CN111048773A - Core-double-shell structure composite nickel-cobalt-manganese ternary positive electrode material, lithium battery and vehicle - Google Patents

Core-double-shell structure composite nickel-cobalt-manganese ternary positive electrode material, lithium battery and vehicle Download PDF

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CN111048773A
CN111048773A CN201911320344.XA CN201911320344A CN111048773A CN 111048773 A CN111048773 A CN 111048773A CN 201911320344 A CN201911320344 A CN 201911320344A CN 111048773 A CN111048773 A CN 111048773A
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cobalt
core
shell layer
positive electrode
shell
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CN111048773B (en
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秦波
朱红斌
孙实
潘飞
董兆盛
蒋程文
吴志龙
周轩宇
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Zhongye Ruimu New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a core-double shell structure composite nickel-cobalt-manganese ternary cathode material, a lithium battery and a vehicle, wherein the core-double shell structure composite nickel-cobalt-manganese ternary cathode material comprises: a core of the formula Li(1+a)(Liz1Nix1Coy1Mn1‑x1‑y1‑z1)O2,0≤a≤0.5,0<x1<1,0<y1<1,0<z1<1,0<1‑x1‑y1‑z1Less than 1; a secondary shell layer coated on at least a portion of the coreOn the outer surface, the sub-shell layer material has the chemical formula Li(1+a)Nix2Coy2M(1‑x2‑y2)O2M is Mn and/or Al, a is more than or equal to 0 and less than or equal to 0.5, x is more than 02<1,0<y2<1,0<1‑x2‑y2Less than 1; and the outermost shell layer is coated on at least one part of the outer surface of the secondary shell layer, and the material of the outermost shell layer is metal oxide. Therefore, the single battery made of the positive electrode material can realize long cycle life on the basis of high specific energy, so that a vehicle loaded with the battery has excellent cruising ability, and the use requirement of consumers is met.

Description

Core-double-shell structure composite nickel-cobalt-manganese ternary positive electrode material, lithium battery and vehicle
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a core-double shell structure composite nickel-cobalt-manganese ternary positive electrode material, a lithium battery and a vehicle.
Background
For new energy automobiles, regardless of national support policies, the key factor determining the development is to meet the demands of consumers. At present, limited by the technical level of power batteries, the endurance mileage of most commercial pure electric vehicles is still low, and consumers have serious mileage anxiety and weak purchasing desire. The pure electric vehicle has the endurance of 320 kilometers, and can meet the use requirements of most consumers; the mileage can be increased to 600 km, and the mileage anxiety of the consumer can be eliminated only when the mileage is close to the mileage of the fuel vehicle in the full oil state. Therefore, the development of a new generation of power battery with high energy density is a necessary requirement and trend for the future technical development of the power battery. With respect to the technology in the industry at present, the technology for improving the energy density of the power battery by reducing the quality of the inactive substances of the battery core is already touched, and the method for improving the energy density of the power battery by using the anode and cathode materials with higher energy density is a more effective method. In the known positive electrode materials, the specific energy of the lithium-rich manganese-based nickel-cobalt-manganese ternary monomer battery can reach over 400Wh/kg, and the specific energy of the nickel-cobalt-aluminum ternary monomer battery with the highest specific energy density is 300Wh/kg when the lithium-rich manganese-based nickel-cobalt-manganese ternary monomer battery is commercially applied, so that the lithium-rich manganese-based nickel-cobalt-manganese ternary positive electrode material is very suitable for being used as a new-generation high-energy-density power lithium battery positive electrode material. Although the lithium-manganese-based nickel-cobalt-manganese ternary positive electrode material has the absolute advantage of high specific energy of the battery, the lithium-manganese-based nickel-cobalt-manganese ternary positive electrode material has the problems that the lithium-manganese-based nickel-cobalt-manganese ternary positive electrode material has an irreversible phase transformation process from a layered structure to a spinel structure in a long-term circulation process, and a Mn element can be dissolved into an electrolyte in a circulation process, so that the circulation life deviation, especially the high-temperature circulation performance deviation, of the lithium-manganese-based nickel-cobalt-manganese ternary positive electrode material is caused, and the service life of a.
Therefore, the existing lithium-rich manganese-based nickel-cobalt-manganese ternary cathode material needs to be further improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the problems associated with the related art. Therefore, one objective of the present invention is to provide a composite nickel-cobalt-manganese ternary positive electrode material with a core-double shell structure, a lithium battery and a vehicle, wherein the single battery made of the positive electrode material can achieve a long cycle life on the basis of high specific energy, so that the vehicle loaded with the battery has excellent cruising ability, and meets the use requirements of consumers.
In one aspect of the invention, the invention provides a core-double shell structure composite nickel-cobalt-manganese ternary cathode material. According to an embodiment of the invention, the ternary positive electrode material comprises:
a core of the formula Li(1+a)(Liz1Nix1Coy1Mn1-x1-y1-z1)O2,0≤a≤0.5,0<x1<1,0<y1<1,0<z1<1,0<1-x1-y1-z1<1;
A secondary shell layer coated on at least a part of the outer surface of the core, the secondary shell layer being made of a material having a chemical formula of Li(1+a)Nix2Coy2M(1-x2-y2)O2M is Mn and/or Al, a is more than or equal to 0 and less than or equal to 0.5, x is more than 02<1,0<y2<1,0<1-x2-y2<1;
And the outermost shell layer is coated on at least one part of the outer surface of the secondary shell layer, and the material of the outermost shell layer is metal oxide.
The chemical formula of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure is Li(1+a)(Liz1Nix1Coy1Mn1-x1-y1-z1)O2The material of (A) as a core, with the chemical formula of Li(1+a)Nix2Coy2M(1-x2-y2)O2The material is used as a secondary shell layer, the metal oxide is used as an outermost shell layer, namely the anode material has a double-shell structure, and the secondary shell layer contains a nickel-cobalt-manganese ternary anode material or a nickel-cobalt-aluminum ternary anode material, so that the manufactured single battery has higher specific energy, while the existing battery anode material has an irreversible phase transformation process from a layered state to a spinel due to the side reaction of the lithium-rich manganese-based nickel-cobalt-manganese ternary material and an electrolyte in the circulation process, and part of the composition of the lithium-rich manganese-based nickel-cobalt-manganese ternary material is LiMnO after the primary circulation2The form of the nickel-cobalt-manganese composite anode material participates in the electrochemical cycle process, the cycle stability of the nickel-cobalt-manganese composite anode material is poor due to the change of the structure, double-shell protection is formed on the surface of the composite nickel-cobalt-manganese composite anode material, thereby inhibiting the irreversible phase change caused by the side reaction of the lithium-rich manganese-based nickel-cobalt-manganese ternary cathode material which is directly contacted with the electrolyte in the long-term circulation process, having good circulation performance, and due to the protection of the double-shell structure, the buffer function between the composite nickel-cobalt-manganese ternary positive electrode material core and the electrolyte can be well achieved, so that the single battery keeps good specific energy, in addition, the metal oxide as the outermost shell layer does not react with the electrolyte of the full battery, the nickel-cobalt-manganese ternary positive electrode material or the nickel-cobalt-aluminum ternary positive electrode material serving as the secondary shell layer has a good physical isolation effect with the electrolyte, so that Mn element is inhibited from being dissolved into the electrolyte in the circulation process. Therefore, the single battery made of the anode material can realize long cycle life on the basis of high specific energy, thereby leading toThe vehicle loaded with the battery has excellent cruising ability and meets the use requirements of consumers.
In addition, the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, the particle size of the positive electrode material is 2 to 16 μm.
In some embodiments of the present invention, the particle size of the inner core is 1 to 9 μm.
In some embodiments of the invention, the thickness of the secondary shell layer is 1-6 μm.
In some embodiments of the present invention, the thickness of the outermost shell layer is 5 to 1000 nm.
In some embodiments of the invention, the secondary outer shell layer and the outer shell layer have micro-holes therein.
In some embodiments of the present invention, the pore size of the micropores is 0.1 to 0.5. mu.m.
In a second aspect of the invention, a lithium battery is provided. According to the embodiment of the invention, the lithium battery has the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure. Thus, the battery can achieve a long cycle life on the basis of having a high specific energy.
In a third aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the lithium battery described above. Therefore, the vehicle loaded with the vehicle with high specific energy and long cycle life has excellent cruising ability, thereby meeting the use requirement of consumers.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1A is a scanning electron microscope image of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure obtained in example 1;
fig. 1B is a scanning electron microscope image of a longitudinal section of the composite nickel-cobalt-manganese ternary cathode material with a core-double shell structure obtained in example 1;
FIG. 2 is an XRD spectrum of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure obtained in example 1;
fig. 3 is a high-temperature cycle performance curve of the core-double shell structure composite nickel-cobalt-manganese ternary cathode material obtained in example 1 at 60 ℃.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a core-double shell structure composite nickel-cobalt-manganese ternary cathode material. According to an embodiment of the invention, the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure comprises a core, a secondary shell layer and an outermost shell layer, wherein the secondary shell layer is coated on at least one part of the outer surface of the core, the outermost shell layer is coated on at least one part of the outer surface of the secondary shell layer, preferably, the secondary shell layer is coated on the whole outer surface of the core, and the outermost shell layer is coated on the whole outer surface of the secondary shell layer, wherein the chemical formula of the core material is Li(1+a)(Liz1Nix1Coy1Mn1-x1-y1-z1)O2,0≤a≤0.5,0<x1<1,0<y1<1,0<z1<1,0<1-x1-y1-z1Less than 1; the chemical formula of the material of the sub-shell layer is Li(1+a)Nix2Coy2M(1-x2-y2)O2M is Mn and/or Al, a is more than or equal to 0 and less than or equal to 0.5, x is more than 02<1,0<y2<1,0<1-x2-y2Less than 1; the outermost shell material is metal oxide, for example, the metal oxide is alumina, zirconia, titania, magnesia. Ternary positive electrode materialWith the chemical formula Li(1+a)(Liz1Nix1Coy1Mn1-x1-y1-z1)O2The material of (A) as a core, with the chemical formula of Li(1+a)Nix2Coy2M(1-x2-y2)O2The material is used as a secondary shell layer, the metal oxide is used as an outermost shell layer, namely the anode material has a double-shell structure, and the secondary shell layer contains a nickel-cobalt-manganese ternary anode material or a nickel-cobalt-aluminum ternary anode material, so that the manufactured single battery has higher specific energy, while the existing battery anode material has an irreversible phase transformation process from a layered state to a spinel due to the side reaction of the lithium-rich manganese-based nickel-cobalt-manganese ternary material and an electrolyte in the circulation process, and part of the composition of the lithium-rich manganese-based nickel-cobalt-manganese ternary material is LiMnO after the primary circulation2The form of the nickel-cobalt-manganese composite anode material participates in the electrochemical cycle process, the cycle stability of the nickel-cobalt-manganese composite anode material is poor due to the change of the structure, double-shell protection is formed on the surface of the composite nickel-cobalt-manganese composite anode material, thereby inhibiting the irreversible phase change caused by the side reaction of the lithium-rich manganese-based nickel-cobalt-manganese ternary cathode material which is directly contacted with the electrolyte in the long-term circulation process, having good circulation performance, and due to the protection of the double-shell structure, the buffer function between the composite nickel-cobalt-manganese ternary positive electrode material core and the electrolyte can be well achieved, so that the single battery keeps good specific energy, in addition, the metal oxide as the outermost shell layer does not react with the electrolyte of the full battery, the nickel-cobalt-manganese ternary positive electrode material or the nickel-cobalt-aluminum ternary positive electrode material serving as the secondary shell layer has a good physical isolation effect with the electrolyte, so that Mn element is inhibited from being dissolved into the electrolyte in the circulation process. Therefore, the single battery made of the positive electrode material can realize long cycle life on the basis of high specific energy, so that a vehicle loaded with the battery has excellent cruising ability, and the use requirement of consumers is met.
According to an embodiment of the present invention, the particle size of the positive electrode material is not particularly limited, and may be selected by a person skilled in the art according to actual needs, and according to an embodiment of the present invention, the particle size of the positive electrode material is 2 to 16 μm, such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, and 16 μm. The inventor finds that if the particle size of the cathode material is too large, the path for lithium ions to migrate in the particles is too long, and the difficulty in lithium ion desorption and intercalation is too large, so that the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor; if the particle size of the anode material is too small, the specific surface area of the anode material is too large, the contact area with the electrolyte is too large, the degree of side reaction is too high, the irreversible phase change degree is too high, and the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor. Therefore, the cycle performance of the composite nickel-cobalt-manganese ternary battery can be ensured by adopting the anode material with the particle size range.
According to still another embodiment of the present invention, the particle size of the core of the positive electrode material is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to an embodiment of the present invention, the particle size of the core is 1 to 9 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, and 9 μm. The inventor finds that if the particle size of the core is too large, the proportion of the lithium-manganese-based nickel-cobalt-manganese ternary positive electrode material in the positive electrode material is high, and the specific energy of the composite nickel-cobalt-manganese ternary monomer battery is high, but the irreversible phase change degree is too high due to the side reaction of the lithium-manganese-based nickel-cobalt-manganese ternary material and the electrolyte, so that the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor, and if the particle size of the core is too small, the proportion of the lithium-manganese-based nickel-cobalt-manganese ternary positive electrode material in the positive electrode material is low, and the specific energy of the composite nickel-cobalt-manganese ternary. Therefore, the battery obtained by adopting the core particle size can have excellent cycle performance and specific energy.
According to another embodiment of the present invention, the thickness of the secondary casing layer of the cathode material is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the thickness of the secondary casing layer is 1 to 6 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, and 6 μm. The inventor finds that although the nickel-cobalt-manganese or nickel-cobalt-aluminum ternary material as the secondary shell layer also has higher specific energy of the battery, the specific energy of the battery is lower than that of the lithium-rich-manganese-based nickel-cobalt-manganese ternary material as the inner core, if the secondary shell layer is too thick, the proportion of the lithium-rich-manganese-based nickel-cobalt-manganese ternary material as the inner core in the positive electrode material is too low, the specific energy of the composite nickel-cobalt-manganese ternary monomer battery is lost to a certain extent, and if the secondary shell layer is too thin, the physical isolation effect is limited, and the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor. Therefore, the adoption of the secondary shell particle size can ensure that the obtained battery has excellent cycle performance and specific energy.
According to another embodiment of the present invention, the thickness of the outermost shell layer of the positive electrode material is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to one embodiment of the present invention, the thickness of the outermost shell layer is 5 to 1000nm, such as 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 105nm, 110nm, 115nm, 120nm, 125nm, 130nm, 135nm, 140nm, 145nm, 150nm, 155nm, 160nm, 165nm, 170nm, 175nm, 180nm, 185nm, 190nm, 195nm, 200nm, 225nm, 250nm, 275nm, 300nm, 325nm, 350nm, 375nm, 400nm, 425nm, 450nm, 475nm, 500nm, 550nm, 525nm, 650nm, etc, 675nm, 700nm, 725nm, 750nm, 775nm, 800nm, 825nm, 850nm, 875nm, 900nm, 925nm, 950nm, 975nm, 1000 nm. The inventor finds that the outermost shell layer does not have the specific energy of the battery, if the outermost shell layer is too thick, the proportion of the materials of the inner core and the secondary shell layer is too low, the specific energy loss of the composite nickel-cobalt-manganese ternary monomer battery is serious, the outermost shell layer does not generate side reaction with electrolyte, if the outermost shell layer is too thin, the protective effect on the secondary shell layer and the inner core cannot be achieved, and the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor. Therefore, the battery obtained by adopting the grain diameter of the outermost shell layer has excellent cycle performance and specific energy.
According to another embodiment of the present invention, the sub-shell layer and the shell layer have micropores thereon, and the pore size of the micropores is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the pore size of the micropores is 0.1 to 0.5 μm, such as 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, and 0.5 μm. The inventor finds that if the pore diameter of the micropore is small, lithium ions cannot migrate in the material particles, so that the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor, if the pore diameter of the micropore is large, the electrolyte directly contacts with the core through the micropore to generate a strong side effect, the crystal phase transformation is serious, the physical isolation effect of the double shell on the core is poor, and the cycle performance of the composite nickel-cobalt-manganese ternary battery is poor. Therefore, micropores with the size within the particle size range are formed on the secondary shell layer and the outermost shell layer, and the obtained ternary battery has excellent cycle performance.
In yet another aspect of the present invention, a lithium battery is provided. According to the embodiment of the invention, the lithium battery has the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure. Thus, the battery can achieve a long cycle life on the basis of having a high specific energy. It should be noted that the features and advantages described above for the core-double shell structure composite nickel-cobalt-manganese ternary cathode material are also applicable to the lithium battery, and are not described herein again.
In yet another aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the lithium battery described above. Therefore, the vehicle loaded with the lithium battery with high specific energy and long cycle life has excellent cruising ability, thereby meeting the use requirement of consumers. It should be noted that the features and advantages described above for the lithium battery are also applicable to the vehicle and will not be described here.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The chemical formula of the inner core of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure is Li1.05[Li0.2Ni0.12Co0.12Mn0.56]O2(ii) a The sub-shell layer material has the chemical formula of Li1.05[Ni0.80Co0.10Mn0.10]O2(ii) a The outermost shell layer is made of aluminum oxide, the particle size of the inner core is 5 micrometers, the thickness of the secondary outer shell layer is 3 micrometers, the thickness of the outermost shell layer is 500nm, the particle size of the anode material is 9 micrometers, the pore diameter of micropores of the secondary outer shell layer is 0.3 micrometer, and the pore diameter of micropores of the outermost shell layer is 0.3 micrometer.
Example 2
The chemical formula of the inner core of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure is Li1.05[Li0.2Ni0.12Co0.12Mn0.56]O2(ii) a The sub-shell layer material has a chemical formula of Li1.05[Ni0.90Co0.07Al0.03]O2(ii) a The outermost shell material is zirconia. Wherein, the particle size of the inner core is 9 μm, the thickness of the secondary shell layer is 6 μm, the thickness of the outermost shell layer is 1000nm, the particle size of the anode material is 16 μm, the pore diameter of the micropores of the secondary shell layer is 0.5 μm, and the pore diameter of the micropores of the outermost shell layer is 0.5 μm.
Example 3
The chemical formula of the inner core of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure is Li1.02[Li0.1Ni0.13Co0.13Mn0.64]O2(ii) a The material of the secondary shell layer is a nickel-cobalt-manganese ternary positive electrode material with the chemical formula of Li1.02[Ni0.50Co0.20Mn0.30]O2(ii) a The outermost shell material is titanium oxide. Wherein, the particle size of the inner core is 1 μm, the thickness of the secondary shell layer is 1 μm, the thickness of the outermost shell layer is 5nm, the particle size of the anode material is 2 μm, the pore diameter of the micropores of the secondary shell layer is 0.1 μm, and the pore diameter of the micropores of the outermost shell layer is 0.1 μm.
Example 4
The chemical formula of the inner core of the composite nickel-cobalt-manganese ternary cathode material with the core-double shell structure is Li1.05[Li0.3Ni0.10Co0.10Mn0.50]O2(ii) a The material of the secondary shell layer is a nickel-cobalt-manganese ternary positive electrode material with the chemical formula of Li1.05[Ni0.60Co0.20Mn0.20]O2(ii) a The outermost shell material is magnesium oxide. Wherein, the particle size of the inner core is 5 μm, the thickness of the secondary shell layer is 6 μm, the thickness of the outermost shell layer is 5nm, the particle size of the anode material is 11 μm, the pore diameter of the micropores of the secondary shell layer is 0.1 μm, and the pore diameter of the micropores of the outermost shell layer is 0.3 μm.
Evaluation:
1. the composite nickel-cobalt-manganese ternary positive electrode materials of examples 1 to 4 were assembled into lithium batteries, and specific energy, cycle performance at 60 degrees celsius, and the amount of Mn dissolved in the electrolyte (after 100 cycles of the lithium battery) were evaluated.
2. Evaluation index and test method:
and (3) testing the specific energy of the lithium battery: refer to column mark YS/T798-;
60 ℃ cycle performance test: refer to column mark YS/T798-;
the dissolving amount of Mn element in the electrolyte (after 100 cycles of the lithium battery): refer to column designation YS/T1006.2-2014.
Examples 1 to 4 correspond to specific energy tests of a lithium battery and results of a dissolution amount of a Mn element in an electrolyte after 100 cycles of the lithium battery are shown in table 1, fig. 1A is a scanning electron microscope image of the core-double shell structure composite nickel-cobalt-manganese ternary cathode material obtained in example 1, fig. 1B is a scanning electron microscope image of a longitudinal section of the core-double shell structure composite nickel-cobalt-manganese ternary cathode material obtained in example 1, fig. 2 is an XRD spectrum of the core-double shell structure composite nickel-cobalt-manganese ternary cathode material obtained in example 1, and fig. 3 is a 60-degree-celsius high-temperature cycle performance curve of the core-double shell structure composite nickel-cobalt-manganese ternary cathode material obtained in example 1.
Table 1 specific energy test results for lithium batteries of examples 1-4
Specific energy (wh/kg) The amount of Mn dissolved in the electrolyte
Example 1 373 Not detected out
Example 2 362 Not detected out
Example 3 369 Not detected out
Example 4 356 Not detected out
In conclusion, as can be seen from table 1, the specific energy of the lithium batteries of examples 1 to 4 is more than 350wh/Kg, and after the lithium batteries of examples 1 to 4 are cycled for 100 times, the dissolving amount of Mn element in the electrolyte is not detected, as can be seen from fig. 1A, the composite nickel-cobalt-manganese ternary positive electrode material particles obtained in example 1 are in a sphere-like shape, the surface of the sphere has micropores, and lithium ions can leave or enter the particle through the micropores to generate desorption and intercalation reactions of the lithium ions, so that the composite nickel-cobalt-manganese ternary battery has good specific energy and cycle performance; as can be seen from fig. 1B, the three layers are present inside the particles of the composite nickel-cobalt-manganese ternary cathode material obtained in example 1, that is, the inner core forms double-shell protection, which indicates that the double-shell protection formed on the surface of the composite nickel-cobalt-manganese ternary cathode material with the core-double-shell structure can effectively inhibit the Mn element from being dissolved into the electrolyte in the circulation process. As can be seen from the XRD pattern of fig. 2, the cathode material of the present application is a composite nickel-cobalt-manganese ternary cathode material. As can be seen from fig. 3, the charge/discharge efficiency of the lithium battery according to example 1 was maintained at 90% or more after 100 cycles at 60 ℃. In conclusion, the lithium battery prepared by the composite nickel-cobalt-manganese ternary cathode material in the embodiment 1 has excellent specific energy and cycle performance, and Mn element is prevented from being dissolved into the electrolyte in the cycle process. Meanwhile, the charging and discharging efficiency of the lithium batteries corresponding to the embodiments 2 to 4 is still maintained above 90% after the lithium batteries are cycled for 100 times at 60 ℃. Therefore, the single battery manufactured by adopting the core-double shell structure composite nickel-cobalt-manganese ternary cathode material has high specific energy density and can realize long cycle life. In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (9)

1. The utility model provides a compound nickel cobalt manganese ternary cathode material of core-double shell structure which characterized in that includes:
a core of the formula Li(1+a)(Liz1Nix1Coy1Mn1-x1-y1-z1)O2,0≤a≤0.5,0<x1<1,0<y1<1,0<z1<1,0<1-x1-y1-z1<1;
A secondary shell layer coated on at least a part of the outer surface of the core, the secondary shell layer being made of a material having a chemical formula of Li(1+a)Nix2Coy2M(1-x2-y2)O2M is Mn and/or Al, a is more than or equal to 0 and less than or equal to 0.5, x is more than 02<1,0<y2<1,0<1-x2-y2<1;
And the outermost shell layer is coated on at least one part of the outer surface of the secondary shell layer, and the material of the outermost shell layer is metal oxide.
2. The positive electrode material according to claim 1, wherein the particle size of the positive electrode material is 2 to 16 μm.
3. The positive electrode material according to claim 1 or 2, wherein the particle size of the core is 1 to 9 μm.
4. The positive electrode material according to claim 1 or 2, wherein the thickness of the sub-shell layer is 1 to 6 μm.
5. The positive electrode material as claimed in claim 1 or 2, wherein the outermost shell layer has a thickness of 5 to 1000 nm.
6. The positive electrode material as claimed in claim 1, wherein the sub-envelope layer and the envelope layer have micropores thereon.
7. The positive electrode material according to claim 6, wherein the pores have a diameter of 0.1 to 0.5 μm.
8. A lithium battery having the core-double shell structured composite nickel-cobalt-manganese ternary positive electrode material according to any one of claims 1 to 7.
9. A vehicle characterized in that it has the lithium battery of claim 8.
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