CN108511712B - Lithium ion conductive agent material, preparation method, lithium battery pole piece and lithium battery - Google Patents
Lithium ion conductive agent material, preparation method, lithium battery pole piece and lithium battery Download PDFInfo
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- CN108511712B CN108511712B CN201810244045.1A CN201810244045A CN108511712B CN 108511712 B CN108511712 B CN 108511712B CN 201810244045 A CN201810244045 A CN 201810244045A CN 108511712 B CN108511712 B CN 108511712B
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- 239000000463 material Substances 0.000 title claims abstract description 92
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 239000006258 conductive agent Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 72
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052718 tin Inorganic materials 0.000 claims description 6
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- 239000012071 phase Substances 0.000 claims description 5
- 239000002227 LISICON Substances 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
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- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
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- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
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- 239000008103 glucose Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000002001 electrolyte material Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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Abstract
The invention discloses a lithium ion electron conductive agent material, a preparation method, a lithium battery pole piece and a lithium battery, wherein the lithium ion electron conductive agent material is of a composite core-shell structure and comprises an inner core made of a solid electrolyte material and an outer shell made of a carbon material; the particle size of the solid electrolyte is 10nm-100um, and the carbon material is particles with the particle size of 1nm-1um or a continuous film with the thickness of 1nm-1 um; the mass ratio of the carbon material to the solid electrolyte material is between 0.001 and 1000; the particle size of the lithium ion electron conductive agent material is 10nm-100 um.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a lithium ion electron conductive agent material, a preparation method, a lithium battery pole piece and a lithium battery.
Background
The lithium ion battery has the characteristics of high output voltage, high energy density, long cycle life, good safety performance, no memory effect and the like, and is successfully applied to the field of mobile power sources as a main energy storage device. In order to further meet the requirements of power grid energy storage, electric vehicles and consumer electronic products on energy storage devices, electrode materials and lithium battery systems with longer cycle life, better safety and higher energy density become research hotspots. The conventional lithium ion battery adopts an electrolytic liquid system which is an organic liquid dissolved with lithium salt, the electrolyte generates heat due to overcharge, internal circuits and other abnormalities, and the danger of spontaneous combustion or explosion exists.
For quasi-solid, semi-solid and all-solid batteries, because the electrode pole piece may not contain or contain a small amount of electrolyte, a lithium ion transmission channel is lacked in the pole piece, which causes the problems of large pole piece polarization, poor rate capability and the like. The existing solution is to add solid electrolyte material into the electrode plate to improve the lithium ion conductivity of the electrode plate.
However, most of solid electrolyte materials are inorganic materials, and crystalline positive electrode materials and crystalline negative electrode materials have problems of poor wettability and low surface resistance. And the solid electrolyte material has the problems of easy agglomeration, poor dispersibility and poor contact with a conductive material and an active material in the pulping process.
Therefore, a new electrode material is urgently needed to be provided to solve the problems of the existing solid electrolyte material in the pole piece.
Disclosure of Invention
The invention provides a lithium ion electron conductive agent material, a preparation method, a lithium battery pole piece and a lithium battery aiming at the defects of the prior art, and the lithium ion electron conductive agent material, the preparation method, the lithium battery pole piece and the lithium battery can be used in liquid, semi-solid and all-solid batteries, and can improve the rate capability, the safety performance, the cycle performance and the like of the batteries.
In a first aspect, an embodiment of the present invention provides a lithium ion electron conductive agent material, which is a composite core-shell structure and includes an inner core made of a solid electrolyte material and an outer shell made of a carbon material;
the particle size of the solid electrolyte is 10nm-100um, and the carbon material is particles with the particle size of 1nm-1um or a continuous film with the thickness of 1nm-1 um; the mass ratio of the carbon material to the solid electrolyte material is between 0.001 and 1000; the particle size of the lithium ion electron conductive agent material is 10nm-100 um.
Preferably, the solid electrolyte material is one or more of garnet type solid electrolyte material, NASCION type solid electrolyte material, LICION type solid electrolyte material and perovskite type solid electrolyte material;
wherein, the LISICON type solid electrolyte is specifically as follows: li14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, and B is one or more of Si, S and P; the NASICON type solid electrolyte specifically comprises: li1+xAxB2+x(PO4)3Wherein x is between 0.01 and 0.5, A is one or more of Al, Y, Ga, Cr, In, Fe, Se and La, and B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and hafnium element Hf; the perovskite type solid electrolyte is specifically as follows: li3xA2/3-xBO3Wherein x is between 0.01 and 0.5, A is one or more of La, Al, Mg, Fe and Ta, and B is one or more of Ti, Nb, Sr and Pr; the garnet-type solid electrolyte specifically comprises: li7A3B2O12Wherein A is one or more of La, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and Hf.
Preferably, the shape of the solid electrolyte material is one or more of a spherical shape, an ellipsoidal shape, a pebble shape, and a random polygonal shape.
In a second aspect, an embodiment of the present invention provides a method for preparing a lithium ion electron conductive agent material according to the first aspect, where the lithium ion electron conductive agent material is obtained by performing surface carbon coating treatment on a solid electrolyte material;
the surface carbon coating comprises a solid phase method and/or a gas phase method.
Preferably, the solid phase method comprises:
mixing a carbon source precursor with a solid electrolyte material, and carrying out high-temperature treatment at 400-1500 ℃ in a protective atmosphere to obtain a carbon coating layer;
the carbon source precursor comprises one or more of phenolic resin, furfural resin, epoxy resin, urea resin, asphalt, citric acid, glucose, sucrose, polyvinyl chloride and polyvinyl butyral; the mass ratio of the carbon source precursor to the solid electrolyte material is between 0.001 and 1000.
Preferably, the gas phase process comprises:
putting the solid electrolyte material into deposition equipment, introducing organic carbon source gas at the temperature of 400-1500 ℃ and under the protective atmosphere at the flow rate of 0.1-10L/min, and carrying out chemical vapor coating on the solid electrolyte material for 1-10 hours to obtain a carbon coating layer;
wherein the organic carbon source gas comprises one or more of acetylene, ethylene, methane, ethane, propane and n-butane.
Further preferably, the protective atmosphere is one or more of a helium atmosphere, a neon atmosphere, an argon atmosphere and a nitrogen atmosphere;
wherein the gas flow under the protective atmosphere is 0.1L/min-10L/min.
In a third aspect, an embodiment of the present invention provides a lithium battery pole piece, including the lithium ion electron conductive agent material described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery including the lithium battery tab of the third aspect.
Preferably, the lithium battery includes a liquid lithium ion battery, a liquid lithium battery, a semi-solid lithium ion battery, a semi-solid lithium battery, and an all-solid lithium battery.
The lithium ion electron conductive agent material provided by the invention has high electron and ion conductivity by compounding the solid electrolyte raw material and the carbon material. In the lithium battery using the material, a more effective channel is provided for the transmission of electrons and ions, and the surface of the solid electrolyte is modified, so that the solid electrolyte has better contact with an electrode active material and a carbon material. The lithium ion electron conductive agent material provided by the invention has the advantages of simple preparation method, easy control of the preparation process and low production cost, and is suitable for industrial production.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a lithium ion electron conductive agent material of example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the cycle performance of the half cells of examples 1 and 2 of the present invention and comparative examples 1 and 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
The embodiment of the invention provides a lithium ion electron conductive agent material, which is a composite core-shell structure and comprises an inner core made of a solid electrolyte material and an outer shell made of a carbon material;
wherein the particle size of the solid electrolyte is 10nm-100um, and the carbon material is particles with the particle size of 1nm-1um or a continuous film with the thickness of 1nm-1 um; the mass ratio of the carbon material to the solid electrolyte material is between 0.001 and 1000; the particle size of the lithium ion electron conductive agent material is 10nm-100 um.
The shape of the solid electrolyte material is one or more of a spherical shape, an ellipsoidal shape, a cobblestone shape and an irregular polygon, and specifically comprises one or more of a garnet type solid electrolyte material, an NASCION type solid electrolyte material, a LICION type solid electrolyte material and a perovskite type solid electrolyte material;
the LISICON-type solid electrolyte specifically comprises: li14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, and B is one or more of Si, S and P;
the NASICON type solid electrolyte is specifically as follows: li1+xAxB2+x(PO4)3Wherein x is between 0.01 and 0.5, A is one or more of Al, Y, Ga, Cr, In, Fe, Se and La, and B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and hafnium element Hf;
the perovskite type solid electrolyte is specifically: li3xA2/3-xBO3Wherein x is in0.01-0.5, A is one or more of La, Al, Mg, Fe and Ta, B is one or more of Ti, Nb, Sr and Pr;
the garnet-type solid electrolyte is specifically: li7A3B2O12Wherein A is one or more of La, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and Hf.
The lithium ion electron conductive agent material can be obtained by performing surface carbon coating treatment on a solid electrolyte material. The method for coating the surface with carbon can be one or both of a solid phase method and a gas phase method.
The solid phase method is to mix a carbon source precursor with a solid electrolyte material and perform high-temperature treatment at 400-1500 ℃ in a protective atmosphere to obtain the carbon coating layer.
Wherein the carbon source precursor comprises one or more of phenolic resin, furfural resin, epoxy resin, urea resin, asphalt, citric acid, glucose, sucrose, polyvinyl chloride and polyvinyl butyral; the mass ratio of the carbon source precursor to the solid electrolyte material is between 0.001 and 1000, preferably between 0.01 and 100.
The vapor phase method is characterized in that a solid electrolyte material is placed in deposition equipment, organic carbon source gas is introduced at the temperature of 400-1500 ℃ and at the flow rate of 0.1-10L/min in a protective atmosphere, and chemical vapor phase coating is carried out on the solid electrolyte material for 1-10 hours to obtain a carbon coating layer; the organic carbon source gas comprises one or more of acetylene, ethylene, methane, ethane, propane and n-butane.
The protective atmosphere in the surface carbon coating method can specifically refer to one or more of helium atmosphere, neon atmosphere, argon atmosphere and nitrogen atmosphere; the gas of protective atmosphere is introduced at a flow rate of 0.1L/min-10L/min.
The lithium ion electron conductive agent material provided by the invention has high electron and ion conductivity by compounding the solid electrolyte raw material and the carbon material. The lithium battery pole piece made of the material is used in lithium batteries such as liquid lithium batteries, semi-solid lithium batteries and all-solid lithium batteries, provides a more effective channel for the transmission of electrons and ions, and modifies the surface of solid electrolyte to ensure that the lithium battery pole piece has better contact with electrode active materials and carbon materials. The lithium ion electron conductive agent material provided by the invention has the advantages of simple preparation method, easy control of the preparation process and low production cost, and is suitable for industrial production.
Example 1
The solid electrolyte material of 200nm Li1.3Al0.3Ti1.7(PO4)3(LATP) and sucrose in a mass ratio of 20: 1 was ground manually for 2 hours, placed in a tube furnace and raised to 400 ℃ at a rate of 1 ℃/minute. Sintering for 4 hours at 400 ℃ in an argon atmosphere to obtain the target lithium ion electron conductive agent material. A Scanning Electron Microscope (SEM) image is shown in FIG. 1. Fig. 1 shows that the lithium ion electron conductive material is polygonal and irregular.
Mixing the obtained target lithium ion additive material with a lithium iron phosphate material, a binder and a conductive agent according to the ratio of 10: 83: 5: and 2, pulping in proportion, coating on an aluminum foil, and drying to obtain the pole piece containing the lithium ion electron conductive agent material.
The metal lithium is taken as a counter electrode, and the electrolyte adopts PEO20And assembling the LiTFSI and the target pole piece into a half cell, and testing the rate capability of the half cell at 60 ℃. As shown in fig. 2.
Example 2
100nm solid electrolyte material Li7La3Zr2O12(LLZO) was placed in a tube furnace with argon as protective gas and a flow rate of 1L/min. Heating to 900 deg.C at 3 deg.C/min, introducing organic carbon source gas toluene at flow rate of 1L/min, and depositing for 4 hr. And naturally cooling to obtain the target lithium ion electron additive material.
Mixing the obtained target lithium ion additive material with a lithium iron phosphate material, a binder and a conductive agent according to the ratio of 10: 83: 5: and 2, pulping in proportion, coating on an aluminum foil, and drying to obtain the pole piece containing the lithium ion electron conductive agent material.
Using metallic lithium as a counter electrodeThe electrolyte adopts PEO20And assembling the LiTFSI and the target pole piece into a half cell, and testing the rate capability of the half cell at 60 ℃. As shown in fig. 2.
Comparative example 1
Mixing a lithium iron phosphate material, a binder and a conductive agent according to a ratio of 93: 5: 2, pulping, coating on an aluminum foil, and drying. And obtaining the required pole piece.
The metal lithium is taken as a counter electrode, and the electrolyte adopts PEO20And assembling the LiTFSI and the pole piece into a half cell, and testing the rate capability of the half cell at 60 ℃. As shown in fig. 2.
Comparative example 2
Mixing a solid electrolyte material LATP, a lithium iron phosphate material, a binder and a conductive agent according to the weight ratio of 10: 83: 5: 2, pulping, coating on an aluminum foil, and drying. And obtaining the required pole piece.
The metal lithium is taken as a counter electrode, and the electrolyte adopts PEO20And assembling the LiTFSI and the pole piece into a half cell, and testing the rate capability of the half cell at 60 ℃. As shown in fig. 2.
Fig. 2 shows that the capacity of the example of the invention is significantly higher than that of the comparative example at 2C and 3C rates, which indicates that the rate performance of the example is better than that of the comparative example, and the battery performance of the lithium ion electronic additive material of the invention is superior. The cycle numbers in the figure are cycle numbers.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. The lithium ion electron conductive agent material is characterized in that the lithium ion electron conductive agent material is of a composite core-shell structure and comprises an inner core made of a solid electrolyte material and an outer shell made of a carbon material;
the particle size of the solid electrolyte is 10nm-100um, and the carbon material is particles with the particle size of 1nm-1um or a continuous film with the thickness of 1nm-1 um; the mass ratio of the carbon material to the solid electrolyte material is between 0.001 and 1000; the particle size of the lithium ion electron conductive agent material is 10nm-100 um;
the solid electrolyte material is one or a mixture of garnet type solid electrolyte material, LISICON type solid electrolyte material and perovskite type solid electrolyte material;
wherein, the LISICON type solid electrolyte is specifically as follows: li14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, and B is one or more of Si, S and P; the perovskite type solid electrolyte is specifically as follows: li3xA2/3-xBO3Wherein x is between 0.01 and 0.5, A is one or more of La, Al, Mg, Fe and Ta, and B is one or more of Ti, Nb, Sr and Pr; the garnet-type solid electrolyte specifically comprises: li7A3B2O12Wherein A is one or more of La, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and Hf.
2. The lithium ion electron conductor material of claim 1, wherein the solid state electrolyte material is one or more of spherical, ellipsoidal, pebble-like, and irregular polygonal in shape.
3. The preparation method of the lithium ion electron conductive agent material according to claim 1, wherein the lithium ion electron conductive agent material is obtained by performing surface carbon coating treatment on a solid electrolyte material;
the surface carbon coating comprises a solid phase method and/or a gas phase method;
wherein the solid phase method comprises:
mixing a carbon source precursor with a solid electrolyte material, and carrying out high-temperature treatment at 400-1500 ℃ in a protective atmosphere to obtain a carbon coating layer;
the carbon source precursor comprises one or more of phenolic resin, furfural resin, epoxy resin, urea resin, asphalt, citric acid, glucose, sucrose, polyvinyl chloride and polyvinyl butyral; the mass ratio of the carbon source precursor to the solid electrolyte material is between 0.001 and 1000;
the gas phase process comprises:
putting the solid electrolyte material into deposition equipment, introducing organic carbon source gas at the temperature of 400-1500 ℃ and under the protective atmosphere at the flow rate of 0.1-10L/min, and carrying out chemical vapor coating on the solid electrolyte material for 1-10 hours to obtain a carbon coating layer;
wherein the organic carbon source gas comprises one or more of acetylene, ethylene, methane, ethane, propane and n-butane;
the solid electrolyte material is one or a mixture of garnet type solid electrolyte material, LISICON type solid electrolyte material and perovskite type solid electrolyte material; the LISICON-type solid electrolyte specifically comprises: li14A(BO4)4Wherein A is one or more of Zr, Cr and Sn, and B is one or more of Si, S and P; the perovskite type solid electrolyte is specifically as follows: li3xA2/3-xBO3Wherein x is between 0.01 and 0.5, A is one or more of La, Al, Mg, Fe and Ta, and B is one or more of Ti, Nb, Sr and Pr; the garnet-type solid electrolyte specifically comprises: li7A3B2O12Wherein A is one or more of La, Ca, Sr, Ba and K, and B is one or more of Zr, Ta, Nb and Hf.
4. The method for preparing the lithium ion electron conductive agent material according to claim 3, wherein the protective atmosphere is one or more of a helium atmosphere, a neon atmosphere, an argon atmosphere and a nitrogen atmosphere;
wherein the gas flow under the protective atmosphere is 0.1L/min-10L/min.
5. A lithium battery pole piece, characterized in that the lithium battery pole piece comprises the lithium ion electron conductive agent material of any one of claims 1-2.
6. A lithium battery comprising the lithium battery pole piece of claim 5 above.
7. The lithium battery of claim 6, wherein the lithium battery comprises a liquid lithium ion battery, a liquid lithium battery, a semi-solid lithium ion battery, a semi-solid lithium battery, an all-solid lithium battery.
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| CN109346651B (en) * | 2018-10-25 | 2021-06-29 | 五邑大学 | Flexible ceramic nanofiber membrane and preparation method and application thereof |
| CN109817871A (en) * | 2019-03-29 | 2019-05-28 | 溧阳天目先导电池材料科技有限公司 | A kind of ion conductor slurry and its preparation method and application |
| CN110729511A (en) * | 2019-10-28 | 2020-01-24 | 溧阳天目先导电池材料科技有限公司 | Lithium ion solid electrolyte material with composite core-shell structure and preparation method thereof |
| CN111403806A (en) * | 2020-04-17 | 2020-07-10 | 中国科学院物理研究所 | Carbon-coated solid electrolyte material and preparation method and application thereof |
| CN111987347B (en) * | 2020-06-22 | 2021-08-03 | 厦门永力鑫新能源科技有限公司 | Phosphate solid electrolyte, solid-phase synthesis method and equipment thereof, and solid-state battery |
| CN113488693B (en) * | 2021-07-01 | 2022-06-28 | 重庆锦添翼新能源科技有限公司 | Double-layer graphene-coated solid electrolyte composite material and preparation method thereof |
| CN117012957B (en) * | 2023-10-08 | 2024-01-19 | 深圳市贝特瑞新能源技术研究院有限公司 | Low-temperature-resistant lithium iron phosphate semi-solid battery, positive electrode slurry thereof and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540398A (en) * | 2008-03-17 | 2009-09-23 | 中国科学院物理研究所 | Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof |
| WO2016011412A1 (en) * | 2014-07-17 | 2016-01-21 | Ada Technologies, Inc. | Extreme long life, high energy density batteries and method of making and using the same |
| CN105932225A (en) * | 2016-06-29 | 2016-09-07 | 中国科学院青岛生物能源与过程研究所 | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016011412A1 (en) * | 2014-07-17 | 2016-01-21 | Ada Technologies, Inc. | Extreme long life, high energy density batteries and method of making and using the same |
| CN105932225A (en) * | 2016-06-29 | 2016-09-07 | 中国科学院青岛生物能源与过程研究所 | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery |
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