CN109273702B - All-solid-state preparation method for uniformly coating graphene on surface of irregular micro-nano particle - Google Patents
All-solid-state preparation method for uniformly coating graphene on surface of irregular micro-nano particle Download PDFInfo
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Abstract
The invention discloses a preparation method of an all-solid-state material for uniformly coating dense graphene on the surface of irregular micro-nano particles, and belongs to the technical field of new energy materials and preparation thereof. The graphite powder layers are separated from each other by utilizing the shearing force generated in the ball milling process and adhered to the surface of the coated microsphere in the friction process, the number of the graphite layers is continuously reduced under the continuous physical friction action, finally, a shell-core structure of the thin graphene coated microsphere is formed, and then the coated product is obtained by screening the size difference between the coated product and the graphite powder. Further, the graphene can be transferred by mixing and ball-milling the microsphere coated product and other irregular micro-nano particle solid powder samples to form a graphene-solid powder compound for various fields. The whole process does not involve any chemical reaction, the process is simple, the cost is low, the environment is protected, the product purity is high, the post-treatment is simple, the raw materials can be repeatedly used, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to an all-solid-state preparation method for uniformly coating graphene on the surface of irregular micro-nano particles.
Background
Since the physicist andrelim, manchester university, england, and costing norwalk were successful in separating graphene from graphite by a micro-mechanical exfoliation method in 2004, graphene is favored in various industries due to its excellent properties such as high strength, low density, high electrical conductivity, high thermal conductivity, high stability, corrosion resistance, abrasion resistance, and the like. Graphene is used as an electric conduction and heat conduction framework, an anti-corrosion medium and the like to be compounded in various materials so as to improve the performance of the materials and expand the application range of the materials.
The graphene composite material has the following four structures: (a) a graphene-loaded composite; (b) a graphene-coated composite material; (c) a graphene-embedded composite material; (d) based on graphene laminated composites. The preparation of the existing graphene composite material mainly comprises three types, namely gas phase composite, liquid phase composite and solid phase composite. The gas phase method usually requires higher temperature, which leads to high production cost and difficult industrial expansion, and particularly, the gas phase method is easy to cause the phenomena of material decomposition, oxidation or reduction in the high-temperature environment of gas phase treatment for active materials. In the prior art, fluorine resin (CYTOP) and CVD-grown graphene are used for composite doping, although the product is stable in air, when the temperature is increased to 500 ℃, fluorine-containing polymer is decomposed, and the doping phenomenon disappears. Still another method is to grow a layer of graphene on the surface of nickel foam by a chemical vapor deposition method, then coat a layer of PMMA to form a three-dimensional structure, wash away metallic nickel and PMMA by acetone and hydrochloric acid to form graphene in a three-dimensional network shape, and then add Polydimethylsiloxane (PDMS) to the graphene in a three-dimensional shape to form a graphene/PDMS composite material. The method introduces other impurity ions and has high process requirements, thus being incapable of large-scale production and preparation.
Liquid phase compounding usually requires a two-step method, firstly graphene or graphene derivatives are synthesized by different methods, then the graphene or graphene derivatives are uniformly mixed with a doped material in a liquid, and the solution is removed by methods such as reduction, filtration and evaporation to obtain a graphene composite material. In the prior art, a lithium iron phosphate/graphene composite material is prepared by mixing a ferrous sulfate solution with a certain concentration with a graphene oxide solution, then dropwise adding an ammonium dihydrogen phosphate solution, controlling the pH value of the solution, filtering to obtain a compound of iron phosphate and graphene oxide, mixing the compound with lithium hydroxide and a reducing agent, carrying out hydrothermal reaction, and filtering to obtain the lithium iron phosphate/graphene doped composite material. PVP, PVAc, and PVP/PVAc are also added to a water/DMF dispersion of graphene oxide, and graphene/polymer doped materials are prepared by heating and reducing, but polymer matrix materials are degraded after high-temperature treatment, resulting in loss of performance. In addition, the coating of the graphene in the material prepared by the method cannot be uniformly distributed, and a large amount of free graphene exists, so that great challenge is caused to subsequent treatment.
The problem of deterioration of the materials can be solved by solid-phase compounding, but the traditional solid-phase compounding only needs simple ball milling on the graphene or graphite powder and the doped materials, the graphene single sheets are easy to mutually attract and agglomerate due to strong van der Waals force, the agglomeration problem between the graphene cannot be solved by the simple ball milling, and the mixture of the doped materials and the graphene is obtained. In the prior art, high-pressure graphite spheres and alumina microspheres are used for ball-milling coating, the coated object needs to be spherical and the size of the coated object is limited to a certain extent, and the subsequent utilization of a graphene product needs to be firstly dispersed and transferred in a chemical solvent.
Disclosure of Invention
The invention aims to provide an all-solid-state preparation method for uniformly coating graphene on the surface of irregular micro-nano particles so as to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the all-solid-state preparation method for uniformly coating the surface of the irregular micro-nano particles with graphene comprises the following steps:
step 1, preparing a graphene-coated microsphere shell-core structure;
and 2, transferring the graphene coated microsphere shell-core structure to the surface of the irregular micro-nano particles to form the graphene coated irregular micro-nano particles.
Further, step 1 specifically includes the following steps:
1) mixing the flake graphite powder and the coated hard microspheres to obtain a mixture A;
2) placing the mixture A into an agate ball milling tank, wherein the flake graphite and the microspheres generate friction in the ball milling process, and the graphene with different thicknesses is transferred and coated on the surfaces of the hard microspheres to obtain a mixture B;
3) screening out graphite powder in the mixture B to obtain a microsphere shell-core structure C coated with graphene with different thicknesses;
4) mixing C with a new batch of coated hard microspheres to obtain a mixture D;
5) and (3) placing the mixture D into an agate ball milling tank, and further carrying out ball milling to further transfer the graphene among different spheres so as to achieve the purpose of stripping, so as to obtain a shell-core structure E of the microsphere coated by the thin graphene.
Further, the step 2 specifically comprises the following steps:
a) mixing the prepared C or E with irregular micro-nano particles to be coated to obtain a mixture F;
b) placing the mixture F into a ball milling tank, and carrying out ball milling to obtain a mixture G;
c) and sieving the mixture G, and removing the microspheres to obtain a thin-layer graphene coated solid matter compound H.
Further, in the step 1), the mass ratio of the crystalline flake graphite powder to the coated hard microspheres is 1:20 to 1: 1; in the step 4), the mass ratio of the C to the new batch of coated hard microspheres is 1:1 to 1: 3.
Further, in the step 2), the total volume of the mixture A is not more than one third of the total volume of the ball milling tank, and the mixture A is ball milled and mixed by a ball mill under the air atmosphere, the rotating speed is between 200rpm and 300rpm, and the ball milling time is between 6h and 16 h; in the step 5), the total volume of the mixture D is not more than one third of the total volume of the ball milling tank, the rotating speed is between 200rpm and 300rpm, and the ball milling time is between 8h and 24 h.
Further, in the step a), the mass ratio of C or E to the irregular micro-nano particles to be coated is 100:1 to 1: 1; in the step b), ball milling is carried out in an air atmosphere, and the rotating speed is between 200rpm and 500 rpm; the ball milling time is between 6h and 12 h.
Further, the material mixed with the coated hard microspheres in the step 2 also comprises earthy graphite and graphite particles; the coated hard microspheres comprise metal microspheres, oxide microspheres, nitride microspheres or carbide microspheres, and the size of the microspheres is between 20 mu m and 5 mm.
Further, the irregular micro-nano particles comprise spherical powder, flaky powder or microcrystals and the like, and the size range of the irregular micro-nano particles is between 100nm and 500 mu m.
Further, the ball milling tank is one of an agate ball milling tank, a polytetrafluoroethylene sealed ball milling tank, a stainless steel sealed ball milling tank, a hard alloy sealed ball milling tank, a corundum sealed ball milling tank, a zirconia sealed ball milling tank, a polyurethane sealed ball milling tank, a silicon carbide sealed ball milling tank or a nylon sealed ball milling tank.
Compared with the prior art, the invention has the following technical effects:
the whole process of the invention is a physical process, the first step of forming the graphene-coated microsphere shell-core structure is to cut and shear the crystalline flake graphite powder at high speed by the metal microspheres and adhere the crystalline flake graphite powder to the surfaces of the microspheres through the shearing force generated in the ball milling process, form graphene layers with uniform thickness and complete structure on the surfaces of the metal microspheres under the continuous shearing action, and further achieve the purpose of further thinning the graphene by further ball milling the metal microspheres coated at a time and a new batch of uncoated metal microspheres. And in the second step, the irregular micro-nano particles are uniformly coated by transferring graphene, namely, a rolling friction force between the graphene-microsphere shell-core structure compound and the coated irregular substance particles is utilized to reach a higher stripping speed under the condition of low-speed ball milling, so that the graphene layer on the surface of the microsphere is transferred to the surface of the coated substance in a continuous friction process to form the graphene-irregular nano particle compound, and the aim of directly coating the graphene is fulfilled.
The method has the advantages of simple process, environmental protection, low price of flake graphite powder and microspheres, simple post-treatment, repeated use for many times, small investment and low cost, only needs to adjust ball milling parameters for different microspheres or subsequent coated samples, high product quality, no adhesion, easy separation of the coated microspheres and the graphite powder, repeated use for many times, no influence on performance, high production efficiency and suitability for industrial production.
Drawings
FIG. 1 is a schematic diagram of the principles of the present invention;
FIG. 2 is a state diagram of the flake graphite-copper balls after the first step of ball milling of the invention;
FIG. 3 is a composite of graphene-copper spherical shell core structure coated in accordance with the present invention;
FIG. 4 is a diagram showing a state of mixing lithium aluminum hydride and graphene-copper ball composite in a tank before the start of ball milling in example 2 of the present invention;
FIGS. 5a and b are comparative graphs of pre-coated lithium aluminum hydride and coated graphene-lithium aluminum hydride composites in example 2 of the present invention;
FIGS. 6a and b are diagrams of a ball product formed by pressing the graphene-lithium aluminum hydride composite in application example 1 of the present invention;
Detailed Description
The following embodiments and applications of the present invention are described in detail, it should be emphasized that the following embodiments are not to be considered as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are included in the scope of the present invention.
The all-solid-state preparation method for uniformly coating the surface of the irregular micro-nano particles with graphene comprises the following steps:
step 1, preparing a graphene-coated microsphere shell-core structure;
and 2, transferring the graphene coated microsphere shell-core structure to the surface of the irregular micro-nano particles to form the graphene coated irregular micro-nano particles.
The step 1 specifically comprises the following steps:
1) mixing the flake graphite powder and the coated hard microspheres to obtain a mixture A;
2) placing the mixture A into an agate ball milling tank, wherein the flake graphite and the microspheres generate friction in the ball milling process, and the graphene with different thicknesses is transferred and coated on the surfaces of the hard microspheres to obtain a mixture B;
3) screening out graphite powder in the mixture B to obtain a microsphere shell-core structure C coated with graphene with different thicknesses;
4) mixing C with a new batch of coated hard microspheres to obtain a mixture D;
5) and (3) placing the mixture D into an agate ball milling tank, and further carrying out ball milling to further transfer the graphene among different spheres so as to achieve the purpose of stripping, so as to obtain a shell-core structure E of the microsphere coated by the thin graphene.
The step 2 specifically comprises the following steps:
a) mixing the prepared uniform thin-layer graphene coated microsphere compound C or E with irregular micro-nano particles to be coated to obtain a mixture F;
b) placing the mixture F into a ball milling tank, and carrying out ball milling to obtain a mixture G;
c) and sieving the mixture G, and removing the microspheres to obtain a thin-layer graphene coated solid matter compound H.
In the step 1), the mass ratio of the crystalline flake graphite powder to the coated hard microspheres is 1:20 to 1: 1; in the step 4), the mass ratio of the C to the new batch of coated hard microspheres is 1:1 to 1: 3.
In the step 2), the total volume of the mixture A is not more than one third of the total volume of the ball milling tank; ball milling and mixing the mixture by a ball mill under the air atmosphere, wherein the rotating speed is between 200rpm and 300 rpm; the ball milling time is between 6h and 16 h; in the step 5), the total volume of the mixture D is not more than one third of the total volume of the ball milling tank; the rotating speed is between 200rpm and 300 rpm; the ball milling time is between 8h and 24 h.
In the step a), the mass ratio of C or E to the irregular micro-nano particles to be coated is 100:1 to 1: 1; in the step c), ball milling is carried out in an air atmosphere, and the rotating speed is between 200rpm and 500 rpm; the ball milling time is between 6h and 12 h.
The material mixed with the coated hard microspheres in the step 2 also comprises earthy graphite and graphite particles; the coated hard microspheres comprise metal microspheres, oxide microspheres, nitride microspheres or carbide microspheres, and the size of the microspheres is between 20 mu m and 5 mm.
The irregular micro-nano particles comprise spherical powder, flaky powder, granular powder or microcrystals and the like, and the size range of the irregular micro-nano particles is between 100nm and 500 mu m.
The ball milling tank is one of an agate ball milling tank, a polytetrafluoroethylene sealed ball milling tank, a stainless steel sealed ball milling tank, a hard alloy sealed ball milling tank, an alumina/corundum sealed ball milling tank, a zirconia sealed ball milling tank, a polyurethane sealed ball milling tank, a silicon carbide sealed ball milling tank or a nylon sealed ball milling tank.
Example (b):
preparing a graphene-coated microsphere shell-core structure;
a) mixing flake graphite (16 meshes, carbon content is more than or equal to 99%) and copper balls (diameter is 400 mu m) according to a proportion, wherein the mass ratio of the flake graphite to the copper balls is 1:10 to 1:1, and the preferred mass ratio is 1: 3; the size of the copper balls is between 20 and 500 mu m, preferably between 200 and 500 mu m, so as to obtain a mixture A;
b) placing the mixture A into an agate ball milling tank, wherein the total volume of the mixture A does not exceed one third of the total volume of the ball milling tank, and preferably the total charging amount is between one fourth and one third of the total volume; ball milling and mixing with a ball mill under air atmosphere, wherein the rotating speed is between 200rpm and 300rpm, and preferably between 230rpm and 280 rpm; the time is between 6h and 16h, preferably between 8h and 12h, and a mixture B is obtained;
c) screening out the scale graphite in the mixture B, and remaining copper balls coated with graphene with different thicknesses to obtain a mixture C;
d) mixing the mixture C and the copper balls according to a mass ratio of 1:1 to 1:3, preferably 1:2, to obtain a mixture D;
e) placing the mixture D into an agate ball milling tank, wherein the total volume of the mixture D is not more than one third of the total volume of the ball milling tank, and preferably the total charging amount is between one fourth and one third of the total volume; ball milling and mixing with a ball mill under air atmosphere, wherein the rotating speed is between 200rpm and 300rpm, and preferably between 230rpm and 280 rpm; the time is between 8h and 24h, preferably between 10h and 18h, and the copper ball E uniformly coated with the thin graphene layer is obtained;
the preparation method of the irregular micro-nano particles coated with graphene by transferring the graphene from a shell-core structure to the surface of the irregular micro-nano particles comprises the following steps:
a) obtaining copper microspheres uniformly coated with graphene with different thicknesses by using the coating method;
b) placing a certain mass of graphene-coated copper microspheres in a ball milling tank, adding other solid powder samples, wherein the size of the powder sample is between 10nm and 500 mu m, preferably the size range is between 100nm and 200 mu m, the mass ratio of the graphene-coated copper microspheres to the powder sample is between 100:1 and 1:1, preferably the mass ratio is between 30:1 and 10:1, carrying out ball milling under an air atmosphere (the sample easy to oxidize is placed in an argon atmosphere or vacuum), the rotating speed is between 200rpm and 500rpm, preferably the rotating speed is between 350rpm and 450rpm, and the ball milling time is between 6h and 12h, preferably the time is between 8h and 12 h.
c) Sieving the mixture obtained in the step b), and removing copper balls to obtain the solid powder sample uniformly coated with the thin graphene.
Example 1:
a) weighing 30g of flake graphite (16 meshes, the carbon content is more than or equal to 99 percent) and 60g of copper balls (the diameter is 400 mu m) and uniformly mixing;
b) placing the mixture into an agate ball milling tank, and carrying out ball milling and mixing by using a ball mill under the air atmosphere, wherein the set rotating speed is 250rpm, and the ball milling time is 10 hours;
c) screening out residual crystalline flake graphite in the mixture obtained in the step b) (the aperture of a sieve is 0.03mm), and remaining copper balls coated with graphene with different thicknesses;
d) putting the coated copper balls obtained in the step c) into a clean agate ball milling tank, adding 120g of clean copper balls with the same specification (the diameter is 400 mu m), and uniformly mixing;
e) setting ball milling parameters as a rotating speed of 250rpm for 12 hours to obtain a uniform thin-layer graphene-coated copper ball product.
Example 2:
a) weighing 50g of the graphene-copper spherical shell-core coated sample obtained in the example 1, and placing the sample in a stainless steel ball milling tank;
b) in a glove box (inert atmosphere), 2g of lithium aluminum hydride powder was added to the ball milling jar, which was closed and filled with argon gas. Setting ball milling parameters as 450rpm and 12 h;
c) and (c) sieving the mixture obtained in the step b) in a glove box (the aperture of a sieve is 0.02mm), and removing copper balls to obtain the graphene-coated lithium aluminum hydride composite.
Example 3:
a) weighing 30g of the graphene-copper spherical shell-core coated sample obtained in the example 1, and placing the sample in a stainless steel ball milling tank;
b) adding 1g of lithium iron phosphate powder into a ball milling tank, uniformly mixing, sealing the ball milling tank, and setting ball milling parameters to be 400rpm for 12 hours;
c) and (c) sieving the mixture obtained in the step b) (the aperture of a sieve is 0.02mm), and removing copper balls to obtain a graphene-coated lithium iron phosphate sample.
Application example 1:
the compact graphene-coated lithium aluminum hydride powder of example 2 was used as the hydrolyzed hydrogen-releasing material.
a) Weighing about 0.84g of graphene-lithium aluminum hydride composite powder sample, putting the sample into a spherical die, and applying pressure of about 12MPa for about 2 minutes to press the sample into balls;
b) cutting aluminum foil wafers with the diameters of 26mm and 22mm and the thickness of 0.03mm, respectively placing the aluminum foils on the upper hemispherical surface and the lower hemispherical surface of the sample ball, and pressing and coating the sample ball by using a customized die;
c) the hydrogen release performance of the sample is tested by adopting a drainage and gas collection method: placing the sample in 15ml of deionized water, and recording experimental data under the normal temperature condition;
d) the aluminum foil coated graphene uniformly coated lithium aluminum hydride pellets react completely within 1h, the reaction is uniform and controllable, and the hydrogen of the product is not lost.
The hydrogen storage mass ratio of the lithium aluminum hydride sample uniformly and densely coated with the aluminum foil coated graphene can reach more than 18%, and the hydrogen storage mass ratio can also reach more than 9% under the condition of containing water.
Application example 2:
as described in embodiment 3, the graphene may further be coated with other metal oxides such as SnO2, Co3O4, Fe2O3, TiO2, and the like as a lithium battery material, so as to achieve good conductivity and increase specific surface area and volumetric energy density. Metals (metal oxides) such as Au, ZnO, NiO and MnO2, conductive polymers such as polyaniline and polypyrrole and the like and graphene are uniformly compounded to form a conductive network structure which is used as an electrode material of the supercapacitor, so that the power density, the energy density, the specific capacitance, the cycle performance and the like of the supercapacitor can be improved.
Application example 3:
active substances such as lithium aluminum hydride, lithium hydride, sodium hydride and the like can be stored in the air atmosphere by adopting a compact graphene uniform coating method, and the safe transportation in the air atmosphere at normal temperature and normal pressure is realized by further coating an aluminum foil, a polymer shell and the like.
Application example 4:
by utilizing the excellent chemical sensing property, high sensitivity and stability of graphene, the sensitivity of gas molecule detection can be greatly improved by adding uniform thin-layer graphene into a detector material for compounding. Thus, for example, NO2 molecular detector, NH3 molecular detector, etc. can be prepared.
Claims (7)
1. The all-solid-state preparation method for uniformly coating graphene on the surface of irregular micro-nano particles is characterized by comprising the following steps:
step 1, preparing a graphene-coated microsphere shell-core structure;
step 2, transferring the graphene coated microsphere shell-core structure to the surface of the irregular micro-nano particles to form graphene coated irregular micro-nano particles;
the step 1 specifically comprises the following steps:
1) mixing the flake graphite powder and the coated hard microspheres to obtain a mixture A;
2) placing the mixture A into an agate ball milling tank, wherein the flake graphite and the microspheres generate friction in the ball milling process, and the graphene with different thicknesses is transferred and coated on the surfaces of the hard microspheres to obtain a mixture B;
3) screening out graphite powder in the mixture B to obtain a microsphere shell-core structure C coated with graphene with different thicknesses;
4) mixing C with a new batch of coated hard microspheres to obtain a mixture D;
5) placing the mixture D into an agate ball-milling tank, further carrying out ball milling to further transfer graphene among different spheres so as to achieve the purpose of peeling, so as to obtain a microsphere shell-core structure E coated by thin-layer graphene;
the step 2 specifically comprises the following steps:
a) mixing the prepared C or E with irregular micro-nano particles to be coated to obtain a mixture F;
b) placing the mixture F into a ball milling tank, and carrying out ball milling to obtain a mixture G;
c) and sieving the mixture G, and removing the microspheres to obtain a thin-layer graphene coated solid matter compound H.
2. The all-solid-state preparation method of the irregular micro-nano particle with the surface uniformly coated with the graphene according to claim 1, wherein in the step 1), the mass ratio of the crystalline flake graphite powder to the coated hard microspheres is 1:20 to 1: 1; in the step 4), the mass ratio of the C to the new batch of coated hard microspheres is 1:1 to 1: 3.
3. The all-solid-state preparation method of graphene uniformly coated on the surface of irregular micro-nano particles according to claim 1, wherein in the step 2), the total volume of the mixture A is not more than one third of the total volume of a ball milling tank, and the mixture A is ball milled and mixed by a ball mill under an air atmosphere, wherein the rotating speed is 200rpm to 300rpm, and the ball milling time is 6h to 16 h; in the step 5), the total volume of the mixture D is not more than one third of the total volume of the ball milling tank, the rotating speed is between 200rpm and 300rpm, and the ball milling time is between 8h and 24 h.
4. The all-solid-state preparation method for uniformly coating graphene on the surface of the irregular micro-nano particle according to claim 1, wherein in the step a), the mass ratio of C or E to the irregular micro-nano particle to be coated is 100:1 to 1: 1; in the step b), ball milling is carried out in an air atmosphere, and the rotating speed is between 200rpm and 500 rpm; the ball milling time is between 6h and 12 h.
5. The all-solid-state preparation method for uniformly coating graphene on the surface of irregular micro-nano particles according to claim 1, wherein the material mixed with the coated hard microspheres in the step 2 further comprises earthy graphite and graphite particles; the coated hard microspheres are one of metal microspheres, oxide microspheres, nitride microspheres or carbide microspheres, and the size of the microspheres is between 20 mu m and 5 mm.
6. The all-solid-state preparation method of graphene uniformly coated on the surface of the irregular micro-nano particle according to claim 1, wherein the irregular micro-nano particle comprises spherical powder, flaky powder or microcrystal, and the size range of the irregular micro-nano particle is 100nm to 500 μm.
7. The all-solid-state preparation method of graphene uniformly coated on the surface of irregular micro-nano particles according to claim 1, wherein the ball milling tank is one of an agate ball milling tank, a polytetrafluoroethylene sealed ball milling tank, a stainless steel sealed ball milling tank, a cemented carbide sealed ball milling tank, a corundum sealed ball milling tank, a zirconia sealed ball milling tank, a polyurethane sealed ball milling tank, a silicon carbide sealed ball milling tank or a nylon sealed ball milling tank.
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