CN116314805B - Negative electrode material binder of lithium ion battery - Google Patents
Negative electrode material binder of lithium ion battery Download PDFInfo
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- CN116314805B CN116314805B CN202310249919.3A CN202310249919A CN116314805B CN 116314805 B CN116314805 B CN 116314805B CN 202310249919 A CN202310249919 A CN 202310249919A CN 116314805 B CN116314805 B CN 116314805B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本申请涉及粘合剂技术领域，具体提供一种锂离子电池负极材料粘结剂，由VAE乳液和聚丙烯酸衍生物乳液按重量比40:1‑1:1混合而成；聚丙烯酸衍生物乳液由亲水性丙烯酸类单体和疏水性丙烯酸类单体按重量比3:7‑9:1在水相体系中聚合反应获得。本申请的锂离子电池负极材料粘接剂兼具了VAE的柔韧性和聚丙烯酸衍生物的分散性、粘接性，共同作为锂离子电池负极材料的粘结剂，具有较好的分散性、粘接性和柔韧性；所得到的负极极片组装的纽扣电池具有更高的库伦效率以及更低的交流阻抗。The present application relates to the technical field of adhesives, and specifically provides a binder for negative electrode materials of lithium-ion batteries, which is prepared by mixing VAE emulsion and polyacrylic acid derivative emulsion at a weight ratio of 40:1-1:1; the polyacrylic acid derivative emulsion is obtained by polymerization reaction of hydrophilic acrylic monomer and hydrophobic acrylic monomer at a weight ratio of 3:7-9:1 in an aqueous phase system. The negative electrode material binder of lithium-ion batteries of the present application combines the flexibility of VAE and the dispersibility and adhesion of polyacrylic acid derivatives, and together as a binder for negative electrode materials of lithium-ion batteries, it has good dispersibility, adhesion and flexibility; the button battery assembled with the obtained negative electrode sheet has higher coulomb efficiency and lower AC impedance.
Description
Technical Field
The application relates to the technical field of binders, in particular to a lithium ion battery negative electrode material binder.
Background
The negative electrode material of the lithium ion battery is mainly a graphite material, and because the surface shape of the graphite material is complex and difficult to disperse, the high requirement is put forward on the binder, so that the wet dispersibility of the graphite material is required to be good, the adhesion to a current collector is required to be good, the flexibility is required to be good, and the cracking, the cracking or the falling of the electrode during the curling is avoided.
Thus, the properties of the binder have a significant impact on the performance of the lithium ion battery.
Disclosure of Invention
In order to solve the technical problems, the application provides a preparation method of a lithium ion battery negative electrode material binder and the lithium ion battery negative electrode material binder.
The application adopts the following technical scheme:
A lithium ion battery negative electrode material binder is prepared by mixing VAE emulsion and polyacrylic acid derivative emulsion according to a weight ratio of 40:1-1:10;
The acrylic acid derivative emulsion is obtained by polymerization reaction of hydrophilic acrylic acid monomers and hydrophobic acrylic acid monomers in a water phase system according to the weight ratio of 3:7-9:1.
Preferably, the solid content of the binder of the anode material of the lithium ion battery is 10-50%.
Preferably, the VAE emulsion has a solids content of 40-70%.
Preferably, the weight ratio of the VAE emulsion to the acrylic acid derivative emulsion is 10:1-1:10.
Preferably, the chemical formula of the hydrophilic acrylic monomer is CH 2＝CR1R2, wherein R 1 is selected from H or C1-C4 alkyl, R 2 is selected from -CONH2、-CONHCH3、-CONHCH2CH3、-CON(CH3)2、-CON(CH2CH3)2、-CONHCH2OH、-CONHCH2CH2OH、-COOCH2CH2OH、-COOCH2CH2CH2OH、-COOCH2CHCH3OH、-COOCH2CH2CH2CH2OH、-COO(CH2CH2O)aH and-COO (one or more of CH 2)bPO3 H), and/or one or more of organic structures containing-COOH, -COOM, - (C 6H5)COOM、-SO3 M and- (C 6H5)SO3 M functional groups), a=1-40, b=1-12, and M is selected from one or more of Li +、Na+ and K +.
Preferably, the chemical formula of the hydrophobic acrylic monomer is CH 2＝CR3R4, wherein R 3 is selected from H or C1-C4 alkyl, R 4 is selected from one or more of-COOC nH2n+1 and-C mH2m CN, n=1-40, and m=0-6.
Preferably, the weight ratio of the hydrophilic acrylic monomer to the hydrophobic acrylic monomer is 5:5 to 9:1.
Preferably, the polymerization reaction is carried out by adding the hydrophilic acrylic monomer and the hydrophobic acrylic monomer together into a reaction system.
Preferably, the polymerization reaction is carried out by adding the hydrophilic acrylic monomer into a reaction system for polymerization reaction, and then adding the hydrophobic acrylic monomer for polymerization reaction.
Preferably, the polymerization reaction is to add 30-70% by weight of the hydrophilic acrylic monomer to perform polymerization reaction, then add 20-80% by weight of the hydrophobic acrylic monomer to perform polymerization reaction, then add the rest of the hydrophilic acrylic monomer to perform polymerization reaction, and then add the rest of the hydrophobic acrylic monomer.
In summary, the application has the following beneficial effects:
The VAE emulsion and the polyacrylic acid derivative emulsion with hydrophilic and hydrophobic properties are adopted to blend, the VAE emulsion has the flexibility of the VAE, the dispersibility and the adhesiveness of the polyacrylic acid derivative, and the obtained adhesive is suitable for serving as an adhesive of a lithium ion battery anode material, and has good dispersibility, adhesiveness and flexibility.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
The application provides a lithium ion battery cathode material binder which is formed by mixing VAE emulsion and polyacrylic acid derivative emulsion according to the weight ratio of 40:1-1:10;
The polyacrylic acid derivative emulsion is obtained by the polymerization reaction of hydrophilic acrylic acid monomers and hydrophobic acrylic acid monomers in a water phase system according to the weight ratio of 3:7-9:1.
The VAE emulsion is emulsion of vinyl acetate/ethylene copolymer, has good flexibility after the VAE emulsion is formed into a film, and combines the high dispersibility and the adhesive force of the polyacrylic acid derivative emulsion, when the adhesive for the negative electrode material of the lithium ion battery is used for dispersing and bonding the negative electrode material, the adhesive has good dispersibility, strong adhesive property and good flexibility, and has proper electrolyte swelling rate, so that alternating current impedance can be reduced.
In a preferred embodiment of the application, the solid content of the binder of the anode material of the lithium ion battery is 10-50%. The solid content testing method comprises accurately weighing an adhesive sample in an open weighing bottle, putting the adhesive sample in a 120 ℃ oven for baking for 2 hours, taking out the adhesive sample, transferring the adhesive sample into a dryer for cooling, and weighing the weighing bottle again. Solid content= (W 2-W1)/W0×100％,W0 is the initial weight of the adhesive sample, W 1 is the net weight of the weighing flask, and W 2 is the weight of the weighing flask after baking.
In a preferred embodiment of the application, the VAE emulsion has a solids content of 40-70%. The VAE emulsion generally contains protective colloid such as polyvinyl alcohol and/or surfactant, can also play a role in dispersing the obtained adhesive, and combines the hydrophilic and hydrophobic properties of the polyacrylic acid derivative chain segments, so that the obtained adhesive has better stability.
In a preferred embodiment of the application, the weight ratio of VAE emulsion to polyacrylic acid derivative emulsion is 10:1-1:10. The weight ratio of the VAE emulsion to the polyacrylic acid derivative emulsion is in the range, and the comprehensive performance of the adhesive is better. For example, the weight ratio may be 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and the like.
In a preferred embodiment of the present application, the hydrophilic acrylic monomer has a chemical formula of CH 2＝CR1R2, wherein R 1 is selected from H or C1-C4 alkyl, R 2 is selected from -CONH2、-CONHCH3、-CONHCH2CH3、-CON(CH3)2、-CON(CH2CH3)2、-CONHCH2OH、-CONHCH2CH2OH、-COOCH2CH2OH、-COOCH2CH2CH2OH、-COOCH2CHCH3OH、-COOCH2CH2CH2CH2OH、-COO(CH2CH2O)aH and-COO (one or more of CH 2)bPO3 H, and/or one or more of organic structures containing-COOH, -COOM, - (C 6H5)COOM、-SO3 M, and- (C 6H5)SO3 M functional groups), a=1-40, b=1-12, and M is selected from one or more of Li +、Na+ and K +.
In a preferred embodiment of the present application, the hydrophobic olefinic acid monomer has the chemical formula CH 2＝CR3R4, wherein R 3 is selected from H or C1-C4 alkyl, R 4 is selected from one or more of-COOC nH2n+1 and-C mH2m CN, n=1-40, and m=0-6. For example, the hydrophobic acrylic monomer may be methyl methacrylate, butyl acrylate, ethyl acrylate, acrylonitrile, octyl acrylate, isooctyl acrylate, 3-butenenitrile, and the like.
In a preferred embodiment of the present application, the weight ratio of hydrophilic acrylic monomer to hydrophobic acrylic monomer is from 5:5 to 9:1. Because the VAE is a relatively hydrophobic polymer, the hydrophilic and hydrophobic acrylic monomers are regulated, so that the adhesive has balanced hydrophilic and hydrophobic properties, and the adhesive has good comprehensive performance.
In a preferred embodiment of the present application, the polymerization is carried out by adding a hydrophilic acrylic monomer and a hydrophobic acrylic monomer together to the reaction system. The hydrophilic acrylic monomer and the hydrophobic acrylic monomer are added into a reaction system together for polymerization reaction, and the polymer in the obtained polyacrylic acid derivative emulsion is a random copolymer.
In a preferred embodiment of the present application, the polymerization is performed by adding a hydrophilic acrylic monomer to the reaction system to perform polymerization and then adding a hydrophobic acrylic monomer to perform polymerization. Firstly adding hydrophilic acrylic monomers into a reaction system for polymerization reaction, then adding hydrophobic acrylic monomers for polymerization reaction, firstly preparing hydrophilic acrylic derivative chain segments, and then grafting hydrophobic acrylic derivative chain segments to obtain the hydrophilic-hydrophobic block copolymer.
In a preferred embodiment of the present application, the polymerization is performed by adding 30 to 70% by weight of the hydrophilic acrylic monomer to perform polymerization, then adding 20 to 80% by weight of the hydrophobic acrylic monomer to perform polymerization, then adding the remaining hydrophilic acrylic monomer to perform polymerization, and then adding the remaining hydrophobic acrylic monomer. Adding a part of hydrophilic acrylic monomer and a proper amount of initiator, performing polymerization reaction to form a hydrophilic chain segment, adding a part of hydrophobic acrylic monomer and a proper amount of initiator, grafting the hydrophilic chain segment to the hydrophobic chain segment, adding the rest of hydrophilic acrylic monomer and a proper amount of initiator, continuously grafting the hydrophilic chain segment, finally adding the rest of hydrophobic acrylic monomer, continuously grafting the hydrophobic chain segment, and forming a multi-block copolymer structure similar to the hydrophilic chain segment, the hydrophobic chain segment, the hydrophilic chain segment and the hydrophobic chain segment, wherein after being mixed with a VAE emulsion, the dispersion of the anode material is better.
The technical scheme of the application is described in detail below with reference to examples and comparative examples. Unless otherwise indicated, the parts in the examples and comparative examples below are parts by weight.
Preparation example 1
15 Parts of acrylamide, 5 parts of hydroxyethyl acrylate, 8 parts of butyl acrylate, 12 parts of methyl acrylate and 130 parts of water are added into a reaction vessel, the temperature is raised to 65 ℃,4 parts of ammonium persulfate solution with the concentration of 10wt% is dropwise added, the temperature of the reaction system is maintained at 70+/-2 ℃, the ammonium persulfate solution is dropwise added for 3 hours, the constant-temperature reaction is continued for 2 hours, the temperature is reduced to below 40 ℃, the pH is regulated to 6.0-6.5, and the solid content is regulated to 20+/-1% by adding water, so that the polyacrylic acid derivative emulsion is obtained.
Preparation example 2
Adding 20 parts of acrylamide, 8 parts of acrylic acid, 6 parts of butyl acrylate, 6 parts of acrylonitrile and 180 parts of water into a reaction container, heating to 65 ℃, dropwise adding 4 parts of ammonium persulfate solution with the concentration of 10wt%, maintaining the temperature of a reaction system at 70+/-2 ℃, dropwise adding the ammonium persulfate solution for 3 hours, continuing to perform constant-temperature reaction for 3 hours, cooling to below 40 ℃, adjusting the pH to 6.0-6.5, and adding water to adjust the solid content to 15+/-1%, thereby obtaining the polyacrylic acid derivative emulsion.
Preparation example 3
Adding 20 parts of acrylamide, 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate, 3 parts of butyl acrylate, 3 parts of acrylonitrile and 200 parts of water into a reaction container, heating to 65 ℃, dropwise adding 4 parts of ammonium persulfate solution with the concentration of 10wt%, maintaining the temperature of a reaction system at 70+/-2 ℃, continuously keeping the constant temperature for 3 hours after the ammonium persulfate solution is dropwise added, cooling to below 40 ℃, adjusting the pH to 6.0-6.5, and adding water to adjust the solid content to 15+/-1%, thereby obtaining the polyacrylic acid derivative emulsion.
Preparation example 4
Adding 20 parts of acrylamide, 8 parts of acrylic acid and 100 parts of water into a reaction vessel, heating to 65 ℃, dropwise adding 3 parts of ammonium persulfate solution with the concentration of 10wt%, maintaining the temperature of a reaction system at 70+/-2 ℃, dropwise adding the ammonium persulfate solution for 2 hours, continuing to perform constant-temperature reaction for 3 hours, adding 6 parts of butyl acrylate and 6 parts of acrylonitrile, dropwise adding 1 part of ammonium persulfate solution with the concentration of 10wt%, dropwise adding the ammonium persulfate solution for 2 hours, continuing to perform constant-temperature reaction for 3 hours, cooling to below 40 ℃, adjusting the pH to 6.0-6.5, and adding water to adjust the solid content to 25+/-1%, thereby obtaining the polyacrylic acid derivative emulsion.
Preparation example 5
20 Parts of acrylamide and 8 parts of acrylic acid are mixed to form a hydrophilic monomer, and 6 parts of butyl acrylate and 6 parts of acrylonitrile are mixed to form a hydrophobic monomer.
14 Parts of hydrophilic monomer and 100 parts of water are added into a reaction vessel, the temperature is raised to 65 ℃,2 parts of ammonium persulfate solution with the concentration of 10wt% is dripped, the temperature of a reaction system is maintained to be 70+/-2 ℃, the ammonium persulfate solution is dripped for 2 hours, the constant temperature reaction is continued for 3 hours, 6 parts of hydrophobic monomer is added, 1 part of ammonium persulfate solution with the concentration of 10wt% is dripped, the constant temperature reaction is continued for 3 hours, the rest 14 parts of hydrophilic monomer is added, 0.5 part of ammonium persulfate solution with the concentration of 10wt% is dripped, the constant temperature reaction is continued for 0.5 hours, the rest 6 parts of hydrophobic monomer is added, the ammonium persulfate solution with the concentration of 10wt% is dripped, the constant temperature reaction is continued for 5 hours, the temperature is reduced to be below 40 ℃, the pH is regulated to be 6.0-6.5, and the solid content is regulated to 25+/-1% by adding water, so as to obtain the polyacrylic acid derivative emulsion.
The VAE emulsions in examples 1-5 below were derived from Dalian chemistry DA-102, and the VAE emulsions in examples 6-10 and comparative examples 1-4 were derived from broad-spectrum chemical GW-706.
Example 1
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 1 were mixed at a weight ratio of 10:1, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 2
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 2 were mixed at a weight ratio of 3:1, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 3
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 3 were mixed in a weight ratio of 1:1, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 4
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 4 were mixed in a weight ratio of 1:3, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 5
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 5 were mixed in a weight ratio of 1:5, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 6
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 1 were mixed in a weight ratio of 1:3, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 7
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 2 were mixed in a weight ratio of 1:3, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 8
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 3 were mixed in a weight ratio of 1:3, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 9
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 4 were mixed in a weight ratio of 1:3, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Example 10
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 5 were mixed in a weight ratio of 1:3, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Comparative example 1
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 2 were mixed at a weight ratio of 45:1, and water was added to adjust the solid content to 20.+ -. 1%, thereby obtaining an adhesive.
Comparative example 2
The VAE emulsion and the polyacrylic acid derivative emulsion of preparation example 2 were mixed in a weight ratio of 1:15, and water was added to adjust the solid content to 15.+ -. 1%, thereby obtaining an adhesive.
Comparative example 3
The adhesive is polyacrylic acid derivative emulsion of preparation example 2, and water is added to adjust the solid content to 15+/-1%.
Comparative example 4
In preparation example 2, acrylamide was adjusted from 20 parts to 5.7 parts, acrylic acid was adjusted from 8 parts to 2.3 parts, butyl acrylate was adjusted from 6 parts to 16 parts, acrylonitrile was adjusted from 6 parts to 16 parts, and the remaining steps were kept unchanged. The acrylic acid derivative emulsion was unstable and precipitated after 2 days of standing.
Preparation of negative electrode slurry and pole piece
(1) Mixing the binder to be tested with 50% water, dispersing for 12 min at 3m/s, adding SP conductive carbon black, stirring for 10 min at 0.5m/s, stirring for 120 min at 6m/s, adjusting the rotation speed to 1m/s, adding 50% of negative electrode material (fir FSN-1), dispersing for 20 min, adding the rest 50% of negative electrode material and the rest 50% of water, dispersing for 30min, and stirring for 120 min at 6 m/s. After the dispersion is finished, the viscosity is regulated to be between 2000 and 3500 mPa.s, and a 150-mesh filter screen is used for filtering to finish discharging. Placing copper foil on a coating machine, adjusting the scale of a scraper of a wet film preparation device, uniformly pouring filtered slurry, sending the slurry into an environment of 100 ℃ for blowing and baking until the slurry is dried, and cutting a pole piece with the specification of 12.5cm multiplied by 5cm and the single-sided surface density of 100-110g/m 2.
And (3) pole piece stripping force test, namely sending the cut pole piece into a 35% RH constant temperature chamber for 30 minutes. The coating layer faces outwards, the copper foil faces inwards to attach two pole pieces, the pole pieces are sent into an electric roller press to be rolled to 1.6g/cm 3, the pole pieces are placed for 30 minutes after being rolled, five stainless steel plates with the specification of 12.5cm multiplied by 5cm are selected, double faced adhesive tapes with corresponding specifications are attached to the stainless steel plates, the pole pieces are attached to the double faced adhesive tapes in a mode that the coating layer faces downwards, a piece of masking paper tape with the width of 2.5cm is attached to the copper foil, and the stripping force of the pole pieces is tested by an electronic stripper after the pole piece steel plates are rolled for one round by an electric roller with certain pressure (1 kg).
And (3) testing the flexibility of the pole piece, namely testing by adopting an ITM-RRD01 softness tester.
And (3) testing the swelling rate of the adhesive film electrolyte, namely forming the adhesive film to be tested into an adhesive film with the average thickness of 100+/-10 mu m. Cutting a test piece with a size of 1X 4cm from the adhesive film, putting the test piece into a105 ℃ air blast drying box for drying for 4 hours, taking out a weighing record M 1, putting the test piece into a small bottle filled with electrolyte (1M LiPF6 in EC:DMC:EMC =1:1:1) for constant temperature soaking for 48 hours, taking out the electrolyte on the surface of the test piece, wiping the electrolyte with filter paper, weighing M 2, and keeping the swelling rate of the adhesive film to be (M 2-M1)/M1 X100%).
The results are shown in Table 1.
TABLE 1
| Stripping force (N/5 cm) | Softness (mN) | Swelling ratio of electrolyte (%) | |
| Example 1 | 1.87 | 98 | 20.2 |
| Example 2 | 2.27 | 107 | 18.4 |
| Example 3 | 2.40 | 125 | 16.7 |
| Example 4 | 2.65 | 132 | 14.8 |
| Example 5 | 2.78 | 140 | 13.7 |
| Example 6 | 2.51 | 127 | 14.5 |
| Example 7 | 2.57 | 130 | 14.1 |
| Example 8 | 2.60 | 134 | 13.3 |
| Example 9 | 2.62 | 127 | 14.8 |
| Example 10 | 2.65 | 125 | 14.6 |
| Comparative example 1 | 1.41 | 94 | 980.4 |
| Comparative example 2 | 2.78 | 178 | 8.9 |
| Comparative example 3 | 2.81 | 189 | 4.3 |
As can be seen from the data in Table 1, the binder for the negative electrode material of the lithium ion battery is used for dispersing and bonding the negative electrode material, has better stripping force, softness and electrolyte swelling rate, and has better performance than acrylic acid derivative emulsion with random structure.
Battery button assembly process
The assembly sequence is from bottom to top negative electrode shell-spring piece-gasket-lithium piece-electrolyte-diaphragm-electrolyte-pole piece-positive electrode shell, and the battery fittings are sealed under 1000kg pressure after being assembled in sequence.
Electrolyte composition 1M LiPF6 in EC:DMC:EMC =1:1:1.
Diaphragm Celgard 2325.
Lithium tablet, kolu 15.0X1.0 mm.
The first coulombic efficiency and impedance data are shown in table 2.
TABLE 2
| First coulombic efficiency/% | Ac impedance/Ω | |
| Example 1 | 92.3 | 37.6 |
| Example 2 | 93.5 | 35.9 |
| Example 3 | 94.1 | 34.2 |
| Example 4 | 94.4 | 32.6 |
| Example 5 | 94.8 | 36.7 |
| Example 6 | 94.2 | 34.7 |
| Example 7 | 94.6 | 34.6 |
| Example 8 | 94.1 | 33.9 |
| Example 9 | 94.9 | 34.1 |
| Example 10 | 95.0 | 33.3 |
| Comparative example 1 | 77.9 | 89.3 |
| Comparative example 2 | 95.2 | 53.7 |
| Comparative example 3 | 95.5 | 58.5 |
As can be seen from the data in table 2, the negative electrode material prepared by the binder of the present application is used in lithium ion batteries, and the lithium ion batteries have the characteristics of high initial coulomb efficiency and low ac impedance due to the characteristics of dispersion, high adhesion, flexibility, etc.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
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| CN109860597A (en) * | 2019-01-14 | 2019-06-07 | 浙江大学 | A water-based composite binder for lithium ion batteries |
| CN113150722A (en) * | 2021-02-25 | 2021-07-23 | 广东银洋环保新材料有限公司 | Adhesive for PVC tablecloth and preparation method thereof |
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| GB0403510D0 (en) * | 2004-02-18 | 2004-03-24 | Mantra Internat Ltd | Bioadhesive compositions and their use in medical electrodes |
| WO2007125924A1 (en) * | 2006-04-26 | 2007-11-08 | Mitsui Chemicals, Inc. | Binder for electrochemical cell electrode |
| US9976048B2 (en) * | 2013-03-26 | 2018-05-22 | Isp Investments Llc | Hydrophobic coating compositions for forming toner receptive coatings |
| CN105440770B (en) * | 2014-06-30 | 2021-05-04 | 四川茵地乐材料科技集团有限公司 | Water-based composition for modifying diaphragm for lithium ion battery, modified diaphragm and battery |
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| CN109860597A (en) * | 2019-01-14 | 2019-06-07 | 浙江大学 | A water-based composite binder for lithium ion batteries |
| CN113150722A (en) * | 2021-02-25 | 2021-07-23 | 广东银洋环保新材料有限公司 | Adhesive for PVC tablecloth and preparation method thereof |
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