CN109921091B - Composite material for lithium ion battery, preparation method of composite material and lithium ion battery containing composite material - Google Patents
Composite material for lithium ion battery, preparation method of composite material and lithium ion battery containing composite material Download PDFInfo
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Abstract
The invention provides a composite material for a lithium ion battery, a preparation method thereof and the lithium ion battery containing the composite material. The invention also provides a preparation method of the composite material and a lithium ion battery containing the composite material, and belongs to the technical field of lithium ion batteries.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite material for a lithium ion battery, a preparation method of the composite material and the lithium ion battery containing the composite material.
Background
With the wide application of lithium ion batteries in the fields of power supplies, digital products and the like, consumers have higher and higher requirements on the safety performance and energy density of the lithium ion batteries. The liquid lithium ion battery may have safety problems such as electrolyte leakage, ignition, explosion and the like in the use process, and meanwhile, the energy density of the conventional liquid lithium ion battery is more and more close to the theoretical limit, and the technical bottleneck is increasingly prominent. Solid-state batteries have better safety and higher energy density, and are a trend in the development of lithium ion batteries.
The current mainstream route of solid electrolyte is to adopt organic-inorganic composite polymer electrolyte and sulfide electrolyte, how to realize stable and rapid conduction of lithium ions in the positive electrode and the negative electrode of the solid battery and in the solid electrolyte phase, improve the material properties of the positive electrode, the negative electrode and the electrolyte, and improve the overall performance of the solid battery, and is the research focus of the solid battery.
In order to improve the performance of the all-solid-state battery, the Chinese patent with the application number of CN201610649224.4 discloses a method for preparing a copper bismuth sulfur film, which comprises the steps of plating metal bismuth on a substrate, then performing vacuum evaporation on a CuS film, and then treating a plating layer on the substrate to prepare the copper bismuth sulfur film. Chinese patent application No. CN201810329907.0 discloses a negative electrode material for an all-solid-state lithium-ion secondary battery, a negative electrode including the same, and an all-solid-state lithium-ion secondary battery having the negative electrode, wherein the negative electrode material contains a negative electrode active material, a solid electrolyte, and a conductive material, the negative electrode active material contains at least one selected from a metal capable of forming an alloy with Li and an oxide of the metal, the solid electrolyte is a sulfide solid electrolyte, the conductive material is a conductive carbon material, but the negative electrode active material further contains a simple substance of silicon, and there is a problem that the negative electrode is easily expanded and dropped during charging and discharging of the lithium-ion battery. At present, most sulfide electrolytes exist in the form of powder particles in solid-state battery application, and the performance of the anode, the cathode and the electrolyte material needs to be continuously and comprehensively optimized so as to meet the requirements of industrial production and application.
Disclosure of Invention
The invention aims to provide a composite material for a lithium ion battery, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte coated nano attapulgite has a rod-shaped structure at a nano level, can form a continuous sulfide electrolyte lithium-conducting structure and has good lithium ion transmission performance.
The second purpose of the invention is to provide a preparation method of the composite material for the lithium ion battery, which can improve the performance of the sulfide electrolyte coated nano attapulgite composite material and improve the lithium ion transmission performance and stability of the composite material within a certain range by controlling the parameters of the ball milling and firing process and selecting the coating material and controlling the thickness and the type of the coating material.
The third purpose of the invention is to provide a lithium ion battery, which contains the sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte coated nano attapulgite composite material can effectively improve the performance of the lithium ion battery when being used in the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite material for the lithium ion battery comprises a sulfide electrolyte and nano attapulgite, wherein the sulfide electrolyte coats the nano attapulgite.
Furthermore, the thickness of the sulfide electrolyte coating layer is less than or equal to 20um, the crystal length of the nano attapulgite rod is 100nm-50um, and the width of the nano attapulgite rod is 10nm-120 nm.
Further, the sulfide electrolyte is one or more of the following substances in combination: aLi2S·b P2S5cLiX, wherein X represents a halogen element, a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bP2S5cMES, wherein Me is Si, Ge, Sn, Al or B, a is more than or equal to 20 and less than or equal to 80, B is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bP2S5·cP2O5Wherein a is more than 67 and less than 80, b is more than 0 and less than 40, and c is more than 0 and less than 25; li4-aSi1-aPaS4Wherein a is more than 0 and less than 1; 70Li2S·(30−a)P2S5·aP2S3Wherein a is more than 0 and less than 30; aLi2S·bSiS2Wherein a is more than or equal to 50 and less than or equal to 70, and b is more than or equal to 30 and less than or equal to 50; li4-aSi1-aAlaS4Wherein a is more than 0 and less than 1; aLi2S·bSiS2·cLi3MO3Wherein M = B, Al, Ga or In, 20 ≤ a ≤ 80, and,20≤b≤40、0≤c≤20；aLi2S·bSiS2·cLi3N, wherein a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bGeS2Wherein a is more than 0 and less than 60, and b is more than 40 and less than 100; 0.5Li2S·0.5[(1-a)GeS2·aGeO2]Wherein a is more than 0 and less than 1; li4+a (Ge1-aGab)S4Wherein a is more than 0 and less than 1, and b is more than 1 and less than 2; liaGebPcS4Wherein a is more than or equal to 3 and less than or equal to 3.3, b is more than or equal to 0 and less than or equal to 0.3, and c is more than or equal to 0.7 and less than or equal to 1.0; a (0.6 Li)2S·0.4SiS2)·bLi4SiO4Wherein a is more than or equal to 80 and less than or equal to 100, and b is more than or equal to 0 and less than or equal to 20; liaGebSecPdSeWherein a is more than 3 and less than 4, b is more than 0 and less than 1, c is more than 0 and less than 2, d is more than 0 and less than 1, and e is more than 2 and less than 4; liaGebAscS4Wherein a is more than or equal to 3 and less than or equal to 3.5, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.5; liaZnbGeS4Wherein a is more than 0 and less than 2, and b is more than 0 and less than 2; aLi2S·bP2S5·cGeS2·dSnSe2Wherein a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, c is more than or equal to 0 and less than or equal to 10, and d is more than or equal to 0 and less than or equal to 10.
A preparation method of the composite material comprises the following steps:
the method comprises the following steps: in the molar ratio, 40-100 parts of Li are weighed in an argon environment2Dissolving S in absolute ethyl alcohol, adding 1.50-80.00 parts of nano attapulgite, fully soaking, vacuumizing in an argon environment or at normal temperature, heating to 50-90 ℃, and removing the solvent absolute ethyl alcohol to obtain the nano attapulgite composite material coated with lithium sulfide;
step two: according to the molar parts, under the argon atmosphere, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 0-30 parts of P2S50 to 30 parts of SiS20 to 30 parts of GeS20 to 30 parts of B2S30 to 30 parts of SnS and 0 to 30 parts of Al2S30 to 30 parts of P2S30 to 30 parts of Ga2S30 to 30 parts of ZnS and 0 to 30 parts of As2S50 to 10 parts of P2O50 to 10 parts of Li4SiO40 to 10 parts of Li3N, 0-10 parts of Li3MO30 to 10 parts of GeO20 to 10 parts of GeSe2And 0-10 parts of LiX, fully mixing and grinding into powder to obtain a system A, adding the system A into a quartz tube, sealing In vacuum, and heating at 200-600 ℃ for 2-6 hours to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, M is B, Al, Ga or In, and X is one of halogen elements.
The lithium ion battery comprises the composite material, and at least one of a positive electrode, an electrolyte and a negative electrode of the lithium ion battery comprises the composite material.
Further, the negative electrode comprises a negative electrode current collector, the surface of the negative electrode current collector is coated with a composite active substance, the composite active substance contains the composite material, and the surface of the composite active substance is plated with an active lithium storage material coating I.
Further, the surface of the negative current collector is plated with an active lithium storage material coating II, and the active lithium storage material coating II is positioned between the negative current collector and the composite active material.
Furthermore, the thickness of the active lithium storage material coating I and the thickness of the active lithium storage material coating II are both 10 nm-100 nm, and the thickness of the composite active substance is 1-5 um.
Furthermore, the active lithium storage materials in the active lithium storage material coating I and the active lithium storage material coating II are one or a combination of more of bismuth, lithium, silicon, tin, antimony, germanium, aluminum, lead, titanium, iron, chromium, molybdenum, nickel, gold and zinc.
Further, the composite active material further includes a binder and a negative electrode active material.
The invention has the beneficial effects that:
the method is different from the traditional lithium-conducting material, and adopts a method of sintering after ball milling and mixing to prepare the lithium-conducting sulfide electrolyte material coated nano attapulgite solid electrolyte. The nano rod-shaped attapulgite structure coated with the lithium-conducting sulfide electrolyte material is formed under certain reaction conditions, the lithium-conducting material on the surface of the structure has a good lithium-conducting function, and the lithium-conducting material on the surface of the rod-shaped structure has a continuous lithium-conducting structure.
The natural attapulgite is a crystalline hydrated magnesium aluminum silicate mineral, has a unique layer chain structure characteristic, has lattice displacement in the structure, and has a needle-shaped, fibrous or fiber aggregation state. The natural attapulgite crystal is rod-shaped, has a rod crystal length of 1-5um and a width of 20-70nm, is a natural nano-structure rod-shaped structure mineral material, has stable performance, and is a good load material.
The nanometer attapulgite is organically modified or lithium cation exchanged natural nanometer attapulgite, and sulfide electrolyte is coated on the surface of the nanometer attapulgite to form a layer of high-speed lithium ion channel on the surface of the nanometer attapulgite. The nanometer attapulgite structure coated by the sulfide electrolyte has a rod-shaped nanometer structure, and particularly in the composite solid lithium ion electrolyte, the solid lithium ion anode and the lithium ion cathode, the nanometer attapulgite structure coated by the sulfide electrolyte forms effective accumulation in the nanometer attapulgite structure, so that the lithium ion transmission in the composite solid lithium ion electrolyte, the solid lithium ion anode and the lithium ion cathode can be improved, the mechanical property of the composite material can be improved, and the composite material has industrial application value.
Meanwhile, the thickness of the coating layer and the type of the coating layer material can be controlled through a ball milling and firing process, the coating material and the like, the performance of the sulfide electrolyte coated nano attapulgite material can be improved within a certain range, and the lithium ion transmission performance and the stability of the material can be improved. According to the invention, the nanometer attapulgite composite material is coated by the sulfide electrolyte, and the nanometer attapulgite is used as a carrier in the pole piece of the lithium ion battery to form a rod-shaped continuous and rapid lithium conducting channel, so that the transmission of lithium ions in the pole piece can be effectively improved, and the lithium ion battery has good application potential particularly in the anode of a solid lithium ion battery with high quality and energy density and the cathode of a lithium ion battery with high energy density.
Drawings
Fig. 1 is a schematic view of a composite anode structure.
Fig. 2 is a schematic view of a composite structure.
In the figure: 1. the cathode current collector 2, active lithium storage material coatings II and 3, composite active substances 4, composite materials 5, active lithium storage material coatings I and 41, sulfide electrolyte 42 and nano attapulgite.
Detailed Description
The present invention is further illustrated by the following embodiments according to fig. 1 and 2, wherein the steps of preparing the positive electrode sheet, the negative electrode sheet and the electrolyte involve "drying" and "pressing" which are conventional experimental means in the art.
Detailed description of the invention
The composite material for the lithium ion battery comprises a sulfide electrolyte 41 and nano attapulgite 42, wherein the sulfide electrolyte 41 coats the nano attapulgite 42.
Further, the thickness of the sulfide electrolyte 41 is less than or equal to 20um, and the lithium ion conductivity of the sulfide electrolyte 41 is 10-5S/cm to 10-2 S/cm; the nano attapulgite 42 is commercialized nano attapulgite, and the rod crystal length of the nano attapulgite 42 is 100nm-50um, and the width is 10nm-120 nm.
Further, the sulfide electrolyte 41 is one or a combination of more of the following substances: aLi2S·b P2S5cLiX, wherein X represents a halogen element, a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bP2S5cMES, wherein Me is Si, Ge, Sn, Al or B, a is more than or equal to 20 and less than or equal to 80, B is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bP2S5·cP2O5Wherein a is more than 67 and less than 80, b is more than 0 and less than 40, and c is more than 0 and less than 25; li4-aSi1-aPaS4Wherein a is more than 0 and less than 1; 70Li2S·(30−a)P2S5·aP2S3Wherein a is more than 0 and less than 30; aLi2S·bSiS2Wherein a is more than or equal to 50 and less than or equal to 70, and b is more than or equal to 30 and less than or equal to 50; li4-aSi1-aAlaS4Wherein a is more than 0 and less than 1; aLi2S·bSiS2·cLi3MO3Wherein M = B, Al,Ga or In, 20-80 of a, 20-40 of b and 0-20 of c; aLi2S·bSiS2·cLi3N, wherein a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bGeS2Wherein a is more than 0 and less than 60, and b is more than 40 and less than 100; 0.5Li2S·0.5[(1-a)GeS2·aGeO2]Wherein a is more than 0 and less than 1; li4+a (Ge1-aGab)S4Wherein a is more than 0 and less than 1, and b is more than 1 and less than 2; liaGebPcS4Wherein a is more than or equal to 3 and less than or equal to 3.3, b is more than or equal to 0 and less than or equal to 0.3, and c is more than or equal to 0.7 and less than or equal to 1.0; a (0.6 Li)2S·0.4SiS2)·bLi4SiO4Wherein a is more than or equal to 80 and less than or equal to 100, and b is more than or equal to 0 and less than or equal to 20; liaGebSecPdSeWherein a is more than 3 and less than 4, b is more than 0 and less than 1, c is more than 0 and less than 2, d is more than 0 and less than 1, and e is more than 2 and less than 4; liaGebAscS4Wherein a is more than or equal to 3 and less than or equal to 3.5, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.5; liaZnbGeS4Wherein a is more than 0 and less than 2, and b is more than 0 and less than 2; aLi2S·bP2S5·cGeS2·dSnSe2Wherein a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, c is more than or equal to 0 and less than or equal to 10, and d is more than or equal to 0 and less than or equal to 10.
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: in the molar ratio, 40-100 parts of Li are weighed in an argon environment2Dissolving S in absolute ethyl alcohol, adding 1.50-80.00 parts of nano attapulgite, fully soaking, vacuumizing in an argon environment or at normal temperature, heating to 50-90 ℃, and removing the solvent absolute ethyl alcohol to obtain the lithium sulfide coated nano attapulgite composite material;
step two: according to the molar parts, under the argon atmosphere, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 0-30 parts of P2S5、0~36 portions ofSiS of20 to 30 parts of GeS20 to 30 parts of B2S30 to 30 parts of SnS and 0 to 30 parts of Al2S30 to 30 parts of P2S30 to 30 parts of Ga2S30 to 30 parts of ZnS and 0 to 30 parts of As2S50 to 10 parts of P2O5、0~10Li4SiO40 to 10 parts of Li3N, 0-10 parts of Li3MO3(M is B, Al, Ga or In) 0-10 parts of GeO20 to 10 parts of GeSe2And 0-10 parts of LiX (X is one of halogen elements), putting the LiX and zirconia balls into a pot made of zirconia, sealing the pot in an argon environment, installing the pot on a ball mill, rotating at the speed of 200-800 r/min, mixing for 10-50 h to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating at the temperature of 200-600 ℃ after vacuum sealing for 2-6 h to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material.
A lithium ion battery containing the composite material comprises the composite material in at least one of a positive electrode, an electrolyte and a negative electrode of the lithium ion battery.
Further, the negative pole includes negative pole mass flow body 1, 1 surface coating of negative pole mass flow body has compound active material 3, contain in the compound active material 3 composite material 4, one deck active lithium storage material cladding I5 has been plated on the surface of compound active material 3.
Further, a layer of active lithium storage material coating II 2 is plated on the surface of the negative current collector 1, and the active lithium storage material coating II 2 is located between the negative current collector 1 and the composite active material 3.
Further, the thickness of active lithium storage material cladding I5 and active lithium storage material cladding II 2 is 10~100nm, the thickness of compound active substance 3 is 1~5 um.
Furthermore, the active lithium storage materials in the active lithium storage material coating I5 and the active lithium storage material coating II 2 are one or a combination of more of bismuth, lithium, silicon, tin, antimony, germanium, aluminum, lead, titanium, iron, chromium, molybdenum, nickel, gold and zinc.
Further, the composite active material 3 further includes a binder and a negative electrode active material.
Further, the negative current collector 1 is a copper foil.
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass parts, 40-96 parts of positive active substance, 1-10 parts of binder, 0-20 parts of lithium conducting material, 1-10 parts of conductive agent and 0.5-5 parts of the sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and then are coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, and the positive active substance comprises one or a combination of more of lithium iron phosphate, lithium cobaltate, nickel cobalt manganese ternary battery material, lithium manganate, nickel cobalt aluminum ternary battery material and sulfur. The binder is at least one of PVDF, PVDF-HFP, oil-based butylbenzene binder, polyimide and polyamide-imide, and the lithium-conducting material is at least one of sulfide system electrolyte, oxide system electrolyte and polymer system electrolyte; the conductive agent is conductive carbon black and/or carbon nanotubes.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass parts, 80-100 parts of solid electrolyte and 1-10 parts of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and the solid electrolyte is prepared after coating and pressing, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: according to the mass parts, 10-20 parts of sulfide electrolyte coated nano attapulgite composite material, 0.5-5 parts of binder and 10-20 parts of negative electrode active substance are uniformly mixed and then coated on a negative electrode current collector, after drying and pressing, the surface of the active lithium storage material is subjected to vacuum plating, and the thickness of a plating layer is 10-100 nm, so that the ultrathin composite negative electrode with the thickness of 8-20 um is obtained. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is at least one of butylbenzene binder and polyacrylate binder. The negative active material is one or more of carbon material, metal bismuth, metal lithium, nitride, silicon-based material, tin-based oxide, tin compound, tin-based alloy, antimony-based alloy, germanium-based alloy, aluminum-based alloy, lead-based alloy, titanium oxide, nano transition metal oxide MO (M = Co, Ni, Cu, Fe), iron oxide, chromium oxide, molybdenum oxide and phosphide. The active lithium storage material is one or a combination of more of bismuth, lithium, silicon, tin, antimony, germanium, aluminum, lead, titanium, iron, chromium, molybdenum, nickel, gold and zinc. The composite cathode is mainly used for a high-volume energy density lithium ion battery.
The present invention will be further illustrated by the following specific examples. The reagents, materials and instruments used in the following description are all conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents may be synthesized by a conventional synthesis method, if not specifically described.
Example 1
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: weighing 40 parts of Li in parts by mole under argon atmosphere2Dissolving S in absolute ethyl alcohol, adding 1.50 parts of nano attapulgite, fully soaking, vacuumizing at normal temperature, heating to 50 ℃, and removing the solvent absolute ethyl alcohol to obtain the lithium sulfide coated nano attapulgite composite material;
step two: according to the molar parts, under the argon environment, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 13.5 parts of P2S5Putting the materials and zirconia balls into a pot made of zirconia, sealing the pot in an argon environment, installing the pot on a ball mill, rotating at the speed of 200r/min, mixing for 20 hours to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating at the temperature of 400 ℃ for 2 hours after vacuum sealing to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 75Li2S·25P2S5。
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass parts, 40 parts of positive active substance, 1 part of binder, 1 part of conductive agent and 0.5 part of the sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and then are coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance is a nickel-cobalt-manganese ternary battery material, the binder is PVDF, and the conductive agent is a carbon nano tube.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 80 portions of solid electrolyte and 1 portion of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed and coated and pressed to prepare the solid electrolyte, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: according to the mass parts, 10 parts of sulfide electrolyte coated nano attapulgite composite material, 0.5 part of binder and 10 parts of negative electrode active substance are uniformly mixed and then coated on a negative electrode current collector, after drying and pressing, the surface of the active lithium storage material is subjected to vacuum plating, the thickness of a plating layer is 10nm, and the ultrathin composite negative electrode with the thickness of 8um is obtained. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is a butylbenzene binder. Wherein the negative electrode active material is a carbon material. Wherein the active lithium storage material is bismuth. The composite cathode is mainly used for high-energy density lithium ion batteries.
Example 2
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: weighing 100 parts of Li in parts by mole under argon atmosphere2S is dissolved in absolute ethyl alcohol, 80.00 parts of nano attapulgite is added to be fully soaked and soaked, the mixture is heated to 90 ℃ under the argon environment, and the solvent ethyl alcohol is removed, so that the nano attapulgite composite material coated with lithium sulfide is obtained;
step two: according to the molar ratio, the nano attapulgite coated with the lithium sulfide obtained in the step one is put in an argon environmentStone composite material, 30 parts of P2S5Putting the LiBr and zirconia balls into a pot made of zirconia, sealing the pot in an argon environment, installing the pot on a ball mill, rotating at the speed of 300r/min, mixing for 30 hours to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating at the temperature of 300 ℃ for 6 hours after vacuum sealing to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 100Li2S·30P2S5·3LiBr。
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass parts, 50 parts of positive active substance, 2 parts of binder, 1 part of lithium conducting material, 3 parts of conductive agent and 3 parts of the nano attapulgite composite material coated by the sulfide electrolyte are uniformly mixed, and then coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance is a nickel-cobalt-aluminum ternary battery material, the binder is an oil-system butylbenzene binder, the lithium conducting material is a sulfide-system electrolyte, and the conductive agent is conductive carbon black.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 100 portions of solid electrolyte and 10 portions of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed and coated and pressed to prepare the solid electrolyte, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: uniformly mixing 12 parts by mass of sulfide electrolyte coated nano attapulgite composite material, 4 parts by mass of binder and 12 parts by mass of negative electrode active material, coating the mixture on a negative electrode current collector, drying and pressing, and performing vacuum plating on the surface of the active lithium storage material, wherein the thickness of a plating layer is 30nm, so as to obtain the ultrathin composite negative electrode with the thickness of 10 microns. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is polyacrylate binder. The negative electrode active material may be a tin compound. Wherein the active lithium storage material is lithium. The composite cathode is mainly used for high-energy density lithium ion batteries.
Example 3
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: weighing 70 parts of Li in parts by mole under the argon environment2Dissolving S in absolute ethyl alcohol, adding 50.00 parts of nano attapulgite, fully soaking, vacuumizing at normal temperature, heating to 60 ℃, and removing the solvent ethanol to obtain the lithium sulfide coated nano attapulgite composite material;
step two: according to the molar parts, under the argon environment, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 28 parts of P2S53 parts of P2O5Putting the materials and zirconia balls into a pot made of zirconia, sealing the pot in an argon environment, installing the pot on a ball mill, rotating at the speed of 800r/min, mixing for 10h to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating at the temperature of 200 ℃ for 3 h after vacuum sealing to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 70Li2S·28P2S5·3P2O5。
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass parts, 60 parts of positive active substance, 4 parts of binder, 5 parts of lithium conducting material, 4 parts of conductive agent and 1 part of the sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and then are coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance is lithium iron phosphate, the binder is polyimide, and the lithium conducting material is oxide system electrolyte; the conductive agent is carbon nanotubes.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 90 portions of solid electrolyte and 6 portions of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed and coated and pressed to prepare the solid electrolyte, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: according to the mass parts, 18 parts of sulfide electrolyte coated nano attapulgite composite material, 1 part of binder and 16 parts of negative electrode active material are uniformly mixed and then coated on a negative electrode current collector, after drying and pressing, the active lithium storage material is subjected to vacuum plating on the surface of the active lithium storage material, the thickness of a plating layer is 40nm, and the ultrathin composite negative electrode with the thickness of 12um is obtained. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is polyacrylate binder. Wherein the negative electrode active material is a nitride. Wherein the active lithium storage material is lithium. The composite cathode is mainly used for high-energy density lithium ion batteries.
Example 4
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: weighing 76.75 parts of Li in parts by mole under the argon atmosphere2Dissolving S in absolute ethyl alcohol, adding 60.00 parts of nano attapulgite, fully soaking, vacuumizing at normal temperature, heating to 70 ℃, and removing solvent ethanol to obtain the nano attapulgite composite material coated with lithium sulfide;
step two: according to the molar parts, under the argon environment, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 36 parts of SiS are mixed25.5 parts of P2S510 parts of Li4SiO410 parts of Li3N, 10 parts of Li3AlO31 part of LiCl and 1 part of P2S3Placing them together with zirconia balls into a zirconia pot, sealing the pot under argon atmosphere, placing the pot on a ball mill, rotating at 400r/min, and mixing for 40h to obtain a thorough mixtureAdding the mixed powder of the system A into a quartz tube, heating at 500 ℃ for 4 hours after vacuum sealing to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 20(0.6 Li)2S·0.4SiS2)·10Li4SiO4、22(0.75Li2S·0.25P2S5)·P2S3、20(0.6Li2S·0.4SiS2)·LiCl、30(0.6Li2S·0.4SiS2)·10Li3AlO3、20(0.6Li2S·0.4SiS2)·10Li3A mixture of N.
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: uniformly mixing 96 parts of positive active substance, 10 parts of binder, 20 parts of lithium conducting material, 10 parts of conductive agent and 5 parts of the nano attapulgite composite material coated with the sulfide electrolyte in parts by mass, and coating, drying and pressing to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance is lithium cobalt oxide, the binder is PVDF, and the lithium conducting material is sulfide system electrolyte and oxide system electrolyte; the conductive agent is conductive carbon black and carbon nano-tubes.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 85 portions of solid electrolyte and 8 portions of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed and coated and pressed to prepare the solid electrolyte, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: according to the mass parts, 20 parts of sulfide electrolyte coated nano attapulgite composite material, 5 parts of binder and 20 parts of negative electrode active material are uniformly mixed and then coated on a negative electrode current collector, after drying and pressing, the active lithium storage material is subjected to vacuum plating on the surface of the active lithium storage material, the thickness of a plating layer is 100nm, and the ultrathin composite negative electrode with the thickness of 20um is obtained. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is a butylbenzene binder. Wherein the negative active material may be a tin-based alloy. Wherein the active lithium storage material is bismuth. The composite cathode is mainly used for high-energy density lithium ion batteries.
Example 5
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: in the molar ratio, 60 parts of Li are weighed in the argon environment2Dissolving S in absolute ethyl alcohol, adding 20.00 parts of nano attapulgite, fully soaking, vacuumizing at normal temperature, heating to 80 ℃, and removing solvent ethanol to obtain the nano attapulgite composite material coated with lithium sulfide;
step two: in parts by mole, under the argon atmosphere, 20 parts of P of the lithium sulfide coated nano attapulgite composite material obtained in the step one2S54 parts of GeS 21 part of GeSe2Putting the materials and zirconia balls into a pot made of zirconia, sealing the pot in an argon environment, installing the pot on a ball mill, rotating at the speed of 450r/min, mixing for 50h to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating at the temperature of 600 ℃ for 5h after vacuum sealing to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 80 (0.75Li electrolyte)2S·0.25P2S5）·4GeS2·GeSe2。
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass portion, 90 portions of positive active substance, 6 portions of binder, 10 portions of lithium conducting material, 6 portions of conductive agent and 5 portions of the sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and then are coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance comprises a nickel-cobalt-aluminum ternary battery material, the binder is an oil system butylbenzene binder, the lithium conducting material is a polymer system electrolyte, and the conductive agent is conductive carbon black.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 95 portions of solid electrolyte and 9 portions of sulfide electrolyte coated nanometer attapulgite composite material are uniformly mixed and coated and pressed to prepare the solid electrolyte, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: uniformly mixing 14 parts by mass of sulfide electrolyte coated nano attapulgite composite material, 2 parts by mass of binder and 14 parts by mass of negative electrode active material, coating the mixture on a negative electrode current collector, drying and pressing, and performing vacuum plating on the surface of the active lithium storage material, wherein the thickness of a plating layer is 80nm, so as to obtain the ultrathin composite negative electrode with the thickness of 16 um. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is a butylbenzene binder. Wherein the negative active material may be an antimony-based alloy. Wherein the active lithium storage material is aluminum. The composite cathode is mainly used for high-energy density lithium ion batteries.
Example 6
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: in the molar ratio, 45 parts of Li are weighed in the argon environment2Dissolving S in absolute ethyl alcohol, adding 50.00 parts of nano attapulgite, fully soaking, vacuumizing at normal temperature, heating to 85 ℃, and removing solvent ethanol to obtain the lithium sulfide coated nano attapulgite composite material;
step two: according to the molar parts, under the argon environment, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 15 parts of P2S54 parts of SnS and 5 parts of Al2S31 part of As2S510 parts of Li3GaO310 parts of Li3InO310 parts of 10 Li3BO3Mixing them with zirconia ballsPutting the mixture into a zirconia pot, sealing the pot in an argon atmosphere, mounting the pot on a ball mill, rotating at the speed of 500r/min, mixing for 45h to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating after vacuum sealing at the heating temperature of 350 ℃ for 6 h to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 60(0.75 Li)2S·0.25P2S5)·10Li3GaO3·10 Li3InO3·10Li3BO3·5Al2S3·4SnS·As2S5。
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass parts, 50 parts of positive active substance, 8 parts of binder, 15 parts of lithium conducting material, 9 parts of conductive agent and 4 parts of the nano attapulgite composite material coated by the sulfide electrolyte are uniformly mixed, and then are coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance is a nickel-cobalt-manganese ternary battery material, the binder is PVDF, and the lithium conducting material is an oxide system electrolyte; the conductive agent is conductive carbon black.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 88 portions of solid electrolyte and 7 portions of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed and coated and pressed to prepare the solid electrolyte, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: uniformly mixing 16 parts by mass of sulfide electrolyte coated nano attapulgite composite material, 3 parts by mass of binder and 18 parts by mass of negative electrode active material, coating the mixture on a negative electrode current collector, drying and pressing, and performing vacuum plating on the surface of the active lithium storage material, wherein the thickness of a plating layer is 60nm, so as to obtain the ultrathin composite negative electrode with the thickness of 15 um. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is a butylbenzene binder. Wherein the negative electrode active material may be an oxide of titanium. Wherein the active lithium storage material is zinc. The composite cathode is mainly used for high-energy density lithium ion batteries.
Example 7
A preparation method of a composite material for a lithium ion battery comprises the following steps:
the method comprises the following steps: weighing 52.5 parts of Li in parts by mole under the argon environment2Dissolving S in absolute ethyl alcohol, adding 20.00 parts of nano attapulgite, fully soaking, vacuumizing at normal temperature, heating to 55 ℃, and removing solvent ethanol to obtain the lithium sulfide coated nano attapulgite composite material;
step two: according to the molar parts, under the argon environment, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 17.5 parts of P2S525 parts of ZnS and 5 parts of GeO2Putting the materials and zirconia balls into a pot made of zirconia, sealing the pot in an argon environment, installing the pot on a ball mill, rotating at the speed of 700r/min, mixing for 25h to obtain a fully mixed A system, adding the mixed powder of the A system into a quartz tube, heating at the temperature of 500 ℃ for 3 h after vacuum sealing to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, and the sulfide electrolyte is 70(0.75 Li)2S·0.25P2S5)·25ZnS·5GeO2。
The application of the sulfide electrolyte coated nano attapulgite composite material in the anode of the lithium ion battery comprises the following steps: according to the mass parts, 55 parts of positive active substance, 9 parts of binder, 8 parts of lithium conducting material, 8 parts of conductive agent and 2 parts of the sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and then are coated, dried and pressed to form a positive pole piece, wherein the positive pole piece can be used for a solid lithium ion battery, the positive active substance is lithium cobalt oxide, the binder is PVDF, and the lithium conducting material is sulfide system electrolyte; the conductive agent is carbon nanotubes.
The application of the nanometer attapulgite composite material coated by the sulfide electrolyte in the solid electrolyte of the lithium ion battery comprises the following steps: according to the mass portion, 96 portions of solid electrolyte and 3 portions of sulfide electrolyte coated nano attapulgite composite material are uniformly mixed, and the solid electrolyte is prepared after coating and pressing, wherein the solid electrolyte comprises a sulfide system, an oxide system and a polymer system.
The application of the sulfide electrolyte coated nano attapulgite composite material in the negative electrode of the lithium ion battery comprises the following steps: uniformly mixing 15 parts by mass of sulfide electrolyte coated nano attapulgite composite material, 4 parts by mass of binder and 16 parts by mass of negative electrode active material, coating the mixture on a negative electrode current collector, drying and pressing the mixture, and performing vacuum plating on the surface of the active lithium storage material, wherein the thickness of a plating layer is 50nm, so as to obtain the ultrathin composite negative electrode with the thickness of 18 um. The negative current collector can be a copper foil or a copper foil subjected to vacuum plating of an active lithium storage material. Wherein the binder is a butylbenzene binder. Wherein the negative electrode active material may be a carbon material. Wherein the active lithium storage material is lithium. The composite cathode is mainly used for high-energy density lithium ion batteries.
The sulfide electrolytes prepared in examples 1 to 7 and commercial polymer polyethylene oxide electrolytes were subjected to room temperature conductivity and lithium ion transference number tests, and the test results are shown in the following table.
From the results of the above table, it can be seen that the conventional polyethylene oxide polymer electrolyte has a conductivity of 1.26X 10 at normal temperature-5S/cm, the transference number of lithium ions is 0.38, and the conductivity of the sulfide electrolyte coated nano attapulgite composite material prepared by the method is about 10 at normal temperature-3S/cm is about, compared with a polymer system, the nano attapulgite rod-shaped structure coated by the sulfide electrolyte has better room-temperature ionic conductivity and lithium ion transference number, and the surface of the nano attapulgite rod-shaped structure coated by the sulfide electrolyte has better lithium ion transmission channels, so that the performance of a lithium ion battery can be effectively improved. The sulfide electrolyte of the invention coats the nanometer concave-convexThe attapulgite structure coated with the sulfide electrolyte has high lithium ion conductivity and stable performance, and the sulfide electrolyte coated attapulgite has good application prospect in high-energy-density lithium ion batteries.
Claims (10)
1. A composite material for a lithium ion battery is characterized in that: the composite material comprises a sulfide electrolyte (41) and nano attapulgite (42), wherein the sulfide electrolyte (41) coats the nano attapulgite (42), and the composite material is applied to at least one of a positive electrode material, a negative electrode material and an electrolyte material.
2. The composite material for a lithium ion battery according to claim 1, characterized in that: the thickness of the sulfide electrolyte (41) coating layer is less than or equal to 20um, the crystal length of the nanometer attapulgite (42) rod is 100nm-50um, and the width is 10nm-120 nm.
3. The composite material for a lithium ion battery according to claim 1, characterized in that: the sulfide electrolyte (41) is a combination of one or more of the following: aLi2S·b P2S5cLiX, wherein X represents a halogen element, a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bP2S5cMES, wherein Me is Si, Ge, Sn, Al or B, a is more than or equal to 20 and less than or equal to 80, B is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bP2S5·cP2O5Wherein a is more than 67 and less than 80, b is more than 0 and less than 40, and c is more than 0 and less than 25; li4-aSi1- aPaS4Wherein a is more than 0 and less than 1; 70Li2S·(30−a)P2S5·aP2S3Wherein a is more than 0 and less than 30; aLi2S·bSiS2Wherein a is more than or equal to 50 and less than or equal to 70, and b is more than or equal to 30 and less than or equal to 50; li4-aSi1-aAlaS4Wherein a is more than 0 and less than 1; aLi2S·bSiS2·cLi3MO3Wherein M = B, Al, Ga or In, 20 ≤ a ≤ 80, and,20≤b≤40、0≤c≤20；aLi2S·bSiS2·cLi3N, wherein a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, and c is more than or equal to 0 and less than or equal to 20; aLi2S·bGeS2Wherein a is more than 0 and less than 60, and b is more than 40 and less than 100; 0.5Li2S·0.5[(1-a)GeS2·aGeO2]Wherein a is more than 0 and less than 1; li4+a (Ge1-aGab)S4Wherein a is more than 0 and less than 1, and b is more than 1 and less than 2; liaGebPcS4Wherein a is more than or equal to 3 and less than or equal to 3.3, b is more than or equal to 0 and less than or equal to 0.3, and c is more than or equal to 0.7 and less than or equal to 1.0; a (0.6 Li)2S·0.4SiS2)·bLi4SiO4Wherein a is more than or equal to 80 and less than or equal to 100, and b is more than or equal to 0 and less than or equal to 20; liaGebSecPdSeWherein a is more than 3 and less than 4, b is more than 0 and less than 1, c is more than 0 and less than 2, d is more than 0 and less than 1, and e is more than 2 and less than 4; liaGebAscS4Wherein a is more than or equal to 3 and less than or equal to 3.5, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.5; liaZnbGeS4Wherein a is more than 0 and less than 2, and b is more than 0 and less than 2; aLi2S·bP2S5·cGeS2·dSnSe2Wherein a is more than or equal to 20 and less than or equal to 80, b is more than or equal to 20 and less than or equal to 40, c is more than or equal to 0 and less than or equal to 10, and d is more than or equal to 0 and less than or equal to 10.
4. A method for preparing a composite material according to any one of claims 1 to 3, comprising the steps of:
the method comprises the following steps: in the molar ratio, 40-100 parts of Li are weighed in an argon environment2Dissolving S in absolute ethyl alcohol, adding 1.50-80.00 parts of nano attapulgite, fully soaking, vacuumizing in an argon environment or at normal temperature, heating to 50-90 ℃, and removing the solvent absolute ethyl alcohol to obtain the nano attapulgite composite material coated with lithium sulfide;
step two: according to the molar parts, under the argon atmosphere, the lithium sulfide coated nano attapulgite composite material obtained in the step one and 0-30 parts of P2S50 to 30 parts of SiS20 to 30 parts of GeS20 to 30 parts of B2S30 to 30 parts of SnS and 0 to 30 parts of Al2S30 to 30 parts of P2S30 to 30 parts of Ga2S30 to 30 parts of ZnS and 0 to 30 parts of As2S50 to 10 parts of P2O50 to 10 parts of Li4SiO40 to 10 parts of Li3N, 0-10 parts of Li3MO30 to 10 parts of GeO20 to 10 parts of GeSe2And 0-10 parts of LiX, fully mixing and grinding into powder to obtain a system A, adding the system A into a quartz tube, sealing In vacuum, and heating at 200-600 ℃ for 2-6 hours to obtain a composite material, wherein the composite material is a sulfide electrolyte coated nano attapulgite composite material, M is B, Al, Ga or In, and X is one of halogen elements.
5. A lithium ion battery comprising the composite material of any one of claims 1 to 3, wherein: at least one of the positive electrode, the electrolyte and the negative electrode of the lithium ion battery comprises the composite material.
6. A lithium-ion battery according to claim 5, the negative electrode comprising a negative current collector (1), characterized in that: the surface of the negative current collector (1) is coated with a composite active substance (3), the composite active substance (3) contains the composite material (4), and the surface of the composite active substance (3) is plated with an active lithium storage material coating I (5).
7. The lithium ion battery of claim 6, wherein: the surface of the negative current collector (1) is plated with an active lithium storage material coating II (2), and the active lithium storage material coating II (2) is located between the negative current collector (1) and the composite active substance (3).
8. A lithium ion battery according to claim 7, wherein: the thickness of active lithium storage material cladding I (5) and active lithium storage material cladding II (2) is 10nm ~100nm, the thickness of compound active material (3) is 1~5 um.
9. A lithium ion battery according to claim 7, wherein: the active lithium storage materials in the active lithium storage material coating I (5) and the active lithium storage material coating II (2) are one or a combination of more of bismuth, lithium, silicon, tin, antimony, germanium, aluminum, lead, titanium, iron, chromium, molybdenum, nickel, gold and zinc.
10. A lithium ion battery according to claim 7, wherein: the composite active material (3) further includes a binder and a negative electrode active material.
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| PB01 | Publication | ||
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Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
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| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tang Weichao Inventor after: Li Suli Inventor after: Zhao Wei Inventor after: Yuan Hao Inventor after: Li Junyi Inventor after: Xu Yanming Inventor after: Gao Yunzhi Inventor before: Tang Weichao Inventor before: Li Suli Inventor before: Zhao Wei Inventor before: Yuan Hao Inventor before: Li Junyi Inventor before: Xu Yanming |
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