CN115411247A - Lithium battery positive electrode material and preparation method thereof - Google Patents

Lithium battery positive electrode material and preparation method thereof Download PDF

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CN115411247A
CN115411247A CN202211069547.8A CN202211069547A CN115411247A CN 115411247 A CN115411247 A CN 115411247A CN 202211069547 A CN202211069547 A CN 202211069547A CN 115411247 A CN115411247 A CN 115411247A
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lithium
cobalt
nickel
lithium battery
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尹群君
万晨程
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Geo Huanpeng Technology Yangzhou Co ltd
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Abstract

The invention provides a preparation method of a lithium battery anode material, which comprises the following steps: s1, preparing bulk phase doped porous nickel cobalt lithium manganate; s2, primary modification; and S3, carrying out secondary modification on the graphene. The invention also discloses a lithium battery anode material prepared by the preparation method of the lithium battery anode material. The lithium battery anode material disclosed by the invention has the advantages of good cycle performance, high capacity retention rate, good structural stability and sufficient lithium ion de-intercalation rate and mobility.

Description

Lithium battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of new energy lithium battery materials, in particular to a lithium battery positive electrode material and a preparation method thereof.
Background
In recent years, with the rapid spread of portable electronic products, lithium batteries as power sources have been rapidly developed. The lithium battery is a clean energy device with the advantages of high energy density, long cycle life, low self-discharge rate, no memory effect, stable discharge voltage, quick charge and discharge, greenness, no pollution and the like. The lithium ion battery is widely applied to a plurality of energy storage batteries and power batteries, a new energy automobile taking a lithium battery as a core component is brought into the strategic plan of the country, the application field is still continuously expanded, and the lithium ion battery is a main choice of sustainable power batteries and is known as an ideal power supply in the 21 st century.
The positive electrode material is one of the key components of the lithium battery, and the performance of the positive electrode material directly influences the battery capacity and the cycle service life of the lithium battery. At present, the commercialized lithium battery positive electrode materials comprise lithium cobaltate, lithium manganate, lithium iron phosphate and the like, wherein the lithium cobaltate has the advantages of high capacity, high filling property and the like, but the cobalt is few in reserve as a strategic resource, high in price and poor in safety performance; the lithium iron phosphate has the advantages of good safety, long cycle life and the like, but the lithium iron phosphate has poor filling performance and lower volumetric specific energy; the lithium manganate has the advantages of high voltage, low price, environmental friendliness, high safety performance and the like, but a lithium ion battery taking the lithium manganate as a positive electrode has the defects of poor high-temperature cycle performance and low filling performance, and due to the Jahn-Teller effect, a manganese oxide octahedral structure of a lithium manganate crystal is unstable in the charge-discharge cycle process, and the dissolution of manganese causes the rapid capacity attenuation and poor cycle stability of the battery. When the temperature rises, the performance of the battery may be further deteriorated. This limits the technological application of lithium manganate in large current and wide temperature range battery.
In order to solve the problems, the chinese patent application No. 201410199548.3 discloses a method for synthesizing a lithium iron silicate/graphene composite positive electrode material, which comprises the steps of pickling, washing, filtering and drying rice hulls to obtain the rice hulls with alkali metal oxide impurities removed; carrying out low-temperature oxidation on the rice hulls from which the alkali metal oxide impurities are removed under an aerobic condition to obtain carbon-containing rice hull ash; adding a lithium source into the carbon-containing rice hull ash and uniformly mixing to obtain a mixture; annealing and activating the mixture at 600-900 ℃ for 1-12 h to obtain Li 2 SiO 3 A graphene composite material; to Li 2 SiO 3 Adding an iron source into the graphene composite material, and then wet-grinding the material; roasting the wet-milled material at 500-800 ℃ for 1-20 h in an inert atmosphere, cooling to room temperature, washing with deionized water, and drying to obtain the lithium iron silicate/graphene composite anode material. Although the proposal utilizes the graphene material to dope the lithium iron silicate, the method can be used for doping the lithium iron silicate to a certain degreeThe electronic conductivity of the lithium iron silicate cathode material is improved, but the problem of structural collapse of the graphene-doped lithium iron silicate cathode material during deep lithium ion deintercalation is not fundamentally solved, and the improvement on the cycle stability of the lithium ion battery is limited.
Therefore, the lithium battery positive electrode material which is good in cycle performance, high in capacity retention rate, good in structural stability and sufficient in lithium ion deintercalation rate and mobility and the preparation method thereof are developed, meet market requirements, have high market value and application prospect, and have very important significance in promoting development of new energy lithium battery technology.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a lithium battery positive electrode material with good cycle performance, high capacity retention rate, good structural stability, and sufficient lithium ion deintercalation rate and mobility, and a preparation method thereof, and to solve the technical problems of low capacity retention rate, insufficient cycle performance, and short service life of the conventional lithium battery positive electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the lithium battery positive electrode material is characterized by comprising the following steps of:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 0.5-1 hour, slowly adding sodium acetate, then stirring vigorously for 1.5-3.5 hours, then placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 15-20 hours at 195-220 ℃, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively, drying in vacuum, then presintering in a muffle furnace at 350-450 ℃ for 2-4 hours at constant temperature, cooling to room temperature, grinding, then placing the mixture into a muffle furnace at 800-900 ℃ for calcining for 18-24 hours, cooling to room temperature, and grinding through a 100-300-mesh sieve to obtain bulk phase doped porous lithium manganate nickel cobalt;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out water bath reaction at 78-86 ℃ until the solution is in a gel state, then sequentially drying and grinding the gel state, calcining the gel state in a muffle furnace at 770-880 ℃ for 4-7h, cooling the gel state, taking out the gel state, grinding the gel state, and sieving the gel state with a 150-300-mesh sieve to obtain primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), ultrasonically dispersing for 12-20 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially filtering, drying and thermally reducing to obtain the lithium battery cathode material.
Preferably, the molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water and sodium acetate in step S1 is (0.1-0.03): 0.01-0.01: (10-20): 15-25): 2-4).
Preferably, the lithium source is at least one of lithium nitrate and lithium acetate; the cobalt source is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the nickel source is at least one of nickel citrate, nickel nitrate, nickel chloride and nickel acetate; the gallium source is at least one of gallium nitrate and gallium chloride; the antimony source is at least one of antimony nitrate and antimony acetate; the tellurium source is sodium tellurate.
Preferably, in the step S2, the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, a selenium source, a rare earth source and a zinc source is 1 (18-25): (0.5-0.8): 0.005: 0.02.
Preferably, the selenium source is sodium selenate; the rare earth source is at least one of gadolinium nitrate and lanthanum chloride; the zinc source is at least one of zinc acetate and zinc chloride.
Preferably, the mass ratio of the graphene oxide, the water and the primary modified bulk phase doped porous nickel cobalt lithium manganate in the step S3 is 0.2 (100-200) to 0.8-1.2.
Preferably, the thermal reduction comprises heating to 850-950 ℃ at a rate of 8-13 ℃ per minute under nitrogen atmosphere for 1-3 hours, and then stopping heating and naturally cooling to room temperature.
The invention also aims to provide the lithium battery cathode material prepared by the preparation method of the lithium battery cathode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the lithium battery cathode material disclosed by the invention can be realized by adopting conventional equipment, has the advantages of low capital investment, simple process, convenience in operation, high preparation efficiency and yield and suitability for large-scale production, and can better exert a synergistic effect on each component through reasonable selection of raw materials, proportion and preparation process parameters, so that the cycle performance and specific capacity of the cathode material are improved. The modification effect can be improved by using a mode of reducing graphene oxide in the preparation process, and the outer layer can be uniformly modified through the interaction between active groups on the surface of the graphene oxide and active hydroxyl groups on the surface of an internal material, so that the cycle performance is better improved.
(2) The lithium battery anode material disclosed by the invention adopts secondary modification, and can effectively isolate electrolyte from an internal anode active substance, thereby improving the stability of the anode material, improving the use safety and prolonging the service life; the outer layer is modified by graphene with good conductivity, and the electrochemical performance of the anode can be further improved. The internal porous structure with the surface sequentially provided with the primary modified layer and the compact modified structure on the surface of the graphene secondary modified layer is adopted, so that the de-intercalation of lithium ions is facilitated, and the cycle performance of the material is improved.
(3) According to the lithium battery anode material disclosed by the invention, the porous nickel cobalt lithium manganate is doped in the internal bulk phase, and is simultaneously introduced with gallium, antimony and tellurium for substitution for the first time, so that the valence states of manganese and nickel in the anode material are reduced, the crystal structure is stabilized, the cycle performance of the material is improved, and the prepared anode material has higher specific capacity and conductivity and longer cycle service life. By introducing selenium, rare earth and zinc on the surface, the stability and the conductivity can be improved more remarkably, the lithium ions can be better embedded and separated, and the safety performance and the cycling stability of the material are improved.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following provides a detailed description of the product of the present invention with reference to the examples.
The thermal reduction in each embodiment of the invention is specifically as follows: and (3) placing the dried crude product in a quartz cup, placing the quartz cup in a reaction chamber of an industrial microwave oven, vacuumizing, introducing nitrogen, then opening an air outlet valve, starting microwave under the protection of nitrogen (2000W, 60s), stopping microwave, cooling and taking out. The graphene oxide is hexa-structured LG-1401 graphene oxide, the C/O of the graphene oxide is 1.58 before reduction, and the C/O is increased to 13.5 after reduction.
Example 1
A preparation method of a lithium battery positive electrode material comprises the following steps:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 0.5 hour, then slowly adding sodium acetate, then violently stirring for 1.5 hours, then placing the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 15 hours at 195 ℃, cooling to room temperature, sequentially washing for 3 times with deionized water and absolute ethyl alcohol, drying to constant weight at 105 ℃ in a vacuum drying oven, then presintering for 2 hours at constant temperature in a 350 ℃ muffle furnace, cooling to room temperature, grinding, then placing the mixture into a 800 ℃ muffle furnace for calcining for 18 hours, cooling to room temperature, and grinding and sieving with a 100-mesh sieve to obtain bulk phase-doped porous nickel cobalt lithium manganate; the chemical formula of the bulk phase doped porous nickel cobalt lithium manganate is LiNi 0.8 Co 0.1 Mn 0.1 Ga 0.01 Sb 0.02 Te 0.01 O 2.013 (ii) a The material is a porous spherical structure, has an average diameter of 200nm, and has a very large number of small pores on the surface;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out bath reaction at 78 ℃ until the solution is in a gel state, then sequentially drying and grinding the gel solution, calcining the gel solution in a muffle furnace at 770 ℃ for 4 hours, cooling the gel solution, taking out the gel solution, grinding the gel solution, and sieving the gel solution with a 150-mesh sieve to obtain primary modified bulk phase doped porous nickel cobalt lithium manganate; the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, a selenium source, a rare earth source and a zinc source is (1) to (0.005); the selenium source is sodium selenate; the rare earth source is gadolinium nitrate; the zinc source is zinc acetate; a Gd-Se-Zn-O layer is formed on the surface of the primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), ultrasonically dispersing for 12 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially filtering, drying and thermally reducing to obtain the lithium battery cathode material.
The molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water, sodium acetate in step S1 is 1; the lithium source is lithium nitrate; the cobalt source is cobalt sulfate; the nickel source is nickel citrate; the gallium source is gallium nitrate; the antimony source is antimony nitrate; the tellurium source is sodium tellurate.
In the step S3, the mass ratio of the graphene oxide to the water to the primary modified bulk phase doped porous nickel cobalt lithium manganate is 0.2.
The thermal reduction consisted of heating to 850 ℃ at a rate of 8 ℃ per minute under nitrogen atmosphere for 1 hour, followed by stopping the heating and natural cooling to room temperature.
The lithium battery positive electrode material is prepared by the preparation method of the lithium battery positive electrode material.
Example 2
A preparation method of a lithium battery positive electrode material comprises the following steps:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 0.6 hour, slowly adding sodium acetate, then stirring vigorously for 2 hours, then placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 16 hours at 200 ℃, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol, carrying out vacuum drying treatment, then presintering for 2.5 hours at constant temperature in a muffle furnace at 370 ℃, cooling to room temperature, grinding, then placing the mixture into a muffle furnace at 830 ℃ for calcining for 20 hours, cooling to room temperature, grinding the mixture through a 150-mesh sieve to obtain bulk phase doped porous nickel cobalt;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out bath reaction at 80 ℃ until the solution is gelatinous, then sequentially drying and grinding the solution, calcining the solution in a muffle furnace at 790 ℃ for 5 hours, cooling the solution, taking out the product, grinding the product and sieving the product with a 180-mesh sieve to obtain primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), ultrasonically dispersing for 15 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially filtering, drying and thermally reducing to obtain the lithium battery cathode material.
In step S1, the molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water, sodium acetate is 1; the lithium source is lithium acetate; the cobalt source is cobalt nitrate; the nickel source is nickel nitrate; the gallium source is gallium chloride; the antimony source is antimony acetate; the tellurium source is sodium tellurate.
In the step S2, the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, a selenium source, a rare earth source and a zinc source is 1.6; the selenium source is sodium selenate; the rare earth source is lanthanum chloride; the zinc source is zinc chloride.
In the step S3, the mass ratio of the graphene oxide to the water to the primary modified bulk phase doped porous nickel cobalt lithium manganate is 0.2.
The thermal reduction consisted of raising the temperature to 890 ℃ at a rate of 10 ℃ per minute under a nitrogen atmosphere for 1.5 hours, followed by discontinuing heating and natural cooling to room temperature.
The lithium battery positive electrode material is prepared by the preparation method of the lithium battery positive electrode material.
Example 3
A preparation method of a lithium battery positive electrode material comprises the following steps:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 0.8 hour, slowly adding sodium acetate, then stirring vigorously for 2.5 hours, then placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 18 hours at 205 ℃, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol, carrying out vacuum drying treatment, then presintering for 3 hours at constant temperature in a 400 ℃ muffle furnace, cooling to room temperature, grinding, then placing the mixture into a 850 ℃ muffle furnace for calcining for 21 hours, cooling to room temperature, and grinding through a 200-mesh sieve to obtain bulk phase doped porous nickel cobalt;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out bath reaction at 82 ℃ until the solution is gelatinous, then sequentially drying and grinding the solution, calcining the solution in a muffle furnace at 820 ℃ for 5.5 hours, cooling the solution, taking out the product, grinding the product, and sieving the product with a 220-mesh sieve to obtain a primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), performing ultrasonic dispersion for 15 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially performing filtration, drying and thermal reduction to obtain the lithium battery cathode material.
In step S1, the molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water, sodium acetate is 1; the lithium source is lithium nitrate; the cobalt source is cobalt chloride; the nickel source is nickel chloride; the gallium source is gallium nitrate; the antimony source is antimony nitrate; the tellurium source is sodium tellurate.
In the step S2, the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, a selenium source, a rare earth source and a zinc source is (1.65); the selenium source is sodium selenate; the rare earth source is gadolinium nitrate; the zinc source is zinc acetate.
In the step S3, the mass ratio of the graphene oxide to the water to the primary modified phase doped porous nickel cobalt lithium manganate is 0.2.
The thermal reduction consisted of raising the temperature to 900 ℃ at a rate of 11 ℃ per minute under a nitrogen atmosphere for 2 hours, followed by stopping the heating and natural cooling to room temperature.
The lithium battery positive electrode material prepared by the preparation method of the lithium battery positive electrode material is provided.
Example 4
A preparation method of a lithium battery positive electrode material comprises the following steps:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 0.9 hour, slowly adding sodium acetate, then stirring vigorously for 3 hours, then placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 19 hours at 215 ℃, cooling to room temperature, respectively washing with deionized water and absolute ethyl alcohol, carrying out vacuum drying treatment, then presintering for 3.5 hours at constant temperature in a muffle furnace at 440 ℃, cooling to room temperature, grinding, then placing the mixture into a muffle furnace at 880 ℃ for calcining for 22 hours, cooling to room temperature, grinding the mixture through a 250-mesh sieve to obtain bulk phase doped porous nickel cobalt;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out bath reaction at 84 ℃ until the solution is gelatinous, then sequentially drying and grinding the solution, calcining the solution in a muffle furnace at 850 ℃ for 6.5 hours, cooling the solution, taking out the product, grinding the product, and screening the product through a 280-mesh sieve to obtain a primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), performing ultrasonic dispersion for 18 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially performing filtration, drying and thermal reduction to obtain the lithium battery cathode material.
In step S1, the molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water, sodium acetate is 1; the lithium source is a mixture formed by mixing lithium nitrate and lithium acetate according to the mass ratio of 3; the cobalt source is a mixture formed by mixing cobalt sulfate, cobalt nitrate and cobalt chloride according to a mass ratio of 1; the nickel source is a mixture formed by mixing nickel citrate, nickel nitrate, nickel chloride and nickel acetate according to a mass ratio of 1; the gallium source is a mixture formed by mixing gallium nitrate and gallium chloride according to the mass ratio of 3; the antimony source is a mixture formed by mixing antimony nitrate and antimony acetate according to a mass ratio of 1; the tellurium source is sodium tellurate.
In the step S2, the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, a selenium source, a rare earth source and a zinc source is 1; the selenium source is sodium selenate; the rare earth source is a mixture formed by mixing gadolinium nitrate and lanthanum chloride according to the mass ratio of 3; the zinc source is a mixture formed by mixing zinc acetate and zinc chloride according to the mass ratio of 1.
In the step S3, the mass ratio of the graphene oxide to the water to the primary modified bulk phase doped porous nickel cobalt lithium manganate is 0.2.
The thermal reduction consisted of raising the temperature to 930 ℃ at a rate of 12 ℃ per minute under a nitrogen atmosphere for 2.5 hours, followed by stopping the heating and natural cooling to room temperature.
The lithium battery positive electrode material prepared by the preparation method of the lithium battery positive electrode material is provided.
Example 5
A preparation method of a lithium battery positive electrode material comprises the following steps:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 1 hour, then slowly adding sodium acetate, stirring vigorously for 3.5 hours, then placing into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 20 hours at 220 ℃, cooling to room temperature, then washing with deionized water and absolute ethyl alcohol respectively, drying in vacuum, presintering for 4 hours at constant temperature in a 450 ℃ muffle furnace, cooling to room temperature, grinding, then placing into a 900 ℃ muffle furnace for calcining for 24 hours, cooling to room temperature, grinding and sieving with a 300-mesh sieve to obtain bulk phase doped porous nickel cobalt lithium manganate;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out bath reaction at 86 ℃ until the solution is in a gel state, drying and grinding the gel state, calcining the gel state in a muffle furnace at 880 ℃ for 7 hours, cooling the gel state, taking out the gel state, grinding the gel state, and sieving the gel state with a 300-mesh sieve to obtain a primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), performing ultrasonic dispersion for 20 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially performing filtration, drying and thermal reduction to obtain the lithium battery cathode material.
In step S1, the molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water, sodium acetate is 1; the lithium source is lithium acetate; the cobalt source is cobalt sulfate; the nickel source is nickel acetate; the gallium source is gallium nitrate; the antimony source is antimony acetate; the tellurium source is sodium tellurate.
In the step S2, the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, a selenium source, a rare earth source and a zinc source is (1.8); the selenium source is sodium selenate; the rare earth source is lanthanum chloride; the zinc source is zinc chloride.
In the step S3, the mass ratio of the graphene oxide to the water to the primary modified bulk phase doped porous nickel cobalt lithium manganate is 0.2.
The thermal reduction consisted of raising the temperature to 950 ℃ at a rate of 13 ℃ per minute under a nitrogen atmosphere for 3 hours, followed by stopping the heating and natural cooling to room temperature.
The lithium battery positive electrode material is prepared by the preparation method of the lithium battery positive electrode material.
Comparative example 1
The formula and preparation method of the lithium battery positive electrode material are basically the same as those of example 1, except that an antimony source is used for replacing a gallium source.
Comparative example 2
The formula and the preparation method of the lithium battery positive electrode material are basically the same as those of the embodiment 1, except that the step S3 and the secondary graphene modification are not carried out.
Comparative example 3
The formula and the preparation method of the lithium battery positive electrode material are basically the same as those of the embodiment 1, except that the step S2 is not adopted and the modification is carried out for one time; and replacing the primary modified bulk phase doped porous nickel cobalt lithium manganate in the step S3 with the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1.
In order to further illustrate the unexpected positive technical effects obtained by the products of the embodiments of the invention, the lithium battery positive electrode materials prepared by the embodiments are subjected to related performance tests, and the test method comprises the following steps: the lithium battery positive electrode materials prepared in the examples, super P (Super P Li lithium battery conductive agent made of Super dense carbon black in Switzerland), PVDF (PVDF in Suwei USA)
Figure BDA0003829183350000081
5130 ) were mixed in a mass ratio of 8. Drying in a vacuum drying oven at 120 ℃ for 12h, and cutting the aluminum foil into round pieces with the diameter of 14mm to obtain battery pole pieces; the electrode sheet was punched into a round shape, and assembled into a CR2032 button cell in an argon glove box using a Celgard 2400 type separator, an electrolyte of 1M lipff 6/EC + DEC (volume ratio 1). The charge-discharge cycle performance of the button cell is tested by adopting a LANDCT2001 battery test system, the test temperature is 25 ℃,the voltage window is 3.0-4.3V, and the charge and discharge multiplying power is 1C. The test results are shown in Table 1.
As can be seen from table 1, the lithium battery positive electrode material disclosed in the embodiment of the present invention has more excellent cycle performance and electrochemical performance compared to the product disclosed in the prior art (e.g., the product disclosed in CN 113036110B).
TABLE 1
Item 1C first discharge gram capacity Capacity retention rate after 100 times of cyclic charge and discharge
Unit of mAh/g ％
Example 1 188.5 97.8
Example 2 190.2 98.2
Example 3 191.0 98.4
Example 4 192.1 98.6
Example 5 192.6 99.0
Comparative example 1 186.2 96.9
Comparative example 2 185.9 95.7
Comparative example 3 181.6 93.4
The foregoing is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the invention in any way; those of ordinary skill in the art can readily practice the present invention as described herein; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any equivalent changes, modifications and evolutions made to the above embodiments according to the substantial technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (8)

1. The preparation method of the lithium battery positive electrode material is characterized by comprising the following steps of:
step S1, preparing bulk phase doped porous nickel cobalt lithium manganate: adding a lithium source, a cobalt source, a manganese source, a nickel source, a gallium source, an antimony source, a tellurium source and ethylene glycol into water, stirring for 0.5-1 hour, slowly adding sodium acetate, then stirring vigorously for 1.5-3.5 hours, then placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 15-20 hours at 195-220 ℃, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively, drying in vacuum, then presintering in a muffle furnace at 350-450 ℃ for 2-4 hours at constant temperature, cooling to room temperature, grinding, then placing the mixture into a muffle furnace at 800-900 ℃ for calcining for 18-24 hours, cooling to room temperature, and grinding through a 100-300-mesh sieve to obtain bulk phase doped porous lithium manganate nickel cobalt;
step S2, primary modification: dispersing the bulk phase doped porous nickel cobalt lithium manganate prepared in the step S1 in water, adding citric acid, a selenium source, a rare earth source and a zinc source into the water, carrying out water bath reaction at 78-86 ℃ until the solution is in a gel state, then sequentially drying and grinding the gel state, calcining the gel state in a muffle furnace at 770-880 ℃ for 4-7h, cooling the gel state, taking out the gel state, grinding the gel state, and sieving the gel state with a 150-300-mesh sieve to obtain primary modified bulk phase doped porous nickel cobalt lithium manganate;
s3, carrying out secondary modification on graphene: and (3) dispersing graphene oxide in water, adding the primary modified bulk phase doped porous nickel cobalt lithium manganate prepared in the step (S2), ultrasonically dispersing for 12-20 minutes by using an ultrasonic device to obtain a suspension with a uniform system, and then sequentially filtering, drying and thermally reducing to obtain the lithium battery cathode material.
2. The method for preparing the positive electrode material of the lithium battery as claimed in claim 1, wherein the molar ratio of lithium in the lithium source, cobalt in the cobalt source, manganese in the manganese source, nickel in the nickel source, gallium in the gallium source, antimony in the antimony source, tellurium in the tellurium source, ethylene glycol, water and sodium acetate in step S1 is 1.
3. The method of claim 1, wherein the lithium source is at least one of lithium nitrate and lithium acetate; the cobalt source is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the nickel source is at least one of nickel citrate, nickel nitrate, nickel chloride and nickel acetate; the gallium source is at least one of gallium nitrate and gallium chloride; the antimony source is at least one of antimony nitrate and antimony acetate; the tellurium source is sodium tellurate.
4. The method for preparing the positive electrode material of the lithium battery as claimed in claim 1, wherein the mass ratio of the bulk phase doped porous nickel cobalt lithium manganate, water, citric acid, selenium source, rare earth source and zinc source in the step S2 is 1 (18-25): 0.5-0.8): 0.005: 0.01.
5. The method of claim 1, wherein the selenium source is sodium selenate; the rare earth source is at least one of gadolinium nitrate and lanthanum chloride; the zinc source is at least one of zinc acetate and zinc chloride.
6. The method for preparing the positive electrode material of the lithium battery as claimed in claim 1, wherein the mass ratio of the graphene oxide, the water and the primary modified bulk phase doped porous nickel cobalt lithium manganate in the step S3 is 0.2 (100-200) to (0.8-1.2).
7. The method of claim 1, wherein the thermal reduction comprises heating to 850-950 ℃ at a rate of 8-13 ℃ per minute in a nitrogen atmosphere for 1-3 hours, and then stopping the heating and naturally cooling to room temperature.
8. A lithium battery positive electrode material prepared by the method for preparing a lithium battery positive electrode material according to any one of claims 1 to 7.
CN202211069547.8A 2022-09-02 2022-09-02 Lithium battery positive electrode material and preparation method thereof Withdrawn CN115411247A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117619859A (en) * 2023-11-28 2024-03-01 吉奥环朋科技(扬州)有限公司 Recycling recovery method of waste lithium ion power battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117619859A (en) * 2023-11-28 2024-03-01 吉奥环朋科技(扬州)有限公司 Recycling recovery method of waste lithium ion power battery
CN117619859B (en) * 2023-11-28 2024-05-24 吉奥环朋科技(扬州)有限公司 Recycling recovery method of waste lithium ion power battery

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