CN108682814B - Preparation method of flaky lithium iron phosphate/carbon composite material - Google Patents
Preparation method of flaky lithium iron phosphate/carbon composite material Download PDFInfo
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- CN108682814B CN108682814B CN201810447360.4A CN201810447360A CN108682814B CN 108682814 B CN108682814 B CN 108682814B CN 201810447360 A CN201810447360 A CN 201810447360A CN 108682814 B CN108682814 B CN 108682814B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation method of a flaky lithium iron phosphate/carbon composite material. The method comprises the following specific steps: (1) FeSO (ferric oxide) is added4·7H2O、LiOH·H2O, CTAB and H3PO4Dispersing in deionized water, and ultrasonically and fully mixing; (2) adding N, N-dimethylformamide, and continuing ultrasonic dissolving to obtain a mixed solution; (3) putting the solution into a high-pressure reaction kettle for hydrothermal reaction, and filtering and washing after the reaction; (4) putting the washed product into a vacuum drying box for vacuum drying; (5) and roasting the dried sample at high temperature to obtain the flaky lithium iron phosphate/carbon composite material. The preparation method is simple, the operation is convenient, the raw materials are cheap and easy to obtain, and the obtained flaky lithium iron phosphate/carbon composite material is uniform in size.
Description
Technical Field
The invention particularly relates to the technical field of electrode materials, and particularly relates to a preparation method of a flaky lithium iron phosphate/carbon composite material.
Background
In the 21 st century of the rapid development and information globalization of this technology, with the increasing development of mobile communication technology and the urgent need of electric automobiles and electric bicycles for high-capacity lithium ion batteries, higher requirements are put forward on the rapid charging and discharging capability of the lithium ion batteries. However, lithium ion batteries have not been completely popularized in actual life, and the performance of electrode materials of the lithium ion batteries is limited in further application. The capacity of most of the existing lithium ion batteries is reduced to different degrees when the lithium ion batteries are charged and discharged rapidly. The main factor affecting the charge and discharge speed is the diffusion rate of lithium ions inside the electrode material. The nano material has the characteristics of large specific surface area, high surface activity, short ion diffusion path, strong peristalsis, high plasticity and the like, can obviously improve the lithium removal/insertion capacity of the material, prolong the cycle service life of an electrode and improve the wettability of the electrode material and an electrolyte solution when being applied to the electrode material of a lithium ion battery, and has obvious advantages compared with a bulk phase material. Currently, research on this aspect is active. A number of metal oxide and phosphate materials have been extensively studied for use as battery materials, such as LiCoO2、LiNiO2、LiMnO2、LiFePO4、VO2And the like are many studied positive electrode materials.
Lithium iron phosphate is widely used for research, and is the most common electrode material with a wide application range at present. Lithium iron phosphate has become a novel anode material of a lithium ion battery due to the characteristics of high theoretical capacity, stable discharge platform, high cycle performance, environmental friendliness, no toxicity and the like, but the electrochemical performance of the lithium iron phosphate under high multiplying power is greatly limited due to the defect of low electron/ion conductivity of the lithium iron phosphate. Through compounding or wrapping of carbon and electrode materials, the conductivity of ions and electrons can be effectively improved, the impedance of an electrode is reduced, the conductivity and structural stability of the electrode material are improved, the phenomenon of electrode material dissolution caused by direct contact of electrolyte and the electrode material is reduced, and the electrolyte is facilitated to form a stable solid electrolyte interface film (SEI) on the surface of the carbon, which is all beneficial to improving the performances of the electrode such as reversible charge-discharge capacity, cycle life and coulombic coefficient.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a simple and feasible preparation method of a flaky lithium iron phosphate/carbon composite material. The lithium iron phosphate/carbon composite material prepared by the invention is flaky, and the section of the composite material is mainly square.
The technical scheme of the invention is realized in such a way.
The invention provides a preparation method of a flaky lithium iron phosphate/carbon composite material, which comprises the following specific steps:
(1) FeSO (ferric oxide) is added4·7H2O、LiOH·H2O, CTAB and H3PO4Dispersing in deionized water, and ultrasonically and fully mixing;
(2) adding N, N-dimethylformamide, and continuing ultrasonic dissolving to obtain a mixed solution;
(3) putting the solution into a high-pressure reaction kettle for hydrothermal reaction, and after the reaction is finished, sequentially filtering, washing and drying;
(4) and roasting the dried sample to obtain the flaky lithium iron phosphate/carbon composite material.
In the present invention, FeSO4·7H2O、LiOH·H2O and H3PO4The feed ratio of (1): (1-3): (1-3); FeSO4·7H2The feeding ratio of O to CTAB is 30: 1-5: 1 mmol/g; the feeding ratio of CTAB to deionized water to N, N-dimethylformamide is (0.1-0.3) g (5-20) ml: (5-20) ml.
In the invention, in the step (3), the hydrothermal reaction temperature is 120-300 ℃, and the reaction time is 12-24 h.
In the invention, in the step (3), the drying temperature is 60-120 ℃, and the drying time is 12-24 h.
In the invention, in the step (4), the roasting temperature is 400-1000 ℃, and the roasting time is 2-8 h.
The flaky lithium iron phosphate/porous carbon composite material obtained in the invention is flaky and uniform in size, and the side length is 15-30 μm.
Compared with the prior art, the invention has the beneficial effects that: the flaky lithium iron phosphate/porous carbon nano composite material prepared by the invention has the advantages of uniform size, simple and convenient operation, high economic and practical applicability, cheap and easily-obtained raw materials, low production cost, and wide application prospect and market potential.
Drawings
Fig. 1 is an SEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 1.
Fig. 2 is an SEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 2.
Fig. 3 is a TEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 3.
Fig. 4 is a TEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 4.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples, but the present invention is not limited to the following examples.
Example 1
A preparation method of a flaky lithium iron phosphate/porous carbon composite material specifically comprises the following steps:
(1) 2mmol of FeSO4·7H2O、4mmolLiOH·H2O, 0.2gCTAB and 2mmolH3PO4Dispersing in 8ml deionized water, and fully mixing by ultrasonic;
(2) adding 10ml of N, N-dimethylformamide, and continuing ultrasonic dissolution to obtain a mixed solution;
(3) putting the solution into a 30ml high-pressure reaction kettle, carrying out hydrothermal reaction for 24 hours at 180 ℃, and filtering and washing after the reaction;
(4) putting the washed product into a vacuum drying box for vacuum drying for 24 hours at the temperature of 90 ℃;
(5) and finally transferring the dried sample to a tubular furnace, and calcining at the high temperature of 600 ℃ for 2 hours to obtain the lithium iron phosphate/porous carbon composite material. Fig. 1 is an SEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 1. The scanning electron microscope image shows that the material is in a uniform sheet structure, and the side length is about 20-25 mu m.
Example 2
A preparation method of a flaky lithium iron phosphate/porous carbon composite material specifically comprises the following steps:
(1) 2mmol of FeSO4·7H2O、2mmolLiOH·H2O, 0.2gCTAB and 2mmolH3PO4Dispersing in 10ml deionized water, and fully mixing by ultrasonic;
(2) adding 10ml of N, N-dimethylformamide, and continuing ultrasonic dissolution to obtain a mixed solution;
(3) putting the solution into a 30ml high-pressure reaction kettle, carrying out hydrothermal reaction for 12h at 160 ℃, and filtering and washing after the reaction;
(4) putting the washed product into a vacuum drying box for vacuum drying for 24 hours at the temperature of 90 ℃;
(5) and finally transferring the dried sample to a tubular furnace, and calcining at the high temperature of 600 ℃ for 2 hours to obtain the lithium iron phosphate/porous carbon composite material. Fig. 2 is an SEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 2. The scanning electron microscope image shows that the material is in a uniform sheet structure, and the side length is about 25-30 mu m.
Example 3
A preparation method of a flaky lithium iron phosphate/porous carbon composite material specifically comprises the following steps:
(1) 2mmol of FeSO4·7H2O、4mmolLiOH·H2O, 0.2gCTAB and 4mmolH3PO4Dispersing in 10ml deionized water, and fully mixing by ultrasonic;
(2) adding 8ml of N, N-dimethylformamide, and continuing ultrasonic dissolution to obtain a mixed solution;
(3) putting the solution into a 30ml high-pressure reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, and filtering and washing after the reaction;
(4) putting the washed product into a vacuum drying box for vacuum drying for 24 hours at the temperature of 60 ℃;
(5) and finally, transferring the dried sample to a tubular furnace, and calcining at the high temperature of 500 ℃ for 2 hours to obtain the lithium iron phosphate/porous carbon composite material. Fig. 3 is a TEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 3. The transmission electron microscope image shows that the material is in a uniform sheet structure, and the side length is about 20-30 mu m.
Example 4
A preparation method of a flaky lithium iron phosphate/porous carbon composite material specifically comprises the following steps:
(1) 2mmol of FeSO4·7H2O、4mmolLiOH·H2O, 0.2gCTAB and 4mmolH3PO4Dispersing in 12ml deionized water, and fully mixing by ultrasonic;
(2) adding 12ml of N, N-dimethylformamide, and continuing ultrasonic dissolution to obtain a mixed solution;
(3) putting the solution into a 30ml high-pressure reaction kettle, carrying out hydrothermal reaction for 24 hours at 180 ℃, and filtering and washing after the reaction;
(4) putting the washed product into a vacuum drying box for vacuum drying for 24 hours at the temperature of 90 ℃;
(5) and finally transferring the dried sample to a tubular furnace, and calcining at the high temperature of 600 ℃ for 4 hours to obtain the lithium iron phosphate/porous carbon composite material. Fig. 4 is a TEM image of the flaky lithium iron phosphate/porous carbon composite material prepared in example 4. The transmission electron microscope image shows that the material is in a uniform sheet structure, and the side length is about 15-25 mu m.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (4)
1. A preparation method of a flaky lithium iron phosphate/carbon composite material is characterized by comprising the following specific steps:
(1) FeSO (ferric oxide) is added4·7H2O、LiOH·H2O, CTAB and H3PO4Dispersing in deionized water, and ultrasonically and fully mixing;
(2) adding N, N-dimethylformamide, and continuing ultrasonic dissolving to obtain a mixed solution;
(3) putting the solution into a high-pressure reaction kettle for hydrothermal reaction, and after the reaction is finished, sequentially filtering, washing and drying;
(4) roasting the dried sample to obtain a flaky lithium iron phosphate/carbon composite material;
FeSO4·7H2O、LiOH·H2o and H3PO4In a molar ratio of 1: (1-3): (1-3); FeSO4·7H2The feeding ratio of O to CTAB is 30: 1-5: 1 mmol/g; the feeding ratio of CTAB to deionized water to N, N-dimethylformamide is (0.1-0.3) g (5-20) ml: (5-20) ml;
in the step (3), the hydrothermal reaction temperature is 120-300 ℃, and the reaction time is 12-24 h.
2. The method according to claim 1, wherein in the step (3), the drying temperature is 60 to 120 ℃ and the drying time is 12 to 24 hours.
3. The preparation method according to claim 1, wherein in the step (4), the roasting temperature is 400-1000 ℃ and the roasting time is 2-8 h.
4. The preparation method according to claim 1, wherein the obtained sheet-shaped lithium iron phosphate/carbon composite material is sheet-shaped and uniform in size, and the side length is 15-30 μm.
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| KR101328381B1 (en) * | 2011-12-13 | 2013-11-13 | 비나텍주식회사 | Manufacturing method of LiFePO4 cathode active material for lithium battery and LiFePO4 cathode active material using the method |
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