CN115863643B - Dispersing softening agent for lithium ion battery anode slurry and application thereof - Google Patents
Dispersing softening agent for lithium ion battery anode slurry and application thereof Download PDFInfo
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- CN115863643B CN115863643B CN202211585169.9A CN202211585169A CN115863643B CN 115863643 B CN115863643 B CN 115863643B CN 202211585169 A CN202211585169 A CN 202211585169A CN 115863643 B CN115863643 B CN 115863643B
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Abstract
The invention discloses a dispersing and softening agent for lithium ion battery anode slurry, which comprises the following components: 10-30wt% of dispersing agent, 20-35wt% of lubricant, 0-5wt% of water inhibitor and the balance solvent; the dispersing and softening agent provided by the invention has the beneficial effects that: the invention reasonably compounds functional groups which are difficult to realize in one molecular structure and have dispersing effect and softening effect, can effectively disperse solid particles in slurry, avoid floating of conductive agent and binder, reduce friction among particles during cold pressing, further improve flexibility of the positive electrode membrane, and reduce risks of winding, hot pressing and doubling light leakage of the positive electrode membrane under the addition of not more than 0.5%.
Description
Technical Field
The invention relates to a dispersion softening agent for positive electrode slurry of a lithium ion battery, in particular to a multi-component compound dispersion softening agent which is particularly suitable for positive electrode slurry with nickel cobalt lithium manganate as an active material, and belongs to the technical field of lithium batteries.
Background
The lithium ion battery has the advantages of large specific energy, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and has wide application in the fields of aviation, national defense, automobiles, 3C and the like.
The lithium ion battery consists of a positive electrode, a negative electrode, a diaphragm and electrolyte, and when the lithium ion battery is formed, the prepared slurry is required to be coated on an aluminum foil to prepare the positive electrode and the negative electrode respectively, so that the viscosity of the slurry is directly related to the coating quality, and along with the rapid development and increasing demands of new energy industry, higher demands are put on the lithium battery, the lithium battery is required to have higher capacity and higher processing efficiency, and the coating thickness and the coating speed of the pole piece are required to be improved.
In the actual operation process, the thick coating of the pole piece needs to improve the solid content of the slurry, solid particles, adhesives and other materials are required to be dispersed uniformly while the solid content is improved, namely, the dispersibility of the slurry is improved, and the coating speed is accelerated, the pole piece is easy to crack in the drying process, so that the flexibility of the pole piece needs to be increased, the cold pressing pressure of the thick pole piece also becomes large after the pole piece is dried, and the ductility of the pole piece also needs to be enhanced. In addition, in the thick quick coating process, the conductive agent, the adhesive and the like can float upwards, the flexibility of the pole piece can be influenced, the brittleness of the pole piece is deteriorated, and the risks of hot-pressing during winding and light leakage of the pole piece in doubling are increased.
Aiming at the problems, the current solution in the industry is to add a dispersing agent into the slurry to improve the dispersing effect of the slurry, the existing dispersing agent can solve the problem of the fluidity of the slurry to a certain extent, but the solving effect on the problems of the flexibility, the ductility and the like of the pole piece is still not ideal, and the adding proportion of the additive in the positive pole slurry is very limited and is generally not more than 0.5 percent, and the capacity of the lithium battery is reduced, so that a multifunctional auxiliary agent capable of solving the problems of the dispersibility of the slurry and the flexibility and the ductility of the pole piece on the premise of not more than 0.5 percent of the adding amount is urgently needed.
Disclosure of Invention
Aiming at the problems of poor dispersibility of the slurry for the lithium ion battery after the solid content is improved and poor flexibility and ductility of the pole piece in the thick coating and quick coating processes, the invention provides the dispersing and softening agent special for the lithium battery positive electrode slurry taking ternary nickel cobalt lithium manganate as a positive electrode active material and application thereof.
The technical scheme for solving the technical problems is as follows:
a dispersing and softening agent for lithium ion battery positive electrode slurry comprises the following components: 10-30wt% of dispersing agent, 20-35wt% of lubricant, 0-5wt% of water inhibitor and the balance solvent;
wherein the dispersing agent is tristyrylphenol polyether phosphate or modified polyurethane, and the modified polyurethane has a structure shown in a formula I:
wherein R is 1 (NCO) 2 Represents one or more of C6-C10 alkyl diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate;
R 2 represents a C2-C8 alkylene group; r is R 3 OH represents a fatty alcohol polyether, preferably a fatty alcohol polyoxyethylene ether, a fatty alcohol polyoxypropylene ether or a lauryl alcohol polymerOne of the oxyvinyl ethers;
n represents an integer of 0 to 50, preferably an integer of 10 to 45.
The term "C2-C8 alkylene" as used herein means a straight-chain or branched alkyl group having 2 to 8 carbon atoms, which is substituted with two hydrogen atoms.
The preparation method of the modified polyurethane comprises the following steps:
1) Pretreatment: r is R 1 (NCO) 2 Vacuum drying is carried out to remove water; by reacting OH-R 2 -OH and R 3 Placing OH in a vacuum drying oven for drying;
2) Synthesis of polyurethane prepolymer: adding pretreated OH-R into a three-neck flask 2 -OH, stirring uniformly; slowly dripping R in 0.5-1.5h 1 (NCO) 2 ，OH-R 2 -OH：R 1 (NCO) 2 The molar ratio is (0.4-0.6): 1, a step of; adding a catalyst dibutyltin dilaurate into the reaction solution, continuing the reaction at room temperature for 1-3h, and testing NCO to reach a preset value under the protection of nitrogen;
3) Modified polyurethane: polyurethane prepolymer obtained in step 2) and R 3 OH is in mole ratio of 1: (0.4-0.6), uniformly stirring, reacting for 3-5h under the condition of room temperature under the protection of nitrogen, and discharging after the reaction is recovered to room temperature when the NCO content is measured to be close to 0, namely the reaction end point.
Preferably, the lubricant is one or more of polyethylene glycol stearate, epoxidized soybean oil, cardanol glycidyl ether or sorbitol polyether ester, more preferably, the sorbitol polyether ester is preferably sorbitol polyether-30 tetraoleate or sorbitol polyether-40 tetraoleate.
Preferably, the water-inhibiting agent is one or more of trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, sulfur-containing silane coupling agent, amino silane coupling agent and epoxy silane coupling agent.
Preferably, the solvent is N-methylpyrrolidone.
The preparation method of the dispersion softening agent comprises the following steps:
1) Filling inert gas into the reaction kettle, and then evacuating, wherein the vacuum degree is kept below 0.1 MPa;
2) Putting the dispersing agent, the lubricating agent, the water-inhibiting agent and the solvent into the reaction kettle according to the proportion, starting stirring, wherein the stirring speed is 30-50rpm, and the stirring time is 0.5-2h;
3) And (5) uniformly stirring, then, emptying, filtering and demagnetizing to obtain the dispersion softening agent.
The dispersing and softening agent provided by the invention has the beneficial effects that:
1) Functional groups which are difficult to realize in a molecular structure and have a dispersing effect and a softening effect are reasonably compounded, so that solid particles in slurry can be effectively dispersed under the condition that the addition amount is not more than 0.5%, the floating of a conductive agent and a binder is avoided, friction among the particles during cold pressing can be reduced, the flexibility of a positive electrode membrane is improved, and the risks of winding, hot pressing and folded light leakage of the positive electrode membrane are reduced;
2) The water inhibitor component can avoid the phenomena of gel, poor thermal stability and the like caused by water absorption of main material particles;
3) The dispersion softening agent does not influence the binding force in the use process and does not deteriorate the performance of the battery cell.
The invention also discloses a lithium ion battery positive electrode slurry containing the dispersion softening agent.
Preferably, the positive electrode slurry of the lithium ion battery further comprises a positive electrode active material, a conductive agent and a binder.
Preferably, the positive electrode active material is lithium nickel cobalt manganese oxide, the conductive agent is selected from one or more of conductive carbon black, superconductive carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nanotubes, and the binder is one or more of vinylidene fluoride homopolymer and vinylidene fluoride copolymer.
The invention also discloses a positive pole piece of the lithium ion battery, and the surface of the positive pole piece is coated with the positive pole slurry of the lithium ion battery.
The invention also discloses a lithium ion battery, which comprises the positive electrode plate.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention.
Table 1 the dispersion softening agent formulations used in examples 1-5 and comparative examples 1-2
Wherein the structural formula of the first modified polyurethane is as follows:the structural formula of the second modified polyurethane is as follows: />R 3 OH represents polyoxyethylene lauryl ether and n=10-45.
Example 1: effect in wet pulping process
The specific preparation steps of the lithium battery positive electrode slurries of examples 1 to 5 and comparative examples 1 to 5 are as follows:
1) Mixing and stirring the binder and the organic solvent uniformly to obtain a glue solution A;
2) Adding the dispersion softening agents listed in table 1 into the glue solution A respectively and stirring uniformly to obtain a glue solution B;
3) Adding a conductive agent into the glue solution B to obtain conductive agent slurry;
4) And adding the positive electrode active material into the conductive agent slurry to obtain positive electrode slurry.
The weight ratio of the raw materials in the method is as follows: conductive agent: dispersing softening agent: binder = 92:6:0.5:1.5; the positive electrode active material is nickel cobalt lithium manganate, the conductive agent is formed by mixing conductive carbon black and carbon nano tubes according to a mass ratio of 1:1, the binder is polyvinylidene fluoride, and the organic solvent is N-methyl pyrrolidone.
In comparative example 3, the dispersion-enhancing agent was not added, in comparative example 4, polyethylene glycol 400 was used as the dispersion-enhancing agent, triphenyl phosphate was used as the dispersion-enhancing agent in comparative example 5, and the other components of the dispersion slurry were the same as those in examples 1 to 5.
The test procedure was as follows:
1. and (3) after the positive membrane is folded in half, rolling the positive membrane back and forth for 3 times by using a compression roller with the weight of 2Kg, then paving the positive membrane, repeating the operation until light leakage occurs at the folding position, and recording folding times. Each group was tested 5 times and averaged.
2. Resistance test of the positive electrode diaphragm the resistance of the positive electrode diaphragm was tested using a CRM-01 pole piece resistance tester. Each group was tested 5 times and averaged.
Table 2 test effect of slurry and positive electrode membrane in wet pulping
As can be seen from the data in Table 1, examples 1 to 5, after the addition of the dispersion softening agent of the present invention, had higher stability of the slurry, and the flexibility and ductility of the apparent pole piece were enhanced, and compared with comparative examples 1 and 2, the solid content of the freshly prepared slurry was increased by 2.5 to 5%, and the viscosity of the slurry of comparative examples 1 to 3 was greatly increased after 24 hours, whereas the viscosity of the slurry of examples 1 to 5 was little changed, still fluidity was good, and the effect of the slurry coating process was better, the number of times of light foldback was significantly increased, indicating that the flexibility and ductility of the pole piece were significantly improved.
Example 2: effect in dry pulping process
The specific preparation process of the lithium battery positive electrode slurries of examples 1 to 5 and comparative examples 1 to 5 is as follows:
1) Dry-mixing the binder, the conductive agent and the positive electrode active material to obtain uniformly mixed powder;
2) Adding part of organic solvent into the powder, and uniformly stirring to obtain initial slurry A;
3) The dispersion softening agent is respectively added into the initial slurry A and stirred uniformly;
4) And on the basis of the step 3), adding the rest organic solvent, and uniformly stirring to obtain the positive electrode slurry.
Wherein, the weight ratio of each raw material is that the positive electrode active material: conductive agent: dispersing softening agent: binder=94:4.5:0.5:1; the positive electrode active material is nickel cobalt lithium manganate, the conductive agent is formed by mixing conductive carbon black and carbon nano tubes according to the mass ratio of 1:1, the binder is polyvinylidene fluoride, and the organic solvent is N-methyl pyrrolidone.
In comparative example 3, no dispersion-softening agent was added, in comparative example 4, polyethylene glycol 400 was used as the dispersion-softening agent, triphenyl phosphate was used as the dispersion-softening agent in comparative example 5, and the other components of the slurry were the same as in examples 1 to 5.
The test procedure was as follows:
1. and (3) after the positive membrane is folded in half, rolling the positive membrane back and forth for 3 times by using a compression roller with the weight of 2Kg, then paving the positive membrane, repeating the operation until light leakage occurs at the folding position, and recording folding times. Each group was tested 5 times and averaged.
2. Resistance test of the positive electrode diaphragm the resistance of the positive electrode diaphragm was tested using a CRM-01 pole piece resistance tester. Each group was tested 5 times and averaged.
Table 3 test effect of dry pulping slurries and positive electrode diaphragms
As can be seen from the data in Table 1, examples 1-5, after the addition of the dispersion softening agent of the present invention, had higher stability of the slurry, and the flexibility and ductility of the apparent pole piece were enhanced, and compared with comparative examples 1 and 2, the solid content of the freshly prepared slurry was increased by 2-5%, and the viscosity of the slurry of comparative examples 1-3 was greatly increased after 24 hours, whereas the viscosity of the slurry of examples 1-5 was not greatly changed, still fluidity was good, and the effect of the slurry coating process was better, and the number of times of folded light leakage was significantly increased, indicating that the flexibility and ductility of the pole piece were significantly improved.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A dispersing and softening agent for lithium ion battery positive electrode slurry comprises the following components: 10-30wt% of dispersing agent, 20-35wt% of lubricant, 0-5wt% of water inhibitor and the balance solvent;
wherein the dispersing agent is modified polyurethane, and the modified polyurethane has a structure shown in a formula I:
wherein R is 1 (NCO) 2 Represents one or more of C6-C10 alkyl diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate;
R 2 represents a C2-C8 alkylene group;
R 3 OH represents a fatty alcohol polyether; the fatty alcohol polyether is one of fatty alcohol polyoxyethylene ether, fatty alcohol polyoxypropylene ether and laurinol polyoxyethylene ether;
n represents an integer of 10 to 45.
2. The dispersion softening agent of claim 1, wherein the lubricant is a formulation of any one or more of polyethylene glycol stearate, epoxidized soybean oil, cardanol glycidyl ether, or sorbitol polyether ester.
3. The dispersion flexibilizer according to claim 2, wherein the sorbitol polyether ester is sorbitol polyether-30 tetraoleate or sorbitol polyether-40 tetraoleate.
4. The dispersion softening agent according to any one of claims 1 to 3, wherein the water-inhibiting agent is one or more of trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, a sulfur-containing silane coupling agent, an aminosilane coupling agent, and an epoxysilane coupling agent, and the solvent is N-methylpyrrolidone.
5. A lithium ion battery positive electrode slurry comprising the dispersion flexibilizer of any one of claims 1-4.
6. The positive electrode slurry for a lithium ion battery according to claim 5, further comprising a positive electrode active material, a conductive agent and a binder.
7. The positive electrode slurry of the lithium ion battery according to claim 6, wherein the positive electrode active material is nickel cobalt lithium manganate, the conductive agent is selected from one or more of superconductive carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nanotubes, and the binder is one or more of vinylidene fluoride homopolymer and vinylidene fluoride copolymer.
8. A positive electrode sheet of a lithium ion battery, characterized in that the surface of the positive electrode sheet is coated with the positive electrode slurry of a lithium ion battery according to any one of claims 5 to 7.
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| CN116589649B (en) * | 2023-07-14 | 2023-12-22 | 宁德时代新能源科技股份有限公司 | Polymer, preparation method, dispersing agent, positive electrode slurry, positive electrode plate, secondary battery and electricity utilization device |
| CN117659331B (en) * | 2024-01-31 | 2024-04-05 | 江苏一特新材料有限责任公司 | Preparation method of three-dimensional network anti-cracking dispersion material and preparation method of positive electrode plate |
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