CN117096547A - Composite modified cellulose nylon diaphragm and preparation method and application thereof - Google Patents
Composite modified cellulose nylon diaphragm and preparation method and application thereof Download PDFInfo
- Publication number
- CN117096547A CN117096547A CN202311197687.8A CN202311197687A CN117096547A CN 117096547 A CN117096547 A CN 117096547A CN 202311197687 A CN202311197687 A CN 202311197687A CN 117096547 A CN117096547 A CN 117096547A
- Authority
- CN
- China
- Prior art keywords
- nylon
- cellulose
- modified cellulose
- composite modified
- lithium
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 127
- 239000001913 cellulose Substances 0.000 title claims abstract description 127
- 239000004677 Nylon Substances 0.000 title claims abstract description 115
- 229920001778 nylon Polymers 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 37
- 239000002608 ionic liquid Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 238000005266 casting Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 229920002647 polyamide Polymers 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 229920006284 nylon film Polymers 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229920001721 polyimide Polymers 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 7
- 239000009719 polyimide resin Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 230000005012 migration Effects 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract 1
- 229920003081 Povidone K 30 Polymers 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 37
- 230000014759 maintenance of location Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010998 test method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 101150047356 dec-1 gene Proteins 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004804 winding 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
Abstract
The invention discloses a composite modified cellulose nylon diaphragm and a preparation method and application thereof, wherein the preparation method comprises the steps of using ionic liquid to dissolve and blend cellulose, nylon, PVP-K30 and polyacrylonitrile to obtain a blend casting solution; preparing a film from the blending casting solution by an extruder; washing redundant solvent on the film by deionized water, and then drying to obtain a cellulose nylon film; soaking a cellulose nylon membrane in lithium bistrifluoromethylsulfonylimide with a certain mass concentration to obtain a modified cellulose nylon membrane; coating the prepared polyamide slurry on a modified cellulose nylon membrane, and drying to obtain a composite modified cellulose nylon membrane; the composite modified cellulose nylon diaphragm is applied to a lithium ion battery, so that migration of lithium ions can be promoted, impedance of the lithium ion battery is reduced, the risk of polarization of the lithium ion battery is reduced, and safety, rate capability and cycle performance of the lithium ion battery are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a composite modified cellulose nylon diaphragm and a preparation method and application thereof.
Background
The diaphragm has the main functions of preventing electron conduction, preventing internal short circuit caused by contact between two electrodes and ensuring that ions in electrolyte can smoothly pass through. The diaphragm plays an important role in electrochemical performance and safety performance of the lithium ion battery.
Polyolefin diaphragms (such as polyethylene PE diaphragms and polypropylene PP diaphragms) commonly used for lithium ion batteries are low in porosity, are not beneficial to rapid migration of ions, and directly influence the rate capability of the lithium ion batteries; secondly, polyolefin diaphragms have poor wettability and liquid retention and are difficult to meet the requirement of long-cycle stability of lithium ion batteries; and the polyolefin diaphragm has poor thermal stability, and is difficult to meet the safety requirement of the lithium ion battery under high voltage charge and discharge.
The cellulose membrane has high porosity, excellent thermal stability and good wettability, so that the cellulose membrane is widely applied, but the existing cellulose membrane still has the problems of low thermal stability, poor liquid absorption and retention and low ionic conductivity, so that the safety performance, the multiplying power performance and the cycling stability of the lithium ion battery are affected.
Disclosure of Invention
In order to solve the technical problems in the prior art, the embodiment of the invention provides a composite modified cellulose nylon diaphragm and a preparation method and application thereof.
According to the preparation method of the composite modified cellulose nylon diaphragm, firstly, cellulose, nylon, PVP-K30 and polyacrylonitrile are dissolved and blended by using ionic liquid to obtain a blend casting solution, then the blend casting solution is formed into a film by an extruder, the film is dried after surplus solvent is washed off by using deionized water to obtain a cellulose nylon diaphragm, the cellulose nylon diaphragm is soaked in lithium bis (trifluoromethylsulfonyl) imide with a certain mass concentration to obtain a modified cellulose nylon diaphragm, and finally, the prefabricated polyamide slurry is coated on the modified cellulose nylon diaphragm, and the composite modified cellulose nylon diaphragm is obtained after drying.
The composite modified cellulose nylon diaphragm prepared by the preparation method provided by the invention, wherein cellulose and nylon form a three-dimensional net-shaped film through crosslinking, and the addition of nylon compensates the problem of low mechanical strength of cellulose, so that the tensile strength of the diaphragm is improved; the double-trifluoromethyl-sulfonyl imide lithium is dispersed on the surface and/or in the pores of the three-dimensional network structure, so that the migration of lithium ions can be promoted, the impedance of the lithium ion battery can be reduced, and the polarization risk of the lithium ion battery can be reduced; the polyimide coating has the characteristic of micropores, not only can strengthen the mechanical strength and high temperature resistance of the diaphragm, but also can avoid the problem of reducing the ionic conductivity of the diaphragm due to the coating of the polyimide coating to a certain extent.
The composite modified cellulose nylon diaphragm provided by the embodiment of the invention has good heat resistance, mechanical property, liquid absorption and liquid retention, and simultaneously has excellent lithium ion mobility under the modification of lithium bistrifluoromethylsulfonimide, so that when the composite modified cellulose nylon diaphragm is applied to a lithium ion battery, the lithium ion battery can have excellent electrochemical performance.
To this end, in a first aspect, an embodiment of the present invention provides a method for preparing a composite modified cellulose nylon membrane, the method comprising:
using ionic liquid to dissolve and blend cellulose, nylon, polyvinylpyrrolidone-K30 and polyacrylonitrile to obtain a blend casting solution;
preparing a film from the blending casting solution by an extruder;
washing redundant solvent on the film by deionized water, and then drying to obtain a cellulose nylon film;
soaking a cellulose nylon membrane in lithium bistrifluoromethylsulfonylimide with a certain mass concentration to obtain a modified cellulose nylon membrane;
coating the prepared polyamide slurry on a modified cellulose nylon membrane, and drying to obtain the composite modified cellulose nylon membrane.
Preferably, the ionic liquid comprises: one or more of imidazole type ionic liquid, piperidine type ionic liquid, pyridine type ionic liquid, pyrrolidine type ionic liquid, quaternary phosphine type ionic liquid, quaternary ammonium type ionic liquid and morpholine type ionic liquid;
the cellulose includes: one or more of polymerized cellulose, lignin fiber, cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose;
the nylon specifically comprises: nylon 6, nylon 66, nylon 11, nylon 12, nylon 61, or one or more of nylon.
Preferably, the mass ratio of the ionic liquid, cellulose, nylon, polyvinylpyrrolidone-K30 and polyacrylonitrile is [1-10]: [0.1-1]:[0.1-1]:[0.1-1]: [0.1-1].
Preferably, the mass concentration of the lithium bistrifluoromethylsulfonylimide is 1% -4%.
Preferably, the temperature of the drying treatment is between 60 ℃ and 80 ℃ and the drying time is between 4 hours and 6 hours;
the temperature of the drying treatment is between 60 ℃ and 80 ℃ and the drying time is between 4 hours and 6 hours.
Preferably, the specific preparation process of the polyamide slurry comprises the following steps: and uniformly mixing polyimide resin powder, a pore-forming agent and an organic solvent to obtain polyamide slurry.
Further preferably, the pore-forming agent includes: one or more of glycerol, diglycerol, ethanol, ethylene glycol, lithium bromide, lithium chloride, and lithium hydroxide;
the organic solvent includes: one or more of N, N-dimethylacetamide, hexamethylphosphoric triamide and dimethyl sulfoxide;
the mass ratio of the polyimide resin powder, the pore-forming agent and the organic solvent is as follows
[1-10]:[1-5]:[1-50]。
In a second aspect, an embodiment of the present invention provides a composite modified cellulose nylon separator prepared by the preparation method according to the first aspect.
Preferably, the composite modified cellulose nylon membrane comprises: cellulose, nylon, lithium bis (trifluoromethylsulfonyl) imide, polyimide;
the cellulose and the nylon form a film with a three-dimensional network structure through crosslinking, the polyimide is coated on the surface of the film, and the lithium bistrifluoromethylsulfonyl imide is dispersed on the surface and/or in pores of the three-dimensional network structure;
the thickness of the composite modified cellulose nylon diaphragm is between 5 and 50 mu m.
In a third aspect, an embodiment of the present invention provides a lithium ion battery, where the lithium ion battery includes the composite modified cellulose nylon separator according to the second aspect.
According to the preparation method of the composite modified cellulose nylon diaphragm, firstly, cellulose, nylon, PVP-K30 and polyacrylonitrile are dissolved and blended by using ionic liquid to obtain a blend casting solution, then the blend casting solution is formed into a film by an extruder, the film is dried after surplus solvent is washed off by using deionized water to obtain a cellulose nylon diaphragm, then the cellulose nylon diaphragm is soaked in lithium bis (trifluoromethylsulfonyl) imide with a certain mass concentration to obtain a modified cellulose nylon diaphragm, finally, the prefabricated polyamide slurry is coated on the modified cellulose nylon diaphragm, and the composite modified cellulose nylon diaphragm is obtained after drying.
The composite modified cellulose nylon diaphragm prepared by the preparation method provided by the invention, wherein cellulose and nylon form a three-dimensional net-shaped film through crosslinking, and the addition of nylon compensates the problem of low mechanical strength of cellulose, so that the tensile strength of the diaphragm is improved; the double-trifluoromethyl-sulfonyl imide lithium is dispersed on the surface and/or in the pores of the three-dimensional network structure, so that the migration of lithium ions can be promoted, the impedance of the lithium ion battery can be reduced, and the polarization risk of the lithium ion battery can be reduced; the polyimide coating has the characteristic of micropores, not only can strengthen the mechanical strength and high temperature resistance of the diaphragm, but also can avoid the problem of reducing the ionic conductivity of the diaphragm due to the coating of the polyimide coating to a certain extent.
The composite modified cellulose nylon diaphragm provided by the embodiment of the invention has good heat resistance, mechanical property, liquid absorption and liquid retention, and simultaneously has excellent lithium ion mobility under the modification of lithium bistrifluoromethylsulfonimide, so that when the composite modified cellulose nylon diaphragm is applied to a lithium ion battery, the lithium ion battery can have excellent electrochemical performance.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
Fig. 1 is a flowchart of a preparation method of a composite modified cellulose nylon diaphragm provided by an embodiment of the invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and to specific examples, but it should be understood that these examples are for the purpose of more detailed description only and should not be construed as limiting the invention in any way, i.e. not as limiting the scope of the invention.
The embodiment of the invention provides a preparation method of a composite modified cellulose nylon diaphragm, which is shown in fig. 1, and specifically comprises the following steps:
step 110, dissolving and blending cellulose, nylon, polyvinylpyrrolidone-K30 and polyacrylonitrile by using an ionic liquid to obtain a blending casting solution;
wherein, ionic liquid includes: one or more of imidazole type ionic liquid, piperidine type ionic liquid, pyridine type ionic liquid, pyrrolidine type ionic liquid, quaternary phosphine type ionic liquid, quaternary ammonium type ionic liquid and morpholine type ionic liquid;
the cellulose includes: one or more of polymerized cellulose, lignin fiber, cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose; the cellulose adopted by the invention is obtained by crushing cellulose pulp through a high-speed universal crusher.
The nylon specifically comprises: one or more of nylon 6, nylon 66, nylon 11, nylon 12, nylon 61, or nylon;
cellulose, nylon and Polyacrylonitrile (PAN) need to be reused after drying in a drying oven at 80 ℃ for 6 hours;
the mass ratio of the ionic liquid, the cellulose, the nylon, the polyvinylpyrrolidone-K30 (PVP-K30) and the polyacrylonitrile is (1-10): [0.1-1]:[0.1-1]:[0.1-1]: [0.1-1];
the invention adopts PVP-K30 as a pore-forming agent to improve the aperture of the diaphragm, so that the diaphragm has good liquid absorption and liquid retention.
Step 120, preparing the blending casting film liquid into a film through an extruder;
the step, the extruder adopts common extruder equipment, including but not limited to a single screw extruder, a double screw extruder or a multi-screw extruder, and the blending casting film liquid can be formed into a film;
the thickness of the obtained film is 5 μm to 50. Mu.m.
Step 130, washing redundant solvents on the film by using deionized water, and then drying to obtain a cellulose nylon film;
wherein the temperature of the drying treatment is between 60 ℃ and 80 ℃ and the drying time is between 4 hours and 6 hours.
Step 140, soaking a cellulose nylon membrane in lithium bistrifluoromethylsulfonyl imide with a certain mass concentration to obtain a modified cellulose nylon membrane;
wherein the mass concentration of the lithium bistrifluoromethylsulfonyl imide is 1% -4%, such as any mass fraction of 1%, 2%, 3%, 4%, but not limited to the recited values; the double-trifluoromethyl-sulfonyl imide lithium is added, so that the composite modified cellulose nylon diaphragm can provide a lithium source, thereby promoting migration of lithium ions and reducing polarization of a lithium ion battery.
Step 150, coating the prepared polyamide slurry on a modified cellulose nylon membrane, and drying to obtain a composite modified cellulose nylon membrane;
specifically, the specific preparation process of the polyamide slurry comprises the following steps: uniformly mixing polyimide resin powder, a pore-forming agent and an organic solvent to obtain polyamide slurry; wherein, the pore-forming agent includes: one or more of glycerol, diglycerol, ethanol, ethylene glycol, lithium bromide, lithium chloride, and lithium hydroxide; the organic solvents include: one or more of N, N-dimethylacetamide, hexamethylphosphoric triamide and dimethyl sulfoxide; the mass ratio of polyimide resin powder, pore-forming agent and organic solvent is (1-10) [1-5 ]:1-50 ];
in the step, the temperature of the drying treatment is between 60 ℃ and 80 ℃ and the drying time is between 4 hours and 6 hours.
According to the invention, the polyamide slurry is coated on the modified cellulose diaphragm to form the porous polyimide coating, so that the high temperature resistance of the cellulose nylon diaphragm can be greatly improved, and meanwhile, the mechanical properties can be improved and consolidated again, and the porous structure does not influence the liquid absorption and liquid retention of the diaphragm.
The composite modified cellulose nylon diaphragm prepared by the preparation method provided by the embodiment of the invention has the thickness of 5-50 mu m.
The composite modified cellulose nylon diaphragm comprises: cellulose, nylon, lithium bis (trifluoromethylsulfonyl) imide, polyimide; the structure is as follows: cellulose and nylon form a three-dimensional network structure film through crosslinking, polyimide is coated on the surface of the film, and lithium bistrifluoromethylsulfonyl imide is dispersed on the surface and/or in pores of the three-dimensional network structure.
The composite modified cellulose nylon diaphragm can form a lithium ion battery with an anode plate, a cathode plate and electrolyte; when the composite modified cellulose nylon diaphragm provided by the embodiment of the invention is applied to a lithium ion battery, migration of lithium ions can be promoted, and impedance of the lithium ion battery is reduced, so that the risk of polarization of the lithium ion battery is reduced, and safety, rate capability and cycling stability of the lithium ion battery are improved.
In order to better understand the technical scheme provided by the invention, the preparation method and the characteristics of the composite modified cellulose nylon diaphragm are respectively described in the following specific examples.
Example 1
The embodiment provides a preparation process and performance test of a composite modified cellulose nylon diaphragm, which comprises the following specific processes:
(1) Using ionic liquid to dissolve and blend cellulose, nylon, PVP-K30 and polyacrylonitrile to obtain a blend casting solution, which specifically comprises the following steps: drying crushed cellulose, nylon 6 and polyacrylonitrile in a drying oven at 80 ℃ for 6 hours for later use; taking 93 g of pyridine type ionic liquid in a three-neck flask, adding 6 g of nylon 6 into the three-neck flask, placing the three-neck flask in an oil bath, heating to 190 ℃ to dissolve for 2 hours, then cooling to 140 ℃, adding 3 g of polyacrylonitrile, stirring for 2 hours, finally cooling to 90 ℃, adding 4 g of cellulose and 4 g of PVPK30 into the three-neck flask, and continuing stirring for 1 hour to obtain uniform and stable blending casting solution.
(2) Preparing the blend casting film liquid obtained in the previous step into a film by an extruder, wherein the film is specifically: and (3) putting the blending casting film liquid into an extruder, extruding through a die head, casting onto a strippable casting carrier, and then carrying out suction filtration through a suction filtration device to extract water to form a film.
(3) And (3) cleaning redundant solvents on the film by using deionized water, and then baking in an oven at 80 ℃ for 10 minutes to carry out drying treatment to obtain the cellulose nylon film.
(4) Soaking a cellulose nylon membrane in a lithium bistrifluoromethylsulfonyl imide solution (the solvent is ethanol) with the mass fraction of 4% for 30 minutes to obtain a modified cellulose nylon membrane;
(5) Coating polyamide slurry on the two side surfaces of the modified cellulose nylon membrane, and baking at 100 ℃ for 10 minutes to obtain a composite modified cellulose nylon membrane with the thickness of 9 mu m; the preparation method of the polyamide slurry specifically comprises the following steps: 20 g of polyimide resin powder, 2 g of lithium bromide, 2 g of ethylene glycol and 76 g of N, N-dimethylacetamide are stirred and dispersed for 6 hours, and the mixture is uniformly mixed to obtain polyamide slurry.
The composite modified cellulose nylon diaphragm prepared in this example was tested for liquid absorption, liquid retention, thermal stability, mechanical properties, and lithium ion conductivity. The test method is as follows, and the test results are shown in Table 1.
Testing liquid retention rate: according to QB/T2303.11-2008, section 11 of Battery Sichuan paper: measurement of liquid absorption rate.
Testing thermal stability: according to the GB/T12027-2004 plastic-film and sheet-heated dimensional change test method, the composite modified cellulose nylon separator of this example was tested for heat shrinkage in the Machine Direction (MD) and Transverse Direction (TD) after being heated at 130℃for 1 hour.
Testing mechanical properties: determination of tensile Properties of plastics according to GB/T1040 3-2006 part 3: test conditions for films and sheets.
Testing lithium ion conductivity: firstly, the lithium ion battery is assembled by using the composite modified cellulose nylon diaphragm prepared by the embodiment, and the specific process is as follows:
preparing a positive electrode plate, namely mixing active substances of lithium cobaltate, conductive carbon black, a binder of polyvinylidene fluoride and a solvent NMP according to a proportion of 64:3:3:30, uniformly stirring and mixing, coating the mixture on an aluminum foil, and drying, cold pressing and cutting the mixture to obtain a positive electrode plate;
preparing a negative electrode plate: active substance graphite, binder styrene-butadiene rubber, thickener sodium carboxymethyl cellulose and deionized water are mixed according to a proportion of 62:2:1:35, uniformly stirring and mixing, coating the mixture on a copper foil, and drying, cold pressing and cutting the mixture to obtain a negative electrode plate;
sequentially stacking the positive electrode plate, the composite modified cellulose nylon diaphragm prepared by the embodiment and the negative electrode plate, winding to obtain a bare cell, placing the bare cell in a shell, and injecting electrolyteAnd packaging to obtain the lithium ion battery, wherein the electrolyte adopts LiPF of 1mol/L 6 Vinyl carbonate EC/dimethyl carbonate DEC (volume ratio of EC to DEC 1:1).
Method for testing lithium ion conductivity: and (3) charging the prepared lithium ion battery to 4.4V at a constant current with a multiplying power of 1C at 25 ℃, then charging to 0.05C at a constant voltage with a voltage of 4.4V, discharging to 2.0V with a discharging current of 1C, and repeating the above process to test the lithium ion conductivity after 500 weeks.
Example 2
The present example provides a preparation process of a composite modified cellulose nylon membrane, which is substantially the same as example 1, except that the mass fraction of the solute of the lithium bistrifluoromethylsulfonylimide solution (the solvent is ethanol) is 1%.
The composite modified cellulose nylon diaphragm prepared in this example was tested for liquid absorption, liquid retention, thermal stability, mechanical properties and lithium ion conductivity, the test method was the same as in example 1, and the test results are shown in table 1.
Example 3
The present example provides a preparation process of a composite modified cellulose nylon membrane, which is substantially the same as example 1, except that the mass fraction of the solute of the lithium bistrifluoromethylsulfonylimide solution (the solvent is ethanol) is 2%.
The composite modified cellulose nylon diaphragm prepared in this example was tested for liquid absorption, liquid retention, thermal stability, mechanical properties and lithium ion conductivity, the test method was the same as in example 1, and the test results are shown in table 1.
Example 4
The embodiment provides a preparation process of a composite modified cellulose nylon diaphragm, which is basically the same as the embodiment 1, except that nylon 66 is adopted as nylon.
The composite modified cellulose nylon diaphragm prepared in this example was tested for liquid absorption, liquid retention, thermal stability, mechanical properties and lithium ion conductivity, the test method was the same as in example 1, and the test results are shown in table 1.
To better illustrate the effect of the examples of the present invention, comparative examples 1 to 3 are compared with the above examples.
Comparative example 1
This comparative example provides a process for preparing a cellulosic nylon separator, which differs from example 1 in that step (4) is not performed by soaking in lithium bis (trifluoromethylsulfonyl) imide solution, and the other preparation steps are the same as in example 1.
The cellulose nylon membrane prepared in this comparative example was tested for liquid absorption, liquid retention, thermal stability, mechanical properties, and lithium ion conductivity in the same manner as in example 1, and the test results are shown in table 1.
Comparative example 2
The comparative example provides a preparation process and performance test of a cellulose membrane, and the specific process is as follows:
(1) 2kg of lignin fiber was put into 3kg of water, and stirred at 10000rpm for 15min until cellulose was dispersed in water in suspension, to obtain a suspension.
(2) Pouring the suspension into an extruder, extruding through a die head, casting onto a strippable casting carrier, carrying out suction filtration through a suction filtration device, extracting water to form a film, controlling the thickness of the film, and drying in a drying device at 93 ℃ under 0.5Mpa to obtain the cellulose membrane with the thickness of 9 mu m.
The cellulose separator prepared in this comparative example was subjected to the same test as in example 1 for liquid absorption, liquid retention, thermal stability, mechanical properties and lithium ion conductivity, and the test results are shown in table 1.
Comparative example 3
The comparative example provides a preparation process and performance test of a ceramic diaphragm, and the specific process is as follows:
(1) 61.1kg deionized water and 0.2kg sodium carboxymethyl cellulose are placed in a dispersing machine to be dispersed for 30 minutes at 2500rpm, 35kg alumina powder is added to be dispersed for 60 minutes at 2500rpm, 0.4kg cross-linking agent aliphatic isocyanate and 0.3kg polyoxyethylene fatty alcohol ether wetting agent are added to be dispersed for 30 minutes at 1500rpm, and finally 3kg adhesive polyvinylidene fluoride is added to be dispersed and stirred for 30 minutes at 400rpm to prepare the alumina ceramic coating slurry.
(2) The alumina ceramic coating slurry was continuously dispersed and stirred at 300rpm for 0.5 hours, and then uniformly coated at a coating speed of 30m/min, and the alumina ceramic coating slurry was coated on one side of a Polyethylene (PE) base film and dried at 45 deg.c to obtain a ceramic separator having a thickness of 9 μm.
The ceramic separator prepared in this comparative example was subjected to the tests of liquid absorption, liquid retention, thermal stability, mechanical properties and lithium ion conductivity, the test method was the same as in example 1, and the test results are shown in table 1.
Table 1 summarizes the performance test results of the separators prepared in examples 1-4 and comparative examples 1-3:
as can be seen from comparison of test data in Table 1, test data of liquid absorption, liquid retention, thermal stability, tensile strength and lithium ion conductivity of the composite modified cellulose nylon membrane prepared in examples 1 to 4 are all superior to those of comparative examples 1 to 3, because the composite modified cellulose nylon membrane prepared in the examples of the invention, wherein cellulose and nylon form a three-dimensional network structure membrane through crosslinking, and the addition of nylon compensates for the problem of low mechanical strength of cellulose, so that the tensile strength of the membrane is improved; the double-trifluoromethyl-sulfonyl imide lithium is dispersed on the surface and/or in the pores of the three-dimensional network structure, so that the migration of lithium ions can be promoted, the impedance of a lithium ion battery can be reduced, and the lithium ion conductivity can be improved; the polyimide coating has the characteristic of micropores, so that the mechanical strength and the high temperature resistance of the diaphragm can be enhanced; through the synergistic effect of the above aspects, the composite modified cellulose nylon diaphragm provided by the invention has the advantages of higher mechanical strength, high temperature resistance, better liquid absorption rate and liquid retention rate, and higher lithium ion conductivity.
In addition, it can be seen from Table 1 that examples 1-3 have some effect on lithium ion conductivity, as well as on liquid absorption and retention as the mass fraction of the lithium bistrifluoromethylsulfonimide solution employed decreases.
In summary, the composite modified cellulose nylon diaphragm provided by the embodiment of the invention has good heat resistance, mechanical property, liquid absorption and liquid retention, and has excellent lithium ion mobility under the modification of lithium bistrifluoromethylsulfonyl imide, so that when the composite modified cellulose nylon diaphragm is applied to a lithium ion battery, the lithium ion battery has excellent electrochemical performance.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the composite modified cellulose nylon diaphragm is characterized by comprising the following steps of:
using ionic liquid to dissolve and blend cellulose, nylon, polyvinylpyrrolidone-K30 and polyacrylonitrile to obtain a blend casting solution;
preparing a film from the blending casting solution by an extruder;
washing redundant solvent on the film by deionized water, and then drying to obtain a cellulose nylon film;
soaking a cellulose nylon membrane in lithium bistrifluoromethylsulfonylimide with a certain mass concentration to obtain a modified cellulose nylon membrane;
coating the prepared polyamide slurry on a modified cellulose nylon membrane, and drying to obtain the composite modified cellulose nylon membrane.
2. The method of claim 1, wherein the ionic liquid comprises: one or more of imidazole type ionic liquid, piperidine type ionic liquid, pyridine type ionic liquid, pyrrolidine type ionic liquid, quaternary phosphine type ionic liquid, quaternary ammonium type ionic liquid and morpholine type ionic liquid;
the cellulose includes: one or more of polymerized cellulose, lignin fiber, cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose;
the nylon specifically comprises: nylon 6, nylon 66, nylon 11, nylon 12, nylon 61, or one or more of nylon.
3. The preparation method according to claim 1, wherein the mass ratio of the ionic liquid, cellulose, nylon, polyvinylpyrrolidone-K30 and polyacrylonitrile is [1-10]:
[0.1-1]:[0.1-1]:[0.1-1]：[0.1-1]。
4. the preparation method according to claim 1, wherein the mass concentration of the lithium bistrifluoromethylsulfonylimide is 1% -4%.
5. The method according to claim 1, wherein the drying treatment is carried out at a temperature of 60 ℃ to 80 ℃ for a drying time of 4 hours to 6 hours;
the temperature of the drying treatment is between 60 ℃ and 80 ℃ and the drying time is between 4 hours and 6 hours.
6. The preparation method according to claim 1, wherein the specific preparation process of the polyamide-based slurry is as follows: and uniformly mixing polyimide resin powder, a pore-forming agent and an organic solvent to obtain polyamide slurry.
7. The method of preparing according to claim 6, wherein the pore-forming agent comprises: one or more of glycerol, diglycerol, ethanol, ethylene glycol, lithium bromide, lithium chloride, and lithium hydroxide;
the organic solvent includes: one or more of N, N-dimethylacetamide, hexamethylphosphoric triamide and dimethyl sulfoxide;
the mass ratio of the polyimide resin powder, the pore-forming agent and the organic solvent is (1-10) [1-5 ]:1-50 ].
8. A composite modified cellulose nylon membrane prepared by the preparation method of any one of claims 1-7.
9. The composite modified cellulose nylon membrane of claim 8, wherein said composite modified cellulose nylon membrane comprises: cellulose, nylon, lithium bis (trifluoromethylsulfonyl) imide, polyimide;
the cellulose and the nylon form a film with a three-dimensional network structure through crosslinking, the polyimide is coated on the surface of the film, and the lithium bistrifluoromethylsulfonyl imide is dispersed on the surface and/or in pores of the three-dimensional network structure;
the thickness of the composite modified cellulose nylon diaphragm is between 5 and 50 mu m.
10. A lithium ion battery comprising the composite modified cellulose nylon separator of claim 8.
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