CN113540575A - Preparation method of modified diaphragm-electrolyte integrated solid electrolyte and battery - Google Patents
Preparation method of modified diaphragm-electrolyte integrated solid electrolyte and battery Download PDFInfo
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- CN113540575A CN113540575A CN202110707773.3A CN202110707773A CN113540575A CN 113540575 A CN113540575 A CN 113540575A CN 202110707773 A CN202110707773 A CN 202110707773A CN 113540575 A CN113540575 A CN 113540575A
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- electrolyte
- diaphragm
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- integrated solid
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 124
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 51
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 45
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 42
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 12
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts 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
- 229960003151 mercaptamine Drugs 0.000 claims description 6
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- NYDIRNCYGNFBTK-UHFFFAOYSA-N n-[[2,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]methyl]prop-2-enamide Chemical compound C1=C(CNC(=O)C=C)C(C)=CC(OCC2OC2)=C1C NYDIRNCYGNFBTK-UHFFFAOYSA-N 0.000 claims description 3
- NFDUZRAWLHASSQ-UHFFFAOYSA-N 2-hydroxyacetic acid;n-methylprop-2-enamide Chemical compound OCC(O)=O.CNC(=O)C=C NFDUZRAWLHASSQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 7
- 230000010354 integration Effects 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 229910010941 LiFSI Inorganic materials 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
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- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 239000006258 conductive agent Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YJDQUDUVBMHAOE-UHFFFAOYSA-N 2-methoxyacetic acid;n-methylprop-2-enamide Chemical compound CNC(=O)C=C.COCC(O)=O YJDQUDUVBMHAOE-UHFFFAOYSA-N 0.000 description 1
- VSYIJNDEXXBJFH-UHFFFAOYSA-N 5-isocyanato-2-methylpent-1-en-3-one Chemical compound CC(=C)C(=O)CCN=C=O VSYIJNDEXXBJFH-UHFFFAOYSA-N 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
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- 208000034158 bleeding Diseases 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- XJUAIBKHPCVJQH-UHFFFAOYSA-N methyl 2-methoxyacetate;prop-2-enamide Chemical compound NC(=O)C=C.COCC(=O)OC XJUAIBKHPCVJQH-UHFFFAOYSA-N 0.000 description 1
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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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The invention discloses a preparation method of a modified diaphragm-electrolyte integrated solid electrolyte and a battery, wherein a modifier, a cross-linking agent and a photoinitiator are dissolved in an electrolyte, and the mixture is ultrasonically dispersed and uniformly stirred to obtain an electrolyte solution containing the modifier, the cross-linking agent and the photoinitiator; immersing the diaphragm into an electrolyte solution containing a modifier, a cross-linking agent and a photoinitiator for dipping; and taking out the diaphragm, and irradiating under ultraviolet light to obtain the modified diaphragm-electrolyte integrated solid electrolyte. According to the invention, the diaphragm matrix and the modifier are polymerized to form an integrated polymer skeleton containing the diaphragm, and the polymer is combined with the diaphragm through a chemical bond, so that the polymer is not easy to fall off, and the service life of a modified layer is prolonged; contain the electrolyte in the time of the integration polymer skeleton formation of diaphragm, form the integration electrolyte, prevented that electrolyte from revealing the risk, promoted electrolyte security. The integrated solid electrolyte of the present invention has high mechanical strength.
Description
Technical Field
The invention relates to a preparation method of a modified diaphragm-electrolyte integrated solid electrolyte and a battery, belonging to the field of lithium battery electrolyte preparation.
Background
Lithium ion batteries are widely used in electronic devices and electric vehicles due to their excellent electrochemical properties (e.g., high energy density, long cycle life, low self-discharge, etc.) and green, non-pollution properties. However, commercial lithium ion batteries using organic liquid electrolytes still suffer from some drawbacks. On the one hand, the flowability of the liquid electrolyte leads to a serious risk of leakage; on the other hand, the porous polyolefin membrane commonly used for the lithium ion battery diaphragm has poor thermal stability, and the strength of the diaphragm is obviously reduced when the internal temperature of the battery rises, so that the risk of puncture short circuit is caused, and the potential safety hazard is increased sharply at high temperature.
In view of the above safety problems, a common solution is to coat organic or inorganic modified materials on a polyolefin organic diaphragm to improve the performance of the diaphragm. However, the inorganic particles or organic coating materials generally used for the modified membrane have weak bonding force with the membrane substrate, so that the modified material is easy to fall off, and the stability of the modified material is still to be improved. In addition, although the modified separator is improved in the liquid retention property, the electrolyte absorbed therein is still in risk of bleeding out under high pressure.
Therefore, it is necessary to provide a new electrolyte design concept, which provides conditions for the safety popularization of lithium ion batteries.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of a modified diaphragm-electrolyte integrated solid electrolyte and a battery. The electrolyte is contained in the integrated polymer skeleton containing the diaphragm while the integrated polymer skeleton is formed, so that the risk of leakage of the electrolyte is prevented, and the adaptability to a high-voltage positive electrode material is enhanced. In addition, the electrolyte is formed by one step of ultraviolet irradiation to initiate the polymerization of the modifier, the process is simple, the large-scale production can be carried out, and the lithium ion battery using the integrated solid electrolyte has stable cycle performance and rate capability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a modified diaphragm-electrolyte integrated solid electrolyte comprises the following steps:
s1, dissolving the modifier, the cross-linking agent and the photoinitiator in the electrolyte, and uniformly stirring after ultrasonic dispersion to obtain an electrolyte solution containing the modifier, the cross-linking agent and the photoinitiator;
s2, immersing the diaphragm into an electrolyte solution containing a modifier, a cross-linking agent and a photoinitiator for immersion;
and S3, taking out the diaphragm, and irradiating under ultraviolet light to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
The invention is further improved in that the modifier is one of acrylic acid, acrylamide, methyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol monomethacrylate, itaconic acid, maleic anhydride, methyl acrylamide glycolate, N- [4- (2, 3-epoxypropoxy) -2, 5-dimethylbenzyl ] acrylamide, 2-methacryloyloxyethyl isocyanate and 2- (1-ethyleneimine) ethyl methacrylate.
The further improvement of the invention is that the cross-linking agent is one of divinylbenzene, N' -cysteamine bisacrylamide, N-methylenebisacrylamide, triallyl isocyanurate and ethylene glycol dimethacrylate.
The invention further improves that the photoinitiator is one of benzophenone, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and tert-butyl peroxybenzoate.
In a further development of the invention, the electrolyte is prepared by the following process: and adding conductive lithium salt into the solvent, and uniformly mixing to obtain the electrolyte with the concentration of 1 mol/L.
The invention is further improved in that the conductive lithium salt is one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate and lithium trifluoromethanesulfonate, and the solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
The further improvement of the invention is that the concentration of the modifier in the electrolyte solution is 15-30 wt%, the concentration of the cross-linking agent in the electrolyte solution is 5-10 wt%, and the concentration of the photoinitiator in the electrolyte solution is 1.5-3 wt%.
The invention is further improved in that the impregnation time is 12 to 24 hours.
The invention has the further improvement that the power of the ultraviolet lamp is 1000 w; the ultraviolet light irradiation time is 3min-30 min.
A solid-state lithium ion battery comprising the modified separator-electrolyte integrated solid-state electrolyte prepared by the method of any one of claims 1 to 9.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses ultraviolet irradiation grafting method to bond the modifier on the surface of the firm diaphragm by means of chemical bond, and contains the electrolyte in the bonding process of the modifier, thus forming the modified diaphragm-electrolyte integrated solid electrolyte. The method for forming the polymer skeleton in situ not only increases the mechanical strength of the diaphragm, but also avoids the defect that inorganic nano particles are easy to fall off in the common modification method, and prolongs the service life of the diaphragm. Wherein the tensile strength of the separator is increased to 3.28-4.22 times. The functional groups such as carboxyl, hydroxyl, ester group, amide group and the like in the polymer coated on the surface of the diaphragm are strong in hydrophilicity and stable in chemical structure, the liquid absorption amount of the diaphragm can be increased, higher electrolyte content is guaranteed, the ionic conductivity is improved, the electrochemical stability of an electrolyte can be improved, and the diaphragm is matched with a high-voltage positive electrode material. According to the invention, the electrolyte is contained in the integrated polymer framework containing the diaphragm while the integrated polymer framework is formed, so that not only are the complete electrolyte components retained, but also the integrated solid electrolyte is formed, the risk of electrolyte leakage is avoided, the electrolyte safety is greatly improved, and meanwhile, the preparation process is simplified. The components of the electrolyte used in the invention can be the same as the components of the commercial electrolyte, and the invention is attached to the existing lithium battery production process, thereby reducing the raw material cost, and being applicable to large-scale production.
The modified diaphragm-electrolyte integrated solid electrolyte can be applied to solid lithium ion batteries, and the corresponding batteries show better cycle performance and rate capability. Taking a lithium iron phosphate/graphite battery as an example, the capacity retention rate after 100 cycles is 97.2% -99.6%, and the lithium iron phosphate/graphite battery shows better cycle stability.
Drawings
Fig. 1 is a graph showing discharge capacity and coulombic efficiency of a solid lithium battery prepared according to example 1 of the present invention.
Fig. 2 is a linear voltammetric scan curve.
Detailed Description
The invention is further described in the following description with reference to the figures and specific preferred embodiments, but without thereby limiting the scope of protection of the invention. The examples are preferred in the experimental process and are only used for more complete illustration of the present invention, but are not to be construed as limiting the scope of the present invention.
The instruments and drug materials used in the present invention are commercially available.
First, the modified separator-electrolyte integrated solid electrolyte of the present invention will be explained.
The invention provides a modified diaphragm-electrolyte integrated solid electrolyte, which is composed of: polyolefin diaphragm, modifier, cross-linking agent, photoinitiator and electrolyte.
The diaphragm material is one of a Polyethylene (PE) single-layer film, a polypropylene (PP) single-layer film and a PP/PE/PP three-layer composite film.
Preferably, the model of the polypropylene (PP) single-layer film is 2500 diaphragm, the model of the Polyethylene (PE) single-layer film is 2325 diaphragm, and the model of the diaphragm and the PP/PE/PP three-layer composite film is 2320 diaphragm.
The performance parameters of the polyolefin separator employed in the present invention are shown in table 1.
TABLE 1 Performance parameters of the separator
The cross-linking agent is: one of divinylbenzene, N' -cysteamine bisacrylamide, N-methylenebisacrylamide, triallyl isocyanurate, and ethylene glycol dimethacrylate.
The photoinitiator is one of benzophenone, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and tert-butyl peroxybenzoate.
The modifier is one of Acrylic Acid (AA), Acrylamide (AM), Methyl Methacrylate (MMA), Dimethylaminoethyl Methacrylate (DM), hydroxyethyl methacrylate (HEMA), polyethylene glycol monomethacrylate (PEGMA), Itaconic Acid (IA), Maleic Anhydride (MAH), Methyl Acrylamide Glycolate Methyl Ether (MAGME), N- [4- (2, 3-epoxypropoxy) -2, 5-dimethylbenzyl ] Acrylamide (AXE), 2-methacryloyloxyethyl isocyanate (MOI) and 2- (1-ethyleneimine) ethyl methacrylate (AZEM).
Preferably, the modifier G1-G6MMA, PEGMA, MAH, MAGME, MOI, AZEM, respectively.
The chemical structure of the modifier used in the present invention is shown in Table 2.
TABLE 2 modifier G1-G6Chemical structure
The electrolyte is prepared by the following steps: and adding conductive lithium salt into the solvent, and uniformly mixing to obtain the electrolyte with the concentration of 1 mol/L. The conductive lithium salt is one of lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiCiO4), lithium tetrafluoroborate (LiBF4) and lithium trifluoromethanesulfonate (LiFSI), and the solvent is one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DEC), diethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC). Preferably, the solvent is a mixed solution of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1: 1.
Next, a process for producing the integrated solid electrolyte according to the second aspect of the present invention is explained.
The invention provides a preparation method of a modified diaphragm-electrolyte integrated solid electrolyte, which specifically comprises the following steps:
and S1, dissolving the modifier, the cross-linking agent and the initiator in the electrolyte according to a certain proportion, and uniformly stirring after ultrasonic dispersion to obtain the electrolyte solution containing the modifier, the cross-linking agent and the initiator.
The concentration of the modifier in the electrolyte solution is 15-30 wt%, the concentration of the cross-linking agent in the electrolyte solution is 5-10 wt%, and the concentration of the photoinitiator in the electrolyte solution is 1.5-3 wt%.
The mixed solution containing the modifier, the crosslinking agent and the photoinitiator was subjected to ultrasonic dispersion so as to be sufficiently dissolved. The time of ultrasonic dispersion has no special requirements and can be adjusted according to actual requirements. For example, in embodiments of the present invention, the ultrasonic dispersion time is 30min to 60 min. The mixed solution was stirred for thorough mixing. The stirring method is not particularly required, and may be selected according to the actual conditions. For example, in embodiments of the present invention, mechanical agitation is used. The stirring time and temperature are not particularly required, and in the embodiment of the present invention, the preferable stirring time is 2 to 5 hours; stirring is carried out at 40-60 ℃.
And S2, immersing the diaphragm into electrolyte solution containing a modifier and an initiator for immersion.
The dipping time is not particularly required, and can be adjusted according to actual requirements. For example, in the examples of the present invention, the dipping time is 12 to 24 hours.
And S3, taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, and then placing the diaphragm under ultraviolet irradiation for a certain time to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
In the embodiment of the present invention, the power of the ultraviolet lamp used is 1000 w. The irradiation time is not particularly required, and can be selected according to actual conditions. For example, in the embodiment of the present invention, the ultraviolet light irradiation time is 3min to 30 min.
The invention uses ultraviolet grafting method to combine the polymer coating layer on the diaphragm substrate by chemical bond, thereby realizing the modification treatment of the diaphragm.
Again, the assembly of the lithium ion battery according to the third aspect of the invention is explained.
The lithium ion battery applied according to the invention comprises a positive plate, a negative plate and a modified diaphragm-electrolyte integrated solid electrolyte which is arranged between the positive plate and the negative plate. The positive plate comprises a positive current collector, and a positive active material, a positive conductive agent and a binder which are coated on the positive current collector.
In the lithium ion battery applied according to the present invention, the positive electrode current collector may be selected from an aluminum foil, a nickel foil, a carbon foil, or a stainless steel sheet.
In the lithium ion battery according to the present invention, the positive active material may be selected according to the actual selection of LiCoO2、LiFePO4NCM523, NCM811 or LiNi0.5Mn1.5O4And the like.
In the lithium ion battery applied according to the present invention, the positive electrode conductive agent may be acetylene black, graphite, Super P, or conductive fiber according to actual choice.
In the lithium ion battery applied according to the present invention, the negative electrode material may be selected according to actual needs. For example, the negative electrode is lithium metal and a lithium metal-based negative electrode material or a carbon-based negative electrode material.
The present invention will be described in more detail with reference to examples.
Example 1
A modified diaphragm-electrolyte integrated solid electrolyte is prepared from: polyolefin diaphragm, modifier, cross-linking agent, photoinitiator and electrolyte.
The preparation method comprises the following steps: firstly, dissolving 15 wt%, 5 wt% and 1.5 wt% of modifier MMA, 5 wt% and 1.5 wt% of cross-linking agent divinylbenzene and photoinitiator benzophenone respectively in electrolyte, wherein the electrolyte is 1mol/L LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) (volume ratio 1:1: 1). Ultrasonically dispersing for 30min, and magnetically stirring for 2h at 40 ℃ to obtain an electrolyte solution containing a modifier, a cross-linking agent and an initiator.
Then, a 2500 th diaphragm is soaked in the prepared mixed electrolyte solution for 12 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 3min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 2
Firstly, dissolving a modifier PEGMA, a cross-linking agent N, N' -cysteamine bisacrylamide and a photoinitiator benzophenone in the electrolyte respectively according to the mass fractions of 20 wt%, 5 wt% and 2 wt%, wherein the electrolyte is 1mol/L LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) (volume ratio 1:1: 1). Ultrasonic dispersion is carried out for 30min, magnetic stirring is carried out for 2h at 50 ℃, and electrolyte solution containing a modifier, a cross-linking agent and an initiator is obtained.
Then, a 2500 th diaphragm is soaked in the prepared mixed electrolyte solution for 12 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 10min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 3
Firstly, dissolving a modifier MAH, a cross-linking agent N, N' -cysteamine bisacrylamide and a photoinitiator benzoyl peroxide in electrolyte respectively according to mass fractions of 20 wt%, 5 wt% and 2 wt%, wherein the electrolyte is selected to be 1mol/L LiClO4Ethylene Carbonate (EC)/diethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) (volume ratio 1:1: 1). Ultrasonic dispersion is carried out for 30min, magnetic stirring is carried out for 2h at 50 ℃, and electrolyte solution containing a modifier, a cross-linking agent and an initiator is obtained.
Then, the 2320 diaphragm is soaked in the prepared mixed electrolyte solution for 16 h.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 10min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 4
Firstly, dissolving a modifier MAGME, a cross-linking agent N, N-methylene bisacrylamide and a photoinitiator dicumyl peroxide in an electrolyte solution according to the mass fractions of 25 wt%, 10 wt% and 2.5 wt%, wherein the electrolyte solution is 1mol/L LiFSI/Ethylene Carbonate (EC)/diethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) (volume ratio is 1:1: 1). Ultrasonic dispersion is carried out for 60min, and magnetic stirring is carried out for 5h at 50 ℃ to obtain electrolyte solution containing modifier, cross-linking agent and initiator.
Then, the 2320 diaphragm is soaked in the prepared mixed electrolyte solution for 24 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 30min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 5
Firstly, a modifier MOI, a crosslinking agent triallyl isocyanurate and a photoinitiator dicumyl peroxide are respectively dissolved in electrolyte with the mass fractions of 30 wt%, 10 wt% and 3 wt%, wherein the electrolyte is selected from 1mol/L LiBF 4/Propylene Carbonate (PC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) (volume ratio is 1:1: 1). Ultrasonically dispersing for 45min, and magnetically stirring for 2h at 60 ℃ to obtain an electrolyte solution containing a modifier, a cross-linking agent and an initiator.
Then, the 2325 diaphragm is soaked in the prepared mixed electrolyte solution for 12 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 20min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 6
Firstly, a modifier AZEM, a cross-linking agent ethylene glycol dimethacrylate and a photoinitiator tert-butyl peroxybenzoate are respectively dissolved in electrolyte with the mass fractions of 20 wt%, 8 wt% and 2 wt%, wherein the electrolyte is selected from 1mol/L LiFSI/Propylene Carbonate (PC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) (volume ratio is 1:1: 1). Ultrasonically dispersing for 50min, and magnetically stirring at 40 ℃ for 6h to obtain an electrolyte solution containing a modifier, a cross-linking agent and an initiator.
Then, the 2325 diaphragm is soaked in the prepared mixed electrolyte solution for 24 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 30min to obtain the modified diaphragm-electrolyte integrated solid electrolyte. Example 7
Firstly, a modifier AZEM, a cross-linking agent divinylbenzene and a photoinitiator benzophenone are respectively dissolved in electrolyte in mass fractions of 15 wt%, 7 wt% and 1.5 wt%, wherein the electrolyte is a 1mol/L LiFSI ethylene carbonate solution. Ultrasonically dispersing for 30min, and magnetically stirring at 40 ℃ for 5h to obtain an electrolyte solution.
Then, the 2500 th separator was immersed in the prepared electrolyte solution for 18 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 30min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 8
Firstly, respectively dissolving a modifier acrylamide, a cross-linking agent N, N' -cysteamine and a photoinitiator benzoyl peroxide in the electrolyte according to mass fractions of 20 wt%, 5 wt% and 2 wt%, wherein the electrolyte is 1mol/L of LiFSI ethylene carbonate solution. Ultrasonically dispersing for 40min, and magnetically stirring at 50 ℃ for 2h to obtain an electrolyte solution.
Then, the 2325 diaphragm is taken out and soaked in the prepared electrolyte solution for 24 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 3min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 9
Firstly, respectively dissolving 30 wt%, 10 wt% and 3 wt% of modifier methyl methacrylate, crosslinking agent N, N-methylene bisacrylamide and photoinitiator dicumyl peroxide in electrolyte, wherein the electrolyte is 1mol/L of LiFSI ethylene carbonate solution. Ultrasonically dispersing for 60min, and magnetically stirring for 3h at 55 ℃ to obtain an electrolyte solution.
Then, the 2320 diaphragm is soaked in the prepared electrolyte solution and is soaked for 12 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 10min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 10
Firstly, respectively dissolving 25 wt%, 8 wt% and 2.5 wt% of modifier polyethylene glycol monomethacrylate, cross-linking agent triallyl isocyanurate and photoinitiator di-tert-butyl peroxide in electrolyte, wherein the electrolyte is 1mol/LLIFSI ethylene carbonate solution. Ultrasonically dispersing for 50min, and magnetically stirring at 60 ℃ for 4h to obtain an electrolyte solution.
Then, a 2500 th diaphragm is soaked in the prepared electrolyte solution for 15 h.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 20min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 11
Firstly, dissolving a modifier of acrylamide-methyl glycolate methyl ether, a cross-linking agent of ethylene glycol dimethacrylate and a photoinitiator of tert-butyl peroxybenzoate into electrolyte respectively in a mass fraction of 22 wt%, 6 wt% and 2.2 wt%, wherein the electrolyte is a 1mol/L LiFSI ethylene carbonate solution. Ultrasonically dispersing for 35min, and magnetically stirring for 3h at 55 ℃ to obtain an electrolyte solution.
Then, a 2500 th diaphragm is taken out and soaked in the prepared electrolyte solution for 22 h.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 15min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Example 12
Firstly, 28 wt%, 6 wt% and 2.8 wt% of modifier 2-methacryloyl ethyl isocyanate, cross-linking agent divinylbenzene and photoinitiator benzophenone are respectively dissolved in electrolyte, wherein the electrolyte is 1mol/L of ethylene carbonate solution of LiFSI. Ultrasonically dispersing for 45min, and magnetically stirring for 4h at 45 ℃ to obtain an electrolyte solution.
Then, a 2500 th diaphragm is taken out and soaked in the prepared electrolyte solution for 17 h.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 25min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
Comparative example 1: separator-electrolyte system without modification treatment
The diaphragm-electrolyte system is not subjected to modification treatment, and the model of a diaphragm sample is 2500 diaphragms. The preparation method comprises the following steps:
preparing electrolyte into 1mol/L LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) (volume ratio 1:1: 1). Soaking 2325 diaphragm in electrolyte for 12 hr.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 3min to obtain a diaphragm-electrolyte system.
Comparative example 2: modified diaphragm-electrolyte integrated electrolyte without using cross-linking agent treatment
A modified diaphragm-electrolyte integrated solid electrolyte is prepared from: polyolefin diaphragm, modifier, photoinitiator and electrolyte.
The preparation method comprises the following steps: firstly, 15 wt% and 1.5 wt% of modifier MMA and 1.5 wt% of photoinitiator benzophenone are respectively dissolved in electrolyte, wherein the electrolyte is 1mol/L LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) (volume ratio 1:1: 1). Ultrasonically dispersing for 30min, and magnetically stirring for 2h at 40 ℃ to obtain an electrolyte solution containing a modifier and an initiator.
Then, a 2500 th diaphragm is soaked in the prepared mixed electrolyte solution for 12 hours.
And taking out the diaphragm, wiping the surface of the diaphragm by using dust-free paper, removing redundant solution on the surface, and then placing the diaphragm under an ultraviolet lamp with the power of 1000w for irradiation for 3min to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
The application of the modified diaphragm-electrolyte integrated solid electrolyte in the preparation of the solid lithium ion battery is as follows: stirring the positive and negative electrode slurry, coating, baking, rolling the pole piece, slitting the pole piece and slitting the electrolyte; the method comprises the steps of pole piece transverse cutting, positive pole piece/solid electrolyte membrane/negative pole piece/solid electrolyte membrane cell winding, cell lamination, tab welding, sealing and packaging.
Example 13
Preparation of lithium ion batteries
The modified diaphragm-electrolyte integrated solid electrolyte prepared by the invention is applied to a solid lithium ion battery, the lithium ion battery uses an all-battery with NCM523 as a positive electrode and graphite as a negative electrode, and the solid electrolyte is applied between the positive electrode and the negative electrode.
The modified separator may be the modified separator-electrolyte integrated solid electrolyte prepared in examples 1 to 6.
In this example, the positive electrode was mixed with NMP at a mass ratio of NCM523: Super P: PVDF of 8:1:1 to obtain a positive electrode slurry, and the positive electrode slurry was coated on an aluminum foil; and mixing the graphite, Super P, PVDF (polyvinylidene fluoride) and NMP in a mass ratio of the graphite to the Super P to the PVDF to obtain negative electrode slurry, and then drying the slurry in vacuum at 105 ℃ for 24 hours to obtain the positive electrode and the negative electrode.
In this example, the positive and negative electrodes and the solid electrolyte membrane were cut into positive and negative electrode sheets and electrolyte sheets using a slicer, wherein the electrolyte used was the modified membrane-electrolyte integrated solid electrolyte in example 1, and the positive electrode sheet/solid electrolyte membrane/negative electrode sheet/solid electrolyte membrane cell was wound, cell laminated, tab welded, sealed and packaged.
And (3) performance testing:
(1) mechanical Property test
The solid electrolytes obtained in example 1, comparative example 1, and comparative example 2, i.e., the separator modified with the modifier and the crosslinking agent together, the separator without modification, and the separator modified without crosslinking agent were each tested. It can be seen that the strength of the electrolyte prepared in example 1 was 62Mpa, and the mechanical strength of comparative example 1(18Mpa) and comparative example 2(37Mpa), which illustrate the great improvement in the mechanical strength of the electrolyte by modification using the crosslinking agent.
(2) Charge and discharge test
The electrolyte sample obtained in example 1 was tested, and the charge and discharge interval was 3.0 to 4.2V, and the charge and discharge were carried out at a current of 0.1C. The lithium ion battery prepared by using the NCM523 as the positive electrode and the graphite as the negative electrode and disposing the integrated electrolyte prepared in example 1 between the positive electrode and the negative electrode still has a specific discharge capacity of 140mAh/g after 100 charge-discharge cycles at a current density of 0.1C as shown in fig. 1, which indicates that the electrolyte has high ionic conductivity and good interface compatibility.
(3) Electrochemical stability test
Using the electrolyte sample obtained in example 1, a cell was assembled using a stainless steel sheet as the counter electrode and a lithium sheet as the reference electrode and tested for linear voltammetry scan curves. As shown in fig. 2, the decomposition potential is 5.2V, and the high-voltage cathode material has good adaptability.
In the modified diaphragm-electrolyte integrated solid electrolyte, the diaphragm matrix and the modifier are polymerized to form an integrated polymer skeleton containing the diaphragm, and the polymer is combined with the diaphragm through a chemical bond and is not easy to fall off, so that the service life of a modified layer is prolonged; contain the electrolyte in the time of the integration polymer skeleton formation of diaphragm, form the integration electrolyte, prevented that electrolyte from revealing the risk, promoted electrolyte security. The integrated solid electrolyte has high mechanical strength, and compared with an unmodified polyolefin diaphragm, the mechanical strength is greatly improved. The integrated solid electrolyte has simple preparation process, can be produced in large scale, and has good electrochemical performance when being applied to lithium ion batteries.
Claims (10)
1. A preparation method of a modified diaphragm-electrolyte integrated solid electrolyte is characterized by comprising the following steps:
s1, dissolving the modifier, the cross-linking agent and the photoinitiator in the electrolyte, and uniformly stirring after ultrasonic dispersion to obtain an electrolyte solution containing the modifier, the cross-linking agent and the photoinitiator;
s2, immersing the diaphragm into an electrolyte solution containing a modifier, a cross-linking agent and a photoinitiator for immersion;
and S3, taking out the diaphragm, and irradiating under ultraviolet light to obtain the modified diaphragm-electrolyte integrated solid electrolyte.
2. The method of claim 1, wherein the modifier is one of acrylic acid, acrylamide, methyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol monomethacrylate, itaconic acid, maleic anhydride, methyl acrylamide glycolate, N- [4- (2, 3-epoxypropoxy) -2, 5-dimethylbenzyl ] acrylamide, 2-methacryloyloxyethyl isocyanate, and 2- (1-ethyleneimine) ethyl methacrylate.
3. The method for preparing the modified membrane-electrolyte integrated solid electrolyte as claimed in claim 1, wherein the cross-linking agent is one of divinylbenzene, N' -cysteamine bisacrylamide, N-methylenebisacrylamide, triallyl isocyanurate, and ethylene glycol dimethacrylate.
4. The method as claimed in claim 1, wherein the photoinitiator is one of benzophenone, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide and t-butyl peroxybenzoate.
5. The method for preparing the modified diaphragm-electrolyte integrated solid electrolyte as claimed in claim 1, wherein the electrolyte is prepared by the following steps: and adding conductive lithium salt into the solvent, and uniformly mixing to obtain the electrolyte with the concentration of 1 mol/L.
6. The method for preparing the modified membrane-electrolyte integrated solid electrolyte according to claim 5, wherein the conductive lithium salt is one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate and lithium trifluoromethanesulfonate, and the solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
7. The method for preparing the modified diaphragm-electrolyte integrated solid electrolyte of claim 1, wherein the concentration of the modifier in the electrolyte solution is 15-30 wt%, the concentration of the cross-linking agent in the electrolyte solution is 5-10 wt%, and the concentration of the photoinitiator in the electrolyte solution is 1.5-3 wt%.
8. The method for preparing the modified membrane-electrolyte integrated solid electrolyte as claimed in claim 1, wherein the impregnation time is 12-24 h.
9. The method for preparing the modified membrane-electrolyte integrated solid-state electrolyte according to claim 1, wherein the power of the ultraviolet lamp is 1000 w; the ultraviolet light irradiation time is 3min-30 min.
10. A solid-state lithium ion battery comprising a modified separator-electrolyte integrated solid-state electrolyte prepared by the method of any one of claims 1 to 9.
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