CN115101888A - Hierarchical porous fiber cloth-based polymer composite membrane and preparation method and application thereof - Google Patents
Hierarchical porous fiber cloth-based polymer composite membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN115101888A CN115101888A CN202210681567.4A CN202210681567A CN115101888A CN 115101888 A CN115101888 A CN 115101888A CN 202210681567 A CN202210681567 A CN 202210681567A CN 115101888 A CN115101888 A CN 115101888A
- Authority
- CN
- China
- Prior art keywords
- fiber cloth
- sea
- zeolite particles
- island
- composite membrane
- 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.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 230
- 239000004744 fabric Substances 0.000 title claims abstract description 165
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000004743 Polypropylene Substances 0.000 claims abstract description 180
- -1 polypropylene Polymers 0.000 claims abstract description 137
- 229920001155 polypropylene Polymers 0.000 claims abstract description 115
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000002245 particle Substances 0.000 claims abstract description 81
- 239000006255 coating slurry Substances 0.000 claims abstract description 78
- 238000001035 drying Methods 0.000 claims abstract description 42
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 238000007731 hot pressing Methods 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 229920002959 polymer blend Polymers 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- 239000002585 base Substances 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 39
- 229920002635 polyurethane Polymers 0.000 claims description 39
- 239000004814 polyurethane Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 38
- 239000002033 PVDF binder Substances 0.000 claims description 36
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002149 hierarchical pore Substances 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 19
- 239000011247 coating layer Substances 0.000 claims description 18
- 238000007756 gravure coating Methods 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920001410 Microfiber Polymers 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- AREWWPRVYOZSFA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;propane-1,2,3-triol Chemical compound OCC(O)CO.OCC(CO)(CO)CO AREWWPRVYOZSFA-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 54
- 238000005406 washing Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
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
-
- 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
- H01M50/44—Fibrous 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
-
- 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
- H01M50/494—Tensile strength
-
- 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
- H01M50/497—Ionic conductivity
Abstract
The invention discloses a hierarchical porous fiber cloth-based polymer composite membrane and a preparation method and application thereof. According to the invention, the COPET/PP sea-island fiber cloth with different warp-weft ratios and different sea-island component ratios is selected, the sea component COPET is removed by using an alkali solution to obtain the superfine polypropylene fiber cloth as a supporting layer, then coating slurry containing a polymer mixture and nano zeolite particles with different particle sizes is coated on the supporting layer, and the multistage pore fiber cloth-based polymer composite membrane is prepared by drying and hot pressing.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a hierarchical porous fiber cloth-based polymer composite membrane and a preparation method and application thereof.
Background
The lithium ion secondary battery has the advantages of high energy density, excellent cycle rate, environmental friendliness and the like, and is widely applied to the fields of digital products, electric vehicles, energy storage and the like. In the construction of lithium batteries, the separator is one of the key internal components. The quality of the performance of the diaphragm determines the internal resistance of the battery, the adhesion with a pole piece and the use stability, and finally influences the discharge capacity, the cycle rate performance, the safety and other characteristics of the battery.
The commercial diaphragm on the market at present mainly comprises a polyolefin diaphragm or a coating polyolefin diaphragm, however, the melting point of the existing diaphragm is relatively low, the liquid absorption rate and the liquid retention rate are not high, and when the battery works at a high temperature, the diaphragm can be curled, the contact area with a pole piece is increased, the internal resistance of the battery is greatly increased, and the cycle performance of the battery is influenced.
In this regard, composite separators have been increasingly attracting attention among battery separators. Chinese patent application CN113285174A discloses that polyphenylene sulfide and alkali soluble polyester are mixed and melt-spun to obtain sea-island type polyphenylene sulfide composite fiber, and then the sea-island type polyphenylene sulfide composite battery diaphragm is obtained by heat treatment, mixing with nanofiber and hot pressing, although good thermal stability, mechanical property and chemical stability can be provided, the diaphragm thickness is difficult to control, and the porosity is not high, the pore size distribution is not uniform, and the liquid absorption rate and ionic conductivity are not high. Chinese patent application CN206893686U discloses a multilayer structure composite battery diaphragm, which improves the heat resistance of the battery diaphragm through the optimization of each layer, but the pore diameter controllability of the multilayer composite diaphragm is low, causing uneven distribution of the pore diameter of the diaphragm, so that the battery is easy to generate local short circuit in the using process and further affects the safety of the whole battery.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a hierarchical pore fiber cloth-based polymer composite membrane, and the hierarchical pore fiber cloth-based polymer composite membrane prepared by the method has high heat resistance, crease-shrinkage resistance and puncture resistance for inhibiting lithium dendrite while ensuring good performances of high liquid absorption rate, high liquid retention rate and high ionic conductivity, and is particularly suitable for a lithium battery diaphragm.
The invention is realized by the following technical scheme:
a preparation method of a hierarchical pore fiber cloth-based polymer composite membrane comprises the following steps:
(1) preparing a fiber cloth base supporting layer: soaking COPET/PP sea-island fiber cloth in alkali solution to remove sea component COPET to obtain the superfine polypropylene fiber cloth-based supporting layer;
the COPET/PP sea-island fiber cloth is woven by sea-island superfine fibers taking polypropylene as an island component and polyethylene glycol terephthalate as a sea component;
(2) preparation of coating slurry: adding an adhesive and a surfactant into the dispersant solution, stirring and mixing uniformly, then adding the polymer mixture and the nano zeolite particles, stirring and mixing uniformly to prepare a coating slurry;
in the coating slurry, the content of a surfactant is 0.5-1 wt%, the content of an adhesive is 1-5 wt%, the content of a polymer mixture is 5-10 wt%, and the content of nano zeolite particles is 5-15 wt%;
(3) preparing a composite membrane: and (3) coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1), and drying and hot-pressing to prepare the hierarchical-pore fiber cloth base polymer composite membrane.
The invention relates to a method for removing sea component COPET in fiber cloth by using alkali solution, wherein polyethylene terephthalate is alkali-soluble polyester. Preferably, in the step (1) of the invention, an aqueous alkali at 80-100 ℃ is adopted to soak the COPET/PP sea-island fiber cloth for 10-30 min; the alkali solution may be selected from any one of sodium hydroxide solution or potassium hydroxide solution.
The sea-island type superfine denier fiber is a composite fiber in which polypropylene is dispersed in polyethylene terephthalate, and viewed from the cross section of the fiber, PP is surrounded by COPET in a fine and dispersed state, namely PP is in an 'island' state, COPET is in a 'sea' state, island components and sea components are continuously, densely and uniformly distributed in the axial direction of the fiber, and if the sea components are removed by a solvent, a bunched superfine denier polypropylene fiber bundle can be obtained.
Preferably, the sea-island type ultrafine fiber according to the present invention has 25 to 45 single-strand ultrafine polypropylene fibers as an island structure.
Preferably, the superfine denier polypropylene fiber is 0.1-0.5 denier.
The COPET/PP sea-island fiber cloth is formed by weaving sea-island superfine fibers in a warp-weft crossed manner, and after a sea component structure is removed, the sea component superfine polypropylene fiber cloth is left, so that certain gaps can be reserved among fibers of the fiber cloth, and the size of the gaps among the fibers of a final superfine polypropylene fiber cloth base supporting layer can be influenced by different proportions of the sea components, preferably, the proportion of the island components in the COPET/PP sea-island fiber cloth is 60-70 wt%, and the proportion of the sea components is 30-40 wt%.
The fiber cloth has controllable warp-weft ratio in the weaving process, and the uniform distribution of gaps among warp-weft fiber interweaving points of the sea component removed superfine denier polypropylene fiber cloth-based supporting layer can be controlled due to the difference of the warp-weft ratio, so that zeolite particles can be uniformly embedded in the sea component removed superfine denier polypropylene fiber cloth-based supporting layer, and the introduced pore structure can be uniformly distributed. Preferably, the warp-weft ratio of the COPET/PP sea-island fiber cloth is (20-50): (15-35), preferably (30-45): (25-30). The warp-weft ratio is the root ratio of the sea-island fiber in the radial direction and the weft direction.
The porosity of the superfine denier polypropylene fiber cloth-based supporting layer is 30-60%, and the pore diameter is 0.5-4 mu m; preferably, the porosity of the superfine denier polypropylene fiber cloth-based supporting layer is 48-55%, and the pore diameter range is 0.5-1 μm.
According to the invention, the ultrafine denier polypropylene fiber cloth obtained by washing sea components of the COPET/PP sea-island fiber cloth is used as a supporting layer, the supporting layer can provide good mechanical property and crease resistance, and simultaneously, the supporting layer has the function of a molecular sieve, particles with small particle sizes can permeate into gaps between single fibers, particles with medium particle sizes can be embedded into gaps between crossing points of weft-direction fibers, and particles with large particle sizes cover the surface layer of the fibers.
In the step (2) of the invention, the dispersant solution is selected from any one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or polyvinylpyrrolidone.
The adhesive is selected from one or more of polyvinyl alcohol, polypropylene alcohol, acrylic adhesives or vinyl acetate adhesives.
The surfactant is selected from one or more of fluorocarbon surfactant, silane surfactant or polyalcohol surfactant; preferably, the fluorocarbon surfactant is selected from one or more of alkylphenol ethoxylates, high-carbon fatty alcohol ethoxylates, fatty acid polyoxyethylene esters or ethylene oxide adducts of polypropylene glycol; the silane surfactant is selected from any one or more of trisiloxane or amine polyether; the polyalcohol surfactant is one or more selected from ethylene oxide adduct of polypropylene glycol, fatty acid diglyceride, ethylene glycol, glycerol pentaerythritol or fatty acid diglyceride.
The nano zeolite particles are selected from any one or more of FAU type zeolite, ZSM-5 zeolite, AFI type zeolite or MFI type zeolite; preferably FAU-type zeolite.
Preferably, the pore diameter of the nano zeolite particles is in the range of 0.1nm to 10 nm.
The nano zeolite particles comprise any one or more of small-particle size zeolite particles, medium-particle size zeolite particles or large-particle size zeolite particles, wherein the small particle size is more than or equal to 0.1 mu m and less than 0.5 mu m, the medium particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m, and the large particle size is more than 1 mu m and less than or equal to 3 mu m; preferably, the nano zeolite particles comprise 20-50 wt% of small-particle size zeolite particles, 30-65 wt% of medium-particle size zeolite particles and 0-40 wt% of large-particle size zeolite particles; more preferably, the nano zeolite particles comprise 30 to 50wt% of small-particle size zeolite particles, 30 to 50wt% of medium-particle size zeolite particles and 20 to 40wt% of large-particle size zeolite particles. Zeolite particles with small particle sizes can permeate into gaps between single fibers and single fibers, the particles of the zeolite particles with medium particle sizes can be embedded into gaps between interweaving points of warp and weft fibers, the zeolite particles with large particle sizes are attached to the surfaces of fiber bundles, and the distribution condition of the zeolite particles in a superfine denier polypropylene fiber cloth-based supporting layer can be controlled by adjusting the proportion of the zeolite particles with different particle sizes, so that a passage with multistage holes can be constructed, the liquid retention rate is effectively improved, the high-cycle capacity retention rate of a lithium ion battery is increased, meanwhile, an ion transmission path is increased through the passage with multistage holes, and the ion conductivity is further improved.
The polymer mixture of the present invention is selected from the group consisting of fluorine-containing polymers and ester-containing polymers. Preferably, the weight ratio of the fluorine-containing polymer to the ester-containing polymer is (3-7): (2-8).
Preferably, the fluorine-containing polymer is one or more selected from polytetrafluoroethylene, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer or tetrafluoroethylene-hexafluoropropylene copolymer, and more preferably polyvinylidene fluoride.
Preferably, the ester-containing polymer is selected from any one or more of polyurethane, polymethyl methacrylate or polymethyl acrylate, and more preferably polyurethane.
As a most preferred embodiment, the polymer mixture is selected from polyvinylidene fluoride and polyurethane blends, and the polymer mixture can be soaked and swelled in electrolyte, has good capacity of absorbing and retaining the electrolyte, and further improves the high cycle capacity retention rate of the lithium ion battery.
In the step (3), the invention can adopt micro-gravure coating, the coating speed is 10-40m/min, and the thickness of the coating layer is 15-25 μm.
After the coating is finished, an oven can be used for drying. The drying temperature is 50-100 ℃, and the drying time is 1-4 h.
The hot pressing step can adopt double-light roller hot pressing at 120-150 ℃.
The invention also provides a hierarchical pore fiber cloth-based polymer composite membrane prepared by the preparation method of the hierarchical pore fiber cloth-based polymer composite membrane.
The invention also provides application of the hierarchical pore fiber cloth-based polymer composite membrane prepared by the preparation method of the hierarchical pore fiber cloth-based polymer composite membrane, and the hierarchical pore fiber cloth-based polymer composite membrane can be particularly used for lithium ion battery separators.
The invention has the following beneficial effects:
according to the invention, COPET/PP sea-island fiber cloth with different warp-weft ratios and different sea-island component ratios is selected, an alkali solution is used for removing the sea component COPET to obtain the superfine polypropylene fiber cloth as a supporting layer, and the multistage pore fiber cloth-based polymer composite membrane is prepared by drying and hot pressing after coating slurry containing a polymer mixture and nano zeolite particles with different particle sizes.
The invention controls the pore space structure size and the pore distribution uniformity of the superfine denier polypropylene fiber cloth base supporting layer by adjusting the warp-weft ratio and the volume ratio of sea-island components of the COPET/PP sea-island type fiber cloth, and simultaneously can control the distribution condition of zeolite particles in the superfine denier polypropylene fiber cloth base supporting layer by adjusting the proportion of the zeolite particles with different particle sizes, thereby constructing a multi-stage pore channel, effectively improving the liquid retention rate, increasing the high cycle capacity retention rate of the lithium ion battery, simultaneously increasing the ion transmission path of the multi-stage pore channel, and further improving the ion conductivity.
The invention adopts the super fine denier polypropylene fiber cloth obtained by washing sea components from the COPET/PP sea-island fiber cloth as the supporting layer, the super fine denier polypropylene fiber cloth has excellent mechanical property, and can keep good anti-shrinkage capability and inhibit the puncture capability of lithium dendrite when being stretched and curled.
Drawings
FIG. 1 is a scanning electron micrograph of an island-in-sea fiber from which no sea component is washed away.
FIG. 2 is a scanning electron microscope image of a sea-island type fiber cloth from which no sea component is washed away.
FIG. 3 is a scanning electron microscope image of sea-island type fiber cloth with sea components washed away.
Fig. 4 is a schematic diagram of the construction of a hierarchical pore structure by introducing nano zeolite particles of different particle sizes on a support layer.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that various changes and modifications can be made by one skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The reagents used in the examples of the present invention and comparative examples are commercially available, but are not limited to these materials.
Example 1:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52 percent, and the aperture range is 0.5-1 mu m;
(2) preparation of coating slurry: adding polypropylene alcohol and alkylphenol ethoxylates into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at a high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than 0.5 mu m) is 3 wt%, and the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 3 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 2:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol ethoxylates is 0.8 wt%, the content of polyvinyl alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (with the particle size of 0.1 mu m or more and less than 0.5 mu m) is 3 wt%, and the content of medium-particle-size FAU-type nano zeolite particles (with the particle size of 0.5 mu m or more and less than 1 mu m) is 5 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth-based supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 3:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 37, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at a high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than 0.5 mu m) is 5wt%, and the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 4:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 37, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding polypropylene alcohol and alkylphenol ethoxylates into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at a high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 2 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 5:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 5wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 3 wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 2 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and performing hot pressing by a double-optical roller at 150 ℃ to obtain the hierarchical porous fiber cloth-based polymer composite membrane.
Example 6:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 37, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 3 wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 4 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 7:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth-based supporting layer: soaking COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52 percent, and the aperture range is 0.5-1 mu m;
(2) preparation of coating slurry: adding polypropylene alcohol and alkylphenol ethoxylates into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene is 0.8 wt%, the content of polyvinyl alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, and the content of small particle size FAU type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than 0.5 mu m) is 10 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 8:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 37, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, and the content of FAU type nano zeolite particles with medium particle size (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 10 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 9:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 37, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52 percent, and the aperture range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, and the content of FAU type nano zeolite particles with large particle size (the particle size is more than 1 mu m and less than or equal to 3 mu m) is 10 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth-based supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and performing hot pressing by a double-optical roller at 150 ℃ to obtain the hierarchical porous fiber cloth-based polymer composite membrane.
Example 10:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 20:15, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 35%, and the pore diameter range is 1.2-1.8 mu m;
(2) preparation of coating slurry: adding polypropylene alcohol and alkylphenol ethoxylates into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 2 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 11:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 50:35, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 40%, and the pore diameter range is 1-1.5 mu m;
(2) preparation of coating slurry: adding polypropylene alcohol and alkylphenol ethoxylates into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol ethoxylates is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than 1 mu m and less than or equal to 3 mu m) is 2 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 12:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 20 wt%, and the island component PP accounts for 80 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 37, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.4 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 45%, and the pore diameter range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 2 wt%. .
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and performing hot pressing by a double-optical roller at 150 ℃ to obtain the hierarchical porous fiber cloth-based polymer composite membrane.
Example 13:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 50wt%, and the island component PP accounts for 50 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 30, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.4 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in aqueous alkali at 90 ℃ for 15min to remove sea component COPET, washing with deionized water, and drying in a baking oven at 90 ℃ to prepare an ultra-fine polypropylene fiber cloth base supporting layer, wherein the porosity is 55%, and the pore diameter range is 3-4 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene ether is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 2 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 14:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 30:25, the sea component COPET accounts for 35 wt%, and the island component PP accounts for 65 wt%; the number of single-strand ultra-fine polypropylene fibers in the sea-island type ultra-fine fibers used as island structures is 35, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures is 0.35.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in aqueous alkali at 90 ℃ for 15min to remove sea component COPET, washing with deionized water, and drying in a baking oven at 90 ℃ to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 48%, and the pore diameter range is 0.6-1.2 mu m;
(2) preparation of coating slurry: adding an ethylene oxide adduct of polypropylene alcohol and polypropylene glycol into an N, N-dimethylformamide solution, stirring at a high speed at normal temperature, and mixing uniformly to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of an ethylene oxide adduct of polypropylene glycol is 0.8 wt%, the content of polypropylene glycol is 3 wt%, the content of a tetrafluoroethylene-hexafluoropropylene copolymer is 5wt%, the content of polyurethane is 5wt%, the content of FAU type nano zeolite particles with small particle sizes (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of FAU type nano zeolite particles with medium particle sizes (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of FAU type nano zeolite particles with large particle sizes (the particle size is more than 1 mu m and less than or equal to 3 mu m) is 5 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Example 15:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 30:25, the sea component COPET accounts for 40wt%, and the island component PP accounts for 60 wt%; the number of single-strand ultra-fine polypropylene fibers as island structures in the sea-island type ultra-fine fibers used was 32, and the number of single-strand ultra-fine polypropylene fibers obtained by washing off the sea structures was 0.37 denier.
(1) Preparing a fiber cloth base supporting layer: soaking the COPET/PP sea-island fiber cloth in aqueous alkali at 90 ℃ for 15min to remove sea component COPET, washing with deionized water, and drying in a baking oven at 90 ℃ to prepare an ultra-fine polypropylene fiber cloth base supporting layer, wherein the porosity is 50%, and the pore diameter range is 0.7-1.4 μm;
(2) preparation of coating slurry: adding polypropylene alcohol and high-carbon fatty alcohol polyoxyethylene ether into the N, N-dimethylformamide solution, stirring at high speed at normal temperature, and mixing uniformly to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of high-carbon fatty alcohol polyoxyethylene ether is 1wt%, the content of polypropylene alcohol is 4 wt%, the content of polyvinylidene fluoride is 4 wt%, the content of polyurethane is 4 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is not less than 0.1 mu m and not more than 0.5 mu m) is 5wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is not less than 0.5 mu m and not more than 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is not less than 1 mu m and not more than 3 mu m) is 5 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and then hot-pressing by a double-optical roller at 150 ℃ to prepare the hierarchical-pore fiber cloth-based polymer composite membrane.
Comparative example 1:
adding polypropylene alcohol and fluorocarbon surfactant into N, N-dimethylformamide solution, stirring at high speed at normal temperature, and mixing to obtain solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (the aperture range is 0.1nm-10nm), stirring at high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of a fluorocarbon surfactant is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, the content of polyurethane is 2 wt%, the content of small-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.1 mu m and less than or equal to 0.5 mu m) is 3 wt%, the content of medium-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 0.5 mu m and less than or equal to 1 mu m) is 5wt%, and the content of large-particle-size FAU-type nano zeolite particles (the particle size is more than or equal to 1 mu m and less than or equal to 3 mu m) is 2 wt%.
Coating with a micro-gravure roll, coating the prepared coating slurry on a dry PE film of Shenzhen star source at a coating rate of 20m/min and a coating thickness of 18 μm; drying in a 70 ℃ oven for 2h, and hot-pressing by a double-optical roller at 150 ℃ to obtain the composite film.
Comparative example 2:
the warp-weft ratio of the COPET/PP sea-island fiber cloth is 45:30, the sea component COPET accounts for 30 wt%, and the island component PP accounts for 70 wt%; the number of single-strand ultra-fine polypropylene fibers serving as island structures in the used sea-island type ultra-fine polypropylene fibers is 37, and the single-strand ultra-fine polypropylene fiber obtained after washing off the sea structures is 0.3 denier.
(1) Preparing a fiber cloth base supporting layer: soaking COPET/PP sea-island fiber cloth in 90 ℃ alkali solution for 15min to remove sea component COPET, cleaning with deionized water, and drying in a 90 ℃ oven to prepare the superfine polypropylene fiber cloth base supporting layer, wherein the porosity is 52 percent, and the aperture range is 0.5-1 mu m;
(2) preparation of coating slurry: adding the polypropylene alcohol and the alkylphenol polyoxyethylene into the N, N-dimethylformamide solution, and stirring and mixing uniformly at a high speed at normal temperature to prepare a solution; adding polyvinylidene fluoride and polyurethane, finally adding FAU type nano zeolite particles (with the porosity and the aperture range of 0.1nm-10nm), stirring at a high speed and mixing uniformly to prepare coating slurry; in the coating slurry, the content of alkylphenol polyoxyethylene is 0.8 wt%, the content of polypropylene alcohol is 3 wt%, the content of polyvinylidene fluoride is 3 wt%, and the content of polyurethane is 2 wt%.
(3) Preparing a composite membrane: coating the coating slurry prepared in the step (2) on the fiber cloth base supporting layer prepared in the step (1) by adopting a micro-gravure coating method, wherein the coating speed is 20m/min, and the thickness of the coating layer is 18 mu m; drying in a 70 ℃ oven for 2h, and hot-pressing by a double-optical roller at 150 ℃ to obtain the composite film.
The performance tests of the composite films prepared in the examples and comparative examples of the present invention were as follows:
(1) liquid absorption rate: the mass of the initially dried separator was weighed and recorded as W dry Soaking the diaphragm in electrolyte (EC/DMC/DEC mixed solution with volume ratio of 1:1:1 is selected for replacing for pollution reduction) for 10 minutes, taking out the diaphragm, wiping off excessive liquid on the surface by using filter paper, and recording the weight as W wet The calculation formula of the diaphragm absorbing the electrolyte is as follows:
(2) liquid retention rate: and after the electrolyte is soaked for 1 hour under the inert atmosphere condition, the mass loss is the loss of the electrolyte, and the mass of the composite membrane just soaked is divided by the mass obtained by subtracting the dry weight from the residual mass, namely the liquid retention rate.
(3) Ionic conductivity: the bulk resistance was measured using the Electrochemical Impedance Spectroscopy (EIS) mode of VMP3B-10 electrochemical workstation (Bio-Logic Science Instruments) using a steel/diaphragm/steel assembly with a perturbation voltage amplitude of 5mV and frequency of 10mHz to 1 MHz. The bulk resistance is related to the ion conductivity by the following formula:
wherein δ is the ionic conductivity (S/cm) of the separator in a state of absorbing the liquid electrolyte; l is a radical of an alcohol 0 Is the membrane thickness (cm); r is b Is the bulk resistance (Ω) of the separator in the state of absorbing the liquid electrolyte; s is the effective contact area (cm) of the diaphragm and the stainless steel sheet 2 )。
(4) High cycle capacity retention: charge at a current density of 0.5C-discharge at a current density of-2C and cycle 1000 times with the ratio of the charge capacity to the discharge capacity of the battery.
(5) Shrinkage resistance: after the composite film is heated in an oven at 90 ℃ for 1h, the smaller the shrinkage rate of the film is, the better the anti-shrinkage capability is.
Table 1: results of relevant Performance test of composite membranes of examples 1 to 15 and comparative examples 1 to 2
The results show that the hierarchical pore fiber cloth-based polymer composite membrane prepared by the method has the excellent performances of high liquid absorption rate, high liquid retention rate, high ionic conductivity and anti-wrinkle ability, and is particularly suitable for lithium ion battery separators.
Compared with the embodiment 4, the composite membrane prepared by adopting the common dry method PE membrane as the supporting layer has poor crease and shrinkage resistance at high temperature, and the contact of the positive electrode and the negative electrode can cause the short circuit of the battery.
The coating slurry of comparative example 2 is not added with nano zeolite particles, and the prepared composite membrane has obviously poor liquid absorption rate and liquid retention rate, low ionic conductivity and low retention rate of high circulation capacity.
Claims (10)
1. A preparation method of a hierarchical pore fiber cloth-based polymer composite membrane is characterized by comprising the following steps:
(1) preparing a fiber cloth base supporting layer: soaking COPET/PP sea-island type fiber cloth in an alkali solution to remove sea component COPET in the sea-island type fiber cloth, and preparing an ultra-fine denier polypropylene fiber cloth base supporting layer;
the COPET/PP sea-island fiber cloth is woven by sea-island superfine fibers taking polypropylene as an island component and polyethylene glycol terephthalate as a sea component;
(2) preparation of coating slurry: adding an adhesive and a surfactant into the dispersant solution, stirring and mixing uniformly, then adding the polymer mixture and the nano zeolite particles, stirring and mixing uniformly to prepare a coating slurry;
in the coating slurry, the content of a surfactant is 0.5-1 wt%, the content of an adhesive is 1-5 wt%, the content of a polymer mixture is 5-10 wt%, and the content of nano zeolite particles is 5-15 wt%;
(3) preparing a composite membrane: and (3) coating the coating slurry prepared in the step (2) on the fiber cloth-based supporting layer prepared in the step (1), and drying and hot-pressing to prepare the hierarchical porous fiber cloth-based polymer composite membrane.
2. The method for preparing a hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the warp-weft ratio of the COPET/PP sea-island type fiber cloth is (20-50): (15-35), preferably (30-45): (25-30); the COPET/PP sea-island fiber cloth comprises 60-70 wt% of island components and 30-40 wt% of sea components.
3. The method of preparing a hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the number of the single-strand ultra-fine polypropylene fibers in the sea-island type ultra-fine fiber as an island structure is 25 to 45; the superfine denier polypropylene fiber is 0.1-0.5 denier.
4. The preparation method of the hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the porosity of the superfine denier polypropylene fiber cloth-based supporting layer is 30% -60%, and the pore diameter is 0.5-4 μm; preferably, the porosity of the superfine denier polypropylene fiber cloth-based supporting layer is 48-55%, and the pore diameter range is 0.5-1 μm.
5. The method for preparing a hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the polymer mixture is selected from the group consisting of fluorine-containing polymers and ester-containing polymers; preferably, the weight ratio of the fluorine-containing polymer to the ester-containing polymer is (3-7): (2-8); the fluorine-containing polymer is selected from one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer or tetrafluoroethylene-hexafluoropropylene copolymer, and preferably polyvinylidene fluoride; the ester-containing polymer is selected from one or more of polyurethane, polymethyl methacrylate or polymethyl acrylate, and preferably is polyurethane.
6. The preparation method of the hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the nano zeolite particles are selected from any one or more of FAU-type zeolite, ZSM-5 zeolite, AFI-type zeolite or MFI-type zeolite; preferably, the pore diameter range of the nano zeolite particles is 0.1nm-10 nm.
7. The preparation method of the hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the nano zeolite particles comprise any one or more of small-size zeolite particles, medium-size zeolite particles or large-size zeolite particles, wherein the small size is 0.1 μm or more and the particle size is less than 0.5 μm, the medium size is 0.5 μm or more and the particle size is less than 1 μm, and the large size is 1 μm or more and the particle size is less than 3 μm; preferably, the nano zeolite particles comprise 20-50 wt% of small-particle size zeolite particles, 30-65 wt% of medium-particle size zeolite particles and 0-40 wt% of large-particle size zeolite particles; more preferably, the nano zeolite particles comprise 30 to 50wt% of small-particle size zeolite particles, 30 to 50wt% of medium-particle size zeolite particles and 20 to 40wt% of large-particle size zeolite particles.
8. The preparation method of the hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein the dispersant solution is selected from any one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or polyvinylpyrrolidone; the adhesive is selected from one or more of polyvinyl alcohol, polypropylene alcohol, acrylic adhesives or vinyl acetate adhesives; the surfactant is selected from one or more of fluorocarbon surfactant, silane surfactant or polyalcohol surfactant; preferably, the fluorocarbon surfactant is selected from one or more of alkylphenol ethoxylates, high-carbon fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester or ethylene oxide adduct of polypropylene glycol; the silane surfactant is selected from any one or more of trisiloxane or amino polyether; the polyalcohol surfactant is one or more selected from ethylene oxide adduct of polypropylene glycol, diglyceride fatty acid ester, ethylene glycol, glycerol pentaerythritol or diglyceride fatty acid ester.
9. The preparation method of the hierarchical porous fiber cloth-based polymer composite membrane according to claim 1, wherein in the step (3), micro-gravure coating is adopted, the coating speed is 10-40m/min, and the thickness of the coating layer is 15 μm-25 μm; the drying temperature is 50-100 ℃, and the drying time is 1-4 h; and in the hot pressing step, double hot rollers at 120-150 ℃ are adopted for hot pressing.
10. The use of the hierarchical porous fiber cloth-based polymer composite membrane prepared by the method of any one of claims 1 to 9 for a lithium ion battery separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210681567.4A CN115101888B (en) | 2022-06-16 | 2022-06-16 | Multistage Kong Qianwei cloth-based polymer composite membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210681567.4A CN115101888B (en) | 2022-06-16 | 2022-06-16 | Multistage Kong Qianwei cloth-based polymer composite membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115101888A true CN115101888A (en) | 2022-09-23 |
| CN115101888B CN115101888B (en) | 2024-03-26 |
Family
ID=83291789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210681567.4A Active CN115101888B (en) | 2022-06-16 | 2022-06-16 | Multistage Kong Qianwei cloth-based polymer composite membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115101888B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938461A (en) * | 2004-03-30 | 2007-03-28 | 帝人纤维株式会社 | Composite fabric of island-in-sea type and process for producing the same |
| US20130302695A1 (en) * | 2011-01-26 | 2013-11-14 | Evonik Degussa Gmbh | Thin macroporous polymeric foils |
| CN103515564A (en) * | 2013-10-15 | 2014-01-15 | 深圳市星源材质科技有限公司 | Composite diaphragm and method for preparing same |
| JP2016107642A (en) * | 2014-12-09 | 2016-06-20 | 旭化成イーマテリアルズ株式会社 | Multilayer porous membrane and separator for electricity storage device |
| US20170062785A1 (en) * | 2015-08-17 | 2017-03-02 | Celgard, Llc | Battery separators and related methods |
| CN109004154A (en) * | 2018-07-23 | 2018-12-14 | 广东蒙泰高新纤维股份有限公司 | A kind of method of wet process copy paper technique manufacture diaphragm of power lithium ion battery |
| WO2019010700A1 (en) * | 2017-07-14 | 2019-01-17 | 北京大学深圳研究生院 | Multi-pore zeolite having layered structure and preparation method therefor |
| CN112038542A (en) * | 2020-09-11 | 2020-12-04 | 广东工业大学 | Fiber cloth-based lithium ion battery diaphragm and preparation method and application thereof |
| CN112981722A (en) * | 2021-01-26 | 2021-06-18 | 广东蒙泰高新纤维股份有限公司 | Method for preparing lithium ion battery diaphragm by sea island COPET-PP composite negative pressure spinning |
| CN114243214A (en) * | 2021-12-30 | 2022-03-25 | 东莞凯德新能源有限公司 | Inorganic ceramic coating diaphragm and preparation method and application thereof |
-
2022
- 2022-06-16 CN CN202210681567.4A patent/CN115101888B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938461A (en) * | 2004-03-30 | 2007-03-28 | 帝人纤维株式会社 | Composite fabric of island-in-sea type and process for producing the same |
| US20130302695A1 (en) * | 2011-01-26 | 2013-11-14 | Evonik Degussa Gmbh | Thin macroporous polymeric foils |
| CN103515564A (en) * | 2013-10-15 | 2014-01-15 | 深圳市星源材质科技有限公司 | Composite diaphragm and method for preparing same |
| JP2016107642A (en) * | 2014-12-09 | 2016-06-20 | 旭化成イーマテリアルズ株式会社 | Multilayer porous membrane and separator for electricity storage device |
| US20170062785A1 (en) * | 2015-08-17 | 2017-03-02 | Celgard, Llc | Battery separators and related methods |
| WO2019010700A1 (en) * | 2017-07-14 | 2019-01-17 | 北京大学深圳研究生院 | Multi-pore zeolite having layered structure and preparation method therefor |
| CN109004154A (en) * | 2018-07-23 | 2018-12-14 | 广东蒙泰高新纤维股份有限公司 | A kind of method of wet process copy paper technique manufacture diaphragm of power lithium ion battery |
| CN112038542A (en) * | 2020-09-11 | 2020-12-04 | 广东工业大学 | Fiber cloth-based lithium ion battery diaphragm and preparation method and application thereof |
| CN112981722A (en) * | 2021-01-26 | 2021-06-18 | 广东蒙泰高新纤维股份有限公司 | Method for preparing lithium ion battery diaphragm by sea island COPET-PP composite negative pressure spinning |
| CN114243214A (en) * | 2021-12-30 | 2022-03-25 | 东莞凯德新能源有限公司 | Inorganic ceramic coating diaphragm and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BO-RAN CAI ET AL.: "Ultraviolet-Cured Al2O3‑Polyethylene Terephthalate/PolyvinylideneFluoride Composite Separator with Asymmetric Design and ItsPerformance in Lithium Batteries", ACS APPLIED ENERGY MATERIALS, vol. 4, pages 5293 - 5303 * |
| 毛绪国等: "双组分聚烯烃复合纤维的生产技术及应用现状", 《合成纤维工业》, vol. 43, no. 6, pages 64 - 69 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115101888B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210265702A1 (en) | Composite lithium battery separator and preparation method therefor | |
| CN104766937B (en) | A kind of environment-friendlylithium lithium ion battery membrane and preparation method thereof | |
| CN109509857A (en) | A kind of porosity lithium ion battery separator and its application with inierpeneirating network structure | |
| KR101387388B1 (en) | Porous membrane and process for preparing the same | |
| KR101446949B1 (en) | Porous membrane and process for preparing the same | |
| DE112008001340T5 (en) | Microporous nonwoven reinforced polymer membrane, manufacturing method and use thereof | |
| CN113451708A (en) | Functional coating diaphragm and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof | |
| CN104466063B (en) | Poly-dopamine surface modification polyether sulfone nanofiber composite diaphragm, preparation method and application | |
| CN113644378B (en) | Functional coating diaphragm and preparation method and application thereof | |
| KR101335380B1 (en) | Porous membrane and process for preparing the same | |
| JP4974448B2 (en) | Manufacturing method of separator for electronic parts | |
| CN110518177B (en) | SiO2PVDF-HFP composite fiber membrane and preparation method and application thereof | |
| TW201332192A (en) | Separator for electrochemical device and manufacture process thereof | |
| CN1089192C (en) | Separator material for alkaline storage batteries | |
| CN110364664A (en) | A kind of Water based metal ion secondary battery diaphragm and its preparation method and application | |
| KR101337921B1 (en) | Porous membrane and process for preparing the same | |
| JP2019087313A (en) | Electrode and method of manufacturing the same, and battery | |
| CN114649560A (en) | Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof | |
| JP2016182817A (en) | Laminate | |
| CN115101888B (en) | Multistage Kong Qianwei cloth-based polymer composite membrane and preparation method and application thereof | |
| CN112635918A (en) | Diaphragm, preparation method thereof and battery | |
| JP7195751B2 (en) | Membrane for electrochemical device and use thereof | |
| JP2016182816A (en) | Laminate and method for producing the same | |
| CN116525867A (en) | Microporous layer slurry, high-porosity gas diffusion layer and preparation method thereof | |
| JP2020161243A (en) | Nonwoven fabric base material for lithium secondary battery separator, and lithium secondary battery separator |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |