A highly dispersed graphene conductive adhesive for batteries and preparation method thereof

Abstract

The present invention discloses a highly dispersed graphene conductive adhesive for batteries and a preparation method thereof, belonging to the technical field of conductive adhesives. The highly dispersed graphene conductive adhesive for batteries prepared by the present invention comprises, by weight, 6 to 8 parts of highly dispersed graphene, 4.5 to 13.5 parts of a binder, and 60 to 90 parts of a solvent; the highly dispersed graphene is prepared by ultrasonically dispersing the graphene in a mixture of hexadecyltrimethylammonium bromide and deionized water, followed by the addition of hexadecyltrimethylammonium bromide, sodium molybdate dihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate, stirring and dispersing the mixture uniformly, and then performing a hydrothermal reaction, washing, drying, grinding, and sieving; the binder comprises an amphiphilic polyethylene glycol-polycaprolactone block copolymer and an amphiphilic polyacrylate.

Description

Technical Field

[0001] The invention relates to a highly dispersed graphene conductive adhesive for batteries and a preparation method thereof. Background Art

[0002] Graphene, a two-dimensional carbon material with excellent physical and chemical properties, shows great potential for application in batteries due to its high conductivity, large specific surface area, and good mechanical strength. However, due to the strong van der Waals forces between graphene sheets, graphene is prone to agglomeration during preparation and application, resulting in poor dispersion and limiting its full performance. Furthermore, the conductivity of the graphene conductive paste directly affects the overall performance of the battery. Therefore, improving the dispersion and conductivity of graphene in the slurry has become a key issue that needs to be addressed.

[0003] Currently, methods for improving graphene dispersibility primarily include surface functionalization, solvent optimization, and the addition of dispersants. However, these methods still have limitations. For example, while surface functionalization can enhance the interaction between graphene and the solvent or matrix, it can also disrupt graphene's intrinsic structure and reduce its conductivity. Furthermore, traditional dispersants often struggle to achieve both efficient dispersion and high conductivity.

[0004] Therefore, developing a method for preparing highly dispersed graphene conductive adhesive for batteries that can effectively increase the dispersion of graphene and significantly improve the conductivity of the conductive adhesive is of great significance for promoting the practical application of graphene in the battery field. Summary of the Invention

[0005] The purpose of the present invention is to provide a highly dispersed graphene conductive adhesive for batteries and a preparation method thereof, so as to solve the technical problems mentioned in the above background technology.

[0006] The technical solution for achieving the purpose of the present invention is:

[0007] In a first aspect, the present invention provides a highly dispersed graphene conductive adhesive for batteries, characterized in that the raw material components, calculated by mass, include 6 to 8 parts by mass of highly dispersed graphene, 4.5 to 13.5 parts by mass of a binder, and 60 to 90 parts by mass of a solvent; the highly dispersed graphene is obtained by ultrasonically dispersing the graphene in a mixture of hexadecyltriylammonium bromide and deionized water, and then sequentially adding sodium molybdate dihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate, stirring and dispersing the mixture evenly, and then performing a hydrothermal reaction, washing, drying, grinding, and sieving.

[0008] Furthermore, the adhesive is obtained by mixing an amphiphilic polyethylene glycol-polycaprolactone block copolymer and an amphiphilic polyacrylate.

[0009] Furthermore, the amphiphilic polyethylene glycol-polycaprolactone block copolymer is obtained by sequentially reacting poly(ethylene glycol) monomethyl ether with succinic anhydride, N-hydroxysuccinimide, serinol, 6-caprolactone, 1H-benzimidazole-5-methanol, and 1,3-propane sultone.

[0010] The reaction mechanism of amphiphilic polyethylene glycol-polycaprolactone block copolymer is as follows:

[0011] .

[0012] Furthermore, the amphiphilic polyacrylate is obtained by copolymerization of dodecafluoroheptyl methacrylate, hydroxyethyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, isooctyl acrylate, and 4-nitrostyrene.

[0013] In a second aspect, the present invention provides a method for preparing a highly dispersed graphene conductive adhesive for batteries as described in the first aspect, comprising the following preparation steps:

[0014] (1) Weigh and mix the highly dispersed graphene, adhesive, and solvent according to the corresponding mass parts;

[0015] (2) The adhesive and solvent are mixed evenly, and then highly dispersed graphene is added. Then, the mixture is stirred for 8 to 10 hours under a nitrogen atmosphere and light, and then homogenized and discharged to obtain highly dispersed graphene conductive adhesive for batteries.

[0016] Furthermore, the preparation steps of the highly dispersed graphene are as follows: at room temperature, 0.045~0.055 parts by mass of hexadecyltriylammonium bromide is fully stirred and dissolved in 80 parts by mass of deionized water, followed by adding 16.5~16.8 parts by mass of graphene, ultrasonically dispersing for 25~35 minutes, then adding 2.7~2.8 parts by mass of sodium molybdate dihydrate, continuing ultrasonic dispersion for 25~35 minutes, then adding 5.5~5.6 parts by mass of bismuth nitrate pentahydrate and 0.08~0.12 parts by mass of cerium nitrate hexahydrate, continuing ultrasonic dispersion for 35~45 minutes, then hydrothermally reacting at 100°C for 23.5~24.5 hours, and naturally cooling to room temperature after the hydrothermal reaction is completed to obtain a precipitate, and then washing the precipitate with deionized water and anhydrous ethanol three times respectively, and then placing it in an oven at 60°C for 11.5~12.5 hours to obtain highly dispersed graphene.

[0017] Furthermore, the mass ratio of the amphiphilic polyethylene glycol-polycaprolactone block copolymer to the amphiphilic polyacrylate in the adhesive is 3-5:1.

[0018] Furthermore, the preparation steps of the amphiphilic polyethylene glycol-polycaprolactone block copolymer are as follows: 10 parts by mass of dry poly (ethylene glycol) monomethyl ether are dissolved in 30 parts by mass of 1,4-dioxane, followed by adding 0.55-0.65 parts by mass of succinic anhydride and 0.72-0.74 parts by mass of 4-dimethylaminopyridine and 0.61-0.63 parts by mass of triethylamine, reacting for 23.5-24.5 hours under a nitrogen atmosphere and room temperature, then removing 1,4-dioxane by rotary evaporation, and then dissolving in 49-51 parts by mass of 1M sodium bicarbonate aqueous solution, cooling to 0-5°C and filtering, adjusting the pH of the filtrate to 4 with 6 mol / L hydrochloric acid, then extracting with chloroform, and then taking the organic phase, washing it twice with deionized water, and concentrating it by rotary evaporation, and The mixture was precipitated in excess diethyl ether, then filtered and dried in vacuum at 40°C to obtain intermediate 1; 8.4 parts by mass of intermediate 1, 0.68-0.7 parts by mass of N-hydroxysuccinimide and 1.02-1.04 parts by mass of N,N-dicyclohexylcarbodiimide were dissolved in 39.5-40 parts by mass of dichloromethane, stirred and reacted at room temperature for 23.5-24.5 hours, filtered to remove the by-product dicyclohexylurea, and the filtrate was precipitated in excess diethyl ether at -10°C, then filtered and dried in vacuum at 40°C to obtain intermediate 2; 4.4 parts by mass of intermediate 2 and 1.26-1.3 parts by mass of serinol were reacted in 22 parts by mass of dimethyl sulfoxide at room temperature for 35-37 hours, and 13-13.5 parts by mass of dimethyl sulfoxide were added after the reaction was completed. The mixture was stirred for 17.5-18.5 hours at 120°C for 3 hours, and the mixture was cooled to room temperature naturally. The mixture was precipitated in an excess of diethyl ether at -10°C, filtered, and dried in vacuum at 40°C to obtain intermediate 4; 0.479 parts by mass of intermediate 3, 1.435-1.44 parts by mass of 6-caprolactone and 0.011-0.013 parts by mass of tin 2-ethylhexanoate were mixed and stirred at 120°C for 17.5-18.5 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, precipitated in an excess of diethyl ether at -10°C, filtered, and dried in vacuum at 40°C to obtain intermediate 4; 0.404 parts by mass of intermediate 4, 0.24-0.26 parts by mass of tetrabutylammonium bromide, 0.30-0.31 parts by mass of 1,8-diazabicyclo[5.4.0]undec-7 -ene, 0.16~0.17 parts by weight of (diethylamino) difluoride sulfur tetrafluoroborate were added to 6.6~6.65 parts by weight of dichloromethane, stirred at room temperature for 48 hours, filtered after the reaction was completed, the solvent was evaporated, and then added to 10 parts by weight of a methanol aqueous solution with a volume ratio of 1:1, 1~2 parts by weight of 6 mol / L hydrochloric acid were added, stirred at 0°C for 3.5~4.5 hours, filtered, and dried in vacuo at 40°C to obtain intermediate 5; 0.26~0.27 parts by weight of 1H-benzimidazole-5-methanol and 0.3 parts by weight of intermediate 5 were added to 11~15 parts by weight of acetonitrile, then stirred at 75~85°C under nitrogen for 71~73 hours, cooled naturally to room temperature after the reaction was completed, the solvent was evaporated, and then dissolved in 6.6~6.The mixture was extracted three times with deionized water in 65 parts by mass of dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, the solvent was evaporated, and the mixture was washed with methanol and dried under vacuum at 40°C to obtain intermediate 6. 0.11 parts by mass of intermediate 6 was dissolved in 20 parts by mass of tetrahydrofuran, followed by the addition of 0.036-0.037 parts by mass of 1,3-propane sultone. The mixture was stirred at room temperature for 23-25 ​​hours, washed three times with diethyl ether, and dried under vacuum at 40°C to obtain an amphiphilic polyethylene glycol-polycaprolactone block copolymer.

[0019] The preparation steps of the amphiphilic polyacrylate are as follows: butyl acetate and ethyl acetate are mixed in a mass ratio of 1:2.25 to prepare an azeotropic mixed solvent with a boiling point of about 90°C; 2.93-2.94 parts by mass of dodecafluoroheptyl methacrylate, 13.01-13.02 parts by mass of hydroxyethyl methacrylate, 9.93-9.95 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 9.21-9.22 parts by mass of isooctyl acrylate, 1.491-1.492 parts by mass of 4-nitrostyrene, 0.40-0.42 parts by mass of azoisobutyronitrile and 25 parts by mass of the azeotropic mixed solvent are mixed, and then the mixture is heated to 90°C, and the mixture is dropwise added to 20 parts by mass of the azeotropic mixed solvent within 2-3 hours, and stirred for reaction for 6-8 hours to obtain the amphiphilic polyacrylate.

[0020] Furthermore, the light intensity is 1-1.2 W / cm, and the wavelength of the light is 400 nm.

[0021] By adopting the above technical solution, the present invention has the following beneficial effects:

[0022] (1) The highly dispersed graphene conductive glue for batteries of the present invention comprises raw material components including highly dispersed graphene, an adhesive and a solvent; wherein the highly dispersed graphene is prepared by ultrasonically dispersing graphene in a mixture of hexadecyltriammonium bromide and deionized water, followed by adding sodium molybdate dihydrate, bismuth nitrate pentahydrate and cerium nitrate hexahydrate in sequence, stirring and dispersing the mixture uniformly, and then performing a hydrothermal reaction, washing, drying, grinding and sieving to obtain a cerium oxide-bismuth molybdate composite material loaded on the graphene. On the one hand, bismuth molybdate has excellent dispersibility and can be well dispersed whether used in water-based coatings, powder coatings, oil-based coatings or inks. The present application introduces bismuth molybdate on the graphene by a hydrothermal method, which can effectively improve the dispersibility of graphene in the highly dispersed graphene slurry. On the other hand, the cerium oxide-bismuth molybdate composite material has good conductivity. Loading the cerium oxide-bismuth molybdate composite material on the graphene can effectively improve the conductivity of the dispersed graphene slurry.

[0023] (2) The adhesive of the present invention is obtained by mixing an amphiphilic polyethylene glycol-polycaprolactone block copolymer and an amphiphilic polyacrylate. The amphiphilic properties of the amphiphilic polyethylene glycol-polycaprolactone block copolymer and the amphiphilic polyacrylate can further help disperse the highly dispersed graphene in the highly dispersed graphene slurry.

[0024] (3) The amphiphilic polyethylene glycol-polycaprolactone block copolymer of the present invention is obtained by reacting poly(ethylene glycol) monomethyl ether with succinic anhydride, N-hydroxysuccinimide, serinol, 6-caprolactone, 1H-benzimidazole-5-methanol and 1,3-propane sultone in sequence. Benzimidazole ionic liquid grafted with sulfonic acid groups is introduced into the amphiphilic polyethylene glycol-polycaprolactone block copolymer. While imparting amphiphilicity to the amphiphilic polyethylene glycol-polycaprolactone block copolymer, the sulfonic acid group-containing benzimidazole ionic liquid enhances the electron transmission ability in the system, thereby improving the conductivity of the amphiphilic polyethylene glycol-polycaprolactone block copolymer and further improving the conductivity of the highly dispersed graphene slurry.

[0025] (4) The amphiphilic polyacrylate of the present invention is obtained by copolymerization of dodecafluoroheptyl methacrylate, hydroxyethyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, isooctyl acrylate, and 4-nitrostyrene. By the addition polymerization of unsaturated bonds, hydrophilic sulfonic acid groups, nitro groups, and hydroxyl groups, as well as hydrophobic dodecafluoroheptyl and isooctane chains are introduced into the polyacrylate molecular chain to give the amphiphilic polyacrylate amphiphilicity. At the same time, the sulfonic acid, nitro groups, and hydroxyl groups are used to enhance the electron transmission ability in the system, thereby improving the conductivity of the amphiphilic polyethylene glycol-polycaprolactone block copolymer and further improving the conductivity of the highly dispersed graphene slurry.

[0026] (5) The adhesive of the present invention is mixed evenly with the solvent and then mixed with the highly dispersed graphene under light. During the mixing process, the benzyl alcohol on the amphiphilic polyethylene glycol-polycaprolactone block copolymer and the Lewis acid sites Bi on the highly dispersed graphene 3+ and Mo 6+ The nitrobenzene on the amphiphilic polyacrylate will react with the Lewis base site Mo on the surface of the highly dispersed graphene to adsorb and activate benzyl alcohol by forming CH-O∙∙Bi and -CH-O∙∙Mo coordination complexes. 5+ Formation of O=NO∙∙Mo 5+ The ligand adsorbs nitrobenzene, further improving the dispersion of highly dispersed graphene in the highly dispersed graphene slurry. Under light, the metal cerium on the highly dispersed graphene and bismuth molybdate generate electrons e - and hole h + , electronic - and hole h + Separation, carriers with the help of Ce 3+ / Ce 4+The ion pairs separate quickly and the holes are transported from the Lewis acid sites Bi on the catalyst surface. 3+ and Mo 6+ The hydroxyl group of benzyl alcohol in the amphiphilic polyethylene glycol-polycaprolactone block copolymer is transferred to the hydroxyl group of the amphiphilic polyethylene glycol-polycaprolactone block copolymer. The hydroxyl group accepts the hole and deoxidizes to aldehyde to generate benzaldehyde. At the same time, the electrons pass through the Lewis base site Mo 5+ The nitro group of nitrobenzene on the amphiphilic polyacrylate is transferred to the nitro group, which is hydrogenated and reduced to amino group to generate aniline. Benzaldehyde and aniline will desorb from the catalyst surface and then condense into aldehyde and amine, forming a Schiff base between the amphiphilic polyethylene glycol-polycaprolactone block copolymer and the amphiphilic polyacrylate, further enhancing the conductivity of the highly dispersed graphene slurry. The specific mechanism is as follows: DETAILED DESCRIPTION

[0027] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0028] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0029] The following examples are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0030] Some of the raw material components of the examples and comparative examples of the present invention are as follows:

[0031] The graphene powder is graphene prepared by liquid phase exfoliation method, with a flake diameter D50 of 5 μm and a layer number of less than 10;

[0032] Poly(ethylene glycol) monomethyl ether has an Mw of 2000;

[0033] The solvent is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl succinate, and dibutyl phthalate. The solvent in the examples and comparative examples of the present invention is N-methylpyrrolidone.

[0034] (Example 1)

[0035] A method for preparing a highly dispersed graphene conductive adhesive for batteries, comprising the following steps:

[0036] (1) Weigh and mix highly dispersed graphene, adhesive, and solvent according to the following mass parts: 6 parts by mass of highly dispersed graphene, 4.5 parts by mass of adhesive, and 60 parts by mass of solvent;

[0037] (2) The adhesive weighed in step (1) was mixed with the solvent and stirred at 800 rpm for 1.5 h, and then highly dispersed graphene was added and stirred for 5 min. Then, the mixture was stirred and mixed for 8 h under nitrogen atmosphere and light intensity of 1 W / cm and wavelength of 400 nm. Then, the mixture was homogenized 10 times with a homogenizer at a pressure of 1000 bar, and the material was discharged and collected after passing through a 150-mesh gauze to obtain a highly dispersed graphene conductive adhesive for batteries.

[0038] The preparation steps of the highly dispersed graphene are as follows: at room temperature, 0.045 parts by mass of hexadecyltriylammonium bromide is fully stirred and dissolved in 80 parts by mass of deionized water, followed by adding 16.5 parts by mass of graphene, ultrasonically dispersing for 25 minutes, then adding 2.7 parts by mass of sodium molybdate dihydrate, continuing ultrasonically dispersing for 25 minutes, then adding 5.5 parts by mass of bismuth nitrate pentahydrate and 0.08 parts by mass of cerium nitrate hexahydrate, continuing ultrasonically dispersing for 35 minutes, then hydrothermally reacting at 100° C. for 23.5 hours, and naturally cooling to room temperature after the hydrothermal reaction is completed to obtain a precipitate, then washing the precipitate with deionized water and anhydrous ethanol three times respectively, and then drying in an oven at 60° C. for 11.5 hours to obtain highly dispersed graphene.

[0039] The mass ratio of the amphiphilic polyethylene glycol-polycaprolactone block copolymer to the amphiphilic polyacrylate in the adhesive is 3:1.

[0040] The preparation steps of the amphiphilic polyethylene glycol-polycaprolactone block copolymer are as follows: 10 parts by mass of dry poly (ethylene glycol) monomethyl ether is dissolved in 30 parts by mass of 1,4-dioxane, followed by adding 0.55 parts by mass of succinic anhydride, 0.72 parts by mass of 4-dimethylaminopyridine and 0.61 parts by mass of triethylamine, reacting for 23.5 hours under a nitrogen atmosphere and at room temperature, then removing 1,4-dioxane by rotary evaporation, and then dissolving in 49 parts by mass of a 1M sodium bicarbonate aqueous solution, cooling to 0° C. and filtering, adjusting the pH of the filtrate to 4 with 6 mol / L hydrochloric acid, then extracting with chloroform, and then taking the organic phase, washing it twice with deionized water, concentrating it by rotary evaporation, and precipitating it in excess diethyl ether, then filtering it, and drying it in vacuo at 40° C. Obtain intermediate 1; 8.4 parts by mass of intermediate 1, 0.68 parts by mass of N-hydroxysuccinimide and 1.02 parts by mass of N,N-dicyclohexylcarbodiimide were dissolved in 39.5 parts by mass of dichloromethane, stirred and reacted at room temperature for 23.5 hours, filtered to remove the by-product dicyclohexylurea, and the filtrate was precipitated in excess diethyl ether at -10°C, then filtered and dried in vacuum at 40°C to obtain intermediate 2; 4.4 parts by mass of intermediate 2 and 1.26 parts by mass of serinol were reacted in 22 parts by mass of dimethyl sulfoxide at room temperature for 35 hours, 13 parts by mass of dichloromethane was added after the reaction was completed, and the mixture was extracted 3 times with deionized water. The organic phase was concentrated under vacuum, precipitated in excess diethyl ether at -10°C, filtered, 40 ℃ vacuum drying to obtain intermediate 3; 0.479 parts by mass of intermediate 3, 1.435 parts by mass of 6-caprolactone and 0.011 parts by mass of 2-ethylhexanoate tin were mixed and stirred at 120℃ for 17.5h. After the reaction was completed, it was naturally cooled to room temperature, precipitated in an excess of diethyl ether at -10℃, filtered, and vacuum dried at 40℃ to obtain intermediate 4; 0.404 parts by mass of intermediate 4, 0.24 parts by mass of tetrabutylammonium bromide, 0.30 parts by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene, and 0.16 parts by mass of (diethylamino) difluoride sulfur tetrafluoroborate were added to 6.6 parts by mass of dichloromethane, stirred at room temperature for 48h, filtered after the reaction was completed, the solvent was evaporated, and then added The mixture was added into 10 parts by mass of a methanol aqueous solution with a volume ratio of 1:1, and 1 part by mass of 6 mol / L hydrochloric acid was added. The mixture was stirred at 0°C for 3.5 hours, filtered, and dried in vacuo at 40°C to obtain intermediate 5. 0.26 parts by mass of 1H-benzimidazole-5-methanol and 0.3 parts by mass of intermediate 5 were added into 11 parts by mass of acetonitrile, and then stirred at 75°C under nitrogen for 71 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, the solvent was evaporated, and then dissolved in 6.6 parts by mass of dichloromethane, extracted with deionized water three times, and the organic phase was dried over anhydrous magnesium sulfate. The solvent was evaporated, washed with methanol, and dried in vacuo at 40°C to obtain intermediate 6. 0.11 parts by mass of intermediate 6 was dissolved in 20 parts by mass of tetrahydrofuran, and then 0.0.36 parts by mass of 1,3-propane sultone was stirred at room temperature for 23 hours, washed with ether three times, and dried in vacuo at 40°C to obtain an amphiphilic polyethylene glycol-polycaprolactone block copolymer.

[0041] The preparation steps of the amphiphilic polyacrylate are as follows: butyl acetate and ethyl acetate are mixed in a mass ratio of 1:2.25 to prepare an azeotropic mixed solvent with a boiling point of about 90°C; 2.93 parts by mass of dodecafluoroheptyl methacrylate, 13.01 parts by mass of hydroxyethyl methacrylate, 9.93 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 9.21 parts by mass of isooctyl acrylate, 1.491 parts by mass of 4-nitrostyrene, 0.40 parts by mass of azoisobutyronitrile and 25 parts by mass of the azeotropic mixed solvent are mixed, and then the mixture is heated to 90°C, and the mixture is dropwise added to 20 parts by mass of the azeotropic mixed solvent within 2 hours, and the mixture is stirred and reacted for 6 hours to obtain the amphiphilic polyacrylate.

[0042] (Example 2)

[0043] A method for preparing a highly dispersed graphene conductive adhesive for batteries, comprising the following steps:

[0044] (1) Weigh and prepare highly dispersed graphene, binder, and solvent according to the following mass parts: 7 parts by mass of highly dispersed graphene, 9 parts by mass of binder, and 75 parts by mass of solvent;

[0045] (2) The adhesive weighed in step (1) was mixed with the solvent and stirred at 800 rpm for 1.5 h, and then highly dispersed graphene was added and stirred for 5 min. Then, the mixture was stirred and mixed for 9 h under nitrogen atmosphere and light intensity of 1.1 W / cm and wavelength of 400 nm. Then, the mixture was homogenized 10 times with a homogenizer at a pressure of 1000 bar, and the material was discharged and collected after passing through a 150 mesh gauze to obtain a highly dispersed graphene conductive adhesive for batteries.

[0046] The preparation steps of the highly dispersed graphene are as follows: at room temperature, 0.05 parts by mass of hexadecyltriylammonium bromide is fully stirred and dissolved in 80 parts by mass of deionized water, followed by adding 16.6 parts by mass of graphene, ultrasonically dispersing for 30 minutes, then adding 2.75 parts by mass of sodium molybdate dihydrate, continuing ultrasonically dispersing for 30 minutes, then adding 5.55 parts by mass of bismuth nitrate pentahydrate and 0.1 parts by mass of cerium nitrate hexahydrate, continuing ultrasonically dispersing for 40 minutes, then hydrothermally reacting at 100° C. for 24 hours, and naturally cooling to room temperature after the hydrothermal reaction is completed to obtain a precipitate, then washing the precipitate with deionized water and anhydrous ethanol three times respectively, and then drying in an oven at 60° C. for 12 hours to obtain highly dispersed graphene.

[0047] The mass ratio of the amphiphilic polyethylene glycol-polycaprolactone block copolymer to the amphiphilic polyacrylate in the adhesive is 4:1.

[0048] The preparation steps of the amphiphilic polyethylene glycol-polycaprolactone block copolymer are as follows: 10 parts by mass of dry poly (ethylene glycol) monomethyl ether is dissolved in 30 parts by mass of 1,4-dioxane, followed by adding 0.6 parts by mass of succinic anhydride, 0.73 parts by mass of 4-dimethylaminopyridine and 0.62 parts by mass of triethylamine, reacting for 24 hours under a nitrogen atmosphere and room temperature, then removing 1,4-dioxane by rotary evaporation, and then dissolving in 50 parts by mass of a 1M sodium bicarbonate aqueous solution, cooling to 2° C. and filtering, adjusting the pH of the filtrate to 4 with 6 mol / L hydrochloric acid, then extracting with chloroform, and then taking the organic phase, washing it twice with deionized water, and then rotary evaporating and concentrating it, and precipitating it in excess diethyl ether, then filtering it, and vacuum drying it at 40° C. to obtain the intermediate The intermediate 1 was prepared by dissolving 8.4 parts by mass of the intermediate 1, 0.69 parts by mass of N-hydroxysuccinimide and 1.03 parts by mass of N,N-dicyclohexylcarbodiimide in 39.75 parts by mass of dichloromethane, stirring and reacting at room temperature for 24 hours. After the reaction was completed, the by-product dicyclohexylurea was filtered to remove the filtrate, and the filtrate was precipitated in an excess of diethyl ether at -10°C, then filtered and dried in a vacuum at 40°C to obtain the intermediate 2; 4.4 parts by mass of the intermediate 2 and 1.28 parts by mass of serinol were reacted in 22 parts by mass of dimethyl sulfoxide at room temperature for 36 hours. After the reaction was completed, 13.25 parts by mass of dichloromethane was added, and the mixture was extracted 3 times with deionized water. The organic phase was concentrated under vacuum, precipitated in an excess of diethyl ether at -10°C, filtered, and dried in a vacuum at 40°C. Drying to obtain intermediate 3; 0.479 parts by mass of intermediate 3, 1.437 parts by mass of 6-caprolactone and 0.012 parts by mass of tin 2-ethylhexanoate were mixed and stirred at 120°C for 18 hours. After the reaction was completed, it was naturally cooled to room temperature and precipitated in an excess of diethyl ether at -10°C. It was filtered and dried in vacuum at 40°C to obtain intermediate 4; 0.404 parts by mass of intermediate 4, 0.25 parts by mass of tetrabutylammonium bromide, 0.305 parts by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene and 0.165 parts by mass of (diethylamino) difluoride sulfur tetrafluoroborate were added to 6.63 parts by mass of dichloromethane and stirred at room temperature for 48 hours. After the reaction was completed, it was filtered and the solvent was evaporated, and then 1 1.5 parts by mass of 6 mol / L hydrochloric acid were added to 0 parts by mass of methanol-water solution with a volume ratio of 1:1, stirred at 0°C for 4 hours, filtered, and dried in vacuum at 40°C to obtain intermediate 5; 0.265 parts by mass of 1H-benzimidazole-5-methanol and 0.3 parts by mass of intermediate 5 were added to 13 parts by mass of acetonitrile, then stirred at 80°C under nitrogen for 72 hours. After the reaction, it was naturally cooled to room temperature, the solvent was evaporated, and then dissolved in 6.625 parts by mass of dichloromethane, extracted with deionized water three times, and the organic phase was dried over anhydrous magnesium sulfate, the solvent was evaporated, washed with methanol, and dried in vacuum at 40°C to obtain intermediate 6; 0.11 parts by mass of intermediate 6 was dissolved in 20 parts by mass of tetrahydrofuran, and then 0.0.365 parts by mass of 1,3-propane sultone was stirred at room temperature for 24 hours, washed with ether three times, and dried in vacuo at 40°C to obtain an amphiphilic polyethylene glycol-polycaprolactone block copolymer.

[0049] The preparation steps of the amphiphilic polyacrylate are as follows: butyl acetate and ethyl acetate are mixed in a mass ratio of 1:2.25 to prepare an azeotropic mixed solvent with a boiling point of about 90°C; 2.935 parts by mass of dodecafluoroheptyl methacrylate, 13.015 parts by mass of hydroxyethyl methacrylate, 9.94 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 9.215 parts by mass of isooctyl acrylate, 1.4915 parts by mass of 4-nitrostyrene, 0.41 parts by mass of azoisobutyronitrile and 25 parts by mass of the azeotropic mixed solvent are mixed, and then the mixture is heated to 90°C, and the mixture is dropwise added to 20 parts by mass of the azeotropic mixed solvent within 2.5 hours, and stirred for reaction for 7 hours to obtain the amphiphilic polyacrylate.

[0050] (Example 3)

[0051] A method for preparing a highly dispersed graphene conductive adhesive for batteries, comprising the following steps:

[0052] (1) Weigh and prepare highly dispersed graphene, binder, and solvent according to the following mass parts: 8 parts by mass of highly dispersed graphene, 13.5 parts by mass of binder, and 90 parts by mass of solvent;

[0053] (2) The adhesive weighed in step (1) was mixed with the solvent and stirred at 800 rpm for 1.5 h, and then highly dispersed graphene was added and stirred for 5 min. Then, the mixture was stirred and mixed for 10 h under a nitrogen atmosphere and light intensity of 1.2 W / cm and a wavelength of 400 nm. Then, the mixture was homogenized 10 times using a homogenizer at a pressure of 1000 bar, and the material was discharged and collected after passing through a 150-mesh gauze to obtain a highly dispersed graphene conductive adhesive for batteries.

[0054] The preparation steps of the highly dispersed graphene are as follows: at room temperature, 0.055 parts by mass of hexadecyltriylammonium bromide is fully stirred and dissolved in 80 parts by mass of deionized water, followed by adding 16.8 parts by mass of graphene, ultrasonically dispersing for 35 minutes, then adding 2.8 parts by mass of sodium molybdate dihydrate, continuing ultrasonically dispersing for 35 minutes, then adding 5.6 parts by mass of bismuth nitrate pentahydrate and 0.12 parts by mass of cerium nitrate hexahydrate, continuing ultrasonically dispersing for 45 minutes, then hydrothermally reacting at 100° C. for 24.5 hours, and naturally cooling to room temperature after the hydrothermal reaction is completed to obtain a precipitate, then washing the precipitate with deionized water and anhydrous ethanol three times respectively, and then drying in an oven at 60° C. for 12.5 hours to obtain highly dispersed graphene.

[0055] The mass ratio of the amphiphilic polyethylene glycol-polycaprolactone block copolymer to the amphiphilic polyacrylate in the adhesive is 5:1.

[0056] The preparation steps of the amphiphilic polyethylene glycol-polycaprolactone block copolymer are as follows: 10 parts by mass of dry poly (ethylene glycol) monomethyl ether is dissolved in 30 parts by mass of 1,4-dioxane, followed by adding 0.65 parts by mass of succinic anhydride, 0.74 parts by mass of 4-dimethylaminopyridine and 0.63 parts by mass of triethylamine, reacting for 24.5 hours under a nitrogen atmosphere and room temperature, then removing 1,4-dioxane by rotary evaporation, and then dissolving in 51 parts by mass of a 1M sodium bicarbonate aqueous solution, cooling to 5° C. and filtering, adjusting the pH of the filtrate to 4 with 6 mol / L hydrochloric acid, then extracting with chloroform, and then taking the organic phase, washing it twice with deionized water, concentrating it by rotary evaporation, and precipitating it in excess diethyl ether, then filtering it, and drying it in vacuo at 40° C. Obtain intermediate 1; 8.4 parts by mass of intermediate 1, 0.7 parts by mass of N-hydroxysuccinimide and 1.04 parts by mass of N,N-dicyclohexylcarbodiimide were dissolved in 40 parts by mass of dichloromethane, stirred and reacted at room temperature for 24.5 hours, filtered to remove the by-product dicyclohexylurea, and the filtrate was precipitated in excess diethyl ether at -10°C, then filtered and dried in vacuum at 40°C to obtain intermediate 2; 4.4 parts by mass of intermediate 2 and 1.3 parts by mass of serinol were reacted in 22 parts by mass of dimethyl sulfoxide at room temperature for 37 hours, 13.5 parts by mass of dichloromethane was added after the reaction was completed, and the mixture was extracted 3 times with deionized water. The organic phase was concentrated under vacuum, precipitated in excess diethyl ether at -10°C, filtered, and dried in vacuum at 40°C. The mixture was dried in vacuo to obtain intermediate 3; 0.479 parts by mass of intermediate 3, 1.44 parts by mass of 6-caprolactone and 0.013 parts by mass of tin 2-ethylhexanoate were mixed and stirred at 120°C for 18.5h. After the reaction was completed, it was naturally cooled to room temperature, precipitated in an excess of diethyl ether at -10°C, filtered, and dried in vacuo at 40°C to obtain intermediate 4; 0.404 parts by mass of intermediate 4, 0.26 parts by mass of tetrabutylammonium bromide, 0.31 parts by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene, and 0.17 parts by mass of (diethylamino) difluoride sulfur tetrafluoroborate were added to 6.65 parts by mass of dichloromethane, stirred at room temperature for 48h, filtered after the reaction was completed, the solvent was evaporated, and then added To 10 parts by mass of a 1:1 methanol-water solution, 2 parts by mass of 6 mol / L hydrochloric acid were added, stirred at 0°C for 4.5 hours, filtered, and dried in vacuo at 40°C to obtain intermediate 5; 0.27 parts by mass of 1H-benzimidazole-5-methanol and 0.3 parts by mass of intermediate 5 were added to 15 parts by mass of acetonitrile, followed by stirring at 85°C under nitrogen for 73 hours. After the reaction, the mixture was naturally cooled to room temperature, the solvent was evaporated, and then dissolved in 6.65 parts by mass of dichloromethane, extracted three times with deionized water, and the organic phase was dried over anhydrous magnesium sulfate, the solvent was evaporated, washed with methanol, and dried in vacuo at 40°C to obtain intermediate 6; 0.11 parts by mass of intermediate 6 was dissolved in 20 parts by mass of tetrahydrofuran, and then 0.0.37 parts by mass of 1,3-propane sultone was stirred at room temperature for 25 hours, washed with ether three times, and dried in vacuo at 40°C to obtain an amphiphilic polyethylene glycol-polycaprolactone block copolymer.

[0057] The preparation steps of the amphiphilic polyacrylate are as follows: butyl acetate and ethyl acetate are mixed in a mass ratio of 1:2.25 to prepare an azeotropic mixed solvent with a boiling point of about 90°C; 2.94 parts by mass of dodecafluoroheptyl methacrylate, 13.02 parts by mass of hydroxyethyl methacrylate, 9.95 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 9.22 parts by mass of isooctyl acrylate, 1.492 parts by mass of 4-nitrostyrene, 0.42 parts by mass of azoisobutyronitrile and 25 parts by mass of the azeotropic mixed solvent are mixed, and then the mixture is heated to 90°C, and the mixture is dropwise added to 20 parts by mass of the azeotropic mixed solvent within 3 hours, and stirred for reaction for 8 hours to obtain the amphiphilic polyacrylate.

[0058] (Comparative Example 1)

[0059] The difference between Comparative Example 1 and Example 2 is that the raw material components of the highly dispersed graphene conductive glue for batteries in Comparative Example 1 include, by mass, 7 parts by mass of graphene, 9 parts by mass of binder, and 75 parts by mass of solvent; the remaining components and steps are the same as those in Example 2.

[0060] (Comparative Example 2)

[0061] The difference between Comparative Example 2 and Example 2 is that the highly dispersed graphene in Comparative Example 2 is obtained by ultrasonically dispersing graphene in deionized water, then adding hexadecyltriammonium bromide and cerium nitrate hexahydrate in sequence, stirring and dispersing them evenly, and then conducting a hydrothermal reaction, washing, drying, grinding, and sieving; the remaining components and steps are the same as those in Example 2.

[0062] (Comparative Example 3)

[0063] The difference between Comparative Example 1 and Example 2 is that the highly dispersed graphene in Comparative Example 3 is obtained by ultrasonically dispersing graphene in deionized water, then adding hexadecyltriammonium bromide, sodium molybdate dihydrate, and bismuth nitrate pentahydrate in sequence, stirring and dispersing them evenly, and then performing a hydrothermal reaction, washing, drying, grinding, and sieving; the remaining components and steps are the same as those in Example 2.

[0064] (Comparative Example 4)

[0065] The difference between Comparative Example 4 and Example 2 is that the adhesive in Comparative Example 4 only uses amphiphilic polyethylene glycol-polycaprolactone block copolymer; the remaining components and steps are the same as those in Example 2.

[0066] (Comparative Example 5)

[0067] The difference between Comparative Example 5 and Example 2 is that the adhesive in Comparative Example 5 only uses amphiphilic polyacrylate; the remaining components and steps are the same as those in Example 2.

[0068] (Comparative Example 6)

[0069] The difference between Comparative Example 6 and Example 2 lies in step (2). Step (2) of Comparative Example 6 is specifically as follows: the adhesive weighed in step (1) is mixed with the solvent and stirred at 800 rpm for 1.5 h, and then highly dispersed graphene is added and stirred and mixed evenly, and then homogenized 10 times with a homogenizer at a pressure of 1000 bar, the material is discharged, and the slurry is collected after passing through a 150-mesh gauze to obtain a highly dispersed graphene conductive adhesive for batteries; the remaining components and steps are the same as those in Example 2.

[0070] (Effect example)

[0071] Conductivity test: The batteries prepared in the examples and comparative examples were evenly coated with highly dispersed graphene conductive glue on a clean 5 cm × 5 cm PET film and dried to obtain a conductive film. The thickness of the conductive film measured by a spiral micrometer was 10 microns. The obtained conductive film was roller-pressed and then the volume resistivity of the film layer was measured using a four-probe tester. Six different points on the conductive film were randomly selected, with a probe spacing of 2 mm. The measurements were made six times and the average value was taken.

[0072] Dispersibility: The appearance of the highly dispersed graphene conductive glue for batteries prepared in the examples and comparative examples was visually inspected. The appearance should be a black liquid slurry with a uniform state, no obvious particles, and a certain fluidity.

[0073] Table 1 below shows the performance test results of the highly dispersed graphene conductive adhesives for batteries prepared in Examples 1 to 3 and Comparative Examples 1 to 6:

[0074] Table 1

[0075] Slurry appearance Volume resistivity (Ω*cm) Example 1 Good dispersion effect and very smooth appearance 0.015 Example 2 Good dispersion effect and very smooth appearance 0.008 Example 3 Good dispersion effect and very smooth appearance 0.010 Comparative Example 1 Large areas of powder aggregation are visible to the naked eye 0.923 Comparative Example 2 Large areas of powder aggregation are visible to the naked eye 0.125 Comparative Example 3 Good dispersion effect and very smooth appearance 0.049 Comparative Example 4 A large number of powder aggregation points can be seen with the naked eye 0.106 Comparative Example 5 A large number of powder aggregation points can be seen with the naked eye 0.093 Comparative Example 6 Two powder gathering points can be seen with the naked eye 0.029

[0076] It can be seen from Table 1 that the highly dispersed graphene conductive adhesives for batteries prepared in Examples 1 to 3 have good conductivity, and the graphene in the highly dispersed graphene conductive adhesives for batteries has good dispersion.

[0077] The difference between Comparative Example 1 and Example 2 is that Comparative Example 1 uses graphene instead of graphene loaded with bismuth molybdate and metallic cerium. The dispersion of the graphene in Comparative Example 1 is poor, and the conductivity of the highly dispersed graphene conductive glue for batteries is weak.

[0078] The difference between Comparative Example 2 and Example 2 is that the highly dispersed graphene in Comparative Example 2 is only loaded with metallic cerium, the dispersion of the graphene in the highly dispersed graphene conductive adhesive for batteries in Comparative Example 2 is poor, and the conductivity of the highly dispersed graphene conductive adhesive for batteries is weak. It can be seen that the dispersion has a greater influence on the conductivity of the highly dispersed graphene conductive adhesive for batteries.

[0079] The difference between Comparative Example 3 and Example 2 is that the highly dispersed graphene in Comparative Example 3 is only loaded with bismuth molybdate, and the conductivity of the highly dispersed graphene conductive glue for batteries prepared in Comparative Example 3 is relatively weak.

[0080] The difference between Comparative Example 4 and Example 2 is that the adhesive of Comparative Example 4 only uses amphiphilic polyethylene glycol-polycaprolactone block copolymer; the conductivity of the highly dispersed graphene conductive adhesive for batteries prepared in Comparative Example 4 is weak, and the dispersion of graphene is poor.

[0081] The difference between Comparative Example 5 and Example 2 is that the adhesive of Comparative Example 5 only uses amphiphilic polyacrylate; the conductivity of the highly dispersed graphene conductive adhesive for batteries prepared in Comparative Example 5 is weak, and the dispersion of graphene is poor.

[0082] The difference between Comparative Example 6 and Example 2 is that in step (2) of Comparative Example 6, the highly dispersed graphene is not irradiated when mixed with the binder and the solvent. The conductivity of the highly dispersed graphene conductive glue for batteries prepared in Comparative Example 6 is weak, and the dispersion of graphene is poor.

[0083] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A highly dispersed graphene conductive adhesive for batteries, characterized in that: The raw material components include, by mass, 6-8 parts by mass of highly dispersed graphene, 4.5-13.5 parts by mass of a binder, and 60-90 parts by mass of a solvent; the highly dispersed graphene is obtained by ultrasonically dispersing the graphene in a mixture of hexadecyltriylammonium bromide and deionized water, followed by sequentially adding sodium molybdate dihydrate, bismuth nitrate pentahydrate, and cerium nitrate hexahydrate, stirring and dispersing the mixture uniformly, and then performing a hydrothermal reaction, washing, drying, grinding, and sieving; The adhesive is obtained by mixing an amphiphilic polyethylene glycol-polycaprolactone block copolymer and an amphiphilic polyacrylate; the amphiphilic polyethylene glycol-polycaprolactone block copolymer is obtained by reacting poly(ethylene glycol) monomethyl ether with succinic anhydride, N-hydroxysuccinimide, serinol, 6-caprolactone, 1H-benzimidazole-5-methanol, and 1,3-propane sultone in sequence; The amphiphilic polyacrylate is obtained by copolymerization of dodecafluoroheptyl methacrylate, hydroxyethyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, isooctyl acrylate, and 4-nitrostyrene; The method for preparing the highly dispersed graphene conductive adhesive for batteries comprises the following steps: (1) Weigh and mix the highly dispersed graphene, adhesive, and solvent according to the corresponding mass parts; (2) The adhesive and the solvent are mixed evenly, and then highly dispersed graphene is added, and then stirred and mixed for 8 to 10 hours under a nitrogen atmosphere and light, and then homogenized and discharged to obtain a highly dispersed graphene conductive adhesive for batteries; The light intensity is 1-1.2 W / cm 2 , the wavelength of light is 400nm.

2. The highly dispersed graphene conductive adhesive for batteries according to claim 1, characterized in that The preparation steps of the highly dispersed graphene are as follows: at room temperature, 0.045-0.055 parts by mass of hexadecyltriylammonium bromide is fully stirred and dissolved in 80 parts by mass of deionized water, then 16.5-16.8 parts by mass of graphene is added, ultrasonic dispersion is continued for 25-35 minutes, then 2.7-2.8 parts by mass of sodium molybdate dihydrate is added, ultrasonic dispersion is continued for 25-35 minutes, then 5.5-5.6 parts by mass of bismuth nitrate pentahydrate and 0.08-0.12 parts by mass of cerium nitrate hexahydrate are added, ultrasonic dispersion is continued for 35-45 minutes, then hydrothermally reacted at 100° C. for 23.5-24.5 hours, and naturally cooled to room temperature after the hydrothermal reaction is completed to obtain a precipitate, then the precipitate is washed three times with deionized water and anhydrous ethanol respectively, and then placed in an oven at 60° C. for 11.5-12.5 hours to obtain highly dispersed graphene.

3. The highly dispersed graphene conductive adhesive for batteries according to claim 1, characterized in that: The mass ratio of the amphiphilic polyethylene glycol-polycaprolactone block copolymer to the amphiphilic polyacrylate in the adhesive is 3-5:

1.

4. The highly dispersed graphene conductive adhesive for batteries according to claim 3, characterized in that The preparation steps of the amphiphilic polyethylene glycol-polycaprolactone block copolymer are as follows: 10 parts by mass of dry poly (ethylene glycol) monomethyl ether is dissolved in 30 parts by mass of 1,4-dioxane, followed by adding 0.55-0.65 parts by mass of succinic anhydride, 0.72-0.74 parts by mass of 4-dimethylaminopyridine and 0.61-0.63 parts by mass of triethylamine, reacting for 23.5-24.5 hours under a nitrogen atmosphere and room temperature, removing 1,4-dioxane by rotary evaporation, and then dissolving in 49-51 parts by mass of a 1M sodium bicarbonate aqueous solution, cooling to 0-5° C. and filtering, adjusting the pH of the filtrate to 4 with 6 mol / L hydrochloric acid, then extracting with chloroform, washing the organic phase with deionized water, concentrating by rotary evaporation, and precipitating on a filter. The intermediate 1 was dissolved in 39.5-40 parts by mass of dichloromethane, 8.4 parts by mass of intermediate 1, 0.68-0.7 parts by mass of N-hydroxysuccinimide and 1.02-1.04 parts by mass of N,N-dicyclohexylcarbodiimide, and the mixture was stirred at room temperature for 23.5-24.5 hours. After the reaction was completed, the mixture was filtered and the filtrate was precipitated in excess diethyl ether at -10°C, and then filtered and dried in vacuum to obtain intermediate 2; 4.4 parts by mass of intermediate 2 and 1.26-1.3 parts by mass of serinol were reacted in 22 parts by mass of dimethyl sulfoxide at room temperature for 35-37 hours. After the reaction was completed, 13-13.5 parts by mass of dichloromethane were added and the mixture was extracted with deionized water. The reaction mixture was taken 3 times, and the organic phase was concentrated under vacuum, precipitated in an excess of diethyl ether at -10°C, filtered, and dried under vacuum to obtain intermediate 3; 0.479 parts by mass of intermediate 3, 1.435~1.44 parts by mass of 6-caprolactone and 0.011~0.013 parts by mass of 2-ethylhexanoate tin were mixed and stirred at 120°C for 17.5~18.5h. After the reaction was completed, it was naturally cooled to room temperature, precipitated in an excess of diethyl ether at -10°C, filtered, and dried under vacuum to obtain intermediate 4; 0.404 parts by mass of intermediate 4, 0.24~0.26 parts by mass of tetrabutylammonium bromide, 0.30~0.31 parts by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene, 0.16 Add 0.17 parts by weight of (diethylamino)sulfur difluoride tetrafluoroborate to 6.6-6.65 parts by weight of dichloromethane, stir at room temperature for 48 hours, filter after the reaction, evaporate the solvent, then add 10 parts by weight of methanol aqueous solution with a volume ratio of 1:1, add 1-2 parts by weight of 6 mol / L hydrochloric acid, stir at 0°C for 3.5-4.5 hours, filter and vacuum dry to obtain intermediate 5; add 0.26-0.27 parts by weight of 1H-benzimidazole-5-methanol and 0.3 parts by weight of intermediate 5 to 11-15 parts by weight of acetonitrile, then stir at 75-85°C under nitrogen for 71-73 hours, cool naturally to room temperature after the reaction, evaporate the solvent, and then dissolve in 6.6-6.The mixture was extracted three times with deionized water in 65 parts by mass of dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, the solvent was evaporated, and the mixture was washed with methanol and dried under vacuum to obtain intermediate 6. 0.11 parts by mass of intermediate 6 was dissolved in 20 parts by mass of tetrahydrofuran, followed by the addition of 0.036-0.037 parts by mass of 1,3-propane sultone. The mixture was stirred at room temperature for 23-25 ​​hours, washed with ether, and dried under vacuum to obtain an amphiphilic polyethylene glycol-polycaprolactone block copolymer.

5. The highly dispersed graphene conductive adhesive for batteries according to claim 3, characterized in that: Butyl acetate and ethyl acetate are mixed in a mass ratio of 1:2.25 to prepare an azeotropic mixed solvent; 2.93-2.94 parts by mass of dodecafluoroheptyl methacrylate, 13.01-13.02 parts by mass of hydroxyethyl methacrylate, 9.93-9.95 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 9.21-9.22 parts by mass of isooctyl acrylate, 1.491-1.492 parts by mass of 4-nitrostyrene, 0.40-0.42 parts by mass of azoisobutyronitrile and 25 parts by mass of the azeotropic mixed solvent are mixed, and then the mixture is heated to 90° C. and added dropwise to 20 parts by mass of the azeotropic mixed solvent within 2-3 hours, and stirred for reaction for 6-8 hours to obtain an amphiphilic polyacrylate.

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