CN116706429A - New material film and preparation method thereof - Google Patents
New material film and preparation method thereof Download PDFInfo
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- CN116706429A CN116706429A CN202310821709.7A CN202310821709A CN116706429A CN 116706429 A CN116706429 A CN 116706429A CN 202310821709 A CN202310821709 A CN 202310821709A CN 116706429 A CN116706429 A CN 116706429A
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000013538 functional additive Substances 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 239000010954 inorganic particle Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000002033 PVDF binder Substances 0.000 claims abstract description 21
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 21
- 239000004642 Polyimide Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 229920001721 polyimide Polymers 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 230000007423 decrease Effects 0.000 claims abstract description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 22
- 239000005017 polysaccharide Substances 0.000 claims description 22
- 150000004676 glycans Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 229920002101 Chitin Polymers 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000855 Fucoidan Polymers 0.000 claims description 3
- 241001061264 Astragalus Species 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229920001491 Lentinan Polymers 0.000 claims description 2
- 235000015459 Lycium barbarum Nutrition 0.000 claims description 2
- 244000241838 Lycium barbarum Species 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 235000006533 astragalus Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229940115286 lentinan Drugs 0.000 claims description 2
- 210000004233 talus Anatomy 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 29
- 239000010410 layer Substances 0.000 description 17
- 238000011049 filling Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- -1 sulfuric acid polysaccharide Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000001180 sulfating effect Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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
- H01M50/409—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
- H01M50/403—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
- H01M50/489—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a new material film and a preparation method thereof, wherein the film comprises a base material component, inorganic particles and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the total weight of the film is taken as a reference, the content of the functional additive gradually decreases from the side close to the positive plate to the side close to the negative plate, and the content of the functional additive on the side close to the positive plate of the film is 10-13 wt%; the content of the functional additive on the side of the film close to the negative plate is 1.2-2.6 wt%. The preparation method comprises the following steps: s1: and (3) adding the inorganic particles into a solvent after ball milling and mixing uniformly, and performing ultrasonic stirring and dispersion. S2: and (3) uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 40-60 ℃ for dissolution, and adding the product of the step S1. S3: and (3) adding different content functional additives into the product of the step (S2) to obtain different content functional additive slurry, coating the obtained slurry on a substrate layer by layer, and drying to obtain the film.
Description
Technical Field
The invention belongs to the technical field of new material films, and particularly relates to a new material film and a preparation method thereof.
Background
Lithium ion batteries are widely used as power sources in electronic products such as computers and mobile phones. In order to meet the market demand, the energy density of the lithium ion battery is gradually improved, and the problem of expansion of the negative electrode of the lithium ion battery is more serious. The expansion of the negative electrode can cause the deformation of the battery, and the safety performance and the normal performance of the battery capacity are affected. In the working period of the battery, lithium ions are repeatedly separated and inserted between the positive electrode and the negative electrode, and the diaphragm always plays roles of ion conduction and electronic insulation. In order to reduce the deformation problem of the battery in the circulation process, one strategy is to coat an adhesive layer on the surface of a new material film, so that the adhesive force between a diaphragm and positive and negative pole pieces can be greatly enhanced, the hardness of the battery is improved, and the deformation is prevented. Currently, the bonding material for the separator is mainly PVDF-HFP. However, after the PVDF-HFP swells through the electrolyte, the internal resistance of the battery is obviously increased, and the performance of the multiplying power of the battery is affected. Therefore, it is important to find a separator that has a large adhesion and little influence on the electrical properties of the battery.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a new material film, which comprises a substrate component, inorganic particles and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the total weight of the film is taken as a reference, the content of the functional additive gradually decreases from the side close to the positive plate to the side close to the negative plate, and the content of the functional additive on the side close to the positive plate of the film is 10-13 wt%; the content of the functional additive on the side of the film close to the negative plate is 1.2-2.6 wt%.
The content of the functional additive in the middle part 22 of the film is lower than that in the side 23 close to the positive plate and higher than that in the side 21 close to the negative plate, and the content of the functional additive gradually decreases from the side close to the positive plate to the side close to the negative plate.
Further, the weight ratio of the ethylene-polytetrafluoroethylene copolymer to the polyvinylidene fluoride to the polyimide is (2-4): (1.2-1.6): (0.8-1.5);
and/or the film thickness is 5-10 μm, such as: 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm;
and/or, the content of the base material component is 30wt% to 85wt%, based on the total weight of the film, such as: 30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 47wt%, 50wt%, 52wt%, 55wt%, 57wt%, 60wt%, 63wt%, 65wt%, 68wt%, 70wt%, 73wt%, 75wt%, 77wt%, 80wt%, 82wt%, 85wt%.
Further, the inorganic particles include graphene fluoride, aluminum oxide, magnesium oxide, and zirconium oxide;
and/or, the mass ratio of the fluorinated graphene, the aluminum oxide, the magnesium oxide and the zirconium oxide is (2-3): (0.7-1.1): (0.8-1.4): (0.5-0.95);
and/or, the content of the inorganic particles is 20-45 wt% based on the total weight of the film;
and/or the particle size of the inorganic particles is 200 nm-1000 nm, such as: 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm.
Further, the functional additive is a sulfated polysaccharide, the sulfated polysaccharide material comprising: at least one of sulfated astragalus polysaccharide, sulfated matrimony vine polysaccharide, sulfated lentinan, sulfated angelicae sinensis polysaccharide, sulfated chitosan, sulfated fucoidan, sulfated cellulose and sulfated chitin.
Further, the dielectric constant of the polyimide is greater than or equal to 3, such as: 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0;
and/or, the crystallinity of the polyvinylidene fluoride is 50% -56%, such as: 50%, 50.1%, 50.2%, 50.3%, 50.4%, 50.5%, 50.6%, 50.7%, 50.8%, 50.9%, 51%, 51.2%, 51.4%, 51.6%, 51.8%, 52%, 52.2%, 52.4%, 52.6%, 52.8%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%.
Another object of the present invention is to provide a method for preparing a new material film, the method comprising the steps of:
s1: and (3) adding the inorganic particles into a solvent after ball milling and mixing uniformly, and performing ultrasonic stirring and dispersion.
S2: and (3) uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 40-60 ℃ for dissolution, and then adding the product of the step S1.
S3: and (2) adding different content of functional additives into the product in the step (S2) to obtain slurries with different content of functional additives, coating the slurries on a substrate layer by layer, and freeze-drying to obtain the film.
Preferably, the solvent is one or more of acetone, N-dimethylformamide, N-dimethylacetamide and ethyl acetate in any proportion.
Preferably, the ball milling time is 10-20 h;
and/or heating and dissolving time in the step S2 is 12-24 hours.
As a preferable scheme, the mass-volume ratio of the inorganic particles and the solvent in the step S1 is (4-8) g: (20-35) mL;
and/or, the mass-to-volume ratio of the substrate component and the solvent in the step S2 is (2-6) g: (25-90) mL.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art ZL202211418631.6, the functional additive vulcanized polysaccharide is coated on at least one side of the film substrate layer to increase the adhesive force of the film, so that the adhesive force of the battery diaphragm is improved, but because sulfuric acid groups are easy to generate hydrogen bond action with metal ion groups, metal ions migrate to the side of a negative plate in the charging and discharging process of the battery, and the sulfuric acid polysaccharide and the metal ions on the side of the negative plate generate hydrogen bonds, so that the migration of the metal ions is greatly influenced, and the cycle rate and the charging capacity of the lithium battery are further influenced.
2. In the invention, a film obtained by mixing a functional additive with other inorganic particles, substrate components and the like is used, the inorganic particles contain fluorinated graphene, the fluorinated graphene has sp3 hybridization orbits and sp2 hybridization orbits, and the sulfated polysaccharide of the functional additive and the fluorinated graphene generate pi.
Drawings
FIG. 1 is a schematic cross-sectional view of a new material film of the present invention after attachment to a positive electrode and a negative electrode;
note that: 1-a cathode plate, 2-a new material film and 3-an anode plate; 21-film near the negative plate side, 22-film middle part, 23-film near the positive plate side.
Detailed Description
The following detailed description of the embodiments of the present invention is provided on the premise of the technical solution of the present invention, and the detailed implementation manner and specific operation process are provided, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Thus, the following detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items below, and thus once an item is defined, no further definition or explanation thereof is required later.
In the description of the present invention, it should be noted that, the azimuth or positional relationship indicated by the terms "front", "rear", etc. are based on azimuth or positional relationship, or azimuth or positional relationship that the inventive product is conventionally put in use, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed", "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In the present invention, unless expressly stated or limited otherwise, a first feature may include first and second features directly contacting each other, either above or below a second feature, or through additional features contacting each other, rather than directly contacting each other. Moreover, the first feature being above, over, and on the second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being below, beneath, and beneath the second feature includes the first feature being directly below and obliquely below the second feature, or simply indicates that the first feature is less level than the second feature.
The method for preparing the sulfated polysaccharide material according to the present invention will be described by taking sulfated chitosan as an example, and comprises the following steps:
1) Pyridine is added into a container, the container is placed in ice bath, chlorosulfonic acid is slowly dripped into the container under the stirring condition, and the container is sealed; the molar ratio of the pyridine to the chlorosulfonic acid can be 1 (0.1-1); the molar ratio of the pyridine to the chlorosulfonic acid is 1 (0.15-0.5).
2) Adding chitosan and formamide into a container, heating until the chitosan and the formamide are completely dissolved, placing the container in an ice bath, adding the sulfating reagent obtained in the step 1), and reacting for 3-6 h; the mass ratio of the formamide to the chitosan to the sulfating agent is 1 (0.1-1) to 0.1-0.5.
The vulcanized polysaccharide such as the vulcanized chitin, the vulcanized cellulose and the like are prepared by the methods which are the same as the above or are familiar in the field, so that the technical effects required by the invention are achieved. The above components not limited by the present invention are commercially available and will not be described herein.
Example 1
A new material film comprising a substrate component, inorganic particles, and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the content of the functional additive is gradually decreased from the side close to the positive plate to the side close to the negative plate by taking the total weight of the film as a reference, and the content of the functional additive on the side close to the positive plate of the film is 13wt%; the content of the functional additive on the side of the film close to the negative plate is 1.2wt%.
The weight ratio of the ethylene-polytetrafluoroethylene copolymer to the polyvinylidene fluoride to the polyimide is 4:1.6:1.5;
the thickness of the film is 10 mu m; the content of the base material component is 62 to 72wt% based on the total weight of the film.
The mass ratio of the fluorinated graphene to the aluminum oxide to the magnesium oxide to the zirconium oxide is 3:1.1:1.4:0.95;
the content of the inorganic particles is 25wt% based on the total weight of the film;
the particle size of the inorganic particles was 300nm.
The functional additive is a sulfated polysaccharide, and the sulfated polysaccharide material comprises sulfated chitosan.
The dielectric constant of the polyimide is equal to 3; the crystallinity of the polyvinylidene fluoride is 56%.
A method for preparing a new material film, comprising the following steps:
s1: ball milling inorganic particles for 20 hours, adding the mixture into a solvent, and performing ultrasonic stirring and dispersion; the mass volume ratio of the inorganic particles to the solvent is 8g:35mL.
S2: uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 60 ℃ for dissolution, and heating for 24 hours; then adding the product of the step S1; the mass volume ratio of the substrate component to the solvent is 6g:90mL.
S3: and (2) adding different content of functional additives into the product in the step (S2) to obtain slurries with different content of functional additives, coating the slurries on a substrate layer by layer, and freeze-drying to obtain the film.
Wherein the solvent is 1:1 acetone and N, N-dimethylformamide.
Example 2
A new material film comprising a substrate component, inorganic particles, and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the content of the functional additive is gradually decreased from the side close to the positive plate to the side close to the negative plate by taking the total weight of the film as a reference, and the content of the functional additive on the side close to the positive plate of the film is 11.5wt%; the content of the functional additive on the side of the film close to the negative plate is 1.2wt%.
The weight ratio of the ethylene-polytetrafluoroethylene copolymer to the polyvinylidene fluoride to the polyimide is 3.5:1.4:1.1;
the thickness of the film is 9 mu m; the content of the base material component is 50-75wt% based on the total weight of the film.
The mass ratio of the fluorinated graphene to the aluminum oxide to the magnesium oxide to the zirconium oxide is 3.2:0.9:1.2:0.48;
the content of the inorganic particles is 30wt% based on the total weight of the film;
the particle size of the inorganic particles was 400nm.
The functional additive is a sulfated polysaccharide, the sulfated polysaccharide material comprising: sulfated cellulose.
The dielectric constant of the polyimide is equal to 3.2; the crystallinity of the polyvinylidene fluoride was 52%.
A method for preparing a new material film, comprising the following steps:
s1: ball milling inorganic particles for 15 hours, adding the mixture into a solvent, and performing ultrasonic and stirring dispersion; the mass volume ratio of the inorganic particles to the solvent is 5g:30mL.
S2: uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 45 ℃ for dissolution, and heating for 18 hours; then adding the product of the step S1; the mass volume ratio of the substrate component to the solvent is 3g:40mL.
S3: and (2) adding different content of functional additives into the product in the step (S2) to obtain slurries with different content of functional additives, coating the slurries on a substrate layer by layer, and freeze-drying to obtain the film.
Wherein the solvent is 2:1 acetone and N, N-dimethylformamide.
Example 3
A new material film comprising a substrate component, inorganic particles, and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the content of the functional additive is gradually decreased from the side close to the positive plate to the side close to the negative plate by taking the total weight of the film as a reference, and the content of the functional additive on the side close to the positive plate of the film is 12wt%; the content of the functional additive on the side of the film close to the negative plate is 1.8wt%.
The weight ratio of the ethylene-polytetrafluoroethylene copolymer to the polyvinylidene fluoride to the polyimide is 4.3:1.7:0.77;
the thickness of the film is 8 mu m; the content of the base material component is 55-78 wt% based on the total weight of the film.
The mass ratio of the fluorinated graphene to the aluminum oxide to the magnesium oxide to the zirconium oxide is 3.1:0.6:0.9:0.63;
the content of the inorganic particles is 35wt% based on the total weight of the film;
the particle size of the inorganic particles was 500nm. The functional additive is a sulfated polysaccharide, the sulfated polysaccharide material comprising: sulfated chitin.
The dielectric constant of the polyimide is equal to 3.5; the crystallinity of the polyvinylidene fluoride is 53%.
A method for preparing a new material film, comprising the following steps:
s1: ball milling inorganic particles for 16 hours, adding the mixture into a solvent, and performing ultrasonic and stirring dispersion; the mass volume ratio of the inorganic particles to the solvent is 7.3g:40mL.
S2: uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 50 ℃ for dissolution, and heating for 18 hours; then adding the product of the step S1; the mass volume ratio of the substrate component to the solvent is 2g:30mL.
S3: and (2) adding different content of functional additives into the product in the step (S2) to obtain slurries with different content of functional additives, coating the slurries on a substrate layer by layer, and freeze-drying to obtain the film.
Wherein the solvent is acetone, N-dimethylformamide and ethyl acetate in a ratio of 1:1:1.
Example 4
A new material film comprising a substrate component, inorganic particles, and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the content of the functional additive is gradually decreased from the side close to the positive plate to the side close to the negative plate by taking the total weight of the film as a reference, and the content of the functional additive on the side close to the positive plate of the film is 11.2wt%; the content of the functional additive on the side of the film close to the negative plate is 1.8wt%.
The weight ratio of the ethylene-polytetrafluoroethylene copolymer to the polyvinylidene fluoride to the polyimide is 3:1.4:1.1;
the thickness of the film is 6 μm; the content of the base material component is 40-60 wt% based on the total weight of the film.
The mass ratio of the fluorinated graphene to the aluminum oxide to the magnesium oxide to the zirconium oxide is 2.8:1:1.3:0.9;
the content of the inorganic particles is 40wt% based on the total weight of the film;
the particle size of the inorganic particles was 600nm.
The functional additive is a sulfated polysaccharide, the sulfated polysaccharide material comprising: sulfated fucoidan.
The dielectric constant of the polyimide is equal to 3.5; the crystallinity of the polyvinylidene fluoride is 55%.
A method for preparing a new material film, comprising the following steps:
s1: ball milling inorganic particles for 15 hours, adding the mixture into a solvent, and performing ultrasonic and stirring dispersion; the mass volume ratio of the inorganic particles to the solvent is 6g:30mL.
S2: uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 55 ℃ for dissolution, and heating for 20 hours; then adding the product of the step S1; the mass volume ratio of the substrate component to the solvent is 6g:100mL.
S3: and (2) adding different content of functional additives into the product in the step (S2) to obtain slurries with different content of functional additives, coating the slurries on a substrate layer by layer, and freeze-drying to obtain the film.
Wherein the solvent is 1:1 of N, N-dimethylformamide and ethyl acetate.
Comparative example 1
The difference between this comparative example and example 1 is that the functional additive of the film is uniformly dispersed throughout the film, and the content of the functional additive of the film is the same as that of the positive electrode sheet side in example 1.
Comparative example 2
The difference between this comparative example and example 1 is that it is identical to that in comparative example 1; the second is that the inorganic particles do not contain fluorinated graphene.
Performance test:
1. peel strength test
The new material films obtained in examples 1 to 4 were subjected to peel strength test, and were cut into samples having a length of about 220mm and a width of about 23 mm; pasting double faced adhesive tape on the steel plate, tearing off the double faced adhesive tape release paper, and pasting a cut new material film sample on the steel plate; the Scotch adhesive is flatly adhered to the middle position of the new material film in parallel to the length direction of the new material film, and back pressure is carried out for 1 time by using a 2kg press roll; then tested using an electronic universal tester, the test speed was set to 100mm/min.
2. Ion conductivity test
The ion conductivity test was performed on the films obtained in examples 1 to 4, and the new material films were cut into 4 round pieces with a diameter of 40mm by a sheet punching machine. The new material film is put into lithium hexafluorophosphate (LiPF) with the concentration of 1.0mol/L 6 ) The method comprises the steps of (1) filling electrolyte with the volume ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) being 1:1:1, sealing, soaking for 2h, filling the electrolyte into a resistance test die, sequentially filling 1 layer of new material film, testing alternating current impedance, filling 1 layer of new material film, testing alternating current impedance resistance until 4 layers of new material film are filled, and respectively measuring four alternating current impedance resistors R1, R2, R3 and R4. In the testing process, the new material film can be ensured to be completely immersed in the electrolyte. The new material film layer number is taken as an abscissa, the resistors R1, R2, R3 and R4 are taken as an ordinate to be used as curves, the slope of the curves is calculated, and the calculation formula is as follows:
R＝K×1；
wherein, R-1 is the resistance value of new material film;
k-slope of curve;
σ＝d/(R×S)；
wherein, sigma-the ion conductivity of the new material film/S/cm;
d-1 layer of new material film thickness/mum;
r-1 layer of new material film resistance value/omega;
s-area/cm of new material film cut during experiment 2 。
3. 130 ℃ heat shrinkage test
The new material films obtained in examples 1 to 4 were subjected to a 130℃heat shrinkage test, and were sampled: cutting the new material film into square new material film 3 blocks with the side length of 100mm by using a new material film sample preparation mould, drawing two parallel lines in the new material film longitudinal (MD) and Transverse (TD) directions respectively, and recording the distance between the MD and TD directions of the sample before baking; then 3 pieces of A4 paper are respectively placed on the upper part and the lower part of the new material film to fix the new material film, and the new material film and the A4 paper are placed in the middle part of the oven together at the temperature of 130 ℃. Closing the box door, and timing for 1h after the temperature is stable; and taking out the new material film after heating, and measuring the longitudinal and transverse marking lengths again after the new material film is restored to room temperature, wherein the calculation formula is as follows:
ΔL MD ＝[(L before MD -L After MD )/L Before MD ]×100％；
ΔL MD -heat shrinkage rate/% of the new material film in MD direction;
L before MD -distance between two parallel lines in MD direction/mm before heating the new material film;
L after MD -distance between two parallel lines in MD direction/mm after heating of the new material film;
ΔL TD ＝[(L front TD -L After TD )/L Front TD ]×100％；
ΔL TD -heat shrinkage rate/% of the new material film in TD direction;
L front TD -distance between two parallel lines in TD direction before heating of new material film/mm;
L after TD -distance between two parallel lines in TD direction/mm after heating the new material film;
the heat shrinkage of the new material film in the transverse and longitudinal directions was calculated, and the average value of 3 test results was taken as the heat shrinkage of the new material film.
4. Air permeability test
Air permeability of new material film: reflecting the permeability of the new material film, i.e., the time required for a volume of gas to pass through a 1 square inch area of new material film at a given pressure. The new material films obtained in group I examples and comparative examples were subjected to a breathability test. The results of the above tests are shown in table 1,
table 1. Test results:
as can be seen from Table 1, the new material film prepared by the invention has excellent peel strength and ion conductivity, excellent shrinkage and air permeability, and the whole performance is improved.
5. The new material batteries obtained in examples 1 to 4 were used for the explanation of the battery of the present invention.
The battery is prepared by the steps of:
1) And (3) preparing a positive plate: mixing lithium cobaltate, conductive carbon black (Super-P) and polyvinylidene fluoride (PVDF) according to the mass ratio of 97:1.5:1.5, dissolving in N-methyl pyrrolidone (NMP), uniformly stirring to obtain positive electrode active slurry, wherein the solid content is 42%, uniformly coating the positive electrode active slurry on two sides of an aluminum foil sheet, and drying, cold pressing, slicing and welding tabs to obtain a positive electrode sheet;
2) Preparing a negative plate:
mixing graphite, conductive carbon black (Super-P), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to the mass ratio of 96.5:1:1:1.5, dissolving in deionized water, uniformly stirring to obtain negative electrode active slurry, wherein the solid content is 40%, uniformly coating positive electrode active slurry on two sides of a copper foil, drying, cold pressing, slicing, and welding tabs to obtain a negative electrode sheet;
3) Preparation of electrolyte: lithium hexafluorophosphate (LiPF) 6 ) Mixing with solvent (mass ratio of ethylene carbonate, diethyl carbonate, methyl ethyl carbonate and vinylene carbonate is 8:85:5:2) according to mass ratio of 8:92 to obtain electrolyte;
4) Preparation of a battery: and winding the obtained positive plate, the obtained negative plate and the new material films obtained in examples 1-4 to assemble a battery core, drying, injecting the obtained electrolyte, and packaging to obtain the battery.
Test case
And (3) testing the cycle performance: the batteries obtained in examples 1 to 4 were subjected to cycle performance test, and charge and discharge schedule was set:
1) Discharging the mixture to the lower limit voltage of 3.0V at 0.2C, and standing for 10min; 2) Charging to upper limit voltage at 0.7C, cutting off 200mA, and standing for 10min; 3) Discharging 0.2C to upper limit voltage (performing initial capacity test), and standing for 10min; 4) Filling 5C, cutting off 3.7C by 4.15V, filling 3.7C, cutting off 3C by 4.25V, filling 3C, cutting off 2C by 4.45V, filling 2C, cutting off 200mA by 4.5V, and standing for 10min; 5) Discharging to 3.0V at 0.7C, and standing for 10min; repeating the steps 4) and 5) 500 times, repeating the steps 2-3 for 500 times, and performing capacity test. Discharging the mixture to the lower limit voltage of 3.0V at 0.2C, and standing for 10min; then charging (multiplying power is as follows) at a certain multiplying power, cutting off the current to 0.025 ℃, and standing for 10min; repeating 1-2 cycles for 5 times until all multiplying power charging tests are completed; charging rate: 0.2C/0.5C/1.0C/2.0C/3.0C/4.0C/5.0C, 0.2C, 1.0C and 5.0C were recorded.
6. K value test
The batteries obtained in examples 1 to 4 were subjected to K value test, and specifically, the voltages of the battery cells O1 and OB were measured by an OCV test instrument, and the K value was calculated by the calculation formula:
K＝(OCV 1 -OCV 2 ) Time interval of two tests;
OCV 1 first test voltage/mV, OCV 2 -a second test voltage/mV;
the time interval between the two tests is 24h. The test results are shown in table 2, table 2:
as can be seen from Table 2, the new material films prepared in examples 1 to 4 of the present invention gave lithium ion batteries having excellent overall properties.
7. The new material films prepared in comparative examples 1 to 2 were subjected to the same performance test as in the above examples, and the test results are shown in table 3,
table 3. Test results:
as can be seen from Table 3, the films prepared in examples of the present invention have better capacity retention, battery capacity, etc., as compared with the films in examples 1 to 4, which are inferior in both capacity retention and battery capacity.
Claims (10)
1. A new material film, characterized in that the film comprises a substrate component, inorganic particles and a functional additive; the substrate component comprises ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide; the total weight of the film is taken as a reference, the content of the functional additive gradually decreases from the side close to the positive plate to the side close to the negative plate, and the content of the functional additive on the side close to the positive plate of the film is 10-13 wt%; the content of the functional additive on the side of the film close to the negative plate is 1.2-2.6 wt%.
2. The new material film according to claim 1, wherein the weight ratio of the ethylene-polytetrafluoroethylene copolymer, polyvinylidene fluoride and polyimide is (2-4): (1.2-1.6): (0.8-1.5);
and/or the thickness of the film is 5-10 mu m;
and/or the number of the groups of groups,
the content of the base material component is 30-85 wt% based on the total weight of the film.
3. The new material film according to claim 1, wherein the inorganic particles include graphene fluoride, aluminum oxide, magnesium oxide, and zirconium oxide;
and/or the number of the groups of groups,
the mass ratio of the fluorinated graphene to the aluminum oxide to the magnesium oxide to the zirconium oxide is (2-3): (0.7-1.1): (0.8-1.4): (0.5-0.95);
and/or the number of the groups of groups,
the content of the inorganic particles is 20-45 wt% based on the total weight of the film; and/or the number of the groups of groups,
the granularity of the inorganic particles is 200 nm-1000 nm.
4. A new material film according to claim 1, characterized in that said functional additive is a sulfated polysaccharide material comprising: at least one of sulfated astragalus polysaccharide, sulfated matrimony vine polysaccharide, sulfated lentinan, sulfated angelicae sinensis polysaccharide, sulfated chitosan, sulfated fucoidan, sulfated cellulose and sulfated chitin.
5. The new material film of claim 1, wherein the polyimide has a dielectric constant of 3 or greater, such as: 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0;
and/or, the crystallinity of the polyvinylidene fluoride is 50-56%.
6. The method for producing a new material film according to any one of claims 1 to 5, characterized in that the method comprises the steps of:
s1: adding inorganic particles into a solvent after ball milling and mixing uniformly, and performing ultrasonic stirring and dispersion;
s2: uniformly mixing the substrate components, adding the substrate components into a solvent, heating to 40-60 ℃ for dissolution, and then adding the product of the step S1;
s3: and (2) adding different content of functional additives into the product in the step (S2) to obtain slurries with different content of functional additives, coating the slurries on a substrate layer by layer, and freeze-drying to obtain the film.
7. The method for preparing a new material film according to claim 6, wherein the solvent is one or more of acetone, N-dimethylformamide, N-dimethylacetamide and ethyl acetate in any ratio.
8. The method for preparing a new material film according to claim 6, wherein the ball milling time is 10-20 hours;
and/or heating and dissolving time in the step S2 is 12-24 hours.
9. The method according to claim 6, wherein the mass-to-volume ratio of the inorganic particles to the solvent in the step S1 is (4-8) g: (20-35) mL;
and/or the number of the groups of groups,
the mass volume ratio of the base material component to the solvent in the step S2 is (2-6) g: (25-90) mL.
10. A new material film according to any one of claims 1 to 5, wherein the new material film is applied to a lithium ion battery.
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