good (carbon material good dispersion), process control and meets battery performance requirements
Diachylon of negative electrode of lead carbon battery.CN105140466A discloses a kind of lead charcoal negative plate, and common cathode lead plaster is coated on into lead calcium plate
On grid alloy, then in the cathode lead plaster of the high carbon content of pole plate coated on both sides, lead charcoal negative plate is dried to obtain by solidification, wherein
The cathode lead plaster composition of high carbon content is：100 parts of lead powder；Carbon Materials A0.5~1 part；5~20 parts of Carbon Materials B；Barium sulfate 0.1
~1.5 parts；0.1~0.5 part of sodium lignosulfonate；0.1~0.5 part of humic acid；0.1~0.5 part of chopped fiber；10~20 parts of water；1.0
~1.4g/cm34~8 parts of sulfuric acid.
But the lead carbon battery that above-mentioned negative material obtains remains the shortcomings that current strength is low, the life-span is not long.
The content of the invention
The purpose of the present invention is：For the problem of discharge cycles number existing for lead carbon battery is low, short life, it is proposed that one
Its negative material used is planted, and includes the lead carbon battery of the negative material.
Technical scheme is：
A kind of negative material used in lead carbon battery, include following component by weight as raw material：Sulfuric acid 5~
10 parts, 0.5~2 part of barium sulfate, 0.5~2 part of silicon carbide powder, 0.1~0.15 part of white carbon, graphene modified polyacrylic acid it is fine
Dimension 0.2~0.4 part, 0.05~0.1 part of titanate coupling agent, 0.1~0.15 part of nonionic surfactant, 7~12 parts of pure water,
50~60 parts of lead powder.
The average particle size range of described white carbon is 50~100 μm.
The average particle size range of described silicon carbide powder is 50~100 μm.
The preparation method of described graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 50~60 parts of hydroxy silicon oils, 10~15 parts of Silane coupling reagent KH-570s, 3~5 parts
KOH, 6~10 parts of ethyl acetate are well mixed, keep reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtain being modified poly- silicon
Oxygen alkane performed polymer；
2nd step, by weight, take 12~15 parts of butyl acrylate, 5~10 parts of methyl acrylate, 1~2 part of emulsifying agent
With 20~30 parts, 0.5~1h of high-speed stirred of deionized water, add 2~4 parts of initiator, at 70~80 DEG C react 0.5~
2h, then 1~2 part of 6~10 parts of modified polyorganosiloxane performed polymers and initiator are added dropwise, 2~3h is reacted at 70~80 DEG C, then use ammonia
Water adjusts pH to 7, obtains acrylic emulsion；
3rd step, 2~4 parts of 5~15 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, disperseed
After uniformly, modified acrylic acid emulsion is obtained；
4th step, by weight, by 40~45 parts of graphene, 3~5 parts of cationic surfactant, silane coupler
KH-5502~4 part, 5~15 parts of organic solvent are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：4~7 is well mixed, then will
Feed liquid is sprayed into fiber by spinning nozzle, then after drying, obtains graphene modacrylic fibers.
A diameter of 0.1~0.5mm of spinning head.
The azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, the formyl of azo two
Amine, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano penta
One or more in acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and ABVN.
The preparation method of negative material used in described lead carbon battery, comprises the following steps：
S1：By barium sulfate, silicon carbide powder, white carbon, graphene modacrylic fibers, titanate coupling agent, non-
Ionic surface active agent, pure water are well mixed, and are slow added into lead powder, are stirred, and are added and are slowly added to sulfuric acid, and control
Temperature is no more than 55 DEG C；
S2：The lead plaster obtained in S1 is coated onto on negative pole screen, 20~40h is dried at 55~65 DEG C of temperature, is born
Pole material.
Beneficial effect
Lead carbon battery made of negative material used in lead carbon battery provided by the invention has that capacitance is big, circulation electric discharge
The advantages of electricity is small is lost afterwards.
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted specific skill in embodiment
Art or condition person, carried out according to the technology described by document in the art or condition or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
Word " comprising " used herein, "comprising", " having " or its any other variant are intended to cover non-exclusionism
Including.Technique, method, article or the equipment for e.g., including listing key element are not necessarily limited by those key elements, but can include it
He is not expressly set out or belonged to this technique, method, article or the intrinsic key element of equipment.
Scope is used as using what the value of range format expression should be interpreted as not only including clearly including in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, " about 0.1% to about 5% " concentration range should be understood to not only include clearly including
About 0.1% to about 5% concentration, 4%) and son in addition to the single concentration (e.g., 1%, 2%, 3% and in the range of alluding to
Section (for example, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Percentage in the present invention is without specified otherwise
In the case of refer to percentage by weight.
Include 5~10 parts of sulfuric acid, barium sulfate by weight in the preparing raw material of negative material provided by the invention
0.5~2 part, 0.5~2 part of silicon carbide powder, 0.1~0.15 part of white carbon, graphene modacrylic fibers 0.2~0.4
Part, 0.05~0.1 part of titanate coupling agent, 0.1~0.15 part of nonionic surfactant, 7~12 parts of pure water, lead powder 50~60
Part.
Wherein, the preparation method step of graphene modacrylic fibers is：
1st step, by weight, by 50~60 parts of hydroxy silicon oils, 10~15 parts of Silane coupling reagent KH-570s, 3~5 parts
KOH, 6~10 parts of ethyl acetate are well mixed, keep reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtain being modified poly- silicon
Oxygen alkane performed polymer；
2nd step, by weight, take 12~15 parts of butyl acrylate, 5~10 parts of methyl acrylate, 1~2 part of emulsifying agent
With 20~30 parts, 0.5~1h of high-speed stirred of deionized water, add 2~4 parts of initiator, at 70~80 DEG C react 0.5~
2h, then 1~2 part of 6~10 parts of modified polyorganosiloxane performed polymers and initiator are added dropwise, 2~3h is reacted at 70~80 DEG C, then use ammonia
Water adjusts pH to 7, obtains acrylic emulsion；
3rd step, 2~4 parts of 5~15 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, disperseed
After uniformly, modified acrylic acid emulsion is obtained；
4th step, by weight, by 40~45 parts of graphene, 3~5 parts of cationic surfactant, silane coupler
KH-5502~4 part, 5~15 parts of organic solvent are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：4~7 is well mixed, then will
Feed liquid is sprayed into fiber by spinning head spinning nozzle, then after drying, obtains graphene modacrylic fibers.
This method will be by anion surfactant on modified acrylic acid emulsion band, and cation form in graphene ribbon
Face activating agent, can because electrostatic interaction makes electric charge opposite on particulate band therein, then after both are mixed after stirring
So that modified graphene is coated on fiber, the chemical property of negative pole can be improved.
Surfactant is not particularly limited, and selected from nonionic well known by persons skilled in the art, anion, sun from
Son and surfactant.One kind or the combination in these surfactants can be used.
Nonionic surfactant includes, for example, line style polyoxyalkylene alkyl class, such as polyethylene glycol oxide hexyl ether, gathers
Ethylene oxide Octyl Ether, polyethylene glycol oxide decyl ethers, polyoxyethylene lauryl ether and polyethylene glycol oxide cetyl ether；It is branched
Polyoxyalkylenes primary alkyl ethers, such as polyethylene glycol oxide 2- ethylhexyl ethers, polyethylene glycol oxide isocetyl ether and polyoxygenated
Ethene iso stearyl ether；The branched secondary alkyl ether of polyoxyalkylene, as polyethylene glycol oxide 1- hexyl hexyl ethers, polyethylene glycol oxide 1- are pungent
Base hexyl ether, polyethylene glycol oxide 1- hexyl Octyl Ethers, polyethylene glycol oxide 1- amyl group heptyl ethers and polyethylene glycol oxide 1- heptyl amyl groups
Ether；Polyoxyalkylene alkenyl ethers class, such as polyethylene glycol oxide oleyl ether；Polyoxyalkylene alkyl phenyl ethers, such as polyethylene glycol oxide
Octyl phenyl ether, polyoxyethylene nonylplenyl ether, and polyethylene glycol oxide dodecylphenyl ether；Polyoxyalkylene alkyl aryl benzene
Base ethers, such as polyethylene glycol oxide tri-styryl phenyl ether, polyethylene glycol oxide diphenylethyllene phenyl ether, polyethylene glycol oxide benzene second
Alkenyl phenyl ether, polyethylene glycol oxide tribenzyl phenyl, polyethylene glycol oxide dibenzylphenyl ether, and polyethylene glycol oxide benzyl phenyl
Ether；Polyoxyalkylene fatty acid ester class, such as polyethylene glycol oxide monolaurate, polyethylene glycol oxide monoleate, polyethylene glycol oxide list
Stearate, polyethylene glycol oxide list myristinate, polyethylene glycol oxide dilaurate, polyethylene glycol oxide dioleate, polyoxy
Change the myristinate of ethene two, and polyethylene glycol oxide distearate；Sorbitan ester class, such as sorbitan list
Palmitate and dehydrated sorbitol mono-fatty acid ester；Polyoxyalkylene sorbitan polyol fatty acid esters, as polyethylene glycol oxide takes off
Water sorbitan monostearate and polyoxyethylene sorbitan monoleate；Glycerine fatty acid esters, such as glycerine list
Stearate, glyceryl monolaurate and glycerol monopalmitate；Polyoxyalkylene sorbitan polyol fatty acid esters；Sucrose-fatty
Esters；Polyoxyalkylene castor oil ethers, such as polyoxyethylene castor oil ether；Polyoxyalkylene hydrogenated castor oil ethers, such as polyoxygenated
Ethylene hydrogenation castor oil ether；Polyoxyalkylene alkyl amino ethers, as polyoxyethylene lauryl base amino ethers and polyethylene glycol oxide are hard
Aliphatic radical amino ethers；Ethylene oxide-propylene oxide block or random copolymer；Oxyethylene group-oxidation third of end alkyl etherificate
Alkenyl block or random copolymer；With the ethylene oxide-propylene oxide block or random copolymer of end sucrose-etherificate.
Anion surfactant includes, for example, fatty acid and their salt, such as oleic acid, palmitic acid, enuatrol, palm fibre
Palmitic acid acid potassium, and triethanolamine oleate；Hydroxyl institute's acids and their salt, such as hydroxyacetic acid, hydroxyacetic acid potassium, lactic acid and lactic acid
Potassium；Polyoxyalkylene alkyl acetic acid class and their salt, such as the decyl ether acetic acid of polyoxyalkylene three and its sodium salt；Carboxyl-polysubstituted
Aromatic compounds salt, such as trimellitic acid potassium and pyromellitic acid potassium；Benzene sulfonamide acids and their salt, such as detergent alkylate
Sulfonic acid and its sodium salt；Polyoxyalkylene alkyl ethers sulfonic acid and their salt, such as polyethylene glycol oxide 2- ethylhexyls ether sulfonic acid and its
Sylvite；Higher fatty acid amides sulfonic acid and their salt, such as stearic acyl methyl taurine and its sodium salt, lauroyl methyl taurine
And its sodium salt, myristoyl methyl taurine and its sodium salt and PMT and its sodium salt；N- acyl group sarcosinates
With their salt, such as Hamposyl L and its sodium salt；Alkyl phosphonic acid and their salt, such as octylphosphonate and its sylvite；Virtue
Race's phosphonic acids and their salt, such as phenyl phosphonic acid esters and its sylvite；Alkyl phosphonic acid phosphonate ester and their salt, such as 2- ethyl hexyls
Base phosphonic acids list -2- ethylhexyls and its sylvite；Nitrogenous alkyl phosphonic acid and their salt, such as aminoethyl phosphonic acid and its diethanol amine
Salt；Alkyl sulfate and their salt, such as 2- ethyl hexyls sulfuric ester and its sodium salt；Polyoxyalkylene sulfuric acid ester and their salt,
Such as polyethylene glycol oxide 2- ethylhexyls ether sulfuric ester and its sodium salt；Alkyl phosphoric acid esters and their salt, such as base succinic acid salt,
Such as two -2- ethylhexyls sodium sulfo-succinates and dioctyl sodium sulfosuccinate；And long-chain N- acyl glutamates, such as the N- months
Osmanthus acyl monosodium glutamate and N- stearoyls-Pidolidone disodium.
Cationic surfactant includes, for example, quaternary ammonium salt, such as hexadecyltrimethylammonium chloride, chlorination lauryl three
Ammonium methyl and ethyl sulfuric acid oleyl Methylethyl ammonium；And (polyoxyalkylenes) alkyl amino ether salt, such as (polyethylene glycol oxide
Base) lauryl amino ether lactate, stearyl ether lactate, and (polyethylene oxide base) lauryl amino ether trimethyl phosphorus
Hydrochlorate.
Embodiment 1
Negative material used in lead carbon battery, include following component by weight as raw material：5 parts of sulfuric acid, sulphur
Sour 0.5 part of barium, 0.5 part of silicon carbide powder (average particle size range is 50~100 μm), white carbon (average particle size range is 50~
100 μm) 0.1 part, 0.2 part of graphene modacrylic fibers, 0.05 part of titanate coupling agent, nonionic surfactant
0.1 part, 7 parts of pure water, 50 parts of lead powder.
The preparation method of described graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 50 parts of hydroxy silicon oils, 10 parts of Silane coupling reagent KH-570s, 3 parts of KOH, ethyl acetate 6
Part is well mixed, keeps reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 12 parts of butyl acrylate, 5 parts of methyl acrylate, 1 part of emulsifying agent and deionized water 20
Part, high-speed stirred 0.5h, 2 parts of initiator is added, 0.5h is reacted at 70 DEG C, then 6 parts of modified polyorganosiloxane performed polymers are added dropwise
With 1 part of azodicarbonamide initiator, 2h is reacted at 70 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtains acrylic emulsion；
3rd step, 2 parts of 5 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, after being uniformly dispersed,
Obtain modified acrylic acid emulsion；
4th step, by weight, by 40 parts of graphene, 3 parts of cationic surfactant, silane resin acceptor kh-550 2
Part, 5 parts of organic solvent are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：4 is well mixed, then will material
Liquid is sprayed into fiber by a diameter of 0.1mm spinning nozzles, then after drying, obtains graphene modacrylic fibers.
Embodiment 2
Negative material used in lead carbon battery, include following component by weight as raw material：10 parts of sulfuric acid, sulphur
Sour 2 parts of barium, 2 parts of silicon carbide powder (average particle size range is 50~100 μm), (average particle size range is 50~100 μ to white carbon
M) 0.15 part, 0.4 part of graphene modacrylic fibers, 0.1 part of titanate coupling agent, nonionic surfactant 0.15
Part, 12 parts of pure water, 60 parts of lead powder.
The preparation method of described graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 60 parts of hydroxy silicon oils, 15 parts of Silane coupling reagent KH-570s, 5 parts of KOH, ethyl acetate
10 parts well mixed, keeps reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 15 parts of butyl acrylate, 10 parts of methyl acrylate, 2 parts of emulsifying agent and deionized water
30 parts, high-speed stirred 1h, add 4 parts of initiator, 2h reacted at 80 DEG C, then be added dropwise 10 parts of modified polyorganosiloxane performed polymers and
2 parts of azodicarbonamide initiator, 3h is reacted at 80 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtain acrylic emulsion；
3rd step, 4 parts of 15 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, after being uniformly dispersed,
Obtain modified acrylic acid emulsion；
4th step, by weight, by 45 parts of graphene, 5 parts of cationic surfactant, silane resin acceptor kh-550 4
Part, 15 parts of organic solvent are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：7 is well mixed, then will material
Liquid is sprayed into fiber by a diameter of 0.5mm spinning nozzles, then after drying, obtains graphene modacrylic fibers.
Embodiment 3
Negative material used in lead carbon battery, include following component by weight as raw material：8 parts of sulfuric acid, sulphur
Sour 0.8 part of barium, 0.9 part of silicon carbide powder (average particle size range is 50~100 μm), white carbon (average particle size range is 50~
100 μm) 0.12 part, 0.3 part of graphene modacrylic fibers, 0.08 part of titanate coupling agent, nonionic surfactant
0.12 part, 9 parts of pure water, 55 parts of lead powder.
The preparation method of described graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 55 parts of hydroxy silicon oils, 12 parts of Silane coupling reagent KH-570s, 4 parts of KOH, ethyl acetate 8
Part is well mixed, keeps reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 13 parts of butyl acrylate, 8 parts of methyl acrylate, 2 parts of emulsifying agent and deionized water 25
Part, high-speed stirred 0.8h, add 3 parts of initiator, 1h reacted at 75 DEG C, then be added dropwise 8 parts of modified polyorganosiloxane performed polymers and
2 parts of azodicarbonamide initiator, 3h is reacted at 75 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtain acrylic emulsion；
3rd step, 3 parts of 10 parts of titanium oxide and anion surfactant will be added in acrylic emulsion, after being uniformly dispersed,
Obtain modified acrylic acid emulsion；
4th step, by weight, by 42 parts of graphene, 4 parts of cationic surfactant, silane resin acceptor kh-550 3
Part, 10 parts of organic solvent are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：5 is well mixed, then will material
Liquid is sprayed into fiber by a diameter of 0.2mm spinning nozzles, then after drying, obtains graphene modacrylic fibers.
Reference examples 1
Difference with embodiment 3 is：Cationic surfactant in modified acrylic acid emulsion preparation process and it is cloudy from
The addition sequence of sub- surfactant is opposite.
Negative material used in lead carbon battery, include following component by weight as raw material：8 parts of sulfuric acid, sulphur
Sour 0.8 part of barium, 0.9 part of silicon carbide powder (average particle size range is 50~100 μm), white carbon (average particle size range is 50~
100 μm) 0.12 part, 0.3 part of graphene modacrylic fibers, 0.08 part of titanate coupling agent, nonionic surfactant
0.12 part, 9 parts of pure water, 55 parts of lead powder.
The preparation method of described graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 55 parts of hydroxy silicon oils, 12 parts of Silane coupling reagent KH-570s, 4 parts of KOH, ethyl acetate 8
Part is well mixed, keeps reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 13 parts of butyl acrylate, 8 parts of methyl acrylate, 2 parts of emulsifying agent and deionized water 25
Part, high-speed stirred 0.8h, add 3 parts of initiator, 1h reacted at 75 DEG C, then be added dropwise 8 parts of modified polyorganosiloxane performed polymers and
2 parts of azodicarbonamide initiator, 3h is reacted at 75 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtain acrylic emulsion；
3rd step, 3 parts of 10 parts of titanium oxide and cationic surfactant will be added in acrylic emulsion, after being uniformly dispersed,
Obtain modified acrylic acid emulsion；
4th step, by weight, by 42 parts of graphene, 4 parts of anion surfactant, silane resin acceptor kh-550 3
Part, 10 parts of organic solvent are well mixed, obtain anion-modified graphene；
6th step, by anion-modified graphene and modified acrylic acid emulsion according to weight than 1：5 is well mixed, then will material
Liquid is sprayed into fiber by a diameter of 0.2mm spinning nozzles, then after drying, obtains graphene modacrylic fibers.
Reference examples 2
Difference with embodiment 3 is：Titanium oxide is not added in the 3rd step in modified acrylic acid emulsion preparation process.
Negative material used in lead carbon battery, include following component by weight as raw material：8 parts of sulfuric acid, sulphur
Sour 0.8 part of barium, 0.9 part of silicon carbide powder (average particle size range is 50~100 μm), white carbon (average particle size range is 50~
100 μm) 0.12 part, 0.3 part of graphene modacrylic fibers, 0.08 part of titanate coupling agent, nonionic surfactant
0.12 part, 9 parts of pure water, 55 parts of lead powder.
The preparation method of described graphene modacrylic fibers, comprises the following steps：
1st step, by weight, by 55 parts of hydroxy silicon oils, 12 parts of Silane coupling reagent KH-570s, 4 parts of KOH, ethyl acetate 8
Part is well mixed, keeps reaction 3h in a nitrogen atmosphere, after being warming up to 90 DEG C, obtains modified polyorganosiloxane performed polymer；
2nd step, by weight, take 13 parts of butyl acrylate, 8 parts of methyl acrylate, 2 parts of emulsifying agent and deionized water 25
Part, high-speed stirred 0.8h, add 3 parts of initiator, 1h reacted at 75 DEG C, then be added dropwise 8 parts of modified polyorganosiloxane performed polymers and
2 parts of azodicarbonamide initiator, 3h is reacted at 75 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtain acrylic emulsion；
3rd step, 3 parts of anion surfactant will be added in acrylic emulsion, after being uniformly dispersed, obtains modified propylene
Yogurt liquid；
4th step, by weight, by 42 parts of graphene, 4 parts of cationic surfactant, silane resin acceptor kh-550 3
Part, 10 parts of organic solvent are well mixed, obtain cation-modified graphene；
6th step, by cation-modified graphene and modified acrylic acid emulsion according to weight than 1：5 is well mixed, then will material
Liquid is sprayed into fiber by a diameter of 0.2mm spinning nozzles, then after drying, obtains graphene modacrylic fibers.
Lead carbon battery prepared by above-described embodiment and reference examples and tested with the performance of the common batteries of model
Wherein, the method for testing of lead carbon battery dynamic charge acceptance is：
After battery is fully charged, 6h is soaked in 25 DEG C of water-baths.At the same temperature, battery is progressively put with I=0.1Ce
The state-of-charge (SOC) of electricity to 90%, 80%, 70%, 60%, after electric discharge terminates every time, with 14.8V, 200A charging 60s, note
Record electric current changes with time.
High rate cyclic life-span (HRPSOC) method of testing is under lead carbon battery partial state of charge：
It is with I=2 × I20 constant-current discharges 5h to 50% state-of-charge, end condition in 1~2h after battery is fully charged
10.5V, then do following a~d circulations：(a) with I=2 × C20 constant-current charges 1min；(b) 10s is stood；(c) with I=2 × C20
Constant-current discharge 1min；(d) 10s is stood；Wherein in cyclic process, charging voltage reaches higher than 17V or discharge voltage less than 10.5V
To end-of-life condition.
The performance test results of prepared lead carbon battery are as follows：
As can be seen from the above table, the lead-carbon battery negative electrode material provided in the present invention has electric current in use
Greatly, the advantages of capacitance is high, particularly its discharge and recharge number are high.Embodiment 3 is relative to reference examples 1 as can be seen that passing through change
Cation and anion surfactant can effectively change graphene for the modified order of polyacrylate emulsion and graphene
Covered effect in polypropylene emulsion, so as to improve the pattern of the fibrous material obtained after drying, improve following for battery
The ring life-span；And embodiment 3 can be seen that by adding titanium dioxide in polyacrylate emulsion relative to reference examples 2, Ke Yili
More graphenes are coated with its particle surface static behaviour in mixed process, and then improve current strength.
Claims (6)
1. the negative material used in a kind of lead carbon battery, it is characterised in that include following component by weight as former
Material：5~10 parts of sulfuric acid, 0.5~2 part of barium sulfate, 0.5~2 part of silicon carbide powder, 0.1~0.15 part of white carbon, graphene are modified
It is 0.2~0.4 part of polyacrylic fibre, 0.05~0.1 part of titanate coupling agent, 0.1~0.15 part of nonionic surfactant, pure
7~12 parts of water, 50~60 parts of lead powder.
2. the negative material used in lead carbon battery according to claim 1, it is characterised in that described white carbon is averaged
Particle size range is 50~100 μm；The average particle size range of described silicon carbide powder is 50~100 μm.
3. the negative material used in lead carbon battery according to claim 1, it is characterised in that described graphene is modified poly-
The preparation method of acrylic fiber, comprises the following steps：1st step, by weight, by 50~60 parts of hydroxy silicon oils, 10~15
Part Silane coupling reagent KH-570,3~5 parts of KOH, 6~10 parts of ethyl acetate are well mixed, in a nitrogen atmosphere, are warming up to 90 DEG C
Reaction 3h is kept afterwards, obtains modified polyorganosiloxane performed polymer；2nd step, by weight, take 12~15 parts of butyl acrylate, third
20~30 parts of 5~10 parts of e pioic acid methyl ester, 1~2 part of emulsifying agent and deionized water, 0.5~1h of high-speed stirred, add initiator 2
~4 parts, 0.5~2h is reacted at 70~80 DEG C, then 1~2 part of 6~10 parts of modified polyorganosiloxane performed polymers and initiator are added dropwise,
2~3h is reacted at 70~80 DEG C, then pH to 7 is adjusted with ammoniacal liquor, obtains acrylic emulsion；3rd step, will be in acrylic emulsion
2~4 parts of 5~15 parts of titanium oxide and anion surfactant are added, after being uniformly dispersed, obtains modified acrylic acid emulsion；4th
Step, by weight, by 40~45 parts of graphene, 3~5 parts of cationic surfactant, 2~4 parts of silane resin acceptor kh-550,
5~15 parts of organic solvent is well mixed, obtains cation-modified graphene；6th step, by cation-modified graphene and modified third
Olefin(e) acid emulsion is according to weight than 1：4~7 is well mixed, then feed liquid is sprayed into fiber by spinning nozzle, then after drying,
Obtain graphene modacrylic fibers.
4. the negative material used in lead carbon battery according to claim 3, it is characterised in that a diameter of the 0.1 of spinning head
~0.5mm.
5. the negative material used in lead carbon battery according to claim 3, it is characterised in that the azo-initiator choosing
From azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloric acid
Salt, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azo
One or more in bis-isobutyronitrile, AMBN and ABVN.
6. the preparation method of the negative material used in lead carbon battery described in any one of Claims 1 to 5, it is characterised in that bag
Include following steps：S1：By barium sulfate, silicon carbide powder, white carbon, graphene modacrylic fibers, titanate coupling agent,
Nonionic surfactant, pure water are well mixed, and are slow added into lead powder, are stirred, and are added and are slowly added to sulfuric acid, and control
Temperature processed is no more than 55 DEG C；S2：The lead plaster obtained in S1 is coated onto on negative pole screen, dry 20 at 55~65 DEG C of temperature~
40h, obtain negative material.
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| CN107331834A (en) * | 2017-05-25 | 2017-11-07 | 天能电池集团有限公司 | A kind of lead accumulator cathode lead plaster and preparation method thereof |
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| CN102074693A (en) * | 2010-12-13 | 2011-05-25 | 华南师范大学 | Additive for high-carbon lead-acid storage-battery polar plate |
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