CN110556574A - Multilayer solid electrolyte, preparation method thereof, solid battery and electronic equipment - Google Patents
Multilayer solid electrolyte, preparation method thereof, solid battery and electronic equipment Download PDFInfo
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- CN110556574A CN110556574A CN201910746547.9A CN201910746547A CN110556574A CN 110556574 A CN110556574 A CN 110556574A CN 201910746547 A CN201910746547 A CN 201910746547A CN 110556574 A CN110556574 A CN 110556574A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000007787 solid Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 77
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 73
- 239000000919 ceramic Substances 0.000 claims abstract description 62
- 239000010416 ion conductor Substances 0.000 claims abstract description 57
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 56
- 229910052744 lithium Inorganic materials 0.000 claims description 56
- 239000003792 electrolyte Substances 0.000 claims description 46
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- -1 polypropylene carbonate Polymers 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 8
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 6
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- QRVIVVYHHBRVQU-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QRVIVVYHHBRVQU-UHFFFAOYSA-H 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001548 drop coating Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229920006158 high molecular weight polymer Polymers 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 239000011888 foil Substances 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 16
- 239000002033 PVDF binder Substances 0.000 description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 15
- 238000000227 grinding Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- 239000006258 conductive agent Substances 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 239000011858 nanopowder Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 8
- 229910010953 LiGePS Inorganic materials 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 229910003480 inorganic solid Inorganic materials 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 229910013188 LiBOB Inorganic materials 0.000 description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910011849 LiFe0.2Mn0.8PO4 Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 description 2
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M10/058—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
- H01M2300/0088—Composites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The embodiment of the invention relates to a multilayer solid electrolyte, a preparation method thereof, a solid battery and electronic equipment, wherein the multilayer solid electrolyte comprises an inorganic active fast lithium ion conductor ceramic matrix and a polymer electrolyte; the inorganic active fast lithium ion conductor ceramic matrix is made of inorganic active fast lithium ion conductor nano particles, and is provided with a first surface and a second surface which are opposite, and polymer electrolytes are respectively arranged on the first surface and the second surface; the polymer electrolyte includes a high molecular polymer and a lithium salt. The solid electrolyte can improve the interface stability of the solid battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a multilayer solid electrolyte, a preparation method thereof, a solid battery and electronic equipment.
Background
In the prior art, lithium ion solid electrolytes mainly include polymer solid electrolytes and inorganic solid electrolytes. The polymer solid electrolyte has the advantages of strong plasticity, good flexibility and nonflammability, however, the polymer solid electrolyte has poor mechanical property and low lithium ion conductivity. The inorganic solid electrolyte is nonflammable, the working temperature range is wide, the working voltage is high, the chemical and electrochemical stability is good, the excellent mechanical property can effectively prevent the influence of lithium dendrite on the battery cycle, however, the inorganic solid electrolyte has rough surface particles, the solid contact between the inorganic solid electrolyte and the electrode can cause larger interface impedance, and part of the inorganic solid electrolyte has the problem that the inorganic solid electrolyte cannot be in direct contact with a lithium cathode due to instability to lithium.
disclosure of Invention
In order to solve at least one of the above technical problems, embodiments of the present invention propose the following technical solutions.
According to a first aspect of the invention, embodiments of the invention provide a multilayer solid-state electrolyte.
<1> a multilayer solid electrolyte comprising an inorganic active fast lithium ion conductor ceramic matrix and a polymer electrolyte;
the inorganic active fast lithium ion conductor ceramic matrix is made of inorganic active fast lithium ion conductor nano particles, and is provided with a first surface and a second surface which are opposite, and the first surface and the second surface are respectively provided with a polymer electrolyte layer;
the polymer electrolyte includes a high molecular polymer and a lithium salt.
<2> the multilayer solid electrolyte according to <1>, the inorganic active fast lithium ion conductor nanoparticles are selected from one or more of the following materials:
Li7La3Zr2O12；
li x La 2/3-x TiO 3, wherein 0 is less than < X < 3;
Li 1+x Al x Ti 2-x (PO 4) 3, wherein 0 < X < 2;
LiAlO2；
li 7+x Ge x P 3-x S 11, wherein 0 < X < 3;
xLi 2 S · (100-X) P 2 S 5, wherein 0 < X < 100;
Li 7-x La 3 Zr 2-x M x O 12, wherein 0.25 < X <2, and M is selected from one or more of Ta, Nb and Al.
<3> the multilayer solid electrolyte according to <1>, the high molecular polymer is selected from one or more of the following materials: polyethylene oxide, polypropylene carbonate, polyethylene carbonate, polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and derivatives of the above-mentioned respective high-molecular polymers; and/or the presence of a gas in the gas,
The lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonic) imide, lithium tris (trifluoromethanesulfonic) methide, lithium bis (oxalato) borate, lithium hexafluoroarsenate, lithium tetrafluoroborate and lithium trifluoromethanesulfonate.
<4> the multilayer solid electrolyte according to <1>, wherein the mass fraction of the high molecular polymer is 50-95% and the mass fraction of the lithium salt is 5-50% based on the mass of the polymer electrolyte; or,
The polymer electrolyte also comprises inorganic active fast lithium ion conductor nano-particles, based on the mass of the polymer electrolyte, the mass fraction of the high molecular polymer is 20-80%, the mass fraction of the lithium salt is 5-50%, and the mass fraction of the inorganic active fast lithium ion conductor nano-particles is more than 0 and less than 20%; preferably, the inorganic active fast lithium ion conductor nanoparticles in the polymer electrolyte are selected from one or more of the following materials:
Li7La3Zr2O12；
Li x La 2/3-x TiO 3, wherein 0 is less than < X < 3;
li 1+x Al x Ti 2-x (PO 4) 3, wherein 0 < X < 2;
LiAlO2；
li 7+x Ge x P 3-x S 11, wherein 0 < X < 3;
xLi 2 S · (100-X) P 2 S 5, wherein 0 < X < 100;
Li 7-x La 3 Zr 2-x M x O 12, wherein 0.25 < X <2, and M is selected from one or more of Ta, Nb and Al.
According to a second aspect of the present invention, embodiments of the present invention provide a method of preparing a multilayer solid electrolyte as set forth in any one of <1> to <4 >.
<5> a method for preparing the multilayer solid electrolyte as stated in any one of <1> to <4>, comprising the steps of:
S1, preparing polymer electrolyte slurry
Adding a high molecular polymer, a lithium salt and inorganic active fast lithium ion conductor nano particles into an organic solvent, and mixing to obtain polymer electrolyte slurry;
s2 preparation of inorganic active fast lithium ion conductor ceramic matrix
Cold-pressing the inorganic active fast lithium ion conductor nano particles into inorganic active fast lithium ion conductor sheet bodies under the pressure of 6-14MPa, and performing heat treatment at the temperature of 700-1100 ℃ to obtain inorganic active fast lithium ion conductor ceramic matrixes;
S3 preparation of multilayer solid electrolyte
And (4) respectively coating the polymer electrolyte slurry obtained in the step (S1) on the first surface and the second surface of the inorganic active fast lithium ion conductor ceramic matrix, and drying in vacuum.
<6> according to the manufacturing method <5>, the polymer electrolyte slurry is coated on the first surface and the second surface of the inorganic active fast lithium ion conductor ceramic substrate by means of spin coating or drop coating.
<7> the production method according to <5>, wherein the organic solvent is one or more of acetonitrile, acetone, N-methylpyrrolidone and N-N dimethylformamide.
According to a third aspect of the present invention, an embodiment of the present invention provides a solid-state lithium battery.
<8> a solid lithium battery comprising the multilayer solid electrolyte as stated in any one of <1> to <4 >.
<9> the lithium solid state battery as stated in <8>, further comprising a positive electrode and a negative electrode;
The positive electrode comprises a positive electrode active material, wherein the positive electrode active material is one or more of elemental sulfur, a sulfur-carbon composite positive electrode, polyacrylonitrile sulfide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium cobaltate, a lithium-rich manganese base, lithium vanadium fluorophosphate and lithium nickel cobalt manganese ternary materials.
According to a fourth aspect of the present invention, an electronic device is provided.
<10> an electronic device comprising the multilayer solid electrolyte as stated in any one of <1> to <4>, or comprising the solid lithium battery as stated in <8> or <9 >.
The embodiment of the invention has the following beneficial effects: the multilayer solid electrolyte provided by the embodiment of the invention takes the inorganic active electrolyte ceramic chip with excellent mechanical property as the electrolyte main body, can effectively prevent the longitudinal growth of lithium dendrites, takes the polymer flexible electrolyte as the interface buffer layer, can reduce the interface impedance between the solid electrolyte and the electrode, effectively avoids the direct contact of the unstable electrolyte of a lithium cathode and the lithium cathode by LATP, LAGP, LGPS and the like, and greatly improves the interface stability of the solid battery.
Drawings
fig. 1 is a schematic view of a multilayer solid electrolyte structure according to an embodiment of the present invention.
FIG. 2 is a graph showing the change in interfacial resistance of a LATP inorganic active fast ion conductor ceramic sheet and a multilayer solid electrolyte to a metallic lithium negative electrode in example 1 of the present invention.
fig. 3 is a graph showing cycle performance of the multilayer solid-state battery in example 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings. Those skilled in the art will appreciate that the present invention is not limited to the drawings and the following examples.
Multilayer solid electrolyte and method for producing same
Referring to fig. 1, an embodiment of the present invention provides a multilayer solid electrolyte including an inorganic active fast lithium ion conductor ceramic matrix 10 and a polymer electrolyte; the inorganic active fast lithium ion conductor ceramic matrix is made of inorganic active fast lithium ion conductor nano particles and is provided with a first surface and a second surface which are opposite, and the first surface and the second surface are respectively provided with polymer electrolyte layers 21 and 22; the polymer electrolyte includes a high molecular polymer and a lithium salt.
preferably, the ceramic matrix has a thickness in a range of 150 to 1000 μm, and the polymer electrolyte layer has a thickness in a range of 10 to 200 μm. The types of the polymer electrolytes on the first surface and the second surface of the ceramic matrix can be the same or different; for example, when a high-voltage ternary positive electrode is used, a high-voltage-resistant polymer electrolyte is required on the positive electrode side, and a polymer electrolyte having good compatibility with a lithium negative electrode can be selected on the negative electrode side. The multilayer solid electrolyte according to the embodiment of the present invention is not limited to three layers, and may be three or more layers.
Preferably, the inorganic active fast lithium ion conductor nanoparticles are selected from one or more of the following materials:
Li7La3Zr2O12；
Li x La 2/3-x TiO 3, wherein 0 is less than < X < 3;
Li 1+x Al x Ti 2-x (PO 4) 3, wherein 0 < X < 2;
LiAlO2；
Li 7+x Ge x P 3-x S 11, wherein 0 < X < 3;
xLi 2 S · (100-X) P 2 S 5, wherein 0 < X < 100;
Li 7-x La 3 Zr 2-x M x O 12, wherein 0.25 < X <2, and M is selected from one or more of Ta, Nb and Al.
Preferably, the high molecular polymer is selected from one or more of the following materials: polyethylene oxide (PEO), polypropylene carbonate (PPC), polyethylene carbonate (PEC), polyvinyl carbonate (PVC), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polymethyl methacrylate (PMMA), and derivatives of the foregoing respective high-molecular polymers.
Preferably, the lithium salt is one or more of lithium perchlorate (LiClO 4), lithium hexafluorophosphate (LiPF 6), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonic) imide (LiTFSI), lithium tris (trifluoromethanesulfonic) methide (LiC (CF 3 SO 2) 3), lithium bis (LiBOB) oxalate, lithium hexafluoroarsenate (LiAsF 6), lithium tetrafluoroborate (LiBF 4), lithium trifluoromethanesulfonate (LiCF 3 SO 3).
preferably, the mass fraction of the high molecular polymer is 50 to 95% and the mass fraction of the lithium salt is 5 to 50% based on the mass of the polymer electrolyte.
Preferably, the polymer electrolyte further comprises inorganic active fast lithium ion conductor nanoparticles, based on the mass of the polymer electrolyte, the mass fraction of the high molecular polymer is 20-80%, the mass fraction of the lithium salt is 5-50%, and the mass fraction of the inorganic active fast lithium ion conductor nanoparticles is greater than 0 and less than 20%.
Preferably, the inorganic active fast lithium ion conductor nanoparticles in the polymer electrolyte are selected from one or more of the following materials:
Li7La3Zr2O12；
li x La 2/3-x TiO 3, wherein 0 is less than < X < 3;
Li 1+x Al x Ti 2-x (PO 4) 3, wherein 0 < X < 2;
LiAlO2；
li 7+x Ge x P 3-x S 11, wherein 0 < X < 3;
xLi 2 S · (100-X) P 2 S 5, wherein 0 < X < 100;
Li 7-x La 3 Zr 2-x M x O 12, wherein 0.25 < X <2, and M is selected from one or more of Ta, Nb and Al.
The embodiment of the invention also provides a preparation method of the multilayer solid electrolyte, which comprises the following steps:
S1, preparing polymer electrolyte slurry
adding a high molecular polymer, a lithium salt and inorganic active fast lithium ion conductor nano particles into an organic solvent, and mixing to obtain polymer electrolyte slurry;
s2 preparation of inorganic active fast lithium ion conductor ceramic matrix
cold-pressing the inorganic active fast lithium ion conductor nano particles into inorganic active fast lithium ion conductor sheet bodies under the pressure of 6-14MPa, and performing heat treatment at the temperature of 700-1100 ℃ to obtain inorganic active fast lithium ion conductor ceramic matrixes;
S3 preparation of multilayer solid electrolyte
and (4) respectively coating the polymer electrolyte slurry obtained in the step (S1) on the first surface and the second surface of the inorganic active fast lithium ion conductor ceramic matrix, and drying in vacuum.
Preferably, the polymer electrolyte paste is coated on the first surface and the second surface of the inorganic active fast lithium ion conductor ceramic matrix by spin coating or drop coating.
Preferably, the organic solvent is one or more of acetonitrile, acetone, N-methylpyrrolidone and N-N dimethylformamide.
The present invention will be described in further detail with reference to specific examples.
Example 1
S1, preparing polymer electrolyte slurry
dissolving LATP and PEO (LiTFSI) in acetonitrile according to the mass ratio of 1: 9, wherein the molar ratio of the PEO to the LiTFSI is 8: 1, stirring for 12h to obtain a polymer electrolyte solution A, dissolving the PEO and the LiTFSI in acetonitrile according to the mass ratio of 8: 1, and stirring for 12h to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.2g of the LATP inorganic active electrolyte nano powder on a press under the pressure of 10MPa for 3 minutes, and then firing the powder in a high-temperature muffle furnace at 900 ℃ for 3 hours to obtain the compact LATP inorganic active electrolyte ceramic chip.
S3 preparation of multilayer solid electrolyte
And respectively spin-coating the solutions A and B on two sides of the LATP inorganic active electrolyte ceramic wafer at the rotating speed of 2000rpm on a spin coater, and then putting the wafer into a vacuum drying oven for heat preservation at 60 ℃ for 12 hours to obtain the multilayer-structure solid electrolyte.
S4, preparing the positive plate
Mixing a positive electrode material SPAN, a binder PEO and a conductive agent acetylene black according to the mass percentage of 70: 15, grinding for 10 minutes, adding an organic solvent N-methylpyrrolidone (NMP), continuously grinding for 15 minutes, coating the uniform slurry on a carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a vacuum oven at 60 ℃ for drying for 24 hours to obtain the SPAN positive electrode plate.
The multilayer solid electrolyte obtained in example 1 had an ionic conductivity of 2 × 10 -4 s/cm at 55 ℃, an ion transport number of 0.26, and an electrochemical window of 4.2V.
And placing a metal lithium sheet in a negative electrode shell, then pasting the multilayer solid electrolyte on the metal lithium sheet, then pasting the SPAN positive plate on the multilayer solid electrolyte, assembling the SPAN positive plate into a solid lithium ion battery in an argon glove box, and normally and stably working at 0.1 ℃ with the first discharge capacity of 1994 mAh/g.
Example 2
S1, preparing polymer electrolyte slurry
Dissolving LATP and PVC (LiClO 4) in acetonitrile according to the mass ratio of 5: 5, wherein the molar ratio of PVC to LiClO 4 is 15: 1, stirring for 12h to obtain a polymer electrolyte solution A, dissolving PPC and LiTFSI in acetonitrile according to the mass ratio of 8: 1, and stirring for 12h to obtain a polymer electrolyte solution B.
s2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.2g of the LATP inorganic active electrolyte nano powder on a press under the pressure of 10MPa for 3 minutes, and then firing the powder in a high-temperature muffle furnace at 900 ℃ for 3 hours to obtain the compact LATP inorganic active electrolyte ceramic chip.
S3 preparation of multilayer solid electrolyte
And respectively spin-coating the solutions A and B on two sides of a LATP inorganic active electrolyte ceramic wafer at the rotating speed of 1000rpm on a spin coater, and then putting the wafer into a vacuum drying oven to preserve heat for 22 hours at 70 ℃ to obtain the multilayer solid electrolyte.
s4, preparing the positive plate
mixing a positive electrode material LiFePO 4, a polymer PEO, a conductive agent acetylene black and a binder PVDF according to the mass percentage of 80: 5: 10: 5, grinding for 15 minutes, adding an organic solvent N-methyl pyrrolidone (NMP), continuing grinding for 20 minutes, coating the uniform slurry on the carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a vacuum oven at 70 ℃ for drying for 12 hours to obtain the positive electrode plate.
The multilayer solid electrolyte obtained in example 2 had an ionic conductivity of 1.6 x 10 -4 s/cm at 45 ℃, an ion transport number of 0.28 and an electrochemical window of 4.2V.
The metal lithium plate is placed in the negative electrode shell, the multilayer solid electrolyte is attached to the metal lithium plate, the LiFePO 4 positive plate is attached to the multilayer solid electrolyte, the solid lithium ion battery is assembled in an argon glove box, the normal stable circulation can be realized at 0.1 ℃, and the first discharge capacity is 139 mAh/g.
Example 3
S1, preparing polymer electrolyte slurry
Weighing SiO 2 -HFP and LiBOB according to the mass ratio of 3: 2: 5, dissolving in acetone, stirring for 16h to obtain a polymer electrolyte solution A, weighing LLZO, PVDF-HFP and LiBOB according to the mass ratio of 2: 6, dissolving in DMF, and stirring for 12h to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
and maintaining the pressure of 0.3g of the LiGePS inorganic active electrolyte nano powder on a press under the pressure of 6MPa for 2 minutes, and then firing the powder in a high-temperature muffle furnace at the temperature of 1100 ℃ for 6 hours to obtain the compact LiGePS inorganic active electrolyte ceramic chip.
s3 preparation of multilayer solid electrolyte
and respectively dripping the solution A and the solution B on two sides of a LiGePS inorganic active electrolyte ceramic chip through a rubber head dropper, and then putting the LiGePS inorganic active electrolyte ceramic chip into a vacuum drying oven for heat preservation at 75 ℃ for 24 hours to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
mixing a positive electrode material LiNi 0.5 Mn 0.3 Co 0.2 O 2, a conductive agent acetylene black and a binder PVDF according to the mass percentage of 80: 10, grinding for 10 minutes, adding an organic solvent N-methyl pyrrolidone (NMP), continuing grinding for 10 minutes, coating the uniform slurry on the carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a vacuum oven at 80 ℃ for drying for 24 hours to obtain a positive electrode plate.
the multilayer solid electrolyte obtained in example 3 had an ionic conductivity of 1.9 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.41 and an electrochemical window of 4.9V.
And (2) placing a metal lithium sheet in a negative electrode shell, then pasting a multilayer-structure solid electrolyte on the metal lithium sheet, then pasting a LiNi 0.5 Mn 0.3 Co 0.2 O 2 positive electrode sheet on the multilayer solid electrolyte, and assembling the solid lithium ion battery in an argon glove box, wherein the 0.1C normal stable circulation can be realized, and the first discharge capacity is 150 mAh/g.
Example 4
S1, preparing polymer electrolyte slurry
Weighing AL 2 O 3 according to the mass ratio of 1: 6: 3, dissolving in acetone, stirring for 8 hours to obtain a polymer electrolyte solution A, weighing PMMA and LiFSI according to the mass ratio of 2: 8, dissolving in DMF, and stirring for 8 hours to obtain a polymer electrolyte solution B.
s2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.23g of the LiGePS inorganic active electrolyte nano powder on a press under the pressure of 10MPa for 2 minutes, and then firing the powder in a high-temperature muffle furnace at the temperature of 1150 ℃ for 5 hours to obtain the compact LiGePS inorganic active electrolyte ceramic chip.
S3 preparation of multilayer solid electrolyte
And respectively spin-coating the solution A and the solution B on two sides of a LiGePS inorganic active electrolyte ceramic wafer at the rotating speed of 1100rpm on a spin coater, and then putting the wafer into a vacuum drying oven to preserve heat for 20 hours at 87 ℃ to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
Mixing a positive electrode material LiCoO 2, a conductive agent acetylene black and a binder PVDF according to the mass percentage of 75: 15: 10, grinding for 12 minutes, adding an organic solvent N-methyl pyrrolidone (NMP), continuing grinding for 15 minutes, coating the uniform slurry on the carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a vacuum oven at 75 ℃ for drying for 20 hours to obtain a positive electrode plate.
The multilayer solid electrolyte obtained in example 4 had an ionic conductivity of 3.4 x 10 -4 s/cm at 25 ℃, an ion mobility of 0.48 and an electrochemical window of 5.0V.
And a metal lithium sheet is placed in a negative electrode shell, then a plurality of layers of solid electrolytes are attached to the metal lithium sheet, then a LiCoO 2 positive plate is attached to the solid electrolytes with the multi-layer structure, and the solid lithium ion battery is assembled in an argon glove box, wherein the solid lithium ion battery can be normally and stably circulated at 0.1 ℃ and has the initial discharge capacity of 134 mAh/g.
Example 5
S1, preparing polymer electrolyte slurry
Weighing LLZO, PPC and LiAsF 6 according to the mass ratio of 15: 58: 27, dissolving in DMF, stirring for 11h to obtain polymer electrolyte solution A, weighing SiO 2 6 according to the mass ratio of 23: 45: 32, dissolving in DMF, and stirring for 11h to obtain polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And keeping the pressure of 0.26g of the LAGP inorganic active electrolyte nano powder on a press under the pressure of 24MPa for 3 minutes, and then firing the powder in a high-temperature muffle furnace at 950 ℃ for 5.5 hours to obtain the compact LAGP inorganic active electrolyte ceramic plate.
S3 preparation of multilayer solid electrolyte
And respectively spin-coating the solutions A and B on two sides of the LAGP inorganic active electrolyte ceramic chip on a spin coater at the rotating speed of 2500rpm, and then putting the LAGP inorganic active electrolyte ceramic chip into a vacuum drying oven to preserve heat for 15 hours at the temperature of 89 ℃ to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
Mixing a positive electrode material LiNi 0.8 Mn 0.1 Co 0.1 O 2, a conductive agent acetylene black and a binder PVDF according to the mass percentage of 85: 10: 5, adding an organic solvent N-methyl pyrrolidone (NMP), grinding for 15 minutes, coating the uniform slurry on the carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a 65 ℃ vacuum oven for drying for 11 hours to obtain a positive electrode plate.
The multilayer solid electrolyte obtained in example 5 had an ionic conductivity of 3.9 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.43 and an electrochemical window of 5.0V.
And a metal lithium sheet is placed in a negative electrode shell, then a plurality of layers of solid electrolytes are attached to the metal lithium sheet, then a LiCoO 2 positive plate is attached to the solid electrolytes with the multi-layer structure, and the solid lithium ion battery is assembled in an argon glove box, wherein the solid lithium ion battery can be normally and stably circulated at 0.1 ℃ and has the first discharge capacity of 170 mAh/g.
Example 6
S1, preparing polymer electrolyte slurry
Weighing LiS 2 (CF 3 SO 2) 3 according to the mass ratio of 19: 46: 35, dissolving in anhydrous acetonitrile, stirring for 9 hours to obtain a polymer electrolyte solution A, weighing ZrO 2 (CF 3 SO 2) 3 according to the mass ratio of 27: 41: 32, dissolving in DMF, and stirring for 13 hours to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And keeping the pressure of 0.21g of the LAGP inorganic active electrolyte nano powder on a press under the pressure of 24MPa for 3 minutes, and then firing the powder in a high-temperature muffle furnace at 950 ℃ for 5.5 hours to obtain the compact LAGP inorganic active electrolyte ceramic chip.
S3 preparation of multilayer solid electrolyte
And respectively spin-coating the solutions A and B on two sides of the LAGP inorganic active electrolyte ceramic chip on a spin coater at the speed of 2200rpm, and then putting the LAGP inorganic active electrolyte ceramic chip into a vacuum drying oven for heat preservation at 65 ℃ for 26 hours to obtain the multilayer solid electrolyte.
s4, preparing the positive plate
Mixing a positive electrode material SPAN, a conductive agent acetylene black and a binder PVDF according to the mass percentage of 60: 30: 10, adding an organic solvent N-methyl pyrrolidone (NMP), grinding for 15 minutes, coating the uniform slurry on a carbon-coated aluminum foil, and then drying the carbon-coated aluminum foil in a 65 ℃ vacuum oven for 11 hours to obtain a positive plate.
the multilayer solid electrolyte obtained in example 6 had an ionic conductivity of 1.08 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.23, and an electrochemical window of 4.3V.
The metal lithium sheet is placed in the negative electrode shell, the multilayer solid electrolyte is attached to the metal lithium sheet, the LiCoO 2 positive plate is attached to the multilayer solid electrolyte, the solid lithium ion battery is assembled in an argon glove box, the normal stable circulation can be realized at 0.1 ℃, and the first discharge capacity is 1678 mAh/g.
Example 7
S1, preparing polymer electrolyte slurry
Dissolving PMMA, PVDF and LiC (CF 3 SO 2) 3 in acetone according to the mass ratio of 20: 45: 35, stirring for 7 hours to obtain a polymer electrolyte solution A, dissolving PEO, PAN and LiC (CF 3 SO 2) 3 in DMF according to the mass ratio of 6: 1: 3, and stirring for 11 hours to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.28g of the LiPSCl inorganic active electrolyte nano powder on a press under the pressure of 24MPa for 3 minutes, and then firing the powder in a high-temperature muffle furnace at 700 ℃ for 4 hours to obtain the compact LiPSCl inorganic active electrolyte ceramic plate.
S3 preparation of multilayer solid electrolyte
and respectively spin-coating the solution A and the solution B on two sides of a LiPSCl inorganic active electrolyte ceramic wafer at the rotating speed of 3000rpm on a spin coater, and then putting the wafer into a vacuum drying oven to preserve heat for 16 hours at the temperature of 80 ℃ to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
Mixing a positive electrode material LiMn 2 O 4, a conductive agent super P and a binder PVDF according to the mass percentage of 78: 12: 10, adding an organic solvent N-methyl pyrrolidone (NMP), grinding for 25 minutes, coating the uniform slurry on a carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a vacuum oven at 90 ℃ for drying for 7 hours to obtain a positive electrode plate.
The multilayer solid electrolyte obtained in example 7 had an ionic conductivity of 1.4 x 10 -4 s/cm at 25 ℃, an ion transport number of 0.13 and an electrochemical window of 4.2V.
And (2) placing a metal lithium sheet in a negative electrode shell, then pasting a plurality of layers of solid electrolytes on the metal lithium sheet, then pasting a LiCoO 2 positive plate on the plurality of layers of solid electrolytes, and assembling the solid lithium ion battery in an argon glove box, wherein the solid lithium ion battery can be normally and stably cycled at 0.1 ℃ and has the initial discharge capacity of 134 mAh/g.
example 8
S1, preparing polymer electrolyte slurry
Weighing PMMA, PEO and LiBF 4 according to the mass ratio of 30: 40, dissolving the weighed substances in acetonitrile, stirring for 15h to obtain a polymer electrolyte solution A, weighing PPC, PAN and LiBF 4 according to the mass ratio of 4: 2: 4, dissolving the weighed substances in DMF, and stirring for 14h to obtain a polymer electrolyte solution B.
s2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.28g of the LATP inorganic active electrolyte nano powder on a press under the pressure of 20MPa for 3 minutes, and then firing the powder in a high-temperature muffle furnace at 850 ℃ for 7 hours to obtain the compact LATP inorganic active electrolyte ceramic sheet.
s3 preparation of multilayer solid electrolyte
And respectively spin-coating the solutions A and B on two sides of a LATP inorganic active electrolyte ceramic wafer at the rotating speed of 1500rpm on a spin coater, and then putting the wafer into a vacuum drying oven for heat preservation at 84 ℃ for 7 hours to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
Mixing a positive electrode material LiFe 0.2 Mn 0.8 PO 4, a conductive agent super P and a binder PVDF-HFP according to the mass percentage of 80: 10, adding an organic solvent N-methyl pyrrolidone (NMP), grinding for 12 minutes, coating the uniform slurry on the carbon-coated aluminum foil, and then putting the carbon-coated aluminum foil on a vacuum oven at 95 ℃ for drying for 8 hours to obtain the positive electrode plate.
The multilayer solid electrolyte obtained in example 8 had an ionic conductivity of 2.3 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.18, and an electrochemical window of 4.3V.
And placing a metal lithium sheet in a negative electrode shell, then pasting a plurality of layers of solid electrolytes on the metal lithium sheet, then pasting a LiFe 0.2 Mn 0.8 PO 4 positive electrode sheet on the plurality of layers of solid electrolytes, and assembling the solid lithium ion battery in an argon glove box, wherein the solid lithium ion battery can be normally and stably circulated at 0.1 ℃ and has the first discharge capacity of 131 mAh/g.
example 9
S1, preparing polymer electrolyte slurry
Weighing LiS 2 3 SO 3 according to the mass ratio of 20: 25: 55, dissolving in acetonitrile, stirring for 14h to obtain a polymer electrolyte solution A, weighing PPC and Li 2 P 2 S 6 3 SO 3 according to the mass ratio of 32: 14: 54, dissolving in acetonitrile, and stirring for 14h to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.26g of LiGPS inorganic active electrolyte nano powder on a press under the pressure of 5MPa for 5 minutes, and then firing the powder in a high-temperature muffle furnace at 1150 ℃ for 7 hours to obtain the compact LiGPS inorganic active electrolyte ceramic sheet.
s3 preparation of multilayer solid electrolyte
And respectively spin-coating the solution A and the solution B on two sides of the LiGPS inorganic active electrolyte ceramic plate on a spin coater at the rotating speed of 2700rpm, and then putting the LiGPS inorganic active electrolyte ceramic plate into a vacuum drying oven for heat preservation at 62 ℃ for 8 hours to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
Mixing a sulfur-carbon positive electrode, a conductive agent super P and a binder PVDF according to the mass percentage of 82: 10: 8, adding an organic solvent N-methylpyrrolidone (NMP), grinding for 12 minutes, coating the uniform slurry on the carbon-coated aluminum foil, and then drying the carbon-coated aluminum foil in a vacuum oven at 55 ℃ for 24 hours to obtain a positive plate.
The multilayer solid electrolyte obtained in example 9 had an ionic conductivity of 4.6 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.51 and an electrochemical window of 4.2V.
And (2) placing a metal lithium sheet in a negative electrode shell, then pasting a plurality of layers of solid electrolytes on the metal lithium sheet, then pasting a positive electrode sheet on the plurality of layers of solid electrolytes, and assembling the solid lithium ion battery in an argon glove box, wherein the solid lithium ion battery can be normally and stably circulated at 0.1 ℃, and the first discharge capacity is 1245 mAh/g.
example 10
S1, preparing polymer electrolyte slurry
PEC, PVDF-HFP and LiPF 6 2 are weighed according to the mass ratio of 10: 31: 55: 4 and are dissolved in DMF, the mixture is stirred for 12 hours to obtain a polymer electrolyte solution A, and PAN, PVDF and LiCF 3 SO 3 3 are weighed according to the mass ratio of 32: 14: 44: 10 and are dissolved in acetone, and the mixture is stirred for 18 hours to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
And maintaining the pressure of 0.2g of the LATP inorganic active electrolyte nano powder on a press under the pressure of 16MPa for 5 minutes, and then firing the powder in a high-temperature muffle furnace at 950 ℃ for 5 hours to obtain the compact LATP inorganic active electrolyte ceramic chip.
s3 preparation of multilayer solid electrolyte
and respectively dripping the solution A and the solution B on two sides of the LATP inorganic active electrolyte ceramic wafer through a rubber head dropper, and then putting the wafer into a vacuum drying oven to preserve heat for 9 hours at 69 ℃ to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
LiNi 0.6 Mn 0.2 Co 0.2 O 2, a conductive agent super P and a binder PVDF are mixed according to the mass percentage of 90: 5, an organic solvent N-methyl pyrrolidone (NMP) is added to the mixture to be ground for 30 minutes, the uniform slurry is coated on the carbon-coated aluminum foil, and then the carbon-coated aluminum foil is placed in a vacuum oven at 85 ℃ to be dried for 24 hours to obtain the positive plate.
The multilayer solid electrolyte obtained in this example 10 had an ionic conductivity of 3.8 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.31, and an electrochemical window of 4.5V.
And (2) placing a metal lithium sheet in a negative electrode shell, then pasting a plurality of layers of solid electrolytes on the metal lithium sheet, then pasting a positive electrode sheet on the plurality of layers of solid electrolytes, and assembling the solid lithium ion battery in an argon glove box, wherein the solid lithium ion battery can be normally and stably circulated at 0.1 ℃, and the first discharge capacity is 145 mAh/g.
Example 11
s1, preparing polymer electrolyte slurry
Weighing PAN, PVDF-HFP and LiPF 6 according to the mass ratio of 8: 22: 47: 23, dissolving in DMF, stirring for 4h to obtain a polymer electrolyte solution A, weighing PMMA, PVDF and LiClO 4 according to the mass ratio of 36: 14: 50, dissolving in acetone, and stirring for 10h to obtain a polymer electrolyte solution B.
S2 preparation of inorganic active fast lithium ion conductor ceramic matrix
and keeping the pressure of 0.16g of the LiGPSCl inorganic active electrolyte nano powder on a press under the pressure of 6MPa for 4.5 minutes, and then firing the powder in a high-temperature muffle furnace at 550 ℃ for 9 hours to obtain the compact LiGPSCl inorganic active electrolyte ceramic plate.
s3 preparation of multilayer solid electrolyte
And respectively dripping the solution A and the solution B on two sides of the LiGPSCl inorganic active electrolyte ceramic wafer through a rubber head dropper, and then putting the LiGPSCl inorganic active electrolyte ceramic wafer into a vacuum drying oven to preserve heat for 21h at 84 ℃ to obtain the multilayer solid electrolyte.
S4, preparing the positive plate
LiNi 0.8 Mn 0.1 Co 0.1 O 2, a conductive agent super P, a binder PVDF and a lithium salt LiTFSI are mixed according to the mass percentage of 70: 5:20, an organic solvent N-methyl pyrrolidone (NMP) is added for grinding for 30 minutes, the uniform slurry is coated on the carbon-coated aluminum foil, and then the carbon-coated aluminum foil is placed in a vacuum oven at the temperature of 92 ℃ for drying for 16 hours to obtain the positive plate.
The multilayer solid electrolyte obtained in example 11 had an ionic conductivity of 2.3 × 10 -4 s/cm at 25 ℃, an ion mobility of 0.41, and an electrochemical window of 4.9V.
And a metal lithium sheet is placed in a negative electrode shell, then the multilayer solid electrolyte is pasted on the metal lithium sheet, then a positive electrode sheet is pasted on the multilayer solid electrolyte, and the solid lithium ion battery is assembled in an argon glove box, wherein the solid lithium ion battery can be normally and stably circulated at 0.1 ℃, and the first discharge capacity is 165 mAh/g.
Obviously, those skilled in the art can understand that, in the above embodiments, the execution sequence of steps S1, S2, and S4 may be selected differently, regardless of the sequence number.
Solid state lithium battery
the embodiment of the invention also provides a solid-state lithium battery which comprises a positive electrode, a negative electrode and one of the multilayer solid electrolytes.
Preferably, the positive electrode includes a positive active material, a current collector, a conductive agent, and a binder. The current collector is carbon-coated aluminum foil or aluminum foil; the conductive agent is one or more of Super P and acetylene black; the binder is one or more of PVDF and PVDF-HFP.
Preferably, the positive active material is one or more of elemental sulfur, a sulfur-carbon composite positive electrode, vulcanized polyacrylonitrile, lithium iron phosphate, lithium iron manganese phosphate, lithium manganate, lithium cobaltate, a lithium-rich manganese base, lithium vanadium fluorophosphate and nickel cobalt lithium manganate.
Preferably, the negative electrode is one or more of metal lithium, metal lithium alloy, graphite negative electrode and silicon-carbon negative electrode.
Electronic device
An embodiment of the present invention further provides an electronic device, where the electronic device includes one of the above multilayer solid electrolytes, or includes one of the above solid lithium batteries.
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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A multilayer solid electrolyte comprising an inorganic active fast lithium ion conductor ceramic matrix and a polymer electrolyte;
The inorganic active fast lithium ion conductor ceramic matrix is made of inorganic active fast lithium ion conductor nano particles, and is provided with a first surface and a second surface which are opposite, and the first surface and the second surface are respectively provided with a polymer electrolyte layer;
The polymer electrolyte includes a high molecular polymer and a lithium salt.
2. The multilayer solid state electrolyte of claim 1, wherein the inorganic active fast lithium ion conductor nanoparticles are selected from one or more of the following materials:
Li7La3Zr2O12；
Li x La 2/3-x TiO 3, wherein 0 is less than < X < 3;
Li 1+x Al x Ti 2-x (PO 4) 3, wherein 0 < X < 2;
LiAlO2；
Li 7+x Ge x P 3-x S 11, wherein 0 < X < 3;
xLi 2 S · (100-X) P 2 S 5, wherein 0 < X < 100;
Li 7-x La 3 Zr 2-x M x O 12, wherein 0.25 < X <2, and M is selected from one or more of Ta, Nb and Al.
3. The multilayer solid electrolyte of claim 1, wherein the high molecular weight polymer is selected from one or more of the following materials: polyethylene oxide, polypropylene carbonate, polyethylene carbonate, polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and derivatives of the above-mentioned respective high-molecular polymers; and/or the presence of a gas in the gas,
The lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonic) imide, lithium tris (trifluoromethanesulfonic) methide, lithium bis (oxalato) borate, lithium hexafluoroarsenate, lithium tetrafluoroborate and lithium trifluoromethanesulfonate.
4. The multilayer solid electrolyte according to claim 1, wherein the mass fraction of the high molecular polymer is 50 to 95% and the mass fraction of the lithium salt is 5 to 50% based on the mass of the polymer electrolyte; or,
The polymer electrolyte also comprises inorganic active fast lithium ion conductor nano-particles, based on the mass of the polymer electrolyte, the mass fraction of the high molecular polymer is 20-80%, the mass fraction of the lithium salt is 5-50%, and the mass fraction of the inorganic active fast lithium ion conductor nano-particles is more than 0 and less than 20%;
Preferably, the inorganic active fast lithium ion conductor nanoparticles in the polymer electrolyte are selected from one or more of the following materials:
Li7La3Zr2O12；
Li x La 2/3-x TiO 3, wherein 0 is less than < X < 3;
Li 1+x Al x Ti 2-x (PO 4) 3, wherein 0 < X < 2;
LiAlO2；
Li 7+x Ge x P 3-x S 11, wherein 0 < X < 3;
xLi 2 S · (100-X) P 2 S 5, wherein 0 < X < 100;
Li 7-x La 3 Zr 2-x M x O 12, wherein 0.25 < X <2, and M is selected from one or more of Ta, Nb and Al.
5. A method of producing a multilayer solid electrolyte according to any of claims 1 to 4, comprising the steps of:
s1, preparing polymer electrolyte slurry
Adding a high molecular polymer, a lithium salt and inorganic active fast lithium ion conductor nano particles into an organic solvent, and mixing to obtain polymer electrolyte slurry;
s2 preparation of inorganic active fast lithium ion conductor ceramic matrix
Cold-pressing the inorganic active fast lithium ion conductor nano particles into inorganic active fast lithium ion conductor sheet bodies under the pressure of 6-14MPa, and performing heat treatment at the temperature of 700-1100 ℃ to obtain inorganic active fast lithium ion conductor ceramic matrixes;
S3 preparation of multilayer solid electrolyte
And (4) respectively coating the polymer electrolyte slurry obtained in the step (S1) on the first surface and the second surface of the inorganic active fast lithium ion conductor ceramic matrix, and drying in vacuum.
6. The method of claim 5, wherein the polymer electrolyte paste is applied to the first surface and the second surface of the inorganic active fast lithium ion conductor ceramic matrix by spin coating or drop coating.
7. The method according to claim 5, wherein the organic solvent is one or more of acetonitrile, acetone, N-methylpyrrolidone, and N-dimethylformamide.
8. A solid-state lithium battery comprising the multilayer solid-state electrolyte according to any one of claims 1 to 4.
9. the lithium solid state battery of claim 8, further comprising a positive electrode and a negative electrode;
The positive electrode comprises a positive electrode active material, wherein the positive electrode active material is one or more of elemental sulfur, a sulfur-carbon composite positive electrode, polyacrylonitrile sulfide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium cobaltate, a lithium-rich manganese base, lithium vanadium fluorophosphate and lithium nickel cobalt manganese ternary materials.
10. An electronic device comprising a multilayer solid-state electrolyte according to any one of claims 1 to 4 or a solid-state lithium battery according to claim 8 or 9.
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| CN110943199A (en) * | 2019-12-16 | 2020-03-31 | 哈尔滨工业大学 | Preparation method of enhanced polymer interface layer for LATP-based all-solid-state lithium battery |
| CN111180788A (en) * | 2020-03-02 | 2020-05-19 | 珠海冠宇电池有限公司 | All-solid-state electrolyte, preparation method thereof and lithium ion battery |
| CN111370760A (en) * | 2020-03-19 | 2020-07-03 | 香港科技大学 | Wide electrochemical window composite solid electrolyte and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367798A (en) * | 2012-04-02 | 2013-10-23 | 三星精密化学株式会社 | Electrolyte for lithium ion secondary battery and lithium ion secondary battery |
| CN105409032A (en) * | 2013-06-21 | 2016-03-16 | 魁北克电力公司 | All-solid-state lithium-sulfur electrochemical cell and method for producing same |
| CN107732297A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院青岛生物能源与过程研究所 | A kind of high voltage withstanding multilevel hierarchy composite solid electrolyte applied to lithium battery |
| CN108352568A (en) * | 2016-07-08 | 2018-07-31 | 株式会社Lg化学 | Multi-layered electrolyte unit, secondary battery including the same, and method of manufacturing the same |
| CN108886164A (en) * | 2016-03-28 | 2018-11-23 | （株）七王能源 | A kind of secondary cell composite electrolyte with multi-layer structure |
-
2019
- 2019-08-12 CN CN201910746547.9A patent/CN110556574A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367798A (en) * | 2012-04-02 | 2013-10-23 | 三星精密化学株式会社 | Electrolyte for lithium ion secondary battery and lithium ion secondary battery |
| CN105409032A (en) * | 2013-06-21 | 2016-03-16 | 魁北克电力公司 | All-solid-state lithium-sulfur electrochemical cell and method for producing same |
| CN108886164A (en) * | 2016-03-28 | 2018-11-23 | （株）七王能源 | A kind of secondary cell composite electrolyte with multi-layer structure |
| CN108352568A (en) * | 2016-07-08 | 2018-07-31 | 株式会社Lg化学 | Multi-layered electrolyte unit, secondary battery including the same, and method of manufacturing the same |
| CN107732297A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院青岛生物能源与过程研究所 | A kind of high voltage withstanding multilevel hierarchy composite solid electrolyte applied to lithium battery |
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| CN112599847A (en) * | 2020-12-25 | 2021-04-02 | 哈尔滨工业大学 | Double-layer solid electrolyte film for lithium battery and preparation method thereof |
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| CN114975889A (en) * | 2021-02-19 | 2022-08-30 | 通用汽车环球科技运作有限责任公司 | Method for manufacturing anode of lithium battery cell |
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