Patent Application
20250034303
The present application claims priority from Chinese Patent Application No. 202310934119.5 filed on Jul. 28, 2023, the contents of which are incorporated herein by reference in their entirety.
The present invention belongs to the technical field of battery dispersing materials, and particularly relates to a preparation method of a comb-shaped positive electrode dispersing material and a preparation method of a low-internal-resistance electrode plate.
A lithium-ion battery is mainly composed of a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the preparation of an electrode plate is a first step in a manufacturing process of the lithium-ion battery, and the quality of the electrode plate is related to a yield of the lithium-ion battery. The preparation of the electrode plate is divided into the steps of slurry stirring, electrode plate coating, rolling cutting and the like, and the slurry stirring is the key step. As for the electrode plate, a slurry is generally composed of a positive electrode material, a binder, a conductive agent, a solvent and the like. With increasing pressures in environmental protection, cost and other aspects, the market is now pursuing a slurry with a higher solid content to reduce the use of an NMP solvent, which also brings great difficulties to slurry dispersion and coating, and the introduction of a positive electrode dispersing material can effectively solve the above problems. However, there are a few of choices on the market at present, the industry has just started, and related patents are rarely disclosed. Moreover, the preparation of the electrode plate still has the problems of cracking, powder falling and uneven coating of the electrode plate at present, so that higher requirements for the positive electrode dispersing material are put forward. It is worth noting that the introduction of the dispersing material may have a negative impact on increase of internal resistance of the electrode plate, the internal resistance of the electrode plate is related to an energy density of the lithium-ion battery, and the relatively high internal resistance of the electrode plate can reduce the energy density, which is not conducive to the promotion and application of products. It is urgent to develop a novel positive electrode dispersing material, which can give consideration to both advantages of good dispersion effect and small internal resistance of the electrode plate.
Therefore, it is necessary to develop a preparation method of a comb-shaped positive electrode dispersing material and a preparation method of a low-internal-resistance electrode plate to solve the problems of a poor effect of the dispersing material and a high internal resistance of the electrode plate.
The present invention aims to provide a preparation method of a comb-shaped positive electrode dispersing material and a preparation method of a low-internal-resistance electrode plate.
A technical solution of the present invention is as follows.
A preparation method of a comb-shaped positive electrode dispersing material comprises the following steps of:
Further, in the step (1), a mass ratio of the unsaturated cyclic monomer to the unsaturated branched polyether and the (methyl) acrylate monomer is 2 to 4:4 to 7:1 to 2.
Further, in the step (2), the initiating agent is any one or more of azodiisobutyronitrile, azodiisoheptylnitrile and dibenzoyl peroxide; and according to a mass percentage, an amount of the initiating agent accounts for 0.1% to 3% of a sum of amounts of the unsaturated cyclic monomer, the unsaturated branched polyether and the (methyl) acrylate monomer.
Further, in the step (2), the reaction temperature is 60° C. to 90° C., and the reaction lasts for 2 hours to 10 hours.
Further, in the step (3), the esterification is carried out at a temperature of 70° C., and the esterification lasts for 3 hours to 6 hours.
Further, in the step (3), a molecular weight of the comb-shaped positive electrode dispersing material ranges from 10,000 g/mol to 60,000 g/mol.
Another technical solution of the present invention is as follows.
A preparation method of a low-internal-resistance electrode plate comprises the following steps of:
Further, in the step (1), a mass ratio of the lithium iron phosphate to the conductive carbon black, the polyvinylidene fluoride, the N-methylpyrrolidone and the comb-shaped positive electrode dispersing material is 95:2:2:66:1.
Further, in the step (2), an areal density of the low-internal-resistance electrode plate ranges from 150 g/m2 to 200 g/m2.
The present invention provides the preparation method of the comb-shaped positive electrode dispersing material and the preparation method of the low-internal-resistance electrode plate, and has the beneficial effects as follows:
The sole FIGURE shows pictures of surfaces of electrode plates prepared in Embodiments 1 to 6 and Comparative Examples 1 to 4 by a preparation method of a low-internal-resistance electrode plate according to the present invention.
In order to give consideration to both advantages of good dispersion effect and small internal resistance of an electrode plate, the present invention provides a preparation method of a comb-shaped positive electrode dispersing material with high dispersion and a low internal resistance, which comprises the following steps.
In step 1), a solvent, an unsaturated cyclic monomer, unsaturated branched polyether and a (methyl) acrylate monomer are mixed to obtain a mixed solution.
In step 2), the mixed solution is heated to 60° C. to 90° C., an initiating agent is added, and a reaction temperature is kept for 2 hours to 10 hours to obtain a semi-finished product.
In step 3), phosphoric acid which is equal to the (methyl) acrylate monomer in mole is added into the semi-finished product for esterification at a temperature of 70° C. for 3 hours to 6 hours and high-temperature dehydration to obtain a final product, which is namely the comb-shaped positive dispersing material with a molecular weight ranging from 10,000 g/mol to 60,000 g/mol.
In the above process, the solvent may be any one or more of N-methylpyrrolidone, N-ethylpyrrolidone and the like, and preferably, the solvent is the N-methylpyrrolidone. By calculation by a mass percentage, there are 20% to 40% of unsaturated cyclic monomer, 40% to 70% of unsaturated branched polyether and 10% to 20% of (methyl) acrylate monomer, a total of which is 100%. The unsaturated cyclic monomer may be any one or more of styrene, methylstyrene, vinylpyridine and N-vinylpyrrolidone. An initiator of the unsaturated branched polyether is any one of allyl alcohol, isobutylene alcohol, isopentenol and the like, a participating chain segment of the unsaturated branched polyether is a copolymer of ethylene oxide and propylene oxide, which may be one or more of allylalcohol polyoxyethylene (300) polyoxypropylene (200) ether, allylalcohol polyoxyethylene (500) polyoxypropylene (500) ether, isobutylene polyoxyethylene (500) polyoxypropylene (1000) ether, isobutylene polyoxyethylene (1000) polyoxypropylene (1500) ether, isopentenyl polyoxyethylene (1500) polyoxypropylene (2000) ether and isopentenyl polyoxyethylene (2500) polyoxypropylene (2500) ether, and a molecular weight of the unsaturated branched polyether ranges from 500 g/mol to 5,000 g/mol. The (meth) acrylate monomer is any one or more of hydroxyethyl methylacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and the like. The initiating agent is an oil-soluble initiating agent, which may be one or more of azodiisobutyronitrile, azodiisoheptylnitrile, dibenzoyl peroxide and the like, preferably, the initiating agent is the azodiisobutyronitrile, and an amount of the initiating agent is 0.1% to 3% of a mass of a polymerizable monomer (the unsaturated cyclic monomer, the unsaturated branched polyether and the (methyl) acrylate monomer).
By the above technical solution, the obtained dispersing material has a good performance, and a viscosity of a slurry system can be significantly reduced by adding the dispersing material into the positive electrode slurry. Moreover, the viscosity of the slurry can be kept stable for a long time, thus laying a good foundation for subsequent electrode plate coating. A preparation process of a low-internal-resistance electrode plate which is flat and smooth in surface and free of cracking is as follows.
Firstly, a positive electrode slurry is prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of positive electrode dispersing material are uniformly mixed, and dispersed by a vacuum defoamer to obtain the slurry; subsequently, the slurry is poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 150 g/m2 to 200 g/m2; and finally, a surface structure and an internal resistance of the electrode plate are tested. Thus, it can be known that the electrode plate is flat and smooth in surface, free of cracking and powder falling, and low in internal resistance.
In order to make the above objects, features and advantages of the present invention clearer and more understandable, technical solutions of the present invention are further described hereinafter with reference to embodiments. However, the present invention is not limited to the listed embodiments, but should also comprise any other commonly known changes within the scope of right claimed by the present invention.
“One embodiment” or “an embodiment” as used herein refers to a specific feature, structure or characteristic that can be included in at least one implementation of the present invention. “In one embodiment” appearing in different places in the specification do not all refer to the same embodiment, nor are they separate or selective embodiments mutually exclusive of other embodiments.
This embodiment showed a preparation method of a comb-shaped positive electrode dispersing material according to the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 200 g of styrene, 700 g of allylalcohol polyoxyethylene (300) polyoxypropylene (200) ether and 100 g of hydroxyethyl methylacrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 90° C., 5 g of initiating agent was added, and a reaction temperature was kept for 2 hours to obtain a semi-finished product.
In step 3), 75 g of phosphoric acid was added into the semi-finished product for esterification and high-temperature dehydration at 70° C. for 3 hours to obtain a final product, which was namely the comb-shaped positive dispersing material.
A low-internal-resistance electrode plate which is flat and smooth in surface and free of cracking was prepared from the above comb-shaped positive dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of comb-shaped positive dispersing material were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 150 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
This embodiment showed a preparation method of a comb-shaped positive electrode dispersing material according to the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 300 g of methylstyrene, 600 g of allylalcohol polyoxyethylene (500) polyoxypropylene (500) ether and 100 g of hydroxypropyl methacrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 80° C., 15 g of initiating agent was added, and a reaction temperature was kept for 4 hours to obtain a semi-finished product.
In step 3), 68 g of phosphoric acid was added into the semi-finished product for esterification and high-temperature dehydration at 70° C. for 4 hours to obtain a final product, which was namely the comb-shaped positive dispersing material.
A low-internal-resistance electrode plate with a smooth and crack-free surface was prepared from the above comb-shaped positive dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of comb-shaped positive dispersing material were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 160 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
This embodiment showed a preparation method of a comb-shaped positive electrode dispersing material according to the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 400 g of vinylpyridine, 500 g of isobutylene polyoxyethylene (500) polyoxypropylene (1000) ether and 100 g of hydroxybutyl methacrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 80° C., 30 g of initiating agent was added, and a reaction temperature was kept for 10 hours to obtain a semi-finished product.
In step 3), 62 g of phosphoric acid was added into the semi-finished product for esterification and high-temperature dehydration at 70° C. for 5 hours to obtain a final product, which was namely the comb-shaped positive dispersing material.
A low-internal-resistance electrode plate with a smooth and crack-free surface was prepared from the above comb-shaped positive dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of comb-shaped positive dispersing material were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 170 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
This embodiment showed a preparation method of a comb-shaped positive electrode dispersing material according to the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 400 g of N-vinylpyrrolidone, 400 g of isobutylene polyoxyethylene (1000) polyoxypropylene (1500) ether and 200 g of hydroxyethyl acrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 70° C., 15 g of initiating agent was added, and a reaction temperature was kept for 8 hours to obtain a semi-finished product.
In step 3), 169 g of phosphoric acid was added into the semi-finished product for esterification and high-temperature dehydration at 70° C. for 6 hours to obtain a final product, which was namely the comb-shaped positive dispersing material.
A low-internal-resistance electrode plate which is flat and smooth in surface and free of cracking was prepared from the above comb-shaped positive dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of comb-shaped positive dispersing material were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 180 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
This embodiment showed a preparation method of a comb-shaped positive electrode dispersing material according to the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 300 g of styrene, isopentenyl polyoxyethylene (1500) polyoxypropylene (2000) ether and 200 g of hydroxypropyl acrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 80° C., 5 g of initiating agent was added, and a reaction temperature was kept for 6 hours to obtain a semi-finished product.
In step 3), 151 g of phosphoric acid was added into the semi-finished product for esterification and high-temperature dehydration at 70° C. for 4 hours to obtain a final product, which was namely the comb-shaped positive dispersing material.
A low-internal-resistance electrode plate which is flat and smooth in surface and free of cracking was prepared from the above comb-shaped positive dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of comb-shaped positive dispersing material were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 190 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
This embodiment showed a preparation method of a comb-shaped positive electrode dispersing material according to the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 200 g of N-vinylpyrrolidone, 600 g of isopentenyl polyoxyethylene (2500) polyoxypropylene (2500) ether and 200 g of hydroxybutyl acrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 90° C., 1 g of initiating agent was added, and a reaction temperature was kept for 4 hours to obtain a semi-finished product.
In step 3), 136 g of phosphoric acid was added into the obtained semi-finished product for esterification and high-temperature dehydration at 70° C. for 6 hours to obtain a final product, which was namely the comb-shaped positive dispersing material.
A low-internal-resistance electrode plate which is flat and smooth in surface and free of cracking was prepared from the above comb-shaped positive dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone and 1 part of comb-shaped positive dispersing material were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 200 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
A preparation method of a positive electrode dispersing material comprised the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 500 g of styrene and 500 g of hydroxyethyl methylacrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 90° C., 5 g of initiating agent was added, and a reaction temperature was kept for 2 hours.
In step 3), 377 g of phosphoric acid was added into the obtained semi-finished product for esterification and high-temperature dehydration at 70° C. for 3 hours to obtain a final product, which was namely a positive electrode slurry dispersing material of a battery.
An electrode plate was prepared from the above dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone, 1 part of positive electrode slurry dispersing material of the battery and the like were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 150 g/m2; and finally, a surface structure and an internal resistance of the electrode plate were tested.
A preparation method of a positive electrode dispersing material comprised the following steps.
In step 1), 1,000 g of N-methylpyrrolidone and 1,000 g of polyethylene glycol (300) propylene glycol (200) methacrylate were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 90° C., 5 g of initiating agent was added, and a reaction temperature was kept for 2 hours to obtain a product, which was a positive electrode slurry dispersing material of a battery.
An electrode plate was prepared from the above dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone, 1 part of positive electrode slurry dispersing material of the battery and the like were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 150 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
A preparation method of a positive electrode dispersing material comprised the following steps.
In step 1), 1,000 g of N-methylpyrrolidone, 300 g of styrene and 700 g of allylalcohol polyoxyethylene (300) polyoxypropylene (200) ether were mixed to obtain a uniform mixed solution.
In step 2), the mixed solution was heated to 90° C., 5 g of initiating agent was added, and a reaction temperature was kept for 2 hours to obtain a product, which was a positive electrode slurry dispersing material of a battery.
An electrode plate was prepared from the above dispersing material, and a preparation process was as follows: firstly, a positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone, 1 part of positive electrode slurry dispersing material of the battery and the like were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 150 g/m2; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
A universal-type commercially available dispersing material is provided and used for dispersion of a positive electrode slurry and preparation and characterization of a positive electrode plate.
An electrode plate was prepared from the above commercially available dispersing material, and a preparation process was as follows.
Firstly, the positive electrode slurry was prepared: 95 parts of lithium iron phosphate (LiFePO4), 2 parts of conductive carbon black, 2 parts of polyvinylidene fluoride, 66 parts of N-methylpyrrolidone, 1 part of commercially available dispersing material and the like were uniformly mixed, and fully dispersed for 4 hours by a vacuum defoamer; subsequently, the dispersed slurry was poured on a spread plate machine for electrode plate coating to obtain an electrode plate with an areal density of 150 g/ma; and subsequently, a surface structure and an internal resistance of the electrode plate were tested.
Related tests on a molecular weight of the dispersing material, a viscosity of the positive electrode slurry, internal resistance of the positive electrode plate and a surface state of the electrode plate were as follows.
Firstly, the molecular weight of the dispersing material, the viscosity of the positive electrode slurry and the like were tested. With reference to Table 1, Table 1 is a test table of the molecular weights of the dispersing materials and the viscosities of the positive electrode slurries. Results in Table 1 show that a dispersing material with an expected molecular weight is obtained. By comparing the initial viscosities and the 72-hour viscosities of the slurries in the embodiments and the comparative examples, it can be concluded that the embodiments have a good dispersion effect and dispersion retention capacity, while the comparative examples generally have a high initial viscosity and a poor 72-hour viscosity. By comparing the embodiments with Comparative Example 1 and Comparative Example 2, it can be seen that the synthesized comb-shaped macromolecular structure is necessary, and copolymerization of unsaturated heterocyclic monomer alone or unsaturated polyether alone has no obvious viscosity reduction effect. By comparing the embodiments with Comparative Example 3, it can be seen that existence of phosphate is also conductive to viscosity reduction and viscosity maintenance of the slurry. By comparing the embodiments with Comparative Example 4, it can be seen that the viscosities of the slurries in the embodiments are obviously better than that of the commercially available dispersing material.
Secondly, surface states of the positive electrode plates obtained in Embodiments 1 to 6 and Comparative Examples 1 to 4 are observed by a microscope and photographed, so as to compare a difference between the samples. With reference to the sole FIGURE, the sole FIGURE shows pictures of surfaces of the electrode plates prepared in Embodiments 1 to 6 and Comparative Examples 1 to 4 by the preparation method of the low-internal-resistance electrode plate according to the present invention. As shown in the sole FIGURE, the surfaces of the positive electrode plates in Embodiments 1 to 6 involved in the present invention are flat and smooth in surface and free of cracking and powder falling, while the surfaces of the positive electrode plates in Comparative Examples 1 to 4 have more or less cracking or surface non-uniformity.
Finally, the internal resistances of the positive electrode plates are tested, and the internal resistances of the positive electrode plates in Embodiments 1 to 6 and Comparative Examples 1 to 4 are compared. With reference to Table 2, Table 2 is a test table of the internal resistances of the electrode plates in Embodiments 1 to 6 and Comparative Examples 1 to 4. It can be seen from Table 2 that the internal resistances of the electrode plates in Embodiments 1 to 6 are obviously lower than those in Comparative Examples 1 to 4, so that the advantage of low internal resistance is achieved. By comparing the embodiments with Comparative examples 1 to 2, it can be seen that the comb-shaped macromolecular structure is necessary, and a polyether monomer alone or copolymerization of heterocyclic monomer alone has no internal resistance reduction effect. By comparing the embodiments with Comparative Example 3, it can be seen that phosphate also has the internal resistance reduction effect. By comparing the embodiments with Comparative Example 4, it can be seen that the internal resistance reduction effects in the embodiments involved in the present invention are obviously better than that of the commercially available dispersing material.
It should be noted that, the embodiments above are only used to illustrate the technical solutions of the present invention, and are not intended to limit the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skills in the art should understand that modifications or equivalent replacements made on the technical solutions of the present invention without deviating from the spirit and scope of the technical solutions of the present invention should be included within the scope of the claims of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310934119.5 | Jul 2023 | CN | national |
