CN116454536B - Coating slurry containing modified montmorillonite for lithium battery separator, and preparation method and application thereof - Google Patents
Coating slurry containing modified montmorillonite for lithium battery separator, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116454536B CN116454536B CN202310648376.2A CN202310648376A CN116454536B CN 116454536 B CN116454536 B CN 116454536B CN 202310648376 A CN202310648376 A CN 202310648376A CN 116454536 B CN116454536 B CN 116454536B
- Authority
- CN
- China
- Prior art keywords
- lithium battery
- modified montmorillonite
- montmorillonite
- parts
- battery separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 86
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- 239000006255 coating slurry Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002562 thickening agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a modified montmorillonite-containing coating slurry for lithium battery diaphragms, a preparation method and application thereof, wherein the modified montmorillonite-containing coating slurry for lithium battery diaphragms is prepared from the following components in parts by weight: ethyl acrylate, styrene, modified montmorillonite, surfactant, initiator, thickener, adhesive and water. Wherein the modified montmorillonite is a product obtained by the reaction of montmorillonite and acrylic acid. The modified montmorillonite adopts hydroxylated montmorillonite as a raw material, and is soaked in acrylic acid for modification. The modified montmorillonite can improve the dispersibility and uniformity of the montmorillonite in the polyolefin matrix, the compatibility of the modified montmorillonite and the polyolefin matrix is good, the coating slurry containing the modified montmorillonite has good adhesion performance, and the modified montmorillonite can be firmly adhered with the lithium battery matrix film, so that the safety and stability of the lithium battery are improved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a coating slurry containing modified montmorillonite for a lithium battery diaphragm, and a preparation method and application thereof.
Background
The lithium battery is widely applied to the fields of electric automobiles, smart phones, notebook computers and the like as a battery with high performance, high efficiency, light weight and environmental protection. The lithium battery mainly comprises parts such as positive and negative electrodes, electrolyte, a diaphragm and the like, the diaphragm of the lithium battery has the main functions of isolating the positive and negative electrodes, preventing the occurrence of safety problems such as short circuit, overcharge, overdischarge and the like, and meanwhile, the lithium battery can be used as an electrolyte reservoir to promote ion conduction, ensure the electrochemical performance of the battery and have important influence on the capacity, the cycle performance and the safety stability of the battery, so that the comprehensive performance of the battery is directly influenced by the advantages and disadvantages of the diaphragm performance.
The traditional lithium battery diaphragm mainly adopts polyolefin materials such as polypropylene, polyethylene, polyimide and the like, but the materials have the problems of short circuit caused by contact between positive and negative electrodes, low mechanical strength, low electrolyte wettability, weak ion exchange capacity and the like due to easy shrinkage when heated at high temperature, and the performance and the safety of the lithium battery are limited. In order to solve the defects of polyolefin material diaphragms, inorganic material coatings are generally coated on the polyolefin diaphragms to modify the diaphragms so as to improve the performance of the diaphragms. However, the compatibility of inorganic materials and organic membranes is poor, resulting in poor mechanical strength and electrochemical stability of the membranes.
CN110277527a discloses a polypropylene microporous membrane, a preparation method thereof and a lithium battery diaphragm, wherein the main components of the diaphragm comprise isotactic polypropylene and beta crystal form nucleating agent, and the polypropylene microporous membrane is prepared by a dry process, has good mechanical properties, but has low thermal shrinkage stability, and can generate volume shrinkage of different degrees under the condition of high temperature to cause internal short circuit.
CN103490028A discloses a lithium battery separator in which a hollow particle membrane layer is coated on a substrate, the hollow particles are silica particles or polyolefin particles, the hollow structure can reduce the overall heat conduction rate, but the hollow particles may gradually wear during the use of the lithium battery, and tiny particles are generated to reduce the safety of the lithium battery.
CN104485436a discloses a ceramic diaphragm for lithium battery with flame retardant property and its preparation method, the main components of the diaphragm comprise polypropylene, polyimide, flame retardant and ceramic powder, which has excellent high temperature resistant property, but the adhesiveness of ceramic powder and organic diaphragm is low, and the ceramic powder falls off to cause performance degradation.
In view of the foregoing, there is a need to develop a technical solution, and apply the technical solution to a lithium battery separator to achieve the performances of high safety, long cycle life, good peeling resistance and the like.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a coating slurry for lithium battery separator containing modified montmorillonite filler and a preparation method thereof, wherein the modified montmorillonite adopts hydroxylated montmorillonite as a raw material, and is soaked in acrylic acid for modification. In the modification process, carboxyl in acrylic acid and hydroxyl on the surface of montmorillonite are subjected to esterification reaction to form an organic montmorillonite composite, so that the surface property of montmorillonite is changed, the dispersibility and stability of montmorillonite in a polymer are improved, and the compatibility between montmorillonite and polyolefin matrix is increased. Subsequently, free radicals are generated by the initiator and react with the styrene molecules to form free radical polymers. And finally, blending the modified montmorillonite with other components to react to generate the styrene polymer/modified montmorillonite composite material. When the coating slurry is brushed on the surface of the diaphragm, the thickness is controlled to be about 2-4 mu m, so that the heat resistance and the peeling strength of the diaphragm product can be improved.
The coating slurry for the lithium battery diaphragm containing the modified montmorillonite is prepared from the following components in parts by weight:
water;
further, the surfactant is selected from anionic surfactant or nonionic surfactant, the binder is aqueous polyacrylate, and the thickener is sodium carboxymethyl cellulose.
Further, the initiator is selected from azo-type or peroxide-type initiators.
Further, the initiator is selected from BPO.
Another object of the present invention is to provide a method for preparing the coating paste for lithium battery separator containing modified montmorillonite, comprising the steps of:
s1, soaking hydroxylated montmorillonite in acrylic acid, performing ultrasonic and heating reaction to obtain a crude product;
s2, washing and air-drying the crude product to obtain the modified montmorillonite;
s3, blending the modified montmorillonite with other components, and heating for reaction to obtain a product.
Further, in step S1, the heating temperature is 80-100 ℃.
Further, in step S1, the reaction time is 2-4h.
Further, in step S1, the reaction is performed under the protection of inert gas.
Further, in step S3, the reaction time is 2-4 hours.
Further, in step S3, the heating temperature is 80-100 ℃.
Preparation of lithium battery separator containing modified montmorillonite: and uniformly coating the two sides of the coating slurry for the lithium battery diaphragm containing the modified montmorillonite on the surface of the lithium battery base film to prepare the lithium battery diaphragm containing the modified montmorillonite.
Further, in the preparation of the lithium battery diaphragm containing the modified montmorillonite, the lithium battery base diaphragm is one of a polypropylene micro diaphragm, a polyethylene diaphragm and a polyimide diaphragm.
The invention has the following beneficial effects: 1. the modified montmorillonite can improve the dispersibility and uniformity of the montmorillonite in the polyolefin matrix, the compatibility of the modified montmorillonite and the polyolefin matrix is good, the coating slurry containing the modified montmorillonite has good adhesion performance, and the modified montmorillonite can be firmly adhered with the lithium battery matrix film, so that the safety and stability of the lithium battery are improved.
2. The montmorillonite has a unique lamellar nano structure, proper interlayer charge and good thermal stability, and the modified montmorillonite is used as coating slurry of the lithium battery diaphragm, so that the absorption space of electrolyte is increased, the electrolyte wettability and thermal stability of the lithium battery diaphragm can be improved, and the safety performance and the cycle life of the lithium battery are improved.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
The ethyl acrylate disclosed by the embodiment of the invention is purchased from new material technology Co., ltd;
the styrene of the embodiment of the invention is purchased from Shandong Chuang chemical industry Co., ltd;
the montmorillonite in the embodiment of the invention is hydroxylated montmorillonite, and is purchased from Zhejianghua characteristic materials limited company;
the surfactant in the embodiment of the invention is an anionic surfactant purchased from Nanjing chime sea commerce and trade company Limited;
the initiator in the embodiment of the invention is peroxide initiator BPO, and is purchased from Guangzhou city edge creation chemical Co., ltd;
the binder in the embodiment of the invention is water-based polyacrylate, and is purchased from Anhui Zhongen chemical industry Co., ltd;
the thickener in the embodiment of the invention is sodium carboxymethyl cellulose, which is purchased from Changzhou Baidu chemical industry Co., ltd;
the polyethylene separator in the embodiment of the invention is a commercially available conventional polyethylene separator.
The parts referred to in the present invention refer to parts by weight unless specifically indicated otherwise.
Example 1
The coating slurry for the lithium battery diaphragm containing the modified montmorillonite is prepared from the following components in parts by weight:
the preparation of the coating slurry for the lithium battery separator containing the modified montmorillonite is as follows:
s1, adding hydroxylated montmorillonite and acrylic acid into a reaction kettle, introducing nitrogen, dispersing and soaking montmorillonite in acrylic acid (montmorillonite: acrylic acid=1:10/m: m), fully stirring to uniformly disperse the montmorillonite, and simultaneously carrying out ultrasonic reaction for 4 hours under the conditions of 100 ℃ and ultrasonic electric power 400W to obtain a crude product;
s2, repeatedly washing the crude product with a proper amount of deionized water, removing unreacted raw materials and byproducts, and airing the washed product under a ventilation condition until the product is completely dried to obtain the modified montmorillonite;
s3, stirring 100 parts of styrene, 100 parts of ethyl acrylate, 1 part of initiator BPO, 1 part of surfactant tetrabutylammonium bromide, 5 parts of water-based polyacrylate, 3 parts of sodium carboxymethyl cellulose and 500 parts of water to form a blending emulsion, adding 10 parts of modified montmorillonite into the blending emulsion, and stirring at 95 ℃ for 3 hours to enable the modified montmorillonite to be uniformly distributed in the blending emulsion, so as to obtain the coating slurry for the lithium battery diaphragm containing the modified montmorillonite.
The preparation method of the lithium battery diaphragm comprises the following steps: and uniformly coating the two sides of the coating slurry for the lithium battery diaphragm containing the modified montmorillonite on the surface of a polyethylene diaphragm, controlling the coating thickness to be 4 mu m, and drying in a vacuum oven at 65 ℃ to obtain the lithium battery diaphragm containing the modified montmorillonite.
Example 2
The coating slurry for the lithium battery diaphragm containing the modified montmorillonite is prepared from the following components in parts by weight:
the preparation of the coating slurry for the lithium battery separator containing the modified montmorillonite is as follows:
s1, adding hydroxylated montmorillonite and acrylic acid into a reaction kettle, introducing nitrogen, dispersing and soaking montmorillonite in acrylic acid (montmorillonite: acrylic acid=1:10/m: m), fully stirring to uniformly disperse the montmorillonite, and simultaneously carrying out ultrasonic reaction for 4 hours under the conditions of 100 ℃ and ultrasonic electric power 400W to obtain a crude product;
s2, repeatedly washing the crude product with a proper amount of deionized water, removing unreacted raw materials and byproducts, and airing the washed product under a ventilation condition until the product is completely dried to obtain the modified montmorillonite;
s3, 110 parts of styrene, 110 parts of ethyl acrylate, 1 part of initiator BPO, 1 part of surfactant tetrabutylammonium bromide, 5 parts of water-based polyacrylate, 3 parts of sodium carboxymethyl cellulose and 500 parts of water are stirred to form a blend emulsion, 15 parts of modified montmorillonite is added into the blend emulsion, and the mixture is stirred and reacted for 3 hours at 95 ℃ to ensure that the modified montmorillonite is uniformly distributed in the blend emulsion, and the coating slurry for the lithium battery diaphragm containing the modified montmorillonite is obtained.
The preparation method of the lithium battery diaphragm comprises the following steps: and uniformly coating the two sides of the coating slurry for the lithium battery diaphragm containing the modified montmorillonite on the surface of a polyethylene diaphragm, controlling the coating thickness to be 4 mu m, and drying in a vacuum oven at 65 ℃ to obtain the lithium battery diaphragm containing the modified montmorillonite.
Comparative example 1
The preparation method, the components and the parts by weight used in comparative example 1 are the same as those in example 1, except that the coating paste for lithium battery separator in comparative example 1 does not contain modified montmorillonite but is replaced with common montmorillonite of equal parts by weight.
Test example 1
1. Heat resistance test: placing the samples of example 1 and comparative example 1 in a forced air oven to simulate the temperature rise process when the battery is in use, recording the transverse length and the longitudinal length of the separator after heating at 150 ℃ for 60min, and calculating the shrinkage rate;
2. peel strength test: the samples of example 1 and comparative example 1 were subjected to peel strength testing by a peel strength tester.
The test results were as follows:
from the above table, it can be seen that: 1. the transverse shrinkage and the longitudinal shrinkage of the example 1 are smaller than those of the comparative example 1, so that the battery separator containing the modified montmorillonite prepared in the example 1 has better dimensional stability at high temperature, is not easy to deform and shrink, and has important significance in ensuring the performance and stability of the battery;
2. the peel strength of example 1 was higher than that of comparative example 1, indicating that the battery separator coating material of example 1 had better adhesion properties and could be more firmly bonded to the base film, thereby improving the safety and stability of the lithium battery.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. The coating slurry for the lithium battery separator containing the modified montmorillonite is characterized by comprising the following components in parts by weight:
100-120 parts of ethyl acrylate
100-140 parts of styrene
10-15 parts of modified montmorillonite
8-10 parts of montmorillonite
1-2 parts of surfactant
1-2 parts of initiator
5-10 parts of binder
3-5 parts of thickening agent
Water;
the modified montmorillonite is a product obtained by the reaction of montmorillonite and acrylic acid, the binder is water-based polyacrylate, and the thickener is sodium carboxymethyl cellulose;
the preparation method of the coating slurry for the lithium battery diaphragm containing the modified montmorillonite comprises the following steps:
s1, soaking hydroxylated montmorillonite in acrylic acid, carrying out ultrasonic and heating reaction to obtain a crude product;
s2, washing and air-drying the crude product to obtain the modified montmorillonite;
s3, blending the modified montmorillonite with other components, and heating for reaction to obtain the coating slurry containing the modified montmorillonite for the lithium battery diaphragm.
2. The coating paste for lithium battery separator containing modified montmorillonite according to claim 1, wherein the surfactant is selected from anionic surfactants or nonionic surfactants.
3. The coating paste for lithium battery separator containing modified montmorillonite according to claim 1, wherein the initiator is selected from azo-type or peroxide-type initiators.
4. The method for preparing a coating paste for lithium battery separator containing modified montmorillonite according to claim 1, wherein in step S1, the heating temperature is 80-100 ℃.
5. The method for preparing a coating paste for lithium battery separator containing modified montmorillonite according to claim 1, wherein in step S1, the reaction time is 2-4h.
6. The method for preparing a coating paste for lithium battery separator containing modified montmorillonite according to claim 1, wherein in step S3, the reaction time is 2-4h.
7. The method for preparing a coating paste for lithium battery separator containing modified montmorillonite according to claim 1, wherein in step S1, the reaction is performed under the protection of inert gas.
8. A lithium battery separator comprising a base film and the coating layer formed by coating the modified montmorillonite-containing lithium battery separator according to any one of claims 1 to 3 on one or both sides of the base film with a coating slurry.
9. The lithium battery separator according to claim 8, wherein the base film is one of a polypropylene micro separator, a polyethylene separator, and a polyimide separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310648376.2A CN116454536B (en) | 2023-06-02 | 2023-06-02 | Coating slurry containing modified montmorillonite for lithium battery separator, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310648376.2A CN116454536B (en) | 2023-06-02 | 2023-06-02 | Coating slurry containing modified montmorillonite for lithium battery separator, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116454536A CN116454536A (en) | 2023-07-18 |
| CN116454536B true CN116454536B (en) | 2023-11-03 |
Family
ID=87125868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310648376.2A Active CN116454536B (en) | 2023-06-02 | 2023-06-02 | Coating slurry containing modified montmorillonite for lithium battery separator, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116454536B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117024896A (en) * | 2023-09-01 | 2023-11-10 | 江门市扬帆实业有限公司 | Flame-retardant color master batch containing modified copolymer and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010027549A (en) * | 2008-07-24 | 2010-02-04 | Hitachi Chem Co Ltd | Separator for electrochemical element and lithium-ion battery using the same |
| KR20140011136A (en) * | 2012-07-17 | 2014-01-28 | 삼성에스디아이 주식회사 | Electrochemical device including ceramic separator structure |
| KR20150069781A (en) * | 2013-12-16 | 2015-06-24 | 주식회사 엘지화학 | A method for manufacturing a high performance separator using environmental-friendly water based binder |
| JP2015230796A (en) * | 2014-06-04 | 2015-12-21 | ユニチカ株式会社 | Separator coating material, slurry for separator formation, separator, and secondary battery |
| CN110277527A (en) * | 2019-07-04 | 2019-09-24 | 中国科学技术大学 | A kind of microporous polypropylene membrane and preparation method thereof and lithium battery diaphragm |
| CN112993489A (en) * | 2021-02-06 | 2021-06-18 | 深圳名仕堂贸易有限公司 | Lithium battery capable of being charged quickly |
| CN113285170A (en) * | 2021-04-16 | 2021-08-20 | 佛山市盈博莱科技股份有限公司 | Preparation method of water-based polyvinylidene fluoride material coating diaphragm |
| CN114316857A (en) * | 2022-01-07 | 2022-04-12 | 瑞红锂电池材料(苏州)有限公司 | Water-based modified acrylate emulsion and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107405902B (en) * | 2014-06-20 | 2019-06-28 | 东丽株式会社 | The micro-porous film of polyolefin multi-layer, its manufacturing method and battery separator |
-
2023
- 2023-06-02 CN CN202310648376.2A patent/CN116454536B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010027549A (en) * | 2008-07-24 | 2010-02-04 | Hitachi Chem Co Ltd | Separator for electrochemical element and lithium-ion battery using the same |
| KR20140011136A (en) * | 2012-07-17 | 2014-01-28 | 삼성에스디아이 주식회사 | Electrochemical device including ceramic separator structure |
| KR20150069781A (en) * | 2013-12-16 | 2015-06-24 | 주식회사 엘지화학 | A method for manufacturing a high performance separator using environmental-friendly water based binder |
| JP2015230796A (en) * | 2014-06-04 | 2015-12-21 | ユニチカ株式会社 | Separator coating material, slurry for separator formation, separator, and secondary battery |
| CN110277527A (en) * | 2019-07-04 | 2019-09-24 | 中国科学技术大学 | A kind of microporous polypropylene membrane and preparation method thereof and lithium battery diaphragm |
| CN112993489A (en) * | 2021-02-06 | 2021-06-18 | 深圳名仕堂贸易有限公司 | Lithium battery capable of being charged quickly |
| CN113285170A (en) * | 2021-04-16 | 2021-08-20 | 佛山市盈博莱科技股份有限公司 | Preparation method of water-based polyvinylidene fluoride material coating diaphragm |
| CN114316857A (en) * | 2022-01-07 | 2022-04-12 | 瑞红锂电池材料(苏州)有限公司 | Water-based modified acrylate emulsion and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Atomic interlamellar ion path in polymeric separator enables long-life and dendrite-free anode in lithium ion batteries";J Zhao et al.;《Journal of Power Sources》;第451卷;第227773-1至227773-9页 * |
| "动力锂离子电池用聚烯烃隔膜改性研究进展";马留可;马小路;陈成;杨宏伟;张江伟;;《电源技术》(第03期);第138-140页 * |
| "锂离子电池隔膜材料EVOLi-OMMT的制备与性能";巩桂芬 等;《复合材料学报》;第39卷(第3期);第1186-1193页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116454536A (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10882990B2 (en) | Multi-functionally modified polymer binder for lithium ion batteries and use thereof in electrochemical energy storage devices | |
| WO2018032665A1 (en) | Acrylonitrile copolymer adhesive and use of same in lithium ion battery | |
| WO2019242318A1 (en) | Waterborne binder, preparation method therefor and use thereof | |
| CN116454536B (en) | Coating slurry containing modified montmorillonite for lithium battery separator, and preparation method and application thereof | |
| CN109301248B (en) | Battery negative plate, preparation method thereof and lithium ion battery | |
| CN102888016A (en) | Preparation method of lithium-ion secondary battery diaphragm with a crosslinking composite layer | |
| TWI752700B (en) | Graft copolymer and use thereof | |
| CN112646444A (en) | Preparation method of mesoporous silica water-based ceramic slurry | |
| CN112029452B (en) | Preparation method and application of adhesive capable of improving battery rate performance | |
| CN105895922A (en) | Preparation method of conductive coating aluminum foil | |
| CN114388795B (en) | Silicon-carbon negative electrode binder of lithium ion battery and preparation method thereof | |
| CN117089315B (en) | Aqueous lithium battery polyimide adhesive, preparation method thereof and lithium battery pole piece | |
| CN116970345B (en) | Application method of binder, carrier and battery | |
| CN113563531B (en) | Graft copolymer aqueous binder, preparation method and application thereof in silicon carbon negative electrode | |
| CN110492101B (en) | Lithium ion battery cathode binder and preparation method and application thereof | |
| CN117059819A (en) | Preparation method of high-magnification carbon-coated aluminum foil current collector for lithium battery | |
| CN113161549B (en) | Photo-crosslinking binder system, slurry composition containing photo-crosslinking binder system and application of slurry composition | |
| CN116217794A (en) | Solution type binder and preparation method and application thereof | |
| CN116179090A (en) | Ultrathin single-sided hot melt adhesive tape applied to lithium battery | |
| CN113512374A (en) | Protective adhesive tape for lithium battery aluminum shell and preparation method thereof | |
| CN117106350B (en) | Composite conductive coating and production method and application thereof | |
| CN115651554B (en) | Battery separator tape with dissolvable adhesive layer and preparation method thereof | |
| CN117050600B (en) | Carbon-coated current collector and preparation method and application thereof | |
| CN115332534A (en) | Open hollow carbon material, preparation method thereof and carbon-coated aluminum foil | |
| CN118255925A (en) | Additive for increasing stripping force of polyacrylic acid binder for lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Chaohan Inventor after: Li Bin Inventor after: Luo Guande Inventor after: Xie Feng Inventor before: Chen Chaohan Inventor before: Li Bin Inventor before: Luo Guande Inventor before: Xie Feng |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |