CN113745636A - Solid-state lithium battery and preparation method thereof - Google Patents
Solid-state lithium battery and preparation method thereof Download PDFInfo
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- CN113745636A CN113745636A CN202111051079.7A CN202111051079A CN113745636A CN 113745636 A CN113745636 A CN 113745636A CN 202111051079 A CN202111051079 A CN 202111051079A CN 113745636 A CN113745636 A CN 113745636A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 194
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 53
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 238000012986 modification Methods 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 53
- 239000000919 ceramic Substances 0.000 claims description 50
- 229910003002 lithium salt Inorganic materials 0.000 claims description 42
- 159000000002 lithium salts Chemical class 0.000 claims description 42
- 239000011230 binding agent Substances 0.000 claims description 39
- 239000003792 electrolyte Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 22
- 239000002228 NASICON Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000005096 rolling process Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 15
- 239000011883 electrode binding agent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000011232 storage material Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 239000002223 garnet Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910021385 hard carbon 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
- 239000000203 mixture Substances 0.000 claims description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 5
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- 229910006204 Li1+xAlxM2−x(PO4)3 Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black 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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010030 laminating Methods 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
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- PGRMNXHYAZYNPG-UHFFFAOYSA-N fluoro hydrogen carbonate Chemical compound OC(=O)OF PGRMNXHYAZYNPG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 description 13
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000005486 organic electrolyte Substances 0.000 description 10
- 238000000840 electrochemical analysis Methods 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 7
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 229910021382 natural graphite Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SRFGYPCGVWVBTC-UHFFFAOYSA-N lithium;dihydrogen borate;oxalic acid Chemical compound [Li+].OB(O)[O-].OC(=O)C(O)=O SRFGYPCGVWVBTC-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses solid-state lithium cell includes: the electrolyte solution comprises a lithium negative electrode layer, a solid electrolyte layer, a positive electrode layer, a polymer gel electrolyte layer and an electrolyte solution dropwise added into any one of the lithium negative electrode layer, the solid electrolyte layer, the positive electrode layer and the polymer gel electrolyte layer; the solid electrolyte layer is positioned in the lithium negative electrode layer, or positioned in the solid electrolyte layer, or positioned in the positive electrode layer; the lithium negative electrode layer comprises metal lithium and a lithium storage modification layer coated on the surface of the metal lithium, and the lithium storage modification layer contains a carbon material or a silver material. The application also provides a preparation method of the solid-state lithium battery. The solid-state lithium battery provided by the application has excellent safety performance, high energy density and long cycle life.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a solid-state lithium battery and a preparation method thereof.
Background
On the basis of the increasingly exhausted fossil energy and the increasingly severe environmental problems, the development of new energy vehicles is a historical inevitable trend, but the requirements on the energy density of new energy vehicles mainly comprising lithium batteries are higher and higher to ensure the acceptance and popularization of the new energy vehicles. In recent years, with the popularization of a high-nickel positive electrode and a silicon-carbon negative electrode, the energy density of a lithium ion battery is greatly improved, but safety problems are also faced, particularly, metal lithium is directly used as the negative electrode, and lithium dendrites grow on the surface of the metal lithium due to factors such as local lithium ion concentration and nonuniform electric field in the circulation process of the metal lithium negative electrode, and the lithium dendrites can penetrate through a diaphragm when growing to a certain degree, so that the safety problems are caused.
Currently commercial lithium ion batteries use organic liquid electrolytes based on carbonates, which are flammable and pose serious safety problems. One important solution to the safety problem of lithium batteries is the use of solid electrolytes, particularly ceramic electrolytes. However, the lithium ion conductivity of the ceramic solid electrolyte is low, and the chemical/electrochemical stability of the interface with the positive electrode and the negative electrode is poor, so that the interface resistance is rapidly increased in the circulation process, and particularly when the negative electrode directly uses metal lithium, the performance of the battery is rapidly attenuated. In addition, the sintered ceramic sheet, because of its inherent brittleness, directly using the ceramic sheet as an electrolyte causes difficulties in assembling a battery, and particularly, an ultra-thin ceramic sheet is used in order not to reduce the energy density of the battery. In addition, the porosity of the pole piece of the conventional lithium ion battery is as high as 20-30%, and high internal resistance of the battery can be caused under the condition that no liquid electrolyte is infiltrated.
Therefore, how to improve the manufacturing process of the solid electrolyte and the solid lithium battery is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
To solve the above technical problems, a first object of the present invention is to provide a solid-state lithium battery; the second purpose of the invention is to provide a preparation method of the solid-state lithium battery; according to the solid-state lithium battery provided by the application, the lithium cathode and the lithium anode are subjected to surface modification, and ceramic particles with wide electrochemical windows are combined, so that the interface compatibility between the anode and the cathode and the solid-state electrolyte layer is improved, and the solid-state lithium battery has excellent safety performance, high energy density and long cycle life.
The technical scheme provided by the invention is as follows:
a solid state lithium battery comprising: the electrolyte solution comprises a lithium negative electrode layer, a solid electrolyte layer, a positive electrode layer, a polymer gel electrolyte layer and an electrolyte solution dropwise added into any one of the lithium negative electrode layer, the solid electrolyte layer, the positive electrode layer and the polymer gel electrolyte layer;
the solid electrolyte layer is positioned between the lithium negative electrode layer and the positive electrode layer;
the polymer gel electrolyte layer is positioned in the lithium negative electrode layer, or in the solid electrolyte layer, or in the positive electrode layer;
the lithium negative electrode layer comprises metal lithium and a lithium storage modification layer coated on the surface of the metal lithium, and the lithium storage modification layer contains a carbon material or a silver material.
Preferably, the lithium storage modification layer comprises a lithium storage material and a negative electrode binder, and the lithium storage material is any one or more of graphite, hard carbon, soft carbon, a carbon nanotube and silver; the negative electrode binder is a polyfluorinated hydrocarbon binder.
The application provides a solid-state lithium battery, lithium negative pole layer include lithium metal and coat in the lithium storage modification layer on lithium metal surface, and preferred lithium storage modification layer is including storing up lithium material and negative pole binder. The lithium storage modification layer is in a porous structure and completely and uniformly covers the surface of the metal lithium, lithium migrated from the positive electrode firstly generates lithiation reaction with the lithium storage material in the modification layer in the charging process, and the formed lithium compound can improve the uniformity of an electric field on the surface of the lithium, so that the uniform deposition and stripping of the subsequent lithium are promoted, and the formation of lithium dendrites and dead lithium is inhibited.
The lithium storage material is preferably any one or more of graphite, hard carbon, soft carbon, carbon nanotubes and silver, and the lithium storage material has lithium affinity, is easy to perform lithiation reaction with lithium, has high conductivity and promotes uniformity of an electric field on the surface of the lithium.
Preferably, the capacity ratio of the lithium storage material to the metallic lithium is 1:20 to 1: 5; and/or the presence of a gas in the gas,
the capacity ratio of the metal lithium to the positive electrode layer is 10:1-1: 1.
The capacity ratio of the lithium storage material to the metal lithium is preferably 1:20-1:5, and in the range, the modification layer can completely and uniformly cover the metal lithium, effectively isolate the direct contact between the lithium and the ceramic electrolyte and inhibit the corresponding side reaction, and also can give consideration to the energy density of the battery, so that the energy density, the safety and the cycle life of the battery are optimized.
Preferably, the solid electrolyte layer includes solid electrolyte layer ceramic particles and a solid electrolyte layer binder,
the solid electrolyte layer ceramic particles are selected from any one of garnet type oxides, Geranite compounds and NASICON type oxides; the structural general formula of the garnet-type oxide is Li7-x-3yAlyLa3Zr2-xMxO12Wherein M is at least one of Nb or Ta, wherein x is more than or equal to 0.1 and less than or equal to 0.7, and y is more than or equal to 0.02 and less than or equal to 0.2;
the structural general formula of the thiogallate compound is Li6-xPS5-xCl1+xWherein x is more than or equal to 0.3 and less than or equal to 0.8;
the general formula of the NASICON type oxide is Li1+xAlxM2-x(PO4)3Wherein M is at least one selected from Ti, Ge or Zr; wherein x is more than or equal to 0.2 and less than or equal to 0.6;
the solid electrolyte layer binder is a polyfluorinated hydrocarbon binder.
The solid electrolyte layer ceramic particles used in the solid electrolyte layer are preferably selected from any one of garnet type oxides, gefite compounds and NASICON type oxides, and the ceramic electrolytes have wider electrochemical windows, have certain oxidation resistance or reduction resistance, are beneficial to improving the interface stability between the ceramic electrolytes and the positive and negative electrodes, and simultaneously have high lithium ion conductivity and improve the power performance of the battery.
The volume ratio is a ratio of the two volumes in terms of weight x gram.
Preferably, the thickness of the solid electrolyte layer is 10-100 μm; and/or the presence of a gas in the gas,
in the solid electrolyte layer ceramic particles, the particle diameters of garnet type oxide, the Geranite compound and the NASICON type oxide are 100nm-10 mu m.
The thickness of the solid electrolyte layer is preferably 10-100 μm, and at this thickness, both the energy density of the battery and the mechanical strength of the ceramic electrolyte layer can be achieved.
Preferably, the polymer gel electrolyte layer includes a gel binder, gel ceramic particles, a lithium salt and an organic solvent,
the gel binder is a polyfluorinated hydrocarbon binder;
the gel ceramic particles are garnet-type oxides; the structural general formula of the garnet-type oxide is Li7-x- 3yAlyLa3Zr2-xMxO12Wherein M is at least one of Nb or Ta, wherein x is more than or equal to 0.1 and less than or equal to 0.7, and y is more than or equal to 0.02 and less than or equal to 0.2;
the lithium salt is any one or more of fluorine-containing lithium salt and boron-containing lithium salt;
the organic solvent is carbonate or fluoro carbonate.
The polymer gel electrolyte layer preferably comprises a gel binder, gel ceramic particles, a lithium salt and an organic solvent, wherein the gel ceramic particles are preferably garnet-type oxides, and the addition of the garnet-type oxides can improve the lithium ion conductivity of the polymer gel electrolyte.
The organic solvent contains fluoro-carbonate, so that the flame retardance of the gel polymer electrolyte and the capability of inhibiting lithium dendrites are further improved, and in addition, the decomposition products of the fluoro-carbonate are beneficial to improving the chemical/electrochemical stability between the positive electrode and the negative electrode and the ceramic electrolyte.
Preferably, in the gel ceramic particles, the particle size of the garnet-type oxide is 50 to 200 nm; and/or the presence of a gas in the gas,
the organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, 4-trifluoromethyl ethylene carbonate and bis (2,2,2 trifluoroethyl) carbonate.
Preferably, the weight ratio of the gel ceramic particles to the gel binder is 5:1-20: 1; and/or the presence of a gas in the gas,
the weight ratio of the organic solvent to the gel binder is 10:1-1: 10; and/or the presence of a gas in the gas,
the concentration of the lithium salt relative to the organic solvent is 0.5 to 5 mol/L.
Further preferably, the weight ratio of the gel ceramic particles to the gel binder is 5:1-20:1, and the particle size of the garnet-type oxide is 50-200nm, so that the lithium ion conductivity of the polymer gel electrolyte can be further improved.
Preferably, the lithium salt comprises at least one fluorine-containing lithium salt, and at least one boron-containing lithium salt; the molar ratio of the fluorine-containing lithium salt to the boron-containing lithium salt is 3:1-10: 1.
Preferably, the lithium salt contains lithium salt containing fluorine and lithium salt containing boron; tests show that the two lithium salts can form an SEI layer containing fluorine, boron and lithium simultaneously, so that the anode and the cathode are protected better, and the cycle performance of the solid-state battery is further improved; more preferably, the molar ratio of the fluorine-containing lithium salt to the boron-containing lithium salt is 3:1 to 10: 1.
Preferably, the fluorine-containing lithium salt is any one or more of lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide and lithium bistrifluorosulfonimide; the boron-containing lithium salt is any one or more of lithium difluoro oxalate borate, lithium tetrafluoroborate and lithium bis oxalate borate.
Preferably, the positive electrode layer comprises lithium-containing oxide, a conductive agent, a positive electrode binder and positive electrode ceramic particles;
the lithium-containing oxide is any one or more of lithium cobaltate, lithium manganate, lithium nickel manganese oxide, lithium iron phosphate, lithium manganese phosphate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material and lithium-rich layered material;
the conductive agent is any one or more of acetylene black, a carbon nanotube, a carbon nanofiber and graphene;
the positive electrode binder is a polyfluorinated hydrocarbon binder;
the positive electrode ceramic particles are NASICON type oxides, and the general structural formula of the NASICON type oxides is Li1+ xAlxM2-x(PO4)3Wherein M is at least one selected from Ti, Ge or Zr(ii) a Wherein x is more than or equal to 0.2 and less than or equal to 0.6.
Preferably, the weight of the positive electrode ceramic particles and the NASICON type oxide accounts for 1-10% of the total weight of the positive electrode;
in the positive electrode ceramic particles, the particle size of the NASICON type oxide is 50-200 nm.
Preferably, the polyfluorinated hydrocarbon binder is specifically any one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer and polyfluorinated ethylene propylene.
The positive electrode layer comprises a lithium-containing oxide, and can be selected from common commercial varieties, such as at least one of lithium cobaltate, lithium manganate, lithium nickel manganate, lithium iron phosphate, lithium manganese phosphate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material and lithium-rich layered material; mixing the lithium-containing oxide with a conductive agent, a binder and positive electrode ceramic particles, coating the mixture on the surface of a collector by adopting a slurry mixing and coating process, and baking, rolling, cutting pieces and the like to obtain a positive electrode, wherein the conductive agent is a common commercial conductive agent used for lithium ion batteries, such as acetylene black, … … and the like; the binder is preferably a polyfluorinated hydrocarbon.
The addition of the anode ceramic particles into the anode is beneficial to reducing the porosity of the whole machine and further improving the transmission performance of lithium ions in the anode, thereby improving the battery performance. The positive electrode ceramic particles are preferably NASICON type oxides.
Preferably, the polymer gel electrolyte layer is coated on the surface of the positive electrode layer, and the solid electrolyte layer is coated on the surface of the lithium negative electrode layer; and the polymer gel electrolyte layer is located between the solid electrolyte layer and the positive electrode layer.
Preferably, the electrolyte is dripped into the gel electrolyte layer and comprises electrolyte lithium salt and electrolyte solvent, wherein the electrolyte lithium salt is bis (trifluoromethane) sulfonyl imide lithium and bis (oxalate) lithium borate, and the electrolyte solvent is fluorinated ethylene carbonate and methyl ethyl carbonate.
A method for preparing a solid-state lithium battery comprises the following steps:
uniformly mixing a lithium storage material and a negative electrode binder in a solvent, stirring into slurry, uniformly coating the slurry on a lithium foil, and drying and rolling to obtain a lithium negative electrode layer; then uniformly mixing the ceramic particles of the solid electrolyte layer and a binder of the solid electrolyte layer in a solvent, stirring into slurry, uniformly coating the slurry on the surface of the lithium negative electrode layer, drying and rolling to obtain the solid electrolyte layer supported by the lithium negative electrode layer, and forming a composite negative electrode layer;
preparing a positive electrode layer by using the lithium-containing oxide; dissolving the gel binder in an organic solvent, adding gel ceramic particles, stirring into slurry, uniformly coating the slurry on the surface of the positive electrode layer, drying, rolling, and then dropwise adding an electrolyte to obtain a polymer gel electrolyte layer supported by the positive electrode layer, so as to form a composite positive electrode layer;
laminating the composite negative electrode layer and the composite positive electrode layer to assemble a solid lithium battery, and applying pressure of 1-10MPa at 40-80 ℃ to form the solid lithium battery;
wherein, the lithium storage material is any one or more of graphite, hard carbon, soft carbon, a carbon nanotube and silver;
the negative electrode binder, the solid electrolyte layer binder and the gel binder are polyfluorinated hydrocarbon binders;
the solvent is any one of N-methyl pyrrolidone and N, N-dimethylformamide;
the solid electrolyte layer ceramic particles are any one of garnet type oxides, Geranite compounds and NASICON type oxides;
the gel ceramic particles are garnet-type oxides;
the electrolyte comprises electrolyte lithium salt and electrolyte solvent, wherein the electrolyte lithium salt is bis (trifluoromethane) sulfonyl imide lithium and bis (oxalate) lithium borate, and the electrolyte solvent is fluorinated ethylene carbonate and methyl ethyl carbonate.
Preferably, the preparation of the positive electrode layer by using the lithium-containing oxide is specifically as follows: uniformly mixing a conductive agent, a positive adhesive and positive ceramic particles in a solvent, carrying out walking on the mixture and the surface of a collector, drying and rolling to obtain the conductive anode material;
wherein the positive electrode binder is polyfluorinated hydrocarbon binder; the positive electrode ceramic particles are NASICON type oxides.
Preferably, the gel ceramic particles are placed in the air for 10min to 10h and then used.
According to the solid-state lithium battery provided by the application, the lithium cathode and the anode are subjected to surface modification, the cathode is modified by using a carbon material or a silver material, so that the uniform deposition and stripping of metal lithium in the charging and discharging process can be guided, the formation of lithium dendrites and dead lithium is inhibited, and the interface stability between the lithium cathode and a ceramic electrolyte is improved; the positive electrode is modified by a polymer gel electrolyte layer, and the polymer gel electrolyte is permeated into the whole battery by pressurization, so that the interface performance between the ceramic electrolyte and the positive electrode and the negative electrode is further improved; the ceramic particles with wide electrochemical windows are combined for use, so that the interface compatibility between the anode and the cathode and the solid electrolyte layer is improved, and the solid lithium battery has excellent safety performance, high energy density and long cycle life.
The application also provides a preparation method of the solid-state lithium battery, which comprises the steps of respectively preparing the composite negative electrode layer and the composite positive electrode layer, and then applying pressure of 1-10MPa at 40-80 ℃ to form the solid-state lithium battery. And applying pressure under the heating condition to enable the polymer gel electrolyte on the surface of the positive electrode to permeate into the whole battery, so that the interface performance between the solid electrolyte layer and the positive and negative electrodes is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be 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 described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a solid-state lithium battery according to an embodiment of the present invention;
reference numerals: 1-a lithium negative electrode layer; 11-a lithium storage modification layer; 2-a solid electrolyte layer; 3-positive electrode layer; 4-polymer gel electrolyte layer.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the 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 application.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or be indirectly disposed on the other element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It will be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like, refer to an orientation or positional relationship illustrated in the drawings for convenience in describing the present application and to simplify description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "plurality" or "a plurality" means two or more unless specifically limited otherwise.
It should be understood that the structures, ratios, sizes, and the like shown in the drawings are only used for matching the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the practical limit conditions of the present application, so that the modifications of the structures, the changes of the ratio relationships, or the adjustment of the sizes, do not have the technical essence, and the modifications, the changes of the ratio relationships, or the adjustment of the sizes, are all within the scope of the technical contents disclosed in the present application without affecting the efficacy and the achievable purpose of the present application.
Example 1
Mixing natural graphite and polyvinylidene fluoride according to a weight ratio of 95:5, uniformly mixing the raw materials in N-methyl pyrrolidone, stirring the mixture into slurry, uniformly coating the slurry on a lithium foil, drying and rolling the slurry to obtain a composite lithium negative electrode layer, and controlling the using amount of a natural graphite layer to enable the capacity ratio of natural graphite to lithium metal to be 1: 10;
mixing Li6.4Al0.033La3Zr1.5Ta0.5O12Uniformly mixing ceramic electrolyte and polytetrafluoroethylene in N-methyl pyrrolidone according to a weight ratio of 95:5, stirring into slurry, uniformly coating the slurry on the surface of a composite lithium negative electrode layer (one side coated with a natural graphite layer), drying and rolling to obtain a solid electrolyte layer supported by a composite lithium negative electrode;
dissolving polyvinylidene fluoride in N-methyl pyrrolidone, and adding 100nm Li in an amount of 10 wt% of polyvinylidene fluoride6.4Al0.033La3Zr1.5Ta0.5O12Stirring into slurry and uniformly coating on LiCoO2The surface of the positive electrode (the positive electrode contains 3% by weight of Li)1.3Al0.3Ti1.7(PO4)3) Drying and rolling to obtain LiCoO2A solid polymer layer supported by the anode is dripped with 1mol/L of organic electrolyte to obtain LiCoO2The positive electrode supported polymer gel electrolyte layer is characterized in that lithium salt in the organic electrolyte is bis (trifluoromethane) sulfonyl imide lithium/bis (lithium) oxalate borate (the molar ratio is 3:1), the organic solvent is fluorinated ethylene carbonate/ethyl methyl carbonate (the volume ratio is 2:1), the weight ratio of the organic electrolyte to polyvinylidene fluoride is 1:1, and LiCoO is controlled2The dosage of the anode is such that the ratio of the capacity of the anode to the capacity of the metal lithium is 1: 2; a solid electrolyte and LiCoO supporting the above composite lithium negative electrode2And (3) laminating the polymer gel electrolyte layer supported by the positive electrode (opposite to the solid electrolyte) to assemble the solid lithium batteryThe cell was subjected to a pressure of 1MPa at 45 ℃ and the cell structure is shown in FIG. 1. The battery is charged and discharged at 3-4.2V, 0.5C (1C is defined as 140mA/g) and 60 ℃, and the capacity retention rate is 91% after 100 cycles.
Comparative example 1
The manufacturing process of the solid-state battery is the same as that of example 1, except that no modification layer is coated on the surface of the lithium negative electrode. The capacity retention was 73% by electrochemical testing under the same conditions, and significant lithium dendrites and dead lithium were observed.
Comparative example 2
The solid-state battery was fabricated as in example 1, except that the modification layer on the surface of the lithium negative electrode did not completely cover the lithium foil. The capacity retention was 85% by electrochemical testing under the same conditions, and lithium dendrites and dead lithium were observed.
Comparative example 3
A solid-state battery was prepared as in example 1, except that a sulfide ceramic electrolyte Li having a narrow electrochemical window was used as the ceramic electrolyte10GeP2S12Instead of garnet-type Li6.4Al0.033La3Zr1.5Ta0.5O12. The capacity retention rate is 68% by electrochemical test under the same conditions.
Comparative example 4
The solid-state battery was prepared as in example 1, except that the polymer modified on the surface of the positive electrode was polyethylene oxide, instead of polyvinylidene fluoride. The capacity retention rate is 54% by electrochemical test under the same conditions.
Comparative example 5
The solid-state battery was prepared as in example 1, except that a single salt, i.e., only lithium bistrifluoromethanesulfonylimide, was used in the dropwise addition of 1mol/L of the organic electrolyte. The capacity retention rate is 67% by electrochemical test under the same conditions.
Comparative example 6
A solid-state battery was prepared as in example 1, except that the organic solvent used was ethylene carbonate/ethyl methyl carbonate, rather than fluorinated ethylene carbonate/ethyl methyl carbonate. The capacity retention rate is 58% by electrochemical test under the same conditions.
Comparative example 7
A solid state battery was prepared as in example 1, except that no pressure was applied under heat after the battery was fabricated. The capacity retention rate is 82% by electrochemical test under the same conditions.
Comparative example 8
The solid-state battery was prepared as in example 1, except that no Li was added to the positive electrode1.3Al0.3Ti1.7(PO4)3. The capacity retention rate is 85% by electrochemical test under the same conditions.
Comparative example 9
A solid-state battery was prepared as in example 1, except that Li was not added to the polymer gel electrolyte6.4Al0.033La3Zr1.5Ta0.5O12. The capacity retention rate is 69% by electrochemical test under the same conditions.
Comparative example 10
The solid-state battery was prepared as in example 1, except that Li was added to the polymer gel electrolyte6.4Al0.033La3Zr1.5Ta0.5O12The particle size was 300 nm. The capacity retention rate is 84% by electrochemical test under the same conditions.
Example 2
Uniformly mixing artificial graphite and polytetrafluoroethylene in N-methyl pyrrolidone according to a weight ratio of 94:6, stirring into slurry, uniformly coating the slurry on a lithium foil, drying and rolling to obtain a composite lithium negative electrode layer, and controlling the using amount of the artificial graphite layer to enable the capacity ratio of the artificial graphite to lithium metal to be 1: 20;
mixing Li5.6PS4.6Cl1.4The ceramic electrolyte and the polytetrafluoroethylene are neutralized and mixed evenly in N-methyl pyrrolidone according to the weight ratio of 94:6, stirred into slurry, evenly coated on a composite lithium negative electrode layer (one side coated with an artificial graphite layer), dried and rolled to obtain a solid electrolyte layer supported by a composite lithium negative electrode;
dissolving polytetrafluoroethylene in N-methyl pyrrolidone, and adding waterAdding 100nm Li in 5 wt% of polyvinylidene fluoride6.5Al0.033La3Zr1.6Ta0.4O12Stirring into slurry and uniformly coating on LiNi0.5Co0.2Mn0.3O2The surface of the positive electrode (the positive electrode contains 5% by weight of Li)1.4Al0.4Ti1.6(PO4)3) Drying and rolling to obtain LiNi0.5Co0.2Mn0.3O2A solid polymer layer supported by the anode is dripped with 1mol/L of organic electrolyte to obtain LiNi0.5Co0.2Mn0.3O2The polymer gel electrolyte layer supported by the positive electrode is characterized in that lithium salt in the organic electrolyte is lithium bis (fluorosulfonyl) imide/lithium difluoro (oxalato) borate (the molar ratio is 6:1), the organic solvent is fluorinated ethylene carbonate/dimethyl carbonate (the volume ratio is 1:1), the weight ratio of the organic electrolyte to polytetrafluoroethylene is 2:1, and LiNi is controlled0.5Co0.2Mn0.3O2The dosage of the anode is such that the ratio of the capacity of the anode to the capacity of the metal lithium is 1: 3; a solid electrolyte and LiNi prepared by supporting the composite lithium negative electrode0.5Co0.2Mn0.3O2The polymer gel electrolyte layers supported by the positive electrode were laminated (solid electrolyte and gel electrolyte were opposed) to assemble a solid lithium battery, and the battery was pressurized at 45 ℃ under 1 MPa. The battery is charged and discharged at 3-4.2V, 0.5C and 60 ℃, and after 100 cycles, the capacity retention rate is 89%.
Example 3
Uniformly mixing silver powder and polyvinylidene fluoride-hexafluoropropylene in N-methyl pyrrolidone according to a weight ratio of 96:4, stirring into slurry, uniformly coating the slurry on a lithium foil, drying and rolling to obtain a composite lithium cathode layer, and controlling the using amount of a silver layer so that the capacity ratio of silver to lithium metal is 1: 5;
mixing Li1.3Al0.3Ti1.7(PO4)3The ceramic electrolyte and the polyvinylidene fluoride are neutralized and mixed evenly in N-methyl pyrrolidone according to the weight ratio of 96:4, and 100nm Li with the weight of 8 percent of the polyvinylidene fluoride is added6.5Al0.033La3Zr1.6Nb0.4O12Stirring the mixture into slurry, uniformly coating the slurry on a composite lithium negative electrode layer (the side coated with a silver layer), drying and rolling the slurry to obtain a solid electrolyte layer supported by a composite lithium negative electrode;
dissolving polyvinylidene fluoride-hexafluoropropylene in N-methyl pyrrolidone, stirring into slurry, and uniformly coating LiNi0.8Co0.15Al0.05O2The surface of the positive electrode (the positive electrode contains 4% by weight of Li)1.3Al0.3Ti1.7(PO4)3) Drying and rolling to obtain LiNi0.8Co0.15Al0.05O2A solid polymer layer supported by the anode is dripped with 1mol/L of organic electrolyte to obtain LiNi0.8Co0.15Al0.05O2And a polymer gel electrolyte layer supported by the positive electrode, wherein lithium salt in the organic electrolyte is lithium hexafluorophosphate/lithium bis (oxalato) borate (molar ratio is 10:1), the organic solvent is difluoroethylene carbonate/diethyl carbonate (volume ratio is 3:1), and the weight ratio of the organic electrolyte to polyvinylidene fluoride-hexafluoropropylene is 3:1, control of LiNi0.8Co0.15Al0.05O2The dosage of the anode is such that the ratio of the capacity of the anode to the capacity of the metal lithium is 1: 2; a solid electrolyte and LiNi prepared by supporting the composite lithium negative electrode0.8Co0.15Al0.05O2The polymer gel electrolyte layers supported by the positive electrode were laminated (solid electrolyte and gel electrolyte were opposed) to assemble a solid lithium battery, and the battery was pressurized at 45 ℃ under 1 MPa. The battery is charged and discharged at 3-4.2V, 0.5C and 60 ℃, and the capacity retention rate is 90% after 100 cycles.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (18)
1. A solid state lithium battery, comprising: the lithium battery comprises a lithium negative electrode layer (1), a solid electrolyte layer (2), a positive electrode layer (3), a polymer gel electrolyte layer (4) and electrolyte dripped into any one of the lithium negative electrode layer (1), the solid electrolyte layer (2), the positive electrode layer (3) and the polymer gel electrolyte layer (4);
the solid electrolyte layer (2) is positioned between the lithium negative electrode layer (1) and the positive electrode layer (3);
the polymer gel electrolyte layer (4) is positioned in the lithium negative electrode layer (1), or in the solid electrolyte layer (2), or in the positive electrode layer (3);
the lithium negative electrode layer (1) comprises metal lithium and a lithium storage modification layer (11) coated on the surface of the metal lithium, and the lithium storage modification layer (11) contains a carbon material or a silver material.
2. The solid-state lithium battery according to claim 1, wherein the lithium storage modification layer (11) comprises a lithium storage material and a negative electrode binder, and the lithium storage material is any one or more of graphite, hard carbon, soft carbon, carbon nanotubes, and silver; the negative electrode binder is a polyfluorinated hydrocarbon binder.
3. The solid state lithium battery of claim 2, wherein the capacity ratio of the lithium storage material to lithium metal is from 1:20 to 1: 5; and/or the presence of a gas in the gas,
the capacity ratio of the metal lithium to the positive electrode layer (3) is 10:1-1: 1.
4. A lithium solid state battery according to claim 1, characterized in that the solid state electrolyte layer (2) comprises solid state electrolyte layer ceramic particles and a solid state electrolyte layer binder,
the solid electrolyte layer ceramic particles are selected from any one of garnet type oxides, Geranite compounds and NASICON type oxides; the structural general formula of the garnet-type oxide is Li7-x-3yAlyLa3Zr2-xMxO12Wherein M is selected from Nb or TaWherein x is more than or equal to 0.1 and less than or equal to 0.7, and y is more than or equal to 0.02 and less than or equal to 0.2;
the structural general formula of the thiogallate compound is Li6-xPS5-xCl1+xWherein x is more than or equal to 0.3 and less than or equal to 0.8;
the general formula of the NASICON type oxide is Li1+xAlxM2-x(PO4)3Wherein M is at least one selected from Ti, Ge or Zr; wherein x is more than or equal to 0.2 and less than or equal to 0.6;
the solid electrolyte layer binder is a polyfluorinated hydrocarbon binder.
5. The lithium solid state battery according to claim 4, characterized in that the thickness of the solid state electrolyte layer (2) is 10 to 100 μm; and/or the presence of a gas in the gas,
in the solid electrolyte layer ceramic particles, the particle diameters of garnet type oxide, the Geranite compound and the NASICON type oxide are 100nm-10 mu m.
6. Solid state lithium battery according to claim 1, characterized in that the polymer gel electrolyte layer (4) comprises a gel binder, gel ceramic particles, a lithium salt and an organic solvent,
the gel binder is a polyfluorinated hydrocarbon binder;
the gel ceramic particles are garnet-type oxides; the structural general formula of the garnet-type oxide is Li7-x- 3yAlyLa3Zr2-xMxO12Wherein M is at least one of Nb or Ta, wherein x is more than or equal to 0.1 and less than or equal to 0.7, and y is more than or equal to 0.02 and less than or equal to 0.2;
the lithium salt is any one or more of fluorine-containing lithium salt and boron-containing lithium salt;
the organic solvent is carbonate or fluoro carbonate.
7. The lithium solid state battery according to claim 6, wherein in the gel ceramic particles, a particle size of the garnet-type oxide is 50 to 200 nm; and/or the presence of a gas in the gas,
the organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, 4-trifluoromethyl ethylene carbonate and bis (2,2,2 trifluoroethyl) carbonate.
8. The solid state lithium battery of claim 6, wherein a weight ratio of the gel ceramic particles to the gel binder is 5:1 to 20: 1; and/or the presence of a gas in the gas,
the weight ratio of the organic solvent to the gel binder is 10:1-1: 10; and/or the presence of a gas in the gas,
the concentration of the lithium salt relative to the organic solvent is 0.5 to 5 mol/L.
9. The solid state lithium battery of claim 6, wherein the lithium salt comprises at least one fluorine-containing lithium salt, and at least one boron-containing lithium salt; the molar ratio of the fluorine-containing lithium salt to the boron-containing lithium salt is 3:1-10: 1.
10. The solid-state lithium battery according to claim 6 or 9, wherein the fluorine-containing lithium salt is any one or more of lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, lithium bistrifluorosulfonylimide; the boron-containing lithium salt is any one or more of lithium difluoro oxalate borate, lithium tetrafluoroborate and lithium bis oxalate borate.
11. The solid-state lithium battery according to claim 1, wherein the positive electrode layer (3) includes a lithium-containing oxide, a conductive agent, a positive electrode binder, positive electrode ceramic particles;
the lithium-containing oxide is any one or more of lithium cobaltate, lithium manganate, lithium nickel manganese oxide, lithium iron phosphate, lithium manganese phosphate, nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material and lithium-rich layered material;
the conductive agent is any one or more of acetylene black, a carbon nanotube, a carbon nanofiber and graphene;
the positive electrode binder is a polyfluorinated hydrocarbon binder;
the positive electrode ceramic particles are NASICON type oxides, and the general structural formula of the NASICON type oxides is Li1+xAlxM2-x(PO4)3Wherein M is at least one selected from Ti, Ge or Zr; wherein x is more than or equal to 0.2 and less than or equal to 0.6.
12. The solid-state lithium battery according to claim 11, wherein the weight of the positive electrode ceramic particles, NASICON-type oxide, accounts for 1 to 10% of the total amount of the positive electrode;
in the positive electrode ceramic particles, the particle size of the NASICON type oxide is 50-200 nm.
13. A solid state lithium battery according to any one of claims 2, 4, 6, 11, wherein the polyfluorinated hydrocarbon binder is specifically any one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyfluorinated ethylene propylene.
14. The lithium solid state battery according to any one of claims 1-7, 11-12, wherein the polymer gel electrolyte layer (4) is coated on the surface of the positive electrode layer (3), and the solid state electrolyte layer (2) is coated on the surface of the lithium negative electrode layer (1); and the polymer gel electrolyte layer (4) is located between the solid electrolyte layer (2) and the positive electrode layer (3).
15. The solid-state lithium battery according to claim 14, wherein the electrolyte is dropped into the gel electrolyte layer (4), and the electrolyte comprises an electrolyte lithium salt and an electrolyte solvent, wherein the electrolyte lithium salt is lithium bistrifluoromethanesulfonylimide and lithium bisoxalatoborate, and the electrolyte solvent is fluorinated ethylene carbonate and ethyl methyl carbonate.
16. A preparation method of a solid-state lithium battery is characterized by comprising the following steps:
uniformly mixing a lithium storage material and a negative electrode binder in a solvent, stirring into slurry, uniformly coating the slurry on a lithium foil, drying and rolling to obtain a lithium negative electrode layer (1); then uniformly mixing the ceramic particles of the solid electrolyte layer and a binder of the solid electrolyte layer in a solvent, stirring into slurry, uniformly coating the slurry on the surface of the lithium negative electrode layer (1), drying and rolling to obtain a solid electrolyte layer (2) supported by the lithium negative electrode layer (1), and forming a composite negative electrode layer;
preparing a positive electrode layer (3) by using the lithium-containing oxide; dissolving the gel binder in an organic solvent, adding gel ceramic particles, stirring into slurry, uniformly coating the slurry on the surface of the positive electrode layer (3), drying, rolling, and then dropwise adding an electrolyte to obtain a polymer gel electrolyte layer (4) supported by the positive electrode layer (3) to form a composite positive electrode layer;
laminating the composite negative electrode layer and the composite positive electrode layer to assemble a solid lithium battery, and applying pressure of 1-10MPa at 40-80 ℃ to form the solid lithium battery;
wherein, the lithium storage material is any one or more of graphite, hard carbon, soft carbon, a carbon nanotube and silver;
the negative electrode binder, the solid electrolyte layer binder and the gel binder are polyfluorinated hydrocarbon binders;
the solvent is any one of N-methyl pyrrolidone and N, N-dimethylformamide;
the solid electrolyte layer ceramic particles are any one of garnet type oxides, Geranite compounds and NASICON type oxides;
the gel ceramic particles are garnet-type oxides;
the electrolyte comprises electrolyte lithium salt and electrolyte solvent, wherein the electrolyte lithium salt is bis (trifluoromethane) sulfonyl imide lithium and bis (oxalate) lithium borate, and the electrolyte solvent is fluorinated ethylene carbonate and methyl ethyl carbonate.
17. The method according to claim 16, wherein the preparation of the positive electrode layer (3) using the lithium-containing oxide is specifically: uniformly mixing a conductive agent, a positive adhesive and positive ceramic particles in a solvent, coating the mixture on the surface of a collector, drying and rolling to obtain the conductive anode material;
wherein the positive electrode binder is polyfluorinated hydrocarbon binder; the positive electrode ceramic particles are NASICON type oxides.
18. The method according to claim 16, wherein the gel ceramic particles are placed in the air for 10min to 10h before use.
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| CN106299276A (en) * | 2016-08-25 | 2017-01-04 | 合肥国轩电池材料有限公司 | A kind of preparation method of ion cathode material lithium silver surface modified lithium titanate |
| CN110828883A (en) * | 2018-08-08 | 2020-02-21 | 比亚迪股份有限公司 | Lithium ion battery, preparation method thereof and electric vehicle |
| CN111710817A (en) * | 2020-06-28 | 2020-09-25 | 昆山宝创新能源科技有限公司 | Solid-state battery and preparation method and application thereof |
| CN112635915A (en) * | 2020-12-21 | 2021-04-09 | 合肥国轩高科动力能源有限公司 | Modified diaphragm for metal lithium cathode and preparation method and application thereof |
| CN113054241A (en) * | 2021-03-04 | 2021-06-29 | 湖南立方新能源科技有限责任公司 | Solid-state lithium battery and preparation method thereof |
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| CN114976216A (en) * | 2022-08-01 | 2022-08-30 | 湖南大学 | Preparation method of solid lithium battery with sandwich-shaped solid electrolyte |
| CN115911532A (en) * | 2023-01-17 | 2023-04-04 | 天祥安氢(上海)科技有限公司 | All-solid-state battery and preparation method thereof |
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