CN111354948B - Ternary high-nickel positive electrode adhesive for lithium ion battery and preparation method thereof - Google Patents
Ternary high-nickel positive electrode adhesive for lithium ion battery and preparation method thereof Download PDFInfo
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- CN111354948B CN111354948B CN202010230210.5A CN202010230210A CN111354948B CN 111354948 B CN111354948 B CN 111354948B CN 202010230210 A CN202010230210 A CN 202010230210A CN 111354948 B CN111354948 B CN 111354948B
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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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- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention relates to a ternary high-nickel anode adhesive for a lithium ion battery and a preparation method thereof, belonging to the technical field of adhesives for battery electrodes. The invention aims to provide a novel fluorine-free ternary high-nickel positive electrode adhesive for a lithium ion battery. The adhesive is a graft polymer taking polyvinyl alcohol or ethylene-vinyl alcohol copolymer as a main chain, and grafted monomers are acrylonitrile and anhydride monomers, wherein the acrylonitrile and the anhydride monomers are grafted on the main chain through reaction with hydroxyl groups, so that the graft polymer containing cyanoethyl and carboxyl is obtained. The adhesive disclosed by the invention does not contain fluorine, is safe and environment-friendly, can overcome the problem that slurry prepared from a high-nickel material is easy to gel, has excellent rheological property and good bonding strength, is simple in preparation method, does not need toxic reagents or special equipment, is simple and safe, and is low in cost. The battery prepared by the adhesive also shows good charge and discharge performance and cycle performance.
Description
Technical Field
The invention relates to a ternary high-nickel anode adhesive for a lithium ion battery and a preparation method thereof, belonging to the technical field of adhesives for battery electrodes.
Background
The lithium ion battery has the advantages of high specific capacity, high voltage, small volume, light weight, no memory and the like, and the application development of the lithium ion battery in the field of electric automobiles is rapid in more than ten years. Along with the application expansion of the electric automobile to the passenger car, the requirement on the specific energy density of the battery is higher and higher so as to improve the driving mileage of the passenger car. The improvement of the specific energy density of the battery depends on the improvement of the battery electrode material technology and develops the positive and negative materials of the battery with higher gram capacity. In recent years, the industrialization of high nickel cathode materials and silicon carbon cathode materials has been greatly improved, and the application of the high nickel cathode materials and the silicon carbon cathode materials in batteries is greatly developed. High nickel material and silicon carbon material agent are one of the development directions of high specific energy batteries.
The electrode material of lithium ion battery is a powdery object with electrochemical activity, and the preparation of the battery electrode is that the electroactive powder, conductive agent, adhesive and solvent are mixed and ground into slurry, then the slurry is coated on a metal thin foil, and then the battery electrode is prepared by the processes of drying, rolling and the like. At present, in the production of batteries, a high nickel material is used for preparing an electrode plate, polyvinylidene fluoride (PVDF) is generally adopted as a binder, and an organic solvent N-methylpyrrolidone (NMP) is adopted as a dispersing agent. In production practice it has been found that: due to the high alkalinity of the high nickel material, the slurry prepared by the PVDF adhesive system is easy to form jelly-like gel, so that the slurry coating is low in smoothness, even loses fluidity, and cannot be normally coated on the pole piece. In addition, the high-nickel cathode material has high charge pressure and strong oxidizability, so that the high-nickel cathode material has strong electrochemical oxidation on an electrolyte solvent in the charge-discharge cycle process, and the battery cycle performance is poor.
The technical method for solving the problem of the cyclicity of the ternary high-nickel battery is to coat the high-nickel anode material by adopting the inorganic oxide so as to reduce the surface activity of the high-nickel material, reduce the oxidative decomposition of the electrolyte and improve the charge-discharge cycle performance of the battery. Research shows that the polymer coated high-nickel cathode material also has the effects of reducing the surface activity of the high-nickel material, reducing the oxidative decomposition of electrolyte and improving the charge-discharge cycle performance of the battery. The adhesive not only has great influence on the processability of the battery pole piece, but also has close correlation on the battery performance such as capacity, cycle life, internal resistance, charge-discharge rate and the like.
Patent CN108432005A discloses a binder composition for positive electrode, which contains a graft copolymer obtained by graft-copolymerizing a monomer containing acrylonitrile as a main component with polyvinyl alcohol, and the binder is a blend of PAN copolymer, PVA homopolymer and PAN-PVA graft copolymer, and further contains only nitrile group and hydroxyl group, and the binding property thereof needs to be further improved.
Disclosure of Invention
Aiming at the problems that a jelly-like gel is easily formed when a PVDF adhesive system is used for preparing a slurry for a high-nickel material, so that the slurry is low in coating smoothness, even loses fluidity, cannot be normally coated on a pole piece and the like, the invention solves the first technical problem by providing a novel fluorine-free ternary high-nickel positive adhesive for a lithium ion battery.
The invention relates to a ternary high-nickel anode adhesive for a lithium ion battery, which is a graft polymer taking polyvinyl alcohol or ethylene-vinyl alcohol copolymer as a main chain, wherein grafted monomers are acrylonitrile and anhydride monomers, the acrylonitrile is grafted to the main chain through an addition reaction with hydroxyl, and the anhydride monomers are grafted to the main chain through an esterification reaction with the hydroxyl to obtain the graft polymer containing cyanoethyl and carboxyl.
Preferably, the amount of acrylonitrile is 5 to 140% by weight of the polyvinyl alcohol or the ethylene-vinyl alcohol copolymer. More preferably, the amount of acrylonitrile is 6-85% by weight of the polyvinyl alcohol or ethylene-vinyl alcohol copolymer.
Preferably, the amount of the acid anhydride monomer is 20 to 200% of the weight of the polyvinyl alcohol or the ethylene-vinyl alcohol copolymer. More preferably, the amount of the acid anhydride monomer is 20 to 100% by weight of the polyvinyl alcohol or the ethylene-vinyl alcohol copolymer.
Preferably, the acid anhydride monomer is at least one of maleic anhydride, succinic anhydride, anhydride and adipic anhydride.
Preferably, the solid content of the graft polymer is 14 to 40% of the total amount of the binder.
Preferably, the polymerization degree of the polyvinyl alcohol is 500-4000, the hydrolysis degree is 50-99%, and the vinyl alcohol molar content of the ethylene-vinyl alcohol copolymer is 50-70%.
Preferably, the polymerization degree of the polyvinyl alcohol is 1500-2800, and the hydrolysis degree is 80-90%.
The invention solves the second technical problem by providing the preparation method of the ternary high-nickel cathode adhesive for the lithium ion battery.
The preparation method of the ternary high-nickel anode adhesive for the lithium ion battery comprises the following steps of: dissolving polyvinyl alcohol or ethylene-vinyl alcohol copolymer in an organic solvent, adding alkali metal hydroxide, adding acrylonitrile for addition reaction at the reaction temperature of 40-60 ℃ for 4-24 h; and adding an anhydride monomer to perform esterification reaction after the reaction is finished, wherein the reaction temperature is 40-80 ℃, the reaction time is 2-12 h, and obtaining the ternary high-nickel cathode adhesive of the lithium ion battery after the reaction is finished.
Preferably, the organic solvent is N-methylpyrrolidone.
Preferably, the alkali metal hydroxide is LiOH, NaOH or KOH.
Compared with the prior art, the invention has the following beneficial effects:
the ternary high-nickel cathode adhesive for the lithium ion battery is fluorine-free, safe and environment-friendly, and can overcome the problem that slurry prepared from a high-nickel material is easy to gelatinize, and the prepared slurry has excellent rheological property. The adhesive strength is good, and the high-nickel positive pole piece prepared by the adhesive is superior to that of a PVDF adhesive. The battery prepared by the adhesive also shows good charge and discharge performance and cycle performance.
The preparation method of the ternary high-nickel cathode adhesive for the lithium ion battery is simple, does not need toxic reagents or special equipment, is simple and safe, and has lower cost.
Drawings
Fig. 1 is a graph of the charge and discharge cycles at 1.0C for the button cell 2 and the comparative button cell in test example 2.
Detailed Description
The invention relates to a ternary high-nickel positive adhesive for a lithium ion battery, which is a graft polymer taking polyvinyl alcohol (PVA) or ethylene-vinyl alcohol copolymer (EVOH) as a main chain, wherein grafted monomers are acrylonitrile and anhydride monomers, the acrylonitrile is grafted to the main chain through an addition reaction with hydroxyl, and the anhydride monomers are grafted to the main chain through an esterification reaction with the hydroxyl to obtain the graft polymer containing cyanoethyl and carboxyl branched chains. The branched chains of PVA and EVOH contain nitrile group and carboxylic group at the same time, and the nitrile group and the carboxylic group can supplement each other, thereby greatly improving the performance of the adhesive and the performance of the prepared battery.
In the adhesive of the present invention, acrylonitrile is grafted to the main chain by an addition reaction with a hydroxyl group, thereby introducing a nitrile group into the graft polymer.
Acrylonitrile can be subjected to an addition reaction with a hydroxyl group, and the addition reaction of acrylonitrile with a hydroxyl group-OH of PVA is carried out by an organic Michael addition reaction to produce PVA-beta-cyanoethyl ether (PVA-O-CH)2-CH2-CN) or EVOH-cyanoethyl ether (EVOH-O-CH)2-CH2-CN). The nitrile group in the adhesive provided by the invention can perform chemical interaction with the transition metal ions on the lattice surface of the anode material in a hanging and mutual-hanging manner, so that the electrocatalytic oxidation reaction on the surface of the anode material is reduced, the electrochemical side reaction of the battery in the charge-discharge cycle process is reduced, and the charge-discharge cycle stability of the battery is improved. The high nickel battery prepared by using the adhesive has good charge and discharge performance and cycle characteristics.
Preferably, the amount of acrylonitrile is 5 to 140% by weight of the PVA or EVOH. Preferably, the amount of acrylonitrile is 6 to 85% by weight of the PVA or EVOH.
The adhesive of the invention is prepared by esterification reaction of anhydride monomers and hydroxyl groups on PVA or EVOH to generate PVA-OOC-R-COOH or EVOH-OOC-R-COOH alkyl acid ester, and the graft copolymer adhesive with specific carboxylic acid groups on the branched chains of PVA and EVOH is prepared, wherein R groups are determined by the anhydride monomers, for example, when the anhydride monomers are succinic anhydride, R is correspondingly-CH2-CH2-. The adhesive of the invention can overcome the problem that the slurry prepared from the high nickel material is easy to be gelatinized, and the prepared slurry has excellent rheological property. The high-nickel positive pole piece prepared by the adhesive has better bonding strength than PVDF adhesive.
Acid anhydride monomers commonly used in the art are suitable for the present invention, and preferably, the acid anhydride monomers are at least one of maleic anhydride, succinic anhydride, -dicarboxylic anhydride and adipic anhydride.
Preferably, the amount of the acid anhydride monomer is 20 to 200% by weight of the PVA or EVOH. More preferably, the amount of the acid anhydride monomer is 20 to 100% by weight of the PVA or EVOH.
Preferably, the solid content of the graft polymer accounts for 14-40% of the total amount of the adhesive, i.e., the solid content of the reaction between PVA or EVOH and acrylonitrile and anhydride monomers accounts for 14-40% of the total amount of the adhesive.
Preferably, the polymerization degree of the polyvinyl alcohol is 500-4000, the hydrolysis degree is 50-99%, and the vinyl alcohol molar content of the ethylene-vinyl alcohol copolymer is 50-70%. More preferably, the polymerization degree of the polyvinyl alcohol is 1500-2800, and the hydrolysis degree is 80-90%.
The preparation method of the ternary high-nickel anode adhesive for the lithium ion battery comprises the following steps of: dissolving polyvinyl alcohol or ethylene-vinyl alcohol copolymer in an organic solvent, adding alkali metal hydroxide, adding acrylonitrile for addition reaction at the reaction temperature of 40-60 ℃ for 4-24 h; and adding an anhydride monomer to perform esterification reaction after the reaction is finished, wherein the reaction temperature is 40-80 ℃, the reaction time is 2-12 h, and obtaining the ternary high-nickel cathode adhesive of the lithium ion battery after the reaction is finished.
By adopting the reaction, two branched chains of beta-cyanoethyl ether and alkyl acid ester can be successfully introduced into PVA or EVOH resin, so that the lithium ion battery ternary high-nickel positive electrode adhesive with excellent performance is obtained.
Preferably, the organic solvent is N-methylpyrrolidone.
Preferably, the alkali metal hydroxide is LiOH, NaOH or KOH.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The solid content in the examples was determined as follows: weighing a certain amount of adhesive, pouring into a plastic container, drying in a forced air oven at 100-120 ℃ for 8hr to volatilize the solvent and unreacted monomer in the sample, storing the dried sample in a drier, cooling and weighing. Solid content of the binder:
solid content = weight after sample drying/weight before sample drying × 100%.
The PVA used in the examples had a degree of polymerization of 2400, a degree of hydrolysis of 88% and a vinyl alcohol molar content of 62% in EVOH.
Example 1
Adding 300g of NMP solvent and 80g of EVOH into a four-neck reaction glass bottle with a condenser tube and a stirring and heating device, heating to 80 ℃ to dissolve the EVOH, cooling the temperature to 40 ℃ when the EVOH is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 60g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature is within 50 ℃, continuing to react for 10 hours after the acrylonitrile is dropwise added, then adding 20g of maleic anhydride, heating to 60 ℃ and reacting for 6 hours to obtain the high-nickel anode adhesive with the solid content of 33.5-34.5%.
Example 2
Adding 300g of NMP solvent and 80g of EVOH into a four-neck reaction glass bottle with a condenser pipe and a stirring and heating device, heating to 80 ℃ to dissolve the EVOH, cooling to 40 ℃ when the EVOH is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 5g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature is within 50 ℃, continuing to react for 10 hours after the acrylonitrile is dropwise added, and then adding 20g of succinic anhydride to react for 4 hours to obtain the high-nickel anode adhesive with the solid content of 24.0-25%.
Example 3
Adding 340g of NMP solvent and 50g of PVA into a four-neck reaction glass bottle with a condenser tube and a stirring and heating device, heating to 80 ℃ to dissolve the PVA, cooling to 40 ℃ when the PVA is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 10g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature is within 50 ℃, continuously reacting for 10 hours after the acrylonitrile is dropwise added, and then adding 10g of maleic anhydride to react for 6 hours to obtain the high-nickel anode adhesive with the solid content of 15.5-16.5%.
Example 4
Adding 440g of NMP solvent and 50g of PVA into a four-neck reaction glass bottle with a condenser tube and a stirring and heating device, heating to 80 ℃ to dissolve the PVA, cooling the temperature to 40 ℃ when the PVA is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 10g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature is within 50 ℃, continuing to react for 10 hours after the dropwise adding of the acrylonitrile is finished, and then adding 50g of maleic anhydride to react for 6 hours to obtain the high-nickel anode adhesive with the solid content of 19.0-20.0%.
Example 5
Adding 400g of NMP solvent and 40g of PVA into a four-neck reaction glass bottle with a condenser tube and a stirring and heating device, heating to 90 ℃ to dissolve the PVA, cooling to 40 ℃ when the PVA is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 30g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature is within 50 ℃, continuing to react for 10 hours after the acrylonitrile is dropwise added, then adding 30g of maleic anhydride, heating to 60 ℃ and reacting for 6 hours to obtain the high-nickel anode adhesive with the solid content of 18.5-19.5%.
Example 6
Adding 375g of NMP solvent and 60g of PVA into a four-neck reaction glass bottle with a condenser tube and a stirring and heating device, heating to 90 ℃ to dissolve the PVA, cooling the temperature to 40 ℃ after the PVA is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 50g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature is within 50 ℃, continuing to react for 10 hours after the acrylonitrile is dropwise added, then adding 15g of succinic anhydride, heating to 60 ℃ and reacting for 6 hours to obtain the high-nickel anode adhesive with the solid content of 23.5-24.5%.
Example 7
Adding 375g of NMP solvent, 20g of EVOH and 40g of PVA into a four-neck reaction glass bottle with a condenser tube and a stirring and heating device, heating to 90 ℃ to dissolve the EVOH and the PVA, cooling to 40 ℃ when the EVOH and the PVA are completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 50g of acrylonitrile, controlling the dropwise adding speed of the acrylonitrile to ensure that the reaction temperature rises within 50 ℃, continuing to react for 10 hours after the addition of the acrylonitrile is finished, adding 15g of succinic anhydride, heating to 60 ℃ and reacting for 6 hours to obtain the high-nickel anode adhesive with the solid content of 23.5-24.5%.
Comparative example 1
Adding 340g of NMP solvent and 50g of PVA into a four-neck reaction glass bottle with a condenser pipe and a stirring and heating device, heating to 90 ℃ to dissolve the PVA, cooling to 40 ℃ when the PVA is completely dissolved, adding 0.5g of NaOH as a catalyst, then dropwise adding 20g of acrylonitrile, controlling the dropping speed of the acrylonitrile to ensure that the reaction temperature rises within 50 ℃, and continuously reacting for 10 hours after the dropping of the acrylonitrile is finished to obtain the adhesive with the solid content of 15.5-16.5%.
Test example 1
The liquid absorption rate and the peel strength of the positive electrode sheet of the binders of examples 1 to 7 were measured. Comparative example 2 used PVDF binder.
And (3) measuring the liquid absorption rate of the adhesive: pouring the adhesive into a plastic container, drying the solvent in a forced air oven at 100-120 ℃, and then transferring the solvent into a vacuum oven to be dried in vacuum for 24 hours at 85-90 ℃. Weighing the vacuum dried sample, soaking in electrolyte at 70 deg.C for 24hr, taking out, and weighing. The liquid absorption rate of the sample:
the liquid absorption rate = (weight after immersion-weight before immersion)/weight before immersion × 100%.
And (3) measuring the bonding and peeling strength of the pole piece: the positive plate using the adhesive of the present invention was prepared according to a method familiar to those skilled in the art, and then the peel strength of the plate was measured using a 90 ° peel strength tester. The pole piece composition with the tested peel strength: NCM 81196%, acetylene black 2.0%, and adhesive 2.0%.
The results are shown in Table 1.
TABLE 1 liquid absorption rate and peel strength of positive electrode sheet of the binders of examples 1 to 7
| Numbering | The liquid absorption rate% | Peel strength N/m |
| Example 1 | 14.2 | 11.5 |
| Example 2 | 5.8 | 15.7 |
| Example 3 | 4.1 | 21.6 |
| Example 4 | 8.5 | 26.8 |
| Example 5 | 11.7 | 23.3 |
| Example 6 | 8.0 | 24.2 |
| Example 7 | 6.6 | 17.1 |
| Comparative example 1 | 98.0 | 7.8 |
| Comparative example 2 | 47.6 | 9.1 |
As can be seen from Table 1: the adhesives prepared in the examples 1 to 7 have smaller liquid absorption rate than the conventional PVDF adhesive, which shows that the adhesives prepared in the examples 1 to 7 have smaller swelling degree in electrolyte and can keep the stability of the geometric dimension of a pole piece in an electrode. The adhesives of the embodiments 1-7 also have higher pole piece peel strength than the conventional PVDF adhesives, and the high pole piece peel strength can inhibit the change of the microstructure of the pole piece in the charge-discharge cycle process of the battery and improve the charge-discharge cycle stability of the battery. And the PVA graft copolymer with high grafting amount prepared by only adopting acrylonitrile as the adhesive comparative example 1 shows great liquid absorption rate and can not meet the use requirement of the battery.
Test example 2
Preparation of the button cell 1: 9.6 g of the high nickel cathode material NCM811 and 0.20 g of the conductive agent acetylene black were uniformly mixed, 0.84g of the binder prepared in example 6 was added, wherein the solid weight of the binder was 0.2g, and 5.0g of NMP solvent was added and stirred to form a uniform cathode slurry. And uniformly coating the slurry on an aluminum foil, drying at 120 ℃, rolling, punching to prepare a circular pole piece with the radius of 12 mm, vacuum-drying at 80 ℃ for 16 ℃, placing in a glove box in a dry argon atmosphere, and assembling the circular pole piece and a metal lithium electrode into a Li/NCM811 button cell 1, wherein the electrolyte is a commercially available electrolyte for a lithium ion battery, and the diaphragm is a polypropylene microporous membrane.
Preparation of the button cell 2: the pole piece composition and button cell fabrication methods were the same as button cell 1, except that the battery pole piece used the adhesive prepared in example 7.
Preparing a comparative button cell: 9.5 g of high nickel cathode material NCM811 and 0.20 g of conductive agent acetylene black are mixed uniformly, and then 0.3g of PVDF adhesive and 6.0g of NMP solvent are added to be stirred to form uniform cathode slurry. And uniformly coating the slurry on an aluminum foil, drying at 120 ℃, rolling, punching to prepare a circular pole piece with the radius of 12 mm, vacuum-drying at 80 ℃ for 16 ℃, placing in a glove box in a dry argon atmosphere, and assembling the circular pole piece and a metal lithium electrode into a Li/NCM811 button cell, wherein the electrolyte is a commercially available electrolyte for lithium ion batteries, and the diaphragm is a polypropylene microporous membrane.
The charge and discharge performance of the three batteries was measured, and the results are shown in table 2.
TABLE 2 Battery Charge and discharge Performance data
As can be seen from Table 2, the electrode plates of the button cells 1 and 2 use the binder of the invention, although the binder is only two thirds of the PVDF binder of the comparative button cells, the bonding strength of the electrode plates is 2-3 times that of the PVDF binder. The high-nickel cathode adhesive has stronger adhesive force than the PVDF adhesive used at present. When the button cell 1, the button cell 2 and the comparative button cell are charged and discharged at 0.2C within the voltage range of 2.75-4.3V, the first charge gram capacity, the first discharge gram capacity and the first efficiency of the button cell 1, the button cell 2 and the comparative button cell are basically equivalent, but the capacity retention rates of the button cell 1 and the button cell 2 are respectively 96.9% and 97.2% when the button cell 1 and the button cell 2 are charged and discharged for 50 times at 1.0C, while the battery capacity retention rate of the comparative button cell is only 87.9%. The battery made by the adhesive has more excellent charge-discharge cycle stability than the battery using the PVDF adhesive at present.
Fig. 1 is a comparison of charge-discharge cycle curves for button cell 2 and a comparative button cell. It can be seen from the figure that the gram capacity of the comparative button cell is gradually lower as the cycle number increases, and the gram capacity of the button cell 2 is less changed as the cycle number increases.
Claims (12)
1. The ternary high-nickel anode adhesive for the lithium ion battery is characterized in that: the adhesive is a graft polymer taking polyvinyl alcohol or ethylene-vinyl alcohol copolymer as a main chain, and grafted monomers are acrylonitrile and anhydride monomers, wherein the acrylonitrile is grafted to the main chain through an addition reaction with hydroxyl, and the anhydride monomers are grafted to the main chain through an esterification reaction with the hydroxyl to obtain the graft polymer containing cyanoethyl and carboxyl.
2. The ternary high-nickel positive electrode binder for the lithium ion battery according to claim 1, characterized in that: the amount of acrylonitrile is 5-140% of the weight of polyvinyl alcohol or ethylene-vinyl alcohol copolymer.
3. The ternary high-nickel positive electrode binder for lithium ion batteries according to claim 2, characterized in that: the amount of acrylonitrile is 6-85% of the weight of polyvinyl alcohol or ethylene-vinyl alcohol copolymer.
4. The ternary high-nickel positive electrode binder for the lithium ion battery according to claim 1, characterized in that: the amount of the anhydride monomer is 20-200% of the weight of the polyvinyl alcohol or the ethylene-vinyl alcohol copolymer.
5. The ternary high-nickel positive electrode binder for lithium ion batteries according to claim 4, characterized in that: the amount of the anhydride monomer is 20-100% of the weight of the polyvinyl alcohol or the ethylene-vinyl alcohol copolymer.
6. The ternary high-nickel positive electrode binder for the lithium ion battery according to any one of claims 1 to 5, characterized in that: the anhydride monomer is at least one of maleic anhydride, succinic anhydride, anhydride and adipic anhydride.
7. The ternary high-nickel positive electrode binder for the lithium ion battery according to any one of claims 1 to 5, characterized in that: the solid content of the adhesive is 14-40%.
8. The ternary high-nickel positive electrode binder for the lithium ion battery according to any one of claims 1 to 5, characterized in that: the polymerization degree of the polyvinyl alcohol is 500-4000, the hydrolysis degree is 50-99%, and the vinyl alcohol molar content of the ethylene-vinyl alcohol copolymer is 50-70%.
9. The ternary high-nickel positive electrode binder for lithium ion batteries according to claim 8, characterized in that: the polymerization degree of the polyvinyl alcohol is 1500-2800, and the hydrolysis degree is 80-90%.
10. The preparation method of the ternary high-nickel positive electrode binder for the lithium ion battery of any one of claims 1 to 9, characterized by comprising the following steps: the method comprises the following steps: dissolving polyvinyl alcohol or ethylene-vinyl alcohol copolymer in an organic solvent, adding alkali metal hydroxide, adding acrylonitrile for addition reaction at the reaction temperature of 40-60 ℃ for 4-24 h; and adding an anhydride monomer to perform esterification reaction after the reaction is finished, wherein the reaction temperature is 40-80 ℃, the reaction time is 2-12 h, and obtaining the ternary high-nickel cathode adhesive of the lithium ion battery after the reaction is finished.
11. The preparation method of the ternary high-nickel positive electrode binder for the lithium ion battery according to claim 10, characterized in that: the organic solvent is N-methyl pyrrolidone.
12. The preparation method of the ternary high-nickel positive electrode binder for the lithium ion battery according to claim 10, characterized in that: the alkali metal hydroxide is LiOH, NaOH or KOH.
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| US10522835B2 (en) * | 2015-12-15 | 2019-12-31 | Denka Company Limited | Binder composition for positive electrodes, slurry for positive electrodes, positive electrode and lithium ion secondary battery |
| JP6936787B2 (en) * | 2016-03-08 | 2021-09-22 | デンカ株式会社 | Negative electrode binder composition, negative electrode slurry, negative electrode and lithium ion secondary battery |
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| CN106207184B (en) * | 2016-08-03 | 2019-03-01 | 宣城研一新能源科技有限公司 | A kind of water adhesive for lithium ion battery and its preparation method and application |
| US20200207898A1 (en) * | 2017-06-13 | 2020-07-02 | Denka Company Limited | Composition and positive-electrode binder composition |
| CN107793967B (en) * | 2017-09-30 | 2019-09-06 | 中国科学院广州能源研究所 | A kind of preparation method of the crosslinking type aqueous binder of lithium ion battery |
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| CN1328102A (en) * | 2001-06-08 | 2001-12-26 | 成都茵地乐电源科技有限公司 | Water adhesive for electrode material of secondary lithium ion battery and its preparing process |
| CN1328104A (en) * | 2001-06-12 | 2001-12-26 | 成都茵地乐电源科技有限公司 | Process for preparing water adhesive of lithium ion battery |
| CN101260282A (en) * | 2008-03-18 | 2008-09-10 | 成都中科来方能源科技有限公司 | Water adhesive for lithium ion battery, preparation method thereof and lithium ion battery positive plate |
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