CN105355881A - Graphene composite material and preparation method thereof - Google Patents
Graphene composite material and preparation method thereof Download PDFInfo
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- CN105355881A CN105355881A CN201510783491.6A CN201510783491A CN105355881A CN 105355881 A CN105355881 A CN 105355881A CN 201510783491 A CN201510783491 A CN 201510783491A CN 105355881 A CN105355881 A CN 105355881A
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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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
- H01M4/5805—Phosphides
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Abstract
The invention discloses a graphene composite material and a preparation method thereof and belongs to the technical field of cell positive material improvement. The graphene composite material has a general formula of LiMn1-xFexPO4, wherein x is greater than or equal to 0.15 and is less than or equal to 0.45. The composite positive material has the nanoscale size. A composite base comprises graphene and carbon nanotubes. The composite base comprises 0.5-5% by mass of the graphene and 0.2-12% by mass of the carbon nanotubes. Through formula optimization, a continuous interpenetrating network structure is formed and is conducive to conducting medium distribution on a two-phase interface and formation of a complete space conductive network. The selected ionic liquid can form a conductive network structure in the base so that the problem that the traditional medium system does not easily form a conductive network or has large electrical resistivity is solved and composite material conductive performances are improved.
Description
Technical field
The present invention relates to the technical field of the improvement of cell positive material, relate to a kind of graphene composite material, more particularly a kind of graphene composite material and preparation method thereof.
Background technology
Mono-layer graphite, is also called Graphene (Graphene), be a kind of by monolayer carbon atom with graphite key (sp
2) lattice structure of tightly packed one-tenth bi-dimensional cellular shape, therefore only have the thickness of a carbon atom, graphite key is the compound keys of covalent bond and metallic bond, can say it is the heaven-made match of insulator and electric conductor.Graphene is the thinnest in the world at present is also the hardest material, conductive coefficient is higher than CNT (carbon nano-tube) and diamond, under normal temperature, its electron mobility is also than carbon nanotube or silicon wafer height, resistivity than copper or silver lower, it is the material that resistivity is minimum in the world at present, the electric charge engineering properties of these uniquenesses makes the composite material greater functionality adding Graphene, not only show excellent mechanics and electric property, also there is excellent processing characteristics, for composite material provides more wide application.But the Graphene of structural integrity is the two dimensional crystal combined by the benzene hexatomic ring not containing any labile bond, chemical stability is high, its surface is in inert condition, interact more weak with other medium (as solvent etc.), and there is stronger Fan get Wa Li between the sheet of Graphene and sheet, easy generation is reunited, and makes it be insoluble in water and other conventional organic solvent, thus limits the further research and apply of Graphene.
Battery is mainly made up of positive pole, negative pole, electrolyte system, barrier film, and wherein positive electrode is the key factor of limiting lithium ion cell discharge capacity, therefore, finds a kind of good positive electrode to be the groundwork studying battery.Many positive electrodes of current research mainly contain the LiMO of layer structure
2(M=Ni, Co, Mn etc.), wherein comprise the mixing of independent a kind of and two kinds, three kinds metallic elements, the ternary system research of Li-Co-Ni-Mn-O many, much had high input large-scale production, but its cyclicity and safety issue need to solve.The LiMn of spinel-type
2o
4have three-dimensional ion channel, the good conductivity of ion, has also dropped into production application, but its structural stability is bad, causes its cyclicity poor.The LiMPO of olivine structural
4(M=Mn, Fe, Ni, Co etc.) have that fail safe is good, cyclicity is good, lower-price characteristic and attract a large amount of researcher, and last decade is for the LiMPO of olivine structural
4the research of material also achieves very large achievement, but the LiMPO of olivine structural
4ionic mobility and electronic conductivity are all lower, therefore be solve conductivity problems to the emphasis of its research, the main way one taked now is the particle as far as possible reducing material, as the material of synthesis nano, another carries out modification to material exactly, mainly contains metallic element or the powder of other good conductivity of doping, carries out coated (as carbon is coated) etc. material.
Due to olivine structural, there is excellent performance, there is good cyclicity and doubly forthright, therefore its research is had great importance.Preparation method about it has had many reports, as high temperature solid-state method, high-energy ball milling method, sol-gal process, liquid phase method etc.LiMn
xfe
1-xpO
4manganese in material and iron are all divalence, and the source of iron that most methods is used and manganese source are all by divalence, but the source of iron of divalence and manganese source very unstable, very easily oxidized, preparation process trouble and each ratio wayward.Therefore, how emphasis research of the present invention improves the electric conductivity of this iron manganese phosphate for lithium of composite material further.
Summary of the invention
The object of the invention is to, for above-mentioned the deficiencies in the prior art, provide a kind of graphene nanocomposite material and preparation method thereof, to solve composite material, the particularly electric conductivity of iron manganese phosphate for lithium electrode material.
Technical scheme of the present invention is achieved in that
A kind of graphene composite material, the general formula of composite material is: LiMn1-xFexPO4, wherein 0.15≤x≤0.45, described composite positive pole is of a size of nanoscale, and in composite base material, be compounded with Graphene, carbon nano-tube, the quality of described Graphene is the 0.5%-5% of described composite base material quality, and the quality of described carbon nano-tube is the 0.2%-12% of described composite base material quality.
Described composite base material is also containing zinc oxide nanowire, and described nanowire diameter 20-60nm, the quality of described zinc oxide nanowire is described composite base material quality 0.1%-1.5%.
The preparation method of graphene composite material, comprises following operating procedure: nano level lithium source, manganese source, source of iron, phosphorus source to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1); (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 35-55 DEG C, ultrasonic disperse time 10-85min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) electroslag remelting equipment is adopted, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF2, Al2O3, CaO slag system, in slag system, the mass percentage content of CaF2 is 75%-85%, the mass percentage content of Al2O3 is the mass percentage content of 12%-18%, CaO is 4%-6%, and have a power failure cooling time: 5min-10min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 400 DEG C-750 DEG C, insulation 10-85min, temperature rise 10 DEG C/min; Be warming up to 900 DEG C-1250 DEG C again, temperature retention time: 1h-4h, temperature rise 5 DEG C/min is cooled to room temperature.
Described Graphene is carried metal Graphene, can for a kind of in load tin dioxide nano-particle Graphene, supported cobaltosic oxide nano particle Graphene, loaded with nano silver particles Graphene, load cerium oxide nanoparicles Graphene.
Described carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 30-50nm, length 10-30 micron.
The ionic liquid of described step (1) is one or more in N-butyl-pyridinium hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, 1-methylimidazole dihydric phosphate, 1-methylimidazole trifluoroacetate.
The complexing agent of described step (3) is the one in ethylenediamine tetra-acetic acid, diethylenetriamine, citric acid, ethyl acetate, Ethyl formate, oxalic acid.
Beneficial effect of the present invention is as follows: by the optimization to formula, form continuous print inierpeneirating network structure, be conducive to conducting medium to distribute on two-phase interface, and form complete space conductive network, simultaneously because the ionic liquid selected forms conductive network structure in the base, overcome traditional sucrose system and not easily form conductive network or the larger shortcoming of resistivity own, improve the electric conductivity of composite material.
The preparation method of composite positive pole adopts complexing agent complexes metal ion, makes it dispersed at atomic level, and obtains nanometer materials by chemical method.The method makes the metal in Graphene, carbon nano-tube and matrix reach molecular level, and other is dispersed, realize nano metal particles to the inner compound of iron manganese phosphate for lithium material structure, coated compared to the carbon of particle surface, there is significant lifting to the electric conductivity of composite material.In addition, by heat treatment and annealing in process within specified temperatures, the composite structure that Graphene, carbon nano-tube and matrix are formed is stablized.Another ionic liquid, as novel excellent multifunctional solvent, solves the difficult problem that inorganic compound and organic compound are difficult to dissolve each other.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but do not form any limitation of the invention.
Lithium source, manganese source, source of iron, phosphorus source are the respective compound of the routine preparing composite material, as: lithium source can be organolithium, but not only selects butyl lithium, phenyl lithium, lithium carbonate; Manganese source can be Organic Manganese, but not only selects three carbonvlmethyl cyclopentadiene manganese, three carbonyl cyclopentadiene manganese, manganese nitrate; Source of iron can be Organic Iron, but not only selects ferric acetyl acetonade, thiocyanation iron, ferric nitrate, ferrocene; Phosphorus source can be phosphate, but not only selects phosphoric acid hydrogen ammonia, potassium hydrogen phosphate.
Main industrial chemicals illustrates: nano-graphene, carbon nano-tube, zinc oxide nanowire are purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd.; Ionic liquid is purchased from Chenzhou, Hunan Province Chemical Industry Science Co., Ltd.
Embodiment 1
A kind of graphene composite material, LiMn
0.85fe
0.15pO
4, described composite positive pole is of a size of nanoscale, and in composite base material, be compounded with Graphene, carbon nano-tube, and the quality of described Graphene is the 0.5g of described composite base material quality, and the quality of described carbon nano-tube is the 0.2g of described composite base material quality.
Composite base material is also containing zinc oxide nanowire 2g, described nanowire diameter 20nm, and the quality of described zinc oxide nanowire is described composite base material quality 0.1%.
The preparation method of graphene composite material, comprise following operating procedure: nano level three carbonvlmethyl cyclopentadiene manganese, ferric acetyl acetonade, phosphoric acid hydrogen ammonia to add in ionic liquid according to the mol ratio of each element of composite material and carries out dissolution process by (1), be carry out weighing at Li: Mn: Fe: P=1.0: 0.85: 0.15: 1 according to mol ratio, total amount is according to 1 mole of meter; (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 35 DEG C, ultrasonic disperse time 10min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, CaF in slag system
2mass percentage content be 75%, Al
2o
3mass percentage content be the mass percentage content of 12%, CaO be 4%, have a power failure cooling time: 5min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 400 DEG C, insulation 10min, temperature rise 10 DEG C/min; Be warming up to 900 DEG C again, temperature retention time: 1h, temperature rise 5 DEG C/min is cooled to room temperature.
Described Graphene is carried metal Graphene, is load tin dioxide nano-particle Graphene.
Described carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 30nm, length 100 microns.
The ionic liquid of described step (1) is N-butyl-pyridinium hexafluorophosphate.
The complexing agent of described step (3) is ethylenediamine tetra-acetic acid.
Embodiment 2
A kind of graphene composite material, LiMn
0.55fe
0.45pO
4, in composite base material, be compounded with Graphene, carbon nano-tube, the quality of described Graphene is the 5g of described composite base material quality, and the quality of described carbon nano-tube is the 12g of described composite base material quality.
Composite base material is also containing zinc oxide nanowire, and nanowire diameter 60nm, the quality of zinc oxide nanowire is composite base material quality 1.5g.
The preparation method of graphene composite material, comprise following operating procedure: nano level phenyl lithium, three carbonyl cyclopentadiene manganese, ferrocene, potassium hydrogen phosphate to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1), be carry out weighing at Li: Mn: Fe: P=1.0: 0.55: 0.45: 1 according to mol ratio, total amount is according to 1 mole of meter; (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 55 DEG C, ultrasonic disperse time 85min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, CaF in slag system
2mass percentage content be 85g, Al
2o
3mass percentage content be the mass percentage content of 18g, CaO be 6g, have a power failure cooling time: 10min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 750 DEG C, insulation 85min, temperature rise 10 DEG C/min; Be warming up to 1250 DEG C again, temperature retention time: 4h, temperature rise 5 DEG C/min is cooled to room temperature.
Described Graphene is carried metal Graphene, for a kind of in supported cobaltosic oxide nano particle Graphene 1.0g, loaded with nano silver particles Graphene 3.5g, load cerium oxide nanoparicles Graphene 0.5g.
Described carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 50nm, length 30 microns.
In the ionic liquid 1-methylimidazole trifluoroacetate of described step (1).
The complexing agent of described step (3) is diethylenetriamine.
Embodiment 3
A kind of graphene composite material, LiMn
0.8fe
0.2pO
4, described composite positive pole is of a size of nanoscale, and in composite base material, be compounded with Graphene, carbon nano-tube, and the quality of described Graphene is the 1.5g of described composite base material quality, and the quality of described carbon nano-tube is the 0.8g of described composite base material quality.
Base material is containing zinc oxide nanowire, and described nanowire diameter 28nm, the quality of described zinc oxide nanowire is described composite base material quality 0.8g.
The preparation method of ink alkene composite material, comprises following operating procedure: nano level lithium source, manganese source, source of iron, phosphorus source to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1); (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 40 DEG C, ultrasonic disperse time 25min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, CaF in slag system
2mass percentage content be 78g, Al
2o
3mass percentage content be the mass percentage content of 14g, CaO be 4.5g, have a power failure cooling time: 6min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 450 DEG C, insulation 15min, temperature rise 10 DEG C/min; Be warming up to 980 DEG C again, temperature retention time: 1.5h, temperature rise 5 DEG C/min is cooled to room temperature.
Described Graphene is carried metal Graphene, supported cobaltosic oxide nano particle Graphene.
Described carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 35nm, length 15 microns.
The ionic liquid of described step (1) is, N-butyl-pyridinium tetrafluoroborate.
The complexing agent of described step (3) is citric acid.
Embodiment 4
A kind of graphene composite material, LiMn
0.7fe
0.3pO
4, and in composite base material, being compounded with Graphene, carbon nano-tube, the quality of described Graphene is the 1.2g of described composite base material quality, and the quality of described carbon nano-tube is the 8.3g of described composite base material quality.
Composite base material is also containing zinc oxide nanowire, and nanowire diameter 35nm, the quality of described zinc oxide nanowire is described composite base material quality 0.65g.
The preparation method of graphene composite material, comprises following operating procedure: nano level lithium source, manganese source, source of iron, phosphorus source to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1); (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 40.5 DEG C, ultrasonic disperse time 45min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, in slag system, the mass percentage content of CaF2 is 83.5g, Al
2o
3mass percentage content be the mass percentage content of 14.6g, CaO be 5.5g, have a power failure cooling time: 7.5min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 550 DEG C, insulation 75min, temperature rise 10 DEG C/min; Be warming up to 1050 DEG C again, temperature retention time: 3.6h, temperature rise 5 DEG C/min is cooled to room temperature.
Graphene is carried metal Graphene, loaded with nano silver particles Graphene.
Carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 42nm, length 28 microns.
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 is: LiMn
0.58fe
0.42pO
4, described composite positive pole is of a size of nanoscale, and in composite base material, be compounded with Graphene, carbon nano-tube, and the quality of described Graphene is the 4.64g of described composite base material quality, and the quality of described carbon nano-tube is the 11.3g of described composite base material quality.
Composite base material is containing zinc oxide nanowire, and nanowire diameter 55nm, the quality of described zinc oxide nanowire is described composite base material quality 1.38g.
The preparation method of graphene composite material, comprises following operating procedure: nano level lithium source, manganese source, source of iron, phosphorus source to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1); (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 51 DEG C, ultrasonic disperse time 82min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, CaF in slag system
2mass percentage content be 82.3g, Al
2o
3mass percentage content be the mass percentage content of 17.5g, CaO be 5.68g, have a power failure cooling time: 5min-10min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 720 DEG C, insulation 75min, temperature rise 10 DEG C/min; Be warming up to 1150 DEG C again, temperature retention time: 3.8h, temperature rise 5 DEG C/min is cooled to room temperature.
Graphene is carried metal Graphene, load cerium oxide nanoparicles Graphene.
Carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 45nm, length 28 microns.
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 is: LiMn
0.62fe
0.38pO
4, and in composite base material, being compounded with Graphene, carbon nano-tube, the quality of described Graphene is the 4.85g of described composite base material quality, and the quality of described carbon nano-tube is the 10.85g of described composite base material quality.
Composite base material is also containing zinc oxide nanowire, and nanowire diameter 56nm, the quality of described zinc oxide nanowire is described composite base material quality 1.48.
The preparation method of graphene composite material, comprises following operating procedure: nano level lithium source, manganese source, source of iron, phosphorus source to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1); (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 52 DEG C, ultrasonic disperse time 82min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, CaF in slag system
2mass percentage content be 84g, Al
2o
3mass percentage content be the mass percentage content of 17.5g, CaO be 5.6g, have a power failure cooling time: 9min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 720 DEG C, insulation 84min, temperature rise 10 DEG C/min; Be warming up to 975 DEG C again, temperature retention time: 3.5h, temperature rise 5 DEG C/min is cooled to room temperature.
Graphene is carried metal Graphene, loaded with nano silver particles Graphene.
Carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 48nm, length 10-30 micron.
The ionic liquid of step (1) is 1-methylimidazole trifluoroacetate.
The complexing agent of step (3) is Ethyl formate.
Contrast test 1
Adopt the raw material in embodiment 1 and preparation process, only replace Graphene, carbon nano-tube and zinc oxide nanowire with carbon nano-fiber and prepare composite material.
Contrast test 2
Adopt the raw material in embodiment 2 and preparation process, only replace Graphene, carbon nano-tube and zinc oxide nanowire with superconduct graphite and prepare composite material.
Contrast test 3
Adopt the raw material in embodiment 3 and preparation process, only replace Graphene, carbon nano-tube and zinc oxide nanowire with superconduction graphite alkene and prepare composite material.
Contrast test 4
Adopt the raw material in embodiment 4 and preparation process, only replace Graphene, carbon nano-tube and zinc oxide nanowire with expanded graphite and prepare composite material.
The each embodiment of table 1 prepares the main performance index of graphene nanocomposite material
As can be seen from Table 1, embodiment prepare anode composite material can long-term work under conditions of high current, can be used on the special installations such as high power energy storage device, also for its popularization and application on electric automobile provides guarantee.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, therefore everyly do not depart from technical solution of the present invention content, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. a graphene composite material, is characterized in that: the general formula of composite material is: LiMn
1-xfe
xpO
4wherein 0.15≤x≤0.45, described composite positive pole is of a size of nanoscale, and in composite base material, be compounded with Graphene, carbon nano-tube, the quality of described Graphene is the 0.5%-5% of described composite base material quality, and the quality of described carbon nano-tube is the 0.2%-12% of described composite base material quality.
2. graphene composite material according to claim 1, is characterized in that: described composite base material is also containing zinc oxide nanowire, and described nanowire diameter 20-60nm, the quality of described zinc oxide nanowire is described composite base material quality 0.1%-1.5%.
3. graphene composite material according to claim 1, it is characterized in that: described Graphene is carried metal Graphene, can for a kind of in load tin dioxide nano-particle Graphene, supported cobaltosic oxide nano particle Graphene, loaded with nano silver particles Graphene, load cerium oxide nanoparicles Graphene.
4. graphene composite material according to claim 1, is characterized in that: described carbon nano-tube is nickel coat multi-walled carbon nano-tubes, thickness 30-50nm, length 10-30 micron.
5. the preparation method of the graphene composite material according to the arbitrary claim of claim 1-4, is characterized in that: comprise following operating procedure: nano level lithium source, manganese source, source of iron, phosphorus source to add in ionic liquid according to the mol ratio of each element of composite material and carry out dissolution process by (1); (2), under ultrasonication, in described mixed system, Graphene, carbon nano-tube, change zinc nano wire is added, maintenance system temperature 35-55 DEG C, ultrasonic disperse time 10-85min; (3) in step (2) system, complexing agent is added and after mixed processing; (4) step (3) drying process, namely obtains the presoma of composite material; (5) adopt electroslag remelting equipment, under inert gas shielding, insert in slag using after the surface finish process of step (4) described presoma as electrode, slag adopts CaF
2, Al
2o
3, CaO slag system, CaF in slag system
2mass percentage content be 75%-85%, Al
2o
3mass percentage content be the mass percentage content of 12%-18%, CaO be 4%-6%, have a power failure cooling time: 5min-10min; (6) described step (5) is put into the heating furnace heating of initial temperature≤200 DEG C, first temperature programming to 400 DEG C-750 DEG C, insulation 10-85min, temperature rise 10 DEG C/min; Be warming up to 900 DEG C-1250 DEG C again, temperature retention time: 1h-4h, temperature rise 5 DEG C/min is cooled to room temperature.
6. the preparation method of graphene composite material according to claim 5, is characterized in that: the ionic liquid of described step (1) is one or more in N-butyl-pyridinium hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, 1-methylimidazole dihydric phosphate, 1-methylimidazole trifluoroacetate.
7. the preparation method of graphene composite material according to claim 5, is characterized in that: the complexing agent of described step (3) is the one in ethylenediamine tetra-acetic acid, diethylenetriamine, citric acid, ethyl acetate, Ethyl formate, oxalic acid.
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