CN107732162B - Lead-carbon battery cathode material with high cycle number and preparation method thereof - Google Patents
Lead-carbon battery cathode material with high cycle number and preparation method thereof Download PDFInfo
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- 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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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Abstract
The invention relates to a lead-carbon battery cathode material with high cycle number and a preparation method thereof, belonging to the technical field of battery manufacturing. The material comprises the following components in parts by weight: 5-10 parts of sulfuric acid, 0.5-2 parts of barium sulfate, 0.5-2 parts of silicon carbide powder, 0.1-0.15 part of white carbon black, 0.2-0.4 part of graphene modified polyacrylic fiber, 0.05-0.1 part of titanate coupling agent, 0.1-0.15 part of nonionic surfactant, 7-12 parts of pure water and 50-60 parts of lead powder. The lead-carbon battery made of the cathode material used by the lead-carbon battery provided by the invention has the advantages of large electric capacity and small electric quantity loss after cyclic discharge.
Description
Technical Field
The invention relates to a lead-carbon battery cathode material with high cycle number and a preparation method thereof, belonging to the technical field of battery manufacturing.
Background
At present, the technical process of the lead-acid storage battery is mature, has the characteristics of large capacity, good safety, low cost, recoverability and the like, still remains the mainstream technology of the weak mixing technology in the future, but the popularization of the technology is restricted by the problems of short service life of large-current charge and discharge of the traditional lead-acid battery and the like, and the defect can be overcome by the novel battery technology of the lead-carbon battery. The lead-carbon battery mixes the carbon material with the traditional cathode material lead to form a composite cathode, and after the carbon material is introduced into the cathode, the sulfation phenomenon under PSoC can be effectively improved, and the charge acceptance and rate capability are improved. After improvement, the charging time of the product is one eighth of that of a lead-acid battery, the cycle life of the product is more than four times of that of the lead-acid battery, and compared with a lithium battery, the product has the advantages of good low-temperature performance, low cost, mature production and recovery process and the like.
CN104577058A discloses a method for preparing a negative active material of a lead-carbon battery, belonging to the technical field of lead-acid battery manufacture. The lead-carbon battery cathode lead paste which has good production quality (good carbon material dispersibility), controllable process and meets the battery performance requirement is further produced by adopting special lead-carbon battery and paste equipment and controlling the dry mixing time, the wet mixing time and the acid mixing time of each stage through the optimized proportion of each component. CN105140466A discloses a lead carbon negative plate, coats ordinary negative pole diachylon on lead-calcium grid alloy, then at the negative pole diachylon of polar plate two sides coating high carbon content, obtains lead carbon negative plate through solidification drying, wherein high carbon content's negative pole diachylon component is: 100 parts of lead powder; 0.5-1 part of carbon material A; 5-20 parts of a carbon material B; 0.1-1.5 parts of barium sulfate; 0.1-0.5 part of sodium lignosulfonate; 0.1-0.5 part of humic acid; 0.1-0.5 parts of short fibers; 10-20 parts of water; 1.0 to 1.4g/cm34-8 parts of sulfuric acid.
However, the lead-carbon battery obtained by the negative electrode material still has the defects of low current intensity and short service life.
Disclosure of Invention
The purpose of the invention is: aiming at the problems of low discharge cycle number and short service life of the lead-carbon battery, a negative electrode material used by the lead-carbon battery and the lead-carbon battery containing the negative electrode material are provided.
The technical scheme is as follows:
a negative electrode material for a lead-carbon battery comprises the following components in parts by weight as raw materials: 5-10 parts of sulfuric acid, 0.5-2 parts of barium sulfate, 0.5-2 parts of silicon carbide powder, 0.1-0.15 part of white carbon black, 0.2-0.4 part of graphene modified polyacrylic fiber, 0.05-0.1 part of titanate coupling agent, 0.1-0.15 part of nonionic surfactant, 7-12 parts of pure water and 50-60 parts of lead powder.
The average particle size range of the white carbon black is 50-100 mu m.
The average grain diameter range of the silicon carbide powder is 50-100 mu m.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 50-60 parts by weight of hydroxyl silicone oil, 10-15 parts by weight of silane coupling agent KH-570, 3-5 parts by weight of KOH and 6-10 parts by weight of ethyl acetate, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 12-15 parts by weight of butyl acrylate, 5-10 parts by weight of methyl acrylate, 1-2 parts by weight of emulsifier and 20-30 parts by weight of deionized water, stirring at a high speed for 0.5-1 h, adding 2-4 parts by weight of initiator, reacting at 70-80 ℃ for 0.5-2 h, then dropwise adding 6-10 parts by weight of modified polysiloxane prepolymer and 1-2 parts by weight of initiator, reacting at 70-80 ℃ for 2-3 h, and adjusting the pH to 7 with ammonia water to obtain an acrylic emulsion;
step 3, adding 5-15 parts of titanium oxide and 2-4 parts of anionic surfactant into the acrylic emulsion, and dispersing uniformly to obtain a modified acrylic emulsion;
step 4, uniformly mixing 40-45 parts by weight of graphene, 3-5 parts by weight of cationic surfactant, 2-4 parts by weight of silane coupling agent KH-550and 5-15 parts by weight of organic solvent to obtain cation modified graphene;
and 6, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 4-7, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret, and drying to obtain the graphene modified polyacrylic acid fibers.
The diameter of the spinning nozzle is 0.1-0.5 mm.
The azo initiator is selected from one or more of dimethyl azodiisobutyrate, azodiisobutyamidine hydrochloride, azodicarbonamide, azodiisopropyl imidazoline hydrochloride, azoisobutyryl cyano formamide, azodicyclohexyl formonitrile, azodicyano valeric acid, azodiisopropyl imidazoline, azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanonitrile.
The preparation method of the cathode material for the lead-carbon battery comprises the following steps:
s1: uniformly mixing barium sulfate, silicon carbide powder, white carbon black, graphene modified polyacrylic acid fiber, titanate coupling agent, nonionic surfactant and pure water, slowly adding lead powder, uniformly stirring, then slowly adding sulfuric acid, and controlling the temperature to be not more than 55 ℃;
s2: and (4) coating the lead plaster obtained in the step S1 on a negative grid plate, and drying at the temperature of 55-65 ℃ for 20-40 h to obtain the negative electrode material.
Advantageous effects
The lead-carbon battery made of the cathode material used by the lead-carbon battery provided by the invention has the advantages of large electric capacity and small electric quantity loss after cyclic discharge.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range. The percentages in the present invention refer to weight percentages unless otherwise specified.
The preparation raw materials of the negative electrode material comprise, by weight, 5-10 parts of sulfuric acid, 0.5-2 parts of barium sulfate, 0.5-2 parts of silicon carbide powder, 0.1-0.15 part of white carbon black, 0.2-0.4 part of graphene modified polyacrylic fiber, 0.05-0.1 part of titanate coupling agent, 0.1-0.15 part of nonionic surfactant, 7-12 parts of pure water and 50-60 parts of lead powder.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 50-60 parts by weight of hydroxyl silicone oil, 10-15 parts by weight of silane coupling agent KH-570, 3-5 parts by weight of KOH and 6-10 parts by weight of ethyl acetate, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 12-15 parts by weight of butyl acrylate, 5-10 parts by weight of methyl acrylate, 1-2 parts by weight of emulsifier and 20-30 parts by weight of deionized water, stirring at a high speed for 0.5-1 h, adding 2-4 parts by weight of initiator, reacting at 70-80 ℃ for 0.5-2 h, then dropwise adding 6-10 parts by weight of modified polysiloxane prepolymer and 1-2 parts by weight of initiator, reacting at 70-80 ℃ for 2-3 h, and adjusting the pH to 7 with ammonia water to obtain an acrylic emulsion;
step 3, adding 5-15 parts of titanium oxide and 2-4 parts of anionic surfactant into the acrylic emulsion, and dispersing uniformly to obtain a modified acrylic emulsion;
step 4, uniformly mixing 40-45 parts by weight of graphene, 3-5 parts by weight of cationic surfactant, 2-4 parts by weight of silane coupling agent KH-550and 5-15 parts by weight of organic solvent to obtain cation modified graphene;
and 6, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 4-7, uniformly mixing, spraying the feed liquid into fibers through a spinning nozzle of a spinning jet, and drying to obtain the graphene modified polyacrylic acid fibers.
According to the method, the modified acrylic emulsion is provided with the anionic surfactant, the graphene is provided with the cationic surfactant, particles in the modified acrylic emulsion are provided with opposite charges due to electrostatic action after stirring, and the modified graphene can be coated on fibers after the modified acrylic emulsion and the graphene are mixed, so that the electrochemical performance of a negative electrode can be improved.
The surfactant is not particularly limited and is selected from nonionic, anionic, cationic and surfactant known to those skilled in the art. One or a combination of these surfactants may be used.
Nonionic surfactants include, for example, linear polyoxyalkylene alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether and polyoxyethylene cetyl ether; branched polyoxyalkylene primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isohexadecyl ether and polyoxyethylene isostearyl ether; branched polyoxyalkylene secondary alkyl ethers such as polyoxyethylene 1-hexyl ether, polyoxyethylene 1-octyl hexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentylheptyl ether and polyoxyethylene 1-heptylpentyl ether; polyoxyalkylene alkenyl ethers such as polyoxyethylene oleyl ether; polyoxyalkylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene dodecylphenyl ether; polyoxyalkylene alkylaryl phenyl ethers such as polyoxyethylene tristyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, and polyoxyethylene benzyl phenyl ether; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene dimyristate, and polyoxyethylene distearate; sorbitan esters such as sorbitan monopalmitate and sorbitan monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerol fatty acid esters such as glycerol monostearate, glycerol monolaurate and glycerol monopalmitate; polyoxyalkylene sorbitol fatty acid esters; sucrose fatty acid esters; polyoxyalkylene castor oil ethers such as polyoxyethylene castor oil ether; polyoxyalkylene hydrogenated castor oil ethers such as polyoxyethylene hydrogenated castor oil ether; polyoxyalkylene alkylamino ethers such as polyoxyethylene lauryl amino ether and polyoxyethylene stearyl amino ether; ethylene oxide-propylene oxide block or random copolymers; a terminally alkyl-etherified oxyethylene-oxypropylene block or random copolymer; and terminal sucrose-etherified ethylene oxide-propylene oxide block or random copolymers.
Anionic surfactants include, for example, fatty acids and their salts, such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, and triethanolamine oleate; hydroxy-containing acids and their salts, such as glycolic acid, potassium glycolate, lactic acid and potassium lactate; polyoxyalkylene alkyl ether acetic acids and their salts, such as polyoxyalkylene tridecyl ether acetic acid and its sodium salt; salts of carboxy-polysubstituted aromatic compounds, such as potassium trimellitate and potassium pyromellitate; alkyl benzene sulphonic acids and their salts, such as dodecyl benzene sulphonic acid and its sodium salt; polyoxyalkylene alkyl ether sulfonic acids and their salts, such as polyoxyethylene 2-ethylhexyl ether sulfonic acid and its potassium salt; higher fatty acid amide sulfonic acids and their salts, such as stearoyl methyl taurine and its sodium salt, lauroyl methyl taurine and its sodium salt, myristoyl methyl taurine and its sodium salt, and palmitoyl methyl taurine and its sodium salt; n-acyl sarcosines and their salts, such as lauroyl sarcosine and its sodium salt; alkyl phosphonic acids and their salts, such as octyl phosphonate and its potassium salts; aromatic phosphonic acids and their salts, such as phenylphosphonate and its potassium salts; alkylphosphonic acid alkylphosphonates and their salts, such as 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester and its potassium salt; nitrogen-containing alkyl phosphonic acids and their salts, such as aminoethylphosphonic acid and its diethanolamine salt; alkyl sulfates and their salts, such as 2-ethylhexyl sulfate and its sodium salt; polyoxyalkylene sulfates and their salts, such as polyoxyethylene 2-ethylhexyl ether sulfate and its sodium salt; alkyl phosphates and their salts, such as sulfosuccinates, e.g., sodium di-2-ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate; and long chain N-acyl glutamates, such as monosodium N-lauroyl glutamate and disodium N-stearoyl-L-glutamate.
Cationic surfactants include, for example, quaternary ammonium salts such as cetyltrimethylammonium chloride, lauryltrimethylammonium chloride and oleylmethylethylammonium ethylsulfate; and (polyoxyalkylene) -alkyl amino ether salts such as (polyoxyethylene) lauryl amino ether lactate, stearyl amino ether lactate, and (polyoxyethylene) lauryl amino ether trimethylphosphate.
Example 1
The cathode material for the lead-carbon battery comprises the following components in parts by weight as raw materials: 5 parts of sulfuric acid, 0.5 part of barium sulfate, 0.5 part of silicon carbide powder (with the average particle size range of 50-100 mu m), 0.1 part of white carbon black (with the average particle size range of 50-100 mu m), 0.2 part of graphene modified polyacrylic fiber, 0.05 part of titanate coupling agent, 0.1 part of nonionic surfactant, 7 parts of pure water and 50 parts of lead powder.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 50 parts of hydroxyl silicone oil, 10 parts of silane coupling agent KH-570, 3 parts of KOH and 6 parts of ethyl acetate in parts by weight, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 12 parts of butyl acrylate, 5 parts of methyl acrylate, 1 part of emulsifier and 20 parts of deionized water by weight, stirring at a high speed for 0.5h, adding 2 parts of initiator, reacting at 70 ℃ for 0.5h, then dropwise adding 6 parts of modified polysiloxane prepolymer and 1 part of azodicarbonamide initiator, reacting at 70 ℃ for 2h, and then adjusting the pH value to 7 by using ammonia water to obtain acrylic emulsion;
step 3, adding 5 parts of titanium oxide and 2 parts of anionic surfactant into the acrylic emulsion, and uniformly dispersing to obtain modified acrylic emulsion;
step 4, uniformly mixing 40 parts of graphene, 3 parts of cationic surfactant, KH-5502 parts of silane coupling agent and 5 parts of organic solvent by weight to obtain cationic modified graphene;
and 6, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 4, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret with the diameter of 0.1mm, and drying to obtain the graphene modified polyacrylic acid fibers.
Example 2
The cathode material for the lead-carbon battery comprises the following components in parts by weight as raw materials: 10 parts of sulfuric acid, 2 parts of barium sulfate, 2 parts of silicon carbide powder (with the average particle size range of 50-100 mu m), 0.15 part of white carbon black (with the average particle size range of 50-100 mu m), 0.4 part of graphene modified polyacrylic fiber, 0.1 part of titanate coupling agent, 0.15 part of nonionic surfactant, 12 parts of pure water and 60 parts of lead powder.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 60 parts of hydroxyl silicone oil, 15 parts of silane coupling agent KH-570, 5 parts of KOH and 10 parts of ethyl acetate in parts by weight, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 15 parts of butyl acrylate, 10 parts of methyl acrylate, 2 parts of emulsifier and 30 parts of deionized water by weight, stirring at a high speed for 1h, adding 4 parts of initiator, reacting at 80 ℃ for 2h, then dropwise adding 10 parts of modified polysiloxane prepolymer and 2 parts of azodicarbonamide initiator, reacting at 80 ℃ for 3h, and then adjusting the pH value to 7 by using ammonia water to obtain acrylic emulsion;
step 3, adding 15 parts of titanium oxide and 4 parts of anionic surfactant into the acrylic emulsion, and uniformly dispersing to obtain modified acrylic emulsion;
step 4, uniformly mixing 45 parts of graphene, 5 parts of cationic surfactant, KH-5504 parts of silane coupling agent and 15 parts of organic solvent by weight to obtain cationic modified graphene;
and 6, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 7, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret with the diameter of 0.5mm, and drying to obtain the graphene modified polyacrylic acid fibers.
Example 3
The cathode material for the lead-carbon battery comprises the following components in parts by weight as raw materials: 8 parts of sulfuric acid, 0.8 part of barium sulfate, 0.9 part of silicon carbide powder (with the average particle size ranging from 50 to 100 mu m), 0.12 part of white carbon black (with the average particle size ranging from 50 to 100 mu m), 0.3 part of graphene modified polyacrylic fiber, 0.08 part of titanate coupling agent, 0.12 part of nonionic surfactant, 9 parts of pure water and 55 parts of lead powder.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 55 parts of hydroxyl silicone oil, 12 parts of silane coupling agent KH-570, 4 parts of KOH and 8 parts of ethyl acetate in parts by weight, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 13 parts of butyl acrylate, 8 parts of methyl acrylate, 2 parts of emulsifier and 25 parts of deionized water by weight, stirring at a high speed for 0.8h, adding 3 parts of initiator, reacting at 75 ℃ for 1h, then dropwise adding 8 parts of modified polysiloxane prepolymer and 2 parts of azodicarbonamide initiator, reacting at 75 ℃ for 3h, and then adjusting the pH value to 7 by using ammonia water to obtain acrylic emulsion;
step 3, adding 10 parts of titanium oxide and 3 parts of anionic surfactant into the acrylic emulsion, and uniformly dispersing to obtain modified acrylic emulsion;
step 4, uniformly mixing 42 parts of graphene, 4 parts of cationic surfactant, KH-5503 parts of silane coupling agent and 10 parts of organic solvent by weight to obtain cationic modified graphene;
and 6, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 5, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret with the diameter of 0.2mm, and drying to obtain the graphene modified polyacrylic acid fibers.
Comparative example 1
The difference from example 3 is that: the adding sequence of the cationic surfactant and the anionic surfactant in the preparation process of the modified acrylic emulsion is opposite.
The cathode material for the lead-carbon battery comprises the following components in parts by weight as raw materials: 8 parts of sulfuric acid, 0.8 part of barium sulfate, 0.9 part of silicon carbide powder (with the average particle size ranging from 50 to 100 mu m), 0.12 part of white carbon black (with the average particle size ranging from 50 to 100 mu m), 0.3 part of graphene modified polyacrylic fiber, 0.08 part of titanate coupling agent, 0.12 part of nonionic surfactant, 9 parts of pure water and 55 parts of lead powder.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 55 parts of hydroxyl silicone oil, 12 parts of silane coupling agent KH-570, 4 parts of KOH and 8 parts of ethyl acetate in parts by weight, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 13 parts of butyl acrylate, 8 parts of methyl acrylate, 2 parts of emulsifier and 25 parts of deionized water by weight, stirring at a high speed for 0.8h, adding 3 parts of initiator, reacting at 75 ℃ for 1h, then dropwise adding 8 parts of modified polysiloxane prepolymer and 2 parts of azodicarbonamide initiator, reacting at 75 ℃ for 3h, and then adjusting the pH value to 7 by using ammonia water to obtain acrylic emulsion;
step 3, adding 10 parts of titanium oxide and 3 parts of cationic surfactant into the acrylic emulsion, and uniformly dispersing to obtain a modified acrylic emulsion;
step 4, uniformly mixing 42 parts of graphene, 4 parts of anionic surfactant, KH-5503 parts of silane coupling agent and 10 parts of organic solvent by weight to obtain anion modified graphene;
and 6, mixing the anion modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 5, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret with the diameter of 0.2mm, and drying to obtain the graphene modified polyacrylic acid fibers.
Comparative example 2
The difference from example 3 is that: titanium oxide is not added in the 3 rd step in the preparation process of the modified acrylic emulsion.
The cathode material for the lead-carbon battery comprises the following components in parts by weight as raw materials: 8 parts of sulfuric acid, 0.8 part of barium sulfate, 0.9 part of silicon carbide powder (with the average particle size ranging from 50 to 100 mu m), 0.12 part of white carbon black (with the average particle size ranging from 50 to 100 mu m), 0.3 part of graphene modified polyacrylic fiber, 0.08 part of titanate coupling agent, 0.12 part of nonionic surfactant, 9 parts of pure water and 55 parts of lead powder.
The preparation method of the graphene modified polyacrylic acid fiber comprises the following steps:
step 1, uniformly mixing 55 parts of hydroxyl silicone oil, 12 parts of silane coupling agent KH-570, 4 parts of KOH and 8 parts of ethyl acetate in parts by weight, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer;
step 2, taking 13 parts of butyl acrylate, 8 parts of methyl acrylate, 2 parts of emulsifier and 25 parts of deionized water by weight, stirring at a high speed for 0.8h, adding 3 parts of initiator, reacting at 75 ℃ for 1h, then dropwise adding 8 parts of modified polysiloxane prepolymer and 2 parts of azodicarbonamide initiator, reacting at 75 ℃ for 3h, and then adjusting the pH value to 7 by using ammonia water to obtain acrylic emulsion;
step 3, adding 3 parts of anionic surfactant into the acrylic emulsion, and uniformly dispersing to obtain modified acrylic emulsion;
step 4, uniformly mixing 42 parts of graphene, 4 parts of cationic surfactant, KH-5503 parts of silane coupling agent and 10 parts of organic solvent by weight to obtain cationic modified graphene;
and 6, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 5, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret with the diameter of 0.2mm, and drying to obtain the graphene modified polyacrylic acid fibers.
The performances of the lead-carbon batteries and the common batteries of the same type prepared in the above examples and comparative examples were tested
The method for testing the dynamic charge acceptance of the lead-carbon battery comprises the following steps:
after the battery is fully charged, the battery is soaked in a water bath at 25 ℃ for 6 hours. The battery was gradually discharged at the same temperature with I of 0.1Ce to a state of charge (SOC) of 90%, 80%, 70%, 60%, and after each discharge was completed, the battery was charged at 14.8V and 200A for 60s, and the change in current with time was recorded.
The method for testing the high-rate cycle life (HRPSOC) of the lead-carbon battery in a partial charge state comprises the following steps:
after the storage battery is fully charged, discharging for 5h to 50% of charge state at constant current I of 2 xI 20 within 1-2 h, wherein the termination condition is 10.5V, and then performing the following a-d cycles: (a) charging at constant current of I2 XC 20 for 1 min; (b) standing for 10 s; (c) discharging at constant current of I2 × C20 for 1 min; (d) standing for 10 s; wherein the end-of-life condition is reached during cycling with a charge voltage above 17V or a discharge voltage below 10.5V.
The performance test results of the prepared lead-carbon battery are as follows:
from the above table, it can be seen that the lead-carbon battery cathode material provided by the invention has the advantages of large current and high electric capacity in the using process, and particularly has high charging and discharging times. Compared with the comparative example 1, the embodiment 3 has the advantages that the coating effect of the graphene in the polypropylene emulsion can be effectively changed by changing the modification sequence of the cationic surfactant and the anionic surfactant to the polyacrylic emulsion and the graphene, so that the morphology of the fiber material obtained after drying can be improved, and the cycle life of the battery can be prolonged; in contrast to comparative example 2, in example 3, it can be seen that titanium dioxide is added to the polyacrylic acid emulsion, and the electrostatic property of the particle surface of the polyacrylic acid emulsion during mixing can be utilized to coat more graphene, thereby improving the current strength.
Claims (2)
1. The negative electrode material for the lead-carbon battery is characterized by comprising the following components in parts by weight as raw materials: 5-10 parts of sulfuric acid, 0.5-2 parts of barium sulfate, 0.5-2 parts of silicon carbide powder, 0.1-0.15 part of white carbon black, 0.2-0.4 part of graphene modified polyacrylic fiber, 0.05-0.1 part of titanate coupling agent, 0.1-0.15 part of nonionic surfactant, 7-12 parts of pure water and 50-60 parts of lead powder;
the average particle size range of the white carbon black is 50-100 mu m; the average grain diameter range of the silicon carbide powder is 50-100 mu m;
the preparation method of the graphene modified polyacrylic acid fiber comprises the following steps: step 1, uniformly mixing 50-60 parts by weight of hydroxyl silicone oil, 10-15 parts by weight of silane coupling agent KH-570, 3-5 parts by weight of KOH and 6-10 parts by weight of ethyl acetate, heating to 90 ℃ in a nitrogen atmosphere, and keeping reacting for 3 hours to obtain a modified polysiloxane prepolymer; step 2, taking 12-15 parts by weight of butyl acrylate, 5-10 parts by weight of methyl acrylate, 1-2 parts by weight of emulsifier and 20-30 parts by weight of deionized water, stirring at a high speed for 0.5-1 h, adding 2-4 parts by weight of initiator, reacting at 70-80 ℃ for 0.5-2 h, then dropwise adding 6-10 parts by weight of modified polysiloxane prepolymer and 1-2 parts by weight of initiator, reacting at 70-80 ℃ for 2-3 h, and adjusting the pH to 7 with ammonia water to obtain an acrylic emulsion; step 3, adding 5-15 parts of titanium dioxide and 2-4 parts of anionic surfactant into the acrylic emulsion, and uniformly dispersing to obtain a modified acrylic emulsion; step 4, uniformly mixing 40-45 parts by weight of graphene, 3-5 parts by weight of cationic surfactant, 2-4 parts by weight of silane coupling agent KH-550and 5-15 parts by weight of organic solvent to obtain cation modified graphene; and 5, mixing the cation modified graphene and the modified acrylic emulsion according to the weight ratio of 1: 4-7, uniformly mixing, spraying the feed liquid into fibers through a spinning spinneret, and drying to obtain graphene modified polyacrylic acid fibers;
the diameter of the spinning nozzle is 0.1-0.5 mm;
the initiator is selected from one or more of dimethyl azodiisobutyrate, azodiisobutyamidine hydrochloride, azodicarbonamide, azodiisopropyl imidazoline hydrochloride, azoisobutyryl cyano formamide, azodicyclohexyl formonitrile, azodicyano valeric acid, azodiisopropyl imidazoline, azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanonitrile.
2. The method for preparing a negative electrode material for a lead-carbon battery according to claim 1, characterized by comprising the steps of: s1: uniformly mixing barium sulfate, silicon carbide powder, white carbon black, graphene modified polyacrylic acid fiber, titanate coupling agent, nonionic surfactant and pure water, slowly adding lead powder, uniformly stirring, slowly adding sulfuric acid, and controlling the temperature to be not more than 55 ℃; s2: and (4) coating the lead plaster obtained in the step S1 on a negative grid plate, and drying at the temperature of 55-65 ℃ for 20-40 h to obtain the negative electrode material.
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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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