CN109065805B - Preparation method of high-liquid-absorption-rate water-based polymer diaphragm - Google Patents
Preparation method of high-liquid-absorption-rate water-based polymer diaphragm Download PDFInfo
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a preparation method of a high-liquid-absorption-rate water-based polymer diaphragm, belonging to the field of manufacturing of lithium ion battery components. The method comprises the following steps: adding a hydrophobic polymer A and a hydrophilic polymer B into a polar organic solvent to form a polymer mixture, heating and stirring to uniformly dissolve the polymer mixture to form a uniform polymer solution; adding the polymer solution into a spray dryer for spray drying to obtain spherical polymer powder; and (3) preparing the polymer powder and the auxiliary agent into slurry, coating the slurry on a base film, and drying to obtain the high-liquid-absorption-rate water-based polymer diaphragm. The method is simple, convenient, environment-friendly and easy to operate, and the prepared polymer diaphragm has high liquid absorption rate, and can effectively improve the high-rate charge-discharge performance and the cycling stability of the battery.
Description
Technical Field
The invention belongs to the field of manufacturing of lithium ion battery components, and particularly relates to a preparation method of a high-liquid-absorption-rate water-based polymer diaphragm.
Background
Lithium ion batteries generally consist of: positive electrode, negative electrode, electrolyte, diaphragm, tab, central terminal, insulating material, safety valve, PTC (positive temperature control terminal), battery case. The core material mainly comprises a positive electrode, a negative electrode, electrolyte and a diaphragm. During charging, lithium ions are extracted from the anode material and migrate to the cathode through the diaphragm and the electrolyte, electrons flow from the anode to the cathode in an external circuit, and are reduced into metal Li after the electrons are obtained by the cathode, and then the metal Li is embedded into a cathode lattice; and the discharge process is reversed. Li is transferred between the positive electrode and the negative electrode of the battery, and electrons with the same quantity are also transferred between the positive electrode and the negative electrode through an external circuit, so that the positive electrode and the negative electrode are subjected to oxidation-reduction reaction and are kept at a certain potential.
The diaphragm has three main functions in the lithium ion battery, on one hand, the diaphragm separates the positive electrode from the negative electrode, only allows ions to pass through, and is an electronic insulator to prevent short circuit; on one hand, the electrolyte is kept to form an ion channel, the ion channel does not participate in electrochemical reaction in the battery, and the highly bent channel can also prevent dendritic crystal growth; and on the other hand, when the temperature of the battery rises to the closed pore temperature, the micropores of the diaphragm are closed, so that the battery stops working. In a battery system, the structure of the diaphragm plays a very important role in the migration of the lithium ion battery in the electrolyte, so that the performance of the diaphragm directly influences the internal resistance, the interface structure, the cycle performance and the like of the battery.
The coating of the polymer coated diaphragm has good affinity to electrolyte, and the electrolyte in the battery can be stored in the amorphous area of the polymer coating, so that the wettability and the liquid absorption rate of the diaphragm to the electrolyte are improved. Compared with oily polymer coating, the water-based polymer coating process has the advantages of small pollution to the environment, high air permeability of the product and the like. However, the conventional coating process uses pure polymer powder as a raw material, has high crystallinity, and the high-crystallinity coating is not favorable for absorption of an electrolyte, thereby reducing the ionic conductivity of the coated separator, affecting the battery performance and the service life.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of low-crystallinity polymer powder and a method for preparing a high-liquid-absorption-rate water-based polymer diaphragm by adopting the low-crystallinity polymer powder.
The technical scheme provided by the invention is as follows:
a preparation method of a high liquid absorption rate water-based polymer diaphragm is characterized by comprising the following steps:
adding a hydrophobic polymer A and a hydrophilic polymer B into a polar organic solvent to form a polymer mixture, heating and stirring to uniformly dissolve the polymer mixture to form a uniform polymer solution;
spray drying the polymer solution to obtain spherical polymer powder;
and (3) preparing the polymer powder and the auxiliary agent into slurry, coating the slurry on a base film, and drying to obtain the high-liquid-absorption-rate water-based polymer diaphragm.
Preferably, the method further comprises the step of modifying the polymer powder, and more preferably, the step of modifying the polymer powder is as follows: and (3) pouring the spherical polymer powder into the modification liquid, modifying at the temperature of 20-100 ℃, filtering, and drying at the temperature of 50-200 ℃ to obtain the modified polymer powder.
Preferably, the hydrophobic polymer A comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile and aramid fiber.
Preferably, the hydrophilic polymer B comprises one or more of polyethylene oxide, cellulose-based polymer, and polymethyl methacrylate.
Preferably, the mass ratio of the hydrophobic polymer A to the hydrophilic polymer B is 1 to (0.001-999), and more preferably 1 to (0.05-20).
Preferably, the polar organic solvent comprises one or more of nitrogen methyl pyrrolidone, nitrogen methyl formamide, nitrogen dimethyl acetamide, acetone, dimethyl sulfoxide.
Preferably, the modifying solution is an aqueous solution of a polar organic solvent, and the mass fraction of the organic solvent is 0.1-5%; more preferably, the polar organic solvent comprises one or more of azomethylpyrrolidone, azomethylformamide, azodimethylacetamide, acetone, dimethylsulfoxide.
Preferably, the atomization drying temperature of the spray drying is 80-300 ℃, and the atomization pressure is 0.05-5 Mpa.
Preferably, the spray drying is carried out by feeding the polymer solution into the spray dryer using a precision feeding device comprising a peristaltic pump, a metering rotor pump, at a feeding rate of 50-1000 ml/h.
Preferably, according to the mass fraction, 10-40% of modified polymer powder, 0.01-0.5% of cellulose ether dispersant, 0.05-0.1% of fluorocarbon surfactant, 0.05-0.3% of sodium carboxymethyl cellulose, 7-18% of acrylate adhesive and the balance of deionized water are prepared into slurry and coated on a base film, and more preferably, the high liquid absorption rate water-based polymer coating diaphragm is obtained after drying at the temperature of 40-90 ℃.
A lithium battery having a high liquid absorption rate aqueous polymer separator prepared by the method of the present invention.
The invention has the beneficial effects that:
1. the invention adopts a spray drying method to prepare the spherical polymer particles mixed by the hydrophobic polymer and the hydrophilic polymer, thereby greatly reducing the crystallinity of the polymer particles and enabling the polymer particles to absorb more electrolyte.
2. According to the invention, the polymer mixed particles are modified, hydrophilic groups can be dissociated to the surfaces of the polymer particles in the modification solution, and the modified polymer particles have better dispersibility in water, thereby being beneficial to the dispersion stability of the polymer in the coating slurry.
3. After the diaphragm prepared by the method is assembled into a battery, the battery has excellent high-rate charge-discharge performance and cycle stability.
Drawings
FIG. 1 is an SEM image of a polymer spherical powder prepared by a spray drying method according to the present invention.
Detailed Description
For further understanding of the present invention, preferred embodiments of the present invention will be described in further detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto.
Example 1
Polyvinylidene fluoride and polymethyl methacrylate are added into N-methyl formamide in the mass ratio of 1: 0.2, and the mass fraction of the polymer mixture in the N-methyl formamide is 1%. The polymer is dissolved evenly by heating and stirring at 60 ℃ to form a uniform polymer solution. The polymer solution was slowly added to a spray dryer at a rate of 100 ml/hr by a peristaltic pump to spray-dry at an atomization drying temperature of 80 ℃ under an atomization pressure of 0.2Mpa, to obtain a spherical polymer powder. And (3) pouring the spherical polymer powder into a 1% N-methyl formamide aqueous solution, modifying at 20 ℃, filtering, and drying at 100 ℃ to obtain modified polymer powder. The crystallinity of the modified polymer powder was measured by differential scanning calorimetry and the polymer powder produced had a crystallinity of 18.6%.
According to the mass fraction, 20% of modified polymer powder, 0.2% of cellulose ether dispersant, 0.05% of fluorocarbon surfactant, 0.3% of sodium carboxymethylcellulose, 7% of acrylate adhesive and the balance of deionized water are prepared into slurry, and the slurry does not settle obviously after standing for 24 hours.
And coating the slurry which is not subjected to standing treatment on a polyethylene diaphragm, and drying at the temperature of 60 ℃ to obtain the high-liquid-absorption-rate water-based polymer coated diaphragm. When the thickness of the coating layer of the high liquid absorption rate water-based polymer coating membrane is controlled to be 2 mu m, the liquid absorption rate of the coating membrane is 208.7 percent, the water content of the coating membrane is 436ppm, and the air permeability is 189s/(100cc in2 & 1.22 kPa).
The prepared polymer coating diaphragm, lithium cobaltate and metallic lithium are assembled into a button cell in a glove box, and a charge-discharge test is carried out under the current of 2C, so that the capacity retention rate is 91.7 percent after 300 cycles.
Comparative example 1
Polyvinylidene fluoride and polymethyl methacrylate are added into N-methyl formamide in the mass ratio of 1: 0.2, and the mass fraction of the polymer mixture in the N-methyl formamide is 1%. The polymer is dissolved evenly by heating and stirring at 60 ℃ to form a uniform polymer solution. The polymer powder is directly dried at 80 ℃ without adopting a spray drying method to obtain the polymer powder. Pouring the polymer powder into a 1% N-methyl formamide aqueous solution, modifying at 20 ℃, filtering, drying at 100 ℃ to obtain modified polymer powder, and testing the crystallinity of the polymer powder by adopting differential scanning calorimetry, wherein the crystallinity of the polyvinylidene fluoride polymer powder is 37.2%.
According to the mass fraction, 20% of polyvinylidene fluoride polymer powder, 0.2% of cellulose ether dispersant, 0.05% of fluorocarbon surfactant, 0.3% of sodium carboxymethyl cellulose, 7% of acrylate adhesive and the balance of deionized water are prepared into slurry, and the slurry is settled obviously after standing for 5 hours.
Coating the slurry which is not subjected to standing treatment on a polyethylene diaphragm, and drying at the temperature of 60 ℃ to obtain the polyvinylidene fluoride polymer coated diaphragm. When the thickness of the coating layer of the polyvinylidene fluoride polymer coating membrane is controlled to be 2 mu m, the liquid absorption rate of the coating membrane is 157.4 percent, the water content of the membrane is 397ppm, and the air permeability is 217s/(100cc in2 & 1.22 kPa).
The prepared polymer coating diaphragm, lithium cobaltate and metallic lithium are assembled into a button cell in a glove box, and a charge-discharge test is carried out under the current of 2C, and the capacity retention rate is 72.4 percent after 300 cycles.
Comparative example 2
Polyvinylidene fluoride and polymethyl methacrylate are added into N-methyl formamide in the mass ratio of 1: 0.2, and the mass fraction of the polymer mixture in the N-methyl formamide is 1%. The polymer is dissolved evenly by heating and stirring at 60 ℃ to form a uniform polymer solution. The polymer solution was slowly added to a spray dryer at a rate of 100 ml/hr by a peristaltic pump to spray-dry at an atomization drying temperature of 80 ℃ under an atomization pressure of 0.2Mpa, to obtain a spherical polymer powder. The crystallinity of the modified polymer powder was measured by differential scanning calorimetry and the polymer powder produced had a crystallinity of 22.3%.
According to the mass fraction, 20% of polymer powder, 0.2% of cellulose ether dispersant, 0.05% of fluorocarbon surfactant, 0.3% of sodium carboxymethyl cellulose, 7% of acrylate adhesive and the balance of deionized water are prepared into slurry, and the slurry is settled obviously after standing for 12 hours.
And coating the slurry which is not subjected to standing treatment on a polyethylene diaphragm, and drying at the temperature of 60 ℃ to obtain the polymer coated diaphragm. When the thickness of the coating layer of the polymer-coated separator was controlled to 2 μm, the liquid absorption of the coated separator was 187.5%, the water content of the separator was 417ppm, and the air permeability was 173s/(100cc in 2.1.22 kPa).
The prepared polymer coating diaphragm, lithium cobaltate and metallic lithium are assembled into a button cell in a glove box, and a charge-discharge test is carried out under the current of 2C, so that the capacity retention rate is 83.7 percent after 300 cycles.
TABLE 1 Properties of Polymer membranes produced by different preparation Processes
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a high liquid absorption rate water-based polymer diaphragm is characterized by comprising the following steps:
adding a hydrophobic polymer A and a hydrophilic polymer B into a polar organic solvent to form a polymer mixture, heating and stirring to uniformly dissolve the polymer mixture to form a uniform polymer solution;
spray drying the polymer solution to obtain spherical polymer powder;
preparing the polymer powder and the auxiliary agent into slurry, coating the slurry on a base film, and drying to obtain the high-liquid-absorption-rate water-based polymer diaphragm;
the preparation method also comprises the step of modifying the polymer powder, wherein the modifying step comprises the following steps: pouring the spherical polymer powder into the modification liquid, modifying at 20-100 ℃, filtering, and drying at 50-200 ℃ to obtain modified polymer powder; the modified solution is an aqueous solution of a polar organic solvent, and the mass fraction of the polar organic solvent is 0.1-5%; the polar organic solvent comprises one or more of N-methyl pyrrolidone, N-methyl formamide, N-dimethyl acetamide, acetone and dimethyl sulfoxide.
2. The method for preparing the high liquid absorption rate water-based polymer membrane as claimed in claim 1, wherein the hydrophobic polymer A comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile and aramid fiber.
3. The method for preparing a high liquid absorption rate water-based polymer membrane as claimed in claim 1, wherein the hydrophilic polymer B comprises one or more of polyethylene oxide, cellulose-based polymer and polymethyl methacrylate.
4. The method of claim 1, wherein the polar organic solvent comprises one or more of N-methylpyrrolidone, N-methylformamide, N-dimethylacetamide, acetone, and dimethylsulfoxide.
5. The method for preparing the high liquid absorption rate water-based polymer diaphragm as claimed in claim 1, wherein the spray drying has an atomization drying temperature of 80-300 ℃ and an atomization pressure of 0.05-5 Mpa.
6. The method for preparing a high liquid absorption rate aqueous polymer membrane according to claim 1, wherein the polymer solution is added into the spray dryer for spray drying by using a precise feeding device, wherein the precise feeding device comprises a peristaltic pump and a metering rotor pump, and the feeding speed is 50-1000 ml/h.
7. The method for preparing the high liquid absorption rate water-based polymer diaphragm as claimed in claim 1, wherein, according to the mass fraction, 10-40% of modified polymer powder, 0.01-0.5% of cellulose ether dispersant, 0.05-0.1% of fluorocarbon surfactant, 0.05-0.3% of sodium carboxymethyl cellulose, 7-18% of acrylate adhesive and the balance of deionized water are prepared into slurry, and the slurry is coated on a base film and dried at 40-90 ℃ to obtain the high liquid absorption rate water-based polymer coating diaphragm.
8. A lithium battery having the high liquid-absorbing rate aqueous polymer separator as claimed in any one of claims 1 to 7.
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| CN110690390A (en) * | 2019-10-09 | 2020-01-14 | 深圳中兴新材技术股份有限公司 | Preparation method of high-adhesion coating diaphragm and prepared coating diaphragm |
| CN113178658A (en) * | 2021-03-23 | 2021-07-27 | 河北金力新能源科技股份有限公司 | Lithium battery diaphragm slurry, high liquid absorption rate diaphragm and preparation method and application thereof |
| CN115207566B (en) * | 2022-08-24 | 2024-10-11 | 宁德卓高新材料科技有限公司 | PMMA/PVDF composite diaphragm and preparation method and application thereof |
| WO2024216474A1 (en) * | 2023-04-17 | 2024-10-24 | 宁德时代新能源科技股份有限公司 | Separator, battery cell, battery, and electric device |
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2018
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