WO2024050726A1 - Flexible polyester film and preparation method therefor, composite current collector, battery and electronic product - Google Patents
Flexible polyester film and preparation method therefor, composite current collector, battery and electronic product Download PDFInfo
- Publication number
- WO2024050726A1 WO2024050726A1 PCT/CN2022/117600 CN2022117600W WO2024050726A1 WO 2024050726 A1 WO2024050726 A1 WO 2024050726A1 CN 2022117600 W CN2022117600 W CN 2022117600W WO 2024050726 A1 WO2024050726 A1 WO 2024050726A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester film
- flexible polyester
- derivatives
- flexible
- current collector
- Prior art date
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 45
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 60
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 32
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 32
- -1 polyethylene terephthalate Polymers 0.000 claims description 30
- 229920000223 polyglycerol Polymers 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- 239000011591 potassium Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 239000012768 molten material Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001360 synchronised effect Effects 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- PEQMCTODPDZUDG-UHFFFAOYSA-N antimony;ethanol Chemical compound [Sb].CCO PEQMCTODPDZUDG-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 claims description 3
- 229940119177 germanium dioxide Drugs 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 3
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims 1
- TWMKXPBVMFGBRH-UHFFFAOYSA-N methanol;terephthalic acid Chemical compound OC.OC.OC(=O)C1=CC=C(C(O)=O)C=C1 TWMKXPBVMFGBRH-UHFFFAOYSA-N 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 30
- 239000010410 layer Substances 0.000 description 26
- 239000011241 protective layer Substances 0.000 description 12
- 238000006068 polycondensation reaction Methods 0.000 description 10
- 239000012528 membrane Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 230000002457 bidirectional effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- WOKDXPHSIQRTJF-UHFFFAOYSA-N 3-[3-[3-[3-[3-[3-[3-[3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)CO WOKDXPHSIQRTJF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000009421 internal insulation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
Definitions
- This application relates to the technical field of polymer materials, and in particular to a flexible polyester film and its preparation method, composite current collectors, batteries and electronic products.
- composite current collectors based on polymer membranes are widely used in the new energy industry. They have the characteristics of low cost, light weight, and good internal insulation. These characteristics enable the composite current collector to reduce the cost of the battery and improve the energy density and safety of the battery when used in batteries.
- the preparation process of a composite current collector based on a polymer film usually results in the formation of a metal material layer on the polymer film.
- a polyester film as the base film
- due to the relatively poor mechanical properties of the base film due to the relatively poor mechanical properties of the base film, it is prone to membrane rupture during the formation of the metal material layer, resulting in a poor yield rate of the composite current collector. is low, and the mechanical properties of the prepared composite current collector are poor.
- this application provides a flexible polyester film, which includes the following components by mass: 96.90 to 99.49 parts of polyester, 0.5 to 3 parts of polyol, and
- the polyols include diethylene glycol, polyethylene glycol, two polyglycerols, three polyglycerols, four polyglycerols, five polyglycerols, six polyglycerols, seven polyglycerols, eight polyglycerols, and nine polyglycerols.
- the active metal compound includes one or more of titanium-based compounds, antimony-based compounds, and germanium-based compounds.
- the titanium-based compound includes one or more of titanium dioxide, potassium fluorotitanate, tetrabutyl titanate, and titanium complex;
- the antimony-based compound includes antimony trioxide, antimony acetate , one or more of antimony ethanol;
- the germanium-based compound includes one or more of germanium dioxide, germanium monoxide, sodium germanate, and potassium germanate.
- the polyester includes polyethylene terephthalate and its derivatives, polytrimethylene terephthalate and its derivatives, polybutylene terephthalate and its derivatives , polyethylene naphthalate and its derivatives, polytrimethylene naphthalate and its derivatives, polybutylene naphthalate and its derivatives, polybutylene 2,5-furandicarboxylate and Its derivatives, polybutylene adipate terephthalate and its derivatives, poly1,4-cyclohexanedimethanol terephthalate and its derivatives, polyethylene terephthalate -One or more of 1,4-cyclohexanedimethanol ester and its derivatives.
- the weight average molecular weight of the polyester is 25,000 to 40,000 Da.
- the polyester has a molecular weight distribution of 1.5 to 2.5.
- the flexible polyester film has a crystallinity of 5% to 20%.
- this application also provides a method for preparing a flexible polyester film, including:
- the molten material is stretched.
- the stretching is bidirectional stretching.
- the bidirectional stretching includes at least one of longitudinal and transverse asynchronous stretching and longitudinal and transverse synchronous stretching.
- the present application also provides a composite current collector, including: a flexible polyester film as described in any one of the above and a conductive layer located on at least one surface of the flexible polyester film.
- the present application also provides a battery, including the composite current collector as described in any one of the above.
- this application also provides an electronic product, including the above-mentioned battery.
- the components of the above-mentioned flexible polyester film include polyester, polyol and active metal compound.
- the polyol can play a bridging role and react with the carboxyl or hydroxyl groups at the end of the polyester to promote further polymerization of the polyester polymer, thus
- the active metal compound catalyzes the polycondensation reaction between polyester molecules and between polyester and polyol, thereby improving the mechanical properties of the polyester film. This application can further obtain flexible polyester with good mechanical properties. membrane.
- the above-mentioned composite current collector has good mechanical properties, can reduce the membrane rupture rate during the preparation process of the composite current collector, and improve the yield of finished products.
- Figure 1 is a flow chart of a method for preparing a flexible polyester film according to an embodiment of the present application
- Figure 2 is a schematic structural diagram of a composite current collector provided by an embodiment of the present application. Explanation of reference signs
- First protective layer 2. First conductive layer; 3. Composite polyester film; 4. Second conductive layer; 5. Second protective layer.
- first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
- “plurality” means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
- One embodiment of the present application provides a flexible polyester film, which includes the following components by mass: 96.90 to 99.49 parts of polyester, 0.5 to 3 parts of polyol, and
- the mixed components undergo in-situ solid-phase polycondensation to improve the mechanical properties of the polyester film.
- the mass fraction of polyol is 0.5 to 3 parts; polyol plays a bridging role in the in-situ solid-phase polycondensation reaction, reacting with the carboxyl or hydroxyl groups at the end of the polyester to promote further polymerization of the polyester molecules, thereby improving the Mechanical properties of the substrate.
- the polyol content is too low, the effect of promoting the polymerization of polyester molecules is not good; when the polyol content is too high, the proportion of single-end reactions increases, making it difficult to further increase the degree of polymerization of polyester molecules; and the polyol content is too high.
- Active metal compounds catalyze the polycondensation reaction between polyester molecules and between polyester and polyol, improving the mechanical properties of the polyester film. Active metal compounds catalyze the polycondensation reaction between polyester molecules and between polyester and polyol, improving the mechanical properties of the polyester film.
- the mass fraction of the active metal compound is 0.01 to 0.1 parts; when the content is too low, the effect of catalyzing the polycondensation reaction between polyester molecules and between polyester and polyol is not good; when the content is too high, the solid phase If the degree of polycondensation reaction is too high, the flexibility of the polyester film will become worse and the elongation at break will decrease, which will lead to an increase in the membrane rupture rate during the preparation of the composite current collector. Within the range of the mass fraction of each component of the present application, a flexible polyester film with good mechanical properties can be obtained.
- the flexible polyester film includes the following mass percentages of each component: 96.90% to 99.49% polyester, 0.5% to 3% polyol, and
- the raw materials of the flexible polyester film are the following mass percentage components: 96.90% to 99.49% polyester, 0.5% to 3% polyol, and
- the polyol includes diethylene glycol, polyethylene glycol, two polyglycerols, three polyglycerols, four polyglycerols, five polyglycerols, six polyglycerols, seven polyglycerols, eight polyglycerols, nine polyglycerols, One or more polyglycerols.
- the active metal compound includes one or more of titanium-based compounds, antimony-based compounds, and germanium-based compounds.
- the titanium-based compound includes one or more of titanium dioxide, potassium fluorotitanate, tetrabutyl titanate, and titanium complex;
- the antimony-based compound includes antimony trioxide, antimony acetate, and antimony ethanol.
- the germanium-based compounds include one or more of germanium dioxide, germanium monoxide, sodium germanate, and potassium germanate.
- the active metal compound catalyzes the polycondensation reaction between polyester polymers and between polyester and diethylene glycol, improving the mechanical properties of the polyester film in situ.
- the polyester includes polyethylene terephthalate and its derivatives, polytrimethylene terephthalate and its derivatives, polybutylene terephthalate and its derivatives, poly Ethylene naphthalate and its derivatives, polytrimethylene naphthalate and its derivatives, polybutylene naphthalate and its derivatives, polybutylene 2,5-furandicarboxylate and its derivatives Materials, polybutylene adipate terephthalate and its derivatives, poly1,4-cyclohexanedimethanol terephthalate and its derivatives, polyethylene terephthalate-1 , one or more of 4-cyclohexanedimethanol ester and its derivatives.
- the polyester has a weight average molecular weight of 25,000 to 40,000 Da.
- a weight average molecular weight that is too low will lead to poor mechanical properties of the polyester film, and a weight average molecular weight that is too high will lead to poor film-forming properties.
- the polyester film can have both good mechanical properties and good film forming properties.
- the polyester has a weight average molecular weight of 29,000 to 36,000 Da.
- the weight average molecular weight of the polyester is 29000Da, 30000Da, 31000Da, 32000Da, 33000Da, 34000Da, 35000Da or 36000Da
- the polyester has a molecular weight distribution of 1.5 to 2.5. A molecular weight distribution that is too low will lead to poor film-forming properties, and a molecular weight distribution that is too high will lead to poor mechanical properties of the polyester film. Within this molecular weight distribution range, the polyester film can have both good mechanical properties and good film-forming properties.
- the polyester has a molecular weight distribution of 1.7 to 2.3. Further optionally, the polyester has a molecular weight distribution of 1.7, 1.8, 1.9, 2.0, 2.1, 2.2 or 2.3.
- the flexible polyester film has a crystallinity of 5% to 20%. Since the solid-phase polycondensation reaction occurs in the amorphous region of the polymer, if the crystallinity is too high, the proportion of the amorphous region will decrease, thereby hindering the occurrence of the solid-phase polycondensation reaction, resulting in limited improvement in the mechanical properties of the polyester film and composite current collector; If the crystallinity is too low and the proportion of invisible regions is too high, the polymer will be easily deoriented during the preparation of the current collector, resulting in a decrease in mechanical properties. Within this crystallinity range, the prepared flexible polyester film has good mechanical properties. Alternatively, the flexible polyester film has a crystallinity of 5%, 8%, 10%, 12%, 15%, 18% or 20%.
- An embodiment of the present application also provides a method for preparing a flexible polyester film.
- the preparation method includes:
- the preparation method of the flexible polyester film includes the following steps:
- the stretching is bidirectional stretching.
- the bidirectional stretching includes at least one of longitudinal and transverse asynchronous stretching and longitudinal and transverse synchronous stretching.
- the biaxial stretching includes at least one of asynchronous stretching in the longitudinal and transverse directions and synchronous stretching in the longitudinal and transverse directions - secondary stretching in the longitudinal direction.
- An embodiment of the present application also provides a composite current collector, including: a flexible polyester film as described above and a conductive layer located on at least one surface of the flexible polyester film.
- the composite current collector prepared with a flexible polyester film as the base film layer has good mechanical properties, can reduce the membrane rupture rate during the preparation process of the composite current collector, and improve the yield.
- the composite current collector further includes a protective layer located on a surface of the conductive layer away from the flexible polyester film.
- the thickness of the conductive layer is 500-2000 nm.
- the thickness of the conductive layer is 700-1200nm.
- the thickness of the conductive layer is 700nm, 800nm, 900nm, 1000nm, 1100nm or 1200nm.
- the thickness of the protective layer is 10-150 nm.
- the thickness of the protective layer is 10nm, 30nm, 50nm, 70nm, 100nm, 120nm or 150nm.
- the thickness of the protective layer is less than or equal to 10% of the thickness of the conductive layer.
- the thickness of the protective layer is 1%, 3%, 5%, 7% or 10% of the thickness of the conductive layer.
- the composite current collector includes: a flexible polyester film 3, a first conductive layer 2 and a second conductive layer 4 respectively located on two opposite surfaces of the flexible polyester film, and a first conductive layer located far away from the first conductive layer.
- the thickness of the flexible polyester film is greater than 1 micron.
- the thickness of the flexible polyester film is 2 to 20 microns.
- the smaller the thickness of the polyester film the greater its ability to promote the improvement of the energy density of the composite current collector.
- the thinner the thickness of the polyester film the greater the difficulty of production and the lower the yield rate.
- the thickness of the flexible polyester film is 2 microns, 5 microns, 8 microns, 10 microns, 15 microns or 20 microns.
- the material of the conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium, and silver.
- the conductive layer is prepared by one or more of physical vapor deposition, electroplating, and chemical plating.
- physical vapor deposition includes: resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, and magnetron sputtering.
- the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, and Ketjen black. , one or more of carbon nanoquantum dots, carbon nanotubes, carbon nanofibers, and graphene.
- the protective layer is prepared by one or more of physical vapor deposition, chemical vapor deposition, in-situ molding, and coating.
- physical vapor deposition is selected from vacuum evaporation or magnetron sputtering
- chemical vapor deposition is selected from atmospheric pressure chemical vapor deposition or plasma enhanced chemical vapor deposition
- in-situ forming is selected from in-situ formation of metal oxide on the surface of the conductive layer
- the method of physical passivation layer; the coating method is selected from die coating, blade coating, and extrusion coating.
- An embodiment of the present application provides a battery, including: any of the above composite current collectors.
- An embodiment of the present application also provides an electronic product, including: the above-mentioned battery.
- a flexible polyester film is prepared using polyethylene terephthalate (PET), diethylene glycol and potassium fluotitanate with a weight average molecular weight of 30,000 and a molecular weight distribution of 2.0.
- the mass percentages of the three raw materials are as follows: 99.49%, 0.5%, 0.01%.
- the polyester film is prepared using a melt-biaxial stretching method, which includes the following steps: crystal drying - melt extrusion - casting - longitudinal stretching - transverse stretching - heat setting.
- a flexible polyester film with a thickness of 6 microns and a crystallinity of 20% was prepared.
- Using the prepared flexible polyester film as the base film layer to prepare a composite current collector includes the following steps:
- Preparation of the conductive layer Place the flexible polyester film prepared above in a vacuum evaporation chamber, and melt and evaporate the aluminum wire in the metal evaporation chamber with a purity greater than 99.99% at a high temperature of 1500°C.
- the metal atoms after evaporation After the cooling system in the vacuum coating chamber, it is deposited on the upper and lower surfaces of the flexible polyester film to form an aluminum metal conductive layer with a thickness of 1 micron.
- Example 2 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.47%, 0.5%, and 0.03%.
- Embodiment 3 is basically the same as Embodiment 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.45%, 0.5%, and 0.05%.
- Example 4 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.43%, 0.5%, and 0.07%, respectively.
- Embodiment 5 is basically the same as Embodiment 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.41%, 0.5%, and 0.09%.
- Embodiment 6 is basically the same as Embodiment 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.4%, 0.5%, and 0.1%.
- Example 7 is basically the same as Example 4, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 98.93%, 1.0%, and 0.07%.
- Example 8 is basically the same as Example 4, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 97.93%, 2.0%, and 0.07%, respectively.
- Embodiment 9 is basically the same as Embodiment 4, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 96.93%, 3.0%, and 0.07%.
- Example 10 is basically the same as Example 8, except that the weight average molecular weight of PET in the flexible polyester film is 25,000, and the molecular weight distribution is 2.0.
- Example 11 is basically the same as Example 8, except that the weight average molecular weight of PET in the flexible polyester film is 35,000, and the molecular weight distribution is 2.0.
- Example 12 is basically the same as Example 8, except that the weight average molecular weight of PET in the flexible polyester film is 40,000 and the molecular weight distribution is 2.0.
- the example is basically the same as Example 11, except that the weight average molecular weight of PET in the flexible polyester film is 35,000, and the molecular weight distribution is 1.5.
- Example 14 is basically the same as Example 11, except that the weight average molecular weight of PET in the flexible polyester film is 35,000, and the molecular weight distribution is 2.5.
- Example 15 is basically the same as Example 11, except that the crystallinity of the flexible polyester film is 15%.
- Example 16 is basically the same as Example 11, except that the crystallinity of the flexible polyester film is 10%.
- Example 17 is basically the same as Example 11, except that the crystallinity of the flexible polyester film is 5%.
- Comparative Example 1 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 100%, 0%, and 0%.
- Comparative Example 2 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.495%, 0.5%, and 0.005%.
- Comparative Example 3 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.35%, 0.5%, and 0.15%.
- Comparative Example 4 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.69%, 0.3%, and 0.01%.
- Comparative Example 5 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 96.79%, 3.2%, and 0.01%.
- Comparative Example 6 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 23,000, and the molecular weight distribution is 2.0.
- Comparative Example 7 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 42,000 and the molecular weight distribution is 2.0.
- Comparative Example 8 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 30,000, and the molecular weight distribution is 1.3.
- Comparative Example 9 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 30,000, and the molecular weight distribution is 2.7.
- Comparative Example 10 is basically the same as Example 1, except that the crystallinity of the flexible polyester film is 22%.
- Comparative Example 11 is basically the same as Example 1, except that the crystallinity of the flexible polyester film is 3%.
- the composite current collectors prepared in Examples 1 to 17 and Comparative Examples 1 to 11 were tested for mechanical properties, including tensile strength, elongation at break, and membrane rupture rate during the preparation process.
- the tensile strength and elongation at break of composite current collectors are tested according to the national standard GB/T 1040.3-2006, where MD represents the longitudinal direction and TD represents the transverse direction.
- the test results are shown in Table 2 below:
- the flexible polyester films prepared in Examples 1 to 17 and Comparative Examples 1 to 11 were tested for their mechanical properties before and after preparing composite current collectors, including tensile strength, elongation at break, and membrane rupture rate during the preparation process.
- the flexible polyester film after preparing the composite current collector is obtained through the following steps: soak the composite current collector in a 1% NaOH solution for 20 minutes, then clean it with pure water, and then dry it at 60°C.
- the tensile strength and elongation at break of flexible polyester films are tested according to the national standard GB/T 1040.3-2006, where MD represents the longitudinal direction and TD represents the transverse direction. The test results are shown in Table 3 below:
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Abstract
The present application relates to a flexible polyester film and a preparation method therefor, a composite current collector, a battery and an electronic product. The flexible polyester film comprises the following components in parts by mass: 96.90-99.49 parts of polyester, 0.5-3 parts of a polyol and 0.01-0.1 parts of an active metal compound.
Description
本申请涉及高分子材料技术领域,特别是涉及一种柔性聚酯膜及其制备方法、复合集流体、电池和电子产品。This application relates to the technical field of polymer materials, and in particular to a flexible polyester film and its preparation method, composite current collectors, batteries and electronic products.
目前,基于高分子聚合物膜的复合集流体广泛应用于新能源行业,其具备成本低、质量轻、内部绝缘性好等特点。这些特点使得复合集流体在电池中应用时能够降低电池的成本、并提升电池的能量密度及安全性。基于高分子聚合物膜的复合集流体的制备过程通常会在高分子聚合物膜上形成金属材料层。然而,传统的以聚酯膜为基膜制备复合集流体过程中,由于基膜力学性能相对较差,导致其在形成金属材料层的过程中易发生破膜,从而造成复合集流体的良品率低,且制备的复合集流体的力学性能较差。At present, composite current collectors based on polymer membranes are widely used in the new energy industry. They have the characteristics of low cost, light weight, and good internal insulation. These characteristics enable the composite current collector to reduce the cost of the battery and improve the energy density and safety of the battery when used in batteries. The preparation process of a composite current collector based on a polymer film usually results in the formation of a metal material layer on the polymer film. However, in the traditional process of preparing a composite current collector using a polyester film as the base film, due to the relatively poor mechanical properties of the base film, it is prone to membrane rupture during the formation of the metal material layer, resulting in a poor yield rate of the composite current collector. is low, and the mechanical properties of the prepared composite current collector are poor.
发明内容Contents of the invention
基于此,有必要提供一种柔性聚酯膜及其制备方法、复合集流体、电池和电子产品,能够提高聚酯膜的力学性能,降低集流体制备过程中的破膜率,提升复合集流体的力学性能。Based on this, it is necessary to provide a flexible polyester film and its preparation method, composite current collector, battery and electronic products, which can improve the mechanical properties of the polyester film, reduce the membrane rupture rate during the preparation process of the current collector, and improve the composite current collector. mechanical properties.
第一方面,本申请提供一种柔性聚酯膜,其包括如下质量份数的各组分:96.90份~99.49份的聚酯、0.5份~3份的多元醇以及In the first aspect, this application provides a flexible polyester film, which includes the following components by mass: 96.90 to 99.49 parts of polyester, 0.5 to 3 parts of polyol, and
0.01份~0.1份的活性金属化合物。0.01 part to 0.1 part of active metal compound.
在一些实施例中,所述多元醇包括二甘醇、聚乙二醇、二聚甘油、三聚甘 油、四聚甘油、五聚甘油、六聚甘油、七聚甘油、八聚甘油、九聚甘油、十聚甘油中的一种或多种。In some embodiments, the polyols include diethylene glycol, polyethylene glycol, two polyglycerols, three polyglycerols, four polyglycerols, five polyglycerols, six polyglycerols, seven polyglycerols, eight polyglycerols, and nine polyglycerols. One or more of glycerin and decaglycerol.
在一些实施例中,所述活性金属化合物包括钛系化合物、锑系化合物、锗系化合物中的一种或多种。In some embodiments, the active metal compound includes one or more of titanium-based compounds, antimony-based compounds, and germanium-based compounds.
在一些实施例中,所述钛系化合物包括二氧化钛、氟钛酸钾、钛酸四丁脂、钛络合物中的一种或多种;所述锑系化合物包括三氧化二锑、醋酸锑、乙醇锑中的一种或多种;所述锗系化合物包括二氧化锗、一氧化锗、锗酸钠、锗酸钾中的一种或多种。In some embodiments, the titanium-based compound includes one or more of titanium dioxide, potassium fluorotitanate, tetrabutyl titanate, and titanium complex; the antimony-based compound includes antimony trioxide, antimony acetate , one or more of antimony ethanol; the germanium-based compound includes one or more of germanium dioxide, germanium monoxide, sodium germanate, and potassium germanate.
在一些实施例中,所述聚酯包括聚对苯二甲酸乙二醇酯及其衍生物、聚对苯二甲酸丙二醇酯及其衍生物、聚对苯二甲酸丁二醇酯及其衍生物、聚萘二甲酸乙二醇酯及其衍生物、聚萘二甲酸丙二醇酯及其衍生物、聚萘二甲酸丁二酯及其衍生物、聚2,5-呋喃二甲酸丁二醇酯及其衍生物、聚己二酸对苯二甲酸丁二醇酯及其衍生物、聚对苯二甲酸1,4-环己烷二甲醇酯及其衍生物、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯及其衍生物中的一种或多种。In some embodiments, the polyester includes polyethylene terephthalate and its derivatives, polytrimethylene terephthalate and its derivatives, polybutylene terephthalate and its derivatives , polyethylene naphthalate and its derivatives, polytrimethylene naphthalate and its derivatives, polybutylene naphthalate and its derivatives, polybutylene 2,5-furandicarboxylate and Its derivatives, polybutylene adipate terephthalate and its derivatives, poly1,4-cyclohexanedimethanol terephthalate and its derivatives, polyethylene terephthalate -One or more of 1,4-cyclohexanedimethanol ester and its derivatives.
在其中一个实施例中,所述聚酯的重均分子量为25000~40000Da。In one embodiment, the weight average molecular weight of the polyester is 25,000 to 40,000 Da.
在其中一个实施例中,所述聚酯的分子量分布为1.5~2.5。In one embodiment, the polyester has a molecular weight distribution of 1.5 to 2.5.
在其中一个实施例中,所述柔性聚酯膜的结晶度为5%~20%。In one embodiment, the flexible polyester film has a crystallinity of 5% to 20%.
第二方面,本申请还提供一种柔性聚酯膜的制备方法,包括:In a second aspect, this application also provides a method for preparing a flexible polyester film, including:
将质量份数分别为96.90份~99.49份的聚酯、0.5份~3份的多元醇以及0.01份~0.1份的活性金属化合物混合、熔融,得到熔融料;Mix and melt 96.90 to 99.49 parts by mass of polyester, 0.5 to 3 parts of polyol and 0.01 to 0.1 part of active metal compound to obtain molten material;
对所述熔融料进行拉伸。The molten material is stretched.
在其中一个实施例中,所述拉伸为双向拉伸。In one embodiment, the stretching is bidirectional stretching.
在其中一个实施例中,所述双向拉伸包括纵向横向异步拉伸和纵向横向同 步拉伸中的至少一种。In one embodiment, the bidirectional stretching includes at least one of longitudinal and transverse asynchronous stretching and longitudinal and transverse synchronous stretching.
第三方面,本申请还提供一种复合集流体,包括:如上述任一所述的柔性聚酯膜和位于所述柔性聚酯膜至少一个表面之上的导电层。In a third aspect, the present application also provides a composite current collector, including: a flexible polyester film as described in any one of the above and a conductive layer located on at least one surface of the flexible polyester film.
第四方面,本申请还提供一种电池,包括如上述任一所述的复合集流体。In a fourth aspect, the present application also provides a battery, including the composite current collector as described in any one of the above.
第五方面,本申请还提供一种电子产品,包括如上述的电池。In a fifth aspect, this application also provides an electronic product, including the above-mentioned battery.
上述柔性聚酯膜的组分包括聚酯、多元醇及活性金属化合物。以包括聚酯、多元醇及活性金属化合物的原料制备柔性聚酯膜中,多元醇可以起到架桥的作用,与聚酯端部的羧基或羟基反应,促进聚酯高分子进一步聚合,从而提升基材力学性能,活性金属化合物催化聚酯分子之间,以及聚酯与多元醇之间的缩聚反应,提升聚酯膜的力学性能,本申请进而可以得到能够得到力学性能良好的柔性聚酯膜。The components of the above-mentioned flexible polyester film include polyester, polyol and active metal compound. In preparing flexible polyester films from raw materials including polyester, polyol and active metal compounds, the polyol can play a bridging role and react with the carboxyl or hydroxyl groups at the end of the polyester to promote further polymerization of the polyester polymer, thus To improve the mechanical properties of the base material, the active metal compound catalyzes the polycondensation reaction between polyester molecules and between polyester and polyol, thereby improving the mechanical properties of the polyester film. This application can further obtain flexible polyester with good mechanical properties. membrane.
上述复合集流体具有良好的力学性能,能够降低复合集流体制备过程中的破膜率,提高成品率。The above-mentioned composite current collector has good mechanical properties, can reduce the membrane rupture rate during the preparation process of the composite current collector, and improve the yield of finished products.
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。In order to more clearly explain the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to describe the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting any creative effort.
图1为本申请一实施例提供的柔性聚酯膜的制备方法流程图;Figure 1 is a flow chart of a method for preparing a flexible polyester film according to an embodiment of the present application;
图2为本申请一实施例提供的复合集流体结构示意图。附图标记说明Figure 2 is a schematic structural diagram of a composite current collector provided by an embodiment of the present application. Explanation of reference signs
1、第一保护层;2、第一导电层;3、复合聚酯膜;4、第二导电层;5、第二保护层。1. First protective layer; 2. First conductive layer; 3. Composite polyester film; 4. Second conductive layer; 5. Second protective layer.
为使本申请的上述目的、特征和优点能够更加明显易懂,下面结合附图对本申请的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本申请。但是本申请能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本申请内涵的情况下做类似改进,因此本申请不受下面公开的具体实施例的限制。In order to make the above objects, features and advantages of the present application more obvious and easy to understand, the specific implementation modes of the present application will be described in detail below with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, the present application can be implemented in many other ways different from those described here. Those skilled in the art can make similar improvements without violating the connotation of the present application. Therefore, the present application is not limited by the specific embodiments disclosed below.
除非另有定义,本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本申请。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing specific embodiments only and is not intended to limit the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
此外,术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本申请的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of this application, "plurality" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
本申请一实施例提供了一种柔性聚酯膜,其包括如下质量份数的各组分:96.90份~99.49份的聚酯、0.5份~3份的多元醇以及One embodiment of the present application provides a flexible polyester film, which includes the following components by mass: 96.90 to 99.49 parts of polyester, 0.5 to 3 parts of polyol, and
0.01份~0.1份的活性金属化合物。0.01 part to 0.1 part of active metal compound.
在聚酯合成化学反应中,混合组分发生原位的固相缩聚,以提高聚酯膜的力学性能。多元醇的质量份数为0.5份~3份;多元醇在原位固相缩聚反应中起到架桥的作用,与聚酯端部的羧基或羟基反应,促进聚酯分子进一步聚合,从而提升基材力学性能。多元醇含量过低时,促进聚酯分子聚合的效果不佳;多元醇含量过高时,其单端反应比例增加,难以起到进一步增加聚酯分子聚合度 的作用;且多元醇含量过高,会降低聚酯膜的成膜性及稳定性。活性金属化合物催化聚酯分子之间,以及聚酯与多元醇之间的缩聚反应,提升聚酯膜的力学性能。活性金属化合物催化聚酯分子之间,以及聚酯与多元醇之间的缩聚反应,提升聚酯膜的力学性能。活性金属化合物的质量份数为0.01份~0.1份;其含量过低时,催化聚酯分子之间以及聚酯与多元醇之间的缩聚反应的效果不佳,其含量过高时,固相缩聚反应程度过高,导致聚酯膜柔韧性变差,断裂伸长率降低,从而造成制备复合集流体的过程中破膜率提高。在本申请的各组分的质量份数的范围内,能够得到力学性能良好的柔性聚酯膜。In the chemical reaction of polyester synthesis, the mixed components undergo in-situ solid-phase polycondensation to improve the mechanical properties of the polyester film. The mass fraction of polyol is 0.5 to 3 parts; polyol plays a bridging role in the in-situ solid-phase polycondensation reaction, reacting with the carboxyl or hydroxyl groups at the end of the polyester to promote further polymerization of the polyester molecules, thereby improving the Mechanical properties of the substrate. When the polyol content is too low, the effect of promoting the polymerization of polyester molecules is not good; when the polyol content is too high, the proportion of single-end reactions increases, making it difficult to further increase the degree of polymerization of polyester molecules; and the polyol content is too high. , will reduce the film-forming properties and stability of the polyester film. Active metal compounds catalyze the polycondensation reaction between polyester molecules and between polyester and polyol, improving the mechanical properties of the polyester film. Active metal compounds catalyze the polycondensation reaction between polyester molecules and between polyester and polyol, improving the mechanical properties of the polyester film. The mass fraction of the active metal compound is 0.01 to 0.1 parts; when the content is too low, the effect of catalyzing the polycondensation reaction between polyester molecules and between polyester and polyol is not good; when the content is too high, the solid phase If the degree of polycondensation reaction is too high, the flexibility of the polyester film will become worse and the elongation at break will decrease, which will lead to an increase in the membrane rupture rate during the preparation of the composite current collector. Within the range of the mass fraction of each component of the present application, a flexible polyester film with good mechanical properties can be obtained.
在一些实施例中,柔性聚酯膜包括如下质量百分比的各组分:96.90%~99.49%的聚酯、0.5%~3%的多元醇以及In some embodiments, the flexible polyester film includes the following mass percentages of each component: 96.90% to 99.49% polyester, 0.5% to 3% polyol, and
0.01%~0.1%的活性金属化合物。0.01% ~ 0.1% active metal compound.
在其中一个实施例中,柔性聚酯膜的原料为如下质量百分比的各组分:96.90%~99.49%的聚酯、0.5%~3%的多元醇以及In one embodiment, the raw materials of the flexible polyester film are the following mass percentage components: 96.90% to 99.49% polyester, 0.5% to 3% polyol, and
0.01%~0.1%的活性金属化合物。0.01% ~ 0.1% active metal compound.
在一些实施例中,多元醇包括二甘醇、聚乙二醇、二聚甘油、三聚甘油、四聚甘油、五聚甘油、六聚甘油、七聚甘油、八聚甘油、九聚甘油、十聚甘油中的一种或多种。In some embodiments, the polyol includes diethylene glycol, polyethylene glycol, two polyglycerols, three polyglycerols, four polyglycerols, five polyglycerols, six polyglycerols, seven polyglycerols, eight polyglycerols, nine polyglycerols, One or more polyglycerols.
在一些实施例中,活性金属化合物包括钛系化合物、锑系化合物、锗系化合物中的一种或多种。In some embodiments, the active metal compound includes one or more of titanium-based compounds, antimony-based compounds, and germanium-based compounds.
在一些实施例中,钛系化合物包括二氧化钛、氟钛酸钾、钛酸四丁脂、钛络合物中的一种或多种;锑系化合物包括三氧化二锑、醋酸锑、乙醇锑中的一种或多种;锗系化合物包括二氧化锗、一氧化锗、锗酸钠、锗酸钾中的一种或多种。在复合集流体制备过程中的高温真空的环境下,活性金属化合物催化聚 酯高分子之间,以及聚酯与二甘醇之间的缩聚反应,原位提升聚酯膜的力学性能。In some embodiments, the titanium-based compound includes one or more of titanium dioxide, potassium fluorotitanate, tetrabutyl titanate, and titanium complex; the antimony-based compound includes antimony trioxide, antimony acetate, and antimony ethanol. One or more of the germanium-based compounds include one or more of germanium dioxide, germanium monoxide, sodium germanate, and potassium germanate. In the high-temperature vacuum environment during the preparation of the composite current collector, the active metal compound catalyzes the polycondensation reaction between polyester polymers and between polyester and diethylene glycol, improving the mechanical properties of the polyester film in situ.
在一些实施例中,聚酯包括聚对苯二甲酸乙二醇酯及其衍生物、聚对苯二甲酸丙二醇酯及其衍生物、聚对苯二甲酸丁二醇酯及其衍生物、聚萘二甲酸乙二醇酯及其衍生物、聚萘二甲酸丙二醇酯及其衍生物、聚萘二甲酸丁二酯及其衍生物、聚2,5-呋喃二甲酸丁二醇酯及其衍生物、聚己二酸对苯二甲酸丁二醇酯及其衍生物、聚对苯二甲酸1,4-环己烷二甲醇酯及其衍生物、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯及其衍生物中的一种或多种。In some embodiments, the polyester includes polyethylene terephthalate and its derivatives, polytrimethylene terephthalate and its derivatives, polybutylene terephthalate and its derivatives, poly Ethylene naphthalate and its derivatives, polytrimethylene naphthalate and its derivatives, polybutylene naphthalate and its derivatives, polybutylene 2,5-furandicarboxylate and its derivatives Materials, polybutylene adipate terephthalate and its derivatives, poly1,4-cyclohexanedimethanol terephthalate and its derivatives, polyethylene terephthalate-1 , one or more of 4-cyclohexanedimethanol ester and its derivatives.
在其中一个实施例中,聚酯的重均分子量为25000~40000Da。重均分子量过低会导致聚酯膜力学性能差,重均分子量过高会导致成膜性较差,在该重均分子量范围下,可以使聚酯膜既具有良好的力学性能,也具有良好的成膜性。可选地,聚酯的重均分子量为29000~36000Da。进一步可选地,聚酯的重均分子量为29000Da、30000Da、31000Da、32000Da、33000Da、34000Da、35000Da或36000DaIn one embodiment, the polyester has a weight average molecular weight of 25,000 to 40,000 Da. A weight average molecular weight that is too low will lead to poor mechanical properties of the polyester film, and a weight average molecular weight that is too high will lead to poor film-forming properties. Within this weight average molecular weight range, the polyester film can have both good mechanical properties and good film forming properties. Optionally, the polyester has a weight average molecular weight of 29,000 to 36,000 Da. Further optionally, the weight average molecular weight of the polyester is 29000Da, 30000Da, 31000Da, 32000Da, 33000Da, 34000Da, 35000Da or 36000Da
在其中一个实施例中,聚酯的分子量分布为1.5~2.5。分子分量分布过低会导致成膜性变差,分子量分布过高会导致聚酯膜力学性能变差。在该分子量分布范围下,可以使聚酯膜既具有良好的力学性能,也具有良好的成膜性。可选地,聚酯的分子量分布为1.7~2.3。进一步可选地,聚酯的分子量分布为1.7、1.8、1.9、2.0、2.1、2.2或2.3。In one embodiment, the polyester has a molecular weight distribution of 1.5 to 2.5. A molecular weight distribution that is too low will lead to poor film-forming properties, and a molecular weight distribution that is too high will lead to poor mechanical properties of the polyester film. Within this molecular weight distribution range, the polyester film can have both good mechanical properties and good film-forming properties. Optionally, the polyester has a molecular weight distribution of 1.7 to 2.3. Further optionally, the polyester has a molecular weight distribution of 1.7, 1.8, 1.9, 2.0, 2.1, 2.2 or 2.3.
在其中一个实施例中,柔性聚酯膜的结晶度为5%~20%。由于固相缩聚反应发生在高分子的无定型区,若结晶度过高,会导致无定型区比例降低,从而阻碍固相缩聚反应的发生,造成聚酯膜及复合集流体力学性能提升有限;若结晶度过低,无形区占比过高,会导致制备集流体的过程中,高分子易发生解取 向,导致力学性能下降。在该结晶度范围内,所制备的柔性聚酯膜具有良好的力学性能。可选地,柔性聚酯膜的结晶度为5%、8%、10%、12%、15%、18%或20%。In one embodiment, the flexible polyester film has a crystallinity of 5% to 20%. Since the solid-phase polycondensation reaction occurs in the amorphous region of the polymer, if the crystallinity is too high, the proportion of the amorphous region will decrease, thereby hindering the occurrence of the solid-phase polycondensation reaction, resulting in limited improvement in the mechanical properties of the polyester film and composite current collector; If the crystallinity is too low and the proportion of invisible regions is too high, the polymer will be easily deoriented during the preparation of the current collector, resulting in a decrease in mechanical properties. Within this crystallinity range, the prepared flexible polyester film has good mechanical properties. Alternatively, the flexible polyester film has a crystallinity of 5%, 8%, 10%, 12%, 15%, 18% or 20%.
本申请一实施例还提供了一种柔性聚酯膜的制备方法,参照图1,该制备方法包括:An embodiment of the present application also provides a method for preparing a flexible polyester film. Referring to Figure 1, the preparation method includes:
S10:将质量份数分别为96.90份~99.49份的聚酯、0.5份~3份的多元醇以及0.01份~0.1份的活性金属化合物混合、熔融,得到熔融料;S10: Mix and melt 96.90 to 99.49 parts of polyester, 0.5 to 3 parts of polyol and 0.01 to 0.1 parts of active metal compounds by mass to obtain molten material;
S20:对熔融料进行拉伸。S20: Stretch the molten material.
在一些实施例中,柔性聚酯膜的制备方法包括以下步骤:In some embodiments, the preparation method of the flexible polyester film includes the following steps:
(1)将质量百分比分别为96.90%~99.49%的聚酯、0.5%~3%的多元醇以及0.01%~0.1%的活性金属化合物混合、熔融,得到熔融料;(1) Mix and melt 96.90% to 99.49% polyester, 0.5% to 3% polyol and 0.01% to 0.1% active metal compound by mass to obtain molten material;
(2)对熔融料进行拉伸。(2) Stretch the molten material.
在一些实施例中,拉伸为双向拉伸。In some embodiments, the stretching is bidirectional stretching.
在一些实施例中,双向拉伸包括纵向横向异步拉伸和纵向横向同步拉伸中的至少一种。In some embodiments, the bidirectional stretching includes at least one of longitudinal and transverse asynchronous stretching and longitudinal and transverse synchronous stretching.
在其中一个实施例中,双向拉伸包括纵向横向纵向异步拉伸和纵向横向同步拉伸-纵向二次拉伸中的至少一种。In one embodiment, the biaxial stretching includes at least one of asynchronous stretching in the longitudinal and transverse directions and synchronous stretching in the longitudinal and transverse directions - secondary stretching in the longitudinal direction.
本申请一实施例还提供了一种复合集流体,包括:如上述任一的柔性聚酯膜和位于柔性聚酯膜至少一个表面之上的导电层。An embodiment of the present application also provides a composite current collector, including: a flexible polyester film as described above and a conductive layer located on at least one surface of the flexible polyester film.
以柔性聚酯膜为基膜层制备的复合集流体,具有良好的力学性能,能够降低复合集流体制备过程中的破膜率,提高成品率。The composite current collector prepared with a flexible polyester film as the base film layer has good mechanical properties, can reduce the membrane rupture rate during the preparation process of the composite current collector, and improve the yield.
在一些实施例中,复合集流体还包括保护层,保护层位于导电层的远离柔性聚酯膜的表面。In some embodiments, the composite current collector further includes a protective layer located on a surface of the conductive layer away from the flexible polyester film.
在其中一个实施例中,导电层的厚度为500~2000nm。可选地,导电层的厚度为700~1200nm。进一步可选地,导电层的厚度为700nm、800nm、900nm、1000nm、1100nm或1200nm。In one embodiment, the thickness of the conductive layer is 500-2000 nm. Optionally, the thickness of the conductive layer is 700-1200nm. Further optionally, the thickness of the conductive layer is 700nm, 800nm, 900nm, 1000nm, 1100nm or 1200nm.
在其中一个实施例中,保护层的厚度为10~150nm。可选地,保护层的厚度为10nm、30nm、50nm、70nm、100nm、120nm或150nm。In one embodiment, the thickness of the protective layer is 10-150 nm. Optionally, the thickness of the protective layer is 10nm, 30nm, 50nm, 70nm, 100nm, 120nm or 150nm.
在其中一个实施例中,保护层的厚度小于或等于导电层的厚度的10%。可选地保护层的厚度为导电层的厚度的1%、3%、5%、7%或10%。In one embodiment, the thickness of the protective layer is less than or equal to 10% of the thickness of the conductive layer. Optionally the thickness of the protective layer is 1%, 3%, 5%, 7% or 10% of the thickness of the conductive layer.
在其中一个实施例中,参照图2,复合集流体包括:柔性聚酯膜3、分别位于柔性聚酯膜两相对表面的第一导电层2和第二导电层4、位于第一导电层远离柔性聚酯膜的表面的第一保护层1,以及位于第二导电层远离柔性聚酯膜的表面的第二保护层5。In one embodiment, referring to Figure 2, the composite current collector includes: a flexible polyester film 3, a first conductive layer 2 and a second conductive layer 4 respectively located on two opposite surfaces of the flexible polyester film, and a first conductive layer located far away from the first conductive layer. The first protective layer 1 on the surface of the flexible polyester film, and the second protective layer 5 on the surface of the second conductive layer away from the flexible polyester film.
在其中一个实施例中,柔性聚酯膜的厚度为1微米以上。可选地,柔性聚酯膜的厚度为2~20微米。聚酯膜的厚度越小,其促进复合集流体能量密度提升的能力越大,同时,聚酯膜的厚度越小,生产的难度会越大,良品率则会越低。在该聚酯膜的厚度范围内,能够在兼顾生产难度及良品率的同时,得到具有较高促进复合集流体能量密度提升能力的聚酯膜。进一步可选地,柔性聚酯膜的厚度为2微米、5微米、8微米、10微米、15微米或20微米。In one embodiment, the thickness of the flexible polyester film is greater than 1 micron. Optionally, the thickness of the flexible polyester film is 2 to 20 microns. The smaller the thickness of the polyester film, the greater its ability to promote the improvement of the energy density of the composite current collector. At the same time, the smaller the thickness of the polyester film, the greater the difficulty of production and the lower the yield rate. Within the thickness range of the polyester film, a polyester film with a high ability to promote the energy density increase of the composite current collector can be obtained while taking into account production difficulty and yield rate. Further optionally, the thickness of the flexible polyester film is 2 microns, 5 microns, 8 microns, 10 microns, 15 microns or 20 microns.
在其中一个实施例中,导电层的材料包括铜、铜合金、铝、铝合金、镍、镍合金、钛、银中的一种或多种。In one embodiment, the material of the conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium, and silver.
在其中一个实施例中,导电层通过物理气相沉积、电镀、化学镀方法中的一种或多种制备。可选地,物理气相沉积包括:电阻加热真空蒸镀、电子束加热真空蒸镀、激光加热真空蒸镀、磁控溅射。In one embodiment, the conductive layer is prepared by one or more of physical vapor deposition, electroplating, and chemical plating. Optionally, physical vapor deposition includes: resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, and magnetron sputtering.
在其中一个实施例中,保护层的材料包括镍、铬、镍基合金、铜基合金、 氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维、石墨烯中的一种或多种。In one embodiment, the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, and Ketjen black. , one or more of carbon nanoquantum dots, carbon nanotubes, carbon nanofibers, and graphene.
在其中一个实施例中,保护层的制备方法为物理气相沉积、化学气相沉积、原位成型、涂布中的一种或多种。可选地,物理气相沉积选自真空蒸镀或磁控溅射;化学气相沉积选自常压化学气相沉积或等离子体增强化学气相沉积;原位成型选自在导电层表面原位形成金属氧化物钝化层的方法;涂布法选自模头涂布、刮刀涂布、挤压涂布。In one embodiment, the protective layer is prepared by one or more of physical vapor deposition, chemical vapor deposition, in-situ molding, and coating. Optionally, physical vapor deposition is selected from vacuum evaporation or magnetron sputtering; chemical vapor deposition is selected from atmospheric pressure chemical vapor deposition or plasma enhanced chemical vapor deposition; in-situ forming is selected from in-situ formation of metal oxide on the surface of the conductive layer The method of physical passivation layer; the coating method is selected from die coating, blade coating, and extrusion coating.
本申请一实施例提供了一种电池,包括:如上述任一的复合集流体。An embodiment of the present application provides a battery, including: any of the above composite current collectors.
本申请一实施例还提供了一种电子产品,包括:如上述的电池。An embodiment of the present application also provides an electronic product, including: the above-mentioned battery.
以下为具体实施例。The following are specific examples.
实施例1Example 1
以重均分子量为3.0万、分子量分布为2.0的聚对苯二甲酸乙二醇酯(PET)、二甘醇和氟钛酸钾为原料制备柔性聚酯膜,三种原料的质量百分比依次为:99.49%、0.5%、0.01%。采用熔融-双向拉伸的方法进行聚酯膜的制备,包括以下步骤:结晶干燥-熔融挤出-铸片-纵向拉伸-横向拉伸-热定型。制备所得为厚度为6微米、结晶度为20%的柔性聚酯膜。A flexible polyester film is prepared using polyethylene terephthalate (PET), diethylene glycol and potassium fluotitanate with a weight average molecular weight of 30,000 and a molecular weight distribution of 2.0. The mass percentages of the three raw materials are as follows: 99.49%, 0.5%, 0.01%. The polyester film is prepared using a melt-biaxial stretching method, which includes the following steps: crystal drying - melt extrusion - casting - longitudinal stretching - transverse stretching - heat setting. A flexible polyester film with a thickness of 6 microns and a crystallinity of 20% was prepared.
以制备所得的柔性聚酯膜为基膜层制备复合集流体,包括以下步骤:Using the prepared flexible polyester film as the base film layer to prepare a composite current collector includes the following steps:
(1)导电层的制备:将上述制备所得的柔性聚酯膜置于真空蒸镀的舱体内,以1500℃的高温将金属蒸发室内的纯度大于99.99%铝丝熔化蒸发,蒸发后的金属原子经过真空镀膜室内的冷却系统,沉积在柔性聚酯膜的上下两个表面,形成厚度为1微米的铝金属导电层。(1) Preparation of the conductive layer: Place the flexible polyester film prepared above in a vacuum evaporation chamber, and melt and evaporate the aluminum wire in the metal evaporation chamber with a purity greater than 99.99% at a high temperature of 1500°C. The metal atoms after evaporation After the cooling system in the vacuum coating chamber, it is deposited on the upper and lower surfaces of the flexible polyester film to form an aluminum metal conductive layer with a thickness of 1 micron.
(2)保护层的制备:通过超声分散的方法将1g碳纳米管均匀分散到999g氮甲基吡咯烷酮(NMP)溶液中,配制成固含量为0.1wt.%的涂布液,然后通过 模头涂布的工艺将涂布液均匀涂覆到金属导电层的表面,其中涂覆量控制在90微米,最后在100℃下进行干燥。(2) Preparation of protective layer: uniformly disperse 1g of carbon nanotubes into 999g of nitrogen methylpyrrolidone (NMP) solution by ultrasonic dispersion, prepare a coating liquid with a solid content of 0.1wt.%, and then pass it through the die In the coating process, the coating liquid is evenly applied to the surface of the metal conductive layer, with the coating amount controlled to 90 microns, and finally dried at 100°C.
实施例2Example 2
实施例2与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.47%、0.5%、0.03%。Example 2 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.47%, 0.5%, and 0.03%.
实施例3Example 3
实施例3与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.45%、0.5%、0.05%。Embodiment 3 is basically the same as Embodiment 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.45%, 0.5%, and 0.05%.
实施例4Example 4
实施例4与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.43%、0.5%、0.07%。Example 4 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.43%, 0.5%, and 0.07%, respectively.
实施例5Example 5
实施例5与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.41%、0.5%、0.09%。 Embodiment 5 is basically the same as Embodiment 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.41%, 0.5%, and 0.09%.
实施例6Example 6
实施例6与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.4%、0.5%、0.1%。Embodiment 6 is basically the same as Embodiment 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.4%, 0.5%, and 0.1%.
实施例7Example 7
实施例7与实施例4基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:98.93%、1.0%、0.07%。Example 7 is basically the same as Example 4, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 98.93%, 1.0%, and 0.07%.
实施例8Example 8
实施例8与实施例4基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:97.93%、2.0%、0.07%。Example 8 is basically the same as Example 4, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 97.93%, 2.0%, and 0.07%, respectively.
实施例9Example 9
实施例9与实施例4基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:96.93%、3.0%、0.07%。Embodiment 9 is basically the same as Embodiment 4, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 96.93%, 3.0%, and 0.07%.
实施例10Example 10
实施例10与实施例8基本相同,区别在于:柔性聚酯膜中PET的重均分子量为2.5万、分子量分布为2.0。Example 10 is basically the same as Example 8, except that the weight average molecular weight of PET in the flexible polyester film is 25,000, and the molecular weight distribution is 2.0.
实施例11Example 11
实施例11与实施例8基本相同,区别在于:柔性聚酯膜中PET的重均分子量为3.5万、分子量分布为2.0。Example 11 is basically the same as Example 8, except that the weight average molecular weight of PET in the flexible polyester film is 35,000, and the molecular weight distribution is 2.0.
实施例12Example 12
实施例12与实施例8基本相同,区别在于:柔性聚酯膜中PET的重均分子量为4.0万、分子量分布为2.0。Example 12 is basically the same as Example 8, except that the weight average molecular weight of PET in the flexible polyester film is 40,000 and the molecular weight distribution is 2.0.
实施例13Example 13
实施例与实施例11基本相同,区别在于:柔性聚酯膜中PET的重均分子量为3.5万、分子量分布为1.5。The example is basically the same as Example 11, except that the weight average molecular weight of PET in the flexible polyester film is 35,000, and the molecular weight distribution is 1.5.
实施例14Example 14
实施例14与实施例11基本相同,区别在于:柔性聚酯膜中PET的重均分子量为3.5万、分子量分布为2.5。Example 14 is basically the same as Example 11, except that the weight average molecular weight of PET in the flexible polyester film is 35,000, and the molecular weight distribution is 2.5.
实施例15Example 15
实施例15与实施例11基本相同,区别在于:柔性聚酯膜的结晶度为15%。Example 15 is basically the same as Example 11, except that the crystallinity of the flexible polyester film is 15%.
实施例16Example 16
实施例16与实施例11基本相同,区别在于:柔性聚酯膜的结晶度为10%。Example 16 is basically the same as Example 11, except that the crystallinity of the flexible polyester film is 10%.
实施例17Example 17
实施例17与实施例11基本相同,区别在于:柔性聚酯膜的结晶度为5%。Example 17 is basically the same as Example 11, except that the crystallinity of the flexible polyester film is 5%.
对比例1Comparative example 1
对比例1与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:100%、0%、0%。Comparative Example 1 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 100%, 0%, and 0%.
对比例2Comparative example 2
对比例2与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.495%、0.5%、0.005%。Comparative Example 2 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.495%, 0.5%, and 0.005%.
对比例3Comparative example 3
对比例3与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.35%、0.5%、0.15%。Comparative Example 3 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.35%, 0.5%, and 0.15%.
对比例4Comparative example 4
对比例4与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:99.69%、0.3%、0.01%。Comparative Example 4 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 99.69%, 0.3%, and 0.01%.
对比例5Comparative example 5
对比例5与实施例1基本相同,区别在于:柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比依次为:96.79%、3.2%、0.01%。Comparative Example 5 is basically the same as Example 1, except that the mass percentages of PET, diethylene glycol, and potassium fluotitanate in the flexible polyester film are: 96.79%, 3.2%, and 0.01%.
对比例6Comparative example 6
对比例6与实施例1基本相同,区别在于:柔性聚酯膜中PET的重均分子量为2.3万、分子量分布为2.0。Comparative Example 6 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 23,000, and the molecular weight distribution is 2.0.
对比例7Comparative example 7
对比例7与实施例1基本相同,区别在于:柔性聚酯膜中PET的重均分子量为4.2万、分子量分布为2.0。Comparative Example 7 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 42,000 and the molecular weight distribution is 2.0.
对比例8Comparative example 8
对比例8与实施例1基本相同,区别在于:柔性聚酯膜中PET的重均分子量为3.0万、分子量分布为1.3。Comparative Example 8 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 30,000, and the molecular weight distribution is 1.3.
对比例9Comparative example 9
对比例9与实施例1基本相同,区别在于:柔性聚酯膜中PET的重均分子量为3.0万、分子量分布为2.7。Comparative Example 9 is basically the same as Example 1, except that the weight average molecular weight of PET in the flexible polyester film is 30,000, and the molecular weight distribution is 2.7.
对比例10Comparative example 10
对比例10与实施例1基本相同,区别在于:柔性聚酯膜的结晶度为22%。Comparative Example 10 is basically the same as Example 1, except that the crystallinity of the flexible polyester film is 22%.
对比例11Comparative example 11
对比例11与实施例1基本相同,区别在于:柔性聚酯膜的结晶度为3%。Comparative Example 11 is basically the same as Example 1, except that the crystallinity of the flexible polyester film is 3%.
实施例1~17及对比例1~11中柔性聚酯膜中PET、二甘醇、氟钛酸钾的质量百分比含量、柔性聚酯膜中PET的重均分子量、分子量分布以及柔性聚酯膜的结晶度等工艺参数列表如下表1:The mass percentage content of PET, diethylene glycol, and potassium fluorotitanate in the flexible polyester film in Examples 1 to 17 and Comparative Examples 1 to 11, the weight average molecular weight and molecular weight distribution of PET in the flexible polyester film, and the flexible polyester film The list of process parameters such as crystallinity is as follows in Table 1:
表1Table 1
将实施例1~17及对比例1~11制得的复合集流体进行力学性能测试,包括拉伸强度、断裂伸长率及制备过程中的破膜率。复合集流体的拉伸强度及断裂伸长率的测试参照国标GB/T 1040.3-2006,其中MD表示纵向方向,TD表示横向方向,测试结果如下表2所示:The composite current collectors prepared in Examples 1 to 17 and Comparative Examples 1 to 11 were tested for mechanical properties, including tensile strength, elongation at break, and membrane rupture rate during the preparation process. The tensile strength and elongation at break of composite current collectors are tested according to the national standard GB/T 1040.3-2006, where MD represents the longitudinal direction and TD represents the transverse direction. The test results are shown in Table 2 below:
表2Table 2
将实施例1~17及对比例1~11制得的柔性聚酯膜进行制备复合集流体前后的力学性能测试,包括拉伸强度、断裂伸长率及制备过程中的破膜率。制备复合集流体后的柔性聚酯膜通过以下步骤得到:将复合集流体置于1%的NaOH的溶液中浸泡20min,然后利用纯水清洗,再于60℃下烘干。柔性聚酯膜的拉伸强度及断裂伸长率的测试参照国标GB/T 1040.3-2006,其中MD表示纵向方向,TD表示横向方向,测试结果如下表3所示:The flexible polyester films prepared in Examples 1 to 17 and Comparative Examples 1 to 11 were tested for their mechanical properties before and after preparing composite current collectors, including tensile strength, elongation at break, and membrane rupture rate during the preparation process. The flexible polyester film after preparing the composite current collector is obtained through the following steps: soak the composite current collector in a 1% NaOH solution for 20 minutes, then clean it with pure water, and then dry it at 60°C. The tensile strength and elongation at break of flexible polyester films are tested according to the national standard GB/T 1040.3-2006, where MD represents the longitudinal direction and TD represents the transverse direction. The test results are shown in Table 3 below:
表3table 3
从上表2和表3的测试结果可知:It can be seen from the test results in Table 2 and Table 3 above:
(1)比较实施例1~6、对比例1~3,可以得出:在权利要求保护的活性金属化合物的份数范围内,提高活性金属化合物的含量,制备复合集流体后的柔性聚酯膜的拉伸强度升高、断裂伸长率降低,制备的复合集流体的拉伸强度及断裂伸长率表现出相同的趋势。超出权利要求的范围时,制备复合集流体后的柔性聚酯膜、制备的复合集流体的拉伸强度降低。(1) Comparing Examples 1 to 6 and Comparative Examples 1 to 3, it can be concluded that by increasing the content of the active metal compound within the range of the fraction of the active metal compound protected by the claims, the flexible polyester after the composite current collector is prepared The tensile strength of the film increases and the elongation at break decreases. The tensile strength and elongation at break of the prepared composite current collector show the same trend. When it exceeds the scope of the claims, the tensile strength of the flexible polyester film after preparing the composite current collector and the prepared composite current collector decreases.
(2)比较实施例4、7~9、对比例4~5,可以得出:在权利要求保护的多元醇的份数百分比范围内,提高二甘醇的含量,制备复合集流体后的柔性聚酯膜的拉伸强度先升高后降低、断裂伸长率先降低后升高,制备的复合集流体的拉伸强度及断裂伸长率表现出相同的趋势。超出权利要求的范围时,制备复合集 流体后的柔性聚酯膜、制备的复合集流体的拉伸强度均降低。(2) Comparing Examples 4, 7 to 9, and Comparative Examples 4 to 5, it can be concluded that by increasing the content of diethylene glycol within the range of the percentage of the claimed polyol, the flexibility of the composite current collector can be improved The tensile strength of the polyester film first increased and then decreased, and the elongation at break decreased first and then increased. The tensile strength and elongation at break of the prepared composite current collector showed the same trend. When exceeding the scope of the claims, the tensile strength of the flexible polyester film after preparing the composite current collector and the prepared composite current collector are reduced.
(3)比较实施例8、10~12、对比例6~7,可以得出:在权利要求保护的聚酯的重均分子量范围内,提高PET的重均分子量,制备复合集流体后的柔性聚酯膜的拉伸强度升高、断裂伸长率降低,制备的复合集流体的拉伸强度及断裂伸长率表现出相同的趋势。超出权利要求的范围时,制备复合集流体后的柔性聚酯膜、制备的复合集流体的拉伸强度均降低。(3) Comparing Examples 8, 10 to 12, and Comparative Examples 6 to 7, it can be concluded that within the weight average molecular weight range of the claimed polyester, the weight average molecular weight of PET is increased, and the flexibility after preparing the composite current collector is The tensile strength and elongation at break of the polyester film increased, and the tensile strength and elongation at break of the prepared composite current collector showed the same trend. When it exceeds the scope of the claims, the tensile strength of the flexible polyester film after preparing the composite current collector and the prepared composite current collector are reduced.
(4)比较实施例11、13~14、对比例8~9,可以得出:在权利要求保护的分子量分布范围内,提高PET的分子量分布,制备复合集流体后的柔性聚酯膜的拉伸强度先升高后降低、断裂伸长率升高,制备的复合集流体的拉伸强度及断裂伸长率表现出相同的趋势。超出权利要求的范围,制备复合集流体后的柔性聚酯膜、制备的复合集流体的拉伸强度均降低。(4) Comparing Examples 11, 13 to 14, and Comparative Examples 8 to 9, it can be concluded that within the molecular weight distribution range protected by the claims, the molecular weight distribution of PET is increased and the stretchability of the flexible polyester film after preparing the composite current collector is The tensile strength first increased and then decreased, and the elongation at break increased. The tensile strength and elongation at break of the prepared composite current collector showed the same trend. Beyond the scope of the claims, the tensile strength of the flexible polyester film after preparing the composite current collector and the prepared composite current collector are reduced.
(5)比较实施例11、15~17、对比例10~11,可以得出:在权利要求保护的柔性聚酯膜的结晶度范围内,降低柔性聚酯膜的结晶度,制备复合集流体后的柔性聚酯膜的拉伸强度先升高后降低、断裂伸长率先降低后升高,制备的复合集流体的拉伸强度及断裂伸长率表现出相同的趋势。超出权利要求的范围,制备复合集流体后的柔性聚酯膜、制备的复合集流体的拉伸强度均降低。(5) Comparing Examples 11, 15-17, and Comparative Examples 10-11, it can be concluded that within the crystallinity range of the flexible polyester film protected by the claims, the crystallinity of the flexible polyester film can be reduced to prepare a composite current collector. The tensile strength of the flexible polyester film first increased and then decreased, and the elongation at break decreased first and then increased. The tensile strength and elongation at break of the prepared composite current collector showed the same trend. Beyond the scope of the claims, the tensile strength of the flexible polyester film after preparing the composite current collector and the prepared composite current collector are reduced.
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.
以上所述实施例仅表达了本申请的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本申请构思的前提下,还可以做出若干变形和改进,这些都属于本申请的保护范围。因此,本申请专利的保护范围应以所附权 利要求为准,说明书及附图可以用于解释权利要求的内容。The above-described embodiments only express several implementation modes of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. Therefore, the protection scope of the patent of this application shall be determined by the appended claims, and the description and drawings may be used to interpret the contents of the claims.
Claims (14)
- 一种柔性聚酯膜,其特征在于,包括如下质量份数的各组分:96.90份~99.49份的聚酯、0.5份~3份的多元醇以及0.01份~0.1份的活性金属化合物。A flexible polyester film is characterized in that it includes the following components in parts by mass: 96.90 to 99.49 parts of polyester, 0.5 to 3 parts of polyol, and 0.01 to 0.1 parts of active metal compounds.
- 根据权利要求1所述的柔性聚酯膜,其特征在于,所述多元醇包括二甘醇、聚乙二醇、二聚甘油、三聚甘油、四聚甘油、五聚甘油、六聚甘油、七聚甘油、八聚甘油、九聚甘油、十聚甘油中的一种或多种。The flexible polyester film according to claim 1, wherein the polyol includes diethylene glycol, polyethylene glycol, two polyglycerol, three polyglycerol, four polyglycerol, five polyglycerol, and six polyglycerol. One or more of heptapolyglycerol, octapolyglycerol, nonapolyglycerol, and decapolyglycerol.
- 根据权利要求1~2任一所述的柔性聚酯膜,其特征在于,所述活性金属化合物包括钛系化合物、锑系化合物、锗系化合物中的一种或多种。The flexible polyester film according to any one of claims 1 to 2, wherein the active metal compound includes one or more of titanium-based compounds, antimony-based compounds, and germanium-based compounds.
- 根据权利要求3所述的柔性聚酯膜,其特征在于,所述钛系化合物包括二氧化钛、氟钛酸钾、钛酸四丁脂、钛络合物中的一种或多种;The flexible polyester film according to claim 3, wherein the titanium compound includes one or more of titanium dioxide, potassium fluotitanate, tetrabutyl titanate, and titanium complex;所述锑系化合物包括三氧化二锑、醋酸锑、乙醇锑中的一种或多种;The antimony-based compound includes one or more of antimony trioxide, antimony acetate, and antimony ethanol;所述锗系化合物包括二氧化锗、一氧化锗、锗酸钠、锗酸钾中的一种或多种。The germanium-based compound includes one or more of germanium dioxide, germanium monoxide, sodium germanate, and potassium germanate.
- 根据权利要求1~4任一所述的柔性聚酯膜,其特征在于,所述聚酯包括聚对苯二甲酸乙二醇酯及其衍生物、聚对苯二甲酸丙二醇酯及其衍生物、聚对苯二甲酸丁二醇酯及其衍生物、聚萘二甲酸乙二醇酯及其衍生物、聚萘二甲酸丙二醇酯及其衍生物、聚萘二甲酸丁二酯及其衍生物、聚2,5-呋喃二甲酸丁二醇酯及其衍生物、聚己二酸对苯二甲酸丁二醇酯及其衍生物、聚对苯二甲酸1,4-环己烷二甲醇酯及其衍生物、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯及其衍生物中的一种或多种。The flexible polyester film according to any one of claims 1 to 4, characterized in that the polyester includes polyethylene terephthalate and its derivatives, polytrimethylene terephthalate and its derivatives , polybutylene terephthalate and its derivatives, polyethylene naphthalate and its derivatives, polytrimethylene naphthalate and its derivatives, polybutylene naphthalate and its derivatives , polybutylene 2,5-furandicarboxylate and its derivatives, polybutylene adipate terephthalate and its derivatives, poly1,4-cyclohexane dimethanol terephthalate and one or more of its derivatives, polyethylene terephthalate-1,4-cyclohexanedimethanol ester and its derivatives.
- 根据权利要求1~5任一所述的柔性聚酯膜,其特征在于,所述聚酯的重均分子量为25000~40000Da。The flexible polyester film according to any one of claims 1 to 5, characterized in that the weight average molecular weight of the polyester is 25,000 to 40,000 Da.
- 根据权利要求1~6任一所述的柔性聚酯膜,其特征在于,所述聚酯的分子 量分布为1.5-2.5。The flexible polyester film according to any one of claims 1 to 6, characterized in that the molecular weight distribution of the polyester is 1.5-2.5.
- 根据权利要求1~7任一所述的柔性聚酯膜,其特征在于,所述柔性聚酯膜的结晶度为5%~20%。The flexible polyester film according to any one of claims 1 to 7, characterized in that the crystallinity of the flexible polyester film is 5% to 20%.
- 一种柔性聚酯膜的制备方法,其特征在于,包括:A method for preparing a flexible polyester film, which is characterized by including:将质量份数分别为96.90份~99.49份的聚酯、0.5份~3份的多元醇以及0.01份~0.1份的活性金属化合物混合、熔融,得到熔融料;Mix and melt 96.90 to 99.49 parts by mass of polyester, 0.5 to 3 parts of polyol and 0.01 to 0.1 part of active metal compound to obtain molten material;对所述熔融料进行拉伸。The molten material is stretched.
- 根据权利要求9所述的柔性聚酯膜的制备方法,其特征在于,所述拉伸为双向拉伸。The method for preparing a flexible polyester film according to claim 9, wherein the stretching is biaxial stretching.
- 根据权利要求10所述的柔性聚酯膜的制备方法,其特征在于,所述双向拉伸包括纵向横向异步拉伸和纵向横向同步拉伸中的至少一种。The method for preparing a flexible polyester film according to claim 10, wherein the biaxial stretching includes at least one of longitudinal and transverse asynchronous stretching and longitudinal and transverse synchronous stretching.
- 一种复合集流体,其特征在于,包括:如权利要求1~8任一所述的柔性聚酯膜和位于所述柔性聚酯膜至少一个表面之上的导电层。A composite current collector, characterized by comprising: the flexible polyester film according to any one of claims 1 to 8 and a conductive layer located on at least one surface of the flexible polyester film.
- 一种电池,其特征在于,包括如权利要求12所述的复合集流体。A battery, characterized by comprising the composite current collector according to claim 12.
- 一种电子产品,其特征在于,包括如权利要求13所述的电池。An electronic product, characterized by comprising the battery according to claim 13.
Priority Applications (1)
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