CN105355881B - A kind of graphene composite material and preparation method thereof - Google Patents
A kind of graphene composite material and preparation method thereof Download PDFInfo
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- CN105355881B CN105355881B CN201510783491.6A CN201510783491A CN105355881B CN 105355881 B CN105355881 B CN 105355881B CN 201510783491 A CN201510783491 A CN 201510783491A CN 105355881 B CN105355881 B CN 105355881B
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- 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
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Abstract
The invention discloses a kind of graphene nanocomposite materials and preparation method thereof, belong to the improved technical field of cell positive material, and technical points include: the general formula of composite material are as follows: LiMn1‑ xFexPO4Wherein 0.15≤x≤0.45, the composite positive pole are compounded with graphene, carbon nanotube having a size of nanoscale in composite base material, the quality of the graphene is the 0.5%-5% of the composite base material quality, and the quality of the carbon nanotube is the 0.2%-12% of the composite base material quality.Pass through the optimization to formula, form continuous inierpeneirating network structure, be conducive to conducting medium to be distributed on two-phase interface, and form complete space conductive network, simultaneously because the ionic liquid selected forms conductive network structure in the base, it overcomes traditional sucrose system and is not easy to be formed conductive network or the larger disadvantage of resistivity itself, improve the electric conductivity of composite material.
Description
Technical field
The present invention relates to the improved technical fields of cell positive material, are related to a kind of graphene composite material, more specifically
Say a kind of graphene composite material and preparation method thereof in ground.
Background technique
Mono-layer graphite, also known as graphene (Graphene), be one kind by single layer of carbon atom with graphite key (sp2) compact reactor
Lattice structure of the product at bi-dimensional cellular shape, therefore the thickness of only one carbon atom, graphite key are answering for covalent bond and metallic bond
Close key, can say be insulator and electric conductor heaven-made match.It is also most hard material that graphene, which is most thin in the world at present, is led
Hot coefficient is higher than carbon nanotubes and diamond, its electron mobility is also higher than carbon nanotube or silicon crystal under room temperature, resistivity ratio
Copper or silver are lower, are that the smallest material of resistivity, these unique charge engineering properties make that graphene is added in the world at present
Composite material more multifunction, not only show excellent mechanics and electric property, also have excellent processing performance, be multiple
Condensation material provides broader practice field.But the graphene of structural integrity is hexa-atomic by the benzene without any labile bond
The two dimensional crystal that ring is composed, chemical stability is high, the inert state in surface, with other media (such as solvent) phase interaction
With weaker, and there are stronger Fan get Wa Li between the piece and piece of graphene, are easy to produce reunion, make its be insoluble in water and its
There are commonly solvents for it, thus limit the further research and application of graphene.
Battery is mainly made of anode, cathode, electrolyte system, diaphragm, and wherein positive electrode is limiting lithium ion electricity
The key factor of tank discharge capacity, therefore, finding a kind of good positive electrode is the groundwork for studying battery.Research at present
More positive electrode mainly have the LiMO of layer structure2(M=Ni, Co, Mn etc.), wherein including individually one kind and two
Kind, the mixing of three kinds of metallic elements, the comparison of the ternary system research of Li-Co-Ni-Mn-O is more, much has been put on a large scale
Production, but there are also to be solved for its cyclicity and safety issue.The LiMn of spinel-type2O4Ion channel with three-dimensional, from
The good conductivity of son, has also put into production application, but its structural stability is bad, causes its cyclicity poor.Olivine
The LiMPO of structure4(M=Mn, Fe, Ni, Co etc.) have safety is good, cyclicity is good, lower-price characteristic and attract a large amount of
Researcher, LiMPO of the last decade for olivine structural4The research of material also achieves very big achievement, but olivine
The LiMPO of structure4Ionic mobility and electronic conductivity are all relatively low, therefore are to solve conductivity problems to the emphasis that it is studied,
The main method taken now is first is that minimize the particle of material, and such as the material of synthesis nano, another is exactly to material
It is modified, mainly has the metallic element for adulterating other good conductivities or powder, (such as carbon coating) is coated to material.
There is excellent performance due to olivine structural, there is preferable cyclicity and forthright again, therefore study it
Have great importance.Preparation method about it has had many reports, as high temperature solid-state method, high-energy ball milling method, colloidal sol are solidifying
Glue method, liquid phase method etc..LiMnxFe1-xPO4Manganese and iron in material are all divalent, and source of iron used in most methods and manganese source are all
It is to use divalent, but the source of iron of divalent and manganese source are very unstable, are easily oxidized, preparation process is troublesome and is difficult to control each
Ratio.Therefore, how emphasis explore and study of the present invention further increases the electric conductivity of the composite material iron manganese phosphate for lithium.
Summary of the invention
It is an object of the invention in view of the above shortcomings of the prior art, provide a kind of graphene nanocomposite material and its
Preparation method, to solve composite material, the especially electric conductivity of iron manganese phosphate for lithium electrode material.
The technical scheme of the present invention is realized as follows:
A kind of graphene composite material, the general formula of composite material are as follows: LiMn1-xFexPO4, wherein 0.15≤x≤0.45,
The composite positive pole is compounded with graphene, carbon nanotube having a size of nanoscale in composite base material, the graphene
Quality is the 0.5%-5% of the composite base material quality, and the quality of the carbon nanotube is the composite base material quality
0.2%-12%.
The composite base material also contains zinc oxide nanowire, the nanowire diameter 20-60nm, the zinc oxide nanowire
Quality is the composite base material quality 0.1%-1.5%.
The preparation method of graphene composite material includes following operating procedure: (1) according to mole of composite material each element
Dissolution process is carried out than nanoscale lithium source, manganese source, source of iron, phosphorus source to be added in ionic liquid；(2) under ultrasonication, to institute
It states and adds graphene in mixed system, carbon nanotube, changes zinc nano wire, 35-55 DEG C of maintenance system temperature, ultrasonic disperse time 10-
85min；(3) after complexing agent and mixed processing being added in step (2) system；(4) step (3) is dried compound to get arriving
The presoma of material；(5) electroslag remelting equipment is used, under inert gas shielding, the surface of step (4) described presoma is polished
As in electrode insertion slag after processing, slag uses CaF2, Al2O3, CaO slag system, and the mass percent of CaF2 contains in slag system
Amount is 75%-85%, and the mass percentage content of Al2O3 is 12%-18%, and the mass percentage content of CaO is 4%-6%,
Have a power failure cooling time: 5min-10min；(6) step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, first
Temperature programming keeps the temperature 10-85min, 10 DEG C/min of temperature rise to 400 DEG C -750 DEG C；900 DEG C -1250 DEG C are warming up to again, when heat preservation
Between: 1h-4h, 5 DEG C/min of temperature rise are cooled to room temperature.
The graphene is load metallic graphite carbon alkene, can be load tin dioxide nano-particle graphene, four oxygen of load
Change three cobalt nanometer particle graphenes, loading nano silvery particle graphene, load one kind in cerium oxide nanoparicles graphene.
The carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 30-50nm, 10-30 microns of length.
The ionic liquid of the step (1) is N- butyl-pyridinium hexafluorophosphate, N- butyl-pyridinium tetrafluoroborate, 1- first
One or more of base imidazoles dihydric phosphate, 1- methylimidazole trifluoroacetate.
The complexing agent of the step (3) is ethylenediamine tetra-acetic acid, diethylenetriamine, citric acid, ethyl acetate, formic acid second
One of ester, oxalic acid.
Beneficial effects of the present invention are as follows: by the optimization to formula, forming continuous inierpeneirating network structure, be conducive to lead
Dielectric is distributed on two-phase interface, and forms complete space conductive network, simultaneously because the ionic liquid selected is in matrix
Middle formation conductive network structure overcomes traditional sucrose system and is not easy to be formed conductive network or the larger disadvantage of resistivity itself,
Improve the electric conductivity of composite material.
The preparation method of composite positive pole uses complexing agent complexation of metal ions, keeps it evenly dispersed in atomic level,
And nanometer materials are obtained by chemical method.This method makes graphene, the metal in carbon nanotube and matrix reach molecule
Rank it is evenly dispersed, realize nano metal particles to compound inside iron manganese phosphate for lithium material structure, compared to particle surface
Carbon coating is obviously improved the electric conductivity of composite material.In addition, at by heat treatment within specified temperatures and annealing
Reason, so that graphene, carbon nanotube and matrix are formed by composite structure and stablize.Another ionic liquid is as novel excellent
Multifunctional solvent, solve the problems, such as that inorganic compound is difficult to dissolve each other with organic compound.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, but does not constitute to of the invention any
Limitation.
Lithium source, manganese source, source of iron, phosphorus source are to prepare the conventional respective compound of composite material, and such as: lithium source can be organic
Lithium, but not only select butyl lithium, phenyl lithium, lithium carbonate；Manganese source can be Organic Manganese, but not only select three carbonvlmethyl rings
Pentadiene manganese, three carbonyl cyclopentadiene manganese, manganese nitrate；Source of iron can be Organic Iron, but not only select ferric acetyl acetonade, sulphur cyanogen
Change iron, ferric nitrate, ferrocene；Phosphorus source can be phosphate, but not only select phosphoric acid hydrogen ammonia, potassium hydrogen phosphate.
Main industrial chemicals explanation: nano-graphene, carbon nanotube, zinc oxide nanowire are purchased from Nanjing Xian Feng nano material
Science and Technology Ltd.；Ionic liquid is purchased from Chenzhou, Hunan Province Chemical Industry Science Co., Ltd.
Embodiment 1
A kind of graphene composite material, LiMn0.85Fe0.15PO4, the composite positive pole is having a size of nanoscale, and multiple
It closes in substrate and is compounded with graphene, carbon nanotube, the quality of the graphene is the 0.5g of the composite base material quality, the carbon
The quality of nanotube is the 0.2g of the composite base material quality.
Composite base material also contains zinc oxide nanowire 2g, the nanowire diameter 20nm, the quality of the zinc oxide nanowire
It is the composite base material quality 0.1%.
The preparation method of graphene composite material includes following operating procedure: (1) according to mole of composite material each element
Than three carbonvlmethyl cyclopentadiene manganese of nanoscale, ferric acetyl acetonade, phosphoric acid hydrogen ammonia to be added in ionic liquid and carry out at dissolution
Reason, is Li: Mn: Fe: P=1.0: 0.85: 0.15: 1 progress weighing according to molar ratio, and total amount is counted according to 1 mole；(2) ultrasonication
Under, graphene, carbon nanotube are added into the mixed system, changes zinc nano wire, 35 DEG C of maintenance system temperature, the ultrasonic disperse time
10min；(3) after complexing agent and mixed processing being added in step (2) system；(4) step (3) is dried compound to get arriving
The presoma of material；(5) electroslag remelting equipment is used, under inert gas shielding, the surface of step (4) described presoma is polished
As in electrode insertion slag after processing, slag uses CaF2、Al2O3, CaO slag system, CaF in slag system2Mass percentage content
For 75%, Al2O3Mass percentage content be 12%, CaO mass percentage content be 4%, have a power failure cooling time: 5min；
(6) step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, first temperature programming is to 400 DEG C, heat preservation
10min, 10 DEG C/min of temperature rise；Be warming up to 900 DEG C again, soaking time: 1h, 5 DEG C/min of temperature rise are cooled to room temperature.
The graphene is load metallic graphite carbon alkene, to load tin dioxide nano-particle graphene.
The carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 30nm, 100 microns of length.
The ionic liquid of the step (1) is N- butyl-pyridinium hexafluorophosphate.
The complexing agent of the step (3) is ethylenediamine tetra-acetic acid.
Embodiment 2
A kind of graphene composite material, LiMn0.55Fe0.45PO4, graphene, carbon nanotube are compounded in composite base material,
The quality of the graphene is the 5g of the composite base material quality, and the quality of the carbon nanotube is the composite base material quality
12g。
Composite base material also contains zinc oxide nanowire, nanowire diameter 60nm, and the quality of zinc oxide nanowire is composite base material
Quality 1.5g.
The preparation method of graphene composite material includes following operating procedure: (1) according to mole of composite material each element
Than nanoscale phenyl lithium, three carbonyl cyclopentadiene manganese, ferrocene, potassium hydrogen phosphate to be added in ionic liquid and carry out at dissolution
Reason, is Li: Mn: Fe: P=1.0: 0.55: 0.45: 1 progress weighing according to molar ratio, and total amount is counted according to 1 mole；(2) ultrasonication
Under, graphene, carbon nanotube are added into the mixed system, changes zinc nano wire, 55 DEG C of maintenance system temperature, the ultrasonic disperse time
85min；(3) after complexing agent and mixed processing being added in step (2) system；(4) step (3) is dried compound to get arriving
The presoma of material；(5) electroslag remelting equipment is used, under inert gas shielding, the surface of step (4) described presoma is polished
As in electrode insertion slag after processing, slag uses CaF2、Al2O3, CaO slag system, CaF in slag system2Mass percentage content
For 85g, Al2O3Mass percentage content be 18g, the mass percentage content of CaO is 6g, is had a power failure cooling time: 10min；
(6) step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, first temperature programming is to 750 DEG C, heat preservation
85min, 10 DEG C/min of temperature rise；Be warming up to 1250 DEG C again, soaking time: 4h, 5 DEG C/min of temperature rise are cooled to room temperature.
The graphene is load metallic graphite carbon alkene, is received for load cobaltosic oxide nanoparticles graphene 1.0g, load
It is a kind of in rice silver particles graphene 3.5g, load cerium oxide nanoparicles graphene 0.5g.
The carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 50nm, 30 microns of length.
In the ionic liquid 1- methylimidazole trifluoroacetate of the step (1).
The complexing agent of the step (3) is diethylenetriamine.
Embodiment 3
A kind of graphene composite material, LiMn0.8Fe0.2PO4, the composite positive pole is having a size of nanoscale, and multiple
It closes in substrate and is compounded with graphene, carbon nanotube, the quality of the graphene is the 1.5g of the composite base material quality, the carbon
The quality of nanotube is the 0.8g of the composite base material quality.
Substrate contains zinc oxide nanowire, and the nanowire diameter 28nm, the quality of the zinc oxide nanowire is described multiple
Close substrate mass 0.8g.
The preparation method of black alkene composite material includes following operating procedure: (1) according to the molar ratio of composite material each element
Nanoscale lithium source, manganese source, source of iron, phosphorus source are added in ionic liquid and carry out dissolution process；(2) under ultrasonication, to described
Add graphene, carbon nanotube in mixed system, change zinc nano wire, 40 DEG C of maintenance system temperature, ultrasonic disperse time 25min；(3)
After complexing agent and mixed processing is added in step (2) system；(4) step (3) is dried to get the forerunner of composite material is arrived
Body；(5) electroslag remelting equipment is used, under inert gas shielding, by conduct after the surface grinding process of step (4) presoma
Electrode is inserted into slag, and slag uses CaF2、Al2O3, CaO slag system, CaF in slag system2Mass percentage content be 78g, Al2O3
Mass percentage content be 14g, the mass percentage content of CaO is 4.5g, is had a power failure cooling time: 6min；(6) by the step
Suddenly (5) are put into heating in the heating furnace of initial temperature≤200 DEG C, and first temperature programming is to 450 DEG C, heat preservation 15min, and 10 DEG C of temperature rise/
min；Be warming up to 980 DEG C again, soaking time: 1.5h, 5 DEG C/min of temperature rise are cooled to room temperature.
The graphene is load metallic graphite carbon alkene, supported cobaltosic oxide nano particle graphene.
The carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 35nm, 15 microns of length.
The ionic liquid of the step (1) is, N- butyl-pyridinium tetrafluoroborate.
The complexing agent of the step (3) is citric acid.
Embodiment 4
A kind of graphene composite material, LiMn0.7Fe0.3PO4, and graphene, carbon nanotube are compounded in composite base material,
The quality of the graphene is the 1.2g of the composite base material quality, and the quality of the carbon nanotube is the composite base material quality
8.3g.
Composite base material also contains zinc oxide nanowire, and nanowire diameter 35nm, the quality of the zinc oxide nanowire is described
Composite base material quality 0.65g.
The preparation method of graphene composite material includes following operating procedure: (1) according to mole of composite material each element
Dissolution process is carried out than nanoscale lithium source, manganese source, source of iron, phosphorus source to be added in ionic liquid；(2) under ultrasonication, to institute
It states and adds graphene, carbon nanotube in mixed system, changes zinc nano wire, 40.5 DEG C of maintenance system temperature, the ultrasonic disperse time
45min；(3) after complexing agent and mixed processing being added in step (2) system；(4) step (3) is dried compound to get arriving
The presoma of material；(5) electroslag remelting equipment is used, under inert gas shielding, the surface of step (4) described presoma is polished
As in electrode insertion slag after processing, slag uses CaF2、Al2O3, CaO slag system, the mass percentage content of CaF2 in slag system
For 83.5g, Al2O3Mass percentage content be 14.6g, the mass percentage content of CaO is 5.5g, have a power failure cooling time:
7.5min；(6) step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, first temperature programming is protected to 550 DEG C
Warm 75min, 10 DEG C/min of temperature rise；Be warming up to 1050 DEG C again, soaking time: 3.6h, 5 DEG C/min of temperature rise are cooled to room temperature.
Graphene is load metallic graphite carbon alkene, loading nano silvery particle graphene.
Carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 42nm, 28 microns of length.
In the ionic liquid 1- methylimidazole trifluoroacetate of step (1).
The complexing agent of step (3) is ethyl acetate.
Embodiment 5
A kind of graphene composite material, the general formula of composite material are as follows: LiMn0.58Fe0.42PO4, the composite positive pole ruler
Very little is nanoscale, and graphene, carbon nanotube are compounded in composite base material, and the quality of the graphene is the composite base material
The 4.64g of quality, the quality of the carbon nanotube are the 11.3g of the composite base material quality.
Composite base material contains zinc oxide nanowire, and nanowire diameter 55nm, the quality of the zinc oxide nanowire is described multiple
Close substrate mass 1.38g.
The preparation method of graphene composite material includes following operating procedure: (1) according to mole of composite material each element
Dissolution process is carried out than nanoscale lithium source, manganese source, source of iron, phosphorus source to be added in ionic liquid；(2) under ultrasonication, to institute
It states and adds graphene, carbon nanotube in mixed system, changes zinc nano wire, 51 DEG C of maintenance system temperature, ultrasonic disperse time 82min；
(3) after complexing agent and mixed processing being added in step (2) system；(4) step (3) is dried to get composite material is arrived
Presoma；(5) electroslag remelting equipment is used, under inert gas shielding, after the surface grinding process of step (4) presoma
As in electrode insertion slag, slag uses CaF2、Al2O3, CaO slag system, CaF in slag system2Mass percentage content be
82.3g Al2O3Mass percentage content be 17.5g, the mass percentage content of CaO is 5.68g, have a power failure cooling time:
5min-10min；(6) step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, first temperature programming to 720
DEG C, keep the temperature 75min, 10 DEG C/min of temperature rise；Be warming up to 1150 DEG C again, soaking time: 3.8h, 5 DEG C/min of temperature rise are cooled to room temperature.
Graphene is load metallic graphite carbon alkene, loads cerium oxide nanoparicles graphene.
Carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 45nm, 28 microns of length.
The ionic liquid of step (1) is 1- methylimidazole trifluoroacetate.
The complexing agent of step (3) is Ethyl formate.
Embodiment 6
A kind of graphene composite material, the general formula of composite material are as follows: LiMn0.62Fe0.38PO4, and it is compound in composite base material
There are graphene, carbon nanotube, the quality of the graphene is the 4.85g of the composite base material quality, the matter of the carbon nanotube
Amount is the 10.85g of the composite base material quality.
Composite base material also contains zinc oxide nanowire, and nanowire diameter 56nm, the quality of the zinc oxide nanowire is described
Composite base material quality 1.48.
The preparation method of graphene composite material includes following operating procedure: (1) according to mole of composite material each element
Dissolution process is carried out than nanoscale lithium source, manganese source, source of iron, phosphorus source to be added in ionic liquid；(2) under ultrasonication, to institute
It states and adds graphene, carbon nanotube in mixed system, changes zinc nano wire, 52 DEG C of maintenance system temperature, ultrasonic disperse time 82min；
(3) after complexing agent and mixed processing being added in step (2) system；(4) step (3) is dried to get composite material is arrived
Presoma；(5) electroslag remelting equipment is used, under inert gas shielding, after the surface grinding process of step (4) presoma
As in electrode insertion slag, slag uses CaF2、Al2O3, CaO slag system, CaF in slag system2Mass percentage content be 84g,
Al2O3Mass percentage content be 17.5g, the mass percentage content of CaO is 5.6g, is had a power failure cooling time: 9min；(6) will
The step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, and first temperature programming keeps the temperature 84min, temperature rise to 720 DEG C
10℃/min；Be warming up to 975 DEG C again, soaking time: 3.5h, 5 DEG C/min of temperature rise are cooled to room temperature.
Graphene is load metallic graphite carbon alkene, loading nano silvery particle graphene.
Carbon nanotube be nickel coat multi-walled carbon nanotube, thickness 48nm, 10-30 microns of length.
The ionic liquid of step (1) is 1- methylimidazole trifluoroacetate.
The complexing agent of step (3) is Ethyl formate.
Comparative test 1
Using the raw material and preparation step in embodiment 1, only replace graphene, carbon nanotube and oxygen with carbon nano-fiber
Change zinc nano wire and prepares composite material.
Comparative test 2
Using the raw material and preparation step in embodiment 2, only replace graphene, carbon nanotube and oxygen with superconduction electro-graphitic
Change zinc nano wire and prepares composite material.
Comparative test 3
Using the raw material and preparation step in embodiment 3, only replace graphene, carbon nanotube and oxygen with superconduction graphite alkene
Change zinc nano wire and prepares composite material.
Comparative test 4
Using the raw material and preparation step in embodiment 4, only replace graphene, carbon nanotube and oxidation with expanded graphite
Zinc nano wire prepares composite material.
Each embodiment of table 1 prepares the main performance index of graphene nanocomposite material
From table 1 it follows that embodiment preparation anode composite material can long-term work under conditions of high current,
It can be used on the special installations such as high power energy storage device, the popularization and application for being also it on electric car provides guarantee.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, therefore
Without departing from the technical solutions of the present invention, to the above embodiments according to the technical essence of the invention any simply to repair
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (6)
1. a kind of graphene composite material, it is characterised in that: the general formula of composite material are as follows: LiMn1-xFexPO4, wherein 0.15≤x
≤ 0.45, the composite gauge is nanoscale, and is compounded with graphene, carbon nanotube in the composite, the graphite
The quality of alkene is the 0.5%-5% of the composite material quality, and the quality of the carbon nanotube is the composite material quality
0.2%-12%；The composite material also contains zinc oxide nanowire, the nanowire diameter 20-60nm, the zinc-oxide nano
The quality of line is the composite material quality 0.1%-1.5%.
2. graphene composite material according to claim 1, it is characterised in that: the graphene is that load stannic oxide is received
Rice corpuscles graphene, supported cobaltosic oxide nano particle graphene, loading nano silvery particle graphene, load ceria are received
It is a kind of in rice corpuscles graphene.
3. graphene composite material according to claim 1, it is characterised in that: the carbon nanotube is that nickel coat multi wall carbon is received
Mitron, thickness 30-50nm, 10-30 microns of length.
4. the preparation method of graphene composite material described in -3 any claims according to claim 1, it is characterised in that: packet
Containing following operating procedure: (1) nanoscale lithium source, manganese source, source of iron, phosphorus source being added according to the molar ratio of composite material each element
Dissolution process is carried out in ionic liquid；(2) under ultrasonication, in the mixed system in above-mentioned steps (1) plus graphene, carbon are received
Mitron changes zinc nano wire, 35-55 DEG C of maintenance system temperature, ultrasonic disperse time 10-85min；(3) add in step (2) system
After entering complexing agent and mixed processing；(4) step (3) is dried to get the presoma of composite material is arrived；(5) electroslag weight is used
Melting apparatus under inert gas shielding, will be used as in electrode insertion slag after the surface grinding process of step (4) presoma,
Slag uses CaF2、Al2O3, CaO slag system, CaF in slag system2Mass percentage content be 75%-85%, Al2O3Quality hundred
Dividing than content is 12%-18%, and the mass percentage content of CaO is 4%-6%, is had a power failure cooling time: 5min-10min；(6)
The step (5) is put into heating in the heating furnace of initial temperature≤200 DEG C, first temperature programming is to 400 DEG C -750 DEG C, heat preservation
10-85min, 10 DEG C/min of temperature rise；Be warming up to 900 DEG C -1250 DEG C again, soaking time: 1h-4h, 5 DEG C/min of temperature rise are cooled to room
Temperature.
5. the preparation method of graphene composite material according to claim 4, it is characterised in that: the step (1) from
Sub- liquid is N- butyl-pyridinium hexafluorophosphate, N- butyl-pyridinium tetrafluoroborate, 1- methylimidazole dihydric phosphate, 1- methyl
One or more of imidazoles trifluoroacetate.
6. the preparation method of graphene composite material according to claim 4, it is characterised in that: the network of the step (3)
Mixture is one of ethylenediamine tetra-acetic acid, diethylenetriamine, citric acid, ethyl acetate, Ethyl formate, oxalic acid.
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| CN107964214A (en) * | 2017-10-26 | 2018-04-27 | 天津科技大学 | Ionic Liquid Modified carbon nano tube/epoxy resin composite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103311541A (en) * | 2012-03-08 | 2013-09-18 | 中国科学院金属研究所 | Composite cathode material for lithium ion batteries and preparation method thereof |
| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| CN103702934A (en) * | 2011-06-27 | 2014-04-02 | 新加坡国立大学 | An approach for manufacturing efficient mesoporous nano-composite positive electrode limn1-xfexpo4 materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020182497A1 (en) * | 2001-05-15 | 2002-12-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Carbon-containing lithium-iron composite phosphorus oxide for lithium secondary battery positive electrode active material and process for producing the same |
| CN103702934A (en) * | 2011-06-27 | 2014-04-02 | 新加坡国立大学 | An approach for manufacturing efficient mesoporous nano-composite positive electrode limn1-xfexpo4 materials |
| CN103311541A (en) * | 2012-03-08 | 2013-09-18 | 中国科学院金属研究所 | Composite cathode material for lithium ion batteries and preparation method thereof |
| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
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