CN105870419A - Preparation method and application of graphene and fullerene composite nano material - Google Patents
Preparation method and application of graphene and fullerene composite nano material Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a graphene and fullerene composite nano material. The method comprises the steps that sulfur-containing resin serves as a solid phase carbon source and sulfur source, transition metal acetate serves as a catalyst precursor, the sulfur-containing resin is close to the air inlet end of a heating furnace, transition metal acetate is close to the air outlet end of the heating furnace, heat treatment is conducted under the protection of inert gas, heat-treated products are collected, acid treatment, washing, filtering and drying are conducted, and the graphene and fullerene composite nano material is obtained, wherein the heat treatment temperature ranges from 600 DEG C to 900 DEG C, the heat treatment time ranges from 10 min to 60 min, and the temperature rising speed ranges from 5 DEG C/min to 20 DEG C/min. The method is a chemical-vapor deposition technology on the basis that the sulfur-containing resin serves as the solid phase carbon source and sulfur source, and transition metal acetate serves as the catalyst, large-scale one-step preparation of the graphene and fullerene composite nano material is achieved, and the problems that in the prior art, the steps are complex, the equipment is expensive, operation is tedious, and batch production is difficult are solved.
Description
Technical field
The present invention relates to graphene-based technical field of composite preparation, more particularly, to the preparation method and applications of a kind of Graphene/fullerene composite nano materials.
Background technology
Fullerene and Graphene have attracted the attention of numerous research worker by the most excellent physicochemical characteristics, it is desirable to fullerene and the special construction of Graphene and superiority mass-energy and bring breakthrough progress to electrochemical energy source material and micro-nano electronic device.Currently, the research and development about fullerene and Graphene has become as Liao Yige world focus.Fullerene and Graphene are all the material with carbon elements of nano-scale, have great specific surface area, good electric conductivity and the chemical characteristic of excellence.But the dissolubility of fullerene and dispersibility are poor, it is difficult to make device, thus its actual application is limited significantly.Select suitable method to prepare " Graphene/fullerene " composite nano materials, a kind of cooperative effect can be produced between them so that it is various physical and chemical performances are strengthened, thus this composite has great application prospect in a lot of fields.
First, fullerene dispersibility this problem poor can effectively be solved by the supporting role of two-dimensional graphene；Meanwhile, the particular interface effect of composite nano materials, small-size effect, quantum size effect etc. so that it is there are the physicochemical properties such as unique optical, electrical, magnetic, heat.Thus, " Graphene/fullerene " composite nano materials will obtain extremely wide application in fields such as electrochemical catalysis and energy storage, bio-sensing, electronic devices.
The performance excellent in view of " Graphene/fullerene " composite nano materials and wide application prospect, explore the high efficiency preparation method of synthesis " Graphene/fullerene " composite nano materials, control fullerene in the growth of graphenic surface and distribution, there is important scientific meaning and practical value.Currently, the preparation process of " Graphene/fullerene " composite nano materials generally includes three steps: (1) first prepares graphene nanometer sheet with the method for chemical oxidation or metal catalytic；(2) fullerene nano-particle is prepared by technology such as arc discharge method, laser evaporization method, flame combustion process；(3) on graphene nanometer sheet, load fullerene by solution dispersion and chemical Coupling method and form composite construction.Obviously, above-mentioned multistep preparation process complex operation and power consumption are higher, are difficulty with the production in enormous quantities of " Graphene/fullerene " composite nano materials.Particularly, fullerene traditional preparation methods (arc discharge method, laser evaporization method, flame combustion process etc.) device therefor structure is complicated and expensive, and the exploitation to follow-up composite brings a great difficult problem.In consideration of it, the industrialization promoting " Graphene/fullerene " composite nano materials will be played vital effect by a kind of preparation method cheap, simple of exploitation.
Summary of the invention
The technical problem to be solved is the technical problem that Graphene/fullerene composite nano materials preparation process is loaded down with trivial details, cost is high, energy consumption is big overcoming prior art to exist, it is provided that the preparation method of a kind of new Graphene/fullerene composite nano materials.
Second object of the present invention is to provide Graphene/fullerene composite nano materials that said method obtains.
Third object of the present invention is to provide the application of above-mentioned Graphene/fullerene composite nano materials.
It is an object of the invention to be achieved by the following technical programs:
A kind of preparation method of Graphene/fullerene composite nano materials; it is using thioretinite as solid-phase carbon source and sulfur source; using transition metal acetate as catalyst precursor; described thioretinite is near the air inlet end of heating furnace; transition metal acetate is near the outlet side of heating furnace; under inert gas shielding, carry out heat treatment, collect heat-treated products, through acid treatment, wash, filter, be drying to obtain Graphene/fullerene composite nano materials；The temperature of described heat treatment is 600～900 DEG C, and heat time heating time is 10 min～60min, and programming rate is 5～20 DEG C/min.
The present invention uses multi-functional " thioretinite " can be as the carbon source of vapour deposition and sulfur source as solid-phase carbon source and sulfur source, the carbon containing discharged in heat treatment process and sulfur-bearing atmosphere.This process belongs to the class chemical vapour deposition technique automatically supplying atmosphere, fundamentally reduces the preparation cost of material.Additionally, thioretinite is near the air inlet end of heating furnace, becoming carbon containing and sulfur-bearing atmosphere after thioretinite gasification, use transition metal acetate as catalyst precursor, in heat treatment process, first acetate be reduced to nano metal nickel and then catalysis carbon-containing atmosphere obtains fullerene；Metallic nickel reacts generation metal sulfide continuation catalysis carbon-containing atmosphere further and obtains Graphene with sulfur-bearing atmosphere.
Preferably, the mass ratio of described thioretinite and transition metal acetate is 1:0.1～0.5.
Preferably, described acid treatment refer to heat-treated products with 1～5mol/L soak with hydrochloric acid 1～3h.
Preferably, before carrying out heat treatment, described thioretinite drying pulverization process, after pulverizing, particle diameter is 50 μm～100 μm.
Preferably, before carrying out heat treatment, described transition metal acetate salt particle diameter after ball-milling treatment, ball milling is 1 μm～5 μm.
Preferably, one or more in nickel acetate, cobaltous acetate, the manganese acetate of described transition metal acetate.
Preferably, one or more in thiourea resin, thiol resin, the sulfonic group resin of described thioretinite.
As a kind of specific embodiment, the above-mentioned preparation method of the present invention comprises the following steps:
(1) selection in solid-phase carbon source/sulfur source and pre-treatment: selecting thioretinite is solid-phase carbon source and sulfur source, dries pulverization process, and after pulverizing, particle diameter is 50 μm～100 μm；
(2) selection of catalyst precursor and pre-treatment: selecting cheap transition metal acetate as catalyst precursor, and place and carry out ball-milling treatment in ball mill, after ball milling, particle diameter is 1 μm～5 μm；
(3) solid-phase carbon source/sulfur source of step (1) gained is positioned over the heating region (air inlet end direction) of tube furnace; the catalyst precursor of step (2) gained is positioned over the heating region (direction, outlet side) of tube furnace; and under the protection of noble gas, carry out a step heat treatment; the temperature of described heat treatment is 600～900 DEG C; heat time heating time is 10 min～60min, and programming rate is 5～20 DEG C/min.
(4) product post processing: the catalysate of step (3) gained is collected, remove impurity, washs, filter, be dried and i.e. prepare " Graphene/fullerene " composite nano materials.
The dedoping step of step (4) is acid treatment, i.e. refer to heat-treated products with 1～5mol/L soak with hydrochloric acid 1～3h.
The present invention also provides for Graphene/fullerene composite nano materials that above-mentioned preparation method obtains.
The present invention also provides for the application of above-mentioned Graphene/fullerene composite nano materials；Specifically, described application is for utilizing Graphene/fullerene composite nano materials to prepare lithium ion battery negative.
Compared with prior art, the method have the advantages that
The invention provides the preparation method of a kind of Graphene/fullerene composite nano materials; it is using thioretinite as solid-phase carbon source and sulfur source; using transition metal acetate as catalyst precursor; described thioretinite is near the air inlet end of heating furnace; transition metal acetate is near the outlet side of heating furnace; under inert gas shielding, carry out heat treatment, collect heat-treated products, through acid treatment, wash, filter, be drying to obtain Graphene/fullerene composite nano materials；The temperature of described heat treatment is 600～900 DEG C, and heat time heating time is 10 min～60min, and programming rate is 5～20 DEG C/min；The method be based on " thioretinite " be solid-phase carbon source/sulfur source, " transient metal sulfide " be the class chemical vapour deposition technique of catalyst, an extensive step prepares " Graphene/fullerene " composite nano materials, solve the problems such as current its step complexity faced, apparatus expensive, complex operation, difficulty batch production.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the present invention prepares " Graphene/fullerene " composite nano materials device therefor device: 1 be catalyst precursor, 2 be solid-phase carbon source/sulfur source, 3 be heating region, 4 be tube furnace, 5 be air inlet end, 6 for outlet side.
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of " Graphene/fullerene " composite nano materials prepared by embodiment 1.
Fig. 3 is scanning electron microscope (SEM) image of " Graphene/fullerene " composite nano materials prepared by embodiment 1, Fig. 3 A be scale be 1 μm figure, Fig. 3 B be scale be 100nm figure.
Fig. 4 is transmission electron microscope (TEM) image of " Graphene/fullerene " composite nano materials prepared by embodiment 1, wherein, Fig. 4 A be scale be 200nm figure, Fig. 4 B be scale be 2nm figure.
Fig. 5 is the constant current charge-discharge curve of " Graphene/fullerene " composite cathode material for lithium ion cell prepared by embodiment 1, and electric current density is 1000mA/g.
Detailed description of the invention
Further illustrate present disclosure below in conjunction with Figure of description and specific embodiment, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the simple modification that the inventive method, step or condition are made or replacement, belong to the scope of the present invention；If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Embodiment
1
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Taking 20g gained " thiourea resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace, and carry out heat treatment (as shown in Figure 1) under the protection of noble gas, the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 5 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " nano composite material prepared by said method, wherein Graphene size is about 150nm, and fullerene size is about 20nm, and composite specific surface area is 425 m2 g-1；Its reversible discharge capacity of negative material being applied to lithium ion battery is 568 mAh g-1.Fig. 2 is the X-ray diffracting spectrum of the composite nano materials prepared by embodiment 1.Fig. 3 is the scanning electron microscope image of the composite nano materials prepared by embodiment 1.Fig. 4 is the transmission electron microscope image of the composite nano materials prepared by embodiment 1.Fig. 5 is the constant current charge-discharge curve (electric current density 1000mA/g) of the combination electrode material prepared by embodiment 1.
Embodiment
2
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiourea resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 300nm, and fullerene size is about 15nm, and composite specific surface area is 448 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 595 mAh g-1。
Embodiment
3
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiourea resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 20 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 250nm, and fullerene size is about 12nm, and composite specific surface area is 430 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 568 mAh g-1。
Embodiment
4
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiourea resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 600 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 200nm, and fullerene size is about 18nm, and composite specific surface area is 441 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 581 mAh g-1。
Embodiment
5
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiourea resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 900 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 400nm, and fullerene size is about 30nm, and composite specific surface area is 395 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 548 mAh g-1。
Embodiment
6
Solid-phase carbon source/sulfur source " thiol resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiol resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 500nm, and fullerene size is about 25nm, and composite specific surface area is 434 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 587 mAh g-1。
Embodiment
7
Solid-phase carbon source/sulfur source " sulfonic group resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " nickel acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " sulfonic group resin " granule and 7g gained " nickel acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 450nm, and fullerene size is about 20nm, and composite specific surface area is 445 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 591 mAh g-1。
Embodiment
8
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " cobaltous acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiourea resin " granule and 7g gained " cobaltous acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 600nm, and fullerene size is about 35nm, and composite specific surface area is 423 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 576 mAh g-1。
Embodiment
9
Solid-phase carbon source/sulfur source " thiourea resin " being placed 80 DEG C of dry 12h in an oven, then carries out break process with pulverizer, broken rear mean diameter is 100 μm；Being placed in ball mill by catalyst precursor " manganese acetate " and carry out ball-milling treatment, after ball milling, mean diameter is 5 μm；Take 20g gained " thiourea resin " granule and 7g gained " manganese acetate " granule is positioned in tube furnace; and under the protection of noble gas, carry out heat treatment (as shown in Figure 1); the temperature of heat treatment is 700 DEG C, and heat time heating time is 30min, and programming rate is 10 DEG C/min；Finally gained catalysate is collected, and is 2h with the 2mol/L soak with hydrochloric acid time, then with distilled water wash, filter, be dried i.e. prepare " Graphene/fullerene " composite nano materials.
" Graphene/fullerene " composite nano materials prepared by said method, wherein Graphene size is about 700nm, and fullerene size is about 40nm, and composite specific surface area is 407 m2 g-1, its reversible discharge capacity of negative material being applied to lithium ion battery is 552 mAh g-1。
Comparative example
1
Experimental technique with embodiment 1, unique unlike, the mass ratio of thiourea resin and nickel acetate is 1:1；" Graphene/fullerene " composite nano materials prepared by described method, wherein Graphene size is about 100m, and almost without fullerene structure, composite specific surface area is 325 m2 g-1；Its reversible discharge capacity of negative material being applied to lithium ion battery is 436 mAh g-1。
Comparative example
2
Experimental technique with embodiment 1, unique unlike, the mean diameter of thioretinite is 20 μm, " Graphene/fullerene " composite nano materials prepared by described method, wherein Graphene size is about 200m, and almost without fullerene structure, composite specific surface area is 307 m2 g-1；Its reversible discharge capacity of negative material being applied to lithium ion battery is 412 mAh g-1。
Comparative example
3
Experimental technique with embodiment 1, unique unlike, the mean diameter of nickel acetate is 10 μm, " Graphene // fullerene " composite nano materials prepared by described method, wherein Graphene size is about 500m, and almost without fullerene structure, composite specific surface area is 286 m2 g-1；Its reversible discharge capacity of negative material being applied to lithium ion battery is 395 mAh g-1。
Claims (10)
1. the preparation method of Graphene/fullerene composite nano materials; it is characterized in that; using thioretinite as solid-phase carbon source and sulfur source; using transition metal acetate as catalyst precursor; described thioretinite is near the air inlet end of heating furnace, and transition metal acetate, near the outlet side of heating furnace, carries out heat treatment under inert gas shielding; collect heat-treated products, through acid treatment, wash, filter, be drying to obtain Graphene/fullerene composite nano materials；The temperature of described heat treatment is 600～900 DEG C, and heat time heating time is 10 min～60min, and programming rate is 5～20 DEG C/min.
The preparation method of Graphene/fullerene composite nano materials the most according to claim 1, it is characterised in that the mass ratio of described thioretinite and transition metal acetate is 1:0.1～0.5.
The preparation method of Graphene/fullerene composite nano materials the most according to claim 1, it is characterised in that described acid treatment refer to heat-treated products with 1～5mol/L soak with hydrochloric acid 1～3h.
The most according to claim 1, the preparation method of Graphene/fullerene composite nano materials, it is characterised in that before carrying out heat treatment, described thioretinite drying pulverization process, after pulverizing, particle diameter is 50 μm～100 μm.
The most according to claim 1, the preparation method of Graphene/fullerene composite nano materials, it is characterised in that before carrying out heat treatment, described transition metal acetate salt particle diameter after ball-milling treatment, ball milling is 1 μm～5 μm.
The preparation method of Graphene/fullerene composite nano materials the most according to claim 1, it is characterised in that described transition metal acetate is selected from one or more in nickel acetate, cobaltous acetate, manganese acetate.
The preparation method of Graphene/fullerene composite nano materials the most according to claim 1, it is characterised in that described thioretinite is selected from one or more in thiourea resin, thiol resin, sulfonic group resin.
8. Graphene/fullerene composite nano materials that preparation method described in any one of claim 1 to 7 obtains.
9. the application of Graphene described in claim 8/fullerene composite nano materials.
Application the most according to claim 9, it is characterised in that described application prepares lithium ion battery negative for utilizing Graphene/fullerene composite nano materials.
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| CN106006617A (en) * | 2016-05-25 | 2016-10-12 | 广东石油化工学院 | Preparation method and application of graphene hollow carbon nanocages |
| CN106847535A (en) * | 2016-12-16 | 2017-06-13 | 吴中区穹窿山天仲高分子材料技术研究所 | A kind of Graphene fulvene compounding material and preparation method and purposes |
| WO2018182976A1 (en) * | 2017-03-27 | 2018-10-04 | Lyten, Inc. | Carbon allotropes |
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| US11309545B2 (en) | 2019-10-25 | 2022-04-19 | Lyten, Inc. | Carbonaceous materials for lithium-sulfur batteries |
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