CN106711447A - Preparation method of compound graphene lithium battery positive electrode material - Google Patents
Preparation method of compound graphene lithium battery positive electrode material Download PDFInfo
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- CN106711447A CN106711447A CN201611178611.0A CN201611178611A CN106711447A CN 106711447 A CN106711447 A CN 106711447A CN 201611178611 A CN201611178611 A CN 201611178611A CN 106711447 A CN106711447 A CN 106711447A
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- lithium battery
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a compound graphene lithium battery positive electrode material. The preparation method comprises the following steps: preparing graphene dispersion liquid, namely adding graphite powder into water at a weight ratio of (1:50000) to (1:500), performing uniform ultrasonic dispersion, transferring the solution into a high-pressure reaction kettle at a preset temperature of 50 DEG C, introducing carbon dioxide gas until the internal pressure of the high-pressure reaction kettle is 100atm, keeping for 40 minutes, and then performing pressure relief at a speed of 50mL/s until achieving normal atmosphere; preparing a lithium iron phosphate precursor solution; uniformly mixing the graphene dispersion liquid with the lithium iron phosphate precursor solution at a volume ratio of (1:20) to (1:9), performing microwave heating until the temperature is 70 DEG C, drying the prepared mixture, and performing calcination for 6-12 hours at a temperature of 650-750 DEG C under inertia protective atmosphere, thereby obtaining the compound graphene lithium battery positive electrode material. The preparation method of the compound graphene lithium battery positive electrode material can be used for solving the problems that since the graphene dispersibility is not high, the rate performance of the electrode material is influenced, and the stability of each batch during a graphene lithium battery positive electrode material industrial application process is low.
Description
Technical field
The present invention relates to anode material of lithium battery preparation field, and in particular to a kind of compound Graphene lithium battery anode material
The preparation method of material.
Background technology
Only one layer of two dimensional crystal of atomic thickness that Graphene is made up of carbon atom.Each carbon atom is by outer in Graphene
After portion's mechanical force, carbon atom face can occur bending and deformation, so that carbon atom need not be rearranged to adapt to external force, and then cause
The structure of Graphene is highly stable, and the interference that the lattice of this stabilization is subject to when causing that electronics is moved in track is also very small.
The high heat conductance of Graphene is conducive to the release heat that high current load is produced in battery system.Commonly used commerciallyization
Electrode of lithium cell has that electrical conductivity and power density are relatively low.By adding organic carbon source and high-valency metal in precursor
The method of ion can improve the electric conductivity of material.At present, the correlative study of Graphene is used in lithium ion battery of new generation
It is a lot.If but the poor dispersion of Graphene, the Graphene of addition influences the high rate performance and intensity of electrode material on the contrary
Performance.Additionally, graphenic surface characteristic is influenceed larger by chemical state, selection repeatability preparation technology high prepares electrode material
To improving the lot stability important role during Graphene anode material of lithium battery commercial application.
The content of the invention
It is an object of the invention to provide a kind of preparation method of compound Graphene anode material of lithium battery, graphite is solved
Each batch during alkene dispersiveness influence electrode material high rate performance not high and Graphene anode material of lithium battery commercial application
The low problem of stability.
The present invention is achieved through the following technical solutions：
A kind of preparation method of compound Graphene anode material of lithium battery, comprises the following steps：
(1) graphene dispersing solution is prepared：By powdered graphite：Water=1:50000~1:500 weight ratio adds powdered graphite
Enter in water, be transferred to after ultrasonic disperse is uniform in the autoclave that preset temperature is 50 DEG C, be passed through carbon dioxide extremely
Pressure is 100atm and keeps 40min in autoclave, then with the speed pressure release of 50mL/s to normal pressure；
(2) LiFePO4 precursor solution is prepared：Prepare lithium carbonate 1.2mol/L~2.0mol/L, lithium hydroxide
0.8mol/L~1mol/L, ammonium dihydrogen phosphate 1.4mol/L~2.0mol/L, phosphoric acid 0.6mol/L~1mol/L, ferric acetate
The mixed aqueous solution of 2mol/L~3mol/L, citric acid 0.5mol/L~2.5mol/L；
(3) by graphene dispersing solution and lithium iron phosphate precursor solution by volume 1:20~1:9 are well mixed, and microwave adds
Heat, by the drying of obtained compound, under inert atmosphere protection, 6h~12h is calcined in 650 DEG C~750 DEG C to 70 DEG C, is obtained final product multiple
Mould assembly Graphene anode material of lithium battery.
Directly preparing graphene dispersing solution and combine it with the preparation process of LiFePO4 can solve to disperse stone
The problem that black alkene aggregate is brought.Quickly system is improve during heating using microwave by a large amount of energy transmissions to mixed liquor
Standby efficiency.
Wherein, each component concentration is in LiFePO4 precursor solution in step (2)：Lithium carbonate 1.2mol/L~
1.5mol/L, lithium hydroxide 0.5mol/L~0.8mol/L, ammonium dihydrogen phosphate 1mol/L~1.4mol/L, phosphoric acid 0.6mol/L~
1mol/L, ferric acetate 2mol/L, citric acid 2mol/L.
Wherein, graphene dispersing solution and the volume ratio of lithium iron phosphate precursor solution are 1 in step (3):15, the temperature of roasting
It is 700 DEG C to spend, and the time of roasting is 10h.
Wherein, the purity of carbon dioxide described in step (1) is 99.99%.
Wherein, inert atmosphere described in step (3) is nitrogen.
The present invention compared with prior art, has the following advantages and advantages：
1st, a kind of preparation method of compound Graphene anode material of lithium battery of the present invention, directly prepares graphene dispersing solution
And combine it with the preparation process of LiFePO4, solve graphene dispersion influence electrode material high rate performance not high
Problem；
2nd, a kind of preparation method of compound Graphene anode material of lithium battery of the present invention, using sol-gal process, solves
The low problem of each lot stability during Graphene anode material of lithium battery commercial application.
Specific embodiment
To make the object, technical solutions and advantages of the present invention become more apparent, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1
A kind of preparation method of compound Graphene anode material of lithium battery of the present invention, comprises the following steps：
(1) graphene dispersing solution is prepared：By powdered graphite：Water=1:Powdered graphite is added to water by 50000 weight ratio
In, it is transferred to after ultrasonic disperse is uniform in the autoclave that preset temperature is 50 DEG C, it is passed through 99.99% carbon dioxide
To high pressure reacting kettle inner pressure is for 100atm and keeps 40min, then with the speed pressure release of 50mL/s to normal pressure；
(2) LiFePO4 precursor solution is prepared：Prepare lithium carbonate 2.0mol/L, lithium hydroxide 1mol/L, biphosphate
Ammonium 2.0mol/L, phosphatase 11 mol/L, ferric acetate 3mol/L, the mixed aqueous solution of citric acid 2.5mol/L；
(3) by graphene dispersing solution and lithium iron phosphate precursor solution by volume 1:20 are well mixed, and heating using microwave is extremely
70 DEG C, by the drying of obtained compound, under nitrogen protection, 6h is calcined in 750 DEG C, obtains final product compound Graphene lithium battery anode
Material.
When 0.1C discharges, specific capacity 165mAh/g, when 1C discharges, specific capacity 163mAh/g, then 1C/0.1C multiplying powers
97.0%.500 circulation sustainment rates 97.5%.
Embodiment 2
A kind of preparation method of compound Graphene anode material of lithium battery of the present invention, comprises the following steps：
(1) graphene dispersing solution is prepared：By powdered graphite：Water=1:Be added to the water for powdered graphite by 500 weight ratio,
It is transferred to after ultrasonic disperse is uniform in the autoclave that preset temperature is 50 DEG C, is passed through 99.99% carbon dioxide extremely
Pressure is 100atm and keeps 40min in autoclave, then with the speed pressure release of 50mL/s to normal pressure；
(2) LiFePO4 precursor solution is prepared：Prepare lithium carbonate 1.2mol/L, lithium hydroxide 0.8mol/L, di(2-ethylhexyl)phosphate
Hydrogen ammonium 1.4mol/L, phosphoric acid 0.6mol/L, ferric acetate 2mol/L, the mixed aqueous solution of citric acid 0.5mol/L；
(3) by graphene dispersing solution and lithium iron phosphate precursor solution by volume 1:9 are well mixed, heating using microwave to 70
DEG C, by the drying of obtained compound, under nitrogen protection, 12h is calcined in 650 DEG C, obtain final product compound Graphene lithium battery anode
Material.
When 0.1C discharges, specific capacity 160mAh/g, when 1C discharges, specific capacity 158mAh/g, then 1C/0.1C multiplying powers
98.75%.500 circulation sustainment rates 97.9%.
Embodiment 3
A kind of preparation method of compound Graphene anode material of lithium battery of the present invention, comprises the following steps：
(1) graphene dispersing solution is prepared：By powdered graphite：Water=1:Powdered graphite is added to water by 5000 weight ratio
In, it is transferred to after ultrasonic disperse is uniform in the autoclave that preset temperature is 50 DEG C, it is passed through 99.99% carbon dioxide
To high pressure reacting kettle inner pressure is for 100atm and keeps 40min, then with the speed pressure release of 50mL/s to normal pressure；
(2) LiFePO4 precursor solution is prepared：Prepare lithium carbonate 1.5mol/L, lithium hydroxide 0.5mol/L, di(2-ethylhexyl)phosphate
Hydrogen ammonium 1mol/L, phosphoric acid 0.6mol/L, ferric acetate 2mol/L, the mixed aqueous solution of citric acid 2mol/L；
(3) by graphene dispersing solution and lithium iron phosphate precursor solution by volume 1:15 are well mixed, and heating using microwave is extremely
70 DEG C, by the drying of obtained compound, under nitrogen protection, 10h is calcined in 700 DEG C, is obtaining final product compound Graphene lithium battery just
Pole material.
When 0.1C discharges, specific capacity 167mAh/g, when 1C discharges, specific capacity 165mAh/g, then 1C/0.1C multiplying powers
98.8%.500 circulation sustainment rates 98.1%.
Above-described specific embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that and the foregoing is only specific embodiment of the invention, be not intended to limit the present invention
Protection domain, all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc. all should include
Within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of compound Graphene anode material of lithium battery, it is characterised in that comprise the following steps：
(1) graphene dispersing solution is prepared：By powdered graphite：Water=1:50000~1:Be added to for powdered graphite by 500 weight ratio
In water, it is transferred to after ultrasonic disperse is uniform in the autoclave that preset temperature is 50 DEG C, is passed through carbon dioxide to high pressure
Reacting kettle inner pressure is 100atm and keeps 40min, then with the speed pressure release of 50mL/s to normal pressure；
(2) LiFePO4 precursor solution is prepared：Preparation lithium carbonate 1.2mol/L~2.0mol/L, lithium hydroxide 0.8mol/L~
1mol/L, ammonium dihydrogen phosphate 1.4mol/L~2.0mol/L, phosphoric acid 0.6mol/L~1mol/L, ferric acetate 2mol/L~3mol/
The mixed aqueous solution of L, citric acid 0.5mol/L~2.5mol/L；
(3) by graphene dispersing solution and lithium iron phosphate precursor solution by volume 1:20~1:9 are well mixed, and heating using microwave is extremely
70 DEG C, by the drying of obtained compound, under inert atmosphere protection, 6h~12h is calcined in 650 DEG C~750 DEG C, obtained final product compound
Graphene anode material of lithium battery.
2. the preparation method of a kind of compound Graphene anode material of lithium battery according to claim 1, it is characterised in that
Each component concentration is in LiFePO4 precursor solution in step (2)：Lithium carbonate 1.2mol/L~1.5mol/L, lithium hydroxide
0.5mol/L~0.8mol/L, ammonium dihydrogen phosphate 1mol/L~1.4mol/L, phosphoric acid 0.6mol/L~1mol/L, ferric acetate
2mol/L, citric acid 2mol/L.
3. the preparation method of a kind of compound Graphene anode material of lithium battery according to claim 2, it is characterised in that
Graphene dispersing solution and the volume ratio of lithium iron phosphate precursor solution are 1 in step (3):15, the temperature of roasting is 700 DEG C, roasting
The time of burning is 10h.
4. the preparation method of a kind of compound Graphene anode material of lithium battery according to claim 1, it is characterised in that
The purity of carbon dioxide described in step (1) is 99.99%.
5. the preparation method of a kind of compound Graphene anode material of lithium battery according to claim 1, it is characterised in that
Inert atmosphere described in step (3) is nitrogen.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611393A (en) * | 2017-09-08 | 2018-01-19 | 郭家林 | A kind of preparation method of sulphur alkene/three-dimensional porous carbon composite |
| CN107768648A (en) * | 2017-10-24 | 2018-03-06 | 武汉新能源研究院有限公司 | A kind of preparation method of new amorphous carbon coated graphite material |
| CN108807897A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | Graphene anode material of lithium battery preparation method |
| CN109103442A (en) * | 2018-09-18 | 2018-12-28 | 四川省有色冶金研究院有限公司 | A kind of preparation method of graphene-coated lithium iron phosphate positive electrode |
| CN112620643A (en) * | 2020-11-20 | 2021-04-09 | 浙江南都电源动力股份有限公司 | Preparation method of graphene-coated lithium metal |
| CN115579463A (en) * | 2022-08-17 | 2023-01-06 | 厦门海辰储能科技股份有限公司 | Graphene lithium iron phosphate composite material, preparation method thereof, pole piece and secondary battery |
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| CN102544516A (en) * | 2012-02-20 | 2012-07-04 | 上海交通大学 | Method for producing graphene-coated lithium iron phosphate |
| CN105226274A (en) * | 2015-07-01 | 2016-01-06 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of LiFePO4/graphene composite material of graphene uniform dispersion |
| CN105366671A (en) * | 2015-12-02 | 2016-03-02 | 江苏金聚合金材料有限公司 | Preparation method of graphene |
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| CN102013477B (en) * | 2010-11-10 | 2012-05-23 | 河北力滔电池材料有限公司 | Method for preparing lithium iron phosphate/carbon composite material of lithium ion battery |
| CN102544516A (en) * | 2012-02-20 | 2012-07-04 | 上海交通大学 | Method for producing graphene-coated lithium iron phosphate |
| CN105226274A (en) * | 2015-07-01 | 2016-01-06 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of LiFePO4/graphene composite material of graphene uniform dispersion |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611393A (en) * | 2017-09-08 | 2018-01-19 | 郭家林 | A kind of preparation method of sulphur alkene/three-dimensional porous carbon composite |
| CN107611393B (en) * | 2017-09-08 | 2022-07-22 | 商洛学院 | Preparation method of sulfolene/three-dimensional porous carbon composite material |
| CN107768648A (en) * | 2017-10-24 | 2018-03-06 | 武汉新能源研究院有限公司 | A kind of preparation method of new amorphous carbon coated graphite material |
| CN108807897A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | Graphene anode material of lithium battery preparation method |
| CN109103442A (en) * | 2018-09-18 | 2018-12-28 | 四川省有色冶金研究院有限公司 | A kind of preparation method of graphene-coated lithium iron phosphate positive electrode |
| CN112620643A (en) * | 2020-11-20 | 2021-04-09 | 浙江南都电源动力股份有限公司 | Preparation method of graphene-coated lithium metal |
| CN112620643B (en) * | 2020-11-20 | 2023-04-07 | 浙江南都电源动力股份有限公司 | Preparation method of graphene-coated lithium metal |
| CN115579463A (en) * | 2022-08-17 | 2023-01-06 | 厦门海辰储能科技股份有限公司 | Graphene lithium iron phosphate composite material, preparation method thereof, pole piece and secondary battery |
| CN115579463B (en) * | 2022-08-17 | 2024-01-23 | 厦门海辰储能科技股份有限公司 | Graphene lithium iron phosphate composite material, preparation method thereof, pole piece and secondary battery |
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