CN107623122B - Preparation method of spherical core-shell structure lithium iron phosphate cathode material for lithium battery - Google Patents
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Abstract
The invention relates to a lithium ion battery anode material, in particular to a preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery, belonging to the technical field of power batteries. A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps: (1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method; (2) preparing lithium iron phosphate microspheres with core-shell structures; (3) and sintering the obtained lithium iron phosphate microsphere powder with the core-shell structure in an inert atmosphere. The spherical core-shell structure lithium iron phosphate cathode material prepared by the method has the advantages of good conductivity, high tap density, uniform particle size, high charging rate, strong cruising ability and good cycle performance; the method has the advantages of simple process, low cost, high efficiency, safety and environmental protection, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a lithium ion battery anode material, in particular to a preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery, belonging to the technical field of power batteries.
Background
The 21 st century people face two serious problems of energy crisis and environmental pollution, so the development and research of clean and renewable new energy sources have profound significance. Wherein, various automobiles account for about 40 percent of petroleum consumption, and 42 percent of global atmospheric pollution is from the emission of traffic vehicles. In 6.1.2010, the four committees such as national development and improvement committee and the like jointly issue a notice about developing a private new energy automobile subsidy trial, and determine 5 cities in Shanghai, Changchun, Shenzhen, Hangzhou and Hefei to start private new energy automobile subsidy trial. In 2013, 7, 12 months and a state department routine meeting, the government official vehicles and buses are proposed to be popularized and used for new energy vehicles, and the support of the central government for the new energy vehicles is emphasized again. The world places great importance on the development of electric vehicles, and the 863 plan of China also ranks the development of electric vehicles as an important development direction. The research on the power battery as the vehicle power becomes the main bottleneck of the development of the power automobile. Currently, the main candidates for power batteries are nickel-metal hydride batteries, lithium ion batteries and fuel cells. Based on the consideration of cost performance, the lithium ion battery has great advantages. Compared with the traditional battery, the lithium ion battery as the energy storage material has the advantages of high voltage, large specific capacity, long cycle life and good safety performance, is widely applied to the fields of portable electronic equipment, electric automobiles, aerospace, military engineering and the like, and has wide application prospect and great economic benefit.
As a green and environment-friendly high-performance secondary battery, the lithium ion battery has the advantages of high energy density, high average output voltage, high output power, small self-discharge, high charging and discharging efficiency, no memory effect and the like, and is increasingly applied to various portable electronic products, communication tools, electric vehicles and hybrid electric vehicles. Since the commercialization of lithium ion batteries, research on positive electrode materials has been the focus of research in this field. The anode material of the lithium ion battery mainly comprises lithium cobaltate, lithium manganate, lithium nickelate, ternary material, lithium iron phosphate and the like. The lithium iron phosphate is environment-friendly and cheap, and the covalent bond of the phosphate radical can provide good chemical stability and safety for the lithium iron phosphate, so that the lithium iron phosphate becomes a lithium ion battery anode material with good application prospect. Lithium iron phosphate has a theoretical capacity of 170mAh/g, and in its structure, Fe3+/Fe2+ has a voltage of 3.4V with respect to metallic lithium, which is not so high as to decompose the electrolyte, nor so low as to reduce the power density. However, lithium iron phosphate also has the disadvantage that its low electron conductivity and slow one-dimensional lithium ion diffusion hinder its high rate charging and discharging. At present, a great deal of work is done to improve the conductivity, for example, to coat a layer of conductive material such as carbon on the surface of lithium iron phosphate particles, or to control the grain size of lithium iron phosphate to be in the nanometer level but often the tap density of the nanometer material is lower. At present, in a plurality of technical methods for preparing lithium iron phosphate, the preparation of spherical lithium iron phosphate materials is an important direction. The foreign literature reports that a lithium iron phosphate material with micron-sized spherical particles with a nano-porous structure is obtained by a novel synthesis method, and the foreign and domestic lithium iron phosphate materials are like the micron-sized spherical particles (for example, Chinese patent CN 1021447110A). However, these methods have certain drawbacks in terms of tap density, conductivity and consistency of the material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery, and the prepared spherical core-shell structure lithium iron phosphate anode material has the advantages of good conductivity, high tap density, uniform particle size, high charging rate and strong cruising ability.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: adding 3-5 parts of styrene monomer, 8-15 parts of lithium salt, 5-10 parts of ferrous salt, 1-3 parts of phosphate, 0.5-1 part of emulsifier and 100 parts of deionized water into a four-mouth round-bottom flask with a condenser pipe and a nitrogen guide pipe in sequence, and introducing nitrogen for 10-15min under the condition of magnetic stirring; slowly heating the reaction system to 70-90 ℃, and slowly adding 0.05-0.1 part of potassium persulfate to initiate polymerization; continuously reacting for 10-15h under the conditions of magnetic stirring and nitrogen protection, and precipitating, filtering, washing and drying by using ethanol to prepare the lithium iron phosphate styrene microspheres;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 5-12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 1-5 parts of graphene and 0.5-1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 30-55 parts of absolute ethyl alcohol and 1-3 parts of ammonia water; magnetically stirring at 30-40 deg.C for 1-3 hr, and dropwise adding 0.5-1 part of ethyl orthosilicate into the reaction solution for reacting for 5-10 hr; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained lithium iron phosphate microsphere powder with the core-shell structure in an inert atmosphere.
Further, the lithium salt in the step (1) is one or two of lithium nitrate and lithium acetate.
Further, the ferrous salt in the step (1) is one or more of ferrous nitrate, ferrous acetate and ferrous sulfate.
Further, the phosphate in the step (1) is one or more of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
Further, the emulsifier in the step (1) is one or two of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Further, the thickness of the graphene in the step (2) is 5-10 nm.
Further, the alkali metal phosphate in the step (2) is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate.
Further, the inert atmosphere in the step (3) is one of nitrogen and argon.
Further, the sintering method in the step (3) includes: the obtained core-shell structure microspheres are sintered for 3 to 6 hours at the temperature of 200-350 ℃ and then sintered for 5 to 8 hours at the temperature of 800-900 ℃.
The invention has the following beneficial effects:
(1) according to the preparation method of the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery, the styrene microspheres are adopted to coat the lithium iron phosphate, the uniformity of the particle size of the nanoscale spherical lithium iron phosphate is ensured after sintering, and the tap density of the lithium iron phosphate is high.
(2) According to the preparation method of the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery, the graphene is coated on the surface of the lithium iron phosphate microsphere by using the silicon dioxide, so that the conductivity of the material is greatly improved, and the material has a higher charging rate and a higher cruising ability; and the graphene is uniformly dispersed on the surface of the spherical lithium iron phosphate, and the cycle performance of the material is improved.
(3) The preparation method of the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery, disclosed by the invention, has the advantages of simple process, low cost, high efficiency, safety, environmental friendliness and suitability for large-scale production.
Drawings
Fig. 1 is a TEM image of a spherical lithium iron phosphate cathode material with a core-shell structure prepared in embodiment 4 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: adding 3 parts of styrene monomer, 8 parts of lithium nitrate, 5 parts of ferrous nitrate, 1 part of ammonium dihydrogen phosphate, 0.5 part of sodium dodecyl sulfate and 100 parts of deionized water into a four-mouth round-bottom flask with a condenser pipe and a nitrogen guide pipe in sequence, and introducing nitrogen for 10min under the condition of magnetic stirring; slowly heating the reaction system to 70 ℃, and slowly adding 0.05 part of potassium persulfate to initiate polymerization; continuously reacting for 10 hours under the conditions of magnetic stirring and nitrogen protection, and precipitating, filtering, washing and drying by using ethanol to prepare the lithium iron phosphate styrene microspheres;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 5 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 1 part of 5 nm-thick graphene and 0.5 part of sodium tripolyphosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 30 parts of anhydrous ethanol and 1 part of ammonia water; magnetically stirring at 30 ℃ for 1 h, weighing 0.5 part of tetraethoxysilane, dropwise adding the tetraethoxysilane into the reaction solution, and continuously reacting for 5 h; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 200 ℃ for 3h in a nitrogen atmosphere, then sintering the core-shell structure microspheres at 800 ℃ for 5h, and cooling the core-shell structure microspheres to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Example 2
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 10 parts of lithium acetate, 8 parts of ferrous acetite, 2 parts of diammonium hydrogen phosphate, 0.8 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask provided with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 12min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 8 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 3 parts of graphene with the thickness of 8nm and 0.8 part of sodium hexametaphosphate, adding the mixture into 100 parts of deionized water, stirring uniformly, and then adding 40 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 2 hr, and dropwise adding 0.8 part of ethyl orthosilicate into the reaction solution to continue reaction for 5 hr; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 280 ℃ for 4.5h under argon atmosphere, sintering the core-shell structure microspheres at 850 ℃ for 6h, and cooling the core-shell structure microspheres to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Example 3
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: adding 5 parts of styrene monomer, 12 parts of lithium nitrate, 10 parts of ferrous sulfate, 3 parts of ammonium dihydrogen phosphate, 1 part of sodium dodecyl sulfate and 100 parts of deionized water into a four-mouth round-bottom flask with a condenser pipe and a nitrogen guide pipe in sequence, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 90 ℃, and slowly adding 0.1 part of potassium persulfate to initiate polymerization; continuously reacting for 15 hours under the conditions of magnetic stirring and nitrogen protection, and precipitating, filtering, washing and drying by using ethanol to prepare the lithium iron phosphate styrene microspheres;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 10 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 5 parts of graphene with the thickness of 10nm and 1 part of sodium pyrophosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 50 parts of absolute ethyl alcohol and 3 parts of ammonia water; magnetically stirring for 3 hours at the temperature of 35 ℃, weighing 1 part of tetraethoxysilane, dropwise adding the tetraethoxysilane into the reaction liquid, and continuously reacting for 10 hours; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 320 ℃ for 6h in a nitrogen atmosphere, sintering the core-shell structure microspheres at 900 ℃ for 7h, and cooling the core-shell structure microspheres to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Example 4
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 12 parts of lithium acetate, 8 parts of ferrous acetate, 3 parts of diammonium hydrogen phosphate, 1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 3 parts of 5 nm-thick graphene and 1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 55 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 3h, and dropwise adding 0.5 parts of ethyl orthosilicate into the reaction solution to continue reacting for 8 h; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 350 ℃ for 6h in a nitrogen atmosphere, sintering at 900 ℃ for 8h, and cooling to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
The morphology of the prepared spherical core-shell structure lithium iron phosphate cathode material was observed by a transmission electron microscope, and the result is shown in fig. 1.
Comparative example 1
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 12 parts of lithium acetate, 8 parts of ferrous acetate, 3 parts of diammonium hydrogen phosphate, 1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1) and 1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 55 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 3h, and dropwise adding 0.5 parts of ethyl orthosilicate into the reaction solution to continue reacting for 8 h; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 350 ℃ for 6h in a nitrogen atmosphere, sintering at 900 ℃ for 8h, and cooling to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Comparative example 2
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 12 parts of lithium acetate, 8 parts of ferrous acetate, 3 parts of diammonium hydrogen phosphate, 1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 3 parts of 5 nm-thick graphene and 1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 55 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 3 hr; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 350 ℃ for 6h in a nitrogen atmosphere, sintering at 900 ℃ for 8h, and cooling to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Comparative example 3
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 12 parts of lithium acetate, 8 parts of ferrous acetate, 3 parts of diammonium hydrogen phosphate, 1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1) and 3 parts of 5 nm-thick graphene, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 55 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 3h, and dropwise adding 0.5 parts of ethyl orthosilicate into the reaction solution to continue reacting for 8 h; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 350 ℃ for 6h in a nitrogen atmosphere, sintering at 900 ℃ for 8h, and cooling to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Comparative example 4
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 12 parts of lithium acetate, 8 parts of ferrous acetate, 3 parts of diammonium hydrogen phosphate, 1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 3 parts of graphene with the thickness of 3.5nm and 1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 55 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 3h, and dropwise adding 0.5 parts of ethyl orthosilicate into the reaction solution to continue reacting for 8 h; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 350 ℃ for 6h in a nitrogen atmosphere, sintering at 900 ℃ for 8h, and cooling to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
Comparative example 5
A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery comprises the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: sequentially adding 4 parts of styrene monomer, 12 parts of lithium acetate, 8 parts of ferrous acetate, 3 parts of diammonium hydrogen phosphate, 1 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a four-neck round-bottom flask with a condenser pipe and a nitrogen guide pipe, and introducing nitrogen for 15min under the condition of magnetic stirring; slowly heating the reaction system to 80 ℃, and slowly adding 0.08 part of potassium persulfate to initiate polymerization; continuously reacting for 12 hours under the conditions of magnetic stirring and nitrogen protection, and preparing the lithium iron phosphate styrene microspheres by using ethanol for precipitation, filtering, washing and drying;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 3 parts of graphene with the thickness of 15nm and 1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 55 parts of absolute ethyl alcohol and 2 parts of ammonia water; magnetically stirring at 35 deg.C for 3h, and dropwise adding 0.5 parts of ethyl orthosilicate into the reaction solution to continue reacting for 8 h; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained core-shell structure microspheres at 350 ℃ for 6h in a nitrogen atmosphere, sintering at 900 ℃ for 8h, and cooling to room temperature to obtain the spherical core-shell structure lithium iron phosphate cathode material for the lithium battery.
And (3) performance detection:
in light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. A preparation method of a spherical core-shell structure lithium iron phosphate anode material for a lithium battery is characterized by comprising the following steps:
(1) preparing lithium iron phosphate styrene microspheres by a soap-free emulsion polymerization method: adding 3-5 parts of styrene monomer, 8-15 parts of lithium salt, 5-10 parts of ferrous salt, 1-3 parts of phosphate, 0.5-1 part of emulsifier and 100 parts of deionized water into a four-mouth round-bottom flask with a condenser pipe and a nitrogen guide pipe in sequence, and introducing nitrogen for 10-15min under the condition of magnetic stirring; slowly heating the reaction system to 70-90 ℃, and slowly adding 0.05-0.1 part of potassium persulfate to initiate polymerization; continuously reacting for 10-15h under the conditions of magnetic stirring and nitrogen protection, and precipitating, filtering, washing and drying by using ethanol to prepare the lithium iron phosphate styrene microspheres;
(2) preparing the lithium iron phosphate microsphere with the core-shell structure: weighing 5-12 parts of the lithium iron phosphate styrene microspheres obtained in the step (1), 1-5 parts of graphene and 0.5-1 part of alkali metal phosphate, adding the mixture into 100 parts of deionized water, uniformly stirring, and then adding 30-55 parts of absolute ethyl alcohol and 1-3 parts of ammonia water; magnetically stirring at 30-40 deg.C for 1-3 hr, and dropwise adding 0.5-1 part of ethyl orthosilicate into the reaction solution for reacting for 5-10 hr; centrifuging, washing and drying the precipitate to obtain core-shell structure lithium iron phosphate microsphere powder;
(3) and sintering the obtained lithium iron phosphate microsphere powder with the core-shell structure in nitrogen or inert atmosphere.
2. The method for preparing the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the lithium salt in the step (1) is one or two of lithium nitrate and lithium acetate.
3. The preparation method of the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the ferrous salt in the step (1) is one or more of ferrous nitrate, ferrous acetate and ferrous sulfate.
4. The method for preparing the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the phosphate in the step (1) is one or more of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
5. The method for preparing the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the emulsifier in the step (1) is one or two of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
6. The preparation method of the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the thickness of the graphene in the step (2) is 5-10 nm.
7. The method for preparing the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the alkali metal phosphate in the step (2) is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate.
8. The method for preparing the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the inert atmosphere in the step (3) is argon.
9. The method for preparing the spherical lithium iron phosphate cathode material with the core-shell structure for the lithium battery as claimed in claim 1, wherein the sintering method in the step (3) comprises: the obtained core-shell structure microspheres are sintered for 3 to 6 hours at the temperature of 200-350 ℃ and then sintered for 5 to 8 hours at the temperature of 800-900 ℃.
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| CN104091934B (en) * | 2014-07-17 | 2017-06-06 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of multi-component composite anode material, its preparation method and the lithium ion battery comprising it |
| CN104157840B (en) * | 2014-08-15 | 2016-06-15 | 南京师范大学 | The preparation method of a kind of lithium ion battery graphene coated silica nanometer pipe composite negative pole material |
| CN104934608A (en) * | 2015-04-13 | 2015-09-23 | 青岛科技大学 | Preparation method of in-situ graphene coated lithium ion battery cathode material |
| CN105845921A (en) * | 2016-05-23 | 2016-08-10 | 无锡市嘉邦电力管道厂 | Preparation method for graphene Li2MnSiO4 positive electrode material |
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