Solution-type adhesives, methods for manufacturing the same, and their use

Abstract

This application discloses a solution-type adhesive, a method for producing the same, and its use. The production of the adhesive mainly comprises the following steps: First, latex particles are obtained by emulsion polymerization of alkyl acrylate monomers, nitrile monomers, and functional monomeric acids. The latex particles have a uniform particle size and are rich in polar functional groups, and can serve as seeds for precipitation polymerization. Nitrile monomers, functional monomeric acids, and acrylamide are used as precipitation polymerization monomers, and the resulting oligomers are deposited on the seed polymer surface by hydrogen bonding and hydrophobicity, forming precipitated particles. Further neutralization with an alkaline solution yields a solution-type adhesive. The solution-type adhesive provided in this application is applied to the negative electrode of a lithium-ion battery, has high adhesive strength, low electrolyte swelling, a certain degree of processing flexibility, a simple manufacturing process, and high lot stability.

Description

Technical Field

[0001] This application relates to the technical field of polymer materials, for example, adhesives, and particularly to a solution-type adhesive used for the negative electrode of a lithium-ion battery.

Background Art

[0002] The negative electrode adhesive is an important polymer material in a lithium-ion battery, and its main role is to adhere the negative electrode active material (such as graphite, silicon carbon, silicon, etc.) and the conductive agent to the current collector. The amount of the adhesive used is not much (accounting for about 1.5 - 5% of the negative electrode material), but the quality of its performance has an important impact on the performance of the lithium battery, such as specific capacity, Coulomb efficiency, internal resistance, and cycle life.

[0003] Currently, the most widely applied negative electrode adhesive is styrene-butadiene rubber emulsion (SBR), and it is necessary to add carboxymethyl cellulose (CMC) as a thickener and a dispersant during its use process. Due to the material composition, it is determined that the content of polar functional groups such as carboxyl groups, ester groups, and nitrile groups contained in SBR / CMC is limited, and the interaction force with the negative electrode material, especially the silicon carbon negative electrode, is relatively weak. Therefore, the overall performance of the battery, especially the low-temperature performance, is becoming increasingly difficult to meet the application requirements. The polyacrylic acid-based adhesive contains a high content of polar functional groups in the polymer. Therefore, during the charge and discharge process, there are complexation and decomplexation effects between the polar functional groups and lithium ions, which can promote lithium ion conduction and reduce the internal resistance of the battery. In addition, the polyacrylic acid-based adhesive can form a hydrogen bonding effect with the surface of the silicon negative electrode, improve the dispersion and adhesion to the negative electrode material, thereby suppressing the volume expansion of the negative electrode active material during the charge and discharge process, improving the performance of the SEI film, and preventing the decomposition of the electrolyte during the electrochemical cycle process.

[0004] Chinese Patent No. 109777328 discloses an aqueous adhesive for lithium-ion battery negative electrodes obtained by emulsion polymerization of hard monomers, soft monomers, functional monomers, acidic monomers and crosslinking agents, which can maintain good liquid absorption rate, adhesive strength and charge / discharge performance. Chinese Patent Application Publication No. 111057184 discloses a method for producing an aqueous adhesive for negative electrode plates, employing a soap-free emulsion polymerization method and copolymerizing hydrophilic monomers, lipophilic monomers and functional monomers to reduce the surface tension of the aqueous adhesive, shorten the dispersion time and improve the production efficiency of negative electrode plates. Emulsion-type polyacrylic acid-based adhesives produced by the above method generally contain a relatively high proportion of hydrophilic electrolyte components, such as acrylates, and have a relatively high degree of swelling in the electrolyte, resulting in relatively high rebound of the electrode plate and relatively low high-temperature cycle performance.

[0005] Chinese Patent No. 111500228 discloses a polyacrylic acid-based adhesive for solution-type batteries. This adhesive is a polymer that simultaneously possesses hydrophilic and hydrophobic units, which precipitates in water and dissolves in water after being converted to a salt when an alkaline solution is added. In the manufactured adhesive polymer, medium- and low molecular weight polymers account for 5 wt% or less of the total polymer amount (the molecular weight of the medium- and low molecular weight polymers is 100,000 or less), and have relatively high adhesive strength. Solution-type adhesives manufactured based on precipitation polymerization have characteristics such as a large molecular weight and low oligomer residue, and when used in the negative electrode of lithium-ion batteries, they have advantages such as high adhesive strength and excellent cycleability. However, general precipitation polymerization requires that the polymerization monomers have relatively good solubility in the solvent, but the resulting copolymer has relatively low solubility in the solvent, and can precipitate and nucleate after the chain length reaches a critical value, producing a precipitate. Therefore, there are relatively large limitations on the types and amounts of polymerization monomers that can be added. Commonly used copolymer monomers, such as acrylic acid, acrylamide, and acrylonitrile, make it difficult to achieve a balance between adhesive strength and electrode flexibility, and further improvements in product performance are necessary. Moreover, factors such as stirring and temperature easily affect the nucleation process of precipitation polymerization, which causes large fluctuations in the molecular weight of the final product, posing a significant challenge to product lot stability. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Specification of Chinese Patent No. 109777328 [Patent Document 2] Chinese Patent Application Publication No. 111057184 Specification [Patent Document 3] Chinese Patent No. 111500228 Specification [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0008] To solve the above technical problems, this application provides a solution-type adhesive, a method for producing the same, and its use. The solution-type adhesive is produced using an aqueous-phase seed precipitation polymerization process. First, latex particles are obtained by emulsion polymerization of alkyl acrylate monomers, nitrile monomers, and functional monomeric acids. The latex particles have a uniform particle size and are rich in polar functional groups, making them suitable as seeds for precipitation polymerization. Nitrile monomers, functional monomeric acids, and acrylamide are used as precipitation polymerization monomers, and the oligomers produced by the reaction are deposited on the seed polymer surface by hydrogen bonding and hydrophobicity, ultimately forming precipitated particles. By changing the type and amount of seeds added, the morphology and size of the precipitated polymer particles can be adjusted, improving the stability of the precipitation polymerization process. Furthermore, the seeds can impart multifunctionality to the product; for example, using copolymer particles with a low vitrification transition temperature as seeds can improve the flexibility of the negative electrode adhesive. [Means for solving the problem]

[0009] The technical proposal adopted in this application is as follows:

[0010] According to a first aspect, this application provides a method for manufacturing a solution-type adhesive, 1) Add the emulsifier and water to the reaction vessel, start stirring, and heat to the set temperature. 2) Adding an emulsifier, water, alkyl acrylate monomer, nitrile monomer, and functional monomer acid to kettle 1 to perform preliminary emulsification and obtain a seed preliminary emulsified liquid, 3) Add deionized water, nitrile monomer, functional monomer acid, and amide monomer to the kettle 2 and mix uniformly to obtain a shell layer monomer mixture; 4) The seed pre-emulsifier and initiator solution are added dropwise to the reaction vessel synchronously for 0.5 to 1 hour, and after the addition is complete, the mixture is kept warm for 15 to 30 minutes. 5) After adjusting the temperature inside the reaction vessel to the set temperature, the shell layer monomer mixture and initiator solution are added dropwise simultaneously for 2-4 hours. After the addition is complete, the temperature is maintained for 1-2 hours. 6) After the temperature of the reaction system has decreased to room temperature, the polymer precipitate is collected and dispersed in deionized water. 7) The dispersion obtained in step 6) is heated to 70-90°C, an alkaline solution is added to adjust the pH to 7-8, the temperature is maintained for 1-2 hours after the pH stabilizes, and then the temperature is lowered and the mixture is discharged to obtain a solution-type adhesive.

[0011] In one embodiment, the seed pre-emulsified liquid contains, by mass ratio of raw materials, 0.1-0.9% emulsifier, 20-30% water, 35-50% alkyl acrylate monomer, 10-20% nitrile monomer, and 15-25% functional monomer acid.

[0012] In one embodiment, the shell layer monomer mixture contains, by mass ratio of raw materials, 20-30% water, 10-40% amide monomer, 20-50% nitrile monomer, and 15-30% functional monomer acid.

[0013] In one embodiment, the mass ratio of monomers in the seed pre-emulsified solution (including alkyl acrylate monomers, nitrile monomers, and functional monomeric acids) to monomers in the shell layer monomer mixture (including amide monomers, nitrile monomers, and functional monomeric acids) is (2-30):(70-95).

[0014] In one embodiment, the alkyl acrylate monomer is at least one of ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, and dodecyl (meth)acrylate.

[0015] In one embodiment, the nitrile monomer is selected from acrylonitrile and / or methacrylonitrile.

[0016] In one embodiment, the functional monomeric acid is at least one selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, and is selectively methacrylic acid.

[0017] In one embodiment, the amide monomer is selected from at least one of acrylamide, N-methacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, 2-methacrylamide, N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, and N-hydroxypropylacrylamide, and is selectively an acrylamide.

[0018] In one embodiment, the emulsifier is selected from surfactants containing at least one ethylenically unsaturated functional group, and is selectively at least one selected from allyloxyisomer alcohol ether sulfate ammonium salt, allyl polyether phosphate, special thiol sulfate containing an allyl group, allyl polyoxyalkylene ether sulfate, allyl alkyl succinate sulfonic acid salt, allyl ether hydroxypropane sulfonic acid salt, and polyoxyethylene styrene phenyl ether sulfate salt. Suitable examples include, but are not limited to, ADEKA's SR-10 (allyloxyisomer alcohol ether sulfate ammonium salt) and Shanghai Zhongcheng Fine Chemical's V-100P (allyl polyether phosphate emulsifier).

[0019] In one embodiment, the initiator is one or more of an organic peroxide initiator, an inorganic peroxide initiator, and a redox initiator, and is selectively at least one selected from ammonium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate and isoascorbic acid, hydrogen peroxide and sodium bisulfite.

[0020] In one embodiment, the total amount of the initiator used accounts for 0.01 to 2% of the sum of the masses of the alkyl acrylate monomer, the functional monomer acid, the nitrile-based monomer, and the amide-based monomer, and is selectively 0.1 to 0.5%.

[0021] In one embodiment, the neutralizing agent is one or more of inorganic alkali metal hydroxides and inorganic metal carbonates, and is selectively selected from one or more of sodium hydroxide, lithium hydroxide, and sodium carbonate.

[0022] In one embodiment, the amount of water added during the manufacturing process is based on the solid content of the polymerization product reaching 10 to 40%, selectively 15 to 30%, and the solid content of the solution-type adhesive reaches 1 to 15%, selectively 3 to 8%.

[0023] In one embodiment, the set temperature in step 1) is 75 to 90 °C.

[0024] In one embodiment, the set temperature in step 5) is 25 to 80 °C.

[0025] According to a second aspect, the present application provides a solution-type adhesive manufactured by the method described in the first aspect, where the solid content of the solution-type adhesive is 1 to 15%.

[0026] In one embodiment, the solid content of the solution-type adhesive is 3 to 8%.

[0027] According to a third aspect, the present application further provides the application of the solution-type adhesive manufactured by the manufacturing method described above in a lithium-ion battery negative electrode plate. The solution-type adhesive is applied to negative electrode active materials such as artificial graphite, natural graphite, hard carbon, silicon, and silicon carbon, and a lithium-ion battery can be obtained by manufacturing and assembling a negative electrode plate using a method known in the art.

Advantages of the Invention

[0028] This application has the following beneficial effects.

[0029] (1) This application employs a seed precipitation polymerization process, in which latex particles rich in polar functional groups are first obtained by emulsion polymerization, and these are then used as seeds. Nitrile monomers, carboxylic acid monomers, and amide monomers are copolymerized monomers, and the oligomers produced by the reaction are deposited on the surface of the polymer seeds by hydrogen bonding and hydrophobicity, ultimately forming precipitated particles. The number and particle size of the seeds are controllable, improving the stability of the precipitation polymerization process.

[0030] (2) The solution-type adhesive of this application comprises a seed copolymer obtained by emulsion polymerization and a shell layer copolymer obtained by precipitation polymerization. The seed copolymer contains a large amount of acrylate monomers, has good electrolyte affinity, can reduce the internal resistance of lithium-ion batteries, and has a relatively low vitrification transition temperature, which can improve the flexibility of the electrode plates. On the other hand, the shell layer copolymer obtained by precipitation polymerization has a large molecular weight, is rich in polar functional groups, can improve adhesive strength, and can suppress the repulsion of the electrode plates.

[0031] (3) The solution-type adhesive of this application is rich in carboxyl groups, and the presence of carboxyl groups improves the interaction between the polymer and the negative electrode active material, conductive agent and dispersant, which is advantageous for stable dispersion of the slurry. Furthermore, a large amount of carboxyl groups gives the polymer a relatively strong thickening effect, which can reduce the amount of thickener added during the slurry manufacturing process.

[0032] (4) The emulsifier used in the manufacturing process of the seeds of this application is a surfactant containing at least one ethylenically unsaturated functional group, which is involved in polymerization and can be grafted onto the polymer, providing good colloidal stability to the latex particles, and at the same time reducing the residue of small molecular substances, thereby effectively improving the electrochemical stability of the lithium-ion battery.

[0033] (5) The solution-type adhesive of this application is rich in nitrile groups and amide groups, and can form relatively strong hydrogen bonds between copolymers, thereby improving the force between the adhesive and the negative electrode active material and current collector. Furthermore, complexing and decomplexing effects exist between polar functional groups and lithium ions, which can promote lithium ion conduction and reduce the internal resistance of the battery.

[0034] Other aspects can become clear after reading and understanding the detailed description. [Modes for carrying out the invention]

[0035] The present application will be further described below with reference to specific embodiments. The embodiments described herein are for illustrative purposes only and do not limit the scope of this application.

[0036] The main raw materials and their origins in the examples and comparative examples are shown in Table 1.

[0037] [Table 1]

[0038] Unless otherwise specified, all other chemical reagents used in each example are purchased from the market and are of analytical purity.

[0039] The test method employed in the following embodiments of this application is as follows:

[0040] Slurry dispersibility evaluation: Observe the appearance of the manufactured negative electrode plate after firing, including the condition of cracks, curls, dark spots, and depressions in the electrode plate.

[0041] Electrolyte swelling evaluation: The adhesive emulsion is dried in an oven at 50°C to form a film, and a film with mass M1 is taken. The film is immersed in the electrolyte and kept warm in an oven at 60°C for 48 hours. The electrolyte on the surface of the film is wiped off with filter paper and weighed to obtain M2. Degree of electrolyte swelling = (M2 - M1) / M1 × 100%.

[0042] Peel strength evaluation: According to the American Society for Testing and Materials (ASTM) standard D3330, the equipment used for testing peel strength is a computer-controlled tensile testing machine (KJ-1065).

[0043] Unless otherwise specified, the number of "parts" of raw materials in each example refers to "parts by mass." [Examples]

[0044] Example 1 (1) Add 0.03 parts SR-10 and 1400 parts deionized water to the reaction vessel, start stirring and set the rotation speed to 200 r / min, blow in nitrogen gas to remove oxygen gas and heat to 85°C, (2) Add 0.2 parts SR-10, 8 parts deionized water, 10 parts EHA, 5 parts AN, and 5 parts MAA in order to the pre-emulsification vessel 1 and start stirring to obtain a seed pre-emulsified liquid. (3) Add 90 parts deionized water, 60 parts AA, 60 parts AM, and 90 parts AN to the mixing vessel 2 and start stirring to obtain a shell layer monomer mixture. (4) Add the seed pre-emulsified solution and the APS solution (dissolve 0.3 parts APS in 10 parts deionized water) dropwise simultaneously, controlling the dropwise time to 1 hour, and keep the temperature at bay for 30 minutes after the dropwise addition is complete. (5) Adjust the temperature inside the reaction vessel to 50°C, and after the temperature has stabilized, begin the synchronous dropwise addition of the shell layer monomer mixture and the pre-prepared initiator solution (the oxidizing agent is 0.3 parts APS dissolved in 40 parts deionized water, and the reducing agent is 0.15 parts IAA isoascorbic acid dissolved in 40 parts deionized water), control the addition time to 3 hours, and maintain the temperature for 2 hours after the addition is complete. (6) After the temperature in the reaction vessel has decreased to room temperature, the polymer precipitate is collected by filtration and dispersed in 4000 parts of deionized water. (7) The precipitate particle dispersion was heated to 80°C, and after the temperature stabilized, a lithium hydroxide solution (mass concentration 15%) was added as a neutralizing agent to adjust the pH to approximately 8.0. After the pH stabilized, the mixture was kept warm for 1.5 hours, and after it cooled to room temperature, it was filtered and drained to obtain a solution-type adhesive.

[0045] Examples 2-8 An emulsion-type adhesive was manufactured using almost the same method as in Example 1, the only difference being the selection of the type and amount of each raw material used, based on Table 2.

[0046] Example 9 A solution-type adhesive was manufactured using the method of Example 1, with the following differences being the adjustments to the raw materials and operating steps: the initiator used in the raw materials was changed from APS to potassium persulfate; the temperature of the reaction vessel in operating step (1) was changed to 75°C; the dropping time in step (4) was 30 minutes and the holding time was 15 minutes; the dropping time of the shell layer monomer mixture and initiator solution in step (5) was controlled to 2 hours and the holding time to 1 hour; and the neutralization temperature in step (7) was controlled to 70°C, and the temperature was kept at 2 hours after the pH stabilized.

[0047] Example 10 A solution-type adhesive was manufactured using the method and raw materials of Example 1, with the following differences being the adjustments to the raw materials and operating steps: the initiator used in the raw materials was changed from APS to sodium persulfate; the temperature of the reaction vessel in operating step (1) was changed to 90°C; the dropping time in step (4) was 45 minutes and the holding time was 20 minutes; the dropping time of the shell layer monomer mixture and initiator solution in step (5) was controlled to 4 hours and the holding time to 1.5 hours; and the neutralization temperature in step (7) was controlled to 90°C, and the temperature was kept at 1 hour after the pH stabilized.

[0048] Comparative Example 1 Compared to the method of Example 1, steps (1), (2), and (4) were omitted, and an aqueous shell layer monomer solution was prepared from step (3), and then the hard monomer adhesive for the shell layer was directly manufactured from step (5).

[0049] Comparative Example 2 Compared to the method of Example 1, only steps (1), (2), and (4) were performed, and no hard monomer was added to the shell layer, resulting in an emulsion-type adhesive.

[0050] Comparative Example 3 The difference compared to the method in Example 1 is that SDS is used instead of SR-10.

[0051] The emulsion-type adhesives produced in the examples and comparative examples were applied to the manufacture of the negative electrode plate of a lithium-ion battery, and the specific steps are as follows.

[0052] (1) Preparation of slurry: 0.5 parts sodium carboxymethylcellulose (CMC-Na) was added to 100 parts deionized water at room temperature and stirred at high speed for about 20 minutes. Then, 1 part carbon black conductive agent (SuperP), 96.5 parts negative electrode active material (graphite), and 2 parts solution-type adhesive were added. After adding each material, the mixture was stirred at high speed for about 10 minutes to ensure uniform mixing. The mixture was then filtered through a 100-mesh filter to obtain the negative electrode slurry.

[0053] (2) Electrode coating: The manufactured negative electrode slurry was uniformly coated onto the current collector (copper foil) to a coating thickness of 100 μm. After drying in an oven at 80°C for 5 minutes, the plates were roll-pressed at room temperature using a roll press to obtain negative electrode plates with a thickness of 70 μm.

[0054] An electrolyte swelling test was performed on each emulsion-type adhesive manufactured, and the slurry dispersibility, peel strength, and electrochemical performance of the manufactured negative electrode plates were evaluated. The test results are shown in Table 3.

[0055] As can be seen from the performance results in Table 3, compared to Comparative Example 1, the slurry produced using the adhesives obtained in Examples 1 to 10 had relatively good dispersion performance, and the electrode plates had relatively good flexibility. This is because the copolymer produced by emulsion polymerization in the core layer is rich in acrylate monomers, and its vitrification transfer temperature is relatively low, which is advantageous for improving flexibility. However, cracking occurred in the adhesive produced without using a seed emulsion, indicating that there are problems with its processability. Compared to Comparative Example 2, the film produced using the adhesives obtained in Examples 1 to 10 had a relatively low degree of electrolyte swelling, and the peel strength of the produced electrode plates was greater. This is because the copolymer produced by precipitation polymerization in the shell layer has a large molecular weight and is rich in polar functional groups, allowing for good hydrogen bonding between molecules, resulting in good electrolyte resistance and high peel strength. Compared to Comparative Example 3, the reactive emulsifier used in the example has the characteristics of high adhesive strength and low electrolyte swelling. This is because the SDS emulsifier becomes free in the adhesive, immerses in the electrolyte and moves, making it difficult to maintain the shape of the latex particles and reducing the adhesive strength.

[0056] [Table 2]

[0057] [Table 3]

Claims

1. A method for manufacturing a solution-type adhesive, 1) Add the emulsifier and water to the reaction vessel, start stirring, and heat to the set temperature. 2) Adding an emulsifier, water, alkyl acrylate monomer, nitrile monomer, and functional monomer acid to the kettle 1 to perform preliminary emulsification and obtain a seed preliminary emulsified liquid, 3) Add deionized water, nitrile monomer, functional monomer acid, and amide monomer to the kettle 2 and mix uniformly to obtain a shell layer monomer mixture; 4) The seed pre-emulsifier and initiator solution described in step 2) are added dropwise to the reaction vessel synchronously for 0.5 to 1 hour, and the temperature is maintained for 15 to 30 minutes after the dropwise addition is complete. 5) After adjusting the temperature inside the reaction vessel to the set temperature, the shell layer monomer mixture and initiator solution described in step 3) are added dropwise simultaneously for 2 to 4 hours, and after the addition is complete, the temperature is maintained for 1 to 2 hours. 6) After the temperature of the reaction system has decreased to room temperature, the polymer precipitate is collected and dispersed in deionized water. A method for producing a solution-type adhesive, comprising the steps of: 7) raising the temperature of the dispersion obtained in step 6) to 70-90°C, adding an alkaline solution to adjust the pH to 7-8, maintaining the temperature for 1-2 hours after the pH has stabilized, then lowering the temperature and discharging the solution to obtain a solution-type adhesive.

2. The method according to claim 1, wherein the seed pre-emulsified liquid contains, by mass ratio of raw materials, 0.1 to 0.9% emulsifier, 20 to 30% water, 35 to 50% alkyl acrylate monomer, 10 to 20% nitrile monomer, and 15 to 25% functional monomer acid.

3. The method according to any one of claims 1 or 2, wherein the shell layer monomer mixture comprises, by mass ratio of raw materials, 20-30% water, 10-40% amide monomer, 20-50% nitrile monomer, and 15-30% functional monomer acid.

4. The method according to any one of claims 1 to 3, wherein the mass ratio of monomers (including alkyl acrylate monomers, nitrile monomers, and functional monomeric acids) in the seed pre-emulsified solution to monomers (including amide monomers, nitrile monomers, and functional monomeric acids) in the shell layer monomer mixture is (2-30):(70-95).

5. The method according to any one of claims 1 to 4, wherein the nitrile monomer is selected from acrylonitrile and / or methacrylonitrile.

6. The method according to any one of claims 1 to 5, wherein the functional monomeric acid is at least one selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.

7. The method according to any one of claims 1 to 6, wherein the amide monomer is selected from at least one of acrylamide, N-methacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, 2-methacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, and N-hydroxypropylacrylamide.

8. The method according to any one of claims 1 to 7, wherein the emulsifier is selected from surfactants containing at least one ethylenically unsaturated functional group.

9. The method according to claim 8, wherein the emulsifier is at least one selected from allyloxyisomer alcohol ether sulfate ammonium salt, allyl polyether phosphate, special thiol sulfate containing an allyl group, allyl polyoxyalkylene ether sulfate, allyl alkyl succinate sulfonic acid salt, allyl ether hydroxypropane sulfonic acid salt, and polyoxyethylene styrene phenyl ether sulfate salt.

10. The method according to claim 9, wherein the emulsifier is selected from ADEKA's SR-10 and / or Shanghai Zhongcheng Fine Chemicals' V-100P.

11. A solution-type adhesive manufactured by the method according to any one of claims 1 to 10, wherein the solid content of the solution-type adhesive is 1 to 15%.

12. The solution-type adhesive according to claim 11, wherein the solid content of the solution-type adhesive is 3 to 8%.

13. Application of the solution-type adhesive according to claim 11 or 12 in a lithium-ion battery anode sheet.

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