CN105514431B - A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof - Google Patents

A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof Download PDF

Info

Publication number
CN105514431B
CN105514431B CN201610008365.8A CN201610008365A CN105514431B CN 105514431 B CN105514431 B CN 105514431B CN 201610008365 A CN201610008365 A CN 201610008365A CN 105514431 B CN105514431 B CN 105514431B
Authority
CN
China
Prior art keywords
fepo
graphene
graphite alkene
spherical graphite
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610008365.8A
Other languages
Chinese (zh)
Other versions
CN105514431A (en
Inventor
秦显忠
杨改
高剑
蔡飞鹏
蒋波
王波
谭春晖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Energy Research Institute of Shandong Academy of Sciences
Original Assignee
Energy Research Institute of Shandong Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Energy Research Institute of Shandong Academy of Sciences filed Critical Energy Research Institute of Shandong Academy of Sciences
Priority to CN201610008365.8A priority Critical patent/CN105514431B/en
Publication of CN105514431A publication Critical patent/CN105514431A/en
Application granted granted Critical
Publication of CN105514431B publication Critical patent/CN105514431B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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 kind of spherical graphite alkene/FePO4Composite material and preparation method thereof, step are as follows：(1) aqueous solution of molysite and phosphorus-containing compound is configured；(2) aqueous solution and alkaline solution cocurrent are added in reaction kettle, it is 24 to keep pH, and temperature is 20 90 DEG C, obtains graphene/FePO of a secondary growth4·2H2O；(3) by graphene/FePO of a secondary growth of preparation4·2H2Disperse in a kettle, to repeat the operation in step (2) after O concentrations, spherical graphite alkene/FePO of diauxic growth is obtained after filtering, washing and dry4·2H2O composite materials；(4) by the graphene/FePO for the diauxic growth being prepared4·2H2Under an inert gas, roasting obtains spherical graphite alkene/FePO to O composite materials4Composite material.The present invention is introduced directly into graphene, ball shape ferric phosphate/graphene composite material grain shape rule, epigranular and the tap density height of preparation in ferric phosphate preparation.Entire preparation process simple operation, this has important application value for the preparation of graphene/composite ferric lithium phosphate material.

Description

A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of spherical graphite alkene/FePO4Composite material and Preparation method, the presoma as lithium-ion battery lithium iron phosphate positive electrode.
Background technology
LiFePO4 (the LiFePO of olivine structural4) because its raw material sources it is extensive, of low cost, environmental-friendly, it is theoretical Specific capacity height (170mAhg-1), many advantages, such as thermal stability and good cycle, be most promising lithium ion battery just One of pole material.But due to its intrinsic crystal structure, LiFePO4With very low electronic conductivity and Li+Diffusion coefficient is led It causes its heavy-current discharge performance poor, restricts its extensive use.Improve LiFePO at present4The research of electric conductivity is concentrated mainly on Two aspects of carbon coating and metal ion mixing.Wherein carbon coating is to improve LiFePO4The maximally efficient feasible one kind of electrical property Mode, and graphene is with sp2The carbon atom accumulation of hydridization connection forms one kind with individual layer bi-dimensional cellular shape lattice structure Novel carbonaceous material, the electron transfer rate specific surface area with high speed act not only as carbon source, are also used as carrier tune Save the structure of particle and form pattern.The document of graphene-coated lithium iron phosphate is relatively more at present, but most of is all in phosphorus Graphene coated can not be ensured into the integrality of graphene coated, to material on its surface in this way in the generating process of sour iron lithium The raising of performance is limited. FePO4·2H2O prepares LiFePO because becoming with fixed Fe/P ratios and similar crystalline structure4 The presoma of positive electrode.Therefore, FePO is synthesized by control4Structure, pattern and the granularity of presoma can prepare electrochemistry The excellent LiFePO of energy4Positive electrode.
Invention content
The purpose of the present invention is exactly to solve the above-mentioned problems, to provide a kind of spherical graphite alkene/FePO4Composite material and its Preparation method, the spherical graphite alkene/FePO prepared using graphene as bottom liquid4Composite material, regular shape, epigranular, jolt ramming Density is high and graphene uniform is coated on iron phosphate grains surface, as a kind of composite precursor prepared by follow-up solid phase lithiumation high Performance LiFePO4Play the role of vital.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of spherical graphite alkene/FePO4The preparation method of composite material, includes the following steps：
(1) molar ratio of the aqueous solution of configuration molysite and phosphorus-containing compound, the ferro element and P elements is (0.9- 1.2)：1, the solution concentration is 0.2-5mol/L；
(2) aqueous solution made from step (1) and alkaline solution cocurrent are added in reaction kettle, holding pH is 2-4, described anti- The temperature for answering system is 20-90 DEG C, reaction time 1-10h, obtains graphene/FePO of a secondary growth4·2H2O；
(3) graphene/FePO for the secondary growth for preparing step (2)4·2H2Disperse in a kettle after O concentrations, weight Operating procedure in multiple step (2), obtains graphene/FePO of diauxic growth4·2H2O is obtained after filtering, washing and dry Spherical graphite alkene/FePO of diauxic growth4·2H2O composite materials；
(4) graphene/FePO for the diauxic growth that step (3) is prepared4·2H2O composite materials are in inert gas Under the conditions of, 3-12 hours postcoolings of 300-600 DEG C of roasting obtain spherical graphite alkene/FePO of the removal crystallization water4Composite material.
It is preferred that：Molysite is FeNO in the step (1)3、FeCl3、Fe2(SO4)3、FeSO4、FeC2O4、(NH4)2SO4· FeSO4One or more of mixture.
It is preferred that：Phosphorus-containing compound is H in the step (1)3PO4、NH4H2PO4、(NH4)2HPO4、LiH2PO4And Na3PO4In One or more of mixtures.
It is preferred that：The alkali compounds has one or more of mixing of ammonium hydroxide, sodium hydroxide, sodium carbonate and sodium bicarbonate Object.
It is preferred that：The inert gas is nitrogen or/and argon gas.
It is preferred that：A concentration of 0.5-10mol/L of the alkaline solution.
It is preferred that：The volume of reaction system is 0.5-100L in reaction kettle.
It is preferred that：The stir speed (S.S.) is 0-1000r/s.
It is preferred that：The quality of graphene is FePO4Theoretical Mass 1%-50wt%.
Spherical graphite alkene/FePO prepared by the above method4Composite material.The composite material is preparing LiFePO4In should With.
Advantageous effect：
If since graphene is directly coated on FePO4Surface, there are the non-uniform problem of graphene dispersion, so being all Graphene oxide is first coated on FePO4When preparing LiFePO4 using reduction step, graphene oxide is restored for surface For graphene, method of the invention needs not move through reduction step, and spherical graphite alkene/FePO is directly prepared4Composite material system It is standby simple for process.
The present invention prepares spherical graphite alkene/FePO using graphene as bottom liquid4Composite precursor is used further to prepare ferric phosphate Lithium anode material can make up lacking for LiFePO4 electron conduction difference by the excellent electrical property of graphene and multiplying power property It falls into.
Compared with prior art, the graphene that the present invention is added is uniformly coated on FePO in the reaction4·2H2O particles Surface.The method of the present invention preparation process simple operation, this has weight for the preparation of spherical graphite alkene/ferric phosphate composite precursor That wants can be very good application value.
The preparation method of the present invention realizes FePO using two secondary growths4Particle surface (diauxic growth) and inside are (primary Growth) can more complete coated graphite alkene material, to improve later stage LiFePO 4 material high rate capability, more than twice The FePO of growth4Particle is too big, is unfavorable for the performance of LiFePO 4 material high rate capability instead.
Specific embodiment
Embodiment 1
3g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar Fe (NO3)3·9H2O and H3PO4It is made into 0.2mol/L mix acid liquors are continuously inputted in aforesaid reaction vessel, and controlling reaction temperature is 60 DEG C, with the weak aqua ammonia tune of 0.5mol/L Save pH value of solution=2, control stirring intensity be 200r/s, reaction 5h after obtain the yellow emulsion i.e. graphene of a secondary growth/ FePO4·2H2O, by graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, will be above-mentioned It containing molysite and phosphorus-containing compound mix acid liquor and lye and flows in aforesaid reaction vessel and adjusts pH=2, be stirred to react 5 hours Sediment is obtained to spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry afterwards4·2H2O.By the precursor Spherical graphite alkene/FePO is obtained after last 500 DEG C of heat treatment 10h under an inert atmosphere4Composite material.
Spherical graphite alkene/FePO obtained by the present embodiment4Spherical powder and granularity point of the composite material granular product for rule Cloth is uniform, good dispersion, D50=4.220um, and tap density reaches 1.31g/m3。
Embodiment 2
3g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar FeSO4With H3PO4It is made into 0.4mol/L Mix acid liquor is continuously inputted in aforesaid reaction vessel, and controlling reaction temperature is 60 DEG C, and pH value of solution is adjusted with the weak aqua ammonia of 1.0mol/L =3, control stirring intensity is 200r/s, and yellow emulsion i.e. graphene/FePO of a secondary growth is obtained after reacting 5h4·2H2O, By graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, containing molysite and is contained above-mentioned The mix acid liquor and lye of phosphorus compound simultaneously flow in aforesaid reaction vessel and adjust pH=3, by sediment after being stirred to react 5 hours Spherical graphite alkene/FePO of diauxic growth is obtained after filtering, washing and dry4·2H2O.By the precursor powder in indifferent gas Spherical graphite alkene/FePO is obtained after the lower 500 DEG C of heat treatment 10h of atmosphere4Composite material.
Spherical graphite alkene/FePO obtained by the present embodiment4Spherical powder and even particle size distribution of the composite material for rule, point It is good to dissipate property, D50=4.520um, tap density reaches 1.36g/m3。
Embodiment 3
5g graphene ultrasonic vibrations is taken to uniformly disperse in a kettle, weigh equimolar Fe (NO3)3·9H2O and H3PO4 It is made into 0.4mol/L mix acid liquors continuously to input in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, with dilute ammonia of 1.0mol/L Water adjusts pH value of solution=2, and control stirring intensity is 200r/s, and the yellow emulsion i.e. graphene of a secondary growth is obtained after reacting 5h /FePO4·2H2O, by graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, will be above-mentioned Mix acid liquor containing molysite and phosphorus-containing compound and lye simultaneously flow in aforesaid reaction vessel and adjust pH=2, and it is small to be stirred to react 5 When after sediment is obtained to spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry4·2H2O.By the presoma Powder under an inert atmosphere 600 DEG C heat treatment 10h after obtain spherical graphite alkene/FePO4Composite material.
Spherical graphite alkene/FePO obtained by the present embodiment4Spherical powder and even particle size distribution of the composite material for rule, point It is good to dissipate property, D50=4.120um, tap density reaches 1.45g/m3。
Embodiment 4
5g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar FeSO4With H3PO4It is made into 0.4mol/L Mix acid liquor is continuously inputted in aforesaid reaction vessel, and controlling reaction temperature is 60 DEG C, and pH value of solution is adjusted with the weak aqua ammonia of 1.0mol/L =2, control stirring intensity is 200r/s, and yellow emulsion i.e. graphene/FePO of a secondary growth is obtained after reacting 10h4· 2H2O, by graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains molysite by above-mentioned With the mix acid liquor of phosphorus-containing compound and lye and flow in aforesaid reaction vessel and adjust pH=2, will be heavy after being stirred to react 5 hours Starch obtains spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry4·2H2O.By the precursor powder lazy Property atmosphere it is lower 600 DEG C heat treatment 10h after obtain spherical graphite alkene/FePO4Composite material.
Spherical graphite alkene/FePO obtained by the present embodiment4Spherical powder and even particle size distribution of the composite material for rule, point It is good to dissipate property, D50=4.620um, tap density reaches 1.51g/m3。
Embodiment 5
5g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar FeSO4With H3PO4It is made into 0.4mol/L Mix acid liquor is continuously inputted in aforesaid reaction vessel, and controlling reaction temperature is 25 DEG C, and pH value of solution is adjusted with the weak aqua ammonia of 1.0mol/L =3, control stirring intensity is 200r/s, and yellow emulsion i.e. graphene/FePO of a secondary growth is obtained after reacting 10h4· 2H2O, by graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains molysite by above-mentioned With the mix acid liquor of phosphorus-containing compound and lye and flow in aforesaid reaction vessel and adjust pH=3, will be heavy after being stirred to react 5 hours Starch obtains spherical graphite alkene/FePO after filtering, washing and dry4·2H2O.By the precursor powder in 400 DEG C of heat treatments Spherical graphite alkene/FePO is obtained after 10h4Composite material.
FePO obtained by the present embodiment4Spherical powder and even particle size distribution of the granular product for rule, good dispersion, D50 =4.920um, tap density reach 1.56g/m3
Comparative example 1
Weigh equimolar Fe (NO3)3·9H2O and H3PO4Being made into 0.2mol/L mix acid liquors, continuously input fills deionization In the reaction kettle of water, controlling reaction temperature is 60 DEG C, adjusts pH value of solution=2 with the weak aqua ammonia of 0.5mol/L, controls stirring intensity For 200r/s, yellow emulsion is obtained after reacting 5h, a secondary growth is obtained after emulsion is filtered, wash and is dried FePO4·2H2O.FePO will be obtained after the precursor powder under an inert atmosphere 500 DEG C of heat treatment 10h4Presoma.
FePO obtained by the present embodiment4Cotton-shaped group of the granular product for former sheet accumulation, D50=5.76um, tap density Up to 0.7 g/m3。
Comparative example 2
Weigh equimolar Fe (NO3)3·9H2O and H3PO4Being made into 0.2mol/L mix acid liquors, continuously input fills deionization In the reaction kettle of water, controlling reaction temperature is 60 DEG C, adjusts pH value of solution=2.1 with the weak aqua ammonia of 0.5mol/L, control stirring is strong It spends for 200r/s, yellow emulsion is obtained after reacting 10h, by the FePO after concentration4·2H2O is uniformly dispersed in reaction kettle, It by the solution containing molysite and phosphorous chemical combination and lye and flows in aforesaid reaction vessel and adjusts pH=2, after being stirred to react 5 hours Sediment is obtained to the FePO of diauxic growth after filtering, washing and dry4·2H2O.By the precursor powder in inert atmosphere FePO is obtained after lower 500 DEG C of heat treatment 10h4Presoma.
FePO obtained by the present embodiment4Granular product is the agglomerate of long great achievement on the basis of the cotton-shaped group accumulated in former sheet, D50=7.81um, tap density reach 0.73g/m3。
Spherical graphite alkene/FePO obtained by the present embodiment4Particle is the spherical shape of dispersion, and D50=2.817um, tap density reaches 1.10g/m3。
Although above-mentioned be described the specific embodiment of the present invention in conjunction with the embodiments, not the present invention is protected The limitation of range, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art The various modifications or changes that can be made are not needed to make the creative labor still within protection scope of the present invention.

Claims (5)

1. a kind of spherical graphite alkene/FePO4The preparation method of composite material, it is characterized in that：Include the following steps：
（1）3g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar Fe (NO3)3·9H2O and H3PO4It is made into 0.2mol/L mix acid liquors are continuously inputted in aforesaid reaction vessel, and controlling reaction temperature is 60 DEG C, with the weak aqua ammonia tune of 0.5mol/L Save pH value of solution=2, control stirring intensity is 200r/s, and yellow emulsion is obtained after reaction 5h, i.e., the graphene of a secondary growth/ FePO4·2H2O；
（2）By graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains iron by above-mentioned Salt and phosphorus-containing compound mix acid liquor and lye simultaneously flow in aforesaid reaction vessel and adjust pH=2, will be heavy after being stirred to react 5 hours Starch obtains spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry4·2H2O；By the spherical stone of diauxic growth Black alkene/FePO4•2H2O powder under an inert atmosphere 500 DEG C heat treatment 10h after obtain spherical graphite alkene/FePO4Composite material.
2. a kind of spherical graphite alkene/FePO4The preparation method of composite material, it is characterized in that：Include the following steps：
（1）3g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar FeSO4With H3PO40.4mol/L is made into mix Acid solution to be closed continuously to input in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, and pH value of solution=3 are adjusted with the weak aqua ammonia of 1.0mol/L, Control stirring intensity is 200r/s, and yellow emulsion, i.e. graphene/FePO of a secondary growth are obtained after reacting 5h4·2H2O；
（2）By graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains iron by above-mentioned The mix acid liquor of salt and phosphorus-containing compound and lye simultaneously flow in aforesaid reaction vessel and adjust pH=3, will after being stirred to react 5 hours Sediment obtains spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry4·2H2O；By the spherical shape of diauxic growth Graphene/FePO4•2H2Spherical graphite alkene/FePO is obtained after the lower 500 DEG C of heat treatment 10h of O powder inert atmospheres4Composite material.
3. a kind of spherical graphite alkene/FePO4The preparation method of composite material, it is characterized in that：Include the following steps：
（1）5g graphene ultrasonic vibrations is taken to uniformly disperse in a kettle, weigh equimolar Fe (NO3)3·9H2O and H3PO4Match It is continuously inputted in aforesaid reaction vessel into 0.4mol/L mix acid liquors, controlling reaction temperature is 60 DEG C, with the weak aqua ammonia of 1.0mol/L Adjust pH value of solution=2, control stirring intensity is 200r/s, and yellow emulsion is obtained after reaction 5h, i.e., the graphene of a secondary growth/ FePO4·2H2O；
（2）By graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains iron by above-mentioned The mix acid liquor of salt and phosphorus-containing compound and lye simultaneously flow in aforesaid reaction vessel and adjust pH=2, will after being stirred to react 5 hours Sediment obtains spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry4·2H2O；By the spherical shape of diauxic growth Graphene/FePO4•2H2O powder under an inert atmosphere 600 DEG C heat treatment 10h after obtain spherical graphite alkene/FePO4Composite material.
4. a kind of spherical graphite alkene/FePO4The preparation method of composite material, it is characterized in that：Include the following steps：
（1）5g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar FeSO4With H3PO40.4mol/L is made into mix Acid solution to be closed continuously to input in aforesaid reaction vessel, controlling reaction temperature is 60 DEG C, and pH value of solution=2 are adjusted with the weak aqua ammonia of 1.0mol/L, Control stirring intensity is 200r/s, and yellow emulsion, i.e. graphene/FePO of a secondary growth are obtained after reacting 10h4·2H2O；
（2）By graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains iron by above-mentioned The mix acid liquor of salt and phosphorus-containing compound and lye simultaneously flow in aforesaid reaction vessel and adjust pH=2, will after being stirred to react 5 hours Sediment obtains spherical graphite alkene/FePO of diauxic growth after filtering, washing and dry4·2H2O；By the spherical shape of diauxic growth Graphene/FePO4•2H2O powder under an inert atmosphere 600 DEG C heat treatment 10h after obtain spherical graphite alkene/FePO4Composite material.
5. a kind of spherical graphite alkene/FePO4The preparation method of composite material, it is characterized in that：Include the following steps：
（1）5g graphene ultrasounds is taken to uniformly disperse in a kettle, weigh equimolar FeSO4With H3PO40.4mol/L is made into mix Acid solution to be closed continuously to input in aforesaid reaction vessel, controlling reaction temperature is 25 DEG C, and pH value of solution=3 are adjusted with the weak aqua ammonia of 1.0mol/L, Control stirring intensity is 200r/s, and yellow emulsion, i.e. graphene/FePO of a secondary growth are obtained after reacting 10h4·2H2O；
（2）By graphene/FePO of the secondary growth after concentration4·2H2O is uniformly dispersed in reaction kettle, contains iron by above-mentioned The mix acid liquor of salt and phosphorus-containing compound and lye simultaneously flow in aforesaid reaction vessel and adjust pH=3, will after being stirred to react 5 hours Sediment obtains spherical graphite alkene/FePO after filtering, washing and dry4·2H2O；By the spherical graphite alkene of diauxic growth/ FePO4•2H2O powder obtains spherical graphite alkene/FePO after being heat-treated 10h at 400 DEG C4Composite material.
CN201610008365.8A 2016-01-07 2016-01-07 A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof Active CN105514431B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610008365.8A CN105514431B (en) 2016-01-07 2016-01-07 A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610008365.8A CN105514431B (en) 2016-01-07 2016-01-07 A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105514431A CN105514431A (en) 2016-04-20
CN105514431B true CN105514431B (en) 2018-06-22

Family

ID=55722241

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610008365.8A Active CN105514431B (en) 2016-01-07 2016-01-07 A kind of spherical graphite alkene/FePO4Composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105514431B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683697A (en) * 2012-05-14 2012-09-19 中南大学 Preparation method of graphene-based LiFePO4/C composite material
CN103427081A (en) * 2013-08-13 2013-12-04 哈尔滨工业大学（威海） Simple preparation method for FePO4
CN104868118A (en) * 2015-04-07 2015-08-26 上海电力学院 Preparation method of sodium ion battery anode FePO4/Graphene composite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683697A (en) * 2012-05-14 2012-09-19 中南大学 Preparation method of graphene-based LiFePO4/C composite material
CN103427081A (en) * 2013-08-13 2013-12-04 哈尔滨工业大学（威海） Simple preparation method for FePO4
CN104868118A (en) * 2015-04-07 2015-08-26 上海电力学院 Preparation method of sodium ion battery anode FePO4/Graphene composite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
氧化石墨烯在二水磷酸铁复合前驱体制备中的作用;杜瑜敏 等;《有色金属科学与工程》;20140630;第5卷(第3期);第16-20页 *

Also Published As

Publication number Publication date
CN105514431A (en) 2016-04-20

Similar Documents

Publication Publication Date Title
JP6172818B2 (en) Method for producing graphene-based LiFePO4 / C composite material
CN106495161B (en) A method of nano-silicon is prepared based on metal intervention metallothermic reduction
CN105720251B (en) A kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof
CN113104828B (en) Preparation method of porous carbon modified sodium iron pyrophosphate phosphate/sodium carbonate ion battery positive electrode material
Lee et al. Synthesis of LiFePO4 material with improved cycling performance under harsh conditions
CN101337666A (en) Method for preparing spherical ferric lithium phosphate by oxidation control crystal-carbon thermal reduction method
CN104518217A (en) Battery grade iron and manganese phosphate and preparation method thereof
CN105449177B (en) A kind of porous cube of ZnSnO for sodium-ion battery3@graphene negative materials and preparation method thereof
CN107359318B (en) Method for synthesizing iron phosphate precursor with spherical-like porous structure and lithium iron phosphate cathode material
CN101434417A (en) Dry preparation of battery grade spherical cobaltosic oxide particle
CN105024072B (en) A kind of method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate
CN102244246B (en) Preparation method of lithium iron phosphate/carbon composite material
CN103996824B (en) Method for modifying lithium ion battery positive material by utilizing perovskite-type fast ionic conductor
CN103825024A (en) Battery-grade ferric phosphate and preparation method
CN104362341A (en) High-density nano-lithium iron phosphate material and preparation method thereof
CN109461931B (en) Preparation method of lithium iron phosphate precursor without wastewater discharge
CN106602023A (en) Method for in-situ synthesis of graphite phase carbon nitride-copper oxide composite material
CN105449208A (en) Spherical micro-nano ferric phosphate/carbon composite material and preparation method thereof
CN107887583A (en) A kind of doped lithium iron phosphate anode material and preparation method thereof
CN103427081A (en) Simple preparation method for FePO4
CN105129758B (en) A kind of porous calcium phosphate manganese vanadium lithium composite positive pole and preparation method thereof
Liu et al. Electrochemical performance of LiFePO4/C synthesized by solid state reaction using different lithium and iron sources
CN102311109A (en) Method for preparing LiFePO4/C composite cathode material by continuous reaction
CN107658469A (en) A kind of quick method for preparing the graphene-based positive electrode of fast charging type
WO2017201911A1 (en) Method for low temperature manufacturing of fexpo4-containing material using ferrophosphorus

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant