A lithium cobalt oxide cathode material, a preparation method and application thereof

Abstract

The application discloses a lithium cobaltate positive electrode material and a preparation method and application thereof, and comprises the following steps: preparing a nano cobalt hydroxide powder, preparing a nano cobalt tetraoxide powder, and preparing an element-doped lithium cobaltate positive electrode material. The lithium cobaltate positive electrode material prepared by the application is doped with multiple elements such as aluminum, lanthanum, copper and tungsten, and the stability of the bulk phase and the surface crystal structure of the lithium cobaltate material is improved by optimizing raw materials, element contents and process parameters, the surface side reaction under high voltage is inhibited, the ion conductivity and the electronic conductivity of the material are greatly improved, and the high-voltage fast-charging performance and the high-voltage cycle stability of the lithium cobaltate positive electrode material are significantly improved. The preparation method provided by the application is good in controllability, simple and easy to implement, suitable for expanding production, and capable of realizing industrialization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lithium ion batteries, and particularly relates to a lithium cobaltate positive electrode material and a preparation method and application thereof. BACKGROUND

[0002] The lithium cobaltate positive electrode material has advantages of high compaction density, high volume energy density and long cycle life, and thus occupies an important position in the market of portable electronic terminal devices such as computers, communications and consumer electronics. With the development of electronic products in the direction of diversification, thinness, high performance and intelligence, the battery market urgently needs small energy storage devices with high energy density and high power density.

[0003] Improving the fast charging performance and charging cut-off voltage of the lithium cobaltate positive electrode is an important way to improve the energy density and power density of the lithium ion battery. However, with the improvement of the fast charging rate and the charging cut-off voltage, the electrochemical performance of the lithium cobaltate positive electrode seriously deteriorates. This is mainly because the interface side reaction between the positive electrode material and the electrolyte is intensified under high charging cut-off voltage, and the high degree of delithiation leads to irreversible phase change. The material polarization under fast charging leads to the intensification of surface side reaction and the generation of irreversible phase change, and thus accelerates the deterioration of the electrochemical performance of the lithium cobaltate positive electrode material.

[0004] Therefore, improving the structural stability and reducing the material polarization are the technical key points that need to be overcome to increase the fast charging performance and charging cut-off voltage of the lithium cobaltate positive electrode, and are also an important direction for developing new advanced lithium ion battery positive electrode materials in recent years. SUMMARY

[0005] In order to overcome the above technical defects, the application provides a high-voltage fast-charging lithium cobaltate positive electrode material doped with an element and a preparation method thereof, which aims to improve the rate performance and cycle performance of the lithium cobaltate positive electrode material under a 4.6V charging cut-off voltage.

[0006] According to one aspect of the application, a lithium cobaltate positive electrode material is provided, which contains a doping element.

[0007] The doping element contains an aluminum element, a lanthanum element, a copper element and a tungsten element.

[0008] In the lithium cobaltate positive electrode material, the content of the doping element is 0.01-10%.

[0009] Optionally, in the lithium cobaltate positive electrode material, the content of the doping element is any value or a range value between any two values of 0.01%, 0.1%, 0.5%, 1%, 5% and 10%.

[0010] In the lithium cobaltate positive electrode material, the molar ratio of the aluminum element, the lanthanum element, the copper element and the tungsten element is x:x:y:y.

[0011] 0.01% < x < 5%;

[0012] 0.01% < y < 5%;

[0013] According to another aspect of the present application, a preparation method of the above lithium cobaltate positive electrode material is provided, comprising the following steps:

[0014] mixing raw materials containing tricobalt tetroxide, lithium carbonate, an aluminum source, a lanthanum source, a copper source, and a tungsten source, and calcining to obtain the lithium cobaltate positive electrode material.

[0015] The aluminum source is selected from at least one of di-aluminum trioxide, aluminum nitrate, aluminum chloride, and aluminum sulfate;

[0016] The lanthanum source is selected from at least one of di-lanthanum trioxide, lanthanum nitrate, lanthanum chloride, lanthanum sulfate, and lanthanum sulfide;

[0017] The copper source is selected from at least one of copper oxide, copper nitrate, copper chloride, copper sulfate, and lanthanum sulfide;

[0018] The tungsten source is selected from at least one of tungsten oxide, tungsten chloride, sodium tungstate, and tungsten sulfide.

[0019] The molar ratio of the tricobalt tetroxide, lithium carbonate, aluminum source, lanthanum source, copper source, and tungsten source is 1-2x: 1.05-2y: x: x: y: y;

[0020] 0.01% < x < 5%;

[0021] 0.01% < y < 5%;

[0022] The molar amount of the tricobalt tetroxide is calculated based on the molar amount of cobalt element;

[0023] The molar amount of the lithium carbonate is calculated based on the molar amount of lithium element;

[0024] The molar amount of the aluminum source is calculated based on the molar amount of aluminum element;

[0025] The molar amount of the lanthanum source is calculated based on the molar amount of lanthanum element;

[0026] The molar amount of the copper source is calculated based on the molar amount of copper element;

[0027] The molar amount of the tungsten source is calculated based on the molar amount of tungsten element.

[0028] The calcining temperature is 600-1000°C;

[0029] Optionally, the calcining temperature is any value or a range value between any two values of 600°C, 700°C, 800°C, 900°C, and 1000°C.

[0030] The heating rate of the calcination is 5-20℃ / min.

[0031] Optionally, the heating rate of the calcination is any value of 5℃ / min, 10℃ / min, 15℃ / min, 20℃ / min or a range value between any two of them.

[0032] The time of the calcination is 2-6h.

[0033] Optionally, the time of the calcination is any value of 2h, 3h, 4h, 5h, 6h or a range value between any two of them.

[0034] Specifically, an element-doped modified high-voltage fast-charging lithium cobalt oxide cathode material and a preparation method thereof are provided, comprising the following steps:

[0035] S1, preparing a nano cobalt hydroxide powder

[0036] 10-50g of polyvinylpyrrolidone and 1-20g of cobalt nitrate hexahydrate are weighed and dispersed in 0.5-1.0L of deionized water, and an oil bath is heated to 60-100℃.

[0037] 5-30mL of 25% ammonia water is added to the above solution, and the solution is incubated and stirred at a stirring speed of 100-1000rmp for 1-24h.

[0038] The reaction product is centrifuged, ultrasonically dispersed and freeze-dried to obtain a nano cobalt hydroxide powder, and the centrifugal speed is 4000-10000r / min.

[0039] S2, preparing a nano cobalt trioxide tetraoxide powder

[0040] The above cobalt hydroxide powder is placed in a muffle furnace and heated and incubated in an air medium, the heating rate is 5-20℃ / min, the temperature is 200-600℃, and the incubation time is 2-6h. After natural cooling, a nano cobalt trioxide tetraoxide powder is obtained.

[0041] S3, preparing an element-doped lithium cobalt oxide cathode material

[0042] According to the atomic molar ratio of 1-2x:1.05-2y:x:x:y:y, wherein 0.01%<x<5% and 0.01%<y<5%, 10-50g of cobalt trioxide tetraoxide, 1-20g of lithium carbonate, an aluminum source, a lanthanum source, a copper source and a tungsten source are weighed, mixed and ground to obtain a precursor dry material.

[0043] The above precursor dry material is placed in a muffle furnace and heated and incubated in an air medium, the heating rate is 5-20℃ / min, the temperature is 600-1000℃, and the incubation time is 2-6h. After the heating process is completed, the product is taken out and air quenched to obtain an element-doped lithium cobalt oxide cathode material.

[0044] The polyvinylpyrrolidone in S1 is at least one of PVP-K12, PVP-K15, PVP-K17, PVP-K25, PVP-K30, PVP-K60, and PVP-K90.

[0045] The reaction condition in S1 is oil bath heating at 60-100℃ for 1-24h.

[0046] The heat treatment condition in S2 is a temperature rising rate of 2-20℃ / min, a temperature of 200-600℃, and a holding time of 2-6h.

[0047] According to another aspect of the present application, a lithium cobaltate cathode is provided, which contains the lithium cobaltate cathode material prepared by the method described above.

[0048] According to another aspect of the present application, a lithium cobaltate battery is provided, which contains the lithium cobaltate cathode described above.

[0049] Compared with the prior art, the present application has the following beneficial effects:

[0050] 1. The high-voltage fast-charging lithium cobaltate cathode material prepared by the present application is doped with aluminum, lanthanum, copper, and tungsten, and by optimizing the raw materials, doping content, and preparation process, the material phase crystal structure reversibility and surface structure stability at high voltage are improved, and the ion conductivity and electronic conductivity of the material are also improved, thereby realizing the improvement of the high-voltage fast-charging performance and cycle stability of the lithium cobaltate cathode material.

[0051] 2. The preparation method provided by the present application is good in controllability, simple and easy to implement, suitable for large-scale production, and realizes industrialization. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 The scanning electron microscope image of the aluminum / lanthanum / copper / tungsten co-doped lithium cobaltate cathode material prepared in Example 1 of the present application;

[0053] Figure 2 The scanning electron microscope image of the unmodified lithium cobaltate cathode material prepared in Comparative Example 1 of the present application;

[0054] Figure 3 The scanning electron microscope image of the aluminum / lanthanum co-doped lithium cobaltate cathode material prepared in Comparative Example 2 of the present application;

[0055] Figure 4 The X-ray powder diffraction spectrum of the aluminum / lanthanum / copper / tungsten co-doped lithium cobaltate cathode material of Example 1, the unmodified lithium cobaltate cathode material of Comparative Example 1, and the aluminum / lanthanum co-doped lithium cobaltate cathode material of Comparative Example 2 of the present application;

[0056] Figure 5 Rate performance test of lithium ion battery assembled with the lithium cobalt oxide cathode material of Example 1 of the present application, the unmodified lithium cobalt oxide cathode material of Comparative Example 1 and the lithium cobalt oxide cathode material co-doped with aluminum and lanthanum of Comparative Example 2 at a constant temperature of 28℃ in a voltage range of 3.0-4.6V;

[0057] Figure 6 Charge-discharge curves of lithium ion battery assembled with the lithium cobalt oxide cathode material co-doped with aluminum and lanthanum of Comparative Example 1 of the present application at a constant temperature of 28℃ in a voltage range of 3.0-4.6V under different rates;

[0058] Figure 7 Charge-discharge curves of lithium ion battery assembled with the unmodified lithium cobalt oxide cathode material of Comparative Example 1 of the present application at a constant temperature of 28℃ in a voltage range of 3.0-4.6V under different rates;

[0059] Figure 8 Charge-discharge curves of lithium ion battery assembled with the lithium cobalt oxide cathode material co-doped with aluminum and lanthanum of Comparative Example 1 of the present application at a constant temperature of 28℃ in a voltage range of 3.0-4.6V under different rates. DETAILED DESCRIPTION

[0060] The specific embodiments of the present application are described below to facilitate the understanding of the present application for those skilled in the art. It should be understood that the protection scope of the present application is not limited by the following examples, and all materials or technical solutions developed based on the present application are within the protection scope.

[0061] Example 1

[0062] 20g of polyvinylpyrrolidone and 5g of cobalt nitrate hexahydrate were weighed and dispersed in 1.0L of deionized water, and heated to 80℃ in an oil bath. 15mL of 25% ammonia water was added to the above solution, and the solution was incubated and stirred at a speed of 400rmp for 1h. The reaction product was centrifuged, washed, ultrasonically dispersed and freeze-dried to obtain a nano cobalt hydroxide powder.

[0063] The above cobalt hydroxide powder was placed in a muffle furnace and heated in an air medium, with a heating rate of 5℃ / min, a temperature of 450℃ and a holding time of 2h. After natural cooling, a nano cobalt oxide powder was obtained.

[0064] Take 20 g of polyvinylpyrrolidone, 5 g of cobalt nitrate hexahydrate and disperse them in 1.0 L of deionized water, heat the oil bath to 80°C. Add 15 mL of 25% ammonia water to the above solution, incubate and stir, stirring speed is 400 rpm, incubation time is 1 h. Centrifugal washing, ultrasonic dispersion and freeze-drying of the above reaction product, prepared nano-cobalt hydroxide powder. Figure 1 The morphology of the material is shown in FIG. 1. As can be seen from the figure, the material is in a flake structure with a thickness of less than 0.5 microns and a flake diameter of less than 5 microns.

[0065] Example 2

[0066] Take 20 g of polyvinylpyrrolidone, 5 g of cobalt nitrate hexahydrate and disperse them in 1.0 L of deionized water, heat the oil bath to 80°C. Add 15 mL of 25% ammonia water to the above solution, incubate and stir, stirring speed is 400 rpm, incubation time is 1 h. Centrifugal washing, ultrasonic dispersion and freeze-drying of the above reaction product, prepared nano-cobalt hydroxide powder.

[0067] Take the above cobalt hydroxide powder and place it in a muffle furnace, heat and incubate in air medium, the heating rate is 5°C / min, the temperature is 450°C, and the incubation time is 2h. After natural cooling, nano-cobalt oxide powder is obtained.

[0068] Take 20 g of polyvinylpyrrolidone, 5 g of cobalt nitrate hexahydrate and disperse them in 1.0 L of deionized water, heat the oil bath to 80°C. Add 15 mL of 25% ammonia water to the above solution, incubate and stir, stirring speed is 400 rpm, incubation time is 1 h. Centrifugal washing, ultrasonic dispersion and freeze-drying of the above reaction product, prepared nano-cobalt hydroxide powder.

[0069] Example 3

[0070] Take 20 g of polyvinylpyrrolidone, 5 g of cobalt nitrate hexahydrate and disperse them in 1.0 L of deionized water, heat the oil bath to 80°C. Add 15 mL of 25% ammonia water to the above solution, incubate and stir, stirring speed is 400 rpm, incubation time is 1 h. Centrifugal washing, ultrasonic dispersion and freeze-drying of the above reaction product, prepared nano-cobalt hydroxide powder.

[0071] Take the above cobalt hydroxide powder and place it in a muffle furnace, heat and incubate in air medium, the heating rate is 5°C / min, the temperature is 450°C, and the incubation time is 2h. After natural cooling, nano-cobalt oxide powder is obtained.

[0072] The cobalt oxide lithium positive electrode material doped with elements was obtained by taking 20 g of polyvinylpyrrolidone and 5 g of cobalt nitrate hexahydrate, dispersing them in 1.0 L of deionized water, and heating the solution to 80°C in an oil bath. 15 mL of 25% ammonia water was added to the above solution, and the solution was heated and stirred at a speed of 400 rpm for 1 h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain a cobalt hydroxide nano-powder.

[0073] Example 4

[0074] The cobalt oxide lithium positive electrode material doped with elements was obtained by taking 20 g of polyvinylpyrrolidone and 5 g of cobalt nitrate hexahydrate, dispersing them in 1.0 L of deionized water, and heating the solution to 80°C in an oil bath. 15 mL of 25% ammonia water was added to the above solution, and the solution was heated and stirred at a speed of 400 rpm for 1 h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain a cobalt hydroxide nano-powder.

[0075] The cobalt oxide lithium positive electrode material doped with elements was obtained by taking 20 g of polyvinylpyrrolidone and 5 g of cobalt nitrate hexahydrate, dispersing them in 1.0 L of deionized water, and heating the solution to 80°C in an oil bath. 15 mL of 25% ammonia water was added to the above solution, and the solution was heated and stirred at a speed of 400 rpm for 1 h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain a cobalt hydroxide nano-powder.

[0076] The cobalt oxide lithium positive electrode material doped with elements was obtained by taking 20 g of polyvinylpyrrolidone and 5 g of cobalt nitrate hexahydrate, dispersing them in 1.0 L of deionized water, and heating the solution to 80°C in an oil bath. 15 mL of 25% ammonia water was added to the above solution, and the solution was heated and stirred at a speed of 400 rpm for 1 h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain a cobalt hydroxide nano-powder.

[0077] Comparative Example 1

[0078] The cobalt oxide lithium positive electrode material doped with elements was obtained by taking 20 g of polyvinylpyrrolidone and 5 g of cobalt nitrate hexahydrate, dispersing them in 1.0 L of deionized water, and heating the solution to 80°C in an oil bath. 15 mL of 25% ammonia water was added to the above solution, and the solution was heated and stirred at a speed of 400 rpm for 1 h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain a cobalt hydroxide nano-powder.

[0079] The cobalt oxide lithium positive electrode material doped with elements was obtained by taking 20 g of polyvinylpyrrolidone and 5 g of cobalt nitrate hexahydrate, dispersing them in 1.0 L of deionized water, and heating the solution to 80°C in an oil bath. 15 mL of 25% ammonia water was added to the above solution, and the solution was heated and stirred at a speed of 400 rpm for 1 h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain a cobalt hydroxide nano-powder.

[0080] Cobalt tetroxide and lithium carbonate were weighed according to an atomic molar ratio of 1:1.05, mixed, and ground to obtain a dry precursor material. The dry precursor material was placed in a muffle furnace and heated in air at 800℃ for 3 hours at a rate of 5℃ / min. After the heating process was completed, the product was removed and air-quenched to obtain lithium cobalt oxide cathode material. Its morphology is as follows. Figure 2 As shown in the figure, the material has a sheet-like structure with a thickness of less than 1 micrometer and a sheet diameter of less than 5 micrometers.

[0081] Comparative Example 2

[0082] 20g of polyvinylpyrrolidone and 5g of cobalt nitrate hexahydrate were weighed and dispersed in 1.0L of deionized water, and heated to 80℃ in an oil bath. 15mL of 25% ammonia solution was added to the above solution, and the mixture was kept at this temperature and stirred at 400rpm for 1h. The reaction product was centrifuged, washed, ultrasonically dispersed, and freeze-dried to obtain nano-cobalt hydroxide powder.

[0083] The cobalt hydroxide powder was placed in a muffle furnace and heated in air at a rate of 5°C / min to a temperature of 450°C for 2 hours. After natural cooling, nano-cobalt tetroxide powder was obtained.

[0084] According to an atomic molar ratio of 0.99:1.05:0.005:0.005, cobalt tetroxide, lithium carbonate, aluminum oxide, and lanthanum oxide were weighed, mixed, and ground to obtain a dry precursor material. The dry precursor material was placed in a muffle furnace and heated in air at a rate of 5℃ / min to a temperature of 800℃ for 3 hours. After the heating process was completed, the product was removed and air-quenched to obtain an aluminum / lanthanum co-doped lithium cobalt oxide cathode material. Its morphology is as follows. Figure 3 As shown in the figure, the material has a sheet-like structure with a smooth surface, a thickness of 1-2 micrometers, and a sheet diameter of less than 5 micrometers.

[0085] Figure 4 The images show the X-ray powder diffraction patterns of the aluminum / lanthanum / copper / tungsten co-doped lithium cobalt oxide cathode material of Example 1, the unmodified lithium cobalt oxide cathode material of Comparative Example 1, and the aluminum / lanthanum co-doped lithium cobalt oxide cathode material of Comparative Example 2. As can be seen from the images, the aluminum / lanthanum / copper / tungsten co-doped lithium cobalt oxide cathode material retains the crystal structure of the lithium cobalt oxide cathode material.

[0086] The evaluation method for the electrochemical performance of lithium cobalt oxide cathode materials in this application is as follows:

[0087] The lithium cobalt oxide positive electrode material, conductive carbon black and polyvinylidene fluoride binder were weighed in a mass ratio of 8:1:1, mixed and ground, then an appropriate amount of N-methyl pyrrolidone was added and grinding was continued until a uniform slurry was formed. The slurry was uniformly scraped on a carbon-coated aluminum foil and transferred to a vacuum oven at 100°C. After complete drying, the aluminum foil was cut into positive electrode pieces with a diameter of 12 mm for standby. A CR2016 type button cell was assembled in an argon atmosphere glove box with a lithium metal sheet as the negative electrode, a Celgard2400 film as the separator, and LB-372 high-voltage electrolyte provided by the Multo Reagent Co., Ltd. The battery was placed in a constant temperature oven at 28°C and subjected to rate and cycle charge-discharge tests within a voltage window of 3.0-4.6V.

[0088] wherein Comparative Example 1 is an unmodified lithium cobalt oxide positive electrode material, Comparative Example 2 is an aluminum / lanthanum co-doped lithium cobalt oxide positive electrode material, and Example 1 is an aluminum / lanthanum / copper / tungsten co-doped lithium cobalt oxide positive electrode material, the rate performance test is as shown in Figure 5 , and the corresponding different rate charge-discharge curves are as shown in Figures 6-8 . At a rate of 1C, the reversible specific capacity of the aluminum / lanthanum / copper / tungsten co-doped lithium cobalt oxide positive electrode material is 219.4 mAh / g. At a rate of 50C, the reversible specific capacity of the aluminum / lanthanum / copper / tungsten co-doped lithium cobalt oxide positive electrode material is 77.4 mAh / g, and the capacity retention rate is 35.3%. As a comparison, the reversible specific capacity of the aluminum / lanthanum co-doped lithium cobalt oxide positive electrode material is 217.4 mAh / g at 1C and 41.4 mAh / g at 50C, and the corresponding capacity retention rate is only 19.0%. The unmodified lithium cobalt oxide can only be tested to 10C, which is significantly lower than the aluminum / lanthanum / copper / tungsten co-doped lithium cobalt oxide positive electrode material. The above results show that multi-element doping of the lithium cobalt oxide positive electrode material can effectively improve the rate performance and reversible specific capacity of the material.

[0089] The present application first prepares nano cobalt hydroxide powder by a liquid phase method, and then obtains nano cobaltosic oxide powder after high temperature annealing. On this basis, the nano cobaltosic oxide powder, lithium carbonate and doping elements are mixed uniformly according to a certain atomic ratio and subjected to high temperature annealing treatment. The present application greatly improves the bulk structure stability of the lithium cobalt oxide positive electrode material, suppresses the side reaction at the interface between the particles and the electrolyte at high voltage, and greatly improves the ionic conductivity and electronic conductivity of the lithium cobalt oxide positive electrode material. Thus, the high-voltage fast charging performance and high-voltage cycle stability of the lithium cobalt oxide positive electrode material are improved. The preparation method provided by the present application has good controllability, is simple and easy to implement, is suitable for large-scale production, and realizes industrialization.

[0090] The above examples are only the preferred modes of the present application, and it should be understood that, for those skilled in the art, some improvements and refinements can be made without departing from the basic principles or characteristics of the present application, and the present application can be implemented in other specific forms. Therefore, the examples should be regarded as exemplary rather than limiting, and no example or drawing of the present application should be equated with the limitation of the claims involved. The scope of the present application is defined by the appended claims rather than the above description, and all changes falling within the meaning and scope of the equivalent elements of the claims should be included. It should be clear that the description is only for clear expression of the content of the application, and those skilled in the art should regard the description as a whole, and the technical solutions in each example can also be properly arranged and combined to form other implementation manners that those skilled in the art can understand.

Claims

1. A lithium cobalt oxide cathode material, characterized in that, The lithium cobalt oxide cathode material contains doping elements; The doping elements include aluminum, lanthanum, copper, and tungsten. In the lithium cobalt oxide cathode material, the content of the doping element is 0.01-10%; In the lithium cobalt oxide cathode material, the molar ratio of aluminum, lanthanum, copper and tungsten is x:x:y:y; Of which, 0.01% <x<5%; 0.01％<y<5％。 2. A method for preparing the lithium cobalt oxide cathode material according to claim 1, characterized in that, Includes the following steps: The raw materials containing cobalt tetroxide, lithium carbonate, aluminum source, lanthanum source, copper source and tungsten source are mixed and calcined to obtain the lithium cobalt oxide cathode material.

3. The preparation method according to claim 2, characterized in that, The aluminum source is selected from at least one of aluminum oxide, aluminum nitrate, aluminum chloride, and aluminum sulfate; The lanthanum source is selected from at least one of lanthanum trioxide, lanthanum nitrate, lanthanum chloride, lanthanum sulfate, and lanthanum sulfide; The copper source is selected from at least one of copper oxide, copper nitrate, copper chloride, copper sulfate, and lanthanum sulfide; The tungsten source is selected from at least one of tungsten oxide, tungsten chloride, sodium tungstate, and tungsten sulfide.

4. The preparation method according to claim 2, characterized in that, The molar ratio of cobalt tetroxide, lithium carbonate, aluminum source, lanthanum source, copper source, and tungsten source is 1-2x:1.05-2y:x:x:y:y; Of which, 0.01% <x<5%; 0.01％<y<5％； The molar amount of cobalt tetroxide is expressed in terms of the molar amount of cobalt element; The molar amount of lithium carbonate is expressed as the molar amount of lithium element. The molar amount of the aluminum source is expressed in terms of the molar amount of aluminum element; The molar amount of the lanthanum source is expressed in terms of the molar amount of lanthanum element; The molar amount of the copper source is expressed in terms of the molar amount of copper element; The molar amount of the tungsten source is expressed in terms of the molar amount of tungsten element.

5. The preparation method according to claim 2, characterized in that, The roasting temperature is 600–1000℃; The heating rate for calcination is 5–20 °C / min; The roasting time is 2 to 6 hours.

6. A lithium cobalt oxide cathode, characterized in that, The lithium cobalt oxide cathode contains the lithium cobalt oxide cathode material according to claim 1 or the lithium cobalt oxide cathode material prepared by the preparation method according to any one of claims 2 to 5.

7. A lithium cobalt oxide battery, characterized in that, The lithium cobalt oxide battery contains the lithium cobalt oxide positive electrode as described in claim 6.

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