CN113745655A - Preparation method of composite polymer all-solid-state electrolyte based on crosslinked polyurethane - Google Patents
Preparation method of composite polymer all-solid-state electrolyte based on crosslinked polyurethane Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000003792 electrolyte Substances 0.000 title claims abstract description 48
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 11
- 239000007784 solid electrolyte Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011243 crosslinked material Substances 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- SSBFISCARUPWGN-UHFFFAOYSA-N [Li].C(C(=O)F)(=O)F Chemical compound [Li].C(C(=O)F)(=O)F SSBFISCARUPWGN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- NMDVDVNJDCUBDD-UHFFFAOYSA-M lithium;2,2-difluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)F NMDVDVNJDCUBDD-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention provides a preparation method of a composite polymer all-solid-state electrolyte based on cross-linked polyurethane, which comprises the following steps: s1, dissolving long-chain polypropylene glycol and diisocyanate in chloroform to obtain an isocyanate-terminated polyurethane precursor; s2, dissolving 3-isocyanic acid propyl triethoxy silane and short-chain polypropylene glycol in tetrahydrofuran to obtain a polyether silane coupling agent; s3, dissolving polyether silane coupling agent and nano silicon dioxide in deionized water for reaction to obtain a nano cross-linked substance; s4, dissolving the isocyanate-terminated polyurethane precursor and the nano cross-linked polymer in chloroform for reaction to obtain a cross-linked polyurethane compound; and S5, adding lithium salt into the crosslinked polyurethane compound, uniformly mixing, coating on a mold, and drying in vacuum to form a film, thereby obtaining the composite polymer all-solid-state electrolyte. By the method, the electrolyte has the characteristics of high conductivity, excellent mechanical property, safety, stability, interface compatibility, low production cost and the like.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to a preparation method of a composite polymer all-solid-state electrolyte based on cross-linked polyurethane.
Background
Solid-state batteries are widely considered as one of the most promising next-generation new energy sources. Compared with the traditional liquid lithium battery, the solid lithium ion battery has the advantages of high safety performance, long cycle life, capability of matching positive and negative electrode materials with high energy density and the like. Solid electrolytes are mainly classified into inorganic solid electrolytes and polymer all-solid electrolytes, and currently, most studied inorganic solid electrolyte systems mainly include perovskite-type, NASICON-type, LISICON-type, garnet-type lithium oxides, Li2S-P2S5, Li2S-P2S5-MS2(M is Si, Ge, Sn, etc.), and other lithium sulfides, and partially halogen-or boron-containing hybrid compounds. The polymer electrolyte system mainly includes polar polymers such as polymethyl methacrylate (PMMA), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), and polyvinyl chloride (PVC).
Inorganic solid electrolytes generally have relatively high ionic conductivity, but have poor interfacial compatibility with electrodes, and assembled batteries tend to have high interfacial resistance, thereby restricting the commercial application of the inorganic solid electrolytes. The polymer all-solid-state electrolyte has low ionic conductivity, and the mechanical property of the material of the electrolyte can not reach the strength of an inorganic material, so that the safety problems of short circuit, thermal runaway and the like caused by the growth of lithium dendrites on the interface of a battery can not be effectively inhibited. However, the polymer all-solid-state electrolyte has better electrode-electrolyte interface compatibility and excellent processability, thereby having great potential in the application of next-generation lithium secondary batteries with high energy density and long cycle life. In order to break through the technical bottlenecks, the composite solid electrolyte based on the polymer material substrate needs to be designed and prepared, and the inorganic filler is introduced to construct a polymer network cross-linking structure, so that the mechanical property of the composite solid electrolyte is improved, the inhibition capability of the composite solid electrolyte on lithium dendrites and dead lithium is enhanced, and the lithium deposition is optimized. Meanwhile, an ion channel is constructed by utilizing a cross-linking structure of the polymer, so that the lithium ion conductivity of the polymer is improved, and the electrochemical performance and the safety performance of the battery are improved on the whole.
In view of the above, there is a need to design an improved method for preparing a cross-linked polyurethane-based composite polymer all-solid-state electrolyte to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of a composite polymer all-solid-state electrolyte based on cross-linked polyurethane, and the electrolyte prepared by the method has the characteristics of high lithium ion conductivity, excellent mechanical property, higher safety and stability, good interface compatibility, lower production cost, good matching with common electrode materials and the like.
In order to achieve the above object, the present invention provides a method for preparing a crosslinked polyurethane-based composite polymer all-solid-state electrolyte, comprising the steps of:
a preparation method of a composite polymer all-solid-state electrolyte based on crosslinked polyurethane comprises the following steps:
s1, dissolving long-chain polypropylene glycol with the molecular weight being more than or equal to 2000 and diisocyanate in chloroform to obtain an isocyanate-terminated polyurethane precursor;
s2, dissolving 3-isocyanic acid propyl triethoxy silane and short-chain polypropylene glycol with the molecular weight less than or equal to 1500 in tetrahydrofuran for reaction to obtain a polyether silane coupling agent;
s3, dissolving the polyether silane coupling agent obtained in the step S2 and nano silicon dioxide particles in deionized water for reaction, and performing centrifugal treatment to obtain a nano cross-linked substance;
s4, dissolving the isocyanate-terminated polyurethane precursor obtained in the step S1 and the nano cross-linked substance obtained in the step S3 in chloroform, and reacting the terminal isocyanate group with the hydroxyl group of the nano cross-linked substance to obtain a cross-linked polyurethane compound;
s5, filtering the cross-linked polyurethane composite obtained in the step S4, adding lithium salt, uniformly mixing, coating on a mold, and vacuum drying to form a film to obtain the composite polymer all-solid-state electrolyte;
wherein, the reactions of step S1, step S2 and step S4 are all performed under the protection of dry nitrogen or argon.
In a further improvement of the present invention, in step S1, the molar ratio of the long-chain polypropylene glycol to the diisocyanate is 1:2 to 2.3, so that the polyurethane precursor is prepared to have isocyanate groups at both ends.
As a further improvement of the invention, the molecular weight of the long-chain polypropylene glycol is one of 2000, 4000, 6000, 8000, 10000 and 20000.
In a further improvement of the invention, in step S2, the molar ratio of the short-chain polypropylene glycol to the 3-isocyanaton-propyltriethoxysilane is 1: 1-1.1, so that the end group of the obtained polyether silane coupling agent contains hydroxyl.
As a further improvement of the invention, the molecular weight of the short-chain polypropylene glycol is one of 200, 400, 500, 600, 800 and 1000.
In a further improvement of the invention, in step S3, the mass ratio of the nano silica to the polyether silane coupling agent is 1: 8-10.
As a further improvement of the invention, the nano silicon dioxide is porous spherical particles with the diameter of 8-12 nm.
In a further improvement of the present invention, in step S4, the mass ratio of the nano-crosslinked material to the isocyanate-terminated polyurethane precursor is 1:8 to 10.
As a further improvement of the invention, the diisocyanate is one of toluene diisocyanate, diphenylmethane diisocyanate, and polyphenyl polymethylene polyisocyanate.
As a further improvement of the present invention, in step S5, the lithium salt is one of lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium sulfoimide, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroquack, lithium tetrametalate, lithium dioxalate borate, and lithium difluorooxalate penta.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a composite polymer all-solid-state electrolyte based on cross-linked polyurethane, which comprises the steps of dissolving long-chain polypropylene glycol and diisocyanate into chloroform for reaction to obtain an isocyanate-terminated polyurethane precursor; dissolving 3-isocyanic acid propyl triethoxy silane and short-chain polypropylene glycol in tetrahydrofuran for reaction to obtain the polyether silane coupling agent. Dissolving polyether silane coupling agent and nano silicon dioxide in deionized water for reaction to obtain a nano cross-linked substance; dissolving the isocyanate-terminated polyurethane precursor and the nano cross-linked material in chloroform for reaction to obtain a cross-linked polyurethane compound; and filtering the crosslinked polyurethane compound, adding lithium salt, uniformly mixing, coating on a mold, and vacuum drying to form a film, thereby obtaining the composite polymer all-solid-state electrolyte. The method uses the cross-linked polyurethane as the all-solid-state electrolyte material, reduces the use of solvents in the operation process, has less pollution to the environment when applied to the prepared composite polymer all-solid-state electrolyte, and solves the problems of environmental protection and flammability.
2. In the invention, nano silicon dioxide particles are added, and short-chain polypropylene glycol and 3-isocyanic acid are arranged on the surfaces of the nano silicon dioxide particles in the reaction processThe polyether silane coupling agent formed by the acid propyl triethoxy silane can be further crosslinked with the end isocyanate group crosslinked polyurethane formed by the long-chain polypropylene glycol and the diisocyanate to obtain a three-dimensional network structure polyurethane compound, so that the mechanical property of the material is greatly enhanced; the 3D polymer network structure constructed by the nano silicon dioxide particles introduced as the cross-linking points is Li+The fast transportation of the composite provides a good ion channel, so the lithium ion conductivity of the material is improved, the electrolyte integrates the stronger mechanical property of a cross-linked polymer structure and the improvement of the electrochemical property brought by the inorganic nano-particle filler, the electrochemical property and the safety performance of the battery are improved on the whole, and the battery has good practicability.
Drawings
FIG. 1 is a flow chart of the preparation method of the composite polymer all-solid-state electrolyte based on the cross-linked polyurethane.
FIG. 2 is a graph showing the temperature-varying impedance test results of a button Li/CPE500/Li symmetric cell assembled with the composite polymer all-solid-state electrolyte according to the present invention.
FIG. 3 is a graph showing the results of the charge-discharge cycle performance test of a button Li/CPE500/Li symmetrical battery assembled by the composite polymer all-solid-state electrolyte of the present invention.
FIG. 4 is a graph showing the result of the charge/discharge rate performance test of a button Li/CPE500/Li symmetric battery assembled by the composite polymer all-solid-state electrolyte of the present invention.
FIG. 5 is a diagram showing the effect of lighting LED lamp in button Li/CPE500/Li symmetrical battery assembled by the composite polymer all-solid electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The preparation method of the composite polymer all-solid-state electrolyte based on the crosslinked polyurethane comprises the following steps:
s1, dissolving long-chain polypropylene glycol with the molecular weight being more than or equal to 2000 and 2, 4-toluene diisocyanate in chloroform to obtain an isocyanate-terminated polyurethane precursor;
s2, dissolving 3-isocyanic acid propyl triethoxy silane and short-chain polypropylene glycol with the molecular weight less than or equal to 1500 in tetrahydrofuran for reaction to obtain a polyether silane coupling agent;
s3, dissolving the polyether silane coupling agent obtained in the step S2 and nano silicon dioxide in deionized water for reaction at the reaction temperature of 80 ℃, and performing centrifugal treatment to obtain a nano cross-linked substance;
s4, dissolving the isocyanate-terminated polyurethane precursor obtained in the step S1 and the nano cross-linked substance obtained in the step S3 in chloroform for reaction at the temperature of 60 ℃ to obtain a cross-linked polyurethane compound;
s5, filtering the cross-linked polyurethane compound obtained in the step S4, uniformly mixing with lithium salt, coating on a mold, and vacuum drying to form a film to obtain the composite polymer all-solid-state electrolyte;
wherein, the reactions of step S1, step S2 and step S4 are all performed under the protection of dry nitrogen.
Specifically, in step S1, the molar ratio of the long-chain polypropylene glycol to the 2, 4-toluene diisocyanate is 1: 2-2.3, the 2, 4-toluene diisocyanate is dissolved by using an appropriate amount of chloroform as a solvent, the polypropylene glycol is slowly added dropwise to the 2, 4-toluene diisocyanate under the protection of nitrogen, the reaction process is controlled, two molecular equivalents of the 2, 4-toluene diisocyanate can completely react with one molecular equivalent of hydroxyl groups at two ends of PPG, so that the prepared cross-linked polyurethane precursor has isocyanate groups at two ends, wherein the molecular weight of the long-chain polypropylene glycol is one of 2000, 4000, 6000, 8000, 10000 and 20000.
In step S2, the molar ratio of the short-chain polypropylene glycol to the 3-isocyanatopropyltriethoxysilane is 1: 1-1.1, the short-chain polypropylene glycol is dissolved in an appropriate amount of tetrahydrofuran as a solvent, the 3-isocyanatopropyltriethoxysilane is slowly added dropwise to the short-chain polypropylene glycol under the protection of nitrogen, and the reaction process is controlled so that the 3-isocyanatopropyltriethoxysilane reacts only with one terminal hydroxyl group of the short-chain polypropylene glycol, wherein the molecular weight of the short-chain polypropylene glycol is 200, 400, 500, 600, 800 or 1000.
Specifically, in the step S3, the mass ratio of the nano silicon dioxide to the polyether silane coupling agent is 1: 8-10; the nano silicon dioxide is porous spherical particles with the particle size of 8-12 nm; and dispersing the polyether silane coupling agent and the nano silicon dioxide in deionized water for reaction at the reaction temperature of 80 ℃ for more than 48 hours, and then performing centrifugal separation to obtain the nano cross-linked substance.
In step S4, dispersing the nano cross-linked product and the isocyanate-terminated polyurethane precursor by using a proper amount of chloroform as a reaction solvent, mixing the nano cross-linked product and the isocyanate-terminated polyurethane precursor, reacting under the protection of nitrogen at the reaction temperature of 60 ℃ for no more than 10 hours, monitoring by using a thin layer chromatography to obtain a cross-linked polyurethane composite so as to increase the mechanical properties of the material, wherein the mass ratio of the nano cross-linked product to the isocyanate-terminated cross-linked polyurethane precursor is 1: 8-10. In step S5, the lithium salt is one of lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium sulfoimide, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroQuicket, lithium Tetraceryl oxalate, lithium Diaceto borate, and lithium Difluoroacetate.
Example 1
Referring to fig. 1, a flow chart of a method for preparing a cross-linked polyurethane-based composite polymer all-solid-state electrolyte according to the present invention is shown, and the method for preparing a composite polymer all-solid-state electrolyte according to the present embodiment includes the following steps:
s1, dissolving polypropylene glycol (PPG) and 2, 4-Toluene Diisocyanate (TDI) in chloroform to react to obtain an isocyanate-terminated polyurethane precursor;
in step S1 of this embodiment, long-chain polypropylene glycol (molecular weight 2000, abbreviated as PPG2000) and TDI are weighed according to a molar ratio of 1: 2-2.3, then a certain amount of chloroform is selected as a solvent to dissolve TDI, PPG2000 is slowly added dropwise to TDI under the protection of nitrogen, and the reaction process is controlled so that two molecular equivalents of TDI can completely react with one molecular equivalent of hydroxyl groups at two ends of PPG2000, thereby obtaining an isocyanate-terminated polyurethane precursor (TDI-PPG 2000-TDI).
S2, dissolving 3-isocyanic acid propyl triethoxy silane (IPTS) and polypropylene glycol (PPG) in tetrahydrofuran to react to obtain a polyether silane coupling agent;
in step S2 of this embodiment, short-chain PPG (molecular weight 500, abbreviated as PPG500) and IPTS are weighed according to a molar ratio of 1: 1-1.1, then a certain amount of chloroform is selected as a solvent to dissolve the PPG500, the IPTS is slowly added dropwise to the PPG500 under the protection of nitrogen, the reaction process is controlled, and the IPTS reacts with only one hydroxyl group of the PPG500, so as to obtain the polyether silane coupling agent (PPG 500-IPTS).
S3, dispersing the polyether silane coupling agent and the nano silicon dioxide in deionized water for reaction, and centrifugally separating to obtain the nano cross-linked substance.
In step S3 of this embodiment, nanometer silica particles and PPG500-IPTS are weighed according to a mass ratio of 1: 8-10, then a certain amount of deionized water is selected as a solvent to dissolve PPG500-IPTS and nanometer silica particles, the mixture is heated at a reaction temperature of 80 ℃ for a reaction time of more than 48 hours, and then centrifugal separation is performed to obtain a reaction product, namely, a nanometer cross-linked product (SiO) is obtained2@PPG500-IPTS)。
S4, dispersing the isocyanate-terminated polyurethane precursor and the nano cross-linked substance in chloroform for reaction to obtain the cross-linked polyurethane composite.
In step S4 of the present embodiment, SiO is weighed in a mass ratio of 1:8 to 102@ PPG500-IPTS and TDI-PPG2000-TDI, then selecting a certain amount of chloroform as solvent to dissolve TDI-PPG2000-TDI and disperse SiO2@ PPG500-IPTS, heating the mixture at a reaction temperature of 60 ℃,the reaction time is more than 48 hours and is not more than 10 hours, and the cross-linked polyurethane compound is obtained by monitoring through thin layer chromatography.
S5, filtering the cross-linked polyurethane composite, adding lithium salt into the cross-linked polyurethane composite, coating the cross-linked polyurethane composite on a polytetrafluoroethylene mold, and drying the mixture in vacuum to form a membrane, thereby obtaining the composite polymer all-solid-state electrolyte membrane (CPE 500).
In step S5 of this example, the electrolyte slurry was filtered through a 100-mesh filter screen, then lithium bis (trifluoromethanesulfonylimide) (LiTFSI) was added and mixed uniformly, and then coated on a teflon mold with a dropper, and the polytetrafluoroethylene mold was left to stand in a vacuum drying oven for 24 hours or more until the composite polymer all-solid electrolyte membrane was dried and molded.
Example 2
Example 2 the composite polymer all-solid-state electrolyte obtained in example 1 was assembled to prepare a button-type symmetrical battery (Li/CPE 500/Li).
Referring to fig. 2, fig. 2 shows a temperature-varying impedance test of a button Li/CPE500/Li symmetric cell according to embodiment 2 of the present invention, in which an Electrochemical Impedance Spectroscopy (EIS) test is performed on the assembled Li/CPE500/Li symmetric cell at a sweep rate of 1mV/s and a frequency of 10-3-105Hz, and ac impedances of the cell are respectively tested at different temperatures of 20 ℃, 40 ℃ and 60 ℃. As can be seen from fig. 2, the impedance of the EIS spectrum of the lithium button cell battery assembled from CPE500 films in the high-and medium-frequency regions is represented by two connected semicircles, the intercept of the first semicircle with the solid axis represents the interfacial impedance of the battery, and the intercept of the second semicircle with the solid axis represents the charge transfer impedance of the battery. The interface resistance and charge transfer resistance of the Li/CPE500/Li battery both decrease significantly with increasing temperature. Wherein the interface impedance of the battery is 3000 omega at 20 ℃, 1000 omega at 40 ℃ and 300 omega at 60 ℃; the charge transfer resistance of the battery was 1000 Ω at 20 ℃, 500 Ω at 40 ℃ and 50 Ω at 60 ℃. The result shows that the micro cross-linking structure formed by the composite polymer all-solid-state electrolyte is beneficial to lithium ion migration, the electrolyte has good contact with the interface of a positive electrode and a negative electrode, particularly a lithium metal negative electrode, the solid-solid interface has high compatibility, and the lithium ion conductivity of the electrolyte is greatly improved.
Referring to FIG. 3, FIG. 3 shows the Li-clasps of example 2The result chart of the charge-discharge cycle performance test of the/CPE 500/Li symmetrical battery under the conditions of 0.1C multiplying power and 60 ℃. The initial voltage is 3.3V based on the discharge platform of the active material LFP in the positive electrode, and the specific discharge capacity of the battery at 0.1C is 150mAhg-1Stabilization continued for 100 cycles. Even if the capacity is obviously attenuated by a small amplitude from the 90 th circle, the specific discharge capacity is still maintained at 141mAhg-1The circulation result of CPE500 prepared by the invention is stable at 0.1C multiplying power. The result fully shows that the electrolyte membrane prepared by the method keeps better electrochemical stability and interface compatibility in the circulating process, and meanwhile, the excellent mechanical property of the electrolyte membrane can better inhibit the growth of lithium dendrites, avoid the thermal runaway risk caused by micro short circuit of a battery, optimize lithium deposition and reduce the generation of dead lithium.
Referring to fig. 4, fig. 4 is a graph showing the results of the charge/discharge rate performance test of the Li/CPE500/Li button cell battery of example 2. LiCPE500/Li symmetrical batteries are charged and discharged at 60 ℃ at the multiplying power of 0.2C, 0.5C, 1C and 2C, and the specific discharge capacity of the batteries subjected to 5 cycles is evaluated under each multiplying power condition. The results showed that the specific discharge capacities at 0.2C, 0.5C, 1C and 2C were 154mAhg, respectively-1、143mAhg-1、135mAhg-1And 128mAhg-1. The result shows that the Li/CPE500/Li symmetrical battery assembled by the CPE500 prepared by the invention can tolerate 2C high-rate charge and discharge, maintains 75% of theoretical capacity retention rate, and can reversibly recover the specific discharge capacity after the rate is recovered to 0.2C, thereby showing excellent high-rate performance and good battery cycling stability.
Referring to fig. 5, fig. 5 is a practical application experiment of the button cell Li/CPE500/Li symmetric battery of example 2, and the assembled button cell can successfully light up the LED lamp, which proves that the electrolyte has a greater application potential in the research of lithium metal negative electrode batteries.
In summary, the preparation method of the composite polymer all-solid-state electrolyte based on the cross-linked polyurethane provided by the invention comprises the steps of dissolving long-chain polypropylene glycol and diisocyanate into chloroform for reaction to obtain an isocyanate-terminated polyurethane precursor; dissolving 3-isocyanatopropyl triethoxysilane and short-chain polypropylene glycol in tetrahydrofuran for reaction to obtain a polyether silane coupling agent; dissolving polyether silane coupling agent and nano silicon dioxide in deionized water for reaction to obtain a nano cross-linked substance; dissolving the isocyanate-terminated polyurethane precursor and the nano cross-linked material in chloroform for reaction to obtain a cross-linked polyurethane compound; and filtering the crosslinked polyurethane compound, adding lithium salt, uniformly mixing, coating on a mold, and vacuum drying to form a film, thereby obtaining the composite polymer all-solid-state electrolyte. The composite polymer all-solid-state electrolyte integrates the stronger mechanical property of a three-dimensional cross-linked polymer structure and the improvement of the electrochemical property brought by the inorganic nano-particle filler, improves the electrochemical property and the safety performance of the battery on the whole, and has good practicability.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a composite polymer all-solid-state electrolyte based on crosslinked polyurethane is characterized by comprising the following steps:
s1, dissolving long-chain polypropylene glycol with the molecular weight being more than or equal to 2000 and diisocyanate in chloroform to obtain an isocyanate-terminated polyurethane precursor;
s2, dissolving 3-isocyanic acid propyl triethoxy silane and short-chain polypropylene glycol with the molecular weight less than or equal to 1500 in tetrahydrofuran for reaction to obtain a polyether silane coupling agent;
s3, dissolving the polyether silane coupling agent obtained in the step S2 and nano silicon dioxide particles in deionized water for reaction, and performing centrifugal treatment to obtain a nano cross-linked substance;
s4, dissolving the isocyanate-terminated polyurethane precursor obtained in the step S1 and the nano cross-linked substance obtained in the step S3 in chloroform, and reacting the terminal isocyanate group with the hydroxyl group of the nano cross-linked substance to obtain a cross-linked polyurethane compound;
s5, filtering the cross-linked polyurethane composite obtained in the step S4, adding lithium salt, uniformly mixing, coating on a mold, and vacuum drying to form a film to obtain the composite polymer all-solid-state electrolyte;
wherein, the reactions of step S1, step S2 and step S4 are all performed under the protection of dry nitrogen or argon.
2. The method of claim 1, wherein in step S1, the molar ratio of the long-chain polypropylene glycol to the diisocyanate is 1: 2-2.3, so that the polyurethane precursor is prepared to have isocyanate groups at both ends.
3. The method of claim 2, wherein the long-chain polypropylene glycol has a molecular weight of one of 2000, 4000, 6000, 8000, 10000, 20000.
4. The method for preparing the crosslinked polyurethane based composite polymer all-solid-state electrolyte according to claim 1, wherein in step S2, the molar ratio of the short-chain polypropylene glycol to the 3-isocyanatopropyltriethoxysilane is 1: 1-1.1, so that the obtained polyether silane coupling agent end groups contain hydroxyl groups.
5. The method for preparing the crosslinked polyurethane-based composite polymer all-solid-state electrolyte according to claim 4, wherein the short-chain polypropylene glycol has a molecular weight of one of 200, 400, 500, 600, 800, and 1000.
6. The preparation method of the crosslinked polyurethane based composite polymer all-solid-state electrolyte according to claim 1, wherein in the step S3, the mass ratio of the nano silica to the polyether silane coupling agent is 1: 8-10.
7. The preparation method of the crosslinked polyurethane based composite polymer all-solid-state electrolyte according to claim 6, wherein the nano-silica is porous spherical particles with a diameter of 8-12 nm.
8. The method for preparing the crosslinked polyurethane-based composite polymer all-solid-state electrolyte according to claim 1, wherein in step S4, the mass ratio of the nanocrosslinker to the isocyanate-terminated polyurethane precursor is 1:8 to 10.
9. The method for preparing the crosslinked polyurethane-based composite polymer all-solid-state electrolyte according to claim 2, wherein the diisocyanate is one of toluene diisocyanate and diphenylmethane diisocyanate.
10. The method of claim 1, wherein in step S5, the lithium salt is one of lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium sulfoimide, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroquacklate, lithium tetracchastetate, lithium dioxalate borate, and lithium difluorooxalatepenate.
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| CN108470937A (en) * | 2018-03-29 | 2018-08-31 | 武汉新能源研究院有限公司 | A kind of synthetic method and lithium ion battery of crosslinking nano composite polymer electrolyte |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN111769320A (en) * | 2019-04-02 | 2020-10-13 | 深圳格林德能源集团有限公司 | Solid polymer electrolyte membrane and preparation method thereof |
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| CN108470937A (en) * | 2018-03-29 | 2018-08-31 | 武汉新能源研究院有限公司 | A kind of synthetic method and lithium ion battery of crosslinking nano composite polymer electrolyte |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN111769320A (en) * | 2019-04-02 | 2020-10-13 | 深圳格林德能源集团有限公司 | Solid polymer electrolyte membrane and preparation method thereof |
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