CN108511786B - All-solid-state lithium battery and preparation method thereof - Google Patents
All-solid-state lithium battery and preparation method thereof Download PDFInfo
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Abstract
The all-solid-state lithium battery comprises a positive plate, a negative plate and a solid electrolyte layer, wherein the positive plate comprises a positive active substance, and the positive active substance comprises positive material particles and a fluorine-containing lithium titanate layer coated on the surfaces of the positive material particles. According to the method for preparing the cathode active material with the cathode material surface coated with the fluorine-containing lithium titanate layer by mixing and sintering the cathode material, the surface of the cathode material can be uniformly modified to obtain the cathode material with controllable surface fluorine content and fluorine-containing lithium titanate layer thickness, when the cathode material is used for an all-solid-state lithium battery, the coating layer structure can be stabilized, interface reaction or element diffusion between the cathode material and a solid electrolyte is avoided, and interface impedance is reduced.
Description
Technical Field
The disclosure relates to the field of solid-state lithium batteries, in particular to an all-solid-state lithium battery and a preparation method thereof.
Background
In the all-solid-state lithium battery, because of the serious interface effect between the anode material and the solid electrolyte and the diffusion problem of elements appearing at the interface, the interface impedance between the anode and the solid electrolyte is greatly increased, thereby greatly influencing the performance of the battery, the prior art usually adopts a method of surface coating the anode material to solve the technical problem, wherein the coating is usually oxide, lithium-containing transition metal oxide or fluoride, and the like, the anode material is usually selected from L iNbO3、LiTaO3、Li4Ti5O12、Al2O3、BaF2Or CaF2Etc., in which the pairs L iNbO3The cathode material coated on the surface is most widely used.
Typically, binary or ternary oxide materials (e.g., L iNbO) are used3) The surface of the anode material is coated, but oxygen atoms and sulfur atoms in the existing sulfur-based electrolyte can diffuse mutually, and the structure of the coating layer is not stable enough, so that the reduction of the interface impedance between the anode material and the electrolyte is not obvious, or the impedance can be gradually increased in the charging and discharging process, the charging and discharging process is blocked, and the service life can be reduced.
Disclosure of Invention
The purpose of the disclosure is to provide an all-solid-state lithium battery and a preparation method thereof, which can solve the problems of large interfacial resistance between a positive electrode and a solid electrolyte and mutual diffusion of elements in a circulation process in the prior art.
In order to achieve the above object, the present disclosure provides an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, wherein the positive electrode sheet includes a positive electrode active material, and the positive electrode active material includes positive electrode material particles and a fluorine-containing lithium titanate layer coated on the surfaces of the positive electrode material particles.
The present disclosure also provides a method of manufacturing an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, the method including the steps of:
(1) adding titanium Tetrafluoride (TiF) to the solvent4) And lithium salt, adding the anode material after stirring until the lithium salt is dissolved, fully stirring, and evaporating the solvent to obtain a reaction precursor; sintering the reaction precursor to obtain a positive active material with a fluorine-containing lithium titanate layer coated on the surface of a positive material;
(2) and sequentially pressing a solid electrolyte layer containing a solid electrolyte and a negative plate on the positive plate containing the positive active material to obtain the all-solid-state lithium battery.
The disclosure also provides an all-solid-state lithium battery prepared by the method.
The inventors of the present disclosure have made numerous experiments and have unexpectedly found that a fluorine-containing lithium titanate layer having a uniform thickness can be formed on the surface of a positive electrode material particle by high-temperature sintering after mixing titanium tetrafluoride, a lithium salt and a positive electrode material in a solution. The anode material coated by the fluorine-containing lithium titanate can avoid interface side reaction between the anode material and the solid electrolyte, prevent elements between interfaces from diffusing, and greatly reduce the interface impedance between the anode material and the solid electrolyte. While the present disclosure proposes the use of titanium Tetrafluoride (TiF)4) The method for preparing the positive active material with the surface of the positive material coated with the fluorine-containing lithium titanate layer by mixing the lithium salt and the positive material in the solution and then sintering at high temperature can uniformly coat the surface of the positive material to obtain the positive material with the controllable coating thickness, and when the positive material is used for the all-solid-state lithium battery, the positive material can be usedThe method has the advantages of avoiding interface reaction or element diffusion between the anode material and the solid electrolyte, reducing interface impedance, improving the cycling stability of the anode material, prolonging the service life of the all-solid-state lithium battery and improving the electrochemical performance of the all-solid-state lithium battery.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The utility model provides an all solid-state lithium battery, including positive plate, negative pole piece and solid electrolyte layer, the positive plate includes anodal active material, anodal active material includes anodal material granule and cladding in the lithium titanate layer that contains fluorine on anodal material granule surface.
The all-solid-state lithium battery adopts the anode material of which the surface is coated with the fluorine-containing lithium titanate layer, the coating layer has uniform thickness, can avoid the interfacial reaction between the anode material and the solid electrolyte, prevent the diffusion of elements between interfaces, greatly reduce the interfacial impedance between the anode material and the solid electrolyte, improve the cycling stability of the anode material, prolong the service life of the all-solid-state battery and improve the electrochemical performance of the all-solid-state battery.
According to the present disclosure, the fluorine-containing lithium titanate layer is a fluorine-doped lithium titanate coating layer formed on the surface of the positive electrode material particles after being treated with titanium tetrafluoride and lithium salt; the F/O atomic ratio of the lithium fluorotitanate layer refers to a value obtained by dividing the percentage content of fluorine element in all atoms in the surface layer of the tested positive electrode material by the percentage content of oxygen element in all elements, and the F/O atomic ratio can represent the fluorine content of the lithium fluorotitanate layer, and can be determined by methods well known to those skilled in the art, for example, the F/O atomic ratio described in the present disclosure is determined by an X-ray photoelectron spectroscopy method. The coating effect is uniform, preferably, the F/O atomic ratio of the fluorine-containing lithium titanate layer can be 0.01-100, and the fluorine content in the coating layer does not change along with the thickness of the coating layer.
According to the present disclosure, the molar ratio of fluorine atoms to titanium atoms in the fluorine-containing lithium titanate coating layer may vary widely, preferably 0.01 to 2.4: 1.
according to the present disclosure, the particle size of the positive electrode active material may vary widely, preferably 0.05 to 1000 μm, and more preferably 1 to 100 μm; the thickness of the lithium fluorotitanate-containing layer is controllable and can be varied within a wide range, and in order to further uniformly coat the positive electrode material and avoid interfacial reaction, the thickness of the lithium fluorotitanate-containing layer is preferably 10nm to 2000nm, and more preferably 50 nm to 1000 nm.
According to the present disclosure, the lithium salt may specifically be L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
According to the present disclosure, the solid electrolyte layer is one or more of a sodium fast ion conductor structure type (NASICON type) solid electrolyte, a perovskite type solid electrolyte, and a sulfur type solid electrolyte.
The NASICON type solid electrolyte is L iM2(PO4)3And a dopant thereof, wherein M is at least one of Ti, Zr, Ge, Sn or Pb, and L iM2(PO4)3The doping element adopted by the dopant of (1) is at least one selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V.
The active solid-state electrolyte of the calcium and titanium is AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3Wherein x +3Y =2, h +2k +5n +4w =6, 0 < x < 2, 0 < Y < 2/3, h, k, n, w are all more than 0, A is L i, at least one of Na elements, B is L a, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd elements, M is SrCa, Ba, Ir and Pt, D is at least one of Nb and Ta.
The sulfur-based solid electrolyte may be a sulfur-containing solid electrolyte well known to those skilled in the art, preferably L i of crystalline titaniumxMyPzSwL i in glassy state2S-P2S5L i in the form of glass-ceramic2S-P2S5Wherein M can be at least one of Si, Ge and Sn, x +4y +5z =2w, x is 2. ltoreq. x.ltoreq.11, y is 0. ltoreq. y.ltoreq.1.5, z is 0. ltoreq. z.ltoreq.3, and w is 3. ltoreq. w.ltoreq.13;
l i of the crystalline titaniumxMyPzSwCan be selected from L i in crystalline state3PS4L i in crystalline form4SnS4L i in crystalline form4GeS4L i in crystalline form10SnP2S12L i in crystalline form10GeP2S12And L i in the crystalline state10SiP2S12L i in the glassy state2S-P2S5Selected from the group consisting of 70L i in glassy state2S-30P2S5Glassy 75L i2S-25P2S5And 80L i in glassy state2S-20P2S5L i in the glass-ceramic state2S-P2S570L i selected from the glass-ceramic state2S-30P2S575L i in the glass-ceramic state2S-25P2S5And 80L i in the form of a glass-ceramic2S-20P2S5At least one of (1).
According to the present disclosure, the cathode material is not particularly limited, and may be a cathode material of a kind conventional in the art, preferably selected from L ico2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、LiFepMnqX1-p-qO4、Li1＋sL1－p－qMpNqO2And L iYSrAt least one of;
wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, p + q is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0.1 and less than or equal to 0.2;
x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, L and M, N are at least one of L I, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B respectively and Y is at least one of Ti, Fe, Ni, Cu and Mo.
In order to further improve the stability of the positive electrode sheet, the positive electrode sheet may further include a positive electrode conductive agent and a first binder, and the content of the positive electrode conductive agent and the first binder may vary widely, and preferably, the content of the positive electrode conductive agent may be 0.1 to 20 parts by weight and the content of the first binder may be 0.01 to 10 parts by weight with respect to 100 parts by weight of the positive electrode active material.
The positive electrode conductive agent and the first binder are well known to those skilled in the art, may be of conventional kinds, and the present invention does not particularly require, and the positive electrode conductive agent is preferably at least one of acetylene black, carbon nanotubes, carbon fibers, and carbon black; the first binder is preferably at least one of polyvinylidene fluoride, polytetrafluoroethylene, and styrene-butadiene rubber.
According to the present disclosure, in order to improve stability and electrical properties of the solid electrolyte layer, the solid electrolyte layer may further include a second binder, which may be used in an amount conventional in the art, and preferably, may be contained in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid electrolyte.
The second binder may be a binder of a kind conventional in the art, and is preferably at least one selected from the group consisting of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethylcellulose, and styrene butadiene latex.
According to the present disclosure, the negative electrode sheet includes a negative electrode current collector and a negative electrode material layer located on a surface of the negative electrode current collector, the negative electrode material layer is lithium or a lithium alloy, or the negative electrode material layer includes a negative electrode active material and a third binder;
in another embodiment of the present disclosure, the negative electrode material layer may be a layer including a negative electrode active material, a third binder, wherein the relative content of the negative electrode active material and the third binder may vary widely, and preferably, the content of the third binder may be 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material.
According to the present disclosure, the negative electrode active material may be a conventional type used in lithium ion batteries, which is well known to those skilled in the art, and is preferably at least one selected from a carbon material, a tin alloy, a silicon alloy, silicon, tin and germanium, and as a common general knowledge of those skilled in the art, when the negative electrode active material is a silicon type material, the negative electrode material layer further contains a negative electrode conductive agent, the function and specific type of which are well known to those skilled in the art, and thus, the description thereof is omitted.
The third binder may be any of various negative binders known to those skilled in the art, and is preferably at least one of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethylcellulose, and styrene butadiene latex.
The present disclosure also provides a method of manufacturing an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, the method including the steps of:
(1) adding titanium tetrafluoride and lithium salt into solvent, stirring to dissolve, adding anode material, stirring, evaporating solvent to obtain reaction precursor, sintering the reaction precursor to obtain anode material with fluorine-containing lithium titanate layer coated on the surface (F-L i)4Ti5O12Layer) of a positive electrode active material;
(2) and sequentially pressing a solid electrolyte layer containing a solid electrolyte and a negative plate on the positive plate containing the positive active material to obtain the all-solid-state lithium battery.
The preparation method disclosed by the invention can be used for uniformly modifying the surface of the anode material to obtain the anode active substance with the surface coated with the fluorine-containing lithium titanate layer with controllable thickness, and when the anode active substance is used for the all-solid-state lithium battery, the anode material and the solid-state electrolyte can be prevented from generating interface reaction or element diffusion, so that the interface impedance is reduced.
In addition to the preparation method disclosed herein, the positive electrode active material having a surface coated with a fluorine-containing lithium titanate layer may be prepared by a chemical vapor deposition method, a chemical vapor transport method, or a vacuum laser sputtering method, but the above method is very expensive. When the preparation method disclosed by the disclosure is adopted, the fluorine-containing lithium titanate layer with uniform coating and controllable thickness can be obtained, and meanwhile, the used raw materials are simple and have a remarkable cost advantage.
According to the present disclosure, the lithium salt may be L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
According to the present disclosure, the solvent is at least one of water, methanol, ethanol, lithium citrate, and lithium amide.
According to the present disclosure, in order to further improve the interfacial performance between the positive electrode material and the solid electrolyte, the electrolyte layer is at least one of a NASICON-type solid electrolyte, a perovskite-type solid electrolyte, and a sulfur-based solid electrolyte.
Wherein the NASICON type solid electrolyte is L iM2(PO4)3And at least one of the dopants thereof, wherein M is Ti, Zr, Ge, Sn or Pb, and the dopant adopts at least one doping element selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V.
The chemical formula of the titanium-calcium open type solid electrolyte is AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3Wherein x +3Y =2, h +2k +5n +4w =6, 0 < x < 2, 0 < Y < 2/3, h, k, n, w are all more than 0, A is at least one of L i and Na elements, B is at least one of L a, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd elements, M is at least one of Sr, Ca, Ba, Ir, Pt elements, and D is at least one of Nb and Ta elements.
The sulfur-based solid electrolyte may be a sulfur-containing solid electrolyte well known to those skilled in the art, preferably L i in a crystalline statexMyPzSwL i in glassy state2S-P2S5L i in the form of glass-ceramic2S-P2S5Wherein M is at least one of Si, Ge and Sn, x +4y +5z =2w, x is 2. ltoreq. x.ltoreq.11, y is 0. ltoreq. y.ltoreq.1.5, z is 0. ltoreq. z.ltoreq.3, w is 3. ltoreq. w.ltoreq.13, wherein L i is in the crystalline statexMyPzSwL i selected from crystalline state3PS4L i in crystalline form4SnS4L i in crystalline form4GeS4L i in crystalline form10SnP2S12L i in crystalline form10GeP2S12L i in crystalline form10SiP2S12L i in the glassy state2S-P2S5Selected from the group consisting of 70L i in glassy state2S-30P2S5Glassy 75L i2S-25P2S5Glassy state 80L i2S-20P2S5L i in the glass-ceramic state2S-P2S570L i selected from the glass-ceramic state2S-30P2S575L i in the glass-ceramic state2S-25P2S580L i in the form of a glass-ceramic2S-20P2S5At least one of (1).
The positive electrode material is not particularly limited, and may be a positive electrode material of a type conventional in the art, and preferably, the positive electrode material is selected from L iCoO2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x- yAlyO2、LiFepMnqX1-p-qO4、Li1＋sL1－p－qMpNqO2And L iYSrWherein X is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, S is more than or equal to 0.1 and less than or equal to 0.2, r is more than or equal to 1 and less than or equal to 2.5, X is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, L and M, N are at least one of L I, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, and Y is at least one of Ti, Fe, Ni, Cu and Mo.
According to the present disclosure, in step (1), the reaction conditions of the cathode material and the titanium tetrafluoride may be varied within a wide range as long as it is satisfied that the titanium tetrafluoride and the lithium salt on the surface of the cathode material may be reacted. Preferred reaction conditions include: the solvent evaporation temperature is 20-100 ℃, and the sintering temperature is 400-1000 ℃; more preferably, it comprises: the evaporation temperature is 70-90 ℃, and the sintering temperature is 650-850 ℃.
In experiments, the inventors of the present disclosure found that when the conditions of the contact reaction of the cathode material with the lithium salt and titanium tetrafluoride are controlled to be within the above range, the cathode material after being treated with the fluorine-containing lithium titanate has a more excellent interface effect with the solid electrolyte.
The relative amounts of the cathode material and the lithium salt and titanium tetrafluoride can be varied in a wide range, and in order to further improve the reaction efficiency, the molar ratio of the cathode material, titanium tetrafluoride and lithium salt (calculated by lithium element) can be preferably 1: (0.01-100): (0.01-100).
According to the present disclosure, the method for preparing the positive electrode sheet may further include: uniformly mixing the positive active material, the positive conductive agent and the first binder in a solvent, coating the mixture on the surface of a positive current collector, and drying and tabletting the mixture to obtain the positive plate containing the positive active material layer;
the relative amounts of the positive electrode active material, the positive electrode conductive agent and the first binder may vary widely, and preferably, the positive electrode conductive agent may be used in an amount of 0.1 to 20 parts by weight and the first binder may be used in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the positive electrode active material; within the preferable dosage range, the positive plate prepared by the method has more stable structure and better electrical property.
Wherein, the positive electrode conductive agent and the first binder may be of a kind conventional in the art, and preferably, the positive electrode conductive agent may be at least one of acetylene black, carbon nanotubes, carbon fibers, and carbon black; the first binder may be at least one of polyvinylidene fluoride, polytetrafluoroethylene, and styrene butadiene rubber.
According to the present disclosure, the method of preparing the solid electrolyte layer may further include: uniformly mixing the solid electrolyte and a second binder in a solvent, coating the mixture on the surface of the positive plate, and drying and tabletting the mixture to obtain the positive plate containing the solid electrolyte layer;
the relative amounts of the above solid electrolyte and second binder may vary widely, and preferably, the second binder may be used in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid electrolyte; within the above preferred range of the amount, the solid electrolyte layer prepared by the above method is superior in charge and discharge performance.
Wherein the second binder may be of a kind conventional in the art, and preferably, the second binder may be at least one selected from the group consisting of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethyl cellulose, and styrene butadiene latex.
According to the present disclosure, the lithium-ion battery comprises a negative electrode current collector and a negative electrode material layer located on the surface of the negative electrode current collector, wherein the negative electrode material layer is lithium or a lithium alloy, or comprises a negative electrode active material and a third binder;
when the negative electrode material layer includes a negative electrode active material and a third binder, the method for preparing the negative electrode sheet may further include: and uniformly mixing the negative electrode active material and the third binder in a solvent, coating the mixture on the surface of a negative electrode current collector, and drying and tabletting to obtain the negative electrode sheet.
The relative amounts of the negative electrode active material and the third binder may vary widely, and preferably, the third binder is used in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material.
Wherein the negative electrode active material and the third binder may be of a kind conventional in the art, and preferably, the negative electrode active material may be at least one selected from the group consisting of a carbon material, a tin alloy, a silicon alloy, silicon, tin, and germanium; the third binder may be at least one of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, and styrene butadiene latex. As a common knowledge of those skilled in the art, when the negative active material is a silicon-based material, the negative material layer further contains a negative conductive agent, and the function, specific type and content thereof are well known to those skilled in the art and will not be described herein again.
The disclosure also provides an all-solid-state lithium battery prepared by the method.
The present disclosure is further described below by way of examples, but the present disclosure is not limited thereto in any way.
Example 1
(1) Containing F-L i4Ti5O12Preparation of positive electrode active material of layer
100 g (g) of the positive electrode active material L iCoO212g of TiF4Uniformly mixing with 2g of anhydrous L iOH, adding into 500 m L of ethanol, stirring for 2 h, evaporating to dryness at 70 ℃, fully grinding the obtained precursor, and sintering at 700 ℃ to obtain a final product F-L i4Ti5O12L iCoO coated with material2And (3) a positive electrode material.
(2) Preparation of Positive electrode sheet C
930g of a catalyst containing a catalyst carrier F-L i4Ti5O12L iCoO coated with material2The positive electrode material (93%), 30g of binder PVDF (3%), 20 g of acetylene black (2%) and 20 g of conductive agent carbon fiber (2%) were added to 1500 g of solvent NMP (N-methylpyrrolidone), and then stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly coated intermittently on both sides of an aluminum foil (aluminum foil size: width 160 mm, thickness 16 μm), and then dried at 393K, and pressed into sheets by a roll press to obtain C.
(3) Preparation of Positive electrode sheet CE containing solid electrolyte layer
In a glove box, 600 g of 70L i in a glass state2S-30P2S5And 1200 g of a toluene solution containing 30g of a butadiene rubber binder, followed by heating and stirring to a stable and uniform solution, the solution was continuously coated on the positive electrode sheet C obtained in step 2, and then dried at 333K, and cut into a 485 mm (length) × 46 mm (width) positive electrode sheet CE containing a solid electrolyte layer.
(4) Preparation of negative electrode A
940 g of negative active material artificial graphite (94%), 30g of binder CMC (3%) and 30g of binder SBR (3%) were added to 1200 g of deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative slurry, which was uniformly coated intermittently on both sides of a copper foil (copper foil size: 160 mm in width, 16 μm in thickness), dried at 393K, and cut into negative electrode sheets A of 480 mm (length) × 45 mm (width) after being pressed into sheets by a roll press.
(5) Preparation of all-solid-state lithium battery CEA
And (3) in a glove box, cutting the CE obtained in the step (3) and the A obtained in the step (4), aligning, placing in a hot press, performing 423K hot pressing for 1 h, vacuumizing and sealing by using an aluminum plastic film, and taking out a sample. The above-described pressed sample was pressed in an isostatic press at 200 MPa for 300 seconds to obtain the all-solid-state lithium battery CEA1 of the present example.
Example 2
The electrolyte and lithium ion battery of this example were prepared using the method of example 1, except that: in the step (1), TiF is added4The amount of the anhydrous L iOH was changed to 6 g and 1 g, and the other steps and operations were the same, to obtain the all-solid lithium battery CEA2 of this example.
Example 3
The electrolyte and lithium ion battery of this example were prepared by the method of example 1, except that L iFePO was used as the positive electrode material in step (1)4Replacement L iCoO2. The whole solid of the present example was obtainedThe lithium battery CEA 3.
Example 4
The electrolyte and lithium ion battery of this example were prepared using the method of example 1, except that: in the step (1), the obtained precursor is sintered at a high temperature of 900 ℃, and other steps and operations are the same. The all-solid-state lithium battery CEA4 of this example was obtained.
Comparative example 1
The electrolyte and lithium ion battery of this example were prepared using the method of example 1, except that: in the step (1), 285ml of tetrabutyl titanate is used for replacing 12gTiF4。
Comparative example 2
An electrolyte and a lithium ion battery of this example were manufactured by the method of example 1, except that L iCoO was used in step (1)2The material was directly subjected to the preparation of positive electrode C, CE, negative electrode A and CEA, but not to L iCoO2Carrying out F-L i4Ti5O12The coating operation of (1).
Test example 1
SEM test and XPS test were performed on the positive electrode active material containing the fluorinated modification layer obtained in examples 1 to 4 and the positive electrode active material obtained in comparative examples 1 to 2, respectively, and the atomic ratio of F/O on the surface of the positive electrode active material, the particle diameter, and the thickness data of the fluorinated modification layer are shown in table 1;
subjecting the positive electrode active material to Ar+After ion etching, the surface F/O atomic ratio was measured, where Ar+The step size of the ion etching is 2 min, and the energy of the used ion beam is 2 keV.
TABLE 1
Test example 2
The all-solid-state lithium batteries CEA1-CEA5 obtained in examples 1-3 and comparative examples 1-2 were subjected to a cycle life test of a battery cell, as follows:
the method comprises the steps of taking 20 batteries prepared in each example AND each comparative example, carrying out charge-discharge cycle test on the batteries at 0.1C on an L AND CT 2001C secondary battery performance detection device under the condition of 298 +/-1K, standing for 10min, charging at constant voltage until 4.2V/0.05C is cut off, standing for 10min, discharging at constant current until 3.0V is obtained, namely 1 cycle, repeating the step, when the battery capacity is lower than 80% of the first discharge capacity in the cycle process, ending the cycle, namely the cycle life of the batteries, AND averaging each group.
TABLE 2
From tables 1-2, the data for examples 1-4 compared to comparative examples 1-2 show that: the all-solid-state lithium battery provided by the disclosure has excellent cycle performance, and the cathode material is subjected to surface treatment to form the cathode active material containing the uniformly covered fluorine-containing lithium titanate layer.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (18)
1. The all-solid-state lithium battery comprises a positive plate, a negative plate and a solid electrolyte layer, and is characterized in that the positive plate comprises a positive active substance, and the positive active substance comprises positive material particles and a fluorine-containing lithium titanate layer coated on the surfaces of the positive material particles.
2. The all-solid-state lithium battery according to claim 1, wherein the fluorine-containing lithium titanate layer is a coating layer of fluorine-doped lithium titanate formed on the surface of the positive electrode material particles after being treated with titanium tetrafluoride and a lithium salt.
3. The all-solid-state lithium battery according to claim 1, wherein a molar ratio of fluorine atoms in the fluorine-containing lithium titanate to titanium atoms in the lithium titanate is 0.01 to 2.4: 1.
4. the all-solid lithium battery according to claim 1, wherein the particle diameter of the positive electrode active material is 0.05 to 1000 μm; the thickness of the fluorine-containing lithium titanate layer is 10-2000 nm.
5. The all solid-state lithium battery according to claim 2, wherein the lithium salt is L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
6. The all solid-state lithium battery according to claim 1, wherein the F/O atomic ratio of the lithium fluorotitanate-containing layer is 0.01 to 100.
7. The all solid-state lithium battery according to claim 1, wherein the solid electrolyte layer is at least one of a sodium fast ion conductor structure type solid electrolyte, a perovskite type solid electrolyte, and a sulfur type solid electrolyte.
8. The all solid-state lithium battery according to claim 7, wherein the sodium fast ion conductor structure type solid electrolyte is L iM2(PO4)3And their blendsAt least one of impurities, wherein M is at least one of Ti, Zr, Ge, Sn or Pb, L iM2(PO4)3The doping element adopted by the dopant of (1) is at least one of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V;
the perovskite type solid electrolyte is AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3Wherein x +3Y =2, h +2k +5n +4w =6, 0 < x < 2, 0 < Y < 2/3, h, k, n, w are all more than 0, a is at least one of L i and Na elements, B is at least one of L a, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd elements, M is at least one of Sr, Ca, Ba, Ir, Pt elements, D is at least one of Nb, Ta elements;
the sulfur-based solid electrolyte is L i in a crystalline statexMyPzSwL i in glassy state2S-P2S5L i in the form of glass-ceramic2S-P2S5Wherein M is at least one of Si, Ge and Sn, x +4y +5z =2w, x is 2. ltoreq. x.ltoreq.11, y is 0. ltoreq. y.ltoreq.1.5, z is 0. ltoreq. z.ltoreq.3, and w is 3. ltoreq. w.ltoreq.13;
l i of the crystalline statexMyPzSwL i selected from crystalline state3PS4L i in crystalline form4SnS4L i in crystalline form4GeS4L i in crystalline form10SnP2S12L i in crystalline form10GeP2S12And L i in the crystalline state10SiP2S12L i in the glassy state2S-P2S5Selected from the group consisting of 70L i in glassy state2S-30P2S5Glassy 75L i2S-25P2S5And 80L i in glassy state2S-20P2S5L i in the glass-ceramic state2S-P2S570L i selected from the glass-ceramic state2S-30P2S575L i in the glass-ceramic state2S-25P2S5And 80L i in the form of a glass-ceramic2S-20P2S5At least one of (1).
9. The all solid-state lithium battery according to claim 1, wherein the positive electrode material is selected from L iCoO2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、LiFepMnqX1-p-qO4、Li1＋ sL1－p－qMpNqO2And L iYSrAt least one of;
wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, p + q is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0.1 and less than or equal to 0.2;
x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, L and M, N are at least one of L I, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B respectively and Y is at least one of Ti, Fe, Ni, Cu and Mo.
10. The all-solid lithium battery according to claim 1, wherein the positive electrode sheet further comprises a positive electrode conductive agent and a first binder, the positive electrode conductive agent is contained in an amount of 0.1 to 20 parts by weight and the first binder is contained in an amount of 0.01 to 10 parts by weight, relative to 100 parts by weight of the positive electrode active material;
the positive conductive agent is at least one of acetylene black, carbon nano tubes, carbon fibers and carbon black; the first binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene and styrene butadiene rubber.
11. The all-solid lithium battery according to claim 1, wherein the solid electrolyte layer further comprises a second binder, the content of the second binder being 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid electrolyte;
the second binder is at least one selected from polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethyl cellulose and styrene-butadiene latex.
12. The all-solid-state lithium battery according to claim 1, wherein the negative electrode sheet comprises a negative electrode current collector and a negative electrode material layer on the surface of the negative electrode current collector, the negative electrode material layer is lithium or a lithium alloy, or the negative electrode material layer comprises a negative electrode active material and a third binder.
13. The all solid-state lithium battery according to claim 12, wherein a content of the third binder is 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material;
the negative electrode active material is at least one selected from carbon materials, tin alloys, silicon, tin and germanium; the third binder is at least one selected from polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose and styrene butadiene latex.
14. A method of producing an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, characterized by comprising the steps of:
(1) adding titanium tetrafluoride and lithium salt into a solvent, stirring until the titanium tetrafluoride and the lithium salt are dissolved, adding a positive electrode material, fully stirring, and evaporating the solvent to obtain a reaction precursor; sintering the reaction precursor to obtain a positive active material with a fluorine-containing lithium titanate layer coated on the surface of a positive material;
(2) and sequentially pressing a solid electrolyte layer containing a solid electrolyte and a negative plate on the positive plate containing the positive active material to obtain the all-solid-state lithium battery.
15. The method of claim 14, wherein the lithium salt is L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
16. The method according to claim 14, wherein in the step (1), the reaction conditions of the reaction of the cathode material with the titanium tetrafluoride and the lithium salt include: the evaporation temperature is 20-100 ℃, the sintering temperature is 400-1000 ℃, and the molar ratio of the anode material, the titanium tetrafluoride and the lithium salt in terms of lithium element is 1: (0.01-100): (0.01-100).
17. The method of claim 14, wherein the solid electrolyte layer is at least one of a sodium fast ion conductor structure type solid electrolyte, a perovskite type solid electrolyte, and a sulfur based solid electrolyte.
18. An all solid-state lithium battery prepared by the method of any one of claims 14 to 17.
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| CN109346697B (en) * | 2018-10-12 | 2020-11-20 | 桑顿新能源科技有限公司 | Positive electrode active material, preparation method thereof and all-solid-state lithium battery |
| CN111129423B (en) * | 2018-10-30 | 2021-08-06 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN111370751B (en) * | 2018-12-25 | 2021-12-07 | 深圳市比亚迪锂电池有限公司 | Solid-state battery, preparation method thereof and electric automobile |
| CN109768215B (en) * | 2018-12-27 | 2022-02-18 | 杭州阳名新能源设备科技有限公司 | Method for processing low-impedance interface of anode of solid-state lithium battery and anode structure |
| CN110600794B (en) * | 2019-09-03 | 2021-12-10 | 南方科技大学 | Solid-state lithium battery and preparation method thereof |
| CN110518283A (en) * | 2019-09-12 | 2019-11-29 | 深圳先进技术研究院 | Solid state secondary battery and its preparation process, electric car |
| CN111403703A (en) * | 2020-03-18 | 2020-07-10 | 武汉理工大学 | Method for double coating of ternary positive electrode material by fluoride and sulfide |
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| CN111682200B (en) * | 2020-07-14 | 2021-10-22 | 万华化学集团股份有限公司 | Positive electrode material for lithium ion battery and preparation method thereof |
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