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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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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