CN105514431A - Spherical graphene/FePO4 composite and preparing method thereof - Google Patents
Spherical graphene/FePO4 composite and preparing method thereof Download PDFInfo
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- CN105514431A CN105514431A CN201610008365.8A CN201610008365A CN105514431A CN 105514431 A CN105514431 A CN 105514431A CN 201610008365 A CN201610008365 A CN 201610008365A CN 105514431 A CN105514431 A CN 105514431A
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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
- 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
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- 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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- 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
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Abstract
The invention discloses a spherical graphene/FePO4 composite and a preparing method thereof. The preparing method includes the following steps of (1) preparing an aqueous solution of ferric salt and a phosphorous compound; 2, adding the aqueous solution and an alkaline solution into a reactor kettle in a parallel-flow mode, keeping the pH being 2-4 and the temperature being 20-90 DEG C, and obtaining primary-growth graphene/FePO4.2H2O; 3, concentrating and dispersing the prepared primary-growth graphene/FePO4.2H2O into the reaction kettle, repeating operation in the step 2, and obtaining a secondary-growth spherical graphene/FePO4.2H2O composite through suction filtration, washing and drying; 4, sintering the prepared secondary-growth graphene/FePO4.2H2O composite under inert gas to obtain the spherical graphene/FePO4 composite. According to the spherical graphene/FePO4 composite and the preparing method, graphene is directly introduced into preparing of FePO4, and particles of the prepared spherical graphene/FePO4 composite are regular in shape, even in granularity and high in tap density. The whole preparing technology is rapid and convenient to operate, and the spherical graphene/FePO4 composite and the preparing method are of great application significance in preparing of a graphene/lithium iron phosphate composite.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of spherical graphite alkene/FePO
4composite material and preparation method thereof, as the presoma of lithium-ion battery lithium iron phosphate positive electrode.
Background technology
LiFePO4 (the LiFePO of olivine structural
4) because its raw material sources are extensive, with low cost, environmental friendliness, the high (170mAhg of theoretical specific capacity
-1), the plurality of advantages such as thermal stability and good cycle is one of the most promising anode material for lithium-ion batteries.But due to the crystal structure that it is intrinsic, LiFePO
4there is very low electronic conductivity and Li
+diffusion coefficient, causes its heavy-current discharge performance poor, governs its extensive use.Improve LiFePO at present
4it is coated with metal ion mixing two aspects that the research of conductivity mainly concentrates on carbon.Wherein carbon is coated is improve LiFePO
4a kind of mode that electrical property is the most effective and feasible, and Graphene is with sp
2the carbon atom that hydridization connects is piled up and is formed a kind of New Type of Carbon material with individual layer bi-dimensional cellular shape lattice structure, has electron transfer rate specific area at a high speed and not only as carbon source, can also regulate the Structure and form pattern of particle as carrier.The document of current graphene-coated lithium iron phosphate is many, but major part is all in the generative process of LiFePO4, graphene coated is surperficial at it, cannot ensure the integrality of graphene coated like this, limited to the raising of material property.FePO
42H
2o becomes preparation LiFePO because having fixing Fe/P ratio and similar crystalline structure
4the presoma of positive electrode.Therefore, by controlling synthesis FePO
4the structure of presoma, pattern and granularity can prepare the LiFePO of excellent electrochemical performance
4positive electrode.
Summary of the invention
Object of the present invention is exactly to solve the problem, and provides a kind of spherical graphite alkene/FePO
4composite material and preparation method thereof take Graphene as spherical graphite alkene/FePO prepared by end liquid
4composite material, regular shape, epigranular, tap density are high and graphene uniform is coated on iron phosphate grains surface, prepare high-performance LiFePO as a kind of composite precursor to follow-up solid phase lithiumation
4serve vital effect.
To achieve these goals, the present invention adopts following technical scheme:
A kind of spherical graphite alkene/FePO
4the preparation method of composite material, comprises the following steps:
(1) configure the aqueous solution of molysite and phosphorus-containing compound, the mol ratio of described ferro element and P elements is (0.9-1.2): 1, and described solution concentration is 0.2-5mol/L;
(2) by the aqueous solution obtained for step (1) and alkaline solution and stream adds in reactor, maintenance pH is 2-4, and the temperature of described reaction system is 20-90 DEG C, and reaction time 1-10h obtains the Graphene/FePO of a secondary growth
42H
2o;
(3) Graphene/FePO of the secondary growth prepared by step (2)
42H
2after O is concentrated, dispersion in a kettle., repeats the operating procedure in step (2), obtain the Graphene/FePO of diauxic growth
42H
2o, obtains the spherical graphite alkene/FePO of diauxic growth after suction filtration, washing and drying
42H
2o composite material;
(4) Graphene/FePO of diauxic growth step (3) prepared
42H
2o composite material is under the condition of inert gas, and 300-600 DEG C of cooling after roasting 3-12 hour, obtains the spherical graphite alkene/FePO removing the crystallization water
4composite material.
Preferred: in described step (1), molysite is FeNO
3, FeCl
3, Fe
2(SO
4)
3, FeSO
4, FeC
2o
4, (NH
4)
2sO
4feSO
4in the mixture of one or more.
Preferred: in described step (1), phosphorus-containing compound is H
3pO
4, NH
4h
2pO
4, (NH
4)
2hPO
4, LiH
2pO
4and Na
3pO
4in the mixture of one or more.
Preferred: described alkali compounds has the mixture of one or more of ammoniacal liquor, NaOH, sodium carbonate and sodium acid carbonate.
Preferred: described inert gas is that nitrogen is or/and argon gas.
Preferred: described alkaline solution concentration is 0.5-10mol/L.
Preferred: the volume of reaction kettle for reaction system is 0.5-100L.
Preferred: described stir speed (S.S.) is 0-1000r/s.
Preferred: the quality of Graphene is FePO
4theoretical Mass 1%-50wt%.
Spherical graphite alkene/FePO prepared by said method
4composite material.This composite material is at preparation LiFePO
4in application.
Beneficial effect:
If due to Graphene is directly coated on FePO
4, there is the problem that graphene dispersion is uneven in surface, so be all first graphene oxide is coated on FePO
4surface, when preparing LiFePO4 again through reduction step, is reduced to Graphene by graphene oxide, and method of the present invention, without the need to through reduction step, directly prepares spherical graphite alkene/FePO
4composite material preparation process is simple.
The present invention is end liquid with Graphene, prepares spherical graphite alkene/FePO
4composite precursor, is used further to prepare lithium iron phosphate positive material, makes up the defect of LiFePO4 electron conduction difference by the electrical property of Graphene excellence and multiplying power property.
Compared with prior art, the Graphene that the present invention adds is coated on FePO in the reaction equably
42H
2o particle surface.The inventive method preparation technology simple operation, this preparation for spherical graphite alkene/ferric phosphate composite precursor have important can well using value.
Preparation method of the present invention adopts two secondary growths to achieve FePO
4particle surface (diauxic growth) and inside (secondary growth) all can be more complete coated graphite alkene material, to the high rate capability improving later stage LiFePO 4 material, more than the FePO of two secondary growths
4particle is too large, is unfavorable for the performance of LiFePO 4 material high rate capability on the contrary.
Embodiment
Embodiment 1
Get 3g Graphene ultrasonic in a kettle. dispersed, take equimolar Fe (NO
3)
39H
2o and H
3pO
4be made into 0.2mol/L mix acid liquor to input continuously in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, and regulate pH value of solution=2 with the weak aqua ammonia of 0.5mol/L, control stirring intensity is 200r/s, obtains the yellow emulsion i.e. Graphene/FePO of a secondary growth after reaction 5h
42H
2o, by the Graphene/FePO of the secondary growth after concentrated
42H
2o disperses in a kettle. uniformly, flowing in aforesaid reaction vessel by above-mentioned containing molysite and phosphorus-containing compound mix acid liquor and alkali lye and regulate pH=2, sediment is obtained the spherical graphite alkene/FePO of diauxic growth by stirring reaction after suction filtration, washing and drying after 5 hours
42H
2o.Spherical graphite alkene/FePO is obtained by after this precursor powder under an inert atmosphere 500 DEG C of heat treatment 10h
4composite material.
The present embodiment gained spherical graphite alkene/FePO
4composite material granular product is regular spherical powder and even particle size distribution, and good dispersion, D50=4.220um, tap density reaches 1.31g/m
3.
Embodiment 2
Get 3g Graphene ultrasonic in a kettle. dispersed, take equimolar FeSO
4with H
3pO
4be made into 0.4mol/L mix acid liquor to input continuously in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, and regulate pH value of solution=3 with the weak aqua ammonia of 1.0mol/L, control stirring intensity is 200r/s, obtains the yellow emulsion i.e. Graphene/FePO of a secondary growth after reaction 5h
42H
2o, by the Graphene/FePO of the secondary growth after concentrated
42H
2o disperses in a kettle. uniformly, above-mentioned mix acid liquor containing molysite and phosphorus-containing compound and alkali lye being flow in aforesaid reaction vessel and regulate pH=3, sediment is obtained the spherical graphite alkene/FePO of diauxic growth by stirring reaction after suction filtration, washing and drying after 5 hours
42H
2o.Spherical graphite alkene/FePO is obtained by after this precursor powder under an inert atmosphere 500 DEG C of heat treatment 10h
4composite material.
The present embodiment gained spherical graphite alkene/FePO
4composite material is regular spherical powder and even particle size distribution, and good dispersion, D50=4.520um, tap density reaches 1.36g/m
3.
Embodiment 3
Get 5g Graphene ultrasonic vibration in a kettle. dispersed, take equimolar Fe (NO
3)
39H
2o and H
3pO
4be made into 0.4mol/L mix acid liquor to input continuously in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, and regulate pH value of solution=2 with the weak aqua ammonia of 1.0mol/L, control stirring intensity is 200r/s, obtains the yellow emulsion i.e. Graphene/FePO of a secondary growth after reaction 5h
42H
2o, by the Graphene/FePO of the secondary growth after concentrated
42H
2o disperses in a kettle. uniformly, above-mentioned mix acid liquor containing molysite and phosphorus-containing compound and alkali lye being flow in aforesaid reaction vessel and regulate pH=2, sediment is obtained the spherical graphite alkene/FePO of diauxic growth by stirring reaction after suction filtration, washing and drying after 5 hours
42H
2o.Spherical graphite alkene/FePO is obtained by after this precursor powder under an inert atmosphere 600 DEG C of heat treatment 10h
4composite material.
The present embodiment gained spherical graphite alkene/FePO
4composite material is regular spherical powder and even particle size distribution, and good dispersion, D50=4.120um, tap density reaches 1.45g/m
3.
Embodiment 4
Get 5g Graphene ultrasonic in a kettle. dispersed, take equimolar FeSO
4with H
3pO
4be made into 0.4mol/L mix acid liquor to input continuously in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, and regulate pH value of solution=2 with the weak aqua ammonia of 1.0mol/L, control stirring intensity is 200r/s, obtains the yellow emulsion i.e. Graphene/FePO of a secondary growth after reaction 10h
42H
2o, by the Graphene/FePO of the secondary growth after concentrated
42H
2o disperses in a kettle. uniformly, above-mentioned mix acid liquor containing molysite and phosphorus-containing compound and alkali lye being flow in aforesaid reaction vessel and regulate pH=2, sediment is obtained the spherical graphite alkene/FePO of diauxic growth by stirring reaction after suction filtration, washing and drying after 5 hours
42H
2o.Spherical graphite alkene/FePO is obtained by after this precursor powder under an inert atmosphere 600 DEG C of heat treatment 10h
4composite material.
The present embodiment gained spherical graphite alkene/FePO
4composite material is regular spherical powder and even particle size distribution, and good dispersion, D50=4.620um, tap density reaches 1.51g/m
3.
Embodiment 5
Get 5g Graphene ultrasonic in a kettle. dispersed, take equimolar FeSO
4with H
3pO
4be made into 0.4mol/L mix acid liquor to input continuously in aforesaid reaction vessel, controlling reaction temperature is 25 DEG C, and regulate pH value of solution=3 with the weak aqua ammonia of 1.0mol/L, control stirring intensity is 200r/s, obtains the yellow emulsion i.e. Graphene/FePO of a secondary growth after reaction 10h
42H
2o, by the Graphene/FePO of the secondary growth after concentrated
42H
2o disperses in a kettle. uniformly, and above-mentioned mix acid liquor containing molysite and phosphorus-containing compound and alkali lye being flow in aforesaid reaction vessel and regulate pH=3, sediment was obtained spherical graphite alkene/FePO after 5 hours by stirring reaction after suction filtration, washing and drying
42H
2o.This precursor powder is obtained spherical graphite alkene/FePO after 400 DEG C of heat treatment 10h
4composite material.
The present embodiment gained FePO
4granular product is regular spherical powder and even particle size distribution, and good dispersion, D50=4.920um, tap density reaches 1.56g/m
3
Comparative example 1
Take equimolar Fe (NO
3)
39H
2o and H
3pO
4be made into 0.2mol/L mix acid liquor to input continuously and fill in the reactor of deionized water, controlling reaction temperature is 60 DEG C, pH value of solution=2 are regulated with the weak aqua ammonia of 0.5mol/L, control stirring intensity is 200r/s, obtain yellow emulsion after reaction 5h, emulsion filtration, washing and drying are obtained afterwards the FePO of a secondary growth
42H
2o.FePO is obtained by after this precursor powder under an inert atmosphere 500 DEG C of heat treatment 10h
4presoma.
The present embodiment gained FePO
4granular product is the cotton-shaped group that former sheet is piled up, and D50=5.76um, tap density reaches 0.7g/m
3.
Comparative example 2
Take equimolar Fe (NO
3)
39H
2o and H
3pO
4be made into 0.2mol/L mix acid liquor to input continuously and fill in the reactor of deionized water, controlling reaction temperature is 60 DEG C, and regulate pH value of solution=2.1 with the weak aqua ammonia of 0.5mol/L, control stirring intensity is 200r/s, yellow emulsion is obtained, by the FePO after concentrated after reaction 10h
42H
2o disperses in a kettle. uniformly, and the solution containing molysite and phosphorous chemical combination and alkali lye being flow in aforesaid reaction vessel and regulate pH=2, sediment is obtained the FePO of diauxic growth by stirring reaction after suction filtration, washing and drying after 5 hours
42H
2o.FePO is obtained by after this precursor powder under an inert atmosphere 500 DEG C of heat treatment 10h
4presoma.
The present embodiment gained FePO
4granular product is the agglomerate of growing up on the cotton-shaped group basis that former sheet is piled up, and D50=7.81um, tap density reaches 0.73g/m
3.
The present embodiment gained spherical graphite alkene/FePO
4particle is the spherical of dispersion, and D50=2.817um, tap density reaches 1.10g/m
3.
The specific embodiment of the present invention is described although above-mentioned in conjunction with the embodiments; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. spherical graphite alkene/FePO
4the preparation method of composite material, is characterized in that: comprise the following steps:
(1) configure the aqueous solution of molysite and phosphorus-containing compound, the mol ratio of described ferro element and P elements is (0.9-1.2): 1, and described solution concentration is 0.2-5mol/L;
(2) by the aqueous solution obtained for step (1) and alkaline solution and stream adds in reactor, maintenance pH is 2-4, and the temperature of described reaction system is 20-90 DEG C, and reaction time 1-10h obtains the Graphene/FePO of a secondary growth
42H
2o;
(3) Graphene/FePO of the secondary growth prepared by step (2)
42H
2after O is concentrated, dispersion in a kettle., repeats the operating procedure in step (2), obtain the Graphene/FePO of diauxic growth
42H
2o, obtains the spherical graphite alkene/FePO of diauxic growth after suction filtration, washing and drying
42H
2o composite material;
(4) Graphene/FePO of diauxic growth step (3) prepared
42H
2o composite material is under the condition of inert gas, and 300-600 DEG C of cooling after roasting 3-12 hour, obtains the spherical graphite alkene/FePO removing the crystallization water
4composite material.
2. preparation method as claimed in claim 1, is characterized in that: in described step (1), molysite is FeNO
3, FeCl
3, Fe
2(SO
4)
3, FeSO
4, FeC
2o
4, (NH
4)
2sO
4feSO
4in the mixture of one or more.
3. preparation method as claimed in claim 1, is characterized in that: in described step (1), phosphorus-containing compound is H
3pO
4, NH
4h
2pO
4, (NH
4)
2hPO
4, LiH
2pO
4and Na
3pO
4in the mixture of one or more.
4. preparation method as claimed in claim 1, is characterized in that: in described step (1), the quality of Graphene is FePO
4theoretical Mass 0-50wt%.
5. preparation method as claimed in claim 1, is characterized in that: described step (2) neutral and alkali compound has the mixture of one or more of ammoniacal liquor, NaOH, sodium carbonate and sodium acid carbonate.
6. preparation method as claimed in claim 1, is characterized in that: described step (2) neutral and alkali solution concentration is 0.5-10mol/L.
7. preparation method as claimed in claim 1, is characterized in that: in described step (2), the stir speed (S.S.) of reaction system is 0-1000r/s.
8. preparation method as claimed in claim 1, is characterized in that: in described step (4), inert gas is that nitrogen is or/and argon gas.
9. spherical graphite alkene/FePO of preparing of the arbitrary described method of claim 1-8
4composite material.
10. spherical graphite alkene/FePO as claimed in claim 9
4composite material is at preparation LiFePO
4in application.
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|---|---|---|---|
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|---|---|---|---|
| CN201610008365.8A CN105514431B (en) | 2016-01-07 | 2016-01-07 | A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108975297A (en) * | 2018-07-17 | 2018-12-11 | 桂林理工大学 | The method that the crystallization water by removing nanoscale iron phosphate prepares high performance lithium iron phosphate positive material |
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| CN108975297A (en) * | 2018-07-17 | 2018-12-11 | 桂林理工大学 | The method that the crystallization water by removing nanoscale iron phosphate prepares high performance lithium iron phosphate positive material |
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