CN109004201B - Preparation method and application of core-shell structured high-voltage positive electrode material suitable for polymer-based solid electrolyte - Google Patents
Preparation method and application of core-shell structured high-voltage positive electrode material suitable for polymer-based solid electrolyte Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011258 core-shell material Substances 0.000 title abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000005253 cladding Methods 0.000 claims abstract description 21
- 239000011257 shell material Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 40
- 239000002131 composite material Substances 0.000 claims description 39
- 239000002861 polymer material Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 229910010252 TiO3 Inorganic materials 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 6
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 239000006256 anode slurry Substances 0.000 claims 1
- 238000005520 cutting process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011261 inert gas Substances 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000011824 nuclear material Substances 0.000 abstract description 5
- -1 anion lithium salts Chemical class 0.000 description 20
- 239000011162 core material Substances 0.000 description 10
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical group [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 229920000379 polypropylene carbonate Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 5
- 229910013075 LiBF Inorganic materials 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 description 3
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 description 3
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical group [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010702 perfluoropolyether Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PYUKXGCMRFTISX-UHFFFAOYSA-N [O].[Ta].[Zr].[La].[Li] Chemical compound [O].[Ta].[Zr].[La].[Li] PYUKXGCMRFTISX-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention discloses a preparation method of a core-shell structured high-voltage anode material suitable for a polymer-based solid electrolyte, which is characterized by comprising the following steps of: respectively adding 0.5-5 parts by mass of a shell material and 100 parts by mass of a nuclear material with high voltage into a cavity of a mechanical cladding machine, introducing inert gases such as protective gas nitrogen or argon into the cavity, starting the mechanical cladding machine, extruding and rubbing the materials and utilizing the heat generated by the materials during the high-speed operation of the machine to generate a mechanochemical effect on the particle surface, cladding the shell material on the surface of the nuclear material after 30-60min, observing the material to be further spherical through a scanning electron microscope, embedding the shell material on the surface of the nuclear material, observing the cladding layer through a projection electron microscope to enable the thickness of the shell material to reach 20-60nm, and thus obtaining the high-voltage positive electrode material. The advantages are that: the high-voltage resistant material with the capability of transmitting lithium ions coats the high-voltage anode material, is convenient to operate and can be produced in large scale.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to a preparation method of a core-shell structured high-voltage anode material suitable for a polymer-based solid electrolyte, and also relates to application of the core-shell structured anode material in a high-voltage polymer solid lithium battery.
Background
Because the solid-state lithium battery has no free electrolyte, the flammability of the battery is greatly reduced, and the safety of the battery is improved. Compared with a liquid lithium ion battery, the solid lithium battery has the performances of higher energy density, better cycle life and the like. Solid-state lithium batteries can be classified into polymer solid-state lithium batteries and inorganic solid-state lithium batteries. The polymer solid-state lithium battery has the characteristics of roll-to-roll production and flexible processing, can be made into a thin-film battery and a flexible battery, can be applied to the fields of intelligent wearing and ultramicro ultrathin intelligent equipment, and is expected to be promising.
In the polymer solid lithium ion battery, the polymer solid electrolyte is used as a core material, has the advantages of light weight, easy film formation, high safety, stability to lithium and the like, and common polymer substrates comprise polyether, polyester, polyamine and polymers of the polyether, the polyester, the polyamine and polysilane, polyphosphate or the like. However, these polymers tend to have low room temperature ionic conductivity and narrow electrochemical window, so that the application of polymer solid electrolyte in high voltage positive electrode material system is limited. The 201710951551.X patent discloses a composite solid electrolyte with a polymer-ceramic-polymer multilayer structure, the 201710040922.9 patent discloses a composite solid electrolyte doped with polymers, lithium salts and organic matters, the 201710829019.0 patent discloses a semi-interpenetrating polymer solid electrolyte cured by ultraviolet light, and the 201510258846.X patent discloses a composite solid electrolyte of polymers, boron cage type anion lithium salts and dopants, wherein the polymer-based solid electrolytes all have high ionic conductivity and wide electrochemical window, but in practical application, the polymer materials are inevitably contacted with a high-voltage positive electrode material, so that the polymers are decomposed into small molecular substances, and the battery performance is poor.
Disclosure of Invention
The purpose of the invention is: aiming at the defects, the preparation method and the application of the high-voltage cathode material with the core-shell structure suitable for the polymer-based solid electrolyte are provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-voltage anode material with a core-shell structure suitable for a polymer-based solid electrolyte comprises the steps of adding 0.5-5 parts by mass of a shell material and 100 parts by mass of a core material with high voltage into a cavity of a mechanical cladding machine, introducing inert gas such as protective gas nitrogen or argon into the cavity, starting the mechanical cladding machine, extruding and rubbing the materials in the high-speed operation process of the machine, utilizing the heat generated by the materials to generate a mechanochemical effect on the particle surface, cladding the shell material on the surface of the core material after 30-60min, observing the material to be further spherical through a scanning electron microscope, embedding the shell material on the surface of the core material, and observing the cladding layer through a projection electron microscope to enable the thickness of the shell material to reach 20-60nm, so that the high-voltage anode material can be obtained.
The core-shell structure of the high-voltage anode material is a one-layer structure or a multi-layer structure.
The shell structure is Li1+xAlxTi2-x(PO4)3(LATP)，Li7-xLa3Zr2-xMxO12(M＝Ta,Nb)(0﹤x﹤2)(LLZMO)，LixLa2/3-xTiO3(LLTO)，LiAlO2(LAO)，Li2ZrO3(LZO)，Li4Ti5O12(LTO)。
The nuclear structure is lithium nickel phosphate (LiMn)xFe(1-x)PO4) Lithium cobalt phosphate (LiCoPO)4) Lithium nickel phosphate (LiNiPO)4) Lithium manganate (LiMnO)4) Lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Ternary material (LiNi)xCoyMnzO2) Manganese-rich lithium material xLi2MnO3﹒(1-x)LiMO2(M＝Ni，Co，Mn)。
The application of the anode material with the core-shell structure in the high-voltage polymer solid-state lithium battery comprises a composite anode, a polymer solid-state electrolyte and a metal lithium cathode, wherein the metal lithium is used as the cathode, the polymer solid-state electrolyte and the composite anode are superposed to form the solid-state lithium battery, and the charge and discharge cutoff voltage of the battery is 3.0-4.3V.
The composite positive electrode comprises 75-90 parts by mass of a shell-core structure positive electrode material, 1-5 parts by mass of a conductive agent, 1-5 parts by mass of a binder, 5-15 parts by mass of a polymer material and 3-8 parts by mass of a lithium salt; the composite positive electrode slurry is obtained by uniformly dispersing in NMP through mechanical stirring, then coated on a current collector, and subjected to drying, rolling and slitting to obtain the composite positive electrode sheet.
The polymer solid electrolyte comprises a polymer material, lithium salt and ceramic powder.
The polymer material comprises one or more of a polyether material, a polyacrylate material, a polyacrylonitrile material and a polyphenylene sulfide material.
Further, the conductive agent includes carbon black (AB), SPUER-P, KS-6, conductive graphite, carbon fiber (VGCF), Carbon Nanotube (CNT), and graphene.
Further, the adhesive is one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene carbonate (PEC), polytrimethylene carbonate (PTMC) and polypropylene carbonate (PPC).
Further, the lithium salt includes lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluorophosphate (LiPF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Bis (trifluoromethanesulfonic) imide Lithium (LiTFSI), tris (trifluoromethanesulfonic) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB).
Further, the polymer material is polymethyl methacrylate, polyether silane, epichlorohydrin rubber and perfluoropolyether.
Further, the ceramic powder is selected from Lithium Lanthanum Zirconium Oxygen (LLZO), Lithium Lanthanum Zirconium Tantalum Oxygen (LLZTO), Lithium Lanthanum Titanium Oxygen (LLTO), and aluminum oxide (Al)2O3) Zirconium oxide (ZrO)2) Titanium oxide (TiO)2) Barium sulfate (BaSO)4)。
Compared with the prior art, the invention achieves the technical effects that: the invention designs a high-voltage anode material with a core-shell structure, wherein a thin high-voltage-resistant inorganic solid electrolyte material is coated on the surface of the high-voltage anode material or a plurality of layers of inorganic materials are coated on the surface of the high-voltage anode material, but the outermost layer is the inorganic solid electrolyte material; in the composite anode, the direct contact between a polymer material and an anode material can be effectively avoided, and the assembled solid-state lithium battery has good interface compatibility and stable cycle performance; the high-voltage resistant material with the lithium ion transmission capacity coats the high-voltage anode material, the operation is convenient, the large-scale batch production can be realized, meanwhile, the high-voltage anode material can be used in the field of polymer solid-state lithium batteries, and the assembled polymer solid-state batteries have stable circulation and higher capacity exertion.
Drawings
FIG. 1 is LLZMO-coated LiNixCoyMnzO2SEM image of (d).
FIG. 2 is a LATP-coated LiNi0.5Mn1.5O4A TEM image of (a).
Detailed Description
The invention is further described with reference to the following figures and examples:
the first embodiment is as follows:
as shown in fig. 1: the invention relates to a preparation method of a high-voltage anode material with a core-shell structure suitable for a polymer-based solid electrolyte, which is characterized in that 2 parts by mass of 150nm Li are respectively added7-xLa3Zr2-xMxO12(M ═ Ta, Nb) (0 < x < 2) (LLZMO) and 100 parts by mass of a ternary material (LiNi) having a high voltagexCoyMnzO2) Adding into the cavity of the mechanical cladding machine, then introducing inert gases such as protective gas nitrogen or argon into the cavity, starting the mechanical cladding machine, wherein the machine is in the high-speed operation process, the material is extruded and rubbed and generates heat by utilizing the material, so that the particle surface generates a mechanochemical effect, after 40min, the shell material is cladded on the surface of the nuclear material, the material is observed to be further spherical through a scanning electron microscope, the shell material is embedded on the surface of the nuclear material, the cladding layer is observed through a projection electron microscope, so that the thickness of the shell material reaches 20nm, and the high-voltage anode material can be obtained.
The application of the anode material with the core-shell structure in the high-voltage polymer solid-state lithium battery comprises a composite anode, a polymer solid-state electrolyte and a metal lithium cathode, wherein the metal lithium is used as the cathode, the polymer solid-state electrolyte and the composite anode are superposed to form the solid-state lithium battery, and the charge and discharge cutoff voltage of the battery is 3.0-4.3V.
The composite positive electrode comprises 80 parts by mass of a shell-core structure positive electrode material, 2 parts by mass of a conductive agent graphene, 3 parts by mass of a binder polypropylene carbonate (PPC), 10 parts by mass of a polymer material perfluoropolyether and 5 parts by mass of a lithium salt lithium tetrafluoroborate (LiBF)4) (ii) a The composite positive electrode slurry is obtained by uniformly dispersing in NMP through mechanical stirring, then coated on a current collector, and subjected to drying, rolling and slitting to obtain the composite positive electrode sheet.
The polymer solid electrolyte comprises polymer materials of polymethyl methacrylate and lithium salt of lithium tetrafluoroborate (LiBF)4) And ceramic powder Lithium Lanthanum Zirconium Oxygen (LLZO), the mass ratio of which is: 60:30:10.
The comparative composite positive electrode described above: li7-xLa3Zr2-xMxO12(M ═ Ta, Nb) (0 < x < 2) (LLZMO), uncoated ternary material (LiNi)xCoyMnzO2) Graphene serving as a conductive agent, polypropylene carbonate (PPC) serving as a binder, perfluoropolyether serving as a polymer material, and lithium salt lithium tetrafluoroborate (LiBF)4) The mass ratio of (A) to (B) is as follows: 2:78:2:3:10:5.
Example two:
as shown in fig. 1 and 2: the invention relates to a preparation method of a high-voltage anode material with a core-shell structure suitable for polymer-based solid electrolyte, which respectively prepares 4 parts by mass of 400nm LixLa2/3-xTiO3(LLTO) and 100 parts by mass of lithium nickel phosphate (LiMn) having a high voltagexFe(1-x)PO4) Adding into a cavity of a mechanical cladding machine, introducing inert gas such as protective gas nitrogen or argon into the cavity, starting the mechanical cladding machine, extruding and rubbing the material and utilizing the heat generated by the material to generate a mechanochemical effect on the particle surface in the high-speed operation process of the machine, and after 60min, LixLa2/3-xTiO3(LLTO) coating with lithium nickel phosphate (LiMn)xFe(1-x)PO4) The surface of the material is further spheroidized by observing the material through a scanning electron microscope, and the shell material is embedded in the surface of the nuclear materialAnd (4) observing the coating layer through a projection electron microscope to enable the thickness of the shell material to reach 23nm, thus obtaining the high-voltage anode material.
The application of the anode material with the core-shell structure in the high-voltage polymer solid-state lithium battery comprises a composite anode, a polymer solid-state electrolyte and a metal lithium cathode, wherein the metal lithium is used as the cathode, the polymer solid-state electrolyte and the composite anode are superposed to form the solid-state lithium battery, and the charge and discharge cutoff voltage of the battery is 3.0-4.3V.
Wherein the composite positive electrode comprises 75 parts by mass of a positive electrode material with a shell-core structure, 2 parts by mass of a conductive agent Carbon Nano Tube (CNT), 3 parts by mass of a binder polyethylene oxide (PEO), 12 parts by mass of a polymer material epichlorohydrin rubber and 8 parts by mass of lithium salt lithium bis (trifluoromethanesulfonic acid) imide (LiTFSI); the composite positive electrode slurry is obtained by uniformly dispersing in NMP through mechanical stirring, then coated on a current collector, and subjected to drying, rolling and slitting to obtain the composite positive electrode sheet.
The polymer solid electrolyte comprises polymer material epichlorohydrin rubber, lithium salt bis (trifluoromethanesulfonic acid) lithium imide (LiTFSI) and ceramic powder Lithium Lanthanum Zirconium Tantalum Oxygen (LLZTO), and the mass ratio is as follows: 60:35:5.
The comparative composite positive electrode described above: LixLa2/3-xTiO3(LLTO), uncoated lithium nickel phosphate (LiMn)xFe(1-x)PO4) The conductive agent Carbon Nano Tube (CNT), the binder polyethylene oxide (PEO), the polymer material epichlorohydrin rubber and lithium salt bis (trifluoromethanesulfonic acid) lithium imide (LiTFSI) are as follows: 4:71:2:3:12:8.
Example three:
as shown in fig. 1 and 2: the invention relates to a preparation method of a high-voltage anode material with a core-shell structure suitable for a polymer-based solid electrolyte, which respectively comprises the following steps of mixing 1.5 parts by mass of 100nm Li1+xAlxTi2-x(PO4)3(LATP) and 100 parts by mass of lithium nickel manganese oxide (LiNi) having high voltage0.5Mn1.5O4) Adding into the cavity of the mechanical cladding machine, introducing inert gas such as protective gas nitrogen or argon, and starting the mechanical cladding machineIn the high-speed operation process, the material is extruded and rubbed and generates heat by itself, so that the particle surface generates mechanochemical effect, and Li is obtained after 30min1+xAlxTi2-x(PO4)3(LATP) coating lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) And after the material is observed to be further spherical through a scanning electron microscope and the shell material is embedded on the surface of the core material, the coating layer is observed through a projection electron microscope, so that the thickness of the shell material reaches 26nm, and the high-voltage anode material can be obtained.
The application of the anode material with the core-shell structure in the high-voltage polymer solid-state lithium battery comprises a composite anode, a polymer solid-state electrolyte and a metal lithium cathode, wherein the metal lithium is used as the cathode, the polymer solid-state electrolyte and the composite anode are superposed to form the solid-state lithium battery, and the charge and discharge cutoff voltage of the battery is 3.0-4.3V.
The composite positive electrode comprises 83 parts by mass of a positive electrode material with a shell-core structure, 1.5 parts by mass of a conductive agent carbon fiber (VGCF), 1.5 parts by mass of a binder polyvinylidene fluoride (PVDF), 9 parts by mass of a polymer material polyether silane and 5 parts by mass of lithium salt lithium hexafluorophosphate (LiPF)6) (ii) a The composite positive electrode slurry is obtained by uniformly dispersing in NMP through mechanical stirring, then coated on a current collector, and subjected to drying, rolling and slitting to obtain the composite positive electrode sheet.
The polymer solid electrolyte comprises a polymer material of polyether silane, lithium salt and lithium hexafluorophosphate (LiPF)6) And ceramic powder Lithium Lanthanum Zirconium Oxygen (LLZO), the mass ratio of which is: 55:30:15.
The comparative composite positive electrode described above: li1+xAlxTi2-x(PO4)3(LATP) uncoated lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) The conductive agent is carbon fiber (VGCF), a binder is polyvinylidene fluoride (PVDF), a polymer material is polyether silane, lithium salt is lithium hexafluorophosphate (LiPF)6) Comprises the following steps: 1.5:81.5:1.5:1.5:9:5.
Example four:
as shown in fig. 1 and 2: the invention is suitable for polymer-based solidA preparation method of a high-voltage cathode material with a core-shell structure of electrolyte, which is to respectively prepare 4 parts by mass of 300nm LiNi1/3Co1/3Mn1/3O2And 100 parts by mass of LiNi0.8Co0.1Mn0.1O2Adding into the cavity of a mechanical cladding machine, introducing protective nitrogen into the cavity, and starting the mechanical cladding machine for 40min to obtain the surface-coated LiNi1/3Co1/3Mn1/3O2LiNi of (2)0.8Co0.1Mn0.1O2Then, 2 parts by mass of 150nm LixLa were added2/3-xTiO3(LLTO) and 100 parts by mass of surface-coated LiNi1/3Co1/3Mn1/3O2LiNi of (2)0.8Co0.1Mn0.1O2Observation of the material by scanning Electron microscopy, LiNi0.8Co0.1Mn0.1O2Further spheroidized and LixLa2/3- xTiO3(LLTO) mosaic on LiNi0.8Co0.1Mn0.1O2After the surface is finished, the coating layer is observed through a projection electron microscope, so that the thickness of the shell material reaches 50-60nm, preferably 55 nm, and the high-voltage anode material can be obtained.
The application of the anode material with the core-shell structure in the high-voltage polymer solid-state lithium battery comprises a composite anode, a polymer solid-state electrolyte and a metal lithium cathode, wherein the metal lithium is used as the cathode, the polymer solid-state electrolyte and the composite anode are superposed to form the solid-state lithium battery, and the charge and discharge cutoff voltage of the battery is 3.0-4.3V.
Wherein the composite positive electrode comprises 80 parts by mass of a secondary-coated shell-core structured positive electrode material, 1.5 parts by mass of a conductive agent conductive graphite, 1.5 parts by mass of a binder polyethylene carbonate (PEC), 10 parts by mass of a polymer material polymethyl methacrylate, and 7 parts by mass of a lithium salt lithium trifluoromethanesulfonate (LiCF)3SO3) (ii) a The composite positive electrode slurry is obtained by uniformly dispersing in NMP through mechanical stirring, then coated on a current collector, and subjected to drying, rolling and slitting to obtain the composite positive electrode sheet.
The polymer solid electrolyte comprises a polymer material polyMethyl methacrylate, lithium salt lithium triflate (LiCF)3SO3) And ceramic powder alumina (Al)2O3) The mass ratio is as follows: 55:35:10.
The comparative composite positive electrode described above: LixLa2/3-xTiO3(LLTO), Primary coated LiNi0.8Co0.1Mn0.1O2Conductive graphite as conductive agent, polyethylene carbonate (PEC) as binder, polymethyl methacrylate as polymer material, and lithium salt of trifluoromethyl sulfonate (LiCF)3SO3) Comprises the following steps: 2:78:1.5:1.5:10:7.
Specific discharge capacity (mAh/g) of the experimental group and the control group in the first to fourth examples is shown in the following table:
compared with the prior art, the invention achieves the technical effects that: the invention designs a high-voltage anode material with a core-shell structure, wherein a thin high-voltage-resistant inorganic solid electrolyte material is coated on the surface of the high-voltage anode material or a plurality of layers of inorganic materials are coated on the surface of the high-voltage anode material, but the outermost layer is the inorganic solid electrolyte material; in the composite anode, the direct contact between a polymer material and an anode material can be effectively avoided, and the assembled solid-state lithium battery has good interface compatibility and stable cycle performance; the high-voltage resistant material with the lithium ion transmission capacity coats the high-voltage anode material, the operation is convenient, the large-scale batch production can be realized, meanwhile, the high-voltage anode material can be used in the field of polymer solid-state lithium batteries, and the assembled polymer solid-state batteries have stable circulation and higher capacity exertion.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (1)
1. The application of a shell-core structured positive electrode material in a high-voltage polymer solid-state lithium battery comprises a composite positive electrode, a polymer solid-state electrolyte and a metal lithium negative electrode, wherein the metal lithium is used as the negative electrode, the polymer solid-state electrolyte and the composite positive electrode are superposed on the metal lithium to form the solid-state lithium battery, and the charge-discharge cutoff voltage of the battery is 3.0-4.3V;
the composite positive electrode comprises 80 parts by mass of a secondary coated positive electrode material with a shell-core structure, 1.5 parts by mass of conductive graphite serving as a conductive agent, 1.5 parts by mass of polyvinyl carbonate serving as a binder, 10 parts by mass of polymethyl methacrylate serving as a polymer material and 7 parts by mass of lithium salt lithium trifluoromethanesulfonate; uniformly dispersing the slurry in NMP by mechanical stirring to obtain composite anode slurry, then coating the slurry on a current collector, and drying, rolling and cutting to obtain a composite anode sheet;
the polymer solid electrolyte comprises polymer materials of polymethyl methacrylate, lithium salt of lithium trifluoromethanesulfonate and ceramic powder alumina, wherein the mass ratio of the polymer materials of polymethyl methacrylate, lithium salt of lithium trifluoromethanesulfonate and ceramic powder alumina is as follows: 55:35: 10;
the preparation method of the secondary coated shell-core structured cathode material comprises the following steps: 4 parts by mass of 300nm LiNi1/3Co1/3Mn1/3O2And 100 parts by mass of LiNi0.8Co0.1Mn0.1O2Adding the mixture into a cavity of a mechanical cladding machine, introducing protective nitrogen into the cavity, and starting the mechanical cladding machine for 40min to obtain the surface-coated LiNi1/3Co1/3Mn1/3O2LiNi of (2)0.8Co0.1Mn0.1O2Then, 2 parts by mass of 150nm LixLa were added2/3-xTiO3And 100 parts by mass of surface-coated LiNi1/3Co1/3Mn1/3O2LiNi of (2)0.8Co0.1Mn0.1O2Adding into the cavity of the mechanical cladding machine, and then placing in the cavityIntroducing protective gas nitrogen or argon, starting the mechanical cladding machine, extruding and rubbing the material and utilizing the material to generate heat during the high-speed operation of the machine, so that the particle surface generates a mechanochemical effect, and observing the material LiNi through a scanning electron microscope0.8Co0.1Mn0.1O2Further spheroidized and LixLa2/3-xTiO3Embedded in LiNi0.8Co0.1Mn0.1O2And on the surface, the thickness of the shell material reaches 50-60nm by observing the coating layer through a transmission electron microscope.
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| CN110148728A (en) * | 2019-05-24 | 2019-08-20 | 隆能科技(南通)有限公司 | A kind of ternary material and preparation method thereof of surface cladding LLTO |
| JP7403289B2 (en) * | 2019-11-27 | 2023-12-22 | 太平洋セメント株式会社 | Positive electrode active material composite for lithium ion secondary battery and method for manufacturing the same |
| TWI724715B (en) | 2019-12-27 | 2021-04-11 | 財團法人工業技術研究院 | Ion-conducting material, core-shell structure containing the same, electrode prepared by the core-shell structure and metal-ion battery empolying the electrode |
| CN113054158B (en) * | 2019-12-27 | 2023-06-06 | 财团法人工业技术研究院 | Ion conducting material, core-shell structure comprising ion conducting material, formed electrode and metal ion battery |
| EP4002519A1 (en) | 2020-11-11 | 2022-05-25 | Evonik Operations GmbH | Transition metal oxide particles encapsulated in nanostructured lithium titanate or lithium aluminate, and the use thereof in lithium ion batteries |
| CN112467116A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Graphite coating material, preparation method thereof and battery cathode |
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