CN117060003A - Lithium ion battery diaphragm and preparation method thereof - Google Patents
Lithium ion battery diaphragm and preparation method thereof Download PDFInfo
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- CN117060003A CN117060003A CN202311015516.9A CN202311015516A CN117060003A CN 117060003 A CN117060003 A CN 117060003A CN 202311015516 A CN202311015516 A CN 202311015516A CN 117060003 A CN117060003 A CN 117060003A
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- Prior art keywords
- lithium ion
- ion battery
- stretching
- polyacrylonitrile fiber
- fibers
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 122
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 100
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 239000004743 Polypropylene Substances 0.000 claims abstract description 18
- 229920001155 polypropylene Polymers 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 238000009998 heat setting Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 229910052727 yttrium Inorganic materials 0.000 claims description 45
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 150000003746 yttrium Chemical class 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 150000001263 acyl chlorides Chemical class 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 5
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920002821 Modacrylic Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/268—Sulfones
-
- 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
-
- 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
- H01M50/44—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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a lithium ion battery diaphragm and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing modified polyacrylonitrile fiber; (2) Mixing the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin into a stirrer, and fully stirring and mixing to obtain a mixture; (3) And placing the mixture in an extruder, extruding the mixture after melting, casting the mixture into a film, and then stretching, heat setting and rolling the film to obtain the lithium ion battery diaphragm. According to the invention, the modified polyacrylonitrile fiber is added in the preparation process of the polyolefin membrane by improving the existing polyolefin membrane, so that the prepared lithium ion battery membrane has excellent mechanical strength and thermal stability, and better improvement of permeability and corrosion resistance.
Description
Technical Field
The invention relates to the field of batteries, in particular to a lithium ion battery diaphragm and a preparation method thereof.
Background
With the rise of electric vehicles, new challenges are presented to the yield and quality of lithium ion batteries. The popularization of electric automobiles in the future depends on the continuous reduction of the cost of lithium ion batteries and the continuous improvement of the safety, and the key to achieve the above-mentioned aim is more economical and safe battery materials. In the construction of lithium batteries, the separator is one of the critical inner layer components. The performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, safety performance and other characteristics of the battery, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. The separator has the main function of separating the positive electrode from the negative electrode of the battery, preventing the two electrodes from being contacted and short-circuited, and also has the function of passing electrolyte ions. The separator material is non-conductive, and its physicochemical properties have a great influence on the performance of the battery.
Currently, polyolefin separators are mainly used as lithium ion battery separators in China, for example: polypropylene, polyethylene, and multilayer composite separators thereof. Such separators have insufficient mechanical strength, thermal stability, permeability and corrosion resistance, and thus, there is a need for targeted improvement thereof.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a lithium ion battery diaphragm and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium ion battery separator, comprising:
(1) Preparing modified polyacrylonitrile fiber:
s1, sequentially carrying out hydroxylation and amination treatment on yttrium diboride powder to prepare aminated yttrium diboride;
s2, hydrolyzing the polyacrylonitrile fiber in alkali liquor, and performing acyl chlorination treatment to obtain acyl chlorinated polyacrylonitrile fiber;
s3, compounding the acyl chloride polyacrylonitrile fiber with the aminated yttrium diboride to prepare a modified polyacrylonitrile fiber;
(2) Mixing the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin into a stirrer, and fully stirring and mixing to obtain a mixture;
(3) And placing the mixture in an extruder, extruding the mixture after melting, casting the mixture into a film, and then stretching, heat setting and rolling the film to obtain the lithium ion battery diaphragm.
Preferably, the thickness of the lithium ion battery separator is 25-65 μm.
Preferably, in step (1), step S1 specifically includes:
weighing yttrium diboride powder, placing the yttrium diboride powder into an ethanol solution, refluxing for 1-3 hours at 80-100 ℃, dropwise adding a hydrogen peroxide solution, continuously preserving heat and refluxing for 2-4 hours, centrifuging to obtain solid powder, washing the solid powder with pure water for three times, and drying in an oven to obtain yttrium diboride hydroxide;
mixing yttrium diboride hydroxide with deionized water, performing ultrasonic homogenization, adding a silane coupling agent KH-550, stirring for 8-12 hours at room temperature, centrifuging to obtain solid powder, washing three times by using pure water, and drying in an oven to obtain the aminated yttrium diboride.
Preferably, in step S1, the particle size of the yttrium diboride powder is 150+ -20 nm; the hydrogen peroxide solution is hydrogen peroxide water solution, and the mass fraction is 20%; the mass fraction of the ethanol solution is 20% -50%.
Preferably, in step S1, the mass ratio of the yttrium diboride powder, the hydrogen peroxide solution and the ethanol solution is 1:2-4:10-20.
Preferably, in the step S1, the mass ratio of the yttrium diboride hydroxide, the silane coupling agent KH-550 and the deionized water is 1:0.3-0.5:10-20.
Preferably, in step (1), step S2 specifically includes:
weighing polyacrylonitrile fibers, placing the polyacrylonitrile fibers in a sodium hydroxide solution, heating to 70-90 ℃, carrying out heat preservation, stirring and mixing for 2-5 hours, then cooling to normal temperature, centrifugally separating out the fibers, washing the fibers with pure water for three times, and drying in an oven to obtain carboxylated polyacrylonitrile fibers;
dispersing the activated polyacrylonitrile fibers in thionyl chloride, heating to 75-80 ℃, refluxing and stirring for 6-8 hours, centrifuging out the fibers, washing three times by using acetone, and drying in an oven to obtain the acyl chloride polyacrylonitrile fibers.
Preferably, in step S2, the mass fraction of the sodium hydroxide solution is 1% -5%; the fineness of the polyacrylonitrile fiber is 1.1-1.6dtex, the length is 3.5+/-0.5 mm, and the density is 1.18g/cm 3 Melting point is more than 260 ℃.
Preferably, in the step S2, the mass ratio of the polyacrylonitrile fiber to the sodium hydroxide solution is 1:10-20; the mass ratio of the activated polyacrylonitrile fiber to the thionyl chloride is 1:8-15.
Preferably, in step (1), step S3 specifically includes:
dispersing acyl chloride polyacrylonitrile fiber in N, N-dimethylformamide, adding aminated yttrium diboride, stirring in a reaction kettle for reaction at 45-55 deg.c for 15-25 hr at 200-300r/min, centrifuging to separate fiber, washing with acetone for three times, and drying to obtain the modified polyacrylonitrile fiber.
Preferably, in step S3, the mass ratio of the acyl chloride polyacrylonitrile fiber, the aminated yttrium diboride and the N, N-dimethylformamide is 1:0.18-0.36:10-20.
Preferably, in step (2), the pore-forming agent is paraffin oil or white oil; the melt flow rate of the polypropylene resin is 6.8-7.5g/10min, and the molecular weight is 25-30 ten thousand.
Preferably, in the step (2), the mass ratio of the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin is 1-3:0.5-1:6-12.
Preferably, in step (3), the extruder temperature is 180-220℃and the extrusion rate is 10-15m/min.
Preferably, in the step (3), the stretching includes two stretching, the first stretching in the longitudinal direction and the second stretching in the transverse direction; the stretching speed of longitudinal stretching is 5mm/s, the multiplying power is 2.5-3.5 times, the stretching speed of transverse stretching is 5mm/s, the multiplying power is 1.5-2.5 times, and the materials are extracted in dichloromethane and trichloroethylene and dried after the stretching is completed.
Preferably, in the step (3), the heat setting temperature is 120-150 ℃ and the time is 20-40min.
In a second aspect, the invention provides a lithium ion battery separator prepared by the method.
The beneficial effects of the invention are as follows:
1. according to the invention, the modified polyacrylonitrile fiber is added in the preparation process of the polyolefin membrane by improving the existing polyolefin membrane, so that the prepared lithium ion battery membrane has excellent mechanical strength and thermal stability, and better improvement of permeability and corrosion resistance.
2. The modified polyacrylonitrile fiber prepared by the invention is based on the polyacrylonitrile fiber, and after the polyacrylonitrile fiber is subjected to activation treatment, yttrium diboride activated on the grafted surface is adsorbed, so that the modified polyacrylonitrile fiber is prepared. In the process of preparing the modified polyacrylonitrile fiber, yttrium diboride is a nanoscale material, and the surface of the yttrium diboride is subjected to hydroxylation (-OH) and amination (-NH) in sequence 2 ) Treating to obtain aminated yttrium diboride; after the polyacrylonitrile fiber is treated by alkali liquor, cyano groups (-CN) contained on the surface of the fiber are converted into carboxyl groups (-COOH), and then the carboxyl groups (-COCl) are subjected to acyl chlorination treatment, so that the acyl chlorinated polyacrylonitrile fiber is obtained; finally, the acyl chloride polyacrylonitrile fiber and the aminated yttrium diboride are mixed and combined, and the acyl chloride group and the amino group are combined into an amide group (-CONH-), so as to obtain the modified polyacrylonitrile fiber.
3. The modified polyacrylonitrile fiber prepared by the invention is modified on the basis of the polyacrylonitrile fiber, so that yttrium diboride and polyacrylonitrile are connected through polyamide groups, and the finally obtained modified polyacrylonitrile fiber is compounded with polypropylene to prepare the battery diaphragm, so that the mechanical strength, the thermal stability, the permeability and the corrosion resistance of the battery diaphragm are improved, and the battery diaphragm can be applied to a lithium ion battery more excellently.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
A preparation method of a lithium ion battery diaphragm comprises the following steps:
(1) Preparing modified polyacrylonitrile fiber:
weighing yttrium diboride powder, placing the yttrium diboride powder into an ethanol solution, refluxing for 2 hours at 90 ℃, dripping hydrogen peroxide solution, continuously preserving heat and refluxing for 3 hours, centrifuging to obtain solid powder, washing the solid powder with pure water for three times, and drying in an oven to obtain yttrium diboride hydroxide; wherein the granularity of the yttrium diboride powder is 150+/-20 nm; the hydrogen peroxide solution is hydrogen peroxide water solution, and the mass fraction is 20%; the mass fraction of the ethanol solution is 30%, and the mass ratio of the yttrium diboride powder to the hydrogen peroxide solution to the ethanol solution is 1:3:15;
mixing yttrium diboride hydroxide with deionized water, carrying out ultrasonic homogenization, adding a silane coupling agent KH-550, stirring for 10 hours at room temperature, centrifuging to obtain solid powder, washing with pure water for three times, and drying in an oven to obtain aminated yttrium diboride; wherein the mass ratio of the yttrium diboride hydroxide to the silane coupling agent KH-550 to the deionized water is 1:0.4:15.
S2, weighing polyacrylonitrile fibers, placing the polyacrylonitrile fibers in a sodium hydroxide solution, heating to 70-90 ℃, preserving heat, stirring and mixing for 3 hours, cooling to normal temperature, centrifugally separating out fibers, and washing three fibers by using pure waterDrying in an oven to obtain carboxylated polyacrylonitrile fibers; wherein the mass fraction of the sodium hydroxide solution is 3%; the fineness of the polyacrylonitrile fiber is 1.1-1.6dtex, the length is 3.5+/-0.5 mm, and the density is 1.18g/cm 3 Melting point is more than 260 ℃;
dispersing activated polyacrylonitrile fibers in thionyl chloride, heating to 80 ℃, refluxing and stirring for 7 hours, centrifuging out fibers, washing with acetone for three times, and drying in an oven to obtain acyl chloride polyacrylonitrile fibers; wherein the mass ratio of the polyacrylonitrile fiber to the sodium hydroxide solution is 1:15; the mass ratio of the activated polyacrylonitrile fiber to the thionyl chloride is 1:12.
S3, dispersing acyl chloride polyacrylonitrile fibers in N, N-dimethylformamide, adding aminated yttrium diboride, stirring and reacting in a reaction kettle at a reaction temperature of 50 ℃ for 20 hours at a stirring speed of 250r/min, centrifuging to separate fibers after the reaction is finished, washing with acetone for three times, and drying to obtain modified polyacrylonitrile fibers; wherein the mass ratio of the acyl chloride polyacrylonitrile fiber to the aminated yttrium diboride to the N, N-dimethylformamide is 1:0.24:15.
(2) Mixing the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin into a stirrer, and fully stirring and mixing to obtain a mixture; wherein the pore-forming agent is paraffin oil or white oil; the melt flow rate of the polypropylene resin is 7.2g/10min, and the molecular weight is 28 ten thousand; the mass ratio of the modified polyacrylonitrile fiber to the pore-forming agent to the polypropylene resin is 2:0.6:9.
(3) Placing the mixture into an extruder, extruding the mixture after melting, casting the mixture into a film, and then stretching, heat setting and rolling the film to obtain a lithium ion battery diaphragm with the thickness of 45 mu m; wherein the temperature of the extruder is 200 ℃, and the extrusion rate is 12m/min; the stretching comprises two stretching steps, wherein the first stretching step is longitudinal stretching and the second stretching step is transverse stretching; the stretching speed of longitudinal stretching is 5mm/s, the multiplying power is 3 times, the stretching speed of transverse stretching is 5mm/s, the multiplying power is 2 times, and the materials are extracted in dichloromethane and trichloroethylene and dried after the stretching is finished; the heat setting temperature was 130℃and the time was 30min.
Example 2
A preparation method of a lithium ion battery diaphragm comprises the following steps:
(1) Preparing modified polyacrylonitrile fiber:
weighing yttrium diboride powder, placing the yttrium diboride powder into an ethanol solution, refluxing for 1h at 80 ℃, dropwise adding a hydrogen peroxide solution, continuously preserving heat and refluxing for 2h, centrifuging to obtain solid powder, washing the solid powder with pure water for three times, and drying in an oven to obtain yttrium diboride hydroxide; wherein the granularity of the yttrium diboride powder is 150+/-20 nm; the hydrogen peroxide solution is hydrogen peroxide water solution, and the mass fraction is 20%; the mass fraction of the ethanol solution is 20%, and the mass ratio of the yttrium diboride powder to the hydrogen peroxide solution to the ethanol solution is 1:2:10;
mixing yttrium diboride hydroxide with deionized water, carrying out ultrasonic homogenization, adding a silane coupling agent KH-550, stirring for 8 hours at room temperature, centrifuging to obtain solid powder, washing with pure water for three times, and drying in an oven to obtain aminated yttrium diboride; wherein the mass ratio of the yttrium diboride hydroxide to the silane coupling agent KH-550 to the deionized water is 1:0.3:10.
S2, weighing polyacrylonitrile fibers, placing the polyacrylonitrile fibers in a sodium hydroxide solution, heating to 70 ℃, preserving heat, stirring and mixing for 2 hours, cooling to normal temperature, centrifugally separating out the fibers, washing the fibers with pure water for three times, and drying in an oven to obtain carboxylated polyacrylonitrile fibers; wherein the mass fraction of the sodium hydroxide solution is 1%; the fineness of the polyacrylonitrile fiber is 1.1-1.6dtex, the length is 3.5+/-0.5 mm, and the density is 1.18g/cm 3 Melting point is more than 260 ℃;
dispersing activated polyacrylonitrile fibers in thionyl chloride, heating to 75 ℃, refluxing and stirring for 6 hours, centrifuging out fibers, washing with acetone for three times, and drying in an oven to obtain acyl chloride polyacrylonitrile fibers; wherein the mass ratio of the polyacrylonitrile fiber to the sodium hydroxide solution is 1:10; the mass ratio of the activated polyacrylonitrile fiber to the thionyl chloride is 1:8.
S3, dispersing acyl chloride polyacrylonitrile fibers in N, N-dimethylformamide, adding aminated yttrium diboride, stirring and reacting in a reaction kettle at a reaction temperature of 45 ℃ for 15 hours at a stirring speed of 200r/min, centrifuging to separate fibers after the reaction is finished, washing with acetone for three times, and drying to obtain modified polyacrylonitrile fibers; wherein the mass ratio of the acyl chloride polyacrylonitrile fiber to the aminated yttrium diboride to the N, N-dimethylformamide is 1:0.18:10.
(2) Mixing the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin into a stirrer, and fully stirring and mixing to obtain a mixture; wherein the pore-forming agent is paraffin oil or white oil; the melt flow rate of the polypropylene resin is 7.2g/10min, and the molecular weight is 28 ten thousand; the mass ratio of the modified polyacrylonitrile fiber to the pore-forming agent to the polypropylene resin is 1:0.5:6.
(3) Placing the mixture into an extruder, extruding the mixture after melting, casting the mixture into a film, and then stretching, heat setting and rolling the film to obtain a lithium ion battery diaphragm with the thickness of 25 mu m; wherein the temperature of the extruder is 180 ℃ and the extrusion rate is 10m/min; the stretching comprises two stretching steps, wherein the first stretching step is longitudinal stretching and the second stretching step is transverse stretching; the stretching speed of longitudinal stretching is 5mm/s, the multiplying power is 2.5 times, the stretching speed of transverse stretching is 5mm/s, the multiplying power is 1.5 times, and the materials are extracted in dichloromethane and trichloroethylene and dried after the stretching is finished; the heat setting temperature was 120℃and the time was 20min.
Example 3
A preparation method of a lithium ion battery diaphragm comprises the following steps:
(1) Preparing modified polyacrylonitrile fiber:
weighing yttrium diboride powder, placing the yttrium diboride powder into an ethanol solution, refluxing for 3 hours at 80-100 ℃, dropwise adding a hydrogen peroxide solution, continuously preserving heat and refluxing for 4 hours, centrifuging to obtain solid powder, washing the solid powder with pure water for three times, and drying in an oven to obtain yttrium diboride hydroxide; wherein the granularity of the yttrium diboride powder is 150+/-20 nm; the hydrogen peroxide solution is hydrogen peroxide water solution, and the mass fraction is 20%; the mass fraction of the ethanol solution is 50%, and the mass ratio of the yttrium diboride powder to the hydrogen peroxide solution to the ethanol solution is 1:4:20;
mixing yttrium diboride hydroxide with deionized water, carrying out ultrasonic homogenization, adding a silane coupling agent KH-550, stirring for 12 hours at room temperature, centrifuging to obtain solid powder, washing with pure water for three times, and drying in an oven to obtain aminated yttrium diboride; wherein the mass ratio of the yttrium diboride hydroxide to the silane coupling agent KH-550 to the deionized water is 1:0.5:20.
S2, weighing polyacrylonitrile fibers, placing the polyacrylonitrile fibers in a sodium hydroxide solution, heating to 90 ℃, preserving heat, stirring and mixing for 5 hours, cooling to normal temperature, centrifugally separating out the fibers, washing the fibers with pure water for three times, and drying in an oven to obtain carboxylated polyacrylonitrile fibers; wherein the mass fraction of the sodium hydroxide solution is 5%; the fineness of the polyacrylonitrile fiber is 1.1-1.6dtex, the length is 3.5+/-0.5 mm, and the density is 1.18g/cm 3 Melting point is more than 260 ℃;
dispersing activated polyacrylonitrile fibers in thionyl chloride, heating to 80 ℃, refluxing and stirring for 8 hours, centrifuging out fibers, washing with acetone for three times, and drying in an oven to obtain acyl chloride polyacrylonitrile fibers; wherein the mass ratio of the polyacrylonitrile fiber to the sodium hydroxide solution is 1:20; the mass ratio of the activated polyacrylonitrile fiber to the thionyl chloride is 1:15.
S3, dispersing acyl chloride polyacrylonitrile fibers in N, N-dimethylformamide, adding aminated yttrium diboride, stirring and reacting in a reaction kettle at a reaction temperature of 55 ℃ for 25 hours at a stirring speed of 300r/min, centrifuging to separate fibers after the reaction is finished, washing with acetone for three times, and drying to obtain modified polyacrylonitrile fibers; wherein the mass ratio of the acyl chloride polyacrylonitrile fiber to the aminated yttrium diboride to the N, N-dimethylformamide is 1:0.36:20.
(2) Mixing the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin into a stirrer, and fully stirring and mixing to obtain a mixture; wherein the pore-forming agent is paraffin oil or white oil; the melt flow rate of the polypropylene resin is 7.2g/10min, and the molecular weight is 28 ten thousand; the mass ratio of the modified polyacrylonitrile fiber to the pore-forming agent to the polypropylene resin is 3:1:12.
(3) Placing the mixture into an extruder, extruding the mixture after melting, casting the mixture into a film, and then stretching, heat setting and rolling the film to obtain a lithium ion battery diaphragm with the thickness of 65 mu m; wherein the temperature of the extruder is 220 ℃, and the extrusion rate is 15m/min; the stretching comprises two stretching steps, wherein the first stretching step is longitudinal stretching and the second stretching step is transverse stretching; the stretching speed of longitudinal stretching is 5mm/s, the multiplying power is 3.5 times, the stretching speed of transverse stretching is 5mm/s, the multiplying power is 2.5 times, and the materials are extracted in dichloromethane and trichloroethylene and dried after the stretching is finished; the heat setting temperature was 150℃and the time was 40min.
Comparative example 1
A lithium ion battery separator is different from example 1 in that modified polyacrylonitrile fiber is replaced by conventional polyacrylonitrile fiber, the fineness of the polyacrylonitrile fiber is 1.1-1.6dtex, the length is 3.5+ -0.5 mm, and the density is 1.18g/cm 3 Melting point is more than 260 ℃. The remainder was the same as in example 1.
Comparative example 2
A lithium ion battery separator differs from example 1 in that the modacrylic fiber is replaced with yttrium diboride, the particle size of the yttrium diboride powder is 150+ -20 nm. The remainder was the same as in example 1.
Comparative example 3
A lithium ion battery separator differs from example 1 in that the modacrylic fiber is replaced with a mixture of polyacrylonitrile fiber and yttrium diboride at a mass ratio of polyacrylonitrile fiber to yttrium diboride of 1:0.24. The remainder was the same as in example 1.
Experimental example
The lithium ion battery separator prepared in example 1 and comparative examples 1 to 3 was tested for tensile strength (GB/T1040.3-2006), acid corrosiveness (25 ℃ C., 0.5mol/L sulfuric acid soak for 120 hours), alkali corrosiveness (25 ℃ C., 0.5mol/L caustic soda soak for 120 hours), heat shrinkage (GB/T36363-2018), and ventilation (GB/T36363-2018). The test results are shown in Table 1.
Table 1 lithium ion battery separator performance test results
From table 1, it can be seen that the lithium ion battery separator prepared in example 1 of the present invention has high transverse or longitudinal tensile strength, higher tensile strength retention rate after acid-base treatment, low thermal shrinkage rate and high ventilation rate, which indicates that the lithium ion battery separator prepared in example 1 of the present invention has high mechanical strength, good thermal stability, strong permeability and excellent corrosion resistance performance, and is suitable for use in lithium ion batteries with relatively high performance requirements.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the lithium ion battery diaphragm is characterized by comprising the following steps:
(1) Preparing modified polyacrylonitrile fiber:
s1, sequentially carrying out hydroxylation and amination treatment on yttrium diboride powder to prepare aminated yttrium diboride;
s2, hydrolyzing the polyacrylonitrile fiber in alkali liquor, and performing acyl chlorination treatment to obtain acyl chlorinated polyacrylonitrile fiber;
s3, compounding the acyl chloride polyacrylonitrile fiber with the aminated yttrium diboride to prepare a modified polyacrylonitrile fiber;
(2) Mixing the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin into a stirrer, and fully stirring and mixing to obtain a mixture;
(3) And placing the mixture in an extruder, extruding the mixture after melting, casting the mixture into a film, and then stretching, heat setting and rolling the film to obtain the lithium ion battery diaphragm.
2. The method for preparing a lithium ion battery separator according to claim 1, wherein the thickness of the lithium ion battery separator is 25-65 μm.
3. The method for preparing a lithium ion battery separator according to claim 1, wherein in step (1), step S1 specifically comprises:
weighing yttrium diboride powder, placing the yttrium diboride powder into an ethanol solution, refluxing for 1-3 hours at 80-100 ℃, dropwise adding a hydrogen peroxide solution, continuously preserving heat and refluxing for 2-4 hours, centrifuging to obtain solid powder, washing the solid powder with pure water for three times, and drying in an oven to obtain yttrium diboride hydroxide; wherein the granularity of the yttrium diboride powder is 150+/-20 nm; the hydrogen peroxide solution is hydrogen peroxide water solution, and the mass fraction is 20%; the mass fraction of the ethanol solution is 20% -50%, and the mass ratio of the yttrium diboride powder to the hydrogen peroxide solution to the ethanol solution is 1:2-4:10-20;
mixing yttrium diboride hydroxide with deionized water, carrying out ultrasonic homogenization, adding a silane coupling agent KH-550, stirring for 8-12 hours at room temperature, centrifuging to obtain solid powder, washing with pure water for three times, and drying in an oven to obtain aminated yttrium diboride; wherein the mass ratio of the yttrium diboride hydroxide to the silane coupling agent KH-550 to the deionized water is 1:0.3-0.5:10-20.
4. The method for preparing a lithium ion battery separator according to claim 1, wherein in step (1), step S2 specifically comprises:
weighing polyacrylonitrile fibers, placing the polyacrylonitrile fibers in a sodium hydroxide solution, heating to 70-90 ℃, carrying out heat preservation, stirring and mixing for 2-5 hours, then cooling to normal temperature, centrifugally separating out the fibers, washing the fibers with pure water for three times, and drying in an oven to obtain carboxylated polyacrylonitrile fibers; wherein the mass fraction of the sodium hydroxide solution is 1% -5%; the fineness of the polyacrylonitrile fiber is 1.1-1.6dtex, the length is 3.5+/-0.5 mm, and the density is 1.18g/cm 3 Melting point is more than 260 ℃;
dispersing activated polyacrylonitrile fibers in thionyl chloride, heating to 75-80 ℃, refluxing and stirring for 6-8 hours, centrifuging out fibers, washing with acetone for three times, and drying in an oven to obtain acyl chloride polyacrylonitrile fibers; wherein the mass ratio of the polyacrylonitrile fiber to the sodium hydroxide solution is 1:10-20; the mass ratio of the activated polyacrylonitrile fiber to the thionyl chloride is 1:8-15.
5. The method for preparing a lithium ion battery separator according to claim 1, wherein in step (1), step S3 specifically comprises:
dispersing acyl chloride polyacrylonitrile fibers in N, N-dimethylformamide, adding aminated yttrium diboride, stirring and reacting in a reaction kettle at 45-55 ℃ for 15-25h at a stirring speed of 200-300r/min, centrifuging to separate fibers after the reaction is finished, washing with acetone for three times, and drying to obtain modified polyacrylonitrile fibers; wherein the mass ratio of the acyl chloride polyacrylonitrile fiber to the aminated yttrium diboride to the N, N-dimethylformamide is 1:0.18-0.36:10-20.
6. The method for preparing a lithium ion battery separator according to claim 1, wherein in the step (2), the pore-forming agent is paraffin oil or white oil; the melt flow rate of the polypropylene resin is 6.8-7.5g/10min, and the molecular weight is 25-30 ten thousand.
7. The method for preparing a lithium ion battery separator according to claim 1, wherein in the step (2), the mass ratio of the modified polyacrylonitrile fiber, the pore-forming agent and the polypropylene resin is 1-3:0.5-1:6-12.
8. The method for preparing a lithium ion battery separator according to claim 1, wherein in the step (3), the temperature of the extruder is 180-220 ℃ and the extrusion rate is 10-15m/min; the heat setting temperature is 120-150 deg.c and the heat setting time is 20-40min.
9. The method for producing a lithium ion battery separator according to claim 1, wherein in the step (3), the stretching includes two stretching, the first longitudinal stretching and the second transverse stretching; the stretching speed of longitudinal stretching is 5mm/s, the multiplying power is 2.5-3.5 times, the stretching speed of transverse stretching is 5mm/s, the multiplying power is 1.5-2.5 times, and the materials are extracted in dichloromethane and trichloroethylene and dried after the stretching is completed.
10. A lithium ion battery separator, characterized in that the lithium ion battery separator is prepared by the method of any one of claims 1-9.
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