CN114843703B - Battery separator with irregularly-shaped particle coating and preparation method thereof - Google Patents
Battery separator with irregularly-shaped particle coating and preparation method thereof Download PDFInfo
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- CN114843703B CN114843703B CN202210550603.3A CN202210550603A CN114843703B CN 114843703 B CN114843703 B CN 114843703B CN 202210550603 A CN202210550603 A CN 202210550603A CN 114843703 B CN114843703 B CN 114843703B
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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
- H01M50/431—Inorganic 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
- H01M50/403—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
- 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
- H01M50/443—Particulate material
-
- 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 application relates to a battery diaphragm with an irregular particle coating and a preparation method thereof, wherein the battery diaphragm comprises a diaphragm base film and a coating covered on the surface of the diaphragm base film, and irregular particles are uniformly distributed in the coating; the structure of the irregularly-shaped particles comprises spherical particles of which the surfaces are coated with PMMA (polymethyl methacrylate), and a polymer layer polymerized after swelling the PMMA part coated with the surfaces, wherein the glass transition temperature of the polymer layer is more than 85 ℃; dispersing irregularly-shaped particles in water, adding a water-based thickener, a water-based adhesive and a water-based wetting agent under stirring, uniformly stirring to obtain slurry, uniformly coating the slurry on one side or two sides of a diaphragm substrate, drying, and rolling to obtain the battery diaphragm with irregularly-shaped particle coating. The hot-press peeling strength between the coating and the pole piece is good, and meanwhile, the heat resistance is good.
Description
Technical Field
The application relates to the technical field of battery diaphragms with coatings, in particular to a battery diaphragm with an irregularly-shaped particle coating and a preparation method thereof.
Background
The battery diaphragm is used as one of four main constituent materials of the lithium battery, and is mainly used for separating an anode and a cathode, and absorbing electrolyte to allow lithium ions to pass through. For the lithium battery of the 3C product, only polyolefin separators, such as PP separators, PE separators and the like, can basically meet the battery performance. However, in recent years, with the rapid development of the new energy automobile industry, higher requirements are put on the performance of the separator in the power battery, such as adhesion between the separator and the pole piece, better heat resistance and the like.
The polyolefin separator is the lithium battery separator which is most widely used at present, but the existing polyolefin separator on the market has the problems of insufficient performance of the electrophilic solution and poor heat resistance. In order to solve the problems of insufficient performance and poor heat resistance of the polyolefin diaphragm electrolyte, the main solution is to coat PVDF coating after coating ceramic on one side or two sides of the polyolefin diaphragm, and the PVDF has the problems of higher price, shortage of supply and the like. In such a large background, more and more suppliers are beginning to search for materials that can replace PVDF. PMMA (polymethyl methacrylate) is one of the hot spots due to the affinity electrolyte, low price and easy control of the glass transition temperature.
In order to synchronously finish ceramic coating and glue coating, the main method at present is to coat inorganic particles by utilizing PMMA, and the common regular spherical coated particles can well realize one-time coating so that a coating film and a pole piece have higher cohesiveness, but the heat resistance of the coating film is difficult to further improve, so that a battery has larger potential safety hazard.
Disclosure of Invention
In order to solve the technical problem of poor heat resistance of polyolefin separators, a battery separator with an irregularly-shaped particle coating and a preparation method thereof are provided. The hot-press peeling strength between the coating and the pole piece is good, and meanwhile, the heat resistance is good.
In order to achieve the above purpose, the application is realized by the following technical scheme:
a battery diaphragm with an irregular particle coating comprises a diaphragm base film and a coating layer covering the surface of the diaphragm base film, wherein irregular particles are uniformly distributed in the coating layer;
the structure of the irregularly shaped particles comprises spherical particles of inorganic particle surface-coated PMMA and a polymer layer polymerized after swelling of the surface-coated PMMA part, wherein the glass transition temperature of the polymer layer is more than 85 ℃.
Further, the inorganic particles are titanium dioxide, silicon dioxide or aluminum oxide, so the spherical particles may be TiO 2 Surface-coated PMMA, siO 2 Surface-coated PMMA or Al 2 O 3 Coating PMMA on the surface; the polymer layer is polyacrylonitrile; the membrane base membrane is a polyolefin membrane and can be of a single-sided coating or double-sided coating structure.
Further, the preparation of the irregularly shaped particles comprises the steps of: dispersing spherical particles of PMMA coated on the surfaces of inorganic particles in water, adding a polymerizable monomer solvent for swelling at normal temperature after deoxidizing by nitrogen, heating to 60-120 ℃, adding an initiator for polymerization reaction, and carrying out solid-liquid separation to obtain irregularly-shaped particles.
Still further, the spherical particles are TiO 2 Surface-coated PMMA, siO 2 Surface-coated PMMA or Al 2 O 3 Coating PMMA on the surface; the polymerizable monomer solvent is acrylonitrile; the initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, ammonium persulfate, potassium persulfate, benzoyl peroxide, tertiary butyl benzoyl peroxide and methyl ethyl ketone peroxide.
Still further, the swelling time is 30min-4h; the temperature of the polymerization reaction is 65-90 ℃ and the time is 1-5h; the time for deoxidizing the nitrogen is at least 10min.
Still further, the solid content of the dispersion formed after the spherical particles are dispersed in water is 6 to 10wt%; the dosage proportion of the spherical particles, the polymerizable monomer solvent and the initiator is as follows; (15-25): (1-5): (0.0025-0.02).
Still further, the irregularly shaped particles are present in an amount of 10 to 50wt% in the slurry forming the coating, the slurry being applied to the surface of the separator base film in an amount of 2 to 5g/m 2 Preferably, the coating amount is 3g/m 2 。
In another aspect, the present application provides a method for preparing the battery separator with the irregularly shaped particle coating, comprising the steps of: dispersing irregularly-shaped particles in water, adding a water-based thickener, a water-based adhesive and a water-based wetting agent under stirring, uniformly stirring to obtain slurry, uniformly coating the slurry on one side or two sides of a diaphragm substrate, drying, and rolling to obtain the battery diaphragm with irregularly-shaped particle coating.
Further, the slurry comprises, by mass, 100% of irregularly-shaped particles, 10-50% of the aqueous thickener, 30-40% of the aqueous binder, 3-8% of the aqueous wetting agent, 0.05-0.5% of the aqueous wetting agent and the balance of water; the stirring speed is 200-800rpm, and the stirring time is 30min-5h.
Further, the aqueous thickener is carboxymethyl cellulose; the aqueous adhesive is an acrylic adhesive; the aqueous wetting agent is a mixture of ethoxylated alcohol and acetylene glycol.
The beneficial technical effects are as follows: existing common spherical TiO 2 Although the PMMA particle coated battery diaphragm can meet the requirement of higher hot-pressing peeling strength between the PMMA particle coated battery diaphragm and the pole piece, the coated film has poor heat resistance, and in the use process of the battery, the temperature rises, and the positive pole and the negative pole can be directly contacted and short-circuited due to shrinkage, so that the battery has larger potential safety hazard. The application is characterized in that the spherical TiO is 2 The PMMA particles are partially swelled by the polymerizable solvent monomer and polymerized to form irregularly shaped TiO 2 The PMMA/PAN particles have larger contact area than spheres, can be more tightly arranged in the coating, and can well resist the shrinkage force of the base film generated by heat when heated, so that the thermal shrinkage rate of the diaphragm is lower, the heat resistance of the diaphragm is improved, and the safety of the battery is ensured.
Drawings
FIG. 1 is an irregularly shaped TiO 2 Synthetic technical route map of/PMMA/PAN particles.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the application, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The numerical values set forth in these examples do not limit the scope of the present application unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
A battery separator with irregularly-shaped particle coating comprises a PP base film and a coating layer covering the surface of the PP base film, wherein irregularly-shaped particles are uniformly distributed in the coating layer, and the irregularly-shaped particles have a structure comprising TiO 2 Spherical particles of surface-coated PMMA (hereinafter abbreviated as TiO 2 PMMA), and a layer of polymerized PAN polymer after partial swelling of the surface-coated PMMA, the irregularly shaped particles being abbreviated as TiO 2 /PMMA/PAN。
Wherein the preparation of irregularly shaped particles comprises the steps of: tiO is mixed with 2 PMMA spherical particles were dispersed in water to form a dispersion having a solids content of 8wt%, N 2 Bubbling for 30min to remove oxygen, adding AN, swelling at normal temperature, heating to 65deg.C, adding KPS initiator, polymerizing for 2 hr, and polymerizing to obtain TiO as raw material 2 The mass ratio of the PMMA spherical particles to the AN to the KPS is 20:1:0.02, cooling after the reaction is finished, and carrying out solid-liquid separation to obtain the TiO 2 The technical route diagram of the PMMA/PAN irregularly-shaped particles is shown in figure 1;
wherein TiO is 2 The preparation process of PMMA spherical particles is to prepare the PMMA spherical particles by TiO 2 The core is obtained by soap-free emulsion polymerization to obtain core-shell TiO 2 PMMA particles: deionized water, N, was added to a 250mL three-necked flask 2 Bubbling for 0.5h, adding TiO according to the mass ratio of 99:1 2 And KH-570 (deionized water (TiO) 2 +kh-570) =9:1, mass ratio), stirring at 35 ℃ for 0.5h; tiO in mass ratio 2 MMA: naSS=3:2:0.04 MMA monomer and NaSS (para-styrene) were slowly addedSodium sulfonate) at 35 ℃ for 2h, slowly adding a KPS solution according to the mass ratio of MMA to KPS=1:0.015, heating to 65 ℃ for polymerization reaction for 2h, cooling, centrifugally washing for 2 times, and obtaining TiO 2 PMMA particles.
Preparation of battery separator with irregularly shaped particle coating: tiO is mixed with 2 Dispersing PMMA/PAN irregularly shaped particles in water, stirring at 400-600rpm for 30-60min, adding carboxymethyl cellulose as water-based thickener, and stirring for 60min; adding an aqueous acrylic adhesive, stirring at a speed of 200-300rpm for 30-60min, adding a mixture of an aqueous wetting agent ethoxylated alcohol and acetylene glycol, continuously stirring for 30-60min, and uniformly stirring to obtain a slurry, wherein the mass percent of the slurry is 100%, and the TiO is the same as that of the slurry 2 20% of PMMA/PAN irregularly shaped particles, 35% of the aqueous thickener, 4% of the aqueous binder, 0.1% of the aqueous wetting agent and the balance of water;
and uniformly coating the slurry on one side of a diaphragm substrate, drying and rolling to obtain the battery diaphragm with the irregularly-shaped particle coating.
Example 2
The battery separator structure having the irregularly shaped particle coating layer of this example was the same as that of example 1, except that in the preparation of the battery separator having the irregularly shaped particle coating layer, the slurry was 100% by mass, the TiO 2 25% of PMMA/PAN irregularly-shaped particles, 30% of aqueous thickener, 4% of aqueous binder, 0.2% of aqueous wetting agent and the balance of water.
Example 3
The battery separator structure having the irregularly shaped particle coating layer of this example was the same as that of example 1, except that in the preparation of the battery separator having the irregularly shaped particle coating layer, the slurry was 100% by mass, the TiO 2 25% of PMMA/PAN irregularly-shaped particles, 35% of aqueous thickener, 8% of aqueous binder, 0.3% of aqueous wetting agent and the balance of water.
Comparative example 1
The battery separator of this comparative exampleThe membrane structure was the same as that of example 1, except that TiO was used 2 PMMA spherical particles instead of TiO 2 Irregularly shaped particles of PMMA/PAN (i.e. in obtaining TiO) 2 After PMMA spherical particles, no AN was added, no subsequent swelling-polymerization process) the slurry was 100% by mass, the TiO 2 25% of PMMA spherical particles, 30% of aqueous thickener, 7% of aqueous binder, 0.3% of aqueous wetting agent and the balance of water.
The performance of the separators of the above examples and comparative examples was tested, and the results are shown in table 1.
Table 1 separator properties of examples and comparative examples
As can be seen from Table 1, comparative examples 1, 2, 3 and comparative example 1 have TiO 2 Coated membranes of PMMA/PAN irregularly shaped particles, which, with control of the same areal density, can be used with conventional spherical TiO 2 The coated membrane of the PMMA particles achieves the same effect of bonding the pole pieces. As can be seen from the heat shrinkage test results, tiO was used 2 The thermal shrinkage of the coated membrane of PMMA/PAN irregularly shaped particles is less than that of the coated membrane using conventional spherical TiO 2 Coated membranes of PMMA particles, i.e. with TiO 2 The heat resistance of the/PMMA/PAN irregularly shaped coated separator is relatively good.
To sum up, compared with the common spherical TiO 2 PMMA coated diaphragm, shaped TiO prepared by the application 2 The PMMA/PAN coated diaphragm has higher hot-pressing peeling strength and better heat resistance.
The above only shows the case of using titanium dioxide as a coating layer for the irregularly shaped particles, and those skilled in the art can select other inorganic particles such as silica, alumina, etc. mentioned in the present application while facing the same technical problems.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
Claims (7)
1. A battery separator with an irregularly shaped particle coating, comprising a separator base film and a coating layer covering the surface of the separator base film, wherein irregularly shaped particles are uniformly distributed in the coating layer;
the structure of the irregularly-shaped particles comprises spherical particles of which the surfaces are coated with PMMA (polymethyl methacrylate), and a polymer layer polymerized after swelling the PMMA part coated with the surfaces, wherein the glass transition temperature of the polymer layer is more than 85 ℃;
the inorganic particles are titanium dioxide, silicon dioxide or aluminum oxide; the polymer layer is polyacrylonitrile; the diaphragm base film is a polyolefin diaphragm;
the preparation of the irregularly shaped particles comprises the following steps:
dispersing spherical particles of PMMA coated on the surfaces of inorganic particles in water, adding a polymerizable monomer solvent for swelling at normal temperature after deoxidizing by nitrogen, heating to 60-120 ℃, adding an initiator for polymerization reaction, and carrying out solid-liquid separation to obtain irregularly-shaped particles.
2. A battery separator with irregularly shaped particle coating according to claim 1, wherein the spherical particles are TiO 2 Surface-coated PMMA, siO 2 Surface-coated PMMA or Al 2 O 3 Coating PMMA on the surface; the polymerizable monomer solvent is acrylonitrile; the initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, ammonium persulfate, potassium persulfate, benzoyl peroxide, tertiary butyl benzoyl peroxide and methyl ethyl ketone peroxide.
3. A battery separator with irregularly shaped particle coatings according to claim 1, wherein the swelling time is 30min-4h; the temperature of the polymerization reaction is 65-90 ℃ and the time is 1-5h; the time for deoxidizing the nitrogen is at least 10min.
4. A battery separator with an irregularly shaped particle coating according to claim 3, wherein the solid content of the dispersion formed after the spherical particles are dispersed in water is 6-10wt%; the mass ratio of the spherical particles, the polymerizable monomer solvent and the initiator is (15-25): 1-5): 0.0025-0.02.
5. A battery separator having a coating of irregularly shaped particles according to any one of claims 1 to 4, wherein the irregularly shaped particles comprise 10 to 50wt% of the coating-forming slurry, and the coating amount of the slurry on the surface of the separator base film is 2 to 5g/m 2 。
6. A method of preparing a battery separator having an irregularly shaped particulate coating according to any one of claims 1 to 5, comprising the steps of: dispersing irregularly-shaped particles in water, adding a water-based thickener, a water-based adhesive and a water-based wetting agent under stirring, uniformly stirring to obtain slurry, uniformly coating the slurry on one side or two sides of a diaphragm substrate, drying, and rolling to obtain the battery diaphragm with irregularly-shaped particle coating.
7. The preparation method according to claim 6, wherein the slurry comprises, by mass, 100%, 10-50% of irregularly shaped particles, 30-40% of the aqueous thickener, 3-8% of the aqueous binder, 0.05-0.5% of the aqueous wetting agent, and the balance water; the stirring speed is 200-800rpm, and the stirring time is 30min-5h.
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| CN202210550603.3A CN114843703B (en) | 2022-05-18 | 2022-05-18 | Battery separator with irregularly-shaped particle coating and preparation method thereof |
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| CN114843703B true CN114843703B (en) | 2023-09-22 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105449141A (en) * | 2015-12-24 | 2016-03-30 | 深圳中兴创新材料技术有限公司 | Preparation method of battery diaphragm and battery membrane |
| CN112142995A (en) * | 2020-08-24 | 2020-12-29 | 深圳市德立新材料科技有限公司 | Organic-inorganic composite grape particle structure material, slurry, diaphragm and preparation method |
| CN113131094A (en) * | 2021-03-01 | 2021-07-16 | 东莞市溢兴新材料科技有限公司 | High-adhesion polymer coating diaphragm and preparation method thereof |
| CN114361706A (en) * | 2021-12-29 | 2022-04-15 | 上海恩捷新材料科技有限公司 | Coated diaphragm and preparation method thereof |
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- 2022-05-18 CN CN202210550603.3A patent/CN114843703B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105449141A (en) * | 2015-12-24 | 2016-03-30 | 深圳中兴创新材料技术有限公司 | Preparation method of battery diaphragm and battery membrane |
| CN112142995A (en) * | 2020-08-24 | 2020-12-29 | 深圳市德立新材料科技有限公司 | Organic-inorganic composite grape particle structure material, slurry, diaphragm and preparation method |
| CN113131094A (en) * | 2021-03-01 | 2021-07-16 | 东莞市溢兴新材料科技有限公司 | High-adhesion polymer coating diaphragm and preparation method thereof |
| CN114361706A (en) * | 2021-12-29 | 2022-04-15 | 上海恩捷新材料科技有限公司 | Coated diaphragm and preparation method thereof |
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