CN115911386A - Self-crosslinking lithium ion battery anode water-based adhesive and preparation method thereof - Google Patents
Self-crosslinking lithium ion battery anode water-based adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-crosslinking lithium ion battery anode water-based adhesive and a preparation method thereof, which consists of emulsion and latex particles dispersed in the emulsion, wherein the latex particles are a copolymer formed by sequentially copolymerizing acrylic monomers, acrylate monomers and organic siloxane monomers; the organic siloxane monomer is an organic silicon active functional monomer containing carbon-carbon double bonds and alkoxy; the solid content of the emulsion is 5-30%, and the mass ratio of the acrylic monomer to the acrylate monomer to the organosiloxane monomer is as follows: (10-60): (20 to 80): (5-20). The water-based binder disclosed by the invention takes water as a dispersion medium, solves the environmental protection problem of the binder for the lithium battery, and is an environment-friendly binder. In addition, the adhesive emulsion can form a chemical crosslinking structure in the using process, the adhesive force and the electrolyte resistance are improved, and the performance of the prepared battery meets the requirements of customers.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, and mainly relates to a self-crosslinking lithium ion battery anode water-based adhesive and a preparation method thereof.
Background
With the development of science and technology and the improvement of the living standard of people's material culture, people have higher and higher requirements on mobile secondary batteries. The lithium ion secondary battery can meet the use requirements of people on the mobile power supply in many aspects, and the lithium ion battery is widely applied to the fields of mobile phone digital products, model airplane toys, electric vehicles, automobiles and the like at present. Meanwhile, the lithium ion battery conforms to the national policy of energy conservation and emission reduction, so that the development of the lithium ion battery is vigorously promoted in the future 10-15 years in new energy planning. Meanwhile, with the continuous increase of economic development in China, the environmental concern of people on life is greatly improved, so that the living environment must be protected while any project is developed, and even if a new energy project is advocated vigorously, the development must be carried out without sacrificing the environmental protection.
In the conventional process for producing the lithium ion battery, especially in the process for preparing the positive electrode plate, the conventional solvent-based adhesive is used, that is, a large amount of solvent is needed to be used as a solvent to dissolve the adhesive in the using process, and then the solvent is evaporated and removed in a heating manner in the preparation process, so that the energy waste is great, the solvent is discharged into the atmosphere (the solvent is difficult to be recovered by 100 percent even if the best recovery device is adopted), and the environment is polluted. Therefore, changing the oil into water for the adhesive becomes an unavoidable problem in the manufacturing process of the lithium ion battery.
At present, researchers at home and abroad do a lot of research work on the adhesive, and CN01108511.8 and cn01108524.X disclose an adhesive, but the adhesive has the following defects in the actual use process: low-temperature baking is needed, so that the generation efficiency is low, the prepared pole piece is brittle and has poor flexibility, the pole piece is easy to break in the preparation process of the battery, the battery is easy to warp in the preparation process, waste products are easy to form, and the production cost of the battery is increased; CN201410731027.8 and CN200910300150.3 adopt low-polarity polymer as a core and high-polarity polymer as a shell to synthesize the lithium ion water-based adhesive with improved flexibility, but the existing polymer is adopted as a reaction core, so that the selectivity and the designability are poor, and the product has no problem in the process of manufacturing the lithium ion battery.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a self-crosslinking lithium ion battery anode aqueous binder which does not contain a low-molecular emulsifier, has a stable structure and is low in surface tension, and the second purpose is to provide a preparation method of the self-crosslinking lithium ion battery anode aqueous binder.
In order to solve the technical problem, the invention adopts the following technical scheme:
the self-crosslinking lithium ion battery anode water-based adhesive is characterized by comprising the following components in percentage by weight: the emulsion is composed of emulsion and latex particles dispersed in the emulsion, wherein the latex particles are a copolymer formed by sequentially copolymerizing an acrylic monomer, an acrylate monomer and an organic siloxane monomer; the acrylic monomer is methacrylic acid or derivative acid thereof, or salt corresponding to the methacrylic acid or the derivative acid thereof, or mixture thereof; the acrylic esters are various esters of methacrylic acid and derivatives thereof, or mixtures thereof; the organic siloxane monomer is organic silicon active functional monomer containing double bond and alkoxy at the same time, or the mixture thereof; the solid content of the emulsion is 5-30%, and the mass ratio of the acrylic monomer to the acrylate monomer to the organosiloxane monomer is as follows: (10-60): (20 to 80): (5-20).
Thus, the water-based adhesive of the invention takes water as a dispersion medium, solves the environmental protection problem of the adhesive for the lithium battery, and is an environment-friendly adhesive. In addition, the adhesive emulsion can form a chemical crosslinking structure in the using process, the adhesive force and the electrolyte resistance are improved, and the performance of the prepared battery meets the requirements of customers.
Further, the methacrylic acid or the derivative acid thereof, or the corresponding salt of the methacrylic acid or the derivative acid thereof, is obtained by mixing any one of acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido isopropyl sulfonic acid, 2-allyl ether 3-hydroxy propane-1-sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methacrylic sulfonic acid, styrene sulfonic acid, and the corresponding salt of the aforementioned acids, or any two of them are mixed in a proportion of more than zero percent, or any three of them are mixed in a proportion of more than zero percent, or any four of them are mixed in a proportion of more than zero percent, or any five of them are mixed in a proportion of more than zero percent, until all the components are mixed in a proportion of more than zero percent; wherein the cation of the salt is ammonium ion, lithium ion, sodium ion or potassium ion, and the whole dosage is 10-60% of the total mass.
Further, the monomers of the acrylic esters and derivatives thereof include acrylamide, ethyl acrylate, propyl acrylate, N/isobutyl acrylate, N-octyl acrylate, 2-isooctyl acrylate, N/isodecyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, acrylmorphine, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methacrylmorphine, hydroxypropyl methacrylate, acrylonitrile, crotononitrile, 5-hexenenitrile, cyclohexene-1-nitrile, 2-nonenenitrile, vinyl acetate, N-methylolacrylamide, hydroxyethylacrylurea, diacetone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, bisphenol A glycerol dimethacrylate, glycerol 1,3-diglycerol alkyd diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, glycidyl methacrylate, polyethylene glycol monomethyl acrylate, polyethylene glycol monomethyl methacrylate, allyl polyethylene glycol, allyl polypropylene glycol, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, isobornyl acrylate, N/isobutyl methacrylate, 2-isooctyl methacrylate, vinyl neodecanoate, dibutyl maleate, octadecyl methacrylate; any one of the components, or any two of the components are mixed in a proportion which is respectively larger than zero percent, or any three of the components are mixed in a proportion which is respectively larger than zero percent, or any four of the components are mixed in a proportion which is respectively larger than zero percent, or any five of the components are mixed in a proportion which is respectively larger than zero percent until all the components are mixed in a proportion which is respectively larger than zero percent.
Further, the organosilicon monomer containing both carbon-carbon double bonds and siloxane is vinyl triethoxysilane, vinyl trimethoxysilane, vinyl trimethoxy ethoxysilane, methacryloxypropyl trimethoxysilane, methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, allyl methoxydiethoxysilane, allyl triethoxysilane, and allyl methoxydiethoxysilane, wherein any one of the components, or any two of the components, are mixed in a proportion of more than zero percent, or any three of the components, or any four of the components, are mixed in a proportion of more than zero percent, until all the components are mixed in a proportion of more than zero percent.
Furthermore, in the film-forming and drying process of the water-based binder, emulsion latex is broken, siloxane is hydrolyzed under the action of water to generate silanol (Si-OH), and Si-O H groups and adjacent Si-O H groups are condensed to form Si-O-Si bonds, so that cross-linking is generated among polymer macromolecules.
Further, the initiator for the binder is any one of potassium persulfate, ammonium persulfate, sodium sulfite, sodium bisulfite, azobisisoheptonitrile, azobisisobutyramidine hydrochloride (AIBA), azobisisobutyrimidazoline hydrochloride (AIBI), and azobisisobutyronitrile, or any two of the above components are mixed in a proportion of more than zero percent, or any three of the above components are mixed in a proportion of more than zero percent, or any four of the above components are mixed in a proportion of more than zero percent, until all the above components are mixed in a proportion of more than zero percent.
The preparation method of the self-crosslinking lithium ion battery anode water-based adhesive is characterized by comprising the following steps,
1) Preparing the emulsifier, acrylic monomers or mixture, acrylate monomers or mixture, organic silicon monomers or mixture with carbon-carbon double bonds, initiator and deionized water according to the components and the proportion required by the process;
2) Adding acrylic monomers or a mixture and deionized water into a reaction device, and stirring to mix uniformly; heating to 50-80 deg.c, adding initiator to initiate polymerization and constant temperature reaction for 0.6-1.5 hr;
3) Controlling the speed of dripping the acrylate monomer or the mixture, finishing the dripping within 1-5 hours, controlling the temperature to be 60-90 ℃, and stirring; then reacting for 2-5 hours at the constant temperature of 60-90 ℃;
4) Similar to 3), dripping organosilicon monomer or mixture with carbon-carbon double bond at 60-90 deg.C for 1-5 hr, and stirring; after the dropwise addition is completed, the temperature is maintained at 60 ℃ to 90 ℃ for a period of time required by the thermostatic process.
Further: the constant temperature reaction time is 0.2-10 hours.
Compared with the prior art, the self-crosslinking lithium ion battery anode water-based adhesive and the preparation method thereof have the following advantages:
1. the adhesive of the invention takes water as a dispersion medium, solves the environmental protection problem of the adhesive for the lithium battery, and is an environment-friendly adhesive.
2. The invention introduces the structure containing acrylic acid and derivative salt thereof into the front section of the synthesis, so that the structure has good dispersion performance and adhesive force, the acrylate derivative in the middle section has good effect of controlling and adjusting the surface tension of the binder, and has good effect of spreading the binder on the surfaces of the anode material particles and the conductive agent, and the organosiloxane structure is introduced into the rear section, so that the binder forms chemical crosslinking in the drying process, therefore, the binder has excellent dispersion and adhesive property on the anode and the conductive agent, and can resist the swelling and erosion of electrolyte.
3. The invention has equivalent capacity exertion and capacity maintenance to the oily binder, and is beneficial to large-scale popularization.
Drawings
FIG. 1 is a schematic representation of the adhesion of an adhesive according to example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following detailed description and examples in conjunction with the accompanying drawings.
The self-crosslinking lithium ion battery anode water-based adhesive consists of emulsion and latex particles dispersed in the emulsion, wherein the latex particles are a copolymer formed by sequentially copolymerizing an acrylic monomer, an acrylate monomer and an organic siloxane monomer; the acrylic monomer is acrylic acid (methacrylic acid) or derivative acid thereof, and salt corresponding to the methacrylic acid or derivative acid thereof; the acrylic esters are various esters of methacrylic acid and derivatives thereof; the organic siloxane monomer is an organic silicon active functional monomer containing double bonds and alkoxy; the solid content of the emulsion is 5-30%, and the mass ratio of the acrylic monomer to the acrylate monomer to the organosiloxane monomer is as follows: (10-60): (20 to 80): (5-20).
The methacrylic acid or derivative acid thereof and the corresponding salt of the methacrylic acid or derivative acid thereof are acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido isopropyl sulfonic acid, 2-allyl ether 3-hydroxy propane-1-sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methacrylic sulfonic acid, styrene sulfonic acid and the corresponding salt thereof, any one of the two or three of the two or more are mixed in a proportion of more than zero percent, or any three of the three or four of the two or five of the four or more are mixed in a proportion of more than zero percent, until all the components are mixed in a proportion of more than zero percent; wherein the cation of the salt is ammonium ion, lithium ion, sodium ion or potassium ion, and the whole dosage is 10-60% of the total mass.
The acrylate and its derivative monomers of the present invention include acrylamide, ethyl acrylate, propyl acrylate, N/isobutyl acrylate, N-octyl acrylate, 2-isooctyl acrylate, N/isodecyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, acrylmorphine, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methacrylmorphine, hydroxypropyl methacrylate, acrylonitrile, butenenitrile, 5-hexenenitrile, cyclohexene-1-carbonitrile, 2-nonenenitrile, vinyl acetate, N-methylolacrylamide, hydroxyethylacrylurea, diacetone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, bisphenol A glycerol dimethacrylate, glycerol 1,3-diglycerol alkyd diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, glycidyl methacrylate, polyethylene glycol monomethyl acrylate, polyethylene glycol monomethyl methacrylate, allyl polyethylene glycol, allyl polypropylene glycol, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, isobornyl acrylate, N/isobutyl methacrylate, 2-isooctyl methacrylate, vinyl neodecanoate, dibutyl maleate, stearyl methacrylate; any one of the components, or any two of the components, is mixed in a proportion which is respectively larger than zero percent, or any three of the components, is mixed in a proportion which is respectively larger than zero percent, or any four of the components, is mixed in a proportion which is respectively larger than zero percent, or any five of the components, is mixed in a proportion which is respectively larger than zero percent until all the components are mixed in a proportion which is respectively larger than zero percent.
The organosilicon monomer containing both carbon-carbon double bonds and siloxane is vinyl triethoxysilane, vinyl trimethoxysilane, vinyl trimethoxy ethoxysilane, methacryloxypropyl trimethoxysilane and methacryloxypropyl methyldimethoxysilane, and the organosilicon monomer containing both carbon-carbon double bonds and siloxane is vinyl triethoxysilane, vinyl trimethoxysilane, vinyl trimethoxy ethoxysilane, methacryloxypropyl trimethoxysilane, methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, allyl methoxy diethoxy silane, any one of or any two of the components are mixed in a proportion of more than zero respectively, or any three of the components are mixed in a proportion of more than zero respectively, or any four of the components are mixed in a proportion of more than zero respectively until all the components are mixed in a proportion of more than zero respectively.
The aqueous binder of the invention breaks the emulsion latex and the siloxane in water during the film-forming and drying process
Under the action, the polymer is hydrolyzed to generate silanol (Si-OH), and Si-OH groups and adjacent Si-O H groups are condensed to form Si-O-Si bonds, so that cross-linking is generated among polymer macromolecules to form a self-crosslinking structure. Namely, the organic siloxane of the organic silicon monomer continuously migrates to the outer layer (surface), and the siloxane mutually condenses to form a chemical crosslinking structure, thereby greatly reducing the electrolyte resistance of the dry film of the adhesive.
The initiator for the self-crosslinking lithium ion battery cathode water-based adhesive is any one of potassium persulfate, ammonium persulfate, sodium sulfite, sodium bisulfite, azobisisoheptonitrile, azobisisobutyramidine hydrochloride (AIBA), azobisisobutyrimidazoline hydrochloride (AIBI), azobisisobutyronitrile and the like, or any two of the two are mixed in a proportion which is respectively larger than zero percent, or any three of the three are mixed in a proportion which is respectively larger than zero percent, or any four of the four are mixed in a proportion which is respectively larger than zero percent until all the components are mixed in a proportion which is respectively larger than zero percent. The initiator of the invention can activate the monomer molecules or low molecules containing double bonds in linear molecular chains to form free radicals in polymerization reaction, and carry out chain reaction, and the initiator can participate in the reaction in the whole process of polymer reaction.
The preparation method of the self-crosslinking lithium ion battery anode water-based adhesive comprises the following steps,
1) Preparing the emulsifier, acrylic monomers or a mixture or salt, acrylic monomers or a mixture, organic silicon monomers or a mixture with carbon-carbon double bonds, an initiator and deionized water according to the components and the proportion required by the process;
2) Adding acrylic monomers or a mixture and deionized water into a reaction device, and stirring to mix uniformly; heating to 50-80 deg.c, adding initiator to initiate polymerization and constant temperature reaction for 0.6-1.5 hr;
3) Controlling the speed of dripping the acrylate monomer or the mixture, finishing the dripping within 1-5 hours, controlling the temperature to be 60-90 ℃, and stirring; then reacting for 2-5 hours at the constant temperature of 60-90 ℃;
4) Similar to 3), dripping an organic silicon monomer or a mixture with carbon-carbon double bonds, controlling the temperature to be 60-90 ℃ during the addition, finishing the dripping within 1-5 hours, and stirring; after the dropwise addition is completed, the temperature is maintained at 60 ℃ to 90 ℃ for a period of time required by the thermostatic process.
The isothermal reaction time is 0.2-10 hours.
Example 1:
in this example, methacrylic acid, acrylic acid monomer, acrylamide, methyl acrylate, hydroxybutyl acrylate, methacryloxypropyl methyldimethoxysilane, and methacryloxypropyl methyldiethoxysilane are used as the monomer with double bond of organosiloxy group, and the mass of the specific composition is as follows:
acrylic monomer (a): 3g of methacrylic sulfonic acid, 17g of acrylic acid, 100 g of deionized water and 52g of lithium hydroxide 10% solution;
acrylate monomer: 5g of acrylamide, 10g of ethyl acrylate, 15g of hydroxybutyl acrylate, 0.3g of initiator sodium persulfate and 100 g of deionized water;
organosiloxane monomer: methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane: 5g, initiator sodium persulfate 0.1 g and deionized water 50 g.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: neutralizing an acrylic monomer with dissolved lithium hydroxide in a reaction bottle until the pH value is about 7, stirring, rotating at 200rpm under the protection of nitrogen, heating to 70 ℃, adding 0.2 g of sodium persulfate, and initiating polymerization for 1 hour; then slowly dropwise adding an acrylate monomer (stirring is required to be kept during dropwise adding), controlling the temperature at 72 ℃ during dropwise adding, completely dropwise adding within 2 hours, keeping the temperature of 72 ℃ constant for 60min, finally controlling the dropwise adding temperature at 75 ℃ by using an organic siloxane monomer, completely dropwise adding within 1 hour, heating to 82 ℃, and keeping the temperature constant for 3 hours to obtain the water-based adhesive with the components, wherein the viscosity is 3000-8000 centipoises.
Example 2:
the difference between the embodiment and the embodiment adopts the technical method of the embodiment and 1 is that the initiator adopts ammonium persulfate, and the emulsion prepared by the method has a slightly larger viscosity of 2500-10000 centipoises. 10g of the binder was dried at 60 ℃ for 24h and 100 ℃ for 24 ℃ to form a film, and the film was weighed, placed in 1M lithium hexafluorophosphate electrolyte (DEC: DMC = 1:1), taken out at 50 ℃ for 24h, removed of the surface electrolyte, weighed, and the electrolyte swelling ratio was calculated.
Taking 18g of the adhesive emulsion synthesized in the embodiment and 48g of deionized water, slowly stirring for 10 minutes, then adding 3g of a conductive agent, dispersing at a high speed for 60 minutes, then adding 144.3g of lithium manganate 2 times, dispersing at a high speed for 120 minutes, then adding a proper amount of water to adjust the viscosity, wherein the solid content of the prepared lithium manganate slurry is 70%, the viscosity is 3500, no obvious precipitate exists after standing for 24 hours, and the prepared lithium manganate slurry is coated on an aluminum foil, so that the appearance is uniform, the adhesive force is good, and the electrical property is good. As shown in detail in figure 1.
Example 3:
the preparation method of the adhesive in this embodiment is basically the same as 1, except that ammonium persulfate is used as the initiator, a methyl group-containing acrylic monomer is used as the acrylic monomer, and the rest is the same as 1, and the specific composition is as follows:
acrylic monomer: 3g of methacrylic sulfonic acid, 20.3g of methacrylic acid, 100 g of deionized water and 52g of lithium hydroxide 10% solution;
acrylate monomer: 5g of acrylamide, 10g of ethyl acrylate, 15g of hydroxybutyl acrylate, 0.3g of initiator ammonium persulfate and 100 g of deionized water;
organosiloxane monomers: methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane: 5g, initiator ammonium persulfate 0.1 g, and deionized water 78.4 g.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: neutralizing an acrylic monomer with dissolved lithium hydroxide to a pH value of about 7 in a reaction bottle, stirring, rotating at 200rpm under the protection of nitrogen, heating to 70 ℃, adding 0.2 g of ammonium persulfate, and initiating polymerization for 1.5 hours; then slowly dripping acrylate monomer (stirring is required to be kept during dripping), controlling the temperature at 72 ℃ during dripping, completely dripping within 2 hours, keeping the temperature of 72 ℃ for 60min, finally controlling the dripping temperature at 75 ℃ for completely dripping within 1 hour by using organic siloxane monomer, heating to 82 ℃, and keeping the temperature for 3 hours to prepare the aqueous adhesive with the components, wherein the viscosity is 2000-5000 centipoises.
Example 4:
the preparation method of the adhesive in this embodiment is basically the same as 1, except that the initiator is ammonium persulfate, the acrylate monomer is acrylonitrile, butyl acrylate and methyl acrylate monomer, and the rest is the same as 1, and the adhesive specifically comprises the following components:
acrylic monomer: 3g of methacrylic sulfonic acid, 17g of acrylic acid, 100 g of deionized water and 52g of lithium hydroxide 10% solution;
acrylate ester monomer: 5g of acrylonitrile, 15g of butyl acrylate, 10g of methyl acrylate, 0.3g of initiator ammonium persulfate and 100 g of deionized water;
organosiloxane monomers: methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane: 5g, initiator ammonium persulfate 0.1 g, and deionized water 78.4 g.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: neutralizing an acrylic monomer with dissolved lithium hydroxide to a pH value of about 7 in a reaction bottle, stirring, rotating at 200rpm under the protection of nitrogen, heating to 70 ℃, adding 0.2 g of ammonium persulfate, and initiating polymerization for 1.5 hours; then slowly dripping acrylate monomer (stirring is required to be kept during dripping), controlling the temperature at 72 ℃ during dripping, completely dripping within 2 hours, keeping the temperature of 72 ℃ for 60min, finally controlling the dripping temperature at 75 ℃ for completely dripping within 1 hour by using organic siloxane monomer, heating to 82 ℃, and keeping the temperature for 3 hours to prepare the aqueous adhesive with the components, wherein the viscosity is 2000-4000 centipoises.
Example 5:
the adhesive of this example was prepared in substantially the same manner as in 4, except that the organosiloxane monomer was different, and the adhesive was otherwise the same as in 1, and had the following specific composition:
acrylic monomer (a): 3g of methacrylic sulfonic acid, 17g of acrylic acid, 100 g of deionized water and 52g of a 10% lithium hydroxide solution;
acrylate ester monomer: 5g of acrylonitrile, 15g of butyl acrylate, 10g of methyl acrylate, 0.3g of initiator ammonium persulfate and 100 g of deionized water;
organosiloxane monomers: vinyltris (methoxyethoxy) silane: 5g, initiator ammonium persulfate 0.1 g, and deionized water 78.4 g.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: neutralizing an acrylic monomer with dissolved lithium hydroxide to a pH value of about 7 in a reaction bottle, stirring, rotating at 200rpm under the protection of nitrogen, heating to 70 ℃, adding 0.2 g of ammonium persulfate, and initiating polymerization for 1.5 hours; then slowly dripping acrylate monomer (stirring is required to be kept during dripping), controlling the temperature at 72 ℃ during dripping, completely dripping within 2 hours, keeping the temperature of 72 ℃ for 60min, finally controlling the dripping temperature at 75 ℃ for completely dripping within 1 hour by using organic siloxane monomer, heating to 82 ℃, and keeping the temperature for 3 hours to prepare the aqueous adhesive with the components, wherein the viscosity is 2000-4000 centipoises.
Example 6:
the preparation method of the adhesive of the embodiment is basically the same as that of 4, except that the amount of the organic siloxane monomer is different, and the mass of the concrete composition is as follows:
acrylic monomer: 3g of methacrylic sulfonic acid, 17g of acrylic acid, 100 g of deionized water and 52g of a 10% lithium hydroxide solution;
acrylate monomer: 5g of acrylamide, 10g of methyl acrylate, 15g of hydroxybutyl acrylate, 0.3g of initiator sodium persulfate and 100 g of deionized water;
organosiloxane monomer: methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane: 3g, initiator sodium persulfate 0.1 g and deionized water 33 g.
The preparation method of the adhesive emulsion for the lithium ion battery comprises the following steps: neutralizing an acrylic monomer with dissolved lithium hydroxide in a reaction flask until the pH value is about 7, stirring, rotating at 200rpm under the protection of nitrogen, heating to 70 ℃, adding 0.2 g of sodium persulfate, and initiating polymerization for 1 hour; then slowly dropwise adding an acrylate monomer (stirring is required to be kept during dropwise adding), controlling the temperature at 72 ℃ during dropwise adding, completely dropwise adding within 2 hours, keeping the temperature of 72 ℃ constant for 60min, finally controlling the dropwise adding temperature at 75 ℃ by using an organic siloxane monomer, completely dropwise adding within 1 hour, heating to 82 ℃, and keeping the temperature constant for 3 hours to prepare the water-based adhesive with the components, wherein the viscosity is 3000-4000 centipoises.
Example 7:
the preparation method of the adhesive of the embodiment is basically the same as that of 4, except that the initiator is azobisisobutyrimidazoline hydrochloride (AIBA), the reaction temperature is controlled at 50-60 ℃, the overall reaction time is prolonged by 6 hours, the prepared adhesive emulsion has the advantages of high viscosity, good fluidity, water resistance, excellent thermal stability and high decomposition temperature.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and although the present invention has been described in detail by referring to the preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions to the technical solutions of the present invention can be made without departing from the spirit and scope of the technical solutions, and all the modifications and equivalent substitutions should be covered by the claims of the present invention.
Claims (8)
1. The self-crosslinking lithium ion battery anode water-based adhesive is characterized by comprising the following components in percentage by weight: the emulsion is composed of emulsion and latex particles dispersed in the emulsion, wherein the latex particles are a copolymer formed by sequentially copolymerizing an acrylic monomer, an acrylate monomer and an organic siloxane monomer; the acrylic monomer is methacrylic acid or derivative acid thereof, or salt corresponding to the methacrylic acid or derivative acid thereof, or mixture thereof; the acrylic esters are various esters of methacrylic acid and derivatives thereof, or mixtures thereof; the organic siloxane monomer is organic silicon active functional monomer containing double bond and alkoxy at the same time, or the mixture thereof; the solid content of the emulsion is 5-30%, and the mass ratio of the acrylic monomer to the acrylate monomer to the organosiloxane monomer is as follows: (10-60): (20 to 80): (5-20).
2. The self-crosslinking lithium ion battery positive electrode aqueous binder of claim 1, wherein the methacrylic acid or a derivative acid thereof, or a salt corresponding to the methacrylic acid or a derivative acid thereof, is acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido isopropyl sulfonic acid, 2-allyl ether 3-hydroxypropane-1-sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methacrylic sulfonic acid, styrene sulfonic acid, or a salt corresponding to any one of the foregoing acids, or any two of them are mixed in a proportion of greater than zero percent each, or any three of them are mixed in a proportion of greater than zero percent each, or any four of them are mixed in a proportion of greater than zero percent each, or any five of them are mixed in a proportion of greater than zero percent each, until all the components are mixed in a proportion of greater than zero percent each; wherein the cation of the salt is ammonium ion, lithium ion, sodium ion or potassium ion, and the whole dosage is 10-60% of the total mass.
3. The self-crosslinking aqueous binder for positive electrodes of lithium ion batteries according to claim 1 or 2, wherein the monomers of acrylates and derivatives thereof include acrylamide, ethyl acrylate, propyl acrylate, N/isobutyl acrylate, N-octyl acrylate, 2-isooctyl acrylate, N/isodecyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, acrylmorphine, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methacrylmorphine, hydroxypropyl methacrylate, acrylonitrile, butenenitrile, 5-hexenenitrile, cyclohexene-1-carbonitrile, 2-nonenenitrile, vinyl acetate, N-methylolacrylamide, hydroxyethylacryloylurea, diacetone acrylamide, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, bisphenol A glycerol dimethacrylate, glycerol 1,3-diglycerol alkyd diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, glycidyl methacrylate, polyethylene glycol monomethyl acrylate, polyethylene glycol monomethyl methacrylate, allyl polyethylene glycol, allyl polypropylene glycol, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, isobornyl acrylate, N/isobutyl methacrylate, 2-isooctyl methacrylate, vinyl neodecanoate, dibutyl maleate and octadecyl methacrylate; any one of the components, or any two of the components are mixed in a proportion which is respectively larger than zero percent, or any three of the components are mixed in a proportion which is respectively larger than zero percent, or any four of the components are mixed in a proportion which is respectively larger than zero percent, or any five of the components are mixed in a proportion which is respectively larger than zero percent until all the components are mixed in a proportion which is respectively larger than zero percent.
4. The self-crosslinking lithium ion battery positive electrode aqueous binder of claim 1 or 2, wherein the organosilicon monomer containing both carbon-carbon double bonds and siloxane is vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethoxydiethoxysilane, or any two thereof are mixed in a proportion of more than zero percent, or any three thereof are mixed in a proportion of more than zero percent, or any four thereof are mixed in a proportion of more than zero percent, until all the components are mixed in a proportion of more than zero percent.
5. The self-crosslinking lithium ion battery anode aqueous binder as claimed in claim 1 or 2, wherein during the film-forming and drying process, emulsion latex is broken, siloxane is hydrolyzed under the action of water to generate silanol (Si-OH), and Si-O H groups and adjacent Si-O H groups are condensed to form Si-O-Si bonds, so that crosslinking is generated among polymer macromolecules.
6. The self-crosslinking lithium ion battery positive electrode aqueous binder as claimed in claim 1 or 2, wherein the initiator for the binder is any one of potassium persulfate, ammonium persulfate, sodium sulfite, sodium bisulfite, azobisisoheptonitrile, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, and azobisisobutyronitrile, or any two of them are mixed in a proportion of more than zero percent, or any three of them are mixed in a proportion of more than zero percent, or any four of them are mixed in a proportion of more than zero percent, until all the above components are mixed in a proportion of more than zero percent.
7. The preparation method of the self-crosslinking lithium ion battery anode water-based adhesive is characterized by comprising the following steps,
1) Preparing the emulsifier, the acrylic monomer or the mixture, the acrylate monomer or the mixture, the organic silicon monomer or the mixture with carbon-carbon double bonds, the initiator and the deionized water according to the components and the proportion of the process requirements, wherein the emulsifier is the emulsifier, the acrylic monomer or the mixture, the acrylate monomer or the mixture, and the organic silicon monomer or the mixture with carbon-carbon double bonds;
2) Adding acrylic monomers or a mixture and deionized water into a reaction device, and stirring to mix uniformly; heating to 50-80 deg.c, adding initiator to initiate polymerization and constant temperature reaction for 0.6-1.5 hr;
3) Controlling the speed of dripping the acrylate monomer or the mixture, finishing the dripping within 1-5 hours, controlling the temperature to be 60-90 ℃, and stirring; then reacting for 2-5 hours at the constant temperature of 60-90 ℃;
4) Similar to 3), dripping an organic silicon monomer or a mixture with carbon-carbon double bonds, controlling the temperature to be 60-90 ℃ during the addition, finishing the dripping within 1-5 hours, and stirring; after the dropwise addition is completed, the temperature is maintained at 60 ℃ to 90 ℃ for a period of time required by the constant temperature process.
8. The preparation method of the self-crosslinking lithium ion battery anode aqueous binder according to claim 7, characterized in that: the constant temperature reaction time is 0.2-10 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116144290A (en) * | 2023-04-21 | 2023-05-23 | 江苏正力新能电池技术有限公司 | Terpolymer adhesive, preparation method thereof and application thereof in silicon-based lithium ion battery |
| CN116462792A (en) * | 2023-06-19 | 2023-07-21 | 广州纳诺新材料技术有限公司 | Lithium battery carbon-coated foil conductive slurry, modified acrylic composite resin emulsion and preparation method thereof |
| CN117143545A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116144290A (en) * | 2023-04-21 | 2023-05-23 | 江苏正力新能电池技术有限公司 | Terpolymer adhesive, preparation method thereof and application thereof in silicon-based lithium ion battery |
| CN116462792A (en) * | 2023-06-19 | 2023-07-21 | 广州纳诺新材料技术有限公司 | Lithium battery carbon-coated foil conductive slurry, modified acrylic composite resin emulsion and preparation method thereof |
| CN116462792B (en) * | 2023-06-19 | 2023-09-01 | 广州纳诺新材料技术有限公司 | Lithium battery carbon-coated foil conductive slurry, modified acrylic composite resin emulsion and preparation method thereof |
| CN117143545A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device |
| CN117143545B (en) * | 2023-10-31 | 2024-03-29 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device |
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