CN113161608A - Polymer solid electrolyte with excellent performance at room temperature and application thereof in lithium ion battery - Google Patents
Polymer solid electrolyte with excellent performance at room temperature and application thereof in lithium ion battery Download PDFInfo
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- CN113161608A CN113161608A CN202110219800.2A CN202110219800A CN113161608A CN 113161608 A CN113161608 A CN 113161608A CN 202110219800 A CN202110219800 A CN 202110219800A CN 113161608 A CN113161608 A CN 113161608A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 119
- 229920000642 polymer Polymers 0.000 title claims abstract description 118
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000004033 plastic Substances 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- -1 2-oxo-1, 3-dioxolan-4-yl Chemical group 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 10
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 5
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QQUZYDCFSDMNPX-UHFFFAOYSA-N ethene;4-methyl-1,3-dioxolan-2-one Chemical compound C=C.CC1COC(=O)O1 QQUZYDCFSDMNPX-UHFFFAOYSA-N 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 4
- 229910012919 LiCoO4 Inorganic materials 0.000 claims description 4
- 229910015866 LiNi0.8Co0.1Al0.1O2 Inorganic materials 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002931 mesocarbon microbead Substances 0.000 claims description 4
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 claims description 2
- ABUUZDFXQZKHPA-UHFFFAOYSA-N 4-methyl-1,3-dioxolan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.CC1COC(=O)O1 ABUUZDFXQZKHPA-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
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- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229920005596 polymer binder Polymers 0.000 claims description 2
- 239000002491 polymer binding agent Substances 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 description 42
- 230000001678 irradiating effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 230000007480 spreading Effects 0.000 description 11
- 238000003892 spreading Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 239000005518 polymer electrolyte Substances 0.000 description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene 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
- 238000000498 ball milling Methods 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- CNYJVFLIXLEHTP-SREVYHEPSA-N (Z)-2-ethyl-3-methylpent-2-enoic acid Chemical compound CC\C(C)=C(\CC)C(O)=O CNYJVFLIXLEHTP-SREVYHEPSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- YKEOBDLNPPIQMU-UHFFFAOYSA-N C(C=C)(=O)OC.C1(OCCO1)=O Chemical compound C(C=C)(=O)OC.C1(OCCO1)=O YKEOBDLNPPIQMU-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006254 polymer film Polymers 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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-performance polymer solid electrolyte at room temperature and a preparation method and application thereof. The polymer solid electrolyte comprises a polymer framework, plastic crystals, lithium salt and a binder; the interpenetrating network structure is formed by ultraviolet light initiated polymerization of a liquid mixture containing a monomer, a cross-linking agent, a binder, a plastic crystal, a lithium salt and a photoinitiator. In the polymer solid electrolyte, a high molecular weight binder and a plastic crystal are lithium ion conductive solids, the binder is inserted in a polymer framework, and the plastic crystal is filled in an interpenetrating network formed by the high molecular weight binder and the polymer framework. The polymer solid electrolyte has good mechanical property and can be bent; the room-temperature conductivity of the polymer solid electrolyte reaches 0.5-5 mS/cm. When the polymer solid electrolyte is used for a lithium ion battery, the polymer solid electrolyte has the characteristics of high conductivity, low interface impedance with metal lithium, high coulombic efficiency, high specific capacity of the battery under high-rate charge-discharge cycle and the like at room temperature.
Description
The technical field is as follows:
the invention belongs to the field of lithium ion battery polymer electrolytes, and particularly relates to a preparation method and application of a polymer solid electrolyte with high room temperature conductivity, excellent compatibility with a metal lithium interface and high electrochemical window.
Technical background:
the lithium metal secondary battery has higher energy density, power density and good cycle performance, so that the lithium metal secondary battery has wide application in the fields of portable equipment, electric vehicles and the like. The liquid electrolyte has high conductivity and good compatibility with the electrode, but has the hidden trouble of easy combustion and explosion. The polymer solid electrolyte is not easy to burnThe polymer solid electrolyte has three defects, so that the commercial application of the solid electrolyte including the polymer solid electrolyte in the lithium metal secondary battery is limited. First, most single polymer solid electrolytes have room temperature lithium ion conductivities as low as 10-7-10-6S/cm (J.Am.chem.Soc.2006, 125, 4619), and lithium ion conductivity is far below room temperature and reaches 10-4S/cm for commercial applications. Secondly, the polymer solid electrolyte has poor compatibility with the anode and the cathode, and the interface impedance is high. The commonly used liquid electrolyte can fully infiltrate the solid positive electrode and the solid negative electrode, and the interface impedance of the commonly used liquid electrolyte is usually 30-300 omega (Advanced Energy Materials 2016, 6, 1502214). When a solid electrolyte is used, the interface impedance is usually 200 Ω or more (chem.2019, 5, 74-96) because the solid/solid interface is difficult to achieve wetting and contact with the liquid/solid interface. Third, the polymer solid electrolyte also has a special problem of low electrochemical window (ACS Sustainable Chemistry)&Engineering 2017, 6, 268-274), resulting in low battery discharge voltage and low battery energy density.
Polyethylene oxide (PEO) is one of the most commonly used polymers for preparing polymer solid electrolytes, and the room temperature ionic conductivity of these PEO-based polymer solid electrolytes is generally 10-6S/cm (J.Am.chem.Soc.2006, 128, 12036-12037.). In order to increase the room temperature ionic conductivity of polymer solid electrolytes, a method of decreasing the molecular weight of PEO is generally used, but as the molecular weight of PEO decreases, the melting point (Tm) or glass transition temperature (Tg) of the polymer decreases, and the polymer changes from a solid state to a liquid state (Macromolecules 1988, 21, 1117-1120); another way to increase the room temperature ionic conductivity is to add a plastic crystal (solid plasticizer) to the polymer solid electrolyte, where the plastic crystal usually comprises nitrile (Energy)&Environmental Science 2012, 5.) or low molecular weight PEO and low molecular weight polyethylene glycol (PEG), etc. (Solid State Ionics 1998, 1101-14), or a lithium salt having a plasticizing effect, such as lithium bistrifluoromethylsulfonate. For example, in patent publication CN111446496A, nitrile plasticizers were added to solid state electrolytes prepared from rubber graft-modified materialsIn the medium, the room temperature ion conductivity reaches 10-4-10-3S/cm. However, nitrile has a certain toxicity, and in addition, the polymer solid electrolyte added with a nitrile plasticizer has poor interfacial compatibility with lithium metal and large interfacial resistance (j.mater.chem.a.2016, 4, 10070-10083), so that the range of commercial application thereof is limited.
Compared with the improvement of the room-temperature ionic conductivity of the polymer solid electrolyte, the research on the improvement of the compatibility between the polymer solid electrolyte and the electrode is not enough, and the difficulty in reducing the interface impedance of a solid/solid interface is high. The invention patent CN107768717A discloses a polycarbonate-based polymer electrolyte with an ultraviolet light cured semi-interpenetrating network structure and a preparation method thereof. Wherein, no chemical bond is connected between the polycarbonate and the solid electrolyte skeleton, and the problem of interface compatibility between the polycarbonate and the lithium metal cathode still exists. The invention patent CN110994015A discloses a method for preparing polymer solid electrolyte by copolymerizing a monomer containing carbonate groups and a crosslinking agent. The polymer solid electrolyte has lower interfacial resistance and better electrochemical performance. However, the preparation process of the polymer solid electrolyte is complicated and a large amount of organic solvent is used, and in addition, the polymer electrolyte is swollen by the small molecule additive during charge and discharge cycles of the battery and thus cannot effectively maintain the solid state. In-situ polymerization, which is a method of forming a solid-state battery by filling a monomer between positive and negative electrodes and using thermally initiated polymerization, is considered to be effective in reducing the interfacial resistance between a polymer electrolyte and an electrode (j.am. The invention patent CN11133851A discloses a method for forming a solid-state battery by in-situ thermal initiation of difunctional monomer polymerization, wherein the battery has better charge-discharge cycle performance at high temperature, but the room-temperature conductivity of the polymer solid electrolyte is only 5.7 multiplied by 10-5S/cm, the room temperature performance of the solid-state battery is poor. Patent CN111490289A discloses a method for preparing polyion liquid electrolyte by photo-initiation polymerization, the polyion liquid electrolyte has better electrochemical performance, and the room temperature conductivity is 2.91 multiplied by 10-4S/cm, but the problem of interfacial compatibility of the polymer electrolyte with the negative electrode still remains.
When a lithium metal secondary solid-state battery is used as a power source, it is necessary to obtain a high energy density in a short time and to rapidly increase power in a specific case. The solid electrolyte can generally obtain better specific capacity under lower charge-discharge cycle rate (0.05C, 0.1C or 0.2C), but the battery capacity is rapidly reduced under high rate cycle or the electrolyte membrane is punctured by lithium dendrite to cause short circuit, so that the requirement of rapid discharge is difficult to meet. Therefore, lithium metal secondary solid-state batteries still present many challenges in terms of high-rate charge-discharge cycling.
The invention content is as follows:
aiming at the problems, the invention aims to solve the problems of low room-temperature ionic conductivity and poor interface compatibility of the existing polymer solid electrolyte, and provides a polymer solid electrolyte with high room-temperature ionic conductivity and excellent interface compatibility.
The invention provides an effective method for preparing polymer solid electrolyte by ultraviolet light initiated polymerization, which is characterized in that a mixture containing a monomer, a cross-linking agent, a binder, plastic crystals, a lithium salt and a photoinitiator is irradiated by ultraviolet light to copolymerize the monomer and the cross-linking agent to form the polymer solid electrolyte. The method does not use organic solvent, is simple to operate, and the prepared polymer solid electrolyte has the advantages of high room-temperature ionic conductivity, excellent interface compatibility, high electrochemical window, high specific capacity under high charge-discharge cycle rate and the like.
In the polymer solid electrolyte, the binder with high molecular weight and the plastic crystal are both lithium ion conductive solids, the binder is inserted into a polymer framework, the plastic crystal is filled in an interpenetrating network formed by the high molecular binder and the polymer framework, and the room temperature conductivity of the polymer solid electrolyte is improved to 10 while the mechanical property of the electrolyte is improved-3S/cm. The monomer and the cross-linking agent are liquid organic micromolecules at normal temperature, can dissolve the binder, the plastic crystal, the lithium salt and the photoinitiator into uniform liquid slurry, and initiate polymerization under ultraviolet illumination to obtain the cross-linked network polymer solid electrolyte. The polymer solid electrolyte has high room temperature conductivity (1.67X 10) when used in a lithium ion battery (example 1)-3S/cm) and good compatibility with the lithium metal interface (resistance to lithium interface R)i48 Ω), and a high electrochemical window (LSV 5.1V).
The invention provides an application of the polymer solid electrolyte, which is used for preparing a lithium ion battery.
The lithium ion battery comprises a positive electrode, a negative electrode and the polymer solid electrolyte between the positive electrode and the negative electrode. Wherein the positive electrode active material is LiFePO4 or LiCoO4、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Al0.1O2、LiNi0.6Co0.2Mn0.2O2One kind of (1). The negative active material is one of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads (MCMB), silicon carbon negative electrode, lithium titanate and metallic lithium. The lithium ion battery assembled by the invention has the characteristics of no leakage, high specific capacity, high coulomb efficiency of cyclic charge and discharge, capability of cyclic charge and discharge under high multiplying power and the like. For example, the assembled lithium iron phosphate of example 1 (LiFePO)4) The positive electrode material | polymer solid electrolyte | metal lithium battery can perform stable cycle charge and discharge under higher multiplying power, and can achieve higher specific capacity [ 0.2C (158mAh/g), 0.5C (132mAh/g), 1C (101mAh/g), 2C (85mAh/g) ] and coulombic efficiency of more than 99.8%.
The technical scheme of the invention is as follows:
the polymer solid electrolyte comprises the following components in percentage by mass:
20% -60% of a polymer skeleton; 1% -40% of a binder; 1% -40% of plastic crystal; 1% -30% of lithium salt; 0.1 to 5 percent of photoinitiator.
The polymer skeleton is composed of one or a mixture of two or more of polyethylene glycol methyl methacrylate, polyethylene glycol monomethyl ether methacrylate, methyl (2-oxo-1, 3-dioxolane) acrylate, methyl methacrylate, vinyl ethylene carbonate, propyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-oxo-1, 3-dioxolan-4-yl) butyl methacrylate, isobutyl acrylate, methacrylic acid, ethylene propylene carbonate, lauryl methacrylate, isooctyl methacrylate, and the like in an arbitrary ratio.
The binder is one or more than two of polyethylene oxide (PEO for short), polyvinylidene fluoride (PVDF for short), polyvinylidene fluoride and hexafluoropropylene copolymer (PVDF-HFP for short) and polycarbonate polymer binder which are mixed in any proportion.
The plastic crystal is one or a mixture of any two or more of ethylene carbonate, dimethyl sulfoxide, sulfolane and 3-methyl-2-oxazolidone.
The lithium salt is LiPF6、LiAsF6、LiBF4、LiClO4、LiCF3SO3Or LiN (CF)3SO2)2One or more than two of the components are mixed in any proportion.
The photoinitiator is one or more than two of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, benzoin dimethyl ether and the like which are mixed in any proportion.
The invention provides a preparation method of a high-performance polymer solid electrolyte, which comprises the following steps:
1) the preparation method comprises the steps of uniformly mixing all components including a monomer, a cross-linking agent, a binder, a plastic crystal, a lithium salt and a photoinitiator, heating and dissolving at 30-100 ℃ to form slurry which is easy to flow, and pouring the slurry into a mold with a flat bottom and a certain depth. The material of the mould comprises polytetrafluoroethylene, polycarbonate, glass, acrylic, stainless steel, polypropylene, lithium metal and the like.
2) In N2Or irradiating with ultraviolet light to initiate polymerization in inert atmosphere such as Ar for 5 s-60 min to obtain semitransparent homogeneous polymer film as solid polymer electrolyte.
The invention also provides a method for using the sameThe polymer solid electrolyte of (3) produces a lithium metal secondary battery: the lithium metal secondary battery comprises a positive electrode, a metallic lithium negative electrode and the polymer solid electrolyte between the positive electrode and the negative electrode; the positive active material is LiFePO4, LiCoO4 or LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Al0.1O2、LiNi0.6Co0.2Mn0.2O2One kind of (1).
Advantages of the invention and excellent properties of the polymer solid electrolyte:
(1) the method is simple and efficient, and the polymer solid electrolyte membrane can be synthesized by only mixing the monomer, the cross-linking agent, the binder, the plastic crystal, the lithium salt and the photoinitiator, heating for dissolution and ultraviolet light-initiated polymerization. The polymer solid electrolyte membrane can be directly assembled into a positive electrode and a negative electrode to assemble a lithium metal secondary battery, and the process that the traditional solid electrolyte needs to be cast by using an organic solvent to prepare a membrane is avoided.
(2) The combination of the cross-linking agent, the adhesive and the plastic crystal greatly improves the mechanical property and the thermal stability of the polymer solid electrolyte membrane.
(3) The room temperature conductivity of the polymer solid electrolyte can reach 0.5-5mS/cm, and the resistance to lithium interface RiAs low as 40 to 100 Ω; the electrochemical window (LSV) can reach 5.1V. The assembled solid lithium metal battery has excellent specific discharge capacity and charge-discharge cycle.
Description of the drawings:
FIG. 1 is a photograph of a polymer solid electrolyte entity of example 1.
Fig. 2 is a graph of the change in conductivity with temperature of the polymer solid electrolyte of example 1.
Fig. 3 is a linear sweep voltammogram at 25 ℃ of a stainless steel | polymer solid state electrolyte | lithium metal battery assembled using the polymer solid state electrolyte of example 1.
Fig. 4 is an electrochemical impedance spectrum at 25 c of a lithium metal/polymer solid electrolyte/lithium metal pair battery assembled using the polymer solid electrolyte of example 1.
FIG. 5 shows the lithium iron phosphate | polymer solid electrolyte | lithium metal batteries assembled using the polymer solid electrolyte of example 1 and tested for cycling charge and discharge performance at 0.2C, 0.5C, 1C, 2C, 0.2C rate at 25 ℃.
Fig. 6 is a plot of the specific capacity of lithium iron phosphate | polymer solid electrolyte | lithium metal batteries assembled using the polymer solid electrolyte of example 1 at 25 ℃ at 0.2C, 0.5C, 1C, 2C, 0.2C rates.
FIG. 7 shows lithium cobaltate LiCO assembled using the polymer solid electrolyte of example 24The specific capacity curve of the lithium titanate negative electrode battery with the polymer solid electrolyte at the temperature of 25 ℃ and the multiplying power of 0.5C.
The production process of the present invention will be described in further detail with reference to specific examples and comparative examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention.
The specific implementation mode is as follows:
according to the preparation method of the polymer solid electrolyte provided by the invention, the polymer solid electrolyte film with the thickness of 200 mu m and the diameter of 15.8mm is prepared.
Preparing a positive pole piece: adding the positive active material containing 80 mass percent of the positive active material, 10 mass percent of carbon black and 10 mass percent of polyvinylidene fluoride (PVDF for short) as a binder into N-methyl pyrrolidone, ball-milling for 48 hours in a ball mill to form viscous slurry, and coating the viscous slurry on an aluminum foil. Finally, the mixture is placed in a vacuum drying oven and dried for 12 hours in vacuum at the temperature of 100 ℃.
Negative pole piece: adding the positive active material containing 80 mass percent of the positive active material, 10 mass percent of carbon black and 10 mass percent of polyvinylidene fluoride (PVDF for short) as a binder into N-methyl pyrrolidone, ball-milling for 48 hours in a ball mill to form viscous slurry, and coating the viscous slurry on an aluminum foil. Finally, placing the mixture in a vacuum drying oven, and carrying out vacuum drying for 12 hours at the temperature of 100 ℃; or a metal lithium sheet is taken as the negative electrode.
Assembling and testing of the battery: respectively assembling a polymer solid electrolyte membrane, two stainless steel sheets, a polymer solid electrolyte, a lithium metal, one stainless steel sheet, the polymer solid electrolyte and two lithium metals into a 2032 type button cell, respectively measuring the electric conductivity, a linear scanning voltammetry curve and an electrochemical impedance spectrogram of the button cell at different temperatures by using a Princeton electrochemical workstation, calculating according to a formula 3 to obtain the lithium ion conductivity, and performing charge-discharge circulation of the battery at different multiplying powers by using a blue battery circulation system (CT 2001A).
Example 1:
benzoin dimethyl ether (0.30g), vinyl ethylene carbonate (4.0g), ethylene carbonate (6.0g), triethylene glycol dimethacrylate (2.0g), PVDF-HFP (molecular weight 600000g/mol) (2.0g) and LiN (CF)3SO2)2(2.0g) are mixed, stirred well, heated to 60 ℃ and held for 5 minutes to form a slurry which is homogeneous in appearance. Pouring the slurry into a glass mold which is preheated to 60 ℃ and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mold, cooling to 25 ℃, and irradiating for 30min by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 210 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.67X 10 at 25 deg.C-3S/cm, and 48. omega. resistance to lithium interface.
Assembled LiFePO4The first-circle discharge capacity of the polymer solid electrolyte lithium metal negative electrode battery is 132mAh/g at a high rate of 0.5C.
Example 2:
2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (0.20g), polyethylene glycol monomethyl ether methacrylate (4.0g), 2-oxo-1, 3-dioxolan-4-yl butyl methacrylate (2.0g), ethylene carbonate (3.0g), ethylene glycol dimethacrylate (2.0g), PEO (molecular weight 600000g/mol) (2).0g)、LiPF6(4.0g) mixing, stirring uniformly, heating to 30 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into a polytetrafluoroethylene mold which is preheated to 30 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mold, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 150 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.30X 10 at 25 deg.C-3S/cm, and an interface resistance to lithium of 51. omega.
Assembled LiCoO4The first-circle discharge capacity of the lithium titanate cathode full cell with the polymer solid electrolyte is 96mAh/g at a high rate of 0.5C.
Example 3:
2-hydroxy-2-methyl-1-phenyl acetone (0.10g), methacrylic acid (2-oxo-1, 3-dioxolan-4-yl) butyl ester (6.0g), polyethylene glycol methacrylate (molecular weight 550g/mol), ethylene carbonate (2.0g), ethylene glycol dimethacrylate (2.0g), PEO (molecular weight 600000g/mol) (2.0g), LiPF6(4.0g) mixing, stirring uniformly, heating to 45 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into a polypropylene mould which is preheated to 45 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mould, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 180 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.56X 10 at 25 deg.C-3S/cm, and an interface resistance to lithium of 51. omega.
Assembled LiNi0.8Co0.1Mn0.1O2The first-circle discharge capacity of the polymer solid electrolyte lithium metal negative electrode battery is 171 mAh/g at a high rate of 0.5C.
Example 4:
2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (0.30g), vinylethylene carbonate (4.0g), sulfolane (2.0g), propyl methacrylate (2.0g), polyethylene glycol dimethacrylate (molecular weight 550g/mol)(2.0g), PEO (molecular weight 200000 g/mol) (2.0g), LiCF3SO3(4.0g) mixing, stirring uniformly, heating to 55 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into a glass mold which is preheated to 55 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mold, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 130 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 2.3X 10 at 25 deg.C-3S/cm, 57. omega. resistance to lithium interface.
Assembled LiNi0.6Co0.2Mn0.2O2The first discharge capacity of the polymer solid electrolyte and the artificial graphite cathode is 12 mAh/g at a high rate of 0.5C.
Example 5:
2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl]-1-propanone (0.30g), lauryl methacrylate (6.0g), dimethyl sulfoxide (6.0g), 2-oxo-1, 3-dioxolan-4-yl) butyl methacrylate (2.0g), polyethylene glycol dimethacrylate (molecular weight 550g/mol) (2.0g), PVDF (molecular weight 1000000g/mol) (2.0g) (2.0g), LiN (CF)3SO2)2(2.0g) mixing, stirring uniformly, heating to 85 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into an acrylic mould which is preheated to 85 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mould, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 180 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 2.56X 10 at 25 deg.C-3S/cm, and an interface resistance to lithium of 56. omega.
Assembled LiNi0.8Co0.1Al0.1O2The first-cycle discharge capacity of the polymer solid electrolyte lithium metal battery is 165mAh/g at a high rate of 0.5C.
Example 6:
2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl)) Phenyl radical]-1-butanone (0.30g), polyethylene glycol methyl methacrylate (molecular weight 750g/mol) (6.0g), ethylene propylene carbonate (2.0g), triethylene glycol dimethacrylate (3.0g), PEO (molecular weight 600000g/mol) (2.0g) (2.0g), LiCF3SO3(4.0g) mixing, stirring uniformly, heating to 75 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into a glass mold which is preheated to 75 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mold, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 160 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.26X 10 at 25 deg.C-3S/cm, and an interface resistance to lithium of 46. omega.
Assembled LiNi0.8Co0.1Mn0.1O2The first-circle discharge capacity of the lithium titanate negative battery with the polymer solid electrolyte is 112 mAh/g at a high rate of 0.5C.
Example 7:
2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl]-1-butanone (0.20g), (2-oxo-1, 3-dioxolane) methyl acrylate (2.0g), isooctyl methacrylate (6.0g), polyethylene glycol dimethacrylate (molecular weight 550g/mol) (2.0g), PVDF-HFP (molecular weight 600000g/mol) (2.0g) (2.0g), LiBF4(4.0g) mixing, stirring uniformly, heating to 100 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into an acrylic mould which is preheated to 100 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mould, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 190 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.68X 10 at 25 deg.C-3S/cm, and an impedance to lithium interface of 45. omega.
Assembled LiNi0.5Co0.2Mn0.3O2The first-circle discharge capacity of the polymer solid electrolyte Li electricity is 126mAh/g at a high rate of 0.5C.
Example 8:
2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl]-1-butanone (0.30g), ethylene carbonate (2.0g), lauryl methacrylate (6.0g), ethylene glycol dimethacrylate (4.0g), PVDF-HFP (molecular weight 200000 g/mol) (2.0g) (4.0g), LiN (CF)3SO2)2(5g) Mixing, stirring, heating to 60 deg.C, holding for 5 min to obtain homogeneous slurry, pouring the slurry into glass mold heated to 60 deg.C in advance and having size of 40 × 50 × 0.2mm, spreading in the mold, cooling to 25 deg.C, and irradiating with ultraviolet ray of 365nm wavelength and power of 2000W for 30min to obtain polymer solid electrolyte membrane with thickness of 154 μm. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 2.34X 10 at 25 deg.C-3S/cm, and 48. omega. resistance to lithium interface.
Assembled LiNi0.6Co0.2Mn0.2O2The first-cycle discharge capacity of the polymer solid electrolyte Li electricity is 165mAh/g at a high rate of 0.5C.
Example 9:
2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (0.10g), propyl methacrylate (8.0g), sulfolane (4.0g), 2-oxo-1, 3-dioxolan-4-yl) butyl methacrylate (1.0g), polyethylene glycol diethylcrotonate (molecular weight 750g/mol) (4.0g), PVDF (molecular weight 600000g/mol) (2.0g) (4.0g), LiCF3SO3(2.0g) mixing, stirring uniformly, heating to 60 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into a polycarbonate mould which is preheated to 60 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mould, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 146 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.64X 10 at 25 deg.C-3S/cm, and an interface resistance to lithium of 49. omega.
Assembled LiNi0.8Co0.1Mn0.1O2I PolymerThe first-cycle discharge capacity of the solid electrolyte Li at a high rate of 0.5C is 159 mAh/g.
Example 10:
2-hydroxy-2-methyl-1-phenyl acetone (0.20g), ethylene propylene carbonate (5.0g), isooctyl methacrylate (2.0g), sulfolane (2.0g), tetraethylene glycol dimethacrylate (4.0g), PVDF-HFP (molecular weight 600000g/mol) (2.0g), LiN (CF3SO2)2(4.0g) were mixed, stirred uniformly, heated to 60 ℃ and kept warm for 5 minutes to form a slurry with a homogeneous appearance, the slurry was poured into a glass mold with dimensions of 40X 50X 0.2mm previously heated to 60 ℃, uniformly laid in the mold, cooled to 25 ℃, irradiated with ultraviolet light with power of 2000W and wavelength of 365nm for 30 minutes to form a polymer solid electrolyte membrane with a thickness of 143 μm. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 1.58X 10 at 25 deg.C-3S/cm, 50. omega. for lithium interface resistance.
Assembled LiNi0.5Co0.2Mn0.3O2The first-circle discharge capacity of the polymer solid electrolyte Li is 167mAh/g under the high multiplying power of 0.5C. Reference example 1:
benzoin dimethyl ether (0.30g), ethylene carbonate (4.0g), polyethylene glycol butyl dimethacrylate (molecular weight 860g/mol) (2.0g), PVDF-HFP (molecular weight 600000g/mol) (2.0g) (4.0g), LiN (CF3SO2)2(5.0g) are mixed, stirred uniformly, heated to 60 ℃ and kept warm for 5 minutes to form slurry with homogeneous appearance, the slurry is poured into a glass mold which is preheated to 60 ℃ and has the size of 40 multiplied by 50 multiplied by 0.2mm, and is uniformly spread in the mold, the temperature is reduced to 25 ℃, the glass mold is irradiated by ultraviolet light with power of 2000W and wavelength of 365nm for 30 minutes to form a polymer solid electrolyte membrane with the thickness of 192 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was found to have a conductivity of 2.3X 10 at 25 deg.C-6S/cm. The conductivity at room temperature is low, and the normal cycle charge and discharge of the battery cannot be met.
Reference example 2:
2-hydroxy-2-methyl-1-phenylpropanone (0.20g), 2-oxo-1, 3-dioxolan-4-yl butyl methacrylate (5.0g), and poly (I-phenyl-N-methyl-ethyl methacrylate)Ethylene glycol diethyl butenoic acid ethyl ester (2.0g), PVDF-HFP (molecular weight 600000g/mol) (2.0g) (2.0g), LiN (CF)3SO2)2(4.0g) mixing, stirring uniformly, heating to 60 ℃ and keeping the temperature for 5 minutes to form slurry with homogeneous appearance, pouring the slurry into a glass mold which is preheated to 60 ℃ in advance and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading the slurry in the mold, cooling to 25 ℃, and irradiating for 30 minutes by using ultraviolet light with the power of 2000W and the wavelength of 365nm to form the polymer solid electrolyte membrane with the thickness of 162 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was measured to have a conductivity of 2X 10 at 25 deg.C-5S/cm, and an impedance to lithium interface of 800. omega. Low room temperature conductivity and high interface impedance.
Assembled LiFePO4The first-circle discharge capacity of the polymer solid electrolyte Li electricity is 80mAh/g at a high rate of 0.5C.
Reference example 3:
mixing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (0.30g), ethylene propylene carbonate (5.0g), polyethylene glycol methacrylate (2.0g), PEO (molecular weight of 600000g/mol) (2.0g) (2.0g) and LiCF3SO3(4.0g), stirring uniformly, heating to 60 ℃ and keeping the temperature for 5 minutes to form slurry with uniform appearance, pouring the slurry into a glass mold which is preheated to 60 ℃ and has the size of 40 multiplied by 50 multiplied by 0.2mm, uniformly spreading in the mold, cooling to 25 ℃, irradiating by ultraviolet light with power of 2000W and wavelength of 365nm for 30 minutes to form a polymer solid electrolyte membrane with the thickness of 170 mu m. The conductivity and the lithium interfacial resistance were measured by the following methods, and the polymer solid electrolyte membrane was measured to have a conductivity of 2X 10 at 25 deg.C-4S/cm, and an interface resistance to lithium of 231. omega. Has higher conductivity but larger interface impedance.
Assembled LiFePO4The first-cycle discharge capacity of the polymer solid electrolyte Li electricity is 102mAh/g at a high rate of 0.5C.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (11)
1. A polymer solid electrolyte is characterized by being composed of the following components in percentage by mass:
0.1% -60% of polymer skeleton; 1% -80% of a binder; 1% -80% of plastic crystal; 1% -80% of lithium salt; 0.1 to 5 percent of photoinitiator.
2. The solid electrolyte of claim 1, wherein: the polymer skeleton is composed of one or a mixture of two or more of polyethylene glycol methyl methacrylate, polyethylene glycol monomethyl ether methacrylate, methyl (2-oxo-1, 3-dioxolane) acrylate, methyl methacrylate, vinyl ethylene carbonate, propyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-oxo-1, 3-dioxolan-4-yl) butyl methacrylate, isobutyl acrylate, methacrylic acid, ethylene propylene carbonate, lauryl methacrylate, isooctyl methacrylate, and the like in an arbitrary ratio.
3. The solid electrolyte of claim 1, wherein: the binder is one or more than two of polyethylene oxide (PEO for short), polyvinylidene fluoride (PVDF for short), polyvinylidene fluoride and hexafluoropropylene copolymer (PVDF-HFP for short) and polycarbonate polymer binder which are mixed in any proportion.
4. The solid electrolyte of claim 1, wherein: the plastic crystal is one or a mixture of any two or more of ethylene carbonate, dimethyl sulfoxide, sulfolane and 3-methyl-2-oxazolidone.
5. The solid electrolyte of claim 1, wherein: the lithium salt is LiPF6、LiAsF6、LiBF4、LiClO4、LiCF3SO3Or LiN (CF)3SO2)2One or more than two of the components are mixed in any proportion.
6. The solid electrolyte of claim 1, wherein: the polymerization method is photoinitiator free radical polymerization.
7. The method for producing a solid electrolyte according to claim 1, characterized in that: mixing all the components including monomer, cross-linking agent, adhesive, plastic crystal, lithium salt and photoinitiator, heating to dissolve at 30-100 deg.c, dissolving in N2Or initiating polymerization by ultraviolet irradiation under inert atmosphere such as Ar, wherein the polymerization time is 5 seconds to 120 minutes.
8. The solid electrolyte of claim 1, wherein: the membrane thickness of the polymer solid electrolyte is 10-240 μm; the room-temperature (25 ℃) lithium ion conductivity of the polymer solid electrolyte is 0.5-5 mS/cm; the room temperature (25 ℃) of the polymer solid electrolyte and the lithium metal has 40-140 omega of lithium interface impedance.
9. The solid electrolyte of claim 1, wherein: for preparing a lithium metal secondary battery comprising a positive electrode, a negative electrode, and a polymer solid electrolyte between the positive and negative electrodes.
10. Use of a solid-state electrolyte according to claim 1, characterized in that: the anode active material is LiFePO4、LiCoO4、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Al0.1O2、LiNi0.6Co0.2Mn0.2O2And the like, in the commercial positive electrode.
11. Use of a solid-state electrolyte according to claim 1, characterized in that: the negative active material is any of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads (MCMB), silicon carbon negative electrodes, lithium titanate, metal lithium and other commercial negative electrodes.
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| CN113839099A (en) * | 2021-09-24 | 2021-12-24 | 哈尔滨理工大学 | Preparation method of high-performance all-solid-state lithium ion battery |
| CN114188518A (en) * | 2021-11-30 | 2022-03-15 | 吉林省东驰新能源科技有限公司 | Organic-inorganic solid interface composite material and preparation method and application thereof |
| CN115050964A (en) * | 2022-06-29 | 2022-09-13 | 北京航空航天大学 | Preparation method of solid electrolyte binder, binder and battery |
| CN115275336A (en) * | 2022-08-02 | 2022-11-01 | 宁德新能源科技有限公司 | Lithium metal battery and application thereof |
| CN115845632A (en) * | 2022-12-06 | 2023-03-28 | 中国科学技术大学 | Anion exchange membrane and preparation method and application thereof |
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2021
- 2021-06-15 CN CN202110219800.2A patent/CN113161608A/en active Pending
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| CN113839099A (en) * | 2021-09-24 | 2021-12-24 | 哈尔滨理工大学 | Preparation method of high-performance all-solid-state lithium ion battery |
| CN114188518A (en) * | 2021-11-30 | 2022-03-15 | 吉林省东驰新能源科技有限公司 | Organic-inorganic solid interface composite material and preparation method and application thereof |
| CN115050964A (en) * | 2022-06-29 | 2022-09-13 | 北京航空航天大学 | Preparation method of solid electrolyte binder, binder and battery |
| CN115050964B (en) * | 2022-06-29 | 2023-11-03 | 北京航空航天大学 | Preparation method of solid electrolyte binder, binder and battery |
| CN115275336A (en) * | 2022-08-02 | 2022-11-01 | 宁德新能源科技有限公司 | Lithium metal battery and application thereof |
| CN115845632A (en) * | 2022-12-06 | 2023-03-28 | 中国科学技术大学 | Anion exchange membrane and preparation method and application thereof |
| CN115845632B (en) * | 2022-12-06 | 2024-05-17 | 中国科学技术大学 | Anion exchange membrane and preparation method and application thereof |
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