CN113241476A - Asymmetric-structure polymer-based solid electrolyte membrane, preparation method and application thereof, and polymer-based solid lithium battery - Google Patents
Asymmetric-structure polymer-based solid electrolyte membrane, preparation method and application thereof, and polymer-based solid lithium battery Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007787 solid Substances 0.000 title claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 49
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 48
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 42
- -1 polyoxyethylene Polymers 0.000 claims abstract description 38
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 25
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000011268 mixed slurry Substances 0.000 claims description 49
- 239000003960 organic solvent Substances 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 12
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 229940014800 succinic anhydride Drugs 0.000 claims description 6
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 claims description 6
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 4
- FEEHEHLHSCDMJK-UHFFFAOYSA-N 2,2-bis(prop-2-enyl)propanedinitrile Chemical compound C=CCC(C#N)(C#N)CC=C FEEHEHLHSCDMJK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 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
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000003792 electrolyte Substances 0.000 abstract description 21
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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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
- H01M10/056—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
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
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- Dispersion Chemistry (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention belongs to the technical field of solid electrolytes, and particularly relates to an asymmetric-structure polymer-based solid electrolyte membrane, a preparation method and application thereof, and a polymer-based solid lithium battery. In the invention, short-chain unsaturated alkyl is introduced into the base membrane by the polyoxyethylene, the polyethylene glycol diacrylate and the polyethylene glycol acrylate, which is beneficial to reducing the crystallinity of macromolecules of the base membrane polymer and improving the ionic conductivity of the base membrane; the modified compound is beneficial to forming a top film with oxidation resistance and high rapid ion migration capacity on the surface of the base film, and the working stability of the polymer-based electrolyte film under the condition of high working voltage is improved; in addition, the base membrane and the top membrane are crosslinked into a bond by UV curing twice, which is beneficial to reducing the interface impedance, improving the physical stability of the interface and improving the high-voltage cycling stability of the polymer-based solid electrolyte membrane. The embodiment shows that the asymmetric-structure polymer-based solid electrolyte membrane prepared by the method provided by the invention has high conductivity and stable high-pressure cycle performance.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes, and particularly relates to an asymmetric-structure polymer-based solid electrolyte membrane, a preparation method and application thereof, and a polymer-based solid lithium battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and no pollution, and is widely applied to a plurality of fields. In the high-voltage lithium ion battery, the non-aqueous electrolyte adopted by the traditional lithium ion battery is easily decomposed under high voltage, so that the use of the high-voltage lithium ion battery is greatly limited; the commercial organic electrolyte is difficult to maintain electrochemical stability under the working voltage higher than 4.3V, and in the high-voltage charging process, the commercial organic electrolyte is easily subjected to the catalytic action of transition metal ions at an interface contacting with the surface of an electrode and is continuously decomposed to form an excessively thick passivation layer, so that the performance of the battery is greatly reduced.
The polymer-based electrolyte has higher safety, excellent appearance design flexibility and higher mass ratio energy, and can effectively solve the problems brought by the use of the traditional electrolyte. However, the current polymer-based electrolyte has a plurality of problems, such as the problems that the PEO-based solid electrolyte has low ionic conductivity at room temperature and cannot adapt to the working voltage of 4.0V or above; the conventional double-layer electrolyte membrane has obvious interfaces, high interface impedance and poor interface stability.
Disclosure of Invention
In view of the above, the present invention provides an asymmetric polymer-based solid electrolyte membrane and a preparation method thereof, and the asymmetric polymer-based solid electrolyte membrane prepared by the preparation method provided by the present invention has no obvious interface delamination, has the characteristics of high room temperature ionic conductivity and low interface impedance, and is beneficial to improving the high voltage cycling stability of a lithium ion battery.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of an asymmetric-structure polymer-based solid electrolyte membrane, which comprises the following steps:
mixing polyoxyethylene, polyethylene glycol diacrylate, polyethylene glycol acrylate, a first photoinitiator, lithium salt and a first organic solvent, coating the obtained first mixed slurry, and performing first UV curing to obtain a base film;
mixing a modified compound, a second photoinitiator and a second organic solvent to obtain a second mixed slurry, wherein the modified compound is an anhydride, a cyano compound or a sulfone compound containing unsaturated double bonds;
and coating the second mixed slurry on the surface of the base film, and sequentially carrying out second UV curing and drying to obtain the asymmetric-structure polymer-based solid electrolyte film with the base film-top film structure.
Preferably, the molar ratio of the polyoxyethylene to the polyethylene glycol diacrylate to the polyethylene glycol acrylate is (0.1-0.5): (0.25-0.45): (0.25-0.45).
Preferably, the lithium salt is one or more of lithium bistrifluoromethylsulfonyl imide, lithium bistrifluoromethylsulfonyl amide, lithium methylsulfonate, lithium perchlorate and lithium hexafluorophosphate.
Preferably, the concentration of the lithium salt in the first mixed slurry is 20 to 50 wt.%.
Preferably, the first photoinitiator and the second photoinitiator are independently one or more of alpha-hydroxyisobutyrophenone, 1-hydroxycyclohexylphenone, 2-hydroxy-2-methylpropiophenone, and ethyl 4-dimethylaminobenzoate.
Preferably, the unsaturated double bond-containing anhydride comprises maleic anhydride and/or succinic anhydride; the cyano compound comprises one or more of succinonitrile, succinonitrile and 4, 4-dicyano-1, 6-heptadiene; the sulfone compound comprises 3-sulfolene and/or 2, 3-dihydro-1, 1-dioxythiophene.
Preferably, the concentration of the modifying compound in the second mixed slurry is 1-5 mol/L.
The invention also provides the asymmetric structure polymer-based solid electrolyte membrane prepared by the preparation method of the technical scheme, which comprises a cross-linked base membrane and a top membrane.
The invention also provides application of the polymer-based solid electrolyte membrane with the asymmetric structure in the technical scheme as a solid electrolyte in a polymer-based solid lithium battery.
The invention also provides a polymer-based solid-state lithium battery, which comprises a positive electrode, a solid-state electrolyte and a negative electrode, wherein the solid-state electrolyte is the polymer-based solid-state electrolyte membrane with the asymmetric structure in the technical scheme; the negative electrode is in contact with a base film of the polymer-based solid electrolyte membrane with the asymmetric structure, and the positive electrode is in contact with a top film of the polymer-based solid electrolyte membrane with the asymmetric structure.
The invention provides a preparation method of an asymmetric-structure polymer-based solid electrolyte membrane, which comprises the following steps: mixing polyoxyethylene, polyethylene glycol diacrylate, polyethylene glycol acrylate, a first photoinitiator, lithium salt and a first organic solvent, coating the obtained first mixed slurry, and performing first UV curing to obtain a base membrane; mixing a modified compound, a second photoinitiator and a second organic solvent to obtain a second mixed slurry, wherein the modified compound is an anhydride, a cyano compound or a sulfone compound containing unsaturated double bonds; and coating the second mixed slurry on the surface of the base film, and sequentially carrying out second UV curing and drying to obtain the asymmetric-structure polymer-based solid electrolyte film with the base film-top film structure.
In the invention, short-chain unsaturated hydrocarbon is introduced into the base membrane by the polyoxyethylene, the polyethylene glycol diacrylate and the polyethylene glycol acrylate, which is beneficial to reducing the crystallinity of macromolecules of the base membrane polymer and improving the ionic conductivity of the base membrane; the unsaturated double bond-containing anhydride, cyano compound or sulfone compound is oxidation-resistant and has a high dielectric constant functional group, so that a top film which is oxidation-resistant and has rapid ion migration capability is formed on the surface of the base film, the problems of poor oxidation resistance and low ion conductivity at room temperature of the polymer-based electrolyte film are solved, and the working stability of the polymer-based electrolyte film under the condition of higher working voltage is improved; in addition, the base membrane and the top membrane are crosslinked into a bond through UV curing, so that interface layering is weakened, interface impedance is reduced, physical stability of the interface is improved, and high voltage circulation stability of the polymer-based solid electrolyte membrane is improved.
The test results of the examples show that the polymer-based solid electrolyte membrane with the asymmetric structure prepared by the preparation method provided by the invention has no obvious delamination of the base membrane and the top membrane, and the interfacial delamination is weakened; good ionic conductivity was shown at different temperatures and the interfacial resistance was low. The battery using the asymmetric polymer-based solid electrolyte membrane as the electrolyte can stably circulate at 2.8-4.3V, and has good high-voltage circulation stability.
Drawings
Fig. 1 is an SEM image of the surface of an asymmetric-structure polymer-based solid electrolyte membrane prepared in example 1;
FIG. 2 is an SEM photograph of a cross-section of an asymmetrically structured polymer-based solid electrolyte membrane prepared in example 1;
FIG. 3 is a graph showing the change in conductivity with temperature of the asymmetrically structured polymer-based solid electrolyte membrane prepared in example 1;
FIG. 4 is an impedance diagram of an asymmetrically structured polymer-based solid electrolyte membrane prepared in example 1;
fig. 5 is a schematic diagram of the battery structure of application example 1;
FIG. 6 is a charge and discharge long cycle test chart of the asymmetric polymer-based solid electrolyte membrane obtained in application example 1;
FIG. 7 is a charge-discharge long cycle test chart of the asymmetric-structured polymer-based solid electrolyte membrane obtained in application example 3;
fig. 8 is a charge-discharge long cycle test chart of the asymmetric-structure polymer-based solid electrolyte membrane obtained in application example 5.
Detailed Description
The invention provides a preparation method of an asymmetric-structure polymer-based solid electrolyte membrane, which comprises the following steps:
mixing polyoxyethylene, polyethylene glycol diacrylate, polyethylene glycol acrylate, a first photoinitiator, lithium salt and a first organic solvent, coating the obtained first mixed slurry, and performing first UV curing to obtain a base film;
mixing a modified compound, a second photoinitiator and a second organic solvent to obtain a second mixed slurry, wherein the modified compound is an anhydride, a cyano compound or a sulfone compound containing unsaturated double bonds;
and coating the second mixed slurry on the surface of the base film, and sequentially carrying out second UV curing and drying to obtain the asymmetric-structure polymer-based solid electrolyte film with the base film-top film structure.
In the present invention, the components are commercially available products well known to those skilled in the art, unless otherwise specified.
According to the invention, polyoxyethylene, polyethylene glycol diacrylate, polyethylene glycol acrylate, a first photoinitiator, lithium salt and a first organic solvent are mixed, and the obtained first mixed slurry is coated and then subjected to first UV curing to obtain the base film.
In the present invention, the molar ratio of the polyoxyethylene, the polyethylene glycol diacrylate and the polyethylene glycol acrylate is preferably (0.1 to 0.5): (0.25-0.45): (0.25 to 0.45), more preferably (0.2 to 0.4): (0.3-0.4): (0.3-0.4). In the present invention, the polyoxyethylene preferably has a molar mass of 105～107g/mol, more preferably 1.5X 105～9×106g/mol. In the invention, the molar mass of the polyethylene glycol diacrylate is preferably 200-1000 g/mol, and more preferably 300-900 g/mol; in the invention, the molar mass of the polyethylene glycol acrylate is preferably 550-750 g/mol, and more preferably 570-730 g/mol.
In the present invention, the first photoinitiator is preferably one or more of α -hydroxyisobutyrophenone, 1-hydroxycyclohexyl phenone, 2-hydroxy-2-methyl propiophenone, and ethyl 4-dimethylaminobenzoate. In the present invention, the first photoinitiator is preferably polyethylene oxide, polyethylene glycol diacrylate, polyethylene glycol acrylate, the first photoinitiator and the lithium salt, and the total mass of the first photoinitiator and the lithium salt is 0.1 to 0.5%, and more preferably 0.2 to 0.4%.
In the inventionIn (3), the lithium salt is preferably lithium bistrifluoromethylsulfonylimide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), lithium bistrifluoromethylsulfonylamide (LiTFSA), lithium methylsulfonate (LiCH)3SO3) Lithium perchlorate (LiClO)4) And lithium hexafluorophosphate (LiPF)6) One or more of (a). In the present invention, the concentration of the lithium salt in the first mixed slurry is preferably 20 to 50 wt.%, more preferably 25 to 45 wt.%. In the invention, the mass ratio of the total mass of the polyoxyethylene, the polyethylene glycol diacrylate and the polyethylene glycol acrylate to the lithium salt is preferably (5-10): (2-3), more preferably (6-9): (2-2.5).
In the present invention, the first organic solvent is preferably one or more of acetonitrile, tetrahydrofuran, N-dimethylformamide, and N-methylpyrrolidone.
In the present invention, the mixing of the polyethylene oxide, the polyethylene glycol diacrylate, the polyethylene glycol acrylate, the first photoinitiator, the lithium salt and the first organic solvent is preferably performed at room temperature, specifically, 18 to 40 ℃. In the invention, the mixing of the polyethylene oxide, the polyethylene glycol diacrylate, the polyethylene glycol acrylate, the first photoinitiator, the lithium salt and the first organic solvent is preferably to mix the polyethylene oxide, the polyethylene glycol diacrylate, the polyethylene glycol acrylate and the first organic solvent, and after the polyethylene oxide, the polyethylene glycol diacrylate and the polyethylene glycol acrylate are fully dissolved in the first organic solvent, the first photoinitiator and the lithium salt are added into the obtained mixed system and stirred; the stirring speed is not particularly limited in the present invention, and the uniform first mixed slurry can be obtained.
After the first mixed slurry is obtained, the first mixed slurry is coated with a film and then subjected to first UV curing to obtain a base film.
The coating film of the present invention is not particularly limited, and a coating film known to those skilled in the art may be used. In the present invention, the coating film is preferably formed by coating the first mixed slurry on a substrate; in an embodiment of the invention, the substrate is preferably a teflon plate. In the inventionThe thickness of the coating film is based on ensuring the thickness of the base film. In the invention, the light energy gathering amount in the first UV curing is preferably 200-300 mJ/cm2More preferably 220 to 280mJ/cm2And is preferably 230 to 270mJ/cm2. According to the invention, the curing and film forming of the base film are promoted through the first UV curing. In the present invention, the thickness of the base film is preferably 50 to 120 μm, and more preferably 70 to 100 μm. The coating amount of the first mixed slurry in the coating film is not particularly limited, so that the thickness of the base film can be ensured.
In the present invention, the polyethylene oxide, polyethylene glycol diacrylate, polyethylene glycol acrylate undergo polymer polymerization under the conditions of photoinitiator and UV.
According to the invention, a modified compound, a second photoinitiator and a second organic solvent are mixed to obtain a second mixed slurry.
In the present invention, the modifying compound is an unsaturated double bond-containing acid anhydride, cyano compound or sulfone compound. In the present invention, the unsaturated double bond-containing acid anhydride preferably includes maleic anhydride and/or succinic anhydride. In the present invention, the cyano compound preferably includes one or more of succinonitrile, succinonitrile and 4, 4-dicyano-1, 6-heptadiene. In the present invention, the sulfone-based compound preferably includes 3-sulfolene and/or 2, 3-dihydro-1, 1-dioxythiophene. In the invention, the concentration of the modified compound in the second mixed slurry is preferably 1-5 mol/L, and more preferably 1.5-4.5 mol/L.
In the present invention, the second photoinitiator is preferably one or more of α -hydroxyisobutyrophenone, 1-hydroxycyclohexyl phenone, 2-hydroxy-2-methyl propiophenone, and ethyl 4-dimethylaminobenzoate. In the present invention, the mass of the second photoinitiator is preferably 0.5 to 1%, more preferably 0.6 to 0.9% of the mass of the modifying compound.
In the present invention, the second organic solvent is preferably one or more of acetonitrile, tetrahydrofuran, N-dimethylformamide, and N-methylpyrrolidone.
The mixing of the modified compound, the second photoinitiator and the second organic solvent is preferably performed at room temperature, specifically, 18-40 ℃. In the present invention, the mixing of the modified compound, the second photoinitiator and the second organic solvent is preferably performed by mixing the modified compound and the second initiator, dissolving the modified compound in the second organic solvent, adding the second photoinitiator to the obtained mixed solution, and stirring; the stirring is not particularly limited in the present invention, and the second mixed slurry can be uniformly obtained.
After the second mixed slurry is obtained, the surface of the base membrane is coated with the second mixed slurry, and second UV curing and drying are sequentially carried out to obtain the polymer-based solid electrolyte membrane with the asymmetric structure of the base membrane-top membrane structure.
After the second mixed slurry is obtained, the second mixed slurry is coated on the surface of the base membrane, second UV curing is sequentially carried out, a top membrane is formed on the surface of the base membrane, and then drying is carried out, so that the polymer-based solid electrolyte membrane with the asymmetric structure of the base membrane-top membrane structure is obtained.
The coating is not particularly limited in the present invention, and may be any coating known to those skilled in the art, specifically, knife coating. The coating amount of the second mixed slurry in the coating is not particularly limited, so that the thickness of the top film can be ensured. In the invention, the light polymerization energy in the second UV curing is preferably 400-700 mJ/cm2More preferably 430 to 670mJ/cm2And is preferably 450 to 650mJ/cm2. According to the invention, the top film is promoted to be cured into a film through the second UV curing, and meanwhile, the base film and the top film are crosslinked into a bond, so that the interface layering is weakened, the interface impedance is reduced, the physical stability of the interface is improved, and further, the high-voltage cycle stability of the polymer-based solid electrolyte film is improved. In the present invention, the thickness of the top film is preferably 10 to 50 μm, and more preferably 10 to 30 μm.
In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 85-115 ℃; the time is preferably 8-12 h. In the present invention, the drying is preferably performed under vacuum; the vacuum degree of the vacuum is preferably-0.08 to-0.1 MPa, and more preferably-0.085 to-0.095 MPa. In the present invention, the drying apparatus is preferably a vacuum oven. The first organic solvent and the second organic solvent are removed by drying.
After drying, the present invention preferably removes the substrate used in the preparation of the base film.
The invention also provides the asymmetric structure polymer-based solid electrolyte membrane prepared by the preparation method of the technical scheme, which comprises a cross-linked base membrane and a top membrane. In the present invention, the thickness of the base film is preferably 50 to 120 μm, and more preferably 70 to 100 μm. In the present invention, the thickness of the top film is preferably 10 to 50 μm, and more preferably 10 to 30 μm. In the invention, the thickness of the asymmetric polymer-based solid electrolyte membrane is preferably 80-150 μm, and more preferably 90-140 μm.
The invention also provides application of the polymer-based solid electrolyte membrane with the asymmetric structure in the technical scheme as a solid electrolyte in a polymer-based solid lithium battery.
The invention also provides a polymer-based solid-state lithium battery, which comprises a positive electrode, a solid-state electrolyte and a negative electrode, wherein the solid-state electrolyte is the polymer-based solid-state electrolyte membrane with the asymmetric structure in the technical scheme; the negative electrode is in contact with a base film of the polymer-based solid electrolyte membrane with the asymmetric structure, and the positive electrode is in contact with a top film of the polymer-based solid electrolyte membrane with the asymmetric structure. The positive electrode and the negative electrode of the polymer-based solid-state lithium battery are not particularly limited in the invention, and the positive electrode and the negative electrode of the polymer-based solid-state lithium battery well known to those skilled in the art can be adopted.
In order to further illustrate the present invention, the following examples are provided to describe the polymer-based solid electrolyte membrane with asymmetric structure, the preparation method and application thereof, and the polymer-based solid lithium battery in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
1g of polyethylene oxide (molar mass 3X 10)5g/mol), 1g of polyethylene glycol diacrylate (the molar mass is 1000g/mol) and 0.95g of polyethylene glycol acrylate (the molar mass is 950g/mol) are dissolved in 6mL of N-methyl pyrrolidone serving as a first organic solvent, then 0.04g of first photoinitiator alpha-hydroxyisobutyrophenone and 0.96g of lithium salt LiTFSI are added into the obtained mixed system, the mixture is stirred for 12 hours at room temperature, the obtained first mixed slurry is coated on a polytetrafluoroethylene plate, then first UV curing is carried out under ultraviolet light, and the photopolymerization energy in the first UV curing is 200mJ/cm2Obtaining a base film with the thickness of 100 mu m;
dissolving 0.98g of maleic anhydride in 2mL of a second organic solvent N, N-dimethylacetamide to obtain a maleic anhydride solution of 5mol/L, adding 1mg of alpha-hydroxyisobutyrophenone into the obtained maleic anhydride solution, and stirring at room temperature until the mixture is uniform to obtain a second mixed slurry;
coating the obtained second mixed slurry on the surface of the obtained base film by scraping, and carrying out second UV curing under ultraviolet light, wherein the light polymerization energy in the second UV curing is 500mJ/cm2Forming a top film with the thickness of 30 mu m on the surface of the base film, and then placing the top film in a vacuum oven with the temperature of 80 ℃ and the vacuum degree of-0.08 MPa for drying for 12h to obtain the polymer-based solid electrolyte film with the asymmetric structure of the base film-top film structure.
The surface of the asymmetrically structured polymer-based solid electrolyte membrane obtained in example 1 was subjected to an electron scanning test, and the obtained SEM image is shown in fig. 1. As can be seen from fig. 1, the surface of the obtained asymmetric-structure polymer-based solid electrolyte membrane is rough but has no pore morphology, and the continuous wrinkle state presents a hill-like morphology, which is formed due to the crosslinked structure in the polymer; in addition, the highly compact micro-morphology indicates that the electrolyte membrane is uniform and without significant phase separation.
The section of the asymmetrically structured polymer-based solid electrolyte membrane obtained in example 1 was subjected to an electron scanning test, and the SEM image thereof is shown in FIG. 2. As can be seen from FIG. 2, the obtained asymmetric-structure polymer-based solid electrolyte membrane has no obvious delamination of the base membrane and the top membrane, which indicates that the base membrane and the top membrane are crosslinked into bonds, and the interfacial delamination is weakened.
The conductivity of the asymmetric-structure polymer-based solid electrolyte membrane obtained in example 1 was measured under different temperature conditions, and the graph of the obtained conductivity as a function of temperature is shown in fig. 3. As can be seen from fig. 3, the asymmetric polymer-based solid electrolyte membrane provided in this example exhibits good ionic conductivity at different temperatures, and the ionic conductivity at room temperature can reach 3.67 × 10-4S·cm-1。
The impedance at the interface of the button cell assembled from the asymmetric polymer-based solid electrolyte membrane obtained in example 1 was measured at room temperature and the impedance plot is shown in fig. 4. As can be seen from fig. 4, the button cell assembled from the asymmetrically structured polymer-based solid electrolyte membrane provided by the present example exhibited good interfacial properties.
Application example 1
Adopts ternary material LiN0.8C0.2M0.2O2The asymmetric polymer-based solid electrolyte membrane obtained in example 1 was used as an electrolyte for cell assembly, the structure of the cell is shown in fig. 5, the negative electrode of the cell was in contact with the base membrane of the asymmetric polymer-based solid electrolyte membrane, and the positive electrode of the cell was in contact with the top membrane of the asymmetric polymer-based solid electrolyte membrane.
The battery obtained in example 1 was subjected to a charge-discharge long cycle test, and the charge-discharge cycle test chart obtained is shown in fig. 6. As can be seen from FIG. 6, the button cell assembled by the polymer-based solid electrolyte membrane with the asymmetric structure shows excellent cycle performance at room temperature, and the specific discharge capacity of the first loop can reach 170mAh g-1。
Example 2
1g of polyethylene oxide (molar mass 1X 10)5g/mol), 1g of polyethylene glycol diacrylate (molar mass of 1000g/mol), 0.95g of polyethylene glycol diacrylate (molar mass of 950g/mol) were dissolved in 6mL of N-methylpyrrolidone, a first organic solvent, and then 0.04g of a first photoinitiator, alpha-hydroxyisobutyrophenone, and 0.96g of lithium salt, LiTFSI, were added to the resulting mixed system at room temperatureStirring for 12h, coating the obtained first mixed slurry on a polytetrafluoroethylene plate, and then carrying out first UV curing under ultraviolet light, wherein the light polymerization energy in the first UV curing is 260mJ/cm2Obtaining a basal membrane with the thickness of 90 mu m;
dissolving 1g of succinic anhydride in 2mL of a second organic solvent N, N-dimethylacetamide to obtain a succinic anhydride solution of 5mol/L, adding 1mg of alpha-hydroxyisobutyrophenone into the succinic anhydride solution, and stirring at room temperature until the mixture is uniform to obtain a second mixed slurry;
coating the obtained second mixed slurry on the surface of the obtained base film by scraping, and carrying out second UV curing under ultraviolet light, wherein the light polymerization energy in the second UV curing is 600mJ/cm2Forming a top film with the thickness of 30 mu m on the surface of the base film, and then placing the top film in a vacuum oven with the temperature of 80 ℃ and the vacuum degree of-0.08 MPa for drying for 12h to obtain the polymer-based solid electrolyte film with the asymmetric structure of the base film-top film structure.
Application example 2
The asymmetric polymer-based solid electrolyte membrane obtained in example 2 was used as an electrolyte, and the remaining technical means were the same as in application example 1, to obtain a battery.
Example 3
1g of polyethylene oxide (molar mass 1X 10)6g/mol), 1g of polyethylene glycol diacrylate (the molar mass is 1000g/mol) and 0.95g of polyethylene glycol acrylate (the molar mass is 950g/mol) are dissolved in 6mL of N-methyl pyrrolidone serving as a first organic solvent, then 0.04g of first photoinitiator alpha-hydroxyisobutyrophenone and 0.96g of lithium salt LiTFSI are added into the obtained mixed system, the mixture is stirred for 12 hours at room temperature, the obtained first mixed slurry is coated on a polytetrafluoroethylene plate, then first UV curing is carried out under ultraviolet light, and the photopolymerization energy in the first UV curing is 280mJ/cm2Obtaining a base film with the thickness of 100 mu m;
dissolving 1.1g of succinonitrile into 1mL of a second organic solvent N, N-dimethylacetamide to obtain a 1mol/L succinonitrile solution, adding 1mg of alpha-hydroxyisobutyrophenone into the succinonitrile solution, and stirring at room temperature until the mixture is uniform to obtain a second mixed slurry;
the second mixed slurry is spread on the basePerforming second UV curing on the surface of the film under ultraviolet light, wherein the light polymerization energy in the second UV curing is 550mJ/cm2Forming a top film with the thickness of 25 mu m on the surface of the base film, and then placing the top film in a vacuum oven with the temperature of 80 ℃ and the vacuum degree of-0.08 MPa for drying for 12h to obtain the polymer-based solid electrolyte film with the asymmetric structure of the base film-top film structure.
Application example 3
The asymmetric polymer-based solid electrolyte membrane obtained in example 3 was used as an electrolyte, and the remaining technical means were the same as in application example 1, to obtain a battery.
The battery obtained in example 3 was subjected to a charge-discharge long cycle test, and the charge-discharge cycle test chart obtained is shown in fig. 7. As can be seen from fig. 7, the button cell assembled by the asymmetric polymer-based solid electrolyte membrane can be circulated and stabilized well in the first ten cycles at room temperature, and can be stably circulated at 2.8-4.3V with a small capacity attenuation in the 20 th cycle, thereby having good high-voltage cycling stability.
Example 4
1g of polyethylene oxide (molar mass 1X 10)6g/mol), 1g of polyethylene glycol diacrylate (the molar mass is 1000g/mol) and 0.95g of polyethylene glycol acrylate (the molar mass is 950g/mol) are dissolved in 6mL of N-methyl pyrrolidone serving as a first organic solvent, then 0.04g of first photoinitiator alpha-hydroxyisobutyrophenone and 0.96g of lithium salt LiTFSI are added into the obtained mixed system, the mixture is stirred for 12 hours at room temperature, the obtained first mixed slurry is coated on a polytetrafluoroethylene plate, then first UV curing is carried out under ultraviolet light, and the photopolymerization energy in the first UV curing is 300mJ/cm2Obtaining a basal membrane with the thickness of 80 mu m;
dissolving 0.8g of succinonitrile into 1mL of second organic solvent N, N-dimethylacetamide to obtain a 1mol/L succinonitrile solution, adding 1mg of alpha-hydroxyisobutyrophenone into the succinonitrile solution, and stirring at room temperature until the mixture is uniform to obtain a second mixed slurry;
coating the obtained second mixed slurry on the surface of the obtained base film by scraping, and carrying out second UV curing under ultraviolet light, wherein the light polymerization energy in the second UV curing is 600mJ/cm2Formed on the surface of the base film to a thickness of 25 μmAnd (3) carrying out top film treatment, and then placing the membrane in a vacuum oven with the temperature of 80 ℃ and the vacuum degree of-0.08 MPa for drying for 12h to obtain the asymmetric structure polymer-based solid electrolyte membrane with the base membrane-top membrane structure.
Application example 4
The asymmetric polymer-based solid electrolyte membrane obtained in example 4 was used as an electrolyte, and the remaining technical means were the same as in application example 1, to obtain a battery.
Example 5
1g of polyethylene oxide (molar mass 3X 10)5g/mol), 1g of polyethylene glycol diacrylate (the molar mass is 1000g/mol) and 0.95g of polyethylene glycol acrylate (the molar mass is 950g/mol) are dissolved in 6mL of N-methyl pyrrolidone serving as a first organic solvent, then 0.04g of first photoinitiator alpha-hydroxyisobutyrophenone and 0.96g of lithium salt LiTFSI are added into the obtained mixed system, the mixture is stirred for 12 hours at room temperature, the obtained first mixed slurry is coated on a polytetrafluoroethylene plate, then first UV curing is carried out under ultraviolet light, and the photopolymerization energy in the first UV curing is 250mJ/cm2Obtaining a base film with the thickness of 100 mu m;
dissolving 1.18g of 3-sulfolene in 1mL of a second organic solvent N, N-dimethylacetamide to obtain 1mol/L of a 3-sulfolene solution, adding 1mg of alpha-hydroxyisobutyrylbenzene into the obtained 3-sulfolene solution, and stirring at room temperature until the mixture is uniform to obtain a second mixed slurry;
coating the obtained second mixed slurry on the surface of the obtained base film by scraping, and carrying out second UV curing under ultraviolet light, wherein the light polymerization energy in the second UV curing is 700mJ/cm2Forming a top film with the thickness of 25 mu m on the surface of the base film, and then placing the top film in a vacuum oven with the temperature of 80 ℃ and the vacuum degree of-0.08 MPa for drying for 12h to obtain the polymer-based solid electrolyte film with the asymmetric structure of the base film-top film structure.
Application example 5
The asymmetric polymer-based solid electrolyte membrane obtained in example 5 was used as an electrolyte, and the remaining technical means were the same as in application example 1, to obtain a battery.
The battery obtained in example 5 was subjected to a charge-discharge long cycle test, and the charge-discharge cycle test chart obtained is shown in fig. 8. As can be seen from FIG. 8, the button cell assembled by the polymer-based solid electrolyte membrane with the asymmetric structure has good cycling stability at room temperature, can stably cycle at 2.8-4.3V for 30 circles without obvious attenuation of capacity, and has good high-voltage cycling stability.
Example 6
1g of polyethylene oxide (molar mass 3X 10)5g/mol), 1g of polyethylene glycol diacrylate (the molar mass is 1000g/mol) and 0.95g of polyethylene glycol acrylate (the molar mass is 950g/mol) are dissolved in 6mL of N-methyl pyrrolidone serving as a first organic solvent, then 0.04g of first photoinitiator alpha-hydroxyisobutyrophenone and LiTFSI are added into the obtained mixed system, the mixture is stirred for 12 hours at room temperature, the obtained first mixed slurry is coated on a polytetrafluoroethylene plate, then first UV curing is carried out under ultraviolet light, and the photopolymerization energy in the first UV curing is 300mJ/cm2Obtaining a base film with the thickness of 100 mu m;
dissolving 1.18g of 2, 3-dihydro-1, 1-dioxythiophene in 1mL of a second organic solvent N, N-dimethyl acetamide to obtain 1mol/L of 2, 3-dihydro-1, 1-dioxythiophene solution, adding 1mg of alpha-hydroxyisobutyrophenone into the obtained 2, 3-dihydro-1, 1-dioxythiophene solution, and stirring at room temperature until the mixture is uniform to obtain second mixed slurry;
coating the obtained second mixed slurry on the surface of the obtained base film by scraping, and carrying out second UV curing under ultraviolet light, wherein the light polymerization energy in the second UV curing is 650mJ/cm2Forming a top film with the thickness of 25 mu m on the surface of the base film, and then placing the top film in a vacuum oven with the temperature of 80 ℃ and the vacuum degree of-0.08 MPa for drying for 12h to obtain the polymer-based solid electrolyte film with the asymmetric structure of the base film-top film structure.
Application example 6
The asymmetric polymer-based solid electrolyte membrane obtained in example 6 was used as an electrolyte, and the remaining technical means were the same as in application example 1, to obtain a battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing an asymmetric-structure polymer-based solid electrolyte membrane is characterized by comprising the following steps:
mixing polyoxyethylene, polyethylene glycol diacrylate, polyethylene glycol acrylate, a first photoinitiator, lithium salt and a first organic solvent, coating the obtained first mixed slurry, and performing first UV curing to obtain a base membrane;
mixing a modified compound, a second photoinitiator and a second organic solvent to obtain a second mixed slurry, wherein the modified compound is an anhydride, a cyano compound or a sulfone compound containing unsaturated double bonds;
and coating the second mixed slurry on the surface of the base film, and sequentially carrying out second UV curing and drying to obtain the asymmetric-structure polymer-based solid electrolyte film with the base film-top film structure.
2. The production method according to claim 1, wherein the molar ratio of the polyethylene oxide, the polyethylene glycol diacrylate and the polyethylene glycol acrylate is (0.1 to 0.5): (0.25-0.45): (0.25-0.45).
3. The method according to claim 1, wherein the lithium salt is one or more of lithium bistrifluoromethylsulfonyl imide, lithium bistrifluoromethylsulfonyl amide, lithium methylsulfonate, lithium perchlorate, and lithium hexafluorophosphate.
4. The method according to claim 1 or 3, wherein the concentration of the lithium salt in the first mixed slurry is 20 to 50 wt.%.
5. The method of claim 1, wherein the first and second photoinitiators are independently one or more of alpha-hydroxyisobutyrophenone, 1-hydroxycyclohexylphenone, 2-hydroxy-2-methylpropiophenone, and ethyl 4-dimethylaminobenzoate.
6. The production method according to claim 1, wherein the unsaturated double bond-containing acid anhydride comprises maleic anhydride and/or succinic anhydride;
the cyano compound comprises one or more of succinonitrile, succinonitrile and 4, 4-dicyano-1, 6-heptadiene;
the sulfone-based compound comprises 3-sulfolene and/or 2, 3-dihydro-1, 1-dioxythiophene.
7. The preparation method according to claim 1 or 6, wherein the concentration of the modifying compound in the second mixed slurry is 1 to 5 mol/L.
8. An asymmetric-structure polymer-based solid electrolyte membrane produced by the production method according to any one of claims 1 to 7, comprising a crosslinked base membrane and a top membrane.
9. Use of the asymmetrically structured polymer-based solid electrolyte membrane according to claim 8 as a solid electrolyte in a polymer-based solid lithium battery.
10. A polymer-based solid lithium battery comprising a positive electrode, a solid electrolyte and a negative electrode, wherein the solid electrolyte is the asymmetrically structured polymer-based solid electrolyte membrane according to claim 8; the negative electrode is in contact with a base film of the polymer-based solid electrolyte membrane with the asymmetric structure, and the positive electrode is in contact with a top film of the polymer-based solid electrolyte membrane with the asymmetric structure.
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