WO2019154263A1

WO2019154263A1 - Graphene nanosheet composite, method for preparing same, and electrode comprising same

Info

Publication number: WO2019154263A1
Application number: PCT/CN2019/074165
Authority: WO
Inventors: 郝奕舟; 陈剑豪; 王天戌
Original assignee: 广州墨羲科技有限公司
Priority date: 2018-02-12
Filing date: 2019-01-31
Publication date: 2019-08-15
Also published as: CN110148746B; CN110148746A

Abstract

A graphene nanosheet composite, a method for preparing same, and an electrode comprising same. The graphene nanosheet composite comprises at least one of a functional substrate (1), a graphene nanosheet material (2) attached to the functional substrate, nano-micro particles (3) attached to the graphene nanosheet material (2), a nano-micro wire (4), and a first nano-micro film (5). The functional substrate is nano-micro sized in at least one dimension. The graphene nanosheet composite can maintain a stable structure.

Description

Graphene nanosheet composite material, manufacturing method thereof and electrode therewith

The present application claims the priority of the Chinese Patent Application No. 201101146036.9 filed on Feb. 12, s.

Technical field

The present disclosure relates to graphene nanosheet composites, methods of making the same, and electrodes comprising the same.

Background technique

Graphene is a two-dimensional crystal composed of carbon atoms and having only one atomic thickness. In 2004, the physicists of the University of Manchester, André Gem and Konstantin Novoselov, succeeded in separating graphene from graphite, confirming that it can exist alone, and the two jointly won the 2010 Nobel Bell Physics Award.

At present, graphene has very promising applications in many aspects, but there are still many technical problems to be solved in the practical process.

Summary of the invention

Some embodiments of the present disclosure provide a graphene nanosheet composite, wherein the graphene nanosheet composite comprises a functional substrate, a graphene nanosheet material attached to the functional substrate, attached thereto At least one of nano-micron particles, nano-micron wires, and first nano-micron films on the graphene nanoplate material, the functional substrate being nano-micron in at least one dimension.

In some embodiments, the graphene nanosheet composite comprises the nano-microparticles or the nano-microwires or the first nano-micron membranes attached to the graphene nanosheet material.

In some embodiments, the graphene nanosheet composite comprises the nano-microparticles attached to the graphene nanosheet material and the first nano-microfilm, or the graphene nanosheets The composite material includes the nano-microwires attached to the graphene nanosheet material and the first nano-micron film.

In some embodiments, the graphene nanosheet composite comprises the nano-microparticles, the nano-microwires, and the first nano-micron film attached to the graphene nanosheet material.

In some embodiments, for example, the functional substrate comprises at least one of nano-microparticles, nano-microwires, nano-microfilms, three-dimensional materials having a nano-micro microstructure.

In some embodiments, for example, the functional substrate comprises nano-microparticles and/or nano-microwires, and a second nanoparticle coated over the nano-microparticles and/or nano-microwires - Micron film.

In some embodiments, for example, the functional substrate comprises a three-dimensional material having a nano-micro microstructure and a second nano-micro film coated over the three-dimensional material having a nano-micro microstructure.

In some embodiments, for example, the graphene nanosheet composite comprises a first nano-micron film located at an outermost layer of the graphene nanosheet composite.

In some embodiments, for example, the graphene nanoplate material comprises a plurality of graphene nanosheets and pores between the plurality of graphene nanosheets.

In some embodiments, for example, each of the graphene nanosheets has an average diameter of from 5 nm to 500 nm, preferably from 10 to 100 nm.

In some embodiments, for example, the pores have an average size of from 5 nm to 200 nm, preferably from 10 nm to 50 nm.

In some embodiments, for example, the graphene nanosheets comprise a single layer of graphene or a multilayer of graphene.

In some embodiments, for example, the multilayer graphene comprises 2-10 layers of carbon atoms, preferably 2-5 layers.

In some embodiments, for example, the nano-microparticles have a diameter of from 5 nm to 10 μm, preferably from 50 nm to 1 μm, preferably from 200 nm to 500 nm.

In some embodiments, for example, the first nano-micron film has a thickness of from 0.3 nm to 3 μm, preferably from 30 nm to 300 nm, or from 3 nm to 30 nm.

In some embodiments, for example, in the three-dimensional material having a nano-micro microstructure, the microstructure has a size of from 100 nm to 100 μm, preferably from 1 μm to 10 μm.

In some embodiments, for example, the graphene nanoplatelets have an average diameter of from 5 nm to 500 nm, preferably from 10 to 100 nm.

In some embodiments, for example, the nano-microparticles comprise any one or a combination of the following: metal nanoparticles, metal microparticles, non-metal nanoparticles, non-metal microparticles, oxide nanoparticles, oxides Microparticles, sulfide nanoparticles, sulfide microparticles, semiconductor nanoparticles, semiconductor microparticles, polymer nanoparticles, polymer microparticles, the metal nanoparticles comprising any one or a combination of the following: Pt nanoparticles , Au nanoparticles, Ag nanoparticles; the metal microparticles comprising any one or a combination of the following: Pt microparticles, Au microparticles, Ag microparticles; the non-metallic nanoparticles comprising sulfur nanoparticles; The non-metallic microparticles include sulfur microparticles; the oxide nanoparticles include any one or a combination of the following: MnO ₂ nanoparticles, lithium composite oxide nanoparticles, LiCoO ₂ nanoparticles, LiMnO ₂ nanoparticles, LiMn ₂ O ₄ nanoparticles, LiFePO ₄ nanoparticles, Li ₄ Ti ₅ O ₁₂ nanoparticles, nickel cobalt manganese acid Lithium nanoparticles, lithium nickel cobalt aluminate nanoparticles, Mn ₃ O ₄ nanoparticles, MnO nanoparticles, NiO nanoparticles, Co ₃ O ₄ nanoparticles, Fe ₂ O ₃ nanoparticles, Fe ₃ O ₄ nanoparticles, V ₂ O ₅ nanoparticles, TiO ₂ nanoparticles; the oxide microparticles include any one or a combination of the following: MnO ₂ micron particles, lithium composite oxide micro particles, LiCoO ₂ micron particles, LiMnO ₂ micron particles, LiMn ₂ O ₄ micron particles, LiFePO ₄ micron particles, Li ₄ Ti ₅ O ₁₂ micron particles, lithium nickel cobalt manganese oxide micro particles, lithium nickel cobalt aluminate micro particles, Mn ₃ O ₄ micro particles, MnO micro particles, NiO micro particles , Co ₃ O ₄ micron particles, Fe ₂ O ₃ micron particles, Fe ₃ O ₄ micron particles, V ₂ O ₅ micron particles, TiO ₂ micron particles; the sulfide nanoparticles include MoS ₂ nanoparticles; the semiconductor nanometer The particles include any one or a combination of the following: Si nanoparticles, ZnO nanoparticles; the semiconductor micro particles include Si micro particles, ZnO micro particles; the polymer nanoparticles include any one or a combination of the following : polyaniline (PANI) nanoparticles, poly 3,4-hexylene dioxythiophene (PEDOT) nanoparticles; the polymer microparticles comprising any one or a combination of the following: polyaniline (PANI) microparticles, Poly 3,4-hexylenedioxythiophene (PEDOT) microparticles.

In some embodiments, for example, the nano-microwires comprise any one or combination of the following: carbon nanotubes, carbon microtubes, carbon nanowires, carbon microwires, metal nanowires, metal microwires, oxidation Nanowires, oxide microwires, polymer nanowires, polymer microwires, sulfide nanowires, sulfide microwires, semiconductor nanowires, semiconductor microwires, including single-walled nanotubes, multi-walled a nanotube; the carbon microtube comprises a multi-walled microtube; the metal nanowire comprises any one or a combination of the following: Cu nanowire, Au nanowire, Ag nanowire, Ni nanowire, Fe nanowire; The metal microwire includes a Cu microwire, an Au microwire, an Ag microwire, a Ni microwire, and an Fe microwire; the oxide nanowire includes a transition metal oxide nanowire, and the transition metal oxide nanowire includes the following Any one or a combination of several: MnO ₂ nanowires, Mn ₃ O ₄ nanowires, MnO nanowires, NiO nanowires, Co ₃ O ₄ nanowires, Fe ₂ O ₃ nanowires, Fe ₃ O ₄ nanowires, V ₂ O ₅ nanowires TiO ₂ nanowires, nanowire lithium composite oxide, LiCoO ₂ nanowire, LiMnO ₂ nanowire, LiMn ₂ O ₄ nanowires, LiFePO ₄ nanowires, Li ₄ Ti ₅ O ₁₂ nanowires, lithium nickel cobalt manganese oxide nanowires a nickel-nickel cobalt aluminate nanowire; the oxide microwire comprising a transition metal oxide microwire comprising any one or a combination of the following: MnO ₂ micron wire, Mn ₃ O ₄ micron line, MnO micro line, NiO micro line, Co ₃ O ₄ micro line, Fe ₂ O ₃ micro line, Fe ₃ O ₄ micro line, V ₂ O ₅ micro line, TiO ₂ micro line, lithium composite oxide micron Line, LiCoO ₂ micron line, LiMnO ₂ micron line, LiMn ₂ O ₄ micron line, LiFePO ₄ micron line, Li ₄ Ti ₅ O ₁₂ micron line, lithium nickel cobalt manganate micro line, nickel cobalt aluminum aluminate micro line; The semiconductor nanowires include any one or a combination of the following: Si nanowires, Ga nanowires, ZnO nanowires; the semiconductor microwires include any one or a combination of the following: Si microwires, Ga microwires ZnO microwire; the polymer nanowire includes any one or more of the following Combination: polyaniline (PANI) nanowires, poly 3,4-hexylenedioxythiophene (PEDOT) nanowires; the polymer microwires include any one or combination of the following: polyaniline (PANI) micron wires , poly 3,4-hexylene dioxythiophene (PEDOT) micron wire.

In some embodiments, for example, the nano-micro film has a thickness on the nanometer or micrometer level, including any one or a combination of the following: a carbon film, a metal film, an oxide film, a polymer film, a sulfide. a film or a semiconductor film comprising any one or a combination of the following: single or multi-layered graphite oxide, single or multi-layer graphene or graphite, amorphous carbon film, diamond film; The metal thin film includes any one or a combination of the following: a Cu thin film, an Au thin film, an Ag thin film, a Ni thin film, and an Fe thin film; the oxide thin film includes a transition metal oxide thin film, and the transition metal oxide thin film includes any of the following One or several combinations: MnO film, Mn ₃ O ₄ film, MnO film, NiO film, Co ₃ O ₄ film, Fe ₂ O ₃ film, Fe ₃ O ₄ film, V ₂ O film, TiO ₂ film, lithium composite oxide thin film, LiCoO ₂ film, LiMnO ₂ film, LiMn ₂ O ₄ film, LiFePO ₄ film, Li ₄ Ti ₅ O ₁₂ film, a film of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum film; the semiconductor The film includes any one or a combination of the following: a Si film, a Ga film, a ZnO film; the polymer film includes any one or a combination of the following: a polyaniline (PANI) film, a poly 3,4-hex Dioxythiophene (PEDOT) film.

In some embodiments, for example, the three-dimensional material having a nano-micro microstructure includes any one or a combination of the following: a carbon material, a metal material, an oxide material, a polymer material, a sulfide material, a semiconductor material. The carbon material includes any one or a combination of the following: graphene, graphene oxide, amorphous carbon, activated carbon, diamond; the metal material includes any one or a combination of the following: Cu, Ni, Au, Ag, Fe; the oxide material comprises a transition metal oxide, the transition metal oxide comprising any one or a combination of the following: MnO ₂ , Mn ₃ O ₄ , MnO, NiO, Co ₃ O ₄ , Fe ₂ O ₃ , Fe ₃ O ₄ , V ₂ O ₅ , TiO ₂ , lithium composite oxide; the semiconductor material comprises any one or a combination of the following: Si, Ga, ZnO; the polymer material A combination of any one or more of the following: polyaniline (PANI), poly 3,4-hexylene dioxythiophene (PEDOT).

In some embodiments, for example, the graphene nanosheet material surface has defects, the defects include vacancy defects and/or edge defects; or the graphene nanosheet material surface is doped with atoms, the atoms including N, O and/or H; or the graphene nanosheet material is surface-attached with a group or atom, the group or atom comprising -NH ₂ , -OH, -N and / or -O; or the graphene nano A polymer monomer or a high molecular oligomer is covalently attached to the surface of the sheet.

In some embodiments, for example, the graphene nanosheet composite has a mass specific surface area of 400 m ² /g or more.

Some embodiments of the present disclosure also provide an electrode comprising a graphene nanosheet composite as previously described.

Some embodiments of the present disclosure also provide a method of fabricating a graphene nanosheet composite, comprising: providing a functional substrate; forming a graphene nanosheet material on the functional substrate; and forming the graphene nanosheet material At least one of nano-microparticles, nano-micrometer wires, and first nano-micron films are formed, the functional substrates being nano-micron in size in at least one dimension.

In some embodiments, for example, forming the graphene nanosheet material comprises: providing a functional substrate using a plasma enhanced chemical vapor deposition (PECVD) method, using a mixed gas of a carbon-containing gas and an auxiliary gas as a carbon source, Graphene nanosheets are grown on a functional substrate.

In some embodiments, for example, in the above method, the volume ratio of the carbon-containing gas to the auxiliary gas is 10:1 to 1:5; and the auxiliary gas includes argon gas and nitrogen gas.

In some embodiments, for example, in the above method, the auxiliary gas further comprises hydrogen.

In some embodiments, for example, in the above method, the volume ratio of the argon gas, the nitrogen gas, and the hydrogen gas in the auxiliary gas is 1-5:1-5:1-20.

In some embodiments, for example, in the above method, the pressure of the mixed gas of the carbon-containing gas and the assist gas is from 0.01 Pa to 500 Pa, preferably from 150 Pa to 300 Pa, and more preferably from 200 Pa to 250 Pa.

In some embodiments, for example, in the above method, the growth temperature of the graphene nanosheets grown on the functional substrate ranges from 650 to 1000 ° C, preferably from 800 to 900 ° C.

In some embodiments, for example, in the above method, the carbon-containing gas includes CH ₄ , C ₂ H ₂ , C ₂ F ₆ .

In some embodiments, for example, in the above method, further comprising an activation step comprising forming a plurality of micropores on the graphene nanosheet material, the micropores having a size of 0.5-5 nm, preferably 1 2nm.

DRAWINGS

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below. It is obvious that the drawings in the following description relate only to some embodiments of the present invention, and are not intended to limit the present invention. .

1 is a schematic structural view of a graphene nanosheet composite material provided by some embodiments of the present disclosure, showing nano-micro particles as a functional substrate and graphene nanosheets attached to a functional substrate;

2 is a schematic structural view of a graphene nanosheet composite material provided by some embodiments of the present disclosure, showing a nano-microwire as a functional substrate and graphene nanosheets attached to the functional substrate 1;

3 is a schematic structural view of a graphene nanosheet composite material according to some embodiments of the present disclosure, showing a nano-micro film as a functional substrate and graphene nanosheets attached to the functional substrate 1;

4 is a schematic illustration of a graphene nanosheet composite structure provided by some embodiments of the present disclosure, wherein the functional substrate is a three-dimensional material having a nano-micro microstructure;

5 is a schematic structural view of a graphene nanosheet in a graphene nanosheet composite material according to some embodiments of the present disclosure;

6 is a schematic structural view of a graphene nanosheet in a graphene nanosheet composite material according to some embodiments of the present disclosure;

7 is a TEM image of graphene nanosheets in a graphene nanosheet composite provided by some embodiments of the invention;

8 is a schematic structural view of a graphene nanosheet composite material according to some embodiments of the present disclosure, wherein graphene nanosheets and nano-microparticles attached to graphene nanosheets are illustrated;

9 is a schematic structural view of a graphene nanosheet composite material according to some embodiments of the present disclosure, in which graphene nanosheets and nano-microwires attached to graphene nanosheets are shown;

10 is a schematic structural view of a graphene nanosheet composite material according to some embodiments of the present disclosure, showing a graphene nanosheet and a nano-micro film attached to the graphene nanosheet;

11 is a schematic structural view of a graphene nanosheet composite material according to some embodiments of the present disclosure, showing graphene nanosheets and nano-micro particles and nano-micro films attached to graphene nanosheets;

FIG. 12 is a graph showing the relationship between the number of charge and discharge times and the ratio of the charge and discharge of the graphene nanosheet composite material to the positive electrode material of the lithium ion battery according to some embodiments of the present disclosure;

13 is a graph showing relationship between charge and discharge times and mass ratio capacity of a graphene nanosheet composite material provided by some embodiments of the present disclosure as a cathode material of a lithium ion battery;

Figure 14 is a graph showing the relationship between the number of charge and discharge times and the ratio of pure nickel-cobalt-manganese composite oxide (NCM) material to mass ratio capacity;

Figure 15 is a three-dimensional porous foamed nickel-graphene film-graphene nanosheet-poly(3,4-ethylenedioxythiophene) (PEDOT) prepared by using commercial activated carbon, common graphene-PEDOT composite material and an embodiment of the present disclosure, respectively. Film composites for the fabrication of electrodes, test results under the same conditions;

16 is a cycle life diagram of an electrode fabricated from a three-dimensional porous foamed nickel-graphene film-graphene nanosheet-poly(3,4-ethylenedioxythiophene) (PEDOT) film composite prepared by some embodiments of the present disclosure;

17 is a photocurrent-photovoltaic curve of an electrode prepared using a Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite material and a control material according to some embodiments of the present disclosure;

18 is a graph showing photoelectric conversion efficiency of electrodes prepared using Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composites and comparative materials of some embodiments of the present disclosure;

19 is a graph showing the relationship between the number of charge and discharge times and the ratio of charge to discharge of a graphene nanosheet composite material of a lithium ion battery as a positive electrode material according to some embodiments of the present disclosure;

20 is a carbon nanowire-Si film-graphene nanosheet-Pt nanowire-carbon film composite (1), common graphene-Pt nanoparticle (2), commercial Pt nanoparticle (a) provided by some embodiments of the present disclosure ( 3) ORR polarization curve;

21 is a carbon nanowire-MnO ₂ nanoparticle-carbon film-graphene nanosheet-MnO ₂ nanoparticle-PANI thin film composite supercapacitor electrode (2), common graphene-MnO ₂ nanometer provided by some embodiments of the present disclosure. Particle composite (1) voltammetric test results.

Detailed ways

The technical solutions of the embodiments of the present invention will be clearly and completely described in the following with reference to the accompanying drawings. It is apparent that the described embodiments are part of the embodiments of the invention, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the described embodiments of the present invention without departing from the scope of the invention are within the scope of the invention.

Graphene has a monoatomic layer structure in which carbon atoms are closely packed, and has good electrical conductivity and high specific surface area. After several years of development, graphene has considerable research and application in electronic devices, optoelectronics and energy. It is an ideal supercapacitor carbon-based material. However, graphene also has disadvantages. Graphene prepared by the conventional method is similar to activated carbon, and it is required to press the electrode under high pressure to keep the electrode structure stable, and the stacking phenomenon is likely to occur in the process, resulting in a decrease in specific surface area and ionic conductivity of the material. Therefore, it is a necessary measure to develop a suitable preparation method, prepare graphene with stable structure, and surface-modify graphene to form a composite electrode material with other materials. 0-dimensional materials (nanoparticles) and 2-dimensional materials (films) have good electrical, thermal and chemical properties. However, the natural state of the 0-dimensional material (nanoparticles) is loose powder. It is a big problem to prepare it into macroscopic devices and components. In addition, 0-dimensional materials (nanoparticles) are prone to agglomeration, and many 0-dimensional after agglomeration The excellent properties of materials (nanoparticles) can be adversely affected; 2D materials (films) are also difficult to form macroscopically shaped device structures, and the microstructure of 2D materials (films) is easily destroyed during the setting process, resulting in loss of performance. Even disappeared.

The "graphene nanosheet" in the present disclosure is a microstructure, which may be a single layer of graphene or a multilayer graphene, wherein the single layer graphene includes a single layer of carbon atoms; the multilayer graphene includes multiple layers of carbon atoms. The layer, preferably the number of layers of the carbon atom layer, is 2-10 layers. The average diameter of each graphene nanosheet is, for example, 5 nm to 500 nm.

The "graphene nanosheet material" in the present disclosure refers to a macrostructure in which a plurality of the above graphene nanosheets are randomly gathered together. For example, as shown in FIG. 5, the graphene nanosheet material 2 includes a plurality of graphene nanosheets 11, and the graphene nanosheets 11 have pores 10 therebetween, so that the graphene nanosheet material 2 has a porous structure. For example, the pores 10 have an average size of 5 nm to 200 nm, preferably 10 nm to 50 nm, further preferably 20 to 50 nm. Compared with the pores with micron-scale pores in the traditional three-dimensional graphene materials, the graphite nanosheet material with nanometer-scale pores has a larger specific surface area, which is more favorable for nanomaterials such as nanoparticles, nanosheets or nanofilms. complex.

The term "nano-micron material" as used in the present disclosure refers to a nano-micron sized material in at least one dimension. The term "nano-micron size" generally refers to a size in the range of 0.1 nm to 1000 nm, and the micron size refers to a size in the interval of 0.1 μm to 1000 μm, and thus the "nano-micron size" of the present disclosure means an interval of 0.1 nm to 1000 μm. size of. The term "nano-micron material" as used in the present disclosure, when it is nano-micron size in only one dimension, may be, for example, a nano-micro film, a nano-micro film, etc.; when it is nano-micron in two dimensions When the size is, for example, it may be a nano-micron line; when it is a nano-micron size in three dimensions, for example, it may be a nano-micro particle. However, the "nano-micron material" of the present disclosure is not limited to the above examples, and for example, the nano-micro material may also be a three-dimensional material including a nano-micron size microstructure. For example, the nano-micron material may be a three-dimensional material having a porous structure of a nano-micron-sized pore structure, and the porous material may have a macroscopically large volume. For example, the functional substrate in the graphene nanosheet composite may be the "nano-micron material" described above. The functional substrate may be, for example, a nano-micro particle, a nano-micro wire, a nano-micro film, or may be a three-dimensional material having a nano-micro microstructure (eg, a porous structure having nano-micro-sized pores), or A combination of the above materials. Figure 4 shows a three-dimensional nanomaterial having a nano-micro microstructure. In the manufacture of traditional nanomaterials and micromaterials, the substrate is generally a non-functional substrate, which provides only a platform for the growth of nanomaterials and micromaterials. The materials are generally glass, metal, ceramics, etc., and the shape is generally flake. After the nano material and the micro material are prepared, the substrate is generally peeled off, and the nano material and the micro material after peeling off the substrate are further applied. However, there are some problems in this approach. One is to strip the substrate before the application of nanomaterials and micro-materials, which complicates the operation, reduces the production efficiency, and increases the production cost. Second, in the process of stripping the substrate, the nano-material, The microstructure of micron materials may be partially or even completely destroyed, thereby affecting the properties of nanomaterials and micromaterials. The inventors of the present disclosure successfully solved the above problems by fabricating nanomaterials and micromaterials using functional substrates. The functional substrate can still function as a traditional substrate, that is, it can still provide a growth platform for the nano material and the micro material, and the nano material and the micro material can be attached to the surface of the functional substrate for growth. Second, the functional substrate itself is nano-micron in at least one dimension and is therefore itself a functional nano-micro material. For example, it can be seen in one embodiment of the present disclosure that the functional substrate is a nickel-cobalt-manganese composite oxide (NCM) nanoparticle, after the graphene nanosheet composite is prepared on the functional substrate, By peeling off the functional substrate and also without further supporting a composite oxide of lithium which functions as the lithium composite oxide, the material can be directly used as a positive electrode material for a lithium ion battery. Conversely, if the graphene nanosheet composite is fabricated using a conventional non-functional substrate, the graphene nanosheet composite is used as a positive electrode material for a lithium ion battery, and the graphene nanosheet material is first peeled off from the conventional substrate. Then, it is necessary to carry a composite oxide of lithium on the graphene nanosheet material, and finally, the graphene nanosheet material loaded with the lithium composite oxide can be used as a positive electrode material for a lithium ion battery. Such an operation is not only cumbersome, but also because the composite oxide of lithium is lately loaded onto the surface of the graphene nanosheet material, in the application process, the composite oxide of lithium is easily detached, thereby deteriorating the material properties. The graphene nanosheet composite provided by the embodiments of the present disclosure has no such problems, because nickel-cobalt-manganese composite oxide (NCM) nanoparticles are used as functional substrates, which are encapsulated by graphene nanosheet layers, in application. It is not easy to fall off during the process, so repeated use will not cause a significant performance degradation.

As described above, the inventors of the present disclosure replace a conventional substrate with a functional substrate which is itself nano-micron in size in at least one dimension, grows on the functional substrate to produce graphene nanosheets, and then further in the graphene nanometer. Functional materials such as nano-micro particles, nano-micro wires, nano-micro films, etc. are prepared on-chip, and have at least the following advantages:

1) The use of a functional substrate for the manufacture of a graphene nanosheet composite material eliminates the need to strip the functional substrate after preparation, simplifies the preparation process, provides production efficiency, and reduces cost.

2) The functional base material may be a core functional material in the next application (for example, a lithium composite oxide in a lithium ion battery positive electrode material), and after the graphene nanosheet composite material is manufactured based on the functional substrate, no further load is required. The core functional material can be directly applied, and since the functional substrate as the core functional material is surrounded by the graphene nanosheet layer, the functional substrate as a core functional material in the application process is not easily peeled off, and the material property is stable.

3) Compared to conventional substrate materials, functional substrates are nano-micron in size in at least one dimension, which can provide a large specific surface area that favors the growth of graphene nanosheets, while also contributing to the graphite thereon. The ene nanosheets maintain a macroscopic three-dimensional structure. Further, the functional substrate is combined with the graphene nanosheets to increase their unique physical and chemical properties, complement each other, promote, and obtain new properties.

4) The fine pores between the graphene nanosheets can further increase the specific surface area of the graphene nanosheet composite, and the graphene nanosheets have a stable three-dimensional structure, and there is less agglomeration between the graphene layers inside. Stacking is beneficial to give full play to the excellent electrical properties of graphene.

5) by using a graphene nanosheet material (that is, before preparing the graphene nanosheet composite of the embodiment of the present disclosure) or a graphene nanosheet composite (ie, preparing the graphene nanosheet composite of the embodiment of the present disclosure) And performing surface modification, the surface modification comprising causing defects such as vacancies, edges, etc. on the surface of the graphene nanosheet, doping atoms on the surface of the graphene nanosheet, and covalently bonding on the surface of the graphene nanosheet The functional group, and/or covalently linking the polymer monomer or the polymer oligomer on the surface of the graphene nanosheet, can greatly improve the hydrophilicity and lipophilicity of the graphene without destroying the three-dimensional structure, greatly Increasing the infiltration of aqueous or non-aqueous liquids in graphene nanosheet materials or graphene nanosheet composites greatly increases the chemical and physical activity of graphene nanosheet materials or graphene nanosheet composites.

6) The graphene nanosheet material has a porous structure, for example, as shown in FIGS. 6 and 8, a plurality of graphene sheets are formed with pores 10, and the average size d of the pores 10 is 5 nm to 200 nm, preferably 10 nm to 50 nm, further preferably 20-50nm. For example, the porous structure includes mesopores having an average pore diameter of less than about 20 nm. This effectively combines the advantages of graphene and porous carbon materials, while providing a sheet structure and a mesoporous structure, increasing the application range of graphene.

7) Loading nano-micro particles or nano-micro wires onto graphene nanosheet materials, nano-micro particles or nano-micro wires are dispersed and isolated by graphene materials, thereby avoiding nano-micro particles or nano- Agglomeration between micro-wires helps maintain excellent performance. As shown in FIG. 8, the nano-micron particles 3 are distributed in the pores 10 in the graphene nanosheet material 2, which solves the problem of agglomeration between the nanoparticles, and is beneficial to give full play to the excellent electrical properties of the nanoparticles.

8) Depositing nanoparticles, nanowires and nano-films on graphene nanosheet materials, nano-particles, nanowires and nano-films have the same three-dimensional structure as graphene nanosheet materials in large size (micron order) (refer to Figure 8) effectively solves the problem that nanomaterials are difficult to form and facilitates the large-scale use of nanomaterials. In addition, nanomaterials generally have poor conductivity, especially non-metallic nanomaterials have poor conductivity and good conductivity. The close contact of the nanosheet material greatly improves the macroscopic conductivity of the nanomaterial.

9) forming a first nano-micron film over the graphene nanosheet material loaded with nano-microparticles and/or nano-microwires, the first nano-micron thin film comprising nano-micron particles, nano-micron lines and The graphene nanosheet material is wrapped to prevent the nano-microparticles and/or the nano-microwires from falling off from the graphene nanosheet material during application, which greatly increases the cycleability and durability of the graphene nanosheet composite. For example, as shown in FIG. 11, the nano-microparticle 3 is attached to the graphene nanosheet 2, and the nano-microfilm 5 is coated on the nano-microparticle 3 to prevent the nano-microparticle 3 from falling off the graphene nanosheet 2. .

10) The method for forming a graphene nanosheet material provided in the present disclosure can form a three-dimensional porous graphene nanosheet material having nanometer-scale pores, which not only saves process and cost, but also saves process and cost compared to conventional three-dimensional graphene material preparation method. Graphene nanosheet materials that can be formed have better properties.

In summary, some embodiments of the present disclosure provide a technical solution on the one hand, which expands the application scenario of graphene-based nano and micro-functional materials, simplifies the preparation method, and reduces the production cost; The embodiments provided by some embodiments of the present disclosure perfectly combine the advantages of materials such as nano-micro particles, nano-micro wires, nano-micro films, and three-dimensional materials with nano-micro microstructures, and are successfully avoided. The shortcomings and shortcomings of various materials when used alone, while maintaining the nano-micron size effect, the macroscopic size of the composite material reaches hundreds of micrometers or more, and effectively maintains the nano-size characteristics under macroscopic dimensions, effectively solving the problem. In the past, nanowires, graphenes, and other nanomaterials lost the problem of nanomaterial properties when used on a macro scale.

The composite material can be applied to fields such as energy storage materials (such as secondary batteries), chemical catalysis, photocatalysis, and biological materials, and is a new generation of nanocomposites with broad application prospects.

The graphene nanosheet composite material provided by the embodiment of the present disclosure and a manufacturing method thereof are exemplarily described below through several specific embodiments.

Example of nickel-cobalt-manganese composite oxide (NCM) nanoparticle-amorphous carbon film-graphene nanosheet-gold (Au) nanoparticle composite material

In one example, forming a nickel-cobalt-manganese composite oxide (NCM) nanoparticle-amorphous carbon film-graphene nanosheet material-gold (Au) nanoparticle composite material comprises the following steps: starting with NCM nanoparticles The material is first coated with an amorphous carbon film (second nano-micro film), and the NCM nanoparticles coated with the amorphous carbon film are used as a functional substrate to grow graphene nanosheet material, and then in the graphene nanosheet. The Au nanoparticles are attached to the material.

For example, coating an amorphous carbon film on NCM nanoparticles includes the following steps. A plasma of CH ₄ gas is used as a precursor, and hydrogen is used as an auxiliary gas to mix CH ₄ gas and hydrogen gas, wherein the volume ratio of the CH ₄ gas to the hydrogen gas is 1:2-1:10. The NCM nanoparticles were placed in a PECVD reactor and heated to 500 ° C. The mixed gas was introduced into a PECVD reactor for 30 min, and an amorphous carbon film was coated on the NCM nanoparticles by PECVD. The amorphous carbon film can improve the adhesion of the surface of the NCM nanoparticle, so that the subsequently grown graphene nanosheet can be more stably attached to the surface of the NCM nanoparticle, thereby greatly increasing the cycle property of the graphene nanosheet composite. Durability.

For example, the graphene nanosheets are grown by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method. For example, a plasma of CH ₄ gas is used as a precursor, and hydrogen, nitrogen, and argon are used as auxiliary gases, and CH ₄ gas, hydrogen, nitrogen, and argon are mixed to form a mixed gas, wherein the CH ₄ gas and the auxiliary are used. The volume ratio of the gas is 10:1-1:5, and the volume ratio of argon, nitrogen and hydrogen is 1-5:1-5:1-20, and the obtained NCM nanoparticles coated with the amorphous carbon film are The PECVD reactor was heated to 800 °C. The foregoing mixed gas was introduced into a PECVD reactor, and graphene nanosheets were grown on NCM nanoparticles coated with an amorphous carbon film by PECVD, and the growth time was controlled to 10 minutes to obtain NCM nanoparticles-amorphous carbon film-graphite. Alkene nanosheet composite. Surface modification was carried out by bombarding with O ₂ plasma for 10 minutes, and activation was carried out using a chemical method. The chemical activation may be, for example, after thorough mixing with KOH (graphene and KOH molar ratio 1:2), heat treatment at 800 ° C for 4 h in an Ar atmosphere, and after removal, it is washed and dried (the powder sample can be activated by this method).

For example, loading Au nanoparticles on graphene nanosheets includes preparing Au nanoparticles. For example, a mixture of 3 mL (30 mmol/L) of aqueous chloroauric acid solution and 8 mL (50 mmol/L) of toluene solution of tetraoctyl ammonium bromide is mixed and stirred, and then a dose of n-dodecyl mercaptan is added to the organic phase. A fresh aqueous solution of sodium borohydride (2.5 mL, 0.4 mol/L) was also added thereto and stirred together. After stirring for 3 h, the organic phase was separated, and the mixture was extracted into 1 mL of a mixture. Then, 40 mL of ethanol was added to remove excess mercaptan, and heat-treated in an oil bath at 140 ° C for 30 to 40 minutes, and filtered to obtain a dark brown precipitate, which was washed with ethanol, centrifuged, and finally The crude product was dispersed in 10 mL of toluene, reprecipitated with 40 mL of ethanol, centrifuged, washed, and dried to obtain Au nanoparticles.

For example, the NCM nanoparticle-amorphous carbon film-graphene nanosheet composite material prepared above and the Au nanoparticle are mixed and ultrasonicated, and then washed and dried to obtain NCM nanoparticle-amorphous carbon film-graphene nanosheet-Au. Nanoparticle composites.

The positive electrode was fabricated by the NCM nanoparticle-amorphous carbon film-graphene nanosheet-Au nanoparticle composite material, the lithium plate was used as a negative electrode, and LiPF ₆ /EC+DMC was used as an electrolyte to assemble a lithium ion battery. Tested at 0-4V, the test results are shown in Figures 12 and 13. Figure 12 shows the relationship between the number of charge and discharge cycles and the ratio of the ratio to the mass ratio. It can be seen that there is a specific capacity of about 140 mAh/g at 5 C, and the specific capacity of 50% at 1 C is maintained even at 10 C, indicating that the sample has excellent performance. Rate performance, mainly because the carbon film, graphene nanosheets and Au nanoparticles on the NCM greatly improve the electrical conductivity of the material, and the graphene nanosheets and Au nanoparticles greatly increase the surface area of the electrode material, thereby The intercalation and deintercalation of lithium ions provides more channels, and the corresponding rate performance is also greatly improved. Figure 13 shows the relationship between the number of charge and discharge cycles and the specific capacity. It can be seen that the specific capacity of more than 80% is maintained after 200 cycles of 10C. As a positive electrode active material, NCM nanoparticles are coated with an amorphous carbon film and a graphene nanosheet layer. Therefore, during the operation of the battery, the NCM nanoparticles do not easily fall off and decompose, so that the material has excellent cycle performance. Figure 14 is a graph showing the relationship between the number of charge and discharge cycles and the ratio of the mass ratio to the mass ratio of the pure NCM nanoparticles which are the same as the NCM nanoparticles of the functional substrate in the present embodiment. As can be seen by comparing Figs. 12 and 14, the graphene nanometer of this example The sheet composite has a larger mass specific capacity at the same cycle number and charge and discharge rate, which is significantly better than that of pure NCM nanoparticles.

This example is a good demonstration of the advantages of the graphene nanosheet composite of the present disclosure. The improvement of the rate performance may be mainly attributed to the combination of graphene nanosheet materials with nanoparticles and films. The graphene nanosheet material itself is a porous material with a large specific surface area, providing more channels for the conduction of ions and electrons. The nanoparticles loaded on the graphene nanosheet material further increase the surface area and expand the current path. The improvement in cycle performance is primarily related to functional substrate materials. The NCM nanoparticles are combined with the amorphous carbon film to provide a platform for the growth of graphene nanosheets on the one hand, and as an active material for the positive electrode materials of lithium ion batteries, on the other hand, in the working process of lithium ion batteries. Key role. Since the NCM nanoparticles as the positive electrode active material are surrounded by the amorphous carbon film and the graphene nanosheet layer, the NCM nanoparticles are not easily peeled off during the lithium ion battery cycle, and are not easily decomposed or contaminated, and NCM The nanoparticles are dispersed by the amorphous carbon film and the graphene nanosheet, and the problem of agglomeration is also avoided between each other, so that the cycle performance is greatly improved. Finally, there is a significant advantage that the functional substrate itself acts as a positive active material for the lithium ion battery. Therefore, after the graphene nanosheet composite material is prepared, the cathode active material is not further loaded, and the substrate is not required to be directly removed. Application, which undoubtedly simplifies the manufacturing process and reduces production costs.

Example of three-dimensional porous foam nickel-graphene film-graphene nanosheet-poly(3,4-ethylenedioxythiophene) (PEDOT) film composite

In one example, forming a three-dimensional porous foamed nickel-graphene film-graphene nanosheet-poly(3,4-ethylenedioxythiophene) (PEDOT) film composite comprises the steps of: using a foamed nickel having a three-dimensional porous structure as The starting material is first coated with a graphene film (second nano-micro film), and the three-dimensional porous foamed nickel coated with the graphene film is used as a functional substrate, and then the graphene nanosheet is regenerated. Finally, a PEDOT film (first nano-micro film) was deposited on the graphene nanosheet. For example, the three-dimensional porous foamed nickel has a pore size of a micron size. The porous structure in the three-dimensional porous foamed nickel may be such that the material is in sufficient contact with the reaction liquid or gas, increasing the reaction area, and providing space for material growth.

For example, a graphene film is coated on a three-dimensional porous foamed nickel by a PECVD method. For example, the three-dimensional foamed nickel obtained after washing and drying is placed in a PECVD reactor and heated to 800 °C. A plasma of CH ₄ gas is used as a precursor, and hydrogen is used as an auxiliary gas to mix CH ₄ gas and hydrogen gas, wherein a volume ratio of the CH ₄ gas to the hydrogen gas is 1:4-1:20. The mixed gas was introduced into a PECVD reactor, and a graphene film was grown on the three-dimensional foamed nickel by a PECVD method to obtain a three-dimensional porous foamed nickel to which a graphene film was attached. The graphene film adheres to the pore surface of the three-dimensional porous foamed nickel to improve the adhesion of the pore surface, and is favorable for better adhesion of the subsequently grown graphene nanosheet.

For example, growing graphene nanosheets includes the following steps. Using a plasma of CH ₄ gas as a precursor, hydrogen, nitrogen and argon as auxiliary gases, mixing CH ₄ gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH ₄ gas and the auxiliary gas The volume ratio is 10:1-1:5, and the volume ratio of argon, nitrogen and hydrogen is 1-5:1-5:1-20, and the three-dimensional porous foamed nickel to which the graphene film is attached is obtained in the PECVD reaction. Heat to 850 ° C in the unit. The mixed gas is introduced into a PECVD reactor, and graphene nanosheets are grown on a three-dimensional porous foamed nickel to which a graphene film is attached by a PECVD method, and the growth time is controlled to 10 minutes to obtain a three-dimensional porous foam nickel-graphene film-graphene. Nanosheet composites. Surface modification was carried out by bombarding with O ₂ plasma for 10 minutes, and activation was carried out using a chemical method. The chemical activation may be, for example, after sufficiently mixing with KOH (graphene and KOH molar ratio 1:2), heat treatment at 800 ° C for 4 h in an Ar atmosphere, taking out and washing and drying (the powder sample can be activated by this method).

For example, depositing a PEDOT film on a graphene nanosheet includes the following steps. 1.3 mL of a solution of iron (p(ots) ₃ ) of p-toluenesulfonate (Fe(ots) ₃ ) and 0.027 g of imidazole in a concentration of more than 60% is sufficiently mixed to form the above-mentioned three-dimensional porous foamed nickel-graphene film-graphene nanosheet. The composite material was immersed in the mixed solution. After 30 minutes, the excess solution on the surface was removed, and then placed in the reaction vessel. 0.05 mL of 3,4-ethylenedioxythiophene monomer (EDOT) was added, and the reaction was carried out at 100 ° C for 3 hours, and then washed. After drying, a three-dimensional porous foam nickel-graphene film-graphene nanosheet-PEDOT film composite material is obtained.

The working electrode was fabricated by three-dimensional porous foamed nickel-graphene film-graphene nanosheet-PEDOT film composite. The platinum electrode was the counter electrode, the Ag/AgCl electrode was used as the auxiliary electrode, and the 1M Li ₂ SO ₄ aqueous solution was used as the electrolyte test electrode. The voltammogram, the test results are shown in Figures 15 and 16. 15 is a test result of different electrodes including the sample of the embodiment under the same conditions, wherein curve (1) corresponds to commercial activated carbon, curve (2) corresponds to ordinary graphene-PEDOT composite material, and curve (3) corresponds to the present invention. The three-dimensional porous foamed nickel-graphene film-graphene nanosheet-PEDOT film composite of the embodiment shows that the specific capacitance provided by the material of the present embodiment is significantly better than that of the activated carbon material and the common graphene-PEDOT composite material. On the one hand, the three-dimensional porous foamed nickel provides a three-dimensional skeleton for composite materials such as graphene nanosheets and PEDOT thin films, so that these materials do not collapse or agglomerate, and the nanometer and micron size properties of these materials are fully utilized; On the other hand, this composite material fully combines the advantages of three-dimensional materials and nano-micron-sized materials, and at the same time avoids their respective shortcomings. Figure 16 is a cycle life diagram of the sample provided in this example, which retains a specific capacity of more than 80% after 100,000 cycles. The improvement of cycle performance is partly due to the encapsulation and protection of graphene film and PEDOT film composite to other materials. During repeated use, the nano-micron materials wrapped inside are not easily peeled off or decomposed.

Example of platinum (Pt) nanowire-graphene nanosheet-TiO ₂ nanoparticle composite material

In one example, forming a platinum (Pt) nanowire-graphene nanosheet-TiO ₂ nanoparticle composite comprises the steps of: making a Pt nanowire, growing a graphene nanosheet with a Pt nanowire as a functional substrate, and then in graphite TiO ₂ nanoparticles are deposited on the ene nanosheets.

For example, preparing a Pt nanowire includes the following steps. Porous alumina was used as a template, a high-purity carbon rod was used as a counter electrode, and chloroplatinic acid was used as a precursor. Using dilute sulfuric acid as the electrolyte, it was anodized for 1 h under DC voltage. During the deposition process, the color of the template was gradually blackened, indicating that the Pt nanowires had been deposited inside the pores. After the deposition is completed, the porous alumina template is dissolved with a NaOH solution, and the remaining black precipitate is washed and dried to obtain a Pt nanowire. For example, the porous alumina has a pore size of nanometer size.

For example, growing a graphene nanosheet with a Pt nanowire as a functional substrate includes the following steps. Using a plasma of CH ₄ gas as a precursor, hydrogen, nitrogen and argon as auxiliary gases, mixing CH ₄ gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH ₄ gas and the auxiliary gas The volume ratio is 10:1 to 1:5, and the volume ratio of argon, nitrogen, and hydrogen is 1-5:1-5:1-20, and the obtained Pt nanowires are heated to 850 ° C in a PECVD reactor. The mixed gas was introduced into a PECVD reactor, and graphene nanosheets were grown on the Pt nanowire by PECVD, and the growth time was controlled to 10 minutes to obtain a Pt nanowire-graphene nanosheet composite, and the graphene nanosheets formed clusters. Completely coated on the Pt nanowires. Surface modification was carried out by bombarding with O ₂ plasma for 10 minutes, and activation was carried out using a chemical method. The chemical activation may be, for example, after sufficiently mixing with KOH (graphene and KOH molar ratio 1:2), heat treatment at 800 ° C for 4 h in an Ar atmosphere, taking out and washing and drying (the powder sample can be activated by this method). For example, a structure in which a graphene nanosheet is grown using a Pt nanowire as a functional substrate can be referred to FIG. 2, and as shown in FIG. 2, a graphene nanosheet 2 is attached to a Pt nanowire as a functional substrate 1.

For example, depositing TiO ₂ nanoparticles on graphene nanosheets includes the following steps. The commercially available TiO ₂ nanoparticles (average particle size <20 nm) are uniformly dispersed in an aqueous solution, and the Pt nanowire-graphene nanosheet composite material prepared above is added, and after fully mixing, the TiO ₂ nanoparticles can be uniform after 4 hours of ultrasonication. It is deposited on graphene nanosheets to obtain Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite. This material was used to test photocatalytic performance.

Photoelectric test, the electrode was prepared by Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite material, and the photocurrent test of the electrode was carried out by potentiostat. Ag/AgCl was used as the reference electrode and Pt was used as the counter electrode. The 300W xenon lamp and the AM1.5 filter simulate sunlight, and the diffuser is used to uniformly illuminate the entire TiO ₂ nanowire electrode region (2.6-2.8 cm ² ). Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite photoanode was immersed in a 1 M NaOH solution and illuminated through a quartz window of a glass cell. For incident photon to current conversion efficiency (IPCE) measurements, a 300W xenon lamp and monochromator were used and the incident light intensity was tested by standard silicon photodiodes. Here, follow the formula below:

The IPC is calculated from the photocurrent measured at 1.5V vs RHE. The test results are shown in Figs. 17, 18, wherein 1 is an electrode test data curve prepared by using the Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite material of the present embodiment, and 2 is the same TiO ₂ nanoparticle and ordinary oxidation. Electrode test data curves prepared from graphene powder composites, 3 are electrode test data curves prepared using the same TiO ₂ nanoparticles. It can be seen from FIG. 17 that the Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite material of the present embodiment has the lowest electrode starting voltage, the largest slope, and the largest current at the same voltage; the material preparation of the present embodiment can be seen from FIG. The electrode has the highest photoelectric conversion efficiency, exceeding 70%. The Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite prepared in this example exhibits the best photoelectric performance without surprise. First, the electrode prepared with pure TiO ₂ nanoparticles, the agglomeration between TiO ₂ nanoparticles is severe, which greatly affects the performance of nanomaterials. Secondly, the electrode prepared by TiO ₂ nanoparticles and common graphene oxide powder composites, although oxidized The graphene powder disperses the TiO ₂ nanoparticles to a certain extent, but without the enhancement of the Pt nanowires, the photoelectric properties thereof are also limited. Finally, the Pt nanowire-graphene nanosheet-TiO ₂ nanoparticle composite of the present embodiment is used. In the electrode prepared by the material, on the one hand, the TiO ₂ nanoparticles are well dispersed into the pores between the graphene nanosheets, solving the problem of agglomeration between the nanoparticles, and the porous structure of the graphene nanosheets provides a very A good three-dimensional porous framework, the increased specific surface area greatly expands the channel of photocurrent; on the other hand, the Pt nanowires are wrapped and dispersed by graphene nanosheets, and the photoelectric properties of Pt nanowires are fully exerted.

Example of nickel-cobalt-manganese composite oxide (NCM) microsphere-amorphous carbon film-graphene nanosheet-gold (Au) nanoparticle composite

In one example, forming a nickel-cobalt-manganese composite oxide (NCM) microsphere-amorphous carbon film-graphene nanosheet-gold (Au) nanoparticle composite comprises the following steps. The NCM microspheres were used as the starting material, and the amorphous carbon film (second nano-micro film) was coated thereon, and the NCM microsphere coated with the amorphous carbon film was used as a functional substrate, and then enhanced by plasma. Graphene nanosheets were grown by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, and then Au nanoparticles were attached to the graphene nanosheets.

For example, coating an amorphous carbon film on an NCM microsphere includes the following steps. A plasma of CH ₄ gas is used as a precursor, and hydrogen is used as an auxiliary gas to mix CH ₄ gas and hydrogen gas, wherein the volume ratio of the CH ₄ gas to the hydrogen gas is 1:2-1:10. The NCM microspheres were placed in a PECVD reactor and heated to 500 ° C. The mixed gas was introduced into a PECVD reactor for 30 minutes, and an amorphous carbon film was coated on the NCM microspheres by PECVD.

For example, growing graphene nanosheets includes the following steps. Using a plasma of CH ₄ gas as a precursor, hydrogen, nitrogen and argon as auxiliary gases, mixing CH ₄ gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH ₄ gas and the auxiliary gas The volume ratio is 10:1-1:5, and the volume ratio of argon, nitrogen and hydrogen is 1-5:1-5:1-20, and the obtained NCM microspheres coated with amorphous carbon are in the PECVD reactor. Heat to 800 ° C. The foregoing mixed gas was introduced into a PECVD reactor, and graphene nanosheets were grown on an amorphous carbon-coated NCM microsphere by PECVD, and the growth time was controlled to 10 minutes to obtain NCM microsphere-amorphous carbon film-graphene. Nanosheet composites. Surface modification was carried out by bombarding with O ₂ plasma for 10 minutes, and activation was carried out using a chemical method. The chemical activation may be, for example, after sufficiently mixing with KOH (graphene and KOH molar ratio 1:2), heat treatment at 800 ° C for 4 h in an Ar atmosphere, taking out and washing and drying (the powder sample can be activated by this method).

The NCM microsphere-amorphous carbon film-graphene nanosheet composite material prepared above and the Au nanoparticle are mixed and ultrasonicated, and then washed and dried to obtain NCM microsphere-amorphous carbon film-graphene nanosheet-Au nanoparticle. Composite material.

A positive electrode was fabricated by using the NCM microsphere-amorphous carbon film-graphene nanosheet-Au nanoparticle composite material, a lithium plate was used as a negative electrode, and LiPF ₆ /EC+DMC was used as an electrolyte to assemble a lithium ion battery. Tested at 0-4V, the test results are shown in Figure 19. Figure 19 shows the relationship between the number of charge and discharge cycles and the ratio of capacity to capacity. It can be seen that there is a capacity of about 140 mAh/g at 5 C, and the capacity of 50% at 1 C is maintained even at 10 C, indicating that the sample has excellent rate performance. Mainly because the carbon film, graphene nanosheets and Au nanoparticles on the NCM microspheres greatly improve the electrical conductivity of the material, and the graphene nanosheets and Au nanoparticles greatly increase the surface area of the electrode material, thereby being lithium ions. The embedding and de-embedding provide more channels, and the corresponding rate performance is greatly improved.

Example of carbon nanowire-silicon (Si) film-graphene nanosheet-platinum (Pt) nanowire-carbon film composite

In one example, forming a carbon nanowire-silicon (Si) film-graphene nanosheet-platinum (Pt) nanowire-carbon film composite comprises the steps of: preparing a carbon nanowire array; depositing on a carbon nanowire array Si film (second nano-micro film); the carbon nanowire array coated with the Si film prepared above is a functional substrate growth graphene nanosheet; preparing Pt nanowires and depositing Pt in situ on graphene nanosheets Nanowire, coated with carbon film (first nano-micro film) on graphene nanosheet-Pt nanowire to form carbon nanowire-Si film-graphene nanosheet-Pt nanowire-carbon film composite, test the Electrocatalytic Oxygen Reduction (ORR) Catalytic Performance of Composites.

For example, preparing a carbon nanowire array comprises preparing a carbon nanowire array by chemical vapor deposition (CVD) using a copper wafer as a substrate. For example, using CH ₄ gas as a precursor, the flow rate of the CH ₄ gas is 10-1000 sccm, Cu is heated to 850 ° C in a CVD reactor, the CH ₄ gas is introduced into a CVD reactor, and the Cu substrate is formed by a CVD method. The carbon nanowire array was grown on a growth time of 1 h to obtain a carbon nanowire array having a height of 2 μm.

For example, depositing a Si thin film on a carbon nanowire array includes: then depositing a Si thin film having a thickness of 50 nm on a carbon nanowire array using magnetron sputtering using Si as a target, and then using a plasma of CH ₄ gas as a precursor Body, hydrogen and argon as auxiliary gases, mixing CH ₄ gas, hydrogen and argon to form a mixed gas, wherein the volume ratio of the CH ₄ gas to the auxiliary gas is 1:2, on the obtained Cu sheet The carbon nanowire-Si film was heated to 850 ° C in a PECVD reactor.

For example, the growth of graphene nanosheets includes a carbon nanowire array coated with a Si thin film by a plasma enhanced chemical vapor deposition (PECVD) method as a functional substrate-grown graphene nanosheet. For example, the foregoing mixed gas is introduced into a PECVD reactor, and graphene nanosheets are grown on the above functional substrate by a PECVD method, and the growth time is controlled to 1 minute to obtain a carbon nanowire-Si thin film-graphene nanosheet. The carbon nanowire-Si film-graphene nanosheet material was scraped off from the copper substrate, and the composite was surface-modified by bombardment with O ₂ plasma for 10 minutes, and activated by a chemical method. The chemical activation may be, for example, after sufficiently mixing with KOH (graphene and KOH molar ratio 1:2), heat treatment at 800 ° C for 4 hours in an Ar atmosphere, taking out, and washing and drying.

For example, the preparation of Pt nanowires includes the use of porous alumina as a template, a high purity carbon rod as a counter electrode, and chloroplatinic acid as a precursor to prepare Pt nanowires. For example, using dilute sulfuric acid as the electrolyte, anodizing for 1 h under DC voltage, the color of the template is gradually blackened during the deposition process, indicating that the Pt nanowires have been deposited inside the pores. After the deposition is completed, the porous alumina template is dissolved with a NaOH solution, and the remaining black precipitate is washed and dried to obtain a Pt nanowire. The size of the Pt nanowire varies depending on the pore size of the alumina template used. For example, the prepared Pt nanowires are dispersed in n-hexane, and after fully ultrasonically stirring, the carbon nanowire-Si film-graphene nanosheet obtained as described above is immersed in the Pt nanowire dispersion for 1 hour, and then taken out and dried. Carbon nanowire-Si film-graphene nanosheet-Pt nanowire composite.

For example, coating a carbon film on a graphene nanosheet-Pt nanowire includes the following steps. A polyaniline (PANI) film was deposited. The aniline was dissolved in 1 M HCl solution to prepare a solution with a concentration of 0.3 M. The mixture was rapidly stirred and rapidly added with a 1:4 molar ratio of ammonium peroxodisulfate to 1 M HCl. The composite material was added to the reaction solution for 1 hour at room temperature, then diluted with 100 mL of water, and washed with water, ethanol and hexane. After drying, the carbon nanowire-Si film-graphene nanosheet-Pt nanowire-carbon film composite was obtained by heat treatment at 500 ° C for 4 hours in an Ar atmosphere. The thickness of the carbon film is nanometer-sized, and the Pt nanowires can be wrapped to prevent the Pt nanowires from falling off the graphene nanosheets.

The ORR polarization curve was tested by linear voltammetry in an electrochemical workstation using the above composite as a working electrode in HClO ₄ with oxygen saturation and a molar concentration of 0.1 M/L. The test results are shown in Figure 20. 1 is the performance data curve of the carbon nanowire-Si film-graphene nanosheet-Pt nanowire-carbon film composite prepared in the present embodiment, 2 is the performance data curve of the common graphene-Pt nanoparticle, and 3 is the commercial Pt. Nanoparticle performance data curve. From the results of FIG. 20, the curve of the carbon nanowire-Si film-graphene nanosheet-Pt nanowire-carbon film composite prepared in this example is located at the far right, indicating the carbon nanowire prepared in this example- The Si film-graphene nanosheet-Pt nanowire-carbon film composite has the best catalytic performance.

Example of carbon nanowire-manganese dioxide (MnO ₂ ) nanoparticle-carbon film-graphene nanosheet-MnO ₂ nanoparticle-polyaniline (PANI) film composite

In one example, forming a carbon nanowire-manganese dioxide (MnO ₂ ) nanoparticle-carbon film-graphene nanosheet-MnO ₂ nanoparticle-polyaniline (PANI) thin film composite includes: preparing a carbon nanowire array, and then Depositing MnO ₂ nanoparticles on the carbon nanowires, and then depositing a carbon film (second nano-micro film) on the carbon nanowire-manganese dioxide (MnO ₂ ) nanoparticle composite, and then using the composite as a functional substrate growing graphene nano-sheet, followed by MnO ₂ nanoparticles deposition again, and then the graphene nanosheet -MnO deposition of polyaniline (PANI) on the thin film ₂ nanoparticles (nano first - micron film).

For example, preparing the carbon nanowire array includes: using CH ₄ gas as a precursor, the flow rate of the CH ₄ gas is 10-1000 sccm, Cu is heated to 850 ° C in a CVD reactor, and the CH ₄ gas is introduced into the CVD reactor. A carbon nanowire array was grown on a Cu substrate by a CVD method, and the growth time was 1 h, and a carbon nanowire array having a height of 2 μm and a diameter of 50 nm was obtained.

For example, MnO ₂ nanoparticles deposition using an electrochemical deposition method comprising MnO ₂ nanoparticles carbon nanowires on carbon nanowire array. For example, using MnSO ₄ as a precursor, a 0.5 M aqueous solution of MnSO _{4 is} disposed, a carbon nanowire array on Cu is used as a positive electrode, a platinum plate is used as a negative electrode, and a current of 1 mA/cm ² is deposited for 10 s, and then -0.5 mA/cm ² . The current was reversed for 5 s and repeated 60 times to obtain MnO ₂ nanoparticles deposited on the carbon nanowires, having a size of about 20 nm.

For example, depositing a carbon film includes: first depositing a PANI film on the composite material by electrochemical oxidation, the composite material is used as a working electrode, the platinum electrode is a counter electrode, the Ag/AgCl electrode is an auxiliary electrode, and the electrolyte is 0.1 M aniline. A solution of 0.1M LiClO ₄ in propylene carbonate (PC) was polymerized on the surface of graphene by cyclic voltammetry at a rate of 50 mV/s. After 50 cycles, the polymerization was completed, and the surface of the sample was washed with a PC electrolyte solvent. The surface of the sample was washed with ethanol, dried and heat-treated at 500 ° C for 4 h in Ar to obtain a carbon nanowire-MnO ₂ nanoparticle-carbon thin film composite material, wherein the thickness of the carbon thin film was 10 nm.

For example, growing the graphene nanosheet comprises: using the above carbon nanowire-MnO ₂ nanoparticle-carbon thin film composite as a functional substrate, and then using a plasma of CH ₄ gas as a precursor, hydrogen and argon as auxiliary gases, The mixture of CH ₄ gas, hydrogen gas and argon gas forms a mixed gas in which the volume ratio of the CH ₄ gas to the auxiliary gas is 1:2, and the obtained composite substrate is heated to 850 ° C in a PECVD reactor. The foregoing mixed gas was introduced into a PECVD reactor, and graphene nanosheets were grown on the substrate by a PECVD method, and the growth time was controlled to 1 minute. Finally, surface modification was carried out by bombarding with O ₂ plasma for 10 minutes, and activation was carried out using a chemical method. The chemical activation may be, for example, after sufficiently mixing with KOH (graphene and KOH molar ratio 1:2), heat treatment at 800 ° C for 4 hours in an Ar atmosphere, taking out, and washing and drying.

For example, re-depositing MnO ₂ nanoparticles includes: MnSO ₄ as a precursor, 0.5M MnSO ₄ aqueous solution, carbon nanowire-MnO ₂ nanoparticle-carbon film-graphene nanosheet composite as positive electrode, platinum plate The negative electrode was deposited at a current of 1 mA/cm ² for 10 s, and then the current of -0.5 mA/cm ² was reversed for 5 s, and repeated 60 times to obtain MnO ₂ nanoparticles deposited on graphene nanosheets having a size of about 20 nm.

For example, depositing a polyaniline (PANI) film on a graphene nanosheet-MnO ₂ nanoparticle comprises: dissolving aniline in a 1 M HCl solution to prepare a solution having a concentration of 0.3 M, rapidly stirring and rapidly adding a molar ratio of aniline to 1:4. The solution of ammonium peroxodisulfate in 1 M HCl was mixed and the mixture was added to the reaction solution for 1 hour at room temperature, then diluted with 100 mL of water, and washed with water, ethanol and hexane. After drying, carbon nanowire-MnO ₂ nanoparticles-carbon film-graphene nanosheet-MnO ₂ nanoparticle-PANI film composite were obtained.

The electrochemical performance test was carried out by electrochemical spectroscopy using linear voltammetry (50 mV/s) using the same area of platinum electrode as the counter electrode and 6 M KOH aqueous solution as the electrolyte. The test results are shown in Fig. 21.

FIG. 21 is a voltammetric test result of the carbon nanowire-MnO ₂ nanoparticle-carbon film-graphene nanosheet-MnO ₂ nanoparticle-PANI thin film composite supercapacitor electrode provided by the embodiment. In the figure, 1 is a capacitance data curve of a common graphene-MnO ₂ nanoparticle composite material, and 2 is a data capacitance curve of the present embodiment. As shown in FIG. 21, the composite capacitor of the present embodiment is much higher than the capacitance of ordinary graphene and MnO ₂ materials.

Example of ceramic bearing ball-graphene nanosheet composite material

The embodiment provides a graphene nanosheet composite material applied to a ceramic bearing ball surface and a ceramic bearing ball-graphene nanosheet composite material structure.

In one example, forming a ceramic bearing ball-graphene nanosheet composite includes the following steps. A graphene film is formed on the substrate by using a ceramic bearing ball as a substrate, and then the graphene nanosheet material is formed using the graphene film as a functional substrate.

For example, forming a graphene film includes: using a ceramic bearing ball as a substrate, using a plasma of CH ₄ gas as a precursor, hydrogen and argon as an auxiliary gas, mixing CH ₄ gas, hydrogen gas, and argon gas to form a mixed gas, wherein The volume ratio of the CH ₄ gas to the auxiliary gas is 1:2, and the mixed gas is introduced into a PECVD reactor, and a graphene nano film is grown on a ceramic bearing ball substrate by a PECVD method to obtain a graphene film attached thereto. Ceramic bearing ball composite.

For example, forming a graphene nanosheet material includes: using a plasma of CH ₄ gas as a precursor, hydrogen, nitrogen, and argon as auxiliary gases, mixing CH ₄ gas, hydrogen, nitrogen, and argon to form a mixed gas, wherein The volume ratio of the CH ₄ gas to the auxiliary gas is 10:1 to 1:5, and the volume ratio of argon, nitrogen and hydrogen is 1-5:1-5:1-20, and the previously obtained graphite is attached. The ceramic bearing ball composite material of the ene film is heated to 850 ° C in a PECVD reactor; the mixed gas is introduced into the PECVD reactor, and the graphene nanosheet material is grown on the ceramic bearing ball composite material with the graphene film attached by PECVD. The growth time was controlled to 1 minute to obtain a ceramic bearing ball-graphene nanosheet composite.

The graphene film and the graphene nanosheet material on the ball can effectively reduce the friction coefficient of the ball, increase the surface lubricity, and reduce the starting torque of the bearing.

The above description is only an exemplary embodiment of the present disclosure, and is not intended to limit the scope of the disclosure. The scope of the disclosure is determined by the appended claims.

Claims

A graphene nanosheet composite material, wherein the graphene nanosheet composite material comprises a functional substrate, a graphene nanosheet material attached to the functional substrate, and a graphene nanosheet material attached thereto At least one of a nano-microparticle, a nano-microwire, and a first nano-micron film, the functional substrate being nano-micron in at least one dimension.
The graphene nanosheet composite according to claim 1, wherein the functional substrate comprises at least one of a nano-micro particle, a nano-micro wire, a nano-micro film, a three-dimensional material having a nano-micro microstructure. Kind.
The graphene nanosheet composite according to claim 1 or 2, wherein the functional substrate comprises the nano-microparticles and/or the nano-microwires, and coated on the nano-microparticles And/or a second nano-micron film over the nano-micron line.
The graphene nanosheet composite according to claim 2, wherein the functional substrate comprises a three-dimensional material having a nano-micro microstructure and a coating on the three-dimensional material having a nano-micro microstructure Two nano-micron film.
The graphene nanosheet composite according to any one of claims 1 to 4, wherein the graphene nanosheet composite material comprises the first nano-micro film, and the first nano-micro film is located The outermost layer of the graphene nanosheet composite.
The graphene nanosheet composite according to any one of claims 1 to 5, wherein the graphene nanosheet material comprises a plurality of graphene nanosheets and pores between the plurality of graphene nanosheets.
The graphene nanosheet composite according to claim 6, wherein each of the graphene nanosheets has an average diameter of 5 nm to 500 nm.
The graphene nanosheet composite according to claim 6 or 7, wherein the pores have an average size of from 5 nm to 200 nm.
The graphene nanosheet composite according to any one of claims 6 to 8, wherein the graphene nanosheet comprises a single layer of graphene or a multilayer of graphene.
The graphene nanosheet composite according to claim 9, wherein the multilayer graphene comprises 2-10 layers of carbon atoms.
The graphene nanosheet composite according to any one of claims 1 to 10, wherein the nano-microparticles have a diameter of 5 nm to 10 μm.
The graphene nanosheet composite according to any one of claims 1 to 11, wherein the first nano-micron film has a thickness of from 0.3 nm to 3 μm.
The graphene nanosheet composite according to any one of claims 2 to 4, wherein, in the three-dimensional material having a nano-micro microstructure, the microstructure has a size of from 100 nm to 100 μm.
The graphene nanosheet composite according to any one of claims 1 to 13, wherein the nano-microparticles comprise any one or a combination of the following: metal nanoparticles, metal micro particles, non-metal nanoparticles Particles, non-metallic microparticles, oxide nanoparticles, oxide microparticles, sulfide nanoparticles, sulfide microparticles, semiconductor nanoparticles, semiconductor microparticles, polymer nanoparticles, polymer microparticles;

The nano-microwire includes any one or a combination of the following: carbon nanotubes, carbon microtubes, carbon nanowires, carbon microwires, metal nanowires, metal microwires, oxide nanowires, oxide microwires a polymer nanowire, a polymer microwire, a sulfide nanowire, a sulfide microwire, a semiconductor nanowire, a semiconductor microwire, the carbon nanotube comprising a single-walled nanotube, a multi-walled nanotube; the carbon microtube Including multi-walled microtubes;

The thickness of the first nano-micro film is on the nanometer or micrometer level, including any one or a combination of the following: a carbon film, a metal film, an oxide film, a polymer film, a sulfide film, a semiconductor film, The carbon film includes a single layer or a plurality of layers of graphite oxide, a single layer or a plurality of layers of graphene or graphite, an amorphous carbon film, and a diamond film.
The graphene nanosheet composite according to claim 14, wherein the metal nanoparticles comprise any one or a combination of the following: Pt nanoparticles, Au nanoparticles, Ag nanoparticles; the metal microparticles include a combination of any one or more of the following: Pt microparticles, Au microparticles, Ag microparticles; the non-metallic nanoparticles comprising sulfur nanoparticles; the non-metallic microparticles comprising sulfur microparticles; the oxide nanoparticles Including any one or a combination of the following: MnO 2 nanoparticles, lithium composite oxide nanoparticles, LiCoO 2 nanoparticles, LiMnO 2 nanoparticles, LiMn 2 O 4 nanoparticles, LiFePO 4 nanoparticles, Li 4 Ti 5 O 12 nanometer particles, lithium nickel cobalt manganese oxide nanoparticles, nickel cobalt cobalt aluminate nanoparticles, Mn 3 O 4 nanoparticles, MnO nanoparticles, NiO nanoparticles, Co 3 O 4 nanoparticles, Fe 2 O 3 nanoparticles, Fe nanoparticles 3 O 4, V 2 O 5 nanoparticles, TiO 2 nanoparticles; any one or several of the oxide microparticles in combination: microparticles comprising MnO 2, a lithium composite Compounds microparticles, LiCoO 2 microparticles, LiMnO 2 microparticles, LiMn 2 O 4 micron particles, LiFePO 4 microparticles, Li 4 Ti 5 O 12 micron particles, nickel-cobalt-lithium manganate microparticles, nickel-cobalt-lithium aluminate microparticles Mn 3 O 4 micron particles, MnO micro particles, NiO micro particles, Co 3 O 4 micro particles, Fe 2 O 3 micro particles, Fe 3 O 4 micro particles, V 2 O 5 micro particles, TiO 2 micro particles; The sulfide nanoparticles comprise MoS 2 nanoparticles; the sulfide microparticles comprise MoS 2 micron particles; the semiconductor nanoparticles comprise any one or a combination of the following: Si nanoparticles, ZnO nanoparticles; the semiconductor The microparticles include any one or a combination of the following: Si microparticles, ZnO microparticles; the polymer nanoparticles include any one or a combination of the following: polyaniline (PANI) nanoparticles, poly 3, 4 - hexamethylenedioxythiophene (PEDOT) nanoparticles; the polymer microparticles comprise any one or combination of the following: polyaniline (PANI) microparticles, poly 3,4-hexamethylenedioxythiophene (PEDOT) Micron ;

The metal nanowires include any one or a combination of the following: Cu nanowires, Au nanowires, Ag nanowires, Ni nanowires, Fe nanowires; any one or a combination of the following of the metal microwires; : including Cu microwire, Au microwire, Ag microwire, Ni microwire, Fe microwire; the oxide nanowire includes transition metal oxide nanowire, and the transition metal oxide nanowire includes any one of the following or Several combinations: MnO 2 nanowires, Mn 3 O 4 nanowires, MnO nanowires, NiO nanowires, Co 3 O 4 nanowires, Fe 2 O 3 nanowires, Fe 3 O 4 nanowires, V 2 O 5 Nanowire, TiO 2 nanowire, lithium composite oxide nanowire, LiCoO 2 nanowire, LiMnO 2 nanowire, LiMn 2 O 4 nanowire, LiFePO 4 nanowire, Li 4 Ti 5 O 12 nanowire, nickel cobalt manganese acid a lithium nanowire, a lithium cobalt aluminum aluminate nanowire; the oxide microwire comprising a transition metal oxide microwire, the transition metal oxide microwire comprising any one or a combination of the following: MnO 2 micron line, Mn 3 O 4 micron line, MnO micron line, NiO micron line, Co 3 O 4 micro Rice noodles, Fe 2 O 3 micron wires, Fe 3 O 4 micro wires, V 2 O 5 micro wires, TiO 2 micro wires, lithium composite oxide micro wires, LiCoO 2 micro wires, LiMnO 2 micro wires, LiMn 2 O 4 micrometers a wire, a LiFePO 4 micron wire, a Li 4 Ti 5 O 12 micron wire, a nickel cobalt cobalt manganese micron wire, a nickel cobalt aluminum aluminate micron wire; the semiconductor nanowire comprising any one or a combination of the following: Si nano a wire, a Ga nanowire, a ZnO nanowire; the semiconductor microwire includes a Si microwire, a Ga microwire, and a ZnO microwire; and the polymer nanowire includes any one or a combination of the following: polyaniline (PANI) Nanowire, poly 3,4-hexadioxythiophene (PEDOT) nanowires; the polymer microwires comprise any one or combination of the following: polyaniline (PANI) micron wires, poly 3,4-hex a dioxetane (PEDOT) micron wire; the metal film comprising any one or a combination of the following: a Cu film, an Au film, an Ag film, a Ni film, an Fe film; the oxide film including a transition metal oxide a film, the transition metal oxide film comprising any one or more of the following groups : MnO film, Mn 3 O 4 film, MnO film, NiO film, Co 3 O 4 film, Fe 2 O 3 film, Fe 3 O 4 film, V 2 O film, TiO 2 film, a lithium composite oxide thin film, of LiCoO 2 film, LiMnO 2 film, LiMn 2 O 4 film, LiFePO 4 film, Li 4 Ti 5 O 12 film, lithium nickel cobalt manganate film, nickel cobalt aluminum aluminate film; the semiconductor film includes any one or several of the following Combination of: Si film, Ga film, ZnO film; the polymer film includes any one or a combination of the following: polyaniline (PANI) film, poly 3,4-hexylene dioxythiophene (PEDOT) film .
The graphene nanosheet composite according to any one of claims 2 to 4, wherein the three-dimensional material having a nano-micro microstructure includes a carbon material, a metal material, an oxide material, a polymer material, and a vulcanization. Material, semiconductor material; the carbon material comprises any one or a combination of the following: graphene, graphene oxide, amorphous carbon, activated carbon, diamond; the metal material includes any one or a combination of the following : Cu, Ni, Au, Ag, Fe; the oxide material comprises a transition metal oxide including MnO 2 , Mn 3 O 4 , MnO, NiO, Co 3 O 4 , Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , TiO 2 , lithium composite oxide; the semiconductor material comprises any one or a combination of the following: Si, Ga, ZnO; the polymer material includes any one of the following Or a combination of several: polyaniline (PANI), poly 3,4-hexylene dioxythiophene (PEDOT).
The graphene nanosheet composite according to any one of claims 1 to 16, wherein the surface of the graphene nanosheet material has a defect including a vacancy defect and/or an edge defect;

Or the graphene nanosheet material is doped with atoms on the surface, the atoms comprising N, O and/or H; or the graphene nanosheet is surface-attached with a group or an atom, the group or atom comprising -NH 2 , -OH, -N and / or -O;

Or the surface of the graphene nanosheet material is covalently linked with a polymer monomer or a polymer oligomer.
The graphene nanosheet composite according to any one of claims 1 to 17, wherein the graphene nanosheet composite has a mass specific surface area of 400 m 2 /g or more.
An electrode comprising the graphene nanosheet composite of any of claims 1-18.
A method for manufacturing a graphene nanosheet composite material, comprising:

Providing a functional substrate;

Forming a graphene nanosheet material on the functional substrate;

Forming at least one of nano-micro particles, nano-micro wires, and first nano-micro films on the graphene nanosheet material,

Wherein the functional substrate is nano-micron in size in at least one dimension.
The method according to claim 20, wherein the forming the graphene nanosheet material comprises: using a plasma enhanced chemical vapor deposition (PECVD) method, using a mixed gas of a carbon-containing gas and an auxiliary gas as a carbon source, Graphene nanosheet material is grown on a functional substrate.
The method according to claim 21, wherein a volume ratio of said carbon-containing gas to said assist gas is from 10:1 to 1:5; and said auxiliary gas comprises argon gas and nitrogen gas.
The method of claim 21 or 22, wherein the auxiliary gas further comprises hydrogen.
The method according to claim 23, wherein a volume ratio of said argon gas, said nitrogen gas and said hydrogen gas in said assist gas is 1-5:1-5:1-20.
The method according to any one of claims 21 to 24, wherein the mixed gas of the carbon-containing gas and the assist gas has a pressure of from 0.01 Pa to 500 Pa.
The method according to any one of claims 21 to 25, wherein the growth temperature of the graphene nanosheet material grown on the functional substrate ranges from 650 to 1000 °C.
The method according to any one of claims 21 to 26 , wherein the carbon-containing gas comprises CH 4 , C 2 H 2 , C 2 F 6 .
The method according to any one of claims 21 to 27, further comprising an activation step, wherein the activating step comprises forming a plurality of micropores on the graphene sheet nanosheet material, the pores having a pore diameter of 0.5- 5nm.