CN115275337A - Composite solid electrolyte membrane, preparation method thereof and lithium ion solid battery - Google Patents
Composite solid electrolyte membrane, preparation method thereof and lithium ion solid battery Download PDFInfo
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- CN115275337A CN115275337A CN202211029870.2A CN202211029870A CN115275337A CN 115275337 A CN115275337 A CN 115275337A CN 202211029870 A CN202211029870 A CN 202211029870A CN 115275337 A CN115275337 A CN 115275337A
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- 239000012528 membrane Substances 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007787 solid Substances 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 197
- 239000002002 slurry Substances 0.000 claims abstract description 89
- 238000005507 spraying Methods 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000889 atomisation Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims description 28
- 159000000002 lithium salts Chemical class 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000005518 polymer electrolyte Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 17
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 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 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- 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 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 3
- 239000010405 anode material Substances 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 230000006978 adaptation Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 238000010345 tape casting Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000010408 film Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000003292 glue Substances 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 241000894007 species Species 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 6
- 229910010941 LiFSI Inorganic materials 0.000 description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000891 common polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 1
- 229910011250 Li3Zr2Si2PO12 Inorganic materials 0.000 description 1
- 229910010603 Li6.25La3Zr2Al0.25O12 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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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- 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)
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Abstract
The invention provides a composite solid electrolyte membrane, a preparation method thereof and a lithium ion solid battery, and particularly relates to the field of solid electrolytes. The preparation method of the composite solid electrolyte membrane comprises the following steps: preparing first electrolyte slurry, forming a film in a tape casting or coating mode, spraying second electrolyte slurry of the high-voltage-resistant cathode material onto the first electrolyte membrane in an atomization spraying mode, and forming the composite solid electrolyte membrane after in-situ solidification. The composite solid electrolyte membrane prepared by the invention can realize the adaptation with a high-voltage anode material, avoid the improvement of the internal resistance of the battery, and improve the capability of inhibiting the growth of lithium dendrites, thereby effectively improving the capacity and the safety of the battery.
Description
Technical Field
The invention relates to the field of lithium ion solid-state batteries, in particular to a composite solid electrolyte membrane, a preparation method thereof and a lithium ion solid-state battery.
Background
In recent years, with the continuous development of electric automobiles, the market puts higher demands on the comprehensive performance of lithium batteries, such as battery capacity, cycle performance and safety performance, and particularly the safety performance is the key of the application of the lithium batteries. However, organic solvent electrolytes commonly used in liquid lithium batteries can generate lithium dendrites during battery cycling, which can cause short circuit of the batteries. Moreover, the organic solvent in the electrolyte is an inflammable substance, and after the short circuit is caused by the penetration of dendrites inside the battery or external collision, the organic solvent is very easy to react with the ternary or quaternary high nickel positive electrode decomposition product commonly adopted by the power battery, so that the ignition and even explosion occur.
The solid-state battery utilizes the solid-state electrolyte to replace the liquid-state electrolyte, so that the potential safety hazard of battery combustion and explosion can be fundamentally solved, and the solid-state electrolyte can be matched with the metal lithium, so that the battery capacity is greatly improved, therefore, the solid-state battery is the main development direction of the lithium battery, and the development core of the solid-state battery is the solid-state electrolyte. The oxide solid electrolyte in the solid electrolyte has the advantages of higher ionic conductivity, stable structure, wide electrochemical window and the like, so that the oxide solid electrolyte is widely applied in the development process of solid batteries. However, the pure ceramic film is difficult to control within 100um, and has poor interface contact with the active component of the battery, and in addition, the pure ceramic film is easy to break in the battery cycle process due to the internal stress, and a high-capacity battery cell cannot be prepared, so that the pure ceramic electrolyte film cannot meet the requirements of a power battery. In order to solve the above problems, it is common to compound an oxide electrolyte with a polymer electrolyte, and to improve the problems existing in the oxide electrolyte by using the flexibility and viscoelasticity of the polymer.
At present, the preparation methods of oxide composite electrolyte flexible membranes mainly comprise a coating method, a casting method, a vapor deposition method, a solution casting method, a co-extrusion method and the like, the traditional preparation methods cannot prepare oxide thin films with compact structures, some traditional preparation methods use a binder or a polymer electrolyte to connect oxide electrolyte particles, but the electrical conductivity of the binder and a common polymer is low, the electrochemical stability window of the common polymer electrolyte is low, the common polymer electrolyte is not suitable for high-nickel ternary or quaternary high-voltage anode materials, some polymer electrolytes are stable to the high-nickel ternary materials, but the ionic conductivity is low, and the battery performance is also adversely affected due to the fact that the content of the polymer is too high.
Therefore, there is a need to develop a method for preparing a composite solid electrolyte to prepare a composite solid electrolyte membrane that is highly dense and stable to a high-nickel ternary cathode material.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a composite solid electrolyte membrane, a preparation method thereof and a solid battery, which can prepare a composite oxide electrolyte flexible membrane material with high density, can keep stability for a positive high-nickel ternary or quaternary positive electrode material, and improve the ionic conductivity of the composite membrane material and the safety performance of the battery.
To achieve the above and other related objects, the present invention provides a method for preparing a composite solid electrolyte membrane, comprising at least the steps of:
preparing a first electrolyte slurry, wherein the first electrolyte slurry is an inorganic oxide electrolyte slurry or an inorganic-organic composite electrolyte slurry;
coating the first electrolyte slurry on a base material, forming a film and drying to obtain a first electrolyte film;
uniformly mixing a polymer monomer, an initiator, a lithium salt and an organic solvent to prepare second electrolyte slurry;
the second electrolyte slurry is coated on the first electrolyte membrane in an atomized spray mode, forming a second electrolyte membrane on the first electrolyte membrane after in-situ curing;
and peeling the substrate to obtain the composite solid electrolyte membrane.
In one example of the present invention, in the inorganic oxide electrolyte slurry, the mass percentage of the oxide electrolyte is 15 to 35%, the mass percentage of the binder is 1 to 5%, and the balance is the organic solvent; in the inorganic-organic composite electrolyte slurry, the mass percent of an oxide electrolyte is 12-25%, the balance is a mixed solution of a polymer electrolyte, a lithium salt and an organic solvent, wherein the total mass of the polymer electrolyte and the lithium salt is 2-5% of the mass of the mixed solution, and the mass ratio of the polymer electrolyte to the lithium salt is 7:1 to 20:1.
in one example of the present invention, the inorganic oxide electrolyte includes LLZO (Li) 7 La 3 Zr 2 O 12 )，LLZAO(Li 6.25 La 3 Zr 2 Al 0.25 O 12 )，LLZTO(Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 )，LLZNO(Li 7 La 3 Zr 1.75 Nb 0.25 O 12 )，LATP(Li 3 Al x Ti 2-x (PO 4 ) 3 )，LAGP(Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 )，LZSPO(Li 3 Zr 2 Si 2 PO 12 )，SiO 2 Or Al 2 O 3 Any one or a combination of at least two of them.
In AN example of the present invention, the organic solvent includes any one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), acetonitrile (AN), or acetone, or a combination of at least two thereof.
In an example of the present invention, the lithium salt includes one or more of lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium dioxalate borate in combination.
In one example of the present invention, the first electrolyte slurry is formed by casting or coating, and the first electrolyte membrane has a thickness of 1 to 100 μm.
In one example of the present invention, when the first electrolyte membrane is prepared, after the drying process is finished, the hot pressing process is further included, and the hot pressing process has hot pressing parameters of 40 to 80 ℃ and 30 to 60MPa for 10 to 80min.
In one example of the present invention, preparing the second electrolyte slurry includes: at normal temperature, adding the lithium salt into the organic solvent, and uniformly mixing and stirring; then adding the polymer monomer and the initiator, and magnetically stirring for 20-40 min at room temperature; in the second electrolyte slurry, the mass percent of the polymer monomer is 5-15%, the mass of the initiator is 1-10% of the mass of the polymer monomer, and the ratio of the organic solvent to the lithium salt is 1:1 to 3:1.
in an example of the present invention, the organic solvent in the second electrolyte slurry is a carbonate or a carbonate-containing organic solvent, including one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, and methylethyl carbonate; the polymer monomer comprises one or a combination of more of triethylene glycol dimethacrylate, ethylene glycol diacrylate and polyethylene glycol monomethyl ether methacrylate; the initiator is azobisisobutyronitrile or benzoyl peroxide.
In one example of the present invention, the atomized spray includes: and injecting the second electrolyte slurry into an ultrasonic atomization generator, atomizing by the ultrasonic atomization generator, and spraying the second electrolyte slurry onto the first electrolyte membrane, wherein the spraying distance is controlled to be 5-10 cm, and the spraying speed is 1-2 cm/s, and the spraying speed is 1-50 mu m.
The invention also provides a composite solid electrolyte membrane prepared by the preparation method.
The invention also provides a lithium ion solid-state battery which comprises the composite solid electrolyte membrane prepared by the preparation method.
According to the preparation method of the composite solid electrolyte membrane, the second electrolyte slurry (polymer electrolyte slurry) of the high-nickel-resistant ternary or quaternary high-voltage positive electrode material is prepared and then sprayed on the surface of the first electrolyte membrane (inorganic oxide or inorganic-organic composite electrolyte membrane), so that the effective control of the thickness of the coating is realized, the high-voltage-resistant characteristic of the electrolyte is improved, the use of the polymer electrolyte is reduced, and the influence on the ionic conductivity of the composite solid electrolyte membrane is reduced.
The second electrolyte slurry is sprayed on the first electrolyte membrane in an atomization spraying mode, polymer molecules can penetrate into gaps of the first electrolyte membrane, and then the composite solid electrolyte membrane is formed through in-situ polymerization, so that the density and the interface contact performance of the first electrolyte membrane are improved, and the flexibility of the first electrolyte membrane is improved. The density of the composite electrolyte membrane is higher, so that the generation of lithium dendrite in the cycle process of the battery can be inhibited, the safety performance of the battery is improved, and the internal resistance of the battery is not obviously increased; in addition, the second electrolyte membrane has the characteristic of stability to high-voltage anode materials such as high-nickel ternary or quaternary electrolyte membranes, so that the second electrolyte membrane can be matched with the high-voltage anode materials, and the capacity of the battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a composite solid electrolyte membrane according to the present invention;
FIG. 2 is a flowchart of a method for manufacturing a composite solid electrolyte membrane according to the present invention in step S1 in one embodiment;
FIG. 3 is a flowchart of a method for producing a composite solid electrolyte membrane according to the present invention at step S1 in another embodiment;
FIG. 4 is a flow chart illustrating a method for manufacturing a composite solid electrolyte membrane according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
It should be understood that the terms "upper", "lower", "left", "right", "middle" and "one" used herein are for clarity of description only, and are not intended to limit the scope of the invention, and that changes or modifications in the relative relationship may be made without substantial technical changes and modifications.
The invention provides a composite solid electrolyte membrane, a preparation method thereof and a lithium ion solid battery, which can realize the adaptation of the composite solid electrolyte membrane and a high-voltage anode material, avoid the improvement of the internal resistance of the battery, and improve the capability of the composite solid electrolyte membrane for inhibiting the growth of lithium dendrites, thereby effectively improving the capacity and the safety of the battery.
Referring to fig. 1, the present invention provides a method for preparing a composite solid electrolyte membrane, which at least comprises the following steps:
s1, preparing first electrolyte slurry;
s2, coating the first electrolyte slurry on a base material, forming a film and drying to obtain a first electrolyte film;
s3, uniformly mixing the polymer monomer, the initiator, the lithium salt and the organic solvent to prepare second electrolyte slurry;
s4, coating the second electrolyte slurry on the first electrolyte membrane in an atomization spraying mode, and forming a second electrolyte membrane on the first electrolyte membrane after in-situ solidification;
and S5, stripping the base material to obtain the composite solid electrolyte membrane.
The first electrolyte slurry in step S1 is an inorganic oxide electrolyte slurry or an inorganic-organic composite electrolyte slurry.
Referring to fig. 1 and 2, when the prepared first electrolyte slurry is an inorganic oxide slurry, step S1 specifically includes the following steps:
s11, adding oxide electrolyte into an organic solvent, mixing and stirring to obtain electrolyte mixed liquor;
s12, mixing and stirring the binder and the solvent until the mixture is clear and free of bubbles to obtain a glue solution;
and S13, adding the glue solution prepared in the step S12 into the electrolyte mixed solution dispersed in the step S11, uniformly stirring, and adjusting the solid content and viscosity of the slurry through an organic solvent and the glue solution to obtain inorganic oxide slurry.
The inorganic oxide electrolyte in step S11 includes LLZO, LLZAO, LLZTO, LLZNO, LATP, LAGP, LZPO, siO 2 Or Al 2 O 3 Any one or a combination of at least two of them, i.e. the inorganic oxide electrolyte may be any one of the listed oxide species, e.g. may be LLZO or LLZAO or LLZTO or LLZNO or LATP or LAGP or LZPO or SiO 2 Or Al 2 O 3 (ii) a Also, combinations of any two or more of the listed oxidizing species are possible, such as compositions of LLZO and LLZAO, compositions of LATP and LAGP, compositions of LLZTO, LLZNO and LATP, LLZO, siO 2 、Al 2 O 3 And LZSPO, and the like, which are not specifically listed here, and when the oxide electrolyte is a few kinds of compositions, the proportions of the components in the compositions are not limited, and they may be mixed in any proportions. The inorganic oxide electrolyte includes, but is not limited to, those listed above, and other inorganic oxide electrolytes having equivalent effects may be used.
The organic solvent in step S11 is denoted as a first solvent, and the first solvent includes any one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, acetonitrile and acetone or a combination of at least two of them, that is, the first solvent may be any one of the solvents listed above, such as N-methylpyrrolidone or N, N-dimethylformamide or N, N-dimethylacetamide or acetonitrile or acetone; combinations of two or more of the above-listed solvents, for example, a mixture of N-methylpyrrolidone and N, N-dimethylformamide, or a mixture of N, N-dimethylacetamide, acetonitrile and acetone, or a mixture of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, acetonitrile and acetone, and the like, are also possible, and when the first solvent is a mixture of several kinds, the proportions of the components in the mixture are not limited, and they may be mixed in any proportions. The first solvent includes, but is not limited to, the above-listed species, and other organic solvents having equivalent effects may be used.
In step S11, a small amount of dispersant is further added to grind the oxide electrolyte solid particles to a particle size of 0.2 to 0.8 μm, for example, any value within the above range such as 0.2 μm, 0.4 μm, 0.6 μm, or 0.8 μm, when preparing the electrolyte mixture. The solid particles of the oxide electrolyte may be refined by adding a dispersant, so that the electrolyte in the prepared first electrolyte slurry is uniformly dispersed to produce a uniformly distributed first electrolyte membrane. The amount of the dispersant added is 0.2 to 1% by mass of the oxide electrolyte, and may be any value within the above range, for example, 0.2%, 0.5%, 0.7%, or 1% by mass of the oxide electrolyte.
When the glue solution is prepared in the step S12, polyvinylidene fluoride (PVDF) may be used as the binder, and any one or a combination of more of the above listed first solvents may be used as the solvent; the concentration of PVDF in the dope is 5-10%, for example, the concentration of PVDF can be 5%, 8%, or 10%; preferably, the concentration of PVDF is 10%.
The mass percentage of the oxide electrolyte in the inorganic oxide electrolyte slurry prepared in step S13 is 15 to 35%, for example, any value in the above range such as 15%, 25%, 30%, or 35%; the mass percentage of the binder is 1 to 5%, for example, 1%, 3%, or 5% or any value within the above range; the balance of organic solvent and a small amount of dispersant.
Referring to fig. 1 and 3, when the prepared first electrolyte slurry is an inorganic-organic composite electrolyte slurry, step S1 specifically includes the following steps:
s101, mixing polymer electrolyte and lithium salt according to a certain proportion, adding an organic solvent, and uniformly stirring to obtain a mother solution;
s102, weighing oxide electrolyte, mixing with an organic solvent, stirring uniformly, adding the mixture into the mother solution, and dispersing uniformly to obtain the inorganic-organic composite electrolyte slurry.
The polymer electrolyte in step S101 includes, but is not limited to, any one or more of polyvinyl chloride (PVC), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), i.e. the polymer electrolyte may be any one of the above listed polymer species, for example, the polymer electrolyte is PVC or PEO or PAN, etc.; the polymer electrolyte may be any two or more combinations of the above listed types, such as a combination of PVC and PEO, or a combination of PAN and PVDF, or a combination of PEO, PAN and PVDF, etc., and is not specifically listed here, and when the polymer electrolyte is a plurality of combinations, the proportions of the components in the composition are not limited, and the components may be mixed in any proportions. The organic solvent may employ any one or more of the first solvents listed above.
The lithium salt includes, but is not limited to, one or more of lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate and lithium dioxalate borate, i.e., the lithium salt may be any of the above listed species, such as lithium perchlorate or lithium hexafluoroarsenate or lithium hexafluorophosphate or lithium bistrifluoromethanesulfonylimide or lithium tetrafluoroborate or lithium trifluoromethanesulfonate or lithium dioxalate borate; the lithium salt may be any combination of two or more of the above-listed species, such as a combination of lithium perchlorate and lithium hexafluoroarsenate, or a combination of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonimide and lithium tetrafluoroborate, or a combination of lithium hexafluorophosphate, lithium trifluoromethanesulfonate and lithium dioxalate borate, and when the lithium salt is a plurality of combinations, the ratio of the components in the composition is not limited, and it is sufficient to mix them in any ratio. The mass ratio of the polymer electrolyte to the lithium salt in preparing the mother liquor is 7:1-20, for example 7:1, 10.
In step S102, the oxide electrolyte may be selected from any one or more combinations of the oxide electrolytes listed above, and will not be described herein again. Weighing the oxide electrolyte in a glove box, then placing the weighed oxide electrolyte in a sample bottle, adding a small amount of organic solvent, uniformly dispersing, pouring into mother liquor, and stirring and dispersing until a white emulsion is formed. The dispersion method is not limited in the present application, and a stirring method conventional in the art, such as ultrasonic + magnetic stirring or magnetic stirring, may be adopted, for example, ultrasonic dispersion is performed for 5 to 10min, then the sample is sealed, heated in a water bath at 60 ℃, and magnetically stirred at 1000rpm for 2h, so as to prepare the inorganic-organic composite electrolyte slurry. In the inorganic-organic composite electrolyte slurry, the mass percentage of the oxide electrolyte is 12 to 25%, for example, 12%, 18% or 25%, and the balance is the polymer electrolyte, the lithium salt and the organic solvent, wherein the total mass of the polymer electrolyte and the lithium salt accounts for 2 to 5% of the mass of the mixed liquid of the polymer electrolyte, the lithium salt and the organic solvent, and for example, the mass ratio of the polymer electrolyte to the lithium salt is 7: 1-20.
Referring to fig. 1, in step S2, the first electrolyte slurry prepared in step S1 is coated on a substrate, formed into a film, and dried to obtain a first electrolyte film, wherein the substrate may be, for example, a wet or dry PP film, a PE film, or the like; the film forming method can be casting or coating, and the specific process can refer to the conventional method in the field, which is not described herein. Preferably, the drying process further comprises a hot pressing process, and the density of the oxide can be further improved through the hot pressing process. The hot pressing treatment specifically comprises: placing the dried flexible membrane at 40-80 ℃ and pressing for 10-80 min under the pressure of 30-60 MPa; wherein, the hot pressing temperature can be any value in the range of 40 ℃, 60 ℃ or 80 ℃ and the like; the pressure can be selected to be any value in the above range such as 30MPa, 40MPa, 50MPa or 60 MPa; the pressing time may be selected to be any value within the above range, such as 10min, 30min, 50min, or 80min. The parameters for the autoclave treatment may be selected within the above range depending on the characteristics of the material. After the hot pressing treatment, a first electrolyte membrane having a relatively high density is obtained, and the thickness of the first electrolyte membrane is 1 to 100 μm, further 10 to 60 μm, for example, any value within the above range such as 10 μm, 30 μm, 50 μm or 60 μm. The first electrolyte membrane can ensure the mechanical property of the composite solid electrolyte membrane in the thickness range, ensure the mechanical property of the composite solid electrolyte membrane, reduce impedance and be beneficial to improving the safety and the capacity of the battery.
Referring to fig. 1, in the step S3, the second electrolyte slurry is configured such that the mass percentage of the polymer monomer is 5 to 15%, for example, 5%, 10%, or 15%, and the initiator is 1 to 10% of the mass of the polymer monomer, for example, the mass of the initiator is 1%, 5%, or 10% of the mass of the polymer monomer, and the like; the balance of lithium salt and organic solvent, the mass ratio of the organic solvent to the lithium salt is 1:1-3:1, such as 1:1, 2:1 or 3:1, and the like.
The polymer monomer includes, but is not limited to, one or more of triethylene glycol dimethacrylate, ethylene glycol diacrylate, and polyethylene glycol monomethyl ether methacrylate, i.e., the polymer monomer may be any one of the above listed species or any combination of two or three species, for example, the polymer monomer may be triethylene glycol dimethacrylate, ethylene glycol diacrylate, or polyethylene glycol monomethyl ether methacrylate, or may be a combination of triethylene glycol dimethacrylate and ethylene glycol diacrylate, or a combination of ethylene glycol diacrylate and polyethylene glycol monomethyl ether methacrylate, or a combination of triethylene glycol dimethacrylate, ethylene glycol diacrylate, and polyethylene glycol monomethyl ether methacrylate. When the polymer monomers are in combination, the proportion of each component in the composition is not limited, and the components can be mixed in any proportion.
The organic solvent in the second electrolyte slurry is referred to as a second solvent, the second solvent is a carbonate or a carbonate-containing organic solvent, the second solvent includes one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate, that is, the second solvent may be any one of the above solvents, such as ethylene carbonate or diethyl carbonate or dimethyl carbonate or methyl ethyl carbonate; combinations of any two or more of the above solvents may also be used, such as a combination of ethylene carbonate and diethyl carbonate, or a combination of dimethyl carbonate and methyl ethyl carbonate, or a combination of diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate. When the second solvent is a combination of several kinds, the ratio of each component in the composition is not limited, and the components can be mixed in any ratio.
The initiator is mainly used for initiating the in-situ polymerization of the polymer monomer, and can be azobisisobutyronitrile or benzoyl peroxide and the like.
When preparing the second electrolyte slurry, firstly weighing the raw materials according to the proportion, adding lithium salt into the second solvent, and mixing and stirring uniformly at normal temperature; then adding polymer monomer and initiator, and magnetically stirring for 20-40 min at room temperature to obtain second electrolyte slurry.
Referring to fig. 1, step S4 is to apply the second electrolyte slurry prepared in step S3 to the first electrolyte membrane prepared in step S2 by atomization spraying. Wherein, the specific steps of atomizing and spraying comprise: and transferring the second electrolyte slurry into an ultrasonic atomization generator, wherein the ultrasonic frequency of the ultrasonic atomization generator is 2-3 MHz, the atomized second electrolyte slurry reaches a spray head through a mist outlet guide pipe, then the spraying distance is controlled to be 5-10 cm, and the second electrolyte slurry moves forwards at the speed of 1-2 cm/s to form a uniform thin film layer on the first electrolyte film. The thickness of the atomized spray is 1 to 50 μm, for example, 10 μm, 30 μm or 50 μm; preferably, the thickness of the atomized spray is 1 to 10 μm, for example 1 μm, 5 μm or 10 μm.
And in-situ curing, namely, placing the electrolyte membrane coated with the second electrolyte slurry at 50-80 ℃, such as 50 ℃, 60 ℃ or 80 ℃, and the like, drying for 3-6 h, such as 3h, 4h, 5h or 6h in vacuum, so that the polymer monomer is polymerized in situ to form a second electrolyte membrane, and rolling to obtain the composite electrolyte membrane. The spraying is carried out in an atomizing spraying mode, the polymer monomer can penetrate into gaps in the first electrolyte membrane, in-situ solidification is realized in the subsequent drying process, and the density of the composite electrolyte is improved while the interface contact between the polymer monomer and the first electrolyte membrane is improved.
Step S5 is to peel off the substrate to obtain the composite solid electrolyte membrane.
The invention also provides a composite solid electrolyte membrane prepared by the preparation method. The composite electrolyte membrane comprises a first electrolyte membrane and a second electrolyte membrane, wherein the second electrolyte membrane is positioned on the surface of the first electrolyte membrane, and the first electrolyte membrane is an inorganic oxide electrolyte membrane or an inorganic-organic composite electrolyte membrane; the second electrolyte membrane is a polymer electrolyte membrane resistant to high nickel ternary or quaternary positive electrode materials. The composite solid electrolyte membrane has high ionic conductivity of inorganic oxide electrolyte, can keep stability for positive high-nickel ternary or quaternary positive electrode materials, and improves the ionic conductivity of the composite membrane material and the safety performance of a battery.
The invention also provides a lithium ion solid-state battery which comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode comprises oxides, high-nickel ternary or quaternary and other high-voltage positive electrode materials, the negative electrode is a carbon or silicon-carbon composite material or lithium metal, and the solid electrolyte is the composite solid electrolyte membrane or the composite solid electrolyte membrane prepared by the method. The density of the composite solid electrolyte in the solid battery is higher, so that the generation of lithium dendrite in the battery in the circulating process is inhibited, the safety performance of the battery is improved, and the internal resistance of the battery is not obviously increased; in addition, the second electrolyte membrane in the composite solid electrolyte membrane has the characteristic of stability to high-voltage anode materials such as high-nickel ternary or quaternary electrolyte membranes, so that the second electrolyte membrane can be matched with the high-voltage anode materials, and the capacity of the battery is improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The preparation of the following examples can be seen in figure 4.
Example 1
The method comprises the following steps: mixing and stirring a PVDF binder and NMP until the mixture is clear, uniform and bubble-free, and preparing a glue solution with the PVDF concentration of 10%; adding the mixture into a mixed solution of LATP and NMP subjected to particle size refinement treatment, mixing and stirring for 1h until the mixture is uniform, and adding a glue solution and a solvent NMP to adjust the mass percent of oxide electrolyte to be 25% and the mass percent of a binder to be 3% so as to prepare first electrolyte slurry;
step two: coating the first electrolyte slurry on a base material by using a mini-type coating machine, and forming a first electrolyte membrane with the thickness of 20 mu m after drying;
step three: mixing ethylene carbonate and LiFSI in a ratio of 2:1, adding a monomer of triethylene glycol dimethacrylate and an initiator of azobisisobutyronitrile, and stirring for 20min at normal temperature to prepare a second electrolyte slurry, wherein the mass percent of the triethylene glycol dimethacrylate in the second electrolyte slurry is 8%, and the mass of the azobisisobutyronitrile is 5% of the mass of the triethylene glycol dimethacrylate;
step four: and spraying the second electrolyte slurry onto the first electrolyte membrane by using an ultrasonic atomization generator, wherein the spraying thickness is 3 mu m, drying in vacuum at 50 ℃ for 4h, rolling, and stripping the base material to obtain the composite solid electrolyte membrane.
Example 2
The method comprises the following steps: placing PEO/LiTFSI in a sample bottle according to the mass ratio of 8:1, adding a small amount of DMF solvent, and stirring for 12 hours in a water bath at 60 ℃ at the rotating speed of 500rmp to form stable and transparent mother liquor; weighing a certain amount of LATP electrolyte, adding DMF (dimethyl formamide) for immersion, performing ultrasonic dispersion for 5min, adding the dispersed LATP into the mother liquor, sealing, and stirring at the rotating speed of 1000rmp in a water bath at 60 ℃ for 2h to prepare first electrolyte slurry; wherein, the mass percent of LATP in the first electrolyte slurry is 20%, the mass percent of PEO and LiTFSI is 5%, and the balance is DMF.
Step two: casting the first electrolyte slurry on a base material by using a small casting machine to form a film, and drying to form a first electrolyte film with the thickness of 50 microns;
step three: diethyl carbonate was mixed with LiFSI in a ratio of 3:1, then adding a monomer ethylene glycol diacrylate and an initiator benzoyl peroxide, and stirring for 20min at normal temperature to prepare a second electrolyte slurry, wherein the mass percent of the ethylene glycol diacrylate in the second electrolyte slurry is 5%, and the mass of the benzoyl peroxide is 1% of the mass of the ethylene glycol diacrylate.
Step four: and spraying the second electrolyte slurry onto the first electrolyte membrane by using an ultrasonic atomization generator, wherein the spraying thickness is 10 mu m, drying in vacuum at 50 ℃ for 4 hours, rolling, and stripping the base material to obtain the composite electrolyte membrane.
Example 3
The method comprises the following steps: mixing and stirring a PVDF binder and NMP until the mixture is clear, uniform and bubble-free, and preparing a glue solution with the PVDF concentration of 10%; adding the mixture into a mixed solution of LLZAO and NMP subjected to particle size refinement treatment, mixing and stirring for 1h until the mixture is uniform, and adjusting the solid content of an oxide to be 15% and the binder to be 1% by adding a glue solution and a solvent NMP to prepare a first electrolyte slurry;
step two: coating the first electrolyte slurry on a base material by using a mini-type coating machine, and forming a 60 mu m first electrolyte membrane after drying;
step three: mixing ethylene carbonate and LiFSI in a ratio of 1:1, adding a monomer of triethylene glycol dimethacrylate and an initiator of azobisisobutyronitrile, and stirring for 40min at normal temperature to prepare a second electrolyte slurry, wherein the mass percent of the triethylene glycol dimethacrylate in the second electrolyte slurry is 12%, the mass of the azobisisobutyronitrile is 8% of the mass of the triethylene glycol dimethacrylate, and the balance is ethylene carbonate and LiFSI;
step four: and spraying the second electrolyte slurry onto the first electrolyte membrane by using an ultrasonic atomization generator, wherein the spraying thickness is 1um, drying for 4 hours in vacuum at 50 ℃, rolling, and stripping the base material to obtain the composite electrolyte membrane.
Example 4
The method comprises the following steps: placing PEO/LiTFSI in a sample bottle according to the mass ratio of 8:1, adding a small amount of DMF solvent, and stirring for 12 hours in a water bath at 60 ℃ at the rotating speed of 500rmp to form stable and transparent mother liquor; weighing a certain amount of LLZAO electrolyte, adding DMF (dimethyl formamide) for immersion, ultrasonically dispersing for 5min, adding the dispersed LLZAO into the mother liquor, sealing, and stirring for 2h at the rotating speed of 1000rmp in a water bath at 60 ℃ to prepare first electrolyte slurry, wherein the mass percent of LATP (Latin oxide) in the first electrolyte slurry is 20%, the mass percent of PEO (polyethylene oxide) and LitFSI (lithium iron phosphate) in the first electrolyte slurry is 5%, and the balance is DMF;
step two: casting the first electrolyte slurry on a base material by using a small casting machine to form a film, and drying to form a first electrolyte film of 100 mu m;
step three: diethyl carbonate was mixed with LiFSI in a ratio of 3:1, adding monomer ethylene glycol diacrylate and initiator benzoyl peroxide, and stirring at normal temperature for 20min to prepare second electrolyte slurry, wherein the mass percent of the ethylene glycol diacrylate in the second electrolyte slurry is 15%, and the mass of the benzoyl peroxide is 10% of the mass of the ethylene glycol diacrylate.
Step four: and spraying the second electrolyte slurry onto the first electrolyte membrane by using an ultrasonic atomization generator, wherein the spraying thickness is 50 microns, drying in vacuum at 50 ℃ for 4 hours, rolling, and stripping the base material to obtain the composite electrolyte membrane.
Comparative example 1
The point different from example 1 is that the spraying thickness of the second electrolyte slurry in step four was 70 μm.
Comparative example 2
The difference from example 2 is that the spraying thickness of the second electrolyte slurry in step four was 100 μm.
Comparative example 3
Mixing a PVDF binder and NMP in a mass ratio of 1:15 to obtain glue solution, and pneumatically stirring until the glue solution is clear and uniform and has no bubbles; adding the mixture into a mixed solution of LATP and NMP subjected to particle size refinement treatment, mechanically stirring for 1h at normal temperature, and adjusting the content of oxide electrolyte to be 25% and the content of binder to be 3% by adding glue solution and solvent NMP; the coating solution was applied to a substrate by a mini-coater and dried in vacuum at 50 ℃ for 12 hours to obtain an oxide electrolyte membrane.
Comparative example 4
The difference from comparative example 3 is that the oxide solid electrolyte in step 1 was replaced with LLZAO.
Performance testing
1. The solid electrolyte membranes prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to an ion conductivity test, and the test structures are shown in table 1.
2. The solid electrolyte membranes obtained in examples 1 to 4 and comparative examples 1 to 4 were prepared into solid batteries, and cycle life tests were performed on each solid battery, respectively, wherein the positive electrode material of the solid battery was NCM811 (the ratio of the amounts of nickel, cobalt, and manganese in the nickel-cobalt-manganese ternary positive electrode material was 8.
Table 1 ion conductivity of solid electrolyte membranes prepared in examples 1 to 4 and comparative examples 1 to 4 at 25 ℃
| Examples/comparative examples | Ionic conductivity (. About.10) -4 ) |
| Example 1 | 0.68 |
| Example 2 | 0.72 |
| Example 3 | 0.64 |
| Example 4 | 0.70 |
| Comparative example 1 | 0.50 |
| Comparative example 2 | 0.53 |
| Comparative example 3 | 0.72 |
| Comparative example 4 | 0.78 |
Table 2: the charge and discharge cycle was carried out at 0.1C for 100 times, and the cycle performance of each solid-state battery
From the test results in tables 1 and 2, the composite solid electrolyte membrane prepared by the method not only has higher ionic conductivity, but also keeps stable to positive high-nickel ternary or quaternary cathode materials, and the capacity is maintained above 90% when the cycle is 100. The comparative example also has high ionic conductivity, but the cycling performance is poor, and the application of the power battery cannot be satisfied.
According to the invention, the high-nickel-resistant anode material polymer electrolyte slurry is sprayed on the oxide electrolyte diaphragm in an atomization spraying manner, and through the subsequent drying process, the solvent is removed and the in-situ polymerization of the polymer monomer is realized, so that the interface contact between the polymer electrolyte layer and the oxide electrolyte layer is improved, and the density of the composite solid electrolyte is improved. The method can realize the adaptation of the composite solid electrolyte membrane and the high-voltage anode material, reduce the using amount of the low-ionic conductivity polymer, avoid the improvement of the internal resistance of the battery, and improve the capability of the composite solid electrolyte membrane for inhibiting the growth of lithium dendrites, thereby effectively improving the capacity and the safety of the battery. Therefore, the invention effectively overcomes some practical problems in the prior art, thereby having high utilization value and use significance.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (10)
1. A method for producing a composite solid electrolyte membrane, characterized by comprising at least the steps of:
preparing a first electrolyte slurry, wherein the first electrolyte slurry is an inorganic oxide electrolyte slurry or an inorganic-organic composite electrolyte slurry;
coating the first electrolyte slurry on a base material, forming a film and drying to obtain a first electrolyte film;
uniformly mixing a polymer monomer, an initiator, a lithium salt and an organic solvent to prepare second electrolyte slurry;
coating the second electrolyte slurry on the first electrolyte membrane in an atomized spraying manner, and forming a second electrolyte membrane on the first electrolyte membrane after in-situ curing;
and peeling the substrate to obtain the composite solid electrolyte membrane.
2. The preparation method according to claim 1, wherein in the inorganic oxide electrolyte slurry, the mass percent of the oxide electrolyte is 15 to 35%, the mass percent of the binder is 1 to 5%, and the balance is the organic solvent; in the inorganic-organic composite electrolyte slurry, the mass percent of an oxide electrolyte is 12-25%, the balance is a mixed solution of a polymer electrolyte, a lithium salt and an organic solvent, wherein the mass percent of the polymer electrolyte and the lithium salt is 2-5% of the mass percent of the mixed solution, and the mass ratio of the polymer electrolyte to the lithium salt is 7:1 to 20:1.
3. the method of claim 2, wherein the inorganic oxide electrolyte comprises LLZO, LLZAO, LLZTO, LLZNO, LATP, LAGP, LZPO, siO 2 Or Al 2 O 3 Any one or a combination of at least two of; the organic solvent comprises any one or the combination of at least two of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, acetonitrile or acetone; the lithium salt comprises one or more of lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate and lithium dioxalate borate.
4. The production method according to claim 1, wherein the first electrolyte slurry is formed into a film by casting or coating, and the thickness of the first electrolyte film is 1 to 100 μm.
5. The production method according to claim 1, further comprising a hot-pressing treatment after the drying treatment is completed when the first electrolyte membrane is produced, wherein the hot-pressing treatment has a hot-pressing parameter of 40 to 80 ℃, a pressure of 30 to 60MPa, and a time of 10 to 80min.
6. The production method according to claim 1, characterized in that producing the second electrolyte slurry includes: at normal temperature, adding the lithium salt into the organic solvent, and uniformly mixing and stirring; then adding the polymer monomer and the initiator, and magnetically stirring at room temperature for 20-40 min; in the second electrolyte slurry, the mass percent of the polymer monomer is 5-15%, the mass of the initiator is 1-10% of the mass of the polymer monomer, and the ratio of the organic solvent to the lithium salt is 1:1 to 3:1.
7. the method according to claim 6, wherein the organic solvent in the second electrolyte slurry is a carbonate or a carbonate-containing organic solvent including one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate; the polymer monomer comprises one or a combination of more of triethylene glycol dimethacrylate, ethylene glycol diacrylate and polyethylene glycol monomethyl ether methacrylate; the initiator is azobisisobutyronitrile or benzoyl peroxide.
8. The production method according to claim 1, wherein the atomized spray coating includes: and injecting the second electrolyte slurry into an ultrasonic atomization generator, atomizing by the ultrasonic atomization generator, and spraying the second electrolyte slurry onto the first electrolyte membrane, wherein the spraying distance is controlled to be 5-10 cm, and the spraying speed is 1-2 cm/s, and the spraying speed is 1-50 mu m.
9. A composite solid electrolyte membrane, characterized by being produced by the production method according to claim 1.
10. A lithium ion solid state battery comprising the composite solid state electrolyte membrane produced by the production method according to claim 1.
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