CN105870419B - A kind of preparation method and applications of graphene/fullerene composite nano materials - Google Patents

Abstract

The invention discloses a preparation method of a graphene/fullerene composite nanomaterial, which uses a sulfur-containing resin as a solid-phase carbon source and a sulfur source, and uses a transition metal acetate as a catalyst precursor. The sulfur-containing resin is close to The gas inlet end of the heating furnace, the transition metal acetate is close to the gas outlet end of the heating furnace, heat treatment is carried out under the protection of inert gas, the heat treatment product is collected, and the graphene/fullerene composite nano material; the heat treatment temperature is 600-900°C, the heating time is 10-60min, and the heating rate is 5-20°C/min; the method is based on "sulfur-containing resin" as a solid-phase carbon source/sulfur source, ""Transition metal sulfide" as a catalyst-like chemical vapor deposition technology, large-scale one-step preparation of "graphene/fullerene" composite nanomaterials, to solve the current problems of complex steps, expensive equipment, cumbersome operations, and difficulty in mass production .

Description

A kind of preparation method and application of graphene/fullerene composite nanomaterial

technical field

The invention relates to the technical field of preparation of graphene-based composite materials, and more specifically, to a preparation method and application of graphene/fullerene composite nanomaterials.

Background technique

Fullerene and graphene have attracted the attention of many researchers due to their excellent physical and chemical properties. It is hoped that the special structure and excellent properties of fullerene and graphene will bring breakthroughs to electrochemical energy materials and micro-nano electronic devices. Progress. Currently, the research and development of fullerene and graphene has become an international hotspot. Both fullerene and graphene are nano-sized carbon materials with large specific surface area, good electrical conductivity and excellent chemical properties. However, the solubility and dispersibility of fullerene are poor, and it is difficult to make devices, so its practical application is greatly limited. Choose a suitable method to prepare "graphene/fullerene" composite nanomaterials, which can produce a synergistic effect and enhance various physical and chemical properties. Therefore, this composite material has great potential in many fields. Application prospect.

First of all, the problem of poor dispersion of fullerenes can be effectively solved by the supporting effect of two-dimensional graphene; at the same time, the special interface effect, small size effect, and quantum size effect of composite nanomaterials make it have unique optical, Physical and chemical properties such as electricity, magnetism, and heat. Therefore, "graphene/fullerene" composite nanomaterials will be widely used in electrochemical catalysis and energy storage, biosensing, electronic devices and other fields.

In view of the excellent performance and broad application prospects of "graphene/fullerene" composite nanomaterials, explore the efficient preparation method of "graphene/fullerene" composite nanomaterials, control the growth and distribution, has important scientific significance and practical value. At present, the preparation process of "graphene/fullerene" composite nanomaterials usually includes three steps: (1) first prepare graphene nanosheets by chemical oxidation or metal catalysis; (2) by arc discharge method, laser evaporation (3) Fullerenes were loaded on graphene nanosheets to form a composite structure by solution dispersion and chemical coupling methods. Obviously, the above multi-step preparation process is cumbersome and energy-intensive, and it is difficult to achieve mass production of "graphene/fullerene" composite nanomaterials. In particular, the equipment used in the traditional preparation methods of fullerenes (arc discharge method, laser evaporation method, flame combustion method, etc.) is complex and expensive, which brings great difficulties to the development of subsequent composite materials. In view of this, the development of a cheap and simple preparation method will play a vital role in promoting the industrialization of "graphene/fullerene" composite nanomaterials.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the technical problems of cumbersome preparation process, high cost and high energy consumption of graphene/fullerene composite nanomaterials existing in the prior art, and provide a new graphene/fullerene composite nanomaterial The method of preparation of the material.

The second object of the present invention is to provide the graphene/fullerene composite nanomaterial obtained by the above method.

The third object of the present invention is to provide the application of the above-mentioned graphene/fullerene composite nanomaterial.

The purpose of the present invention is achieved through the following technical solutions:

A kind of preparation method of graphene/fullerene composite nano material, is to use sulfur-containing resin as solid-phase carbon source and sulfur source, with transition metal acetate as catalyst precursor, described sulfur-containing resin is close to the inlet of heating furnace At the gas end, the transition metal acetate is close to the gas outlet of the heating furnace, heat-treated under the protection of an inert gas, and the heat-treated product is collected, treated with acid, washed, filtered, and dried to obtain a graphene/fullerene composite nanomaterial; The heat treatment temperature is 600-900°C, the heating time is 10 min-60 min, and the heating rate is 5-20°C/min.

The present invention adopts multifunctional "sulfur-containing resin" as the solid-phase carbon source and sulfur source, and the carbon-containing and sulfur-containing atmosphere released during the heat treatment process can be used as the carbon source and sulfur source for vapor deposition. This process belongs to the quasi-chemical vapor deposition technology of self-supply atmosphere, which fundamentally reduces the preparation cost of materials. In addition, the sulfur-containing resin is close to the gas inlet end of the heating furnace. After the sulfur-containing resin is gasified, it becomes a carbon-containing and sulfur-containing atmosphere. A transition metal acetate is used as the catalyst precursor. During the heat treatment, the acetate is first reduced to nano-metal Nickel further catalyzes a carbon-containing atmosphere to obtain fullerenes; metal nickel further reacts with a sulfur-containing atmosphere to form metal sulfides and continues to catalyze a carbon-containing atmosphere to obtain graphene.

Preferably, the mass ratio of the sulfur-containing resin to the transition metal acetate is 1:0.1-0.5.

Preferably, the acid treatment refers to immersing the heat-treated product in 1-5 mol/L hydrochloric acid for 1-3 hours.

Preferably, before heat treatment, the sulfur-containing resin is dried and crushed, and the particle size after crushing is 50 μm-100 μm.

Preferably, before heat treatment, the transition metal acetate salt is ball milled, and the particle size after ball milling is 1 μm˜5 μm.

Preferably, the transition metal acetate is selected from one or more of nickel acetate, cobalt acetate and manganese acetate.

Preferably, the sulfur-containing resin is selected from one or more of thiourea resins, mercapto resins, and sulfonic acid resins.

As a specific embodiment, the above-mentioned preparation method of the present invention comprises the following steps:

(1) Selection and pretreatment of solid-phase carbon source/sulfur source: select sulfur-containing resin as solid-phase carbon source and sulfur source, dry and pulverize, and the particle size after pulverization is 50 μm to 100 μm;

(2) Selection and pretreatment of catalyst precursors: select cheap transition metal acetate as catalyst precursors, and place them in a ball mill for ball milling treatment. The particle size after ball milling is 1 μm to 5 μm;

(3) Place the solid-phase carbon source/sulfur source obtained in step (1) in the heating zone of the tube furnace (in the direction of the gas inlet), and place the catalyst precursor obtained in step (2) in the heating zone of the tube furnace. temperature zone (to the direction of the gas outlet), and conduct one-step heat treatment under the protection of inert gas. The temperature of the heat treatment is 600-900°C, the heating time is 10 min-60min, and the heating rate is 5-20°C/min.

(4) Product post-processing: Collect, remove impurities, wash, filter, and dry the catalytic product obtained in step (3) to obtain a "graphene/fullerene" composite nanomaterial.

The impurity removal process in step (4) is acid treatment, that is, the heat-treated product is soaked in 1-5 mol/L hydrochloric acid for 1-3 hours.

The present invention also provides the graphene/fullerene composite nanomaterial obtained by the above preparation method.

The present invention also provides the application of the above-mentioned graphene/fullerene composite nanomaterial; specifically, the application is to use the graphene/fullerene composite nanomaterial to prepare a lithium ion battery negative electrode.

Compared with the prior art, the present invention has the following beneficial effects:

The invention provides a preparation method of a graphene/fullerene composite nanomaterial, which uses a sulfur-containing resin as a solid-phase carbon source and a sulfur source, and uses a transition metal acetate as a catalyst precursor. The sulfur-containing resin is close to The gas inlet end of the heating furnace, the transition metal acetate is close to the gas outlet end of the heating furnace, heat treatment is carried out under the protection of inert gas, the heat treatment product is collected, and the graphene/fullerene composite nano material; the heat treatment temperature is 600-900°C, the heating time is 10-60min, and the heating rate is 5-20°C/min; the method is based on "sulfur-containing resin" as a solid-phase carbon source/sulfur source, " "Transition metal sulfide" as a catalyst-like chemical vapor deposition technology, large-scale one-step preparation of "graphene/fullerene" composite nanomaterials, to solve the current problems of complex steps, expensive equipment, cumbersome operations, and difficulty in mass production .

Description of drawings

Fig. 1 is a schematic diagram of the equipment and devices used in the preparation of "graphene/fullerene" composite nanomaterials in the present invention: 1 is a catalyst precursor, 2 is a solid-phase carbon source/sulfur source, 3 is a heating zone, and 4 is a tube furnace , 5 is the air inlet end, and 6 is the air outlet end.

FIG. 2 is an X-ray diffraction (XRD) pattern of the “graphene/fullerene” composite nanomaterial prepared in Example 1.

Figure 3 is a scanning electron microscope (SEM) image of the "graphene/fullerene" composite nanomaterial prepared in Example 1, Figure 3A is a graph with a scale of 1 μm, and Figure 3B is a graph with a scale of 100 nm.

Figure 4 is a transmission electron microscope (TEM) image of the "graphene/fullerene" composite nanomaterial prepared in Example 1, wherein Figure 4A is a graph with a scale of 200nm, and Figure 4B is a graph with a scale of 2nm.

Fig. 5 is the constant current charge and discharge curve of the "graphene/fullerene" lithium-ion battery composite negative electrode material prepared in Example 1, and the current density is 1000mA/g.

Detailed ways

The content of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but it should not be construed as a limitation of the present invention. Without departing from the spirit and essence of the present invention, simple modifications or replacements made to the methods, steps or conditions of the present invention all belong to the scope of the present invention; unless otherwise specified, the technical means used in the embodiments are those skilled in the art. well-known conventional means.

Example 1

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "nickel acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 5°C/min; finally, the obtained catalytic product is collected and soaked in 2mol/L hydrochloric acid for 2h, then washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" nanocomposite material prepared by the above method, wherein the size of graphene is about 150nm, the size of fullerene is about 20nm, and the specific surface area of the composite material is 425 m ² g ^-1 ; it is used in lithium-ion batteries The reversible discharge capacity of the anode material is 568 mAh g ^-1 . FIG. 2 is an X-ray diffraction pattern of the composite nanomaterial prepared in Example 1. 3 is a scanning electron microscope image of the composite nanomaterial prepared in Example 1. 4 is a transmission electron microscope image of the composite nanomaterial prepared in Example 1. Fig. 5 is the constant current charge and discharge curve (current density 1000mA/g) of the composite electrode material prepared in Example 1.

Example 2

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "nickel acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected, soaked in 2mol/L hydrochloric acid for 2h, washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the size of graphene is about 300nm, the size of fullerene is about 15nm, and the specific surface area of the composite material is 448 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 595 mAh g ^-1 .

Example 3

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "nickel acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 20°C/min; finally, the catalyzed product is collected, soaked in 2mol/L hydrochloric acid for 2h, washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the graphene size is about 250nm, the fullerene size is about 12nm, and the specific surface area of the composite material is 430 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 568 mAh g ^-1 .

Example 4

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "nickel acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 600°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected and soaked in 2mol/L hydrochloric acid for 2h, then washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the graphene size is about 200nm, the fullerene size is about 18nm, and the specific surface area of the composite material is 441 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 581 mAh g ^-1 .

Example 5

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "nickel acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 900°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected and soaked in 2mol/L hydrochloric acid for 2h, then washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the size of graphene is about 400nm, the size of fullerene is about 30nm, and the specific surface area of the composite material is 395 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 548 mAh g ^-1 .

Example 6

Place the solid-phase carbon source/sulfur source "mercapto resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill for ball milling After ball milling, the average particle size is 5 μm; 20 g of the obtained "mercapto resin" particles and 7 g of the obtained "nickel acetate" particles are placed in a tube furnace and heat treated under the protection of an inert gas (as shown in Figure 1). The heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected, soaked in 2mol/L hydrochloric acid for 2h, washed with distilled water, filtered, and dried to obtain " Graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the size of graphene is about 500nm, the size of fullerene is about 25nm, and the specific surface area of the composite material is 434 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 587 mAh g ^-1 .

Example 7

Place the solid-phase carbon source/sulfur source "sulfonic acid resin" in an oven for 12 hours at 80°C, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "nickel acetate" in a ball mill Carry out ball milling treatment, the average particle size after ball milling is 5 μ m; take 20 g of the obtained "sulfonic acid resin" particles and 7 g of the obtained "nickel acetate" particles and place them in a tube furnace, and carry out heat treatment under the protection of inert gas (as shown in Figure 1 shown), the heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected and soaked in 2mol/L hydrochloric acid for 2h, then washed with distilled water, filtered, and dried That is, the "graphene/fullerene" composite nanomaterial is obtained.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the size of graphene is about 450nm, the size of fullerene is about 20nm, and the specific surface area of the composite material is 445 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 591 mAh g ^-1 .

Example 8

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven to dry at 80°C for 12 hours, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "cobalt acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "cobalt acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected, soaked in 2mol/L hydrochloric acid for 2h, washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the size of graphene is about 600nm, the size of fullerene is about 35nm, and the specific surface area of the composite material is 423 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 576 mAh g ^-1 .

Example 9

Place the solid-phase carbon source/sulfur source "thiourea resin" in an oven for 12 hours at 80°C, and then crush it with a pulverizer. The average particle size after crushing is 100 μm; put the catalyst precursor "manganese acetate" in a ball mill for Ball milling, the average particle size after ball milling is 5 μm; 20g of the obtained "thiourea resin" particles and 7g of the obtained "manganese acetate" particles are placed in a tube furnace, and heat treatment is carried out under the protection of an inert gas (as shown in Figure 1 ), the heat treatment temperature is 700°C, the heating time is 30min, and the heating rate is 10°C/min; finally, the obtained catalytic product is collected, soaked in 2mol/L hydrochloric acid for 2h, washed with distilled water, filtered, and dried. Obtained "graphene/fullerene" composite nanomaterials.

The "graphene/fullerene" composite nanomaterial prepared by the above method, in which the size of graphene is about 700nm, the size of fullerene is about 40nm, and the specific surface area of the composite material is 407 m ² g ^-1 , is used in lithium-ion batteries The reversible discharge capacity of the anode material is 552 mAh g ^-1 .

Comparative example 1

The experimental method is the same as in Example 1, the only difference is that the mass ratio of thiourea resin to nickel acetate is 1:1; the "graphene/fullerene" composite nanomaterial prepared by the method, wherein the graphene size is about 100m , almost no fullerene structure, the specific surface area of the composite material is 325 m ² g ^-1 ; the reversible discharge capacity of the negative electrode material used in lithium ion batteries is 436 mAh g ^-1 .

Comparative example 2

The experimental method is the same as in Example 1, the only difference is that the average particle size of the sulfur-containing resin is 20 μm, and the “graphene/fullerene” composite nanomaterial prepared by the method has a graphene size of about 200 μm and almost no richerene. Leene structure, the specific surface area of the composite material is 307 m ² g ^-1 ; the reversible discharge capacity of the negative electrode material used in lithium ion batteries is 412 mAh g ^-1 .

Comparative example 3

The experimental method is the same as in Example 1, the only difference is that the average particle size of nickel acetate is 10 μm, and the "graphene//fullerene" composite nanomaterial prepared by the method has a graphene size of about 500 μm and almost no richerene. Leene structure, the specific surface area of the composite material is 286 m ² g ^-1 ; the reversible discharge capacity of the negative electrode material used in lithium-ion batteries is 395 mAh g ^-1 .

Claims (7)

1. the preparation method of a kind of graphene/fullerene composite nano materials, it is characterised in that solid carbon is used as using thioretinite Source and sulphur source, using transition metal acetate as catalyst precursor, the thioretinite is close to the air inlet end of heating furnace, transition Metal acetate salt is heat-treated under inert gas shielding close to the outlet side of heating furnace, collects heat-treated products, at acid Manage, wash, filtering, being drying to obtain graphene/fullerene composite nano materials；The temperature of the heat treatment is 600~900 DEG C, Heating time is 10 min~60min, and programming rate is 5~20 DEG C/min；Thioretinite and the transition metal acetate Mass ratio is 1：0.1~0.5；Before being heat-treated, the thioretinite drying pulverization process, particle diameter is 50 after crushing μm~100 μm；Before being heat-treated, the transition metal acetate is through ball-milling treatment, and particle diameter is 1 μm~5 μm after ball milling.

2. the preparation method of graphene/fullerene composite nano materials according to claim 1, it is characterised in that the acid Processing refers to 1~3h of salt acid soak of 1~5mol/L of heat-treated products.

3. the preparation method of graphene/fullerene composite nano materials according to claim 1, it is characterised in that the mistake Metal acetate salt is crossed to be selected from more than one or both of nickel acetate, cobalt acetate, manganese acetate.

4. the preparation method of graphene/fullerene composite nano materials according to claim 1, it is characterised in that described to contain Sulphur resin is selected from more than one or both of thiourea resin, thiol resin, sulfonic group resin.

5. graphene/fullerene composite nano materials that any one of Claims 1-4 preparation method obtains.

6. the application in battery electrode is prepared of graphene described in claim 5/fullerene composite nano materials.

7. application according to claim 6, it is characterised in that the application is to utilize graphene/fullerene composite Nano Material prepares negative electrode of lithium ion battery.