CN115763828A - Polymer composite membrane and preparation method thereof, composite current collector, pole piece, secondary battery and electric device - Google Patents
Polymer composite membrane and preparation method thereof, composite current collector, pole piece, secondary battery and electric device Download PDFInfo
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- CN115763828A CN115763828A CN202211478483.7A CN202211478483A CN115763828A CN 115763828 A CN115763828 A CN 115763828A CN 202211478483 A CN202211478483 A CN 202211478483A CN 115763828 A CN115763828 A CN 115763828A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 174
- 239000002131 composite material Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 title claims description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 197
- 239000011787 zinc oxide Substances 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 73
- 239000002184 metal Substances 0.000 claims abstract description 73
- 230000008021 deposition Effects 0.000 claims abstract description 47
- 239000010410 layer Substances 0.000 claims description 145
- 238000000151 deposition Methods 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 229920006254 polymer film Polymers 0.000 claims description 42
- 239000002105 nanoparticle Substances 0.000 claims description 38
- 230000004048 modification Effects 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 33
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 33
- 230000004888 barrier function Effects 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 150000003751 zinc Chemical class 0.000 claims description 24
- -1 polypropylene Polymers 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000011241 protective layer Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002096 quantum dot Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229960000314 zinc acetate Drugs 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229960001939 zinc chloride Drugs 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 23
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- 239000000853 adhesive Substances 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 10
- 238000007740 vapor deposition Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 238000009832 plasma treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 5
- 229940007718 zinc hydroxide Drugs 0.000 description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 238000007607 die coating method Methods 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
Abstract
The application provides a polymer composite film and preparation method, compound mass flow body, pole piece, secondary battery and power consumption device thereof, and the polymer composite film includes: the nano-zinc oxide coating comprises a polymer base film and a nano-zinc oxide deposition layer formed on the surface of at least one side of the polymer base film, wherein the thickness of the nano-zinc oxide deposition layer is 50 nm-150 nm. The application provides a polymer composite film can promote the cohesion between polymer rete and the metal layer in the compound mass flow body, promotes the structural stability of compound mass flow body from this.
Description
Technical Field
The application relates to the technical field of electrochemistry, in particular to a polymer composite film and a preparation method thereof, a composite current collector, a pole piece, a secondary battery and an electric device.
Background
At present, a composite current collector based on a high molecular polymer film is widely concerned and applied in the new energy industry. A conventional composite current collector generally includes a high molecular polymer film layer, and a metal (aluminum, copper, etc.) layer formed on the high molecular polymer film layer by a Physical Vapor Deposition (PVD) method or the like. Compared with the traditional current collector, the composite current collector based on the high-molecular polymer film has the characteristics of low cost, light weight, good internal insulation and the like. The characteristics enable the composite current collector to reduce the cost of the battery and improve the energy density and the safety of the battery when the composite current collector is applied to the battery.
However, in the conventional composite current collector, the bonding force between the high molecular polymer film layer and the metal layer is generally weak, which easily causes the separation of the high molecular polymer film layer and the metal layer during the use of the composite current collector, and affects the normal use of the composite current collector. In addition, the conventional composite current collector is generally prepared by a vapor deposition method, but the inventors found that the following problems exist in this method: (1) the energy consumption of the vapor deposition method is high; (2) in the process of depositing the bonding layer on the film surface through vapor deposition, the heat quantity of the film surface is higher due to the desublimation of deposited atoms on the polymer film surface and the attenuation of kinetic energy, and in addition, the generation of hole defects is caused due to the thinner polymer film. Therefore, in order to solve the above problems, it is necessary to provide a polymer film surface modification method with low energy consumption and easy operation, and develop a polymer film with improved surface adhesion performance and no void defect by using the modification method.
Disclosure of Invention
Based on this, this application provides a polymer composite film and preparation method, compound mass flow body, pole piece, secondary cell and power consumption device thereof, can promote the cohesion between polymer rete and the metal layer, promotes the structural stability of compound mass flow body from this.
A first aspect of the present application provides a polymer composite film comprising:
a polymer-based film; and
and the zinc oxide nano deposition layer is formed on the surface of at least one side of the polymer base film, wherein the thickness of the zinc oxide nano deposition layer is 50-150 nm.
According to any one of the embodiments of the first aspect of the present application, the polymer composite film satisfies at least one of the following conditions:
(1) The average grain diameter of zinc oxide grains contained in the zinc oxide nano-deposition layer is 20 nm-80 nm;
(2) The thickness of the polymer-based film is 2-20 μm; and
(3) The polymer comprises one or more of polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polystyrene, polyamide and derivatives of the above polymers.
A second aspect of the present application provides a method of preparing a polymer composite membrane, comprising:
performing surface modification treatment on the polymer film layer to obtain a polymer base film; and
and depositing zinc oxide nano particles on the surface of at least one side of the polymer base film to form a zinc oxide nano deposition layer to obtain the polymer composite film, wherein the thickness of the zinc oxide nano deposition layer is 50 nm-150 nm.
According to any embodiment of the second aspect of the present application, the surface modification treatment of the polymer film layer comprises:
the surface of the polymer film layer is subjected to dielectric barrier discharge plasma modification treatment,
optionally, in the dielectric barrier discharge plasma modification treatment process, the voltage of the alternating current input to the two electrodes of the dielectric barrier discharge plasma device is 10kV to 16kV;
optionally, the time of the dielectric barrier discharge plasma modification treatment is 5s to 60s.
According to any of the embodiments of the second aspect of the present application, the depositing zinc oxide nanoparticles on the surface of at least one side of the polymer-based film comprises:
placing the polymer-based film in an aqueous solution of a zinc salt; and
under the action of ultrasound, adding an alkaline reagent into the aqueous solution of the zinc salt containing the polymer-based membrane until the concentration of the alkaline reagent in the solution reaches a target value, so that the zinc salt and the alkaline reagent are in contact reaction to form the zinc oxide nanoparticles.
According to any embodiment of the second aspect of the present application, the preparation method satisfies at least one of the following conditions:
(1) The concentration of the aqueous solution of the zinc nitrate salt is 0.05 mol/L-0.25 mol/L;
(2) The molar ratio of the zinc salt to the alkaline reagent is (1.0-2.5) to 1;
(3) The reaction time is 0.5 min-5.0 min;
(4) The target value is 0.02 mol/L-0.25 mol/L;
(5) The zinc salt comprises one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc bromide and zinc acetate;
(6) The alkaline reagent comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water.
According to any embodiment of the second aspect of the present application, after said subjecting said polymer based film to an aqueous solution of a zinc salt, further comprises:
the aqueous solution is subjected to an ultrasonic treatment,
optionally, the ultrasonic power of the ultrasonic treatment is 200W-700W.
A third aspect of the present application provides a composite current collector comprising the polymer composite film of the first aspect of the present application or the polymer composite film produced according to the production method of the second aspect of the present application.
According to any embodiment of the third aspect of the present application, the composite current collector further comprises:
a metal layer formed on at least one side surface of the polymer composite film; and
and the protective layer is formed on the surface of at least one side of the metal layer, which is relatively far away from the polymer composite film.
According to any embodiment of the third aspect of the present application, the composite current collector satisfies at least one of the following conditions:
(1) The thickness of the polymer composite film is 2-20 μm;
(2) The thickness of the metal layer is 500 nm-2000 nm, and 700 nm-1200 nm can be selected; and
(3) The thickness of the protective layer is 10 nm-150 nm, and 20 nm-100 nm can be selected.
According to any embodiment of the third aspect of the present application, the composite current collector satisfies at least one of the following conditions:
(1) The material of the metal layer comprises one or more of copper, copper alloy, aluminum alloy, nickel alloy, titanium and silver; and
(2) The material of the protective layer comprises one or more of nickel, chromium, nickel-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, ketjen black, carbon nano quantum dots, carbon nano tubes, carbon nano fibers and graphene.
A fourth aspect of the present application provides a pole piece comprising the composite current collector of the third aspect of the present application.
According to any embodiment of the fourth aspect of the present application, the pole piece comprises a positive pole piece and/or a negative pole piece.
A fifth aspect of the present application provides a secondary battery comprising the pole piece of the fourth aspect of the present application.
A sixth aspect of the present application provides an electric device including the secondary battery of the fifth aspect of the present application.
The electric device of the present application includes the secondary battery provided by the present application, and thus has at least the same advantages as the secondary battery.
The application provides a polymer composite film includes polymer base film and zinc oxide nano-deposit layer, wherein, because zinc oxide nano-deposit layer is similar with the crystal structure of metal, therefore easily make metal atom inlay to zinc oxide crystal inside, can promote the cohesion between polymer film layer and the metal layer from this. In addition, the zinc oxide deposition layer also endows the surface of the polymer base film with a moderate rough structure, and enhances the roughness of the surface of the polymer base film, so that the zinc oxide deposition layer can be riveted with the metal layer, thereby improving the performance of the polymer base film for adhering metal atoms and further improving the bonding force between the polymer base film and the metal layer. In addition, the surface of the zinc oxide nano deposition layer is rich in oxygen atoms, so that the surface tension can be improved, and the oxygen atoms are easy to interact with metal atoms, so that the improvement of the bonding force between the metal layer and the polymer film layer is further promoted.
In addition, the surface modification method of the polymer base film has the advantages of low energy consumption, easiness in operation and the like, the surface adhesion of the polymer composite film developed by the modification method can be improved, the defect of a hole is avoided, and the adhesive force between the base film and a metal layer is improved by taking the polymer composite film as a composite current collector prepared by the base film.
In addition, the preparation method of the polymer composite membrane provided by the application solves the following problems existing in the existing chemical vapor deposition method: (1) the energy consumption of the vapor deposition method is high; (2) in the process of depositing the bonding layer on the film surface through vapor deposition, the heat quantity of the film surface is higher due to the desublimation of deposited atoms on the polymer film surface and the attenuation of kinetic energy, and in addition, the generation of hole defects is caused due to the thinner polymer film.
Drawings
Fig. 1 is a schematic structural view of a polymer composite membrane according to an embodiment of the present disclosure.
Fig. 2 is a schematic structural diagram of a composite current collector according to an embodiment of the present application.
Detailed Description
To facilitate an understanding of the present application, the present application will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present application are shown in the drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value may, as its lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. It is noted that, unless otherwise indicated, the term "and/or" as used herein is intended to include any and all combinations of one or more of the associated listed items, with the "above" or "below" being inclusive of the present number and the "plurality" of the "one or more" being inclusive of two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is provided only as a representative group and should not be construed as exhaustive.
The inventor finds in the research process that, in the conventional composite current collector, the bonding force between the polymer film and the metal layer is poor, mainly because of the difference between the surface structures and the chemical environments of the polymer film and the metal layer, and meanwhile, the inventor also finds that the conventional vapor deposition method for preparing the composite current collector has the following problems: (1) the energy consumption of the vapor deposition method is high; (2) in the process of depositing the bonding layer on the film surface through vapor deposition, the heat quantity of the film surface is higher due to the desublimation of deposited atoms on the polymer film surface and the attenuation of kinetic energy, and in addition, the generation of hole defects is caused due to the thinner polymer film. In order to solve the above-mentioned problems, the inventors have proposed the following means in view of surface modification of the polymer film and the metal layer.
A first aspect of an embodiment of the present application provides a polymer composite film, as shown in fig. 1, the polymer composite film 1 including: a polymer-based film 11; and a zinc oxide nano-deposition layer 12 formed on a surface of at least one side of the polymer-based film, wherein the thickness of the zinc oxide nano-deposition layer is 50nm to 150nm.
The application provides a polymer composite film includes polymer base film and zinc oxide nano-deposit layer, wherein, because zinc oxide nano-deposit layer is similar with the crystal structure of metal, therefore easily make metal atom inlay to zinc oxide crystal inside, can promote the cohesion between polymer film layer and the metal layer from this. In addition, the zinc oxide deposition layer also endows the surface of the polymer base film with a moderately rough structure, and enhances the roughness of the surface of the polymer base film, so that the zinc oxide deposition layer can be riveted with the metal layer, thereby improving the performance of the polymer base film for adhering metal atoms and further improving the bonding force between the polymer base film and the metal layer. In addition, the surface of the zinc oxide nano deposition layer is rich in oxygen atoms, so that the surface tension can be improved, and the oxygen atoms are easy to interact with metal atoms, so that the improvement of the bonding force between the metal layer and the polymer film layer is further promoted.
It is understood that the zinc oxide nano-deposition layer can be arranged on the surface of one side of the polymer base film, and can also be arranged on the surfaces of two opposite sides of the polymer base film; when setting up simultaneously, the thickness of the zinc oxide nanometer sedimentary deposit of both sides can be the same, also can be different, and concrete setting mode can be selected according to actual need.
In some embodiments, the zinc oxide nano-deposition layer has a thickness of 50nm to 150nm. For example, the thickness of the zinc oxide nano-deposition layer may be 70nm,90nm,110nm,130nm,150nm, or within a range consisting of any of the above values. The thickness of the zinc oxide nano-deposition layer is in a proper range, so that the surface structure and the property of the polymer base film can be effectively improved, the bonding force between the polymer base film and the metal layer is improved, and the cost of raw materials can be saved.
In some embodiments, the zinc oxide nano-deposition layer comprises zinc oxide grains having an average grain size of 20nm to 80nm. For example, the zinc oxide grains may have an average grain size of 30nm,40nm,50nm,60nm,70nm, or any value within the ranges set forth above. When the average particle size of the zinc oxide crystal grains is relatively large or small, it may be disadvantageous to achieve improvement in the surface adhesion property of the polymer-based film.
In some embodiments, the polymer-based film has a thickness of 2 μm to 20 μm. For example, the polymer based film may have a thickness of 5 μm,10 μm,15 μm,20 μm, or any range of values therein. The thickness of the polymer base film is controlled in a proper range, and the energy density of the composite current collector can be improved while the production difficulty (the thinner the film, the larger the production difficulty and the lower the yield) is considered.
In some embodiments, the kind of the polymer is not particularly limited, and may be selected according to actual needs. For example, the polymer may include one or more of polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polystyrene, polyamide, and derivatives of the above polymers.
A second aspect of an embodiment of the present application provides a method of preparing a polymer composite film, including the steps of:
s10, performing surface modification treatment on the polymer film layer to obtain a polymer base film; and
s20, depositing zinc oxide nano particles on the surface of at least one side of the polymer base film to form a zinc oxide nano deposition layer, and obtaining the polymer composite film, wherein the thickness of the zinc oxide nano deposition layer is 50 nm-150 nm.
In the preparation method, firstly, the surface of the polymer film layer is subjected to surface modification treatment, so that the polarity of the surface of the polymer film layer can be improved, and the deposition of zinc oxide nano particles on the surface of the polymer film layer is promoted; and then, after zinc oxide nano particles are deposited on the surface of the polymer-based film, the surface structure and the chemical environment of the polymer-based film can be improved, so that the bonding force between the polymer-based film and a metal layer can be enhanced. The preparation method has the advantages of simple and feasible process and easy amplification.
In some embodiments, the polymer film layer may be prepared by a melt extrusion-biaxial stretching process.
In some embodiments, the surface modification treatment of the polymer film layer in step S10 includes the following steps:
s100, performing dielectric barrier discharge plasma modification treatment on the surface of the polymer film layer.
The surface of the polymer film layer is subjected to dielectric barrier discharge plasma modification treatment, so that the polarity of the surface of the polymer film layer can be improved, oxygen-containing functional groups can be generated on the surface, and active reaction sites can be provided for the subsequent deposition of zinc oxide nanoparticles, thereby facilitating the promotion of the deposition of the zinc oxide nanoparticles on the surface of the polymer film layer in the subsequent steps.
In some embodiments, the voltage of the alternating current input to the two electrodes of the dielectric barrier discharge plasma apparatus during the dielectric barrier discharge plasma modification treatment is 10kV to 16kV. For example, the voltage of the alternating current may be 11kV,12kV,13kV,14kV,15kV or in a range composed of any of the above values. When the voltage of the alternating current input to the two electrodes is relatively low, the effect of modification treatment is not obvious easily; when the voltage of the alternating current input to the two electrodes is relatively high, the effect of increasing the surface polarity of the polymer film may not be achieved, and the mechanical properties of the polymer film may be reduced.
In some embodiments, the time of the dielectric barrier discharge plasma modification treatment is 5s to 60s. For example, the time of the dielectric barrier discharge plasma modification treatment may be 10s,20s,30s,40s,50s or in the range consisting of any of the above values. When the treatment time is relatively short, the effect of improving the surface polarity of the polymer film layer may not be obvious; when the treatment time is relatively long, the surface polarity of the polymer film cannot be further improved, and the mechanical properties of the polymer film may be reduced.
As one non-limiting example of the dielectric barrier discharge plasma apparatus, the apparatus may include a power supply unit, a high voltage transformer, upper and lower electrodes, dielectric glass, a gas supply system, and a chamber body. Wherein, the air supply system provides compressed air for the cabin body, and after the air is introduced, the working pressure in the cabin body can be 206.8kPa, and the working temperature can be room temperature (25 ℃ -27 ℃); the power supply unit outputs 220V and 50Hz alternating current which can be converted into 10kV to 16kV and 325Hz alternating current through the high-voltage transformer, the output alternating current is input into the two electrodes for plasma treatment, and the distance between the electrodes can be 4mm.
In some embodiments, the step S20 of depositing zinc oxide nanoparticles on the surface of at least one side of the polymer-based film comprises the steps of:
s200, placing the polymer-based membrane in an aqueous solution of zinc salt; and
s210, adding an alkaline reagent into the aqueous solution containing the zinc salt of the polymer-based membrane under the action of ultrasound until the concentration of the alkaline reagent in the solution reaches a target value, so that the zinc salt and the alkaline reagent are in contact reaction to form the zinc oxide nanoparticles.
The polymer base membrane is placed in the aqueous solution of zinc salt, and an alkaline reagent is added, so that in-situ deposition on the surface of the polymer base membrane can be realized, then a zinc oxide nano particle deposition layer is obtained, and uniform deposition of zinc oxide nano particles is realized.
It should be noted that, an exemplary reaction process of obtaining the deposited layer of zinc oxide nanoparticles after reacting zinc salt with alkaline reagent is as follows: firstly, after a polymer base membrane is treated by plasma, oxygen-containing functional groups, namely active reaction sites, are generated on the surface of the polymer base membrane; then, the polymer base membrane enters a zinc salt aqueous solution, an oxygen-containing functional group on the surface of the base membrane is taken as an active site, and the base membrane and zinc ions in the solution are subjected to complexing action, so that the zinc ions are fixedly deposited on the surface of the base membrane, and the zinc ions fixed on the surface of the base membrane react with hydroxide radicals in an alkaline reagent added into the solution later, so that zinc hydroxide nanoparticles are generated; and finally, the zinc hydroxide nano-particles generate instantaneous local high temperature and high pressure under the effect of ultrasonic cavitation to realize dehydration and refinement of the zinc hydroxide nano-particles and generate refined zinc oxide nano-particles, so that a zinc oxide nano-particle deposition layer is generated on the surface of the polymer base film.
In some embodiments, the aqueous solution of the zinc salt has a concentration of 0.05 to 0.25mol/L. For example, the concentration of the aqueous solution of zinc salt may be 0.10mol/L,0.15mol/L,0.20mol/L,0.25mol/L or in the range consisting of any of the above values.
In some embodiments, the target value is between 0.02mol/L and 0.25mol/L. For example, the target value may be 0.05mol/L,0.10mol/L,0.15mol/L,0.20mol/L or within a range consisting of any of the above values.
In some embodiments, the molar ratio of the zinc nitrate to the sodium hydroxide is (1.0-2.5): 1.
In this application embodiment, the concentration of zinc nitrate and sodium hydroxide can influence the deposition rate and the particle size of zinc oxide nano-deposit layer. When the concentration is relatively high, the growth rate may be high, and the generated zinc oxide nano-ions have large sizes, so that the roughness of the surface of the zinc oxide nano-deposition layer is large, and the bonding force between the formed polymer composite film and the metal layer is easily reduced. When the concentration is relatively low, the growth rate may be too low, so that the deposition effect of the zinc oxide nano-deposition layer is poor, and the bonding force between the formed polymer composite film and the metal layer is easily reduced.
In some embodiments, the reaction time is between 0.5min and 5.0min. For example, the reaction time may be 1.0min,1.5min,2.0min,2.5min,3.0min,3.5min,4.0min,4.5min, or within a range of any of the above values.
In the embodiment of the application, the deposition rate and the particle size of the zinc oxide nano-deposition layer can be influenced by the reaction time. If the reaction time is relatively short, a complete zinc oxide deposition layer is not easy to form, the modification effect is poor, and the bonding force between the formed polymer composite film and the metal layer is poor; if the reaction time is relatively long, the zinc oxide nanoparticles on the surface of the deposition layer have overlarge size, which easily causes overlarge roughness of the film surface, and further causes the reduction of the adhesive force between the polymer composite film and the metal layer.
In some embodiments, the type of the zinc salt is not particularly limited, and may be selected according to actual needs as long as it is water-soluble. For example, the zinc salt may include one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc bromide, and zinc acetate.
In some embodiments, the kind of the alkaline agent is not particularly limited, and may be selected according to actual needs as long as the substitution reaction with the zinc salt can be performed. For example, the alkaline agent may include one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia.
In some embodiments, after step S10, the following steps are further included:
and S30, carrying out ultrasonic treatment on the aqueous solution.
The ultrasonic treatment can enable the zinc hydroxide nanoparticles generated in the step S20 to generate instant local high temperature and high pressure under the effect of ultrasonic cavitation, so that the zinc hydroxide nanoparticles are dehydrated and refined, refined zinc oxide nanoparticles are generated, and a zinc oxide nanoparticle deposition layer is generated on the surface of the polymer base membrane.
In some embodiments, the ultrasonic power of the ultrasonic treatment is 200W-700W. For example, the ultrasonic power may be 300W,400W,500W,600W or within a range of any of the above values. The size of the zinc oxide nanoparticles can also be affected by the ultrasonic treatment. If the ultrasonic power is relatively low, the size of the formed zinc oxide nano-ions is too large, so that the roughness of the surface of the zinc oxide nano-deposition layer is easily larger, and further the bonding force between the polymer composite film and the metal layer is reduced. If the ultrasonic power is relatively high, the size of the formed zinc oxide nano particles is too small, and the surface of the zinc oxide nano deposition layer is too flat, so that the bonding force between the polymer composite film and the metal layer is reduced.
In some embodiments, after step S20, a washing and drying step for the formed polymer composite membrane is further included.
As a non-limiting example of the above step S20, the polymer-based membrane may be placed in a zinc nitrate solution of 0.05mol/L to 0.25mol/L, and an ultrasonic system in the tank may be turned on, with an ultrasonic power of 200W to 700W and an ultrasonic frequency of 37Hz. And then adding a high-concentration sodium hydroxide solution into the solution until the concentration of the sodium hydroxide in the solution is 0.025-0.125 mol/L, the concentration ratio of the zinc nitrate to the sodium hydroxide is 2. And then removing liquid from the film after the reaction treatment by an air knife, washing the film in pure water for 1-5 min, putting the washed film in a blast oven, and drying the film at 70 ℃ to obtain the polymer composite film with zinc oxide deposited on the surface.
A third aspect of embodiments herein provides a composite current collector comprising a polymer composite film according to the first aspect of the present application or a polymer composite film produced according to the production method of the second aspect of the present application.
In some embodiments, as shown in fig. 2, the composite current collector further comprises: a metal layer 2 formed on at least one side surface of the polymer composite film; and a protective layer 3 formed on a surface of at least one side of the metal layer relatively distant from the polymer composite film.
In some embodiments, the polymer composite film has a thickness of 2 μm to 20 μm. For example, the polymer composite film may have a thickness of 5 μm,8 μm,11 μm,14 μm,17 μm or any range of values therein. The thickness setting of the polymer composite film can meet the application requirements of the composite current collector and can also consider the difficulty and the cost of the preparation process.
In some embodiments, the metal layer has a thickness of 500nm to 2000nm, optionally 700nm to 1200nm. The thickness of the metal layer is controlled within a proper range, so that the composite current collector has high conductivity.
In some embodiments, the material of the metal layer is not particularly limited, and may be selected according to actual requirements. For example, the material of the metal layer may include one or more of copper, a copper alloy, aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, and silver.
It is understood that the metal layer may be disposed on a surface of one side of the polymer composite film, or may be disposed on surfaces of both opposite sides of the polymer composite film; when the metal layers are arranged simultaneously, the thicknesses of the metal layers on the two sides can be the same or different, and the specific arrangement mode can be selected according to actual requirements.
In some embodiments, the preparation method of the metal layer formed on the polymer composite film is not particularly limited, and may be selected according to actual requirements. For example, the material can be prepared by physical vapor deposition (such as resistance-heated vacuum evaporation, electron beam-heated vacuum evaporation, laser-heated vacuum evaporation, magnetron sputtering, or the like), electroplating, electroless plating, or the like.
In some embodiments, the protective layer has a thickness of 10nm to 150nm, optionally 20nm to 100nm. Optionally, the thickness of the protective layer must not exceed one tenth of the thickness of the metal layer. The thickness of the protective layer is controlled within a proper range, so that the metal layer can be better prevented from being chemically corroded or physically damaged.
In some embodiments, the material of the protective layer is not particularly limited, and may be selected according to actual requirements. The material of the protective layer may include one or more of nickel, chromium, a nickel-based alloy, a copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, ketjen black, carbon nano-quantum dots, carbon nanotubes, carbon nanofibers, and graphene.
It is understood that the protective layer may be disposed on a surface of one side of the polymer composite film, or may be disposed on surfaces of both opposite sides of the polymer composite film; when the protective layers are arranged simultaneously, the thicknesses of the protective layers on the two sides can be the same or different, and the specific arrangement mode can be selected according to actual requirements.
In some embodiments, the preparation method of the protective layer formed on the metal layer is not particularly limited, and may be selected according to actual requirements. For example, one or more of physical vapor deposition, chemical vapor deposition, in-situ formation, coating, and the like may be included. Wherein, the vapor deposition method is preferably vacuum evaporation and magnetron sputtering; the chemical vapor deposition is preferably atmospheric pressure chemical vapor deposition and plasma enhanced chemical vapor deposition; in-situ forming is preferably carried out on the surface of the metal layer to form a metal oxide passivation layer in situ; the coating method is preferably die coating, blade coating and extrusion coating.
The application provides a compound mass flow body has the polymer composite membrane of zinc oxide nanometer sedimentary deposit including surface deposition, and the adhesion stress between polymer composite membrane and the metal layer can effectively be promoted to the zinc oxide nanometer sedimentary deposit, promotes compound mass flow body's structural stability.
A fourth aspect of embodiments of the present application provides a pole piece comprising the composite current collector of the third aspect of the present application.
In some embodiments, the pole pieces comprise positive pole pieces and/or negative pole pieces.
A fifth aspect of an embodiment of the present application provides a secondary battery comprising the pole piece of the fourth aspect of the present application.
In some embodiments, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. In the process of charging and discharging the battery, active ions are embedded and separated back and forth between the positive pole piece and the negative pole piece. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable ions to pass through.
A sixth aspect of the embodiments of the present application provides an electric device including the secondary battery of the fifth aspect of the present application.
Examples
The following examples more particularly describe the disclosure of the present application for specific embodiments that are intended as illustrative only, since various modifications and changes within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
Preparation of polymer composite membranes
The commercial 4.5 μm biaxially oriented PP film was placed in a dielectric barrier discharge plasma apparatus, the inlet regulating valve of the gas supply system was opened, and compressed air was introduced into the chamber to maintain the pressure in the chamber at 206.8kPa and the temperature at 25 ℃. Then, a power supply unit is turned on to input 220V and 50Hz alternating current to the high-voltage transformer, the alternating current is converted into 10kV and 325Hz alternating current through the high-voltage transformer, the alternating current is input to two electrodes with the distance of 4mm, dielectric barrier discharge plasma treatment is started, and the treatment time is 5s. And obtaining the plasma modified polymer-based film after the treatment is finished.
And (3) placing the plasma modified polymer-based membrane in 0.05mol/L zinc nitrate solution, and starting an ultrasonic system in the tank body, wherein the ultrasonic power is 200W, and the ultrasonic frequency is 37Hz. Then adding high-concentration sodium hydroxide solution into the solution until the concentration of the sodium hydroxide in the solution is 0.025mol/L, and reacting for 0.5min. And removing liquid from the membrane after the reaction treatment by using an air knife, and washing the membrane in pure water for 2min. And (3) putting the cleaned membrane into a blast oven, and drying at 70 ℃ to obtain the polymer composite membrane with the zinc oxide deposited on the surface.
Preparation of composite current collector
Preparing a metal layer: the prepared polymer composite film is placed in a vacuum evaporation chamber, high-purity copper wires (the purity is more than 99.99%) in a metal evaporation chamber are melted and evaporated at the high temperature of 1500 ℃, evaporated metal atoms are deposited on two surfaces of a high-molecular base film through a cooling system in the vacuum coating chamber, and a copper metal conducting layer with the thickness of 1 mu m is formed.
Preparing a protective layer: 1g of graphene is uniformly dispersed into 999g of N-methyl pyrrolidone (NMP) solution by an ultrasonic dispersion method to prepare a coating liquid with the solid content of 0.1wt.%, and then the coating liquid is uniformly coated on the surface of the metal conductive layer by a die head coating process, wherein the coating amount is controlled at 80 mu m, and finally, the metal conductive layer is dried at 75 ℃.
Example 2
The preparation method of example 2 is similar to that of example 1 except that: in the dielectric barrier discharge plasma treatment, the voltage of the alternating current inputted to the two electrodes was 13kV.
Example 3
The preparation method of example 3 is similar to that of example 1 except that: in the dielectric barrier discharge plasma treatment, the voltage of the alternating current supplied to the two electrodes was 16kV.
Example 4
The preparation method of example 2 is similar to that of example 2 except that: the treatment time of dielectric barrier discharge plasma surface modification is 30s.
Example 5
The preparation of example 5 is similar to that of example 2, except that: the treatment time of dielectric barrier discharge plasma surface modification is 60s.
Example 6
The preparation of example 6 is similar to that of example 2, except that: the concentrations of zinc nitrate and sodium hydroxide were 0.15mol/L and 0.075mol/L, respectively.
Example 7
The preparation of example 7 is similar to that of example 2, except that: the concentrations of zinc nitrate and sodium hydroxide were 0.25mol/L and 0.125mol/L, respectively.
Example 8
The preparation of example 8 is similar to that of example 6, except that: the ultrasonic power is 500W.
Example 9
The preparation of example 9 is similar to that of example 6, except that: the ultrasonic power is 700W.
Example 10:
the preparation of example 10 is similar to that of example 8, except that: the reaction time for preparing the zinc oxide deposition layer was 3.0min.
Example 11:
the preparation of example 11 is similar to that of example 8, except that: the reaction time for preparing the zinc oxide deposition layer was 5.0min.
Example 12:
the preparation of example 12 is similar to that of example 10, except that: the 4.5 μm biaxially oriented PP film was replaced by a 4.5 μm biaxially oriented PET film.
Comparative example 1:
essentially the same as in example 1, except that: in the dielectric barrier discharge plasma treatment, the voltage of the alternating current inputted to the two electrodes was 9kV.
Comparative example 2:
essentially the same as in example 1, except that: in the dielectric barrier discharge plasma treatment, the voltage of the alternating current input to the two electrodes was 17kV.
Comparative example 3:
essentially the same as example 2, except that: the treatment time of dielectric barrier discharge plasma surface modification is 4s.
Comparative example 4:
essentially the same as example 2, except that: the treatment time for dielectric barrier discharge plasma surface modification was 61s.
Comparative example 5:
essentially the same as in example 4, except that: the concentrations of zinc nitrate and sodium hydroxide were 0.04mol/L and 0.02mol/L, respectively.
Comparative example 6:
essentially the same as example 4, except that: the concentrations of zinc nitrate and sodium hydroxide were 0.26mol/L and 0.13mol/L, respectively.
Comparative example 7:
essentially the same as in example 4, except that: the concentrations of zinc nitrate and sodium hydroxide were 0.15mol/L and 0.10mol/L, respectively.
Comparative example 8:
essentially the same as in example 4, except that: the concentrations of zinc nitrate and sodium hydroxide were 0.15mol/L and 0.06mol/L, respectively.
Comparative example 9:
essentially the same as in example 6, except that: the ultrasonic power was 190W.
Comparative example 10:
essentially the same as in example 6, except that: the ultrasonic power was 710W.
Comparative example 11:
essentially the same as in example 8, except that: the reaction time when preparing the zinc oxide deposition layer was 0.4min.
Comparative example 12:
essentially the same as in example 8, except that: the reaction time for preparing the zinc oxide deposition layer was 5.1min.
Comparative example 13:
essentially the same as in example 1, except that: the 4.5 mu m biaxial tension PP film is not subjected to dielectric barrier discharge plasma surface modification treatment.
Comparative example 14:
essentially the same as in example 1, except that: the preparation of the polymer composite membrane adopts a chemical vapor deposition method, namely, a 4.5 mu m biaxially oriented PP membrane treated by plasma is placed in a chemical vapor deposition device, a gas source takes dimethyl zinc as a zinc source, the flow rate is 500sccm, tertiary butanol as an oxygen source, the flow rate is 50sccm, the pressure in a reaction cabin body is 5.0 multiplied by 10 -3 Pa, depositing a 50nm zinc oxide layer on the film surface.
The polymer composite films or composite current collectors prepared in the examples 1 to 12 and the comparative examples 1 to 14 are subjected to related performance tests, and the test results are shown in the following table 1; wherein, the surface tension and roughness in comparative example 13 represent the surface tension and roughness of the unmodified PP film.
The test conditions or test standards of each performance test item are as follows:
(1) Surface tension: and testing the surface tension of the polymer-based membrane after the dielectric barrier discharge plasma surface modification and the polymer composite membrane after the nano zinc oxide deposition according to GB/T14216-2008.
(2) Surface roughness: and testing the surface roughness of the polymer-based membrane after the dielectric barrier discharge plasma surface modification and the polymer composite membrane after the nano zinc oxide deposition according to GB/T31227-2014.
(3) Average grain size of the surface grains: firstly, preparing a sample of the prepared polymer composite membrane according to a sample preparation standard of a wide-angle X-ray diffractometer (WAXD), then placing the prepared sample in the WAXD, taking Cu Ka as an X-ray source, and performing 1-degree min within a 2 theta angle range of 10-80 degrees -1 The scanning speed of the X-ray diffraction spectrometer is continuously scanned to obtain an X-ray diffraction spectrogram, 2 theta angles corresponding to different diffraction peaks are read out from the spectrogram and substituted into a Scherrer formula to calculate crystal grain diameters corresponding to the different diffraction peaks, and the crystal grain diameters corresponding to the different diffraction peaks are averaged to obtain the average grain diameter of the crystal grains.
(4) Binding power: adhering a layer of Permacel P-94 double-sided adhesive tape on a 1mm thick aluminum foil, adhering a sample (composite current collector or polymer composite film with zinc oxide deposited on the surface) on the double-sided adhesive tape, covering a layer of ethylene acrylic acid copolymer film (Dupont Nurcel0903, thickness of 50 μm) on the sample, and then 1.3 × 105N/m 2 Hot pressing at 120 deg.C for 10s, cooling to room temperature, and cutting into small strips of 150mm × 15 mm. And finally, fixing the small ethylene acrylic acid copolymer film of the sample on an upper clamp of a tensile machine, fixing the rest part on a lower clamp, stripping the fixed ethylene acrylic acid copolymer film and the fixed ethylene acrylic acid copolymer film at an angle of 180 degrees and at a speed of 100mm/min, and testing the stripping force, namely the bonding force between the polymer composite film and the metal layer in the composite current collector and the bonding force between the zinc oxide nano deposition layer and the polymer base film in the polymer composite film deposited by surface zinc oxide.
(5) The number of holes: the prepared polymer composite membrane is placed in a surface quality detection system (a micro-vision Charge Coupled Device (CCD)), the surface is scanned, then an optical signal is converted into an electric signal to be transmitted to a computer, and the number of surface holes with the aperture smaller than 100 mu m of a finished product of the composite copper current collector in unit area is counted (generally, the finished product cannot have holes with the aperture larger than 100 mu m).
TABLE 1
By comparing examples 1 to 3 and comparative examples 1 to 2, it can be seen that: when the voltage of alternating current input to the two electrodes is within the protection range of the application, the voltage is increased, the surface tension and the roughness of the polymer base membrane after plasma modification are increased, so that the cohesive force between the zinc oxide nano-deposition layer and the polymer base membrane is increased firstly and then reduced, the surface tension and the roughness of the polymer composite membrane are increased after the zinc oxide nano-particles are deposited, the average particle size of the zinc oxide nano-particles is increased, and finally, the cohesive force between the polymer composite membrane and the metal layer is increased firstly and then reduced. After the application is beyond the protection range, the adhesive force between the zinc oxide nano deposition layer and the polymer base film and the adhesive force between the polymer composite film and the metal layer are obviously reduced, namely the surface adhesive property of the polymer composite film and the structural stability of the composite current collector are deteriorated.
Comparing examples 2, 4, 5 and comparative examples 3 to 4, it can be seen that: when the plasma surface treatment time is within the protection range of the application, the treatment time is prolonged, the surface tension and the roughness of the polymer base film after plasma modification are increased, so that the binding force between the zinc oxide nano-deposition layer and the polymer base film is increased firstly and then reduced, after the zinc oxide nano-particles are deposited, the surface tension of the polymer composite film is increased firstly and then basically unchanged, the roughness is increased, the average particle size of the zinc oxide nano-particles is increased, and finally, the binding force between the polymer composite film and the metal layer is increased firstly and then reduced. After the application is beyond the protection range, the adhesive force between the zinc oxide nano deposition layer and the polymer base film and the adhesive force between the polymer composite film and the metal layer are obviously reduced, namely the surface adhesive property of the polymer composite film and the structural stability of the composite current collector are deteriorated.
Comparing examples 4, 6, 7 and comparative examples 5 to 8, it can be seen that: when the concentrations of zinc nitrate and sodium hydroxide and the proportion of the zinc nitrate and the sodium hydroxide are in the protection range of the application, the change of the concentrations has no influence on the performance of a polymer base membrane obtained by a plasma surface modification treatment process, and mainly has influence on the performance of a polymer composite membrane obtained after zinc oxide nano particles are deposited, namely, the concentrations are improved, the surface roughness of the polymer composite membrane and the average particle size of the zinc oxide nano particles are increased, the surface tension is basically unchanged after being increased, and finally, the cohesive force between the polymer composite membrane and a metal layer is increased and reduced. After the protection range of the present application is exceeded, the adhesive force between the polymer composite film and the metal layer is significantly reduced, i.e. the surface adhesive property of the polymer composite film and the structural stability of the composite current collector are deteriorated.
By comparing examples 6, 8, 9 and comparative examples 9 to 10, it can be seen that: when the ultrasonic power is within the protection range of the application, the ultrasonic power mainly influences the performance of the polymer composite film obtained after the nano particles are deposited, namely the ultrasonic power is increased, the surface roughness of the polymer composite film and the average particle size of the zinc oxide nano particles are reduced, the surface tension is increased and then reduced, and finally the adhesive force between the polymer composite film and the metal layer is increased and then reduced. After the protection range of the present application is exceeded, the adhesive force between the polymer composite film and the metal layer is significantly reduced, i.e. the surface adhesive property of the polymer composite film and the structural stability of the composite current collector are deteriorated.
By comparing examples 8, 10, 11 and comparative examples 11 to 12, it can be seen that: when the deposition reaction time is within the protection range of the application, the deposition time mainly influences the performance of the polymer composite film obtained by depositing the zinc oxide nanoparticles, namely, the deposition time is prolonged, the surface roughness of the polymer composite film and the average particle size of the zinc oxide nanoparticles are increased, the surface tension is basically unchanged after being increased, and finally, the cohesive force between the polymer composite film and the metal layer is increased and reduced. After the protection range of the present application is exceeded, the adhesive force between the polymer composite film and the metal layer is significantly reduced, i.e. the surface adhesive property of the polymer composite film and the structural stability of the composite current collector are deteriorated.
Comparing example 10 with comparative example 13, it can be seen that: after the surface zinc oxide deposition treatment, the surface adhesion performance of the polymer composite film is obviously improved, so that in the prepared composite current collector, the adhesive force between the polymer composite film and the metal layer is obviously improved, namely the structural stability of the composite current collector is effectively improved.
Comparing examples 1-12 with comparative example 14, it can be seen that the number of surface voids is significantly reduced in the polymer composite film prepared using the method provided herein, as compared to the chemical vapor deposition preparation method.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.
Claims (15)
1. A polymer composite film, comprising:
a polymer-based film; and
and the zinc oxide nano deposition layer is formed on the surface of at least one side of the polymer base film, wherein the thickness of the zinc oxide nano deposition layer is 50-150 nm.
2. The polymer composite film according to claim 1, wherein the polymer composite film satisfies at least one of the following conditions:
(1) The average grain diameter of zinc oxide grains contained in the zinc oxide nano deposition layer is 20 nm-80 nm;
(2) The thickness of the polymer-based film is 2-20 μm; and
(3) The polymer comprises one or more of polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polystyrene, polyamide and derivatives of the above polymers.
3. A method of making a polymer composite membrane, comprising:
performing surface modification treatment on the polymer film layer to obtain a polymer base film; and
and depositing zinc oxide nano particles on the surface of at least one side of the polymer base film to form a zinc oxide nano deposition layer to obtain the polymer composite film, wherein the thickness of the zinc oxide nano deposition layer is 50 nm-150 nm.
4. The preparation method according to claim 3, wherein the surface modification treatment of the polymer film layer comprises:
the surface of the polymer film layer is subjected to dielectric barrier discharge plasma modification treatment,
optionally, in the dielectric barrier discharge plasma modification treatment process, the voltage of the alternating current input to the two electrodes of the dielectric barrier discharge plasma device is 10kV to 16kV;
optionally, the time of the dielectric barrier discharge plasma modification treatment is 5s to 60s.
5. The method of claim 3 or 4, wherein the depositing zinc oxide nanoparticles on the surface of at least one side of the polymer-based film comprises:
placing the polymer-based film in an aqueous solution of a zinc salt; and
under the action of ultrasound, adding an alkaline reagent into the aqueous solution of the zinc salt containing the polymer-based membrane until the concentration of the alkaline reagent in the solution reaches a target value, so that the zinc salt and the alkaline reagent are in contact reaction to form the zinc oxide nanoparticles.
6. The production method according to claim 5, wherein the production method satisfies at least one of the following conditions:
(1) The concentration of the zinc salt aqueous solution is 0.05 mol/L-0.25 mol/L;
(2) The molar ratio of the zinc salt to the alkaline reagent is (1.0-2.5) to 1;
(3) The reaction time is 0.5 min-5.0 min;
(4) The target value is 0.02 mol/L-0.25 mol/L;
(5) The zinc salt comprises one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc bromide and zinc acetate;
(6) The alkaline reagent comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water.
7. The method according to claim 5 or 6, wherein after said placing said polymer-based film in an aqueous solution of zinc salt, further comprising:
subjecting the aqueous solution to an ultrasonic treatment,
optionally, the ultrasonic power of the ultrasonic treatment is 200W-700W.
8. A composite current collector comprising the polymer composite film according to claim 1 or 2 or the polymer composite film produced by the production method according to any one of claims 3 to 7.
9. The composite current collector of claim 8, further comprising:
a metal layer formed on at least one side surface of the polymer composite film; and
and the protective layer is formed on the surface of at least one side of the metal layer, which is relatively far away from the polymer composite film.
10. The composite current collector of claim 9, wherein the composite current collector satisfies at least one of the following conditions:
(1) The thickness of the polymer composite film is 2-20 μm;
(2) The thickness of the metal layer is 500 nm-2000 nm, and 700 nm-1200 nm can be selected; and
(3) The thickness of the protective layer is 10 nm-150 nm, and 20 nm-100 nm can be selected.
11. The composite current collector of claim 9 or 10, wherein the composite current collector satisfies at least one of the following conditions:
(1) The material of the metal layer comprises one or more of copper, copper alloy, aluminum alloy, nickel alloy, titanium and silver; and
(2) The material of the protective layer comprises one or more of nickel, chromium, nickel-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, ketjen black, carbon nano quantum dots, carbon nano tubes, carbon nano fibers and graphene.
12. A pole piece comprising the composite current collector of any one of claims 8 to 11.
13. The pole piece of claim 12, wherein the pole piece comprises a positive pole piece and/or a negative pole piece.
14. A secondary battery comprising the pole piece of claim 12 or 13.
15. An electric device comprising the secondary battery according to claim 14.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211478483.7A CN115763828A (en) | 2022-11-21 | 2022-11-21 | Polymer composite membrane and preparation method thereof, composite current collector, pole piece, secondary battery and electric device |
| PCT/CN2022/138273 WO2024108680A1 (en) | 2022-11-21 | 2022-12-12 | Polymer composite film, preparation method therefor, composite current collector, electrode sheet, secondary battery and electrical apparatus |
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| CN202211478483.7A CN115763828A (en) | 2022-11-21 | 2022-11-21 | Polymer composite membrane and preparation method thereof, composite current collector, pole piece, secondary battery and electric device |
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| CN115763828A true CN115763828A (en) | 2023-03-07 |
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| CN (1) | CN115763828A (en) |
| WO (1) | WO2024108680A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117691121A (en) * | 2023-12-13 | 2024-03-12 | 广东盈华电子科技有限公司 | Composite copper foil for enhancing adhesion force between copper foil and base material |
| CN117702095A (en) * | 2023-12-13 | 2024-03-15 | 广东盈华电子科技有限公司 | Preparation method of composite copper foil |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009301898A (en) * | 2008-06-13 | 2009-12-24 | Denso Corp | Collector, method for manufacturing the same, electrode, and electrical storage battery |
| KR102003884B1 (en) * | 2016-12-20 | 2019-07-25 | (주) 에이치피엠글로벌 | Packaging film coated with zinc oxide nanoparticles and preparation method thereof |
| CN109873160B (en) * | 2017-12-05 | 2021-05-18 | 宁德时代新能源科技股份有限公司 | Current collector, pole piece thereof and battery |
| US11407901B2 (en) * | 2018-06-13 | 2022-08-09 | The Boeing Company | System and method for protecting a surface from UV radiation |
| CN112563512A (en) * | 2020-12-10 | 2021-03-26 | 湖北亿纬动力有限公司 | Electrode current collector and preparation method and application thereof |
| CN115312786A (en) * | 2022-09-06 | 2022-11-08 | 扬州纳力新材料科技有限公司 | Method for producing modified polymer film, and use thereof |
-
2022
- 2022-11-21 CN CN202211478483.7A patent/CN115763828A/en not_active Withdrawn
- 2022-12-12 WO PCT/CN2022/138273 patent/WO2024108680A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117691121A (en) * | 2023-12-13 | 2024-03-12 | 广东盈华电子科技有限公司 | Composite copper foil for enhancing adhesion force between copper foil and base material |
| CN117702095A (en) * | 2023-12-13 | 2024-03-15 | 广东盈华电子科技有限公司 | Preparation method of composite copper foil |
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| WO2024108680A1 (en) | 2024-05-30 |
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