WO2019100974A1 - 一种高效制备高定向、高致密二维材料薄膜的方法 - Google Patents

一种高效制备高定向、高致密二维材料薄膜的方法 Download PDF

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WO2019100974A1
WO2019100974A1 PCT/CN2018/115292 CN2018115292W WO2019100974A1 WO 2019100974 A1 WO2019100974 A1 WO 2019100974A1 CN 2018115292 W CN2018115292 W CN 2018115292W WO 2019100974 A1 WO2019100974 A1 WO 2019100974A1
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film
dimensional material
mold
solution
dimensional
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PCT/CN2018/115292
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English (en)
French (fr)
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任文才
钟晶
成会明
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中国科学院金属研究所
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Priority to US16/765,861 priority Critical patent/US11820053B2/en
Publication of WO2019100974A1 publication Critical patent/WO2019100974A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/042—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould by rotating a mould around its axis of symmetry
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/22—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/38—Moulds, cores or other substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/42—Removing articles from moulds, cores or other substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/46—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B29C69/001—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore a shaping technique combined with cutting, e.g. in parts or slices combined with rearranging and joining the cut parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs

Definitions

  • the invention relates to the field of preparation and application of two-dimensional materials, in particular to a new method for preparing highly oriented, high-density two-dimensional material thin films by using a centrifugal casting process with high efficiency.
  • two-dimensional materials such as graphene have many excellent physical and chemical properties different from those of bulk materials, in electronics, optoelectronics, flexible display, sensing, energy storage, catalysis, separation membrane, thermal management. , functional coatings, composite materials and other fields have broad application prospects.
  • two-dimensional materials prepared by chemical stripping are often only a few microns in size, so assembling them into macroscopically controllable macroscopic materials is a prerequisite for their application. It is well known that two-dimensional materials have strong anisotropy, and the physical properties of the in-plane and vertical in-plane directions are vastly different.
  • the commonly used methods for preparing two-dimensional material films include vacuum suction filtration, flat blade coating, surface spray coating and layer self-assembly.
  • the two-dimensional materials in the films obtained by the vacuum suction filtration and the layer self-assembly process have better orientation, but the two methods are inefficient and are not suitable for the preparation of large-area thick films.
  • the other two processes have high film forming efficiency, the driving force for driving the two-dimensional material self-assembly is small and uncontrollable, and the arrangement of the two-dimensional materials inside the film is rather confusing.
  • the self-assembly orientation of the two-dimensional material is more difficult due to the large viscosity of the solution.
  • the density of the film obtained by the above method still needs to be further improved to improve the contact between the two-dimensional materials, thereby maximally transferring the intrinsic properties of the micro-sized two-dimensional material into the macroscopic body material.
  • it is urgent to develop a high-efficiency film forming technology that can achieve highly oriented, high-density assembly of two-dimensional materials, thereby promoting the wide application of two-dimensional materials.
  • the solution containing the two-dimensional material is uniformly coated on the inner surface of the mold by centrifugal force.
  • the shear force formed by the relative movement between the liquid layers is used to promote the two-dimensional nano material in the circumferential direction in the solution.
  • the layer orientation is arranged regularly.
  • the centrifugal force is used to promote the dense packing of the two-dimensional material, thereby obtaining a highly oriented, high-density two-dimensional material film, which effectively improves the performance of the film.
  • the invention relates to a method for efficiently preparing a high-oriented, high-density two-dimensional material film, which adopts a round tube with a smooth inner surface as a casting mold, and a solution containing a two-dimensional material is poured into a mold when the mold rotates at a high speed in the circumferential direction, and utilizes The centrifugal force uniformly coats the solution on the inner surface of the mold.
  • a shear force is formed which causes the two-dimensional material to be regularly arranged in the circumferential direction of the solution.
  • the centrifugal force promotes the high-density accumulation of the two-dimensional material, thereby obtaining a highly oriented, highly dense two-dimensional material film.
  • the method for efficiently preparing a highly oriented, high-density two-dimensional material film is as follows:
  • Rotation of the casting mold the circular tubular mold with smooth inner surface rotates at a high speed around the axis, and the rotational speed of the circular tubular mold ranges from 100 r/min to 50000 r/min, forming a centrifugal force for uniformly adhering the solution on the inner wall of the mold;
  • the material of the circular tubular mold is one of quartz glass, ceramic, polymer, metal or a combination of two or more, and the inner diameter is 50 mm to 1000 mm.
  • a preferred range is from 100 mm to 500 mm.
  • the method for efficiently preparing a highly oriented, high-density two-dimensional material film adopts a two-dimensional material which is a material having a thickness of less than 100 nm and a lateral dimension to a thickness ratio greater than 1, including but not limited to graphene and graphite oxide.
  • a two-dimensional material which is a material having a thickness of less than 100 nm and a lateral dimension to a thickness ratio greater than 1, including but not limited to graphene and graphite oxide.
  • organic polymer materials include, but are not limited to, polyethylene glycol, polyurethane, polydimethylsilane, nanocellulose, epoxy, polyethylene or natural rubber, inorganic materials including but not limited to two-dimensional different from the former Materials, carbon nanotubes, fullerenes, carbon black, nano-nonmetals, nano-oxides or nano-metals.
  • the method for efficiently preparing a high-oriented, high-density two-dimensional material film the solution of the two-dimensional material or the composite material thereof is added to the casting mold by continuous feeding or one-time feeding; in the casting process, the two-dimensional material is contained
  • the composition and concentration of the solution are changed as needed, thereby obtaining a vertically laminated heterostructure film composed of a film of a different two-dimensional material in the thickness direction or a gradient composite material in which the content of the two-dimensional material in the thickness direction is gradually changed.
  • the method for efficiently preparing a highly oriented, high-density two-dimensional material film has an auxiliary heating temperature of from 25 ° C to 500 ° C, preferably from 50 ° C to 100 ° C.
  • the method for efficiently preparing a highly oriented, high-density two-dimensional material film the obtained two-dimensional material or a composite material film thereof is directly peeled off from the mold, and the mold is not damaged and reused.
  • the method for efficiently preparing a high-oriented, high-density two-dimensional material film the obtained two-dimensional material or a composite material thereof is in a three-dimensional tubular shape, cut into a planar film, an annular film or cut into a complete band in the circumferential direction.
  • the film is formed, or the graphene fiber is prepared by twisting.
  • the method for efficiently preparing a highly oriented, high-density two-dimensional material film directly prepares a patterned highly oriented, highly dense two-dimensional material film by using a template.
  • the solution containing the two-dimensional material can be uniformly coated on the inner surface of the mold to form a film having a uniform thickness, and the thickness of the film can be arbitrarily regulated.
  • the liquid is rotated by the high-speed rotation of the mold, and the relative displacement between the liquid layers during the rotation process can form shear stress, and the two-dimensional nano materials in the solution are aligned in the circumferential direction, thereby making the obtained film two-dimensional.
  • the materials are regularly aligned in a planar direction, and the centrifugal force simultaneously promotes high-density packing of the two-dimensional material.
  • the shearing stress and the centrifugal force of the liquid layer can be controlled by changing the rotational speed of the mold and the concentration and viscosity of the solution, thereby macroscopically regulating the arrangement state and the density of the two-dimensional nano material in the film product, and The mixed solution of the two-dimensional material can still be regularly aligned in a relatively viscous state, thereby preparing a highly oriented two-dimensional composite film.
  • the invention is simple and easy to control, and the composition and concentration of the solution containing the two-dimensional material can be changed as needed during the casting process, thereby obtaining a vertically laminated heterostructure film or thickness composed of films of different two-dimensional materials in the thickness direction. Gradient composites with varying amounts of two-dimensional materials in the direction.
  • the film product produced in the present invention is a cylindrical film which can be prepared by simple subsequent processing, including strips and fibers, or a patterned film can be directly prepared by using a template.
  • the two-dimensional material in the film obtained by the invention is highly oriented and densely packed, so that the excellent electrical, thermal and mechanical properties brought about by the two-dimensional structural features can be fully reflected in the macroscopic film, and the film is significantly improved. performance.
  • the invention adopts the centrifugal casting process commonly used in the metallurgical industry, and has the advantages of good universality, simple process, easy operation, fast film forming speed and easy enlargement, and is expected to realize large-scale, high-efficiency and rapid production, high orientation and high.
  • the invention adopts a centrifugal casting process to prepare a high-oriented, high-density two-dimensional material film, a composite material film of two-dimensional materials, a composite material film of two-dimensional materials and polymers, and the like.
  • the two-dimensional material composite film with gradient concentration in the thickness direction and the vertical heterostructure film composed of different two-dimensional material films in thickness direction make full use of the inherent structural properties of the two-dimensional material to greatly improve the electrical properties of the film.
  • Thermal, mechanical and other properties lay the foundation for its applications in high performance conductive/thermal conductive films, thermal management materials, high strength films, electronic/optoelectronic devices, dense energy storage, gas/ion separation membranes and proton transport membranes.
  • Figure 1 Schematic diagram of the preparation of a highly oriented, highly dense two-dimensional material film by centrifugal casting.
  • Figure 2 Graphene film prepared from graphene oxide as a raw material.
  • a a graphene film attached to the inner wall of the mold after reduction;
  • b a graphene film after peeling off in water;
  • c a graphene film after drying;
  • d a scanning electron micrograph of a cross section of the graphene film, showing Highly oriented, highly dense layered structure;
  • e Stripped and transferred into a strip of graphene film;
  • f Striped graphene film on a stock rod.
  • FIG. 3 Thin film diagram of a composite of graphene oxide and polyurethane prepared by a centrifugal casting process. Among them, (a) a composite film of graphene oxide and polyurethane attached to the inner wall of the mold; (b) peeling of the composite film; and (c) a composite film of oxidized graphene and polyurethane which are peeled off.
  • Figure 4 Two-dimensional material prepared by centrifugal casting process and its heterostructure film. Among them, (a) graphene film; (b) black phosphorus nanosheet film; (c) tungsten disilicide film; (d) hexagonal boron nitride film; (e) graphene / hexagonal boron nitride / diselenization A cross-sectional scanning electron micrograph of a tungsten vertical laminated heterostructure film in which all two-dimensional materials exhibit highly oriented, highly dense layered structural features; (f) a patterned graphene film prepared using IMR as a template.
  • a round tube with a smooth inner surface is used as a casting mold.
  • the solution containing the two-dimensional material is added to a high-speed rotating mold, and the solution is evenly distributed under the action of centrifugal force.
  • the existing displacement between the liquid layers can form a layer-oriented rule for promoting the two-dimensional material along the circumferential direction.
  • the shearing force of the arrangement, while the centrifugal force promotes the high-density accumulation of the two-dimensional material, thereby preparing a highly oriented, highly dense two-dimensional material film.
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (average sheet size of about 1 ⁇ m and a concentration of 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a film having a thickness of 3 ⁇ m to 20 ⁇ m. The film was cut along the axis and peeled off from the mold to obtain a graphene oxide film having a strength of about 90 MPa.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (average sheet size of about 1 ⁇ m and a concentration of 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a film having a thickness of 3 ⁇ m to 20 ⁇ m. The film was cut along the axis and peeled off from the mold to obtain a graphene oxide film whose strength was increased to 125 MPa.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (average sheet size of about 1 ⁇ m and a concentration of 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a film having a thickness of 3 ⁇ m to 20 ⁇ m. The film was cut along the axis and peeled off from the mold to obtain a highly oriented, highly dense graphene oxide film, the strength of which was further increased to 145 MPa.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous graphene oxide solution (average sheet size of about 1 ⁇ m and a concentration of 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a graphene oxide film having a thickness of 3 ⁇ m to 20 ⁇ m. Then, a hydriodic acid solution having a concentration of 10% by weight was sprayed onto the surface of the graphene oxide film, and reduction was carried out at 120 °C.
  • the film was cut along the axis and immersed in water to be peeled off from the surface of the mold, and repeatedly rinsed with deionized water to obtain a graphene film having a strength of 170 MPa and an electric conductivity of 220 S/cm.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous graphene oxide solution (average sheet size of about 1 ⁇ m and a concentration of 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a graphene oxide film having a thickness of 3 ⁇ m to 20 ⁇ m. Then, a hydriodic acid solution having a concentration of 10% by weight was sprayed onto the surface of the graphene oxide film, and reduction was carried out at 120 °C.
  • the film was cut along the axis and immersed in water to be peeled off from the surface of the mold, and repeatedly rinsed with deionized water to obtain a graphene film having a strength of 250 MPa and an electric conductivity of 390 S/cm.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (average sheet size of about 1 micron and a concentration of 2 mg/ml) is continuously added to the casting mold, and the solution is evaporated to obtain a highly oriented, high-density graphene oxide having a thickness of 3 ⁇ m to 20 ⁇ m. film.
  • a hydriodic acid solution having a concentration of 10% by weight was sprayed onto the surface of the graphene oxide film, and reduction was carried out at 120 °C.
  • the film is cut along the axis and immersed in water to peel it off from the mold surface, and repeatedly rinsed with deionized water to obtain a highly oriented, high-density graphene film, the strength of which is further increased to 290 MPa, and the conductivity is further improved to 470S/cm.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • the aqueous graphene oxide solution (average sheet size about 20 ⁇ m, concentration 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a highly oriented, high-density graphene oxide having a thickness of 3 ⁇ m to 20 ⁇ m. film. Then, a hydriodic acid solution having a concentration of 10% by weight was sprayed onto the surface of the graphene oxide film, and reduction was carried out at 120 °C.
  • the film is cut along the axis and immersed in water to be peeled off from the mold surface, and repeatedly rinsed with deionized water to obtain a highly oriented, high-density graphene film, the strength of which is further increased to 600 MPa, and the conductivity is further improved to 600S/cm.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a casting mold having an inner diameter of 50 mm to 1000 mm is used, and the casting mold is a quartz glass tube, a ceramic tube, a polymer plastic tube or a metal tube, and the rotation speed of the mold is set to 500 r/min to 2500 r/min, and the auxiliary heating is performed.
  • the temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (concentration of 2 mg/ml to 10 mg/ml) was continuously added to a casting mold, and the solution was evaporated to dryness to obtain a film having a thickness of 3 ⁇ m to 20 ⁇ m. The film was cut along the axis and peeled off from the mold to obtain a graphene oxide film.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (concentration: 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a film having a thickness of 3 ⁇ m to 20 ⁇ m. The film is cut in the circumferential direction and peeled off from the mold to obtain a plurality of highly oriented, highly dense graphene oxide film rings.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • An aqueous solution of graphene oxide (concentration: 2 mg/ml) was continuously added to the casting mold, and the solution was evaporated to dryness to obtain a film having a thickness of 3 ⁇ m to 20 ⁇ m.
  • the film was cut along a spiral, the rotation speed of the mold was 35 r/min when cutting, and the advance speed of the cutting tool was 8 mm/min, and a complete high-oriented, high-density graphene oxide film strip was obtained.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1200 r/min, and the auxiliary heating temperature was set to 80 °C.
  • SDS sodium dodecyl sulfate
  • the composite film is cut along the axis, immersed in water to be peeled off from the mold surface, and repeatedly rinsed with deionized water to obtain a highly oriented, high-density composite film of graphene and single-walled carbon nanotubes, the density of which is 1.5g/cm 3 , strength 105MPa, electrical conductivity 168S/cm, specific surface area ⁇ 1m 2 /g, the volume and mass capacity of the all-solid supercapacitor made by cutting the hybrid film into strips as electrodes It is 193 F/cm 3 and 128 F/g.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1200 r/min, and the auxiliary heating temperature was set to 80 °C.
  • the composite film is cut along the axis, immersed in water to be peeled off from the mold surface, and repeatedly rinsed with deionized water to obtain a highly oriented, high-density composite film of graphene and single-walled carbon nanotubes, the density of which is 1.18g/cm 3 , the strength is 78MPa, the electrical conductivity is 163S/cm, the specific surface area is 50m 2 /g, and the volumetric capacity and mass capacity of the all-solid supercapacitor made by cutting the hybrid film into strips as electrodes are respectively 224 F/cm 3 and 190 F/g.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1200 r/min, and the auxiliary heating temperature was set to 80 °C.
  • the composite film is cut along the axis, immersed in water to be peeled off from the mold surface, and repeatedly rinsed with deionized water to obtain a highly oriented, high-density composite film of graphene and single-walled carbon nanotubes, the density of which is 1.06g/cm 3 , strength 47MPa, electrical conductivity 158S/cm, specific surface area 141m 2 /g, the volumetric capacity and mass capacity of the all-solid supercapacitor made by cutting the hybrid film into strips as electrodes 414 F/cm 3 and 391 F/g.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • the solution is a mixed solution of an aqueous graphene oxide solution and a water-soluble polyurethane; in the mixed solution, the concentration of graphene oxide is 10 mg/ml, and the concentration of polyurethane is 10 mg/g.
  • the mixed solution was added to the casting mold at one time, and the solution was evaporated to dryness to obtain a film having a film thickness of 3 ⁇ m to 20 ⁇ m. The film is cut along the axis and peeled off from the mold to obtain a composite film of oriented graphene oxide and polyurethane.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • the solution is a mixed solution of an aqueous graphene oxide solution and a water-soluble polyurethane; in the mixed solution, the concentration of graphene oxide is 10 mg/ml, and the concentration of polyurethane is 10 mg/g.
  • the mixed solution was added to the casting mold at one time, and the solution was evaporated to dryness to obtain a film having a film thickness of 3 ⁇ m to 20 ⁇ m.
  • the composite film is cut along the axis and peeled off from the surface of the mold to obtain a composite film of oriented graphene oxide and polyurethane. Finally, the composite film was placed in an oven at 200 ° C for 2 hours to reduce it, and its in-plane and vertical conductivity were 0.3 S/m and 0.007 S/m, respectively.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1500 r/min, and the auxiliary heating temperature was set to 80 °C.
  • the solution is a mixed solution of an aqueous graphene oxide solution and a water-soluble polyurethane; in the mixed solution, the concentration of graphene oxide is 10 mg/ml, and the concentration of polyurethane is 10 mg/g.
  • the mixed solution was added to the casting mold at one time, and the solution was evaporated to dryness to obtain a film having a film thickness of 3 ⁇ m to 20 ⁇ m.
  • the composite film is cut along the axis and peeled off from the surface of the mold to obtain a composite film of highly oriented graphene oxide and polyurethane. Finally, the composite film was placed in an oven at 200 ° C for 2 hours to reduce it, and its in-plane and vertical conductivity were 0.36 S/m and 0.002 S/m, respectively.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • other two-dimensional nanomaterials such as: hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide, black phosphorus, Mxenes, montmorillonite, etc. are used.
  • the solution concentration is from 1 mg/g to 10 mg/g, and the solution is continuously added to a casting mold, and the solution is evaporated to dryness to obtain a film having a film thickness of 3 ⁇ m to 20 ⁇ m.
  • the film is cut along the axis and peeled off from the mold to obtain a highly oriented, highly dense two-dimensional material film.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • two-dimensional materials eg, graphene, graphene oxide, hydrogenated graphene, fluorinated graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide
  • graphene, graphene oxide, hydrogenated graphene, fluorinated graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide are used.
  • the solution concentration is 1mg / ml ⁇ 10mg / ml
  • the solution is continuously added to the casting mold
  • the solution is evaporated to dryness to obtain a film thickness of 3 ⁇ m ⁇ 20 ⁇ m thick film.
  • the film is cut along the axis and peeled off from the mold to obtain a highly oriented, highly dense mixed two-dimensional material film.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • other two-dimensional nanomaterials such as: hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide, black phosphorus, Mxenes, montmorillonite, etc. are used.
  • the solution concentration is from 1 mg/ml to 10 mg/ml, and the solution is continuously added to a casting mold, and the solution is evaporated to dryness to obtain a film having a film thickness of 3 ⁇ m to 20 ⁇ m.
  • the film was cut along a spiral, the rotation speed of the mold was 35 r/min when cutting, and the advance speed of the cutting tool was 8 mm/min, and a complete film strip of high-oriented, high-density two-dimensional material was obtained.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having an inner diameter of 110 mm was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • different two-dimensional materials are used (eg, graphene, graphene oxide, hydrogenated graphene, fluorinated graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, selenium selenide).
  • Embodiment 1 The difference from Embodiment 1 is that:
  • a quartz glass tube having a surface having an inner diameter of 110 mm and covered with a patterned template was used as a casting mold, and the mold rotation speed was set to 1000 r/min, and the auxiliary heating temperature was set to 80 °C.
  • different two-dimensional materials are used (eg, graphene, graphene oxide, hydrogenated graphene, fluorinated graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, selenium selenide).
  • aqueous solution of tungsten, black phosphorus, Mxenes, montmorillonite, etc., solution concentration of 1 mg / ml ⁇ 10 mg / ml the solution is continuously added to the casting mold, the solution is evaporated to dry, the patterned template is removed, the film is removed After cutting along the axis, it is peeled off from the mold to obtain a highly oriented, highly dense patterned two-dimensional material film.
  • the graphene film prepared by using graphene oxide as a raw material replicates the inner surface features of the mold and is a three-dimensional tubular shape, exhibiting a highly oriented, highly dense layered structure, which can be cut into a flat film. It is also possible to cut into a continuous continuous strip film in the circumferential direction.
  • the composite film of graphene oxide and polyurethane prepared by centrifugal casting process is evenly attached on the inner surface of the mold, and can be directly peeled off from the inner surface of the mold to obtain the internal graphene oxide height. Oriented composite film.
  • a plurality of two-dimensional materials and a vertical heterostructure film composed of different two-dimensional materials can be prepared by a centrifugal casting process, and the two-dimensional material in the film exhibits a highly oriented, highly dense layered layer. Structural features, and can be graphically well implemented.
  • the method of the invention has high universality and can be applied to the preparation of various two-dimensional materials such as graphene and composite film and laminated heterostructure film, and greatly improves the electrical, thermal and mechanical properties of the film.

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Abstract

一种高效制备高定向、高致密二维材料薄膜的方法，采用内表面光滑的圆型管作为浇铸模具，模具高速沿圆周方向旋转时将含有二维材料的溶液倒入模具中，利用离心力将溶液均匀涂覆在模具内表面，在离心旋转过程中，形成促使二维材料在溶液中沿圆周方向层层定向规则排列的剪切力，同时离心力会促使二维材料的高致密堆积，进而得到高定向、高致密的二维材料薄膜。该方法适于石墨烯等各种二维材料及其复合材料薄膜和叠层异质结构薄膜的制备，极大提高薄膜的电学、热学、力学等性能，用于高性能导电/导热薄膜、热管理材料、高强度薄膜、电子/光电子器件、致密储能、气体/离子分离膜和质子传输膜等领域。

Description

一种高效制备高定向、高致密二维材料薄膜的方法 技术领域
本发明涉及二维材料的制备和应用领域，具体为一种利用离心浇铸工艺高效率制备高度定向、高致密二维材料薄膜的新方法。
背景技术
由于独特的二维结构特征，石墨烯等二维材料具有多种不同于其块体材料的优异物理化学性质，在电子、光电子、柔性显示、传感、储能、催化、分离膜、热管理、功能涂层、复合材料等领域具有广阔的应用前景。然而，由化学剥离法制备的二维材料往往只有数微米大小，因此将其组装成宏观可控的宏观体材料是实现其应用的前提。众所周知，二维材料具有很强的各项异性，其面内和垂直面内方向的物理性质存在巨大的差异。以石墨烯为例，其面内的导电性、导热性和力学性质要远高于垂直于面内方向的性质。因此，将二维材料组装成平面方向定向排列且致密堆积的薄膜材料有利于保持和充分发挥二维材料由其二维结构特征带来的固有的优异的电学、热学和力学等性质。
目前，常用的制备二维材料薄膜的方法主要有真空抽滤法、平板刮涂法、表面喷涂法和层层自组装法。真空抽滤和层层自组装工艺得到的薄膜中二维材料定向性较好，但是这两种方法效率低，不适于大面积较厚薄膜的制备。其它两种工艺虽然制膜效率高，但是驱动二维材料定向自组装的驱动力较小且不可控，得到的薄膜内部二维材料的排列比较混乱。尤其当利用这些方法制备二维材料与高分子复合膜时，由于溶液粘度较大，使得二维材料的自组装定向更加困难。此外，上述方法得到的薄膜的致密度仍待进一步提高，以改善二维材料之间的接触，从而最大程度地将微米尺寸二维材料的本征性能转移到宏观体材料中。综上所述，为了提高二维材料薄膜的性能，目前亟需开发一种高效率且能实现二维材料高度定向、高致密组装的制膜技术，从而促进二维材料的广泛应用。
发明内容
本发明的目的在于提供一种利用离心浇铸工艺高效率制备高度定向、高致密二维材料薄膜的新方法。利用离心力将含有二维材料的溶液均匀涂覆在模具内表面，在离心旋转的过程中，一方面利用液层间的相对运动形成的剪切力，促使二维纳米材料在溶液中沿圆周方向层层定向规则排列，一方面利用离心力促使二维材料致密堆积，进而得到高定向、高致密的二维材料薄膜，有效提高薄膜的各项性能。
本发明的技术方案是：
一种高效制备高定向、高致密二维材料薄膜的方法，该方法采用内表面光滑的圆型管作为浇铸模具，模具高速沿圆周方向旋转时将含有二维材料的溶液倒入模具中，利用离心力将溶液均匀涂覆在模具内表面，在离心旋转的过程中，一方面由于液层间的相对运动，形成促使二维材料在溶液中沿圆周方向层层定向规则排列的剪切力，另一方面离心力促使二维材料高致密堆积，进而得到高度定向、高致密的二维材料薄膜。
所述的高效制备高定向、高致密二维材料薄膜的方法，具体步骤如下：
(1)浇注模具的旋转：将内表面光滑的圆管状模具高速绕轴线旋转，圆管状模具的转速范围为100r/min～50000r/min，形成将溶液均匀粘附在模具内壁上的离心力；
(2)含二维材料溶液的浇铸：将含有二维材料的溶液加入到上述高速旋转的模具内部，通过离心力使溶液均匀涂覆在模具内壁上，在离心旋转过程中，利用相邻液层的相对运动，促使溶液中的二维材料沿圆周方法层层定向排列，利用离心力使二维材料致密堆积，含有二维材料的溶液浓度范围0.1mg/ml～100mg/ml；
(3)溶液的蒸干：在离心旋转过程中，采用加热辅助的方式促进浇铸得到的薄膜中溶剂的蒸发；
(4)薄膜的剥离：采用机械剥离的方法将薄膜从模具内壁剥离下来，得到高度定向、高致密的二维材料的薄膜制品。
所述的高效制备高定向、高致密二维材料薄膜的方法，圆管状模具的材质是石英玻璃、陶瓷、高分子、金属之一种或两种及以上的复合，其内径为50mm～1000mm，优选范围是100mm～500mm。
所述的高效制备高定向、高致密二维材料薄膜的方法，采用的二维材料是指厚度在100纳米以下且横向尺寸与厚度比远大于1的材料，包括但不限于石墨烯、氧化石墨烯、氢化石墨烯、氟化石墨烯、六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒化钨、黑磷烯、Mxenes之一种或两种及以上复合。
所述的高效制备高定向、高致密二维材料薄膜的方法，该方法制备二维材料的复合材料薄膜，与二维材料复合的材料为有机高分子材料或无机材料之一种或两种及以上的复合；有机高分子材料包括但不限于聚乙二醇、聚氨酯、聚二甲基硅烷、纳米纤维素、环氧、聚乙烯或天然橡胶，无机材料包括但不限于与前者不同的二维材料、碳纳米管、富勒烯、炭黑、纳米非金属、纳米氧化物或纳米金属。
所述的高效制备高定向、高致密二维材料薄膜的方法，二维材料或其复合材料的溶液采用连续加料或一次性加料的方式加入到浇铸模具中；在浇铸过程中，含有二维材料的溶液成分和浓度按需改变，进而获得在厚度方向由不同二维材料的薄膜构成的垂直叠层异质结构薄膜或者厚度方向二维材料的含量逐渐变化的梯度复合材料。
所述的高效制备高定向、高致密二维材料薄膜的方法，辅助加热温度在25℃～500℃，优选范围为50℃～100℃。
所述的高效制备高定向、高致密二维材料薄膜的方法，得到的二维材料或其复合材料的薄膜直接从模具上剥离下来，对模具没有损伤，重复利用。
所述的高效制备高定向、高致密二维材料薄膜的方法，得到的二维材料或其复合材料的薄膜呈三维立体的管状，切割成平面膜、环状膜或沿圆周方向切割成完整的带状膜，或通过加捻制备石墨烯纤维。
所述的高效制备高定向、高致密二维材料薄膜的方法，通过使用模板直接制备图形化的 高定向、高致密的二维材料薄膜。
本发明的特点及有益效果是：
1、本发明中通过离心浇铸旋转过程中产生的离心力，可以使含有二维材料的溶液均匀地涂覆在模具的内表面，形成厚度均匀的薄膜，且薄膜厚度可任意调控。
2、本发明中由模具的高速旋转带动液体旋转，旋转过程中液层间存在的相对位移可以形成剪应力，促进溶液中的二维纳米材料沿圆周方向定向排列，从而使所得薄膜中二维材料规则地沿平面方向层层定向排列，而离心力会同时促使二维材料高致密堆积。
3、本发明中可以通过改变模具的旋转转速和溶液的浓度、粘度来调控液层间剪切应力和离心力的大小，从而宏观调控二维纳米材料在薄膜制品中的排列状态和致密程度，并且可使二维材料的混合溶液在比较粘稠的状态下仍能得到规则的定向排列，进而制备高度定向的二维材料的复合材料薄膜。
4、本发明简单易控，含有二维材料的溶液的成分和浓度可以在浇铸过程中按需改变，进而获得在厚度方向由不同二维材料的薄膜构成的垂直叠层异质结构薄膜或者厚度方向二维材料的含量逐渐变化的梯度复合材料。
5、本发明中制得薄膜制品是一张圆筒状的薄膜，可以通过简单的后续加工制备不同形貌的材料，包括条带和纤维，也可以通过使用模板直接制备图形化薄膜。
6、本发明获得的薄膜中二维材料高度定向且高致密堆积，因此二维结构特征所带来的优异的电学、热学和力学等性能等在宏观薄膜中可以得到充分体现，显著提高薄膜的性能。
7、本发明采用冶金工业中常用的离心浇铸工艺，具有普适性好，工艺简单、操作容易、制膜速度快、易于放大的优点，有望实现大规模、高效率快速化生产高度定向、高致密的二维材料及其复合材料的薄膜。
综上所述，本发明采用离心浇铸工艺可以大规模、高效制备高定向、高致密的二维材料薄膜、不同二维材料的复合材料薄膜、二维材料与高分子等其他材料的复合材料薄膜、厚度方向浓度呈梯度分布的二维材料复合材料薄膜、以及厚度方向由不同二维材料薄膜构成的垂直异质结构薄膜，充分利用二维材料固有的结构性能特点，极大提高薄膜的电学、热学、力学等性能，为其在高性能导电/导热薄膜、热管理材料、高强度薄膜、电子/光电子器件、致密储能、气体/离子分离膜和质子传输膜等领域的应用奠定基础。
附图说明
图1.离心浇铸法制备高定向、高致密的二维材料薄膜的流程示意图。
图2.以氧化石墨烯为原料制备的石墨烯薄膜图。其中，a.还原后贴附在模具内壁上的石墨烯薄膜；b.在水中剥离后的石墨烯薄膜；c.干燥后的石墨烯薄膜；d.石墨烯薄膜截面的扫描电镜照片，呈现出高定向、高致密的层状结构特征；e.加工成带状石墨烯薄膜的剥离与转移；f.储料棒上的带状石墨烯薄膜。
图3.采用离心浇铸工艺制备的氧化石墨烯与聚氨酯的复合材料薄膜图。其中，(a)贴附在模具内壁上的氧化石墨烯与聚氨酯的复合薄膜；(b)复合薄膜的剥离；(c)剥离下来的氧 化石墨烯与聚氨酯的复合薄膜。
图4.采用离心浇筑工艺制备的二维材料及其异质结构薄膜。其中，(a)石墨烯薄膜；(b)黑磷纳米片薄膜；(c)二硒化钨薄膜；(d)六方氮化硼薄膜；(e)石墨烯/六方氮化硼/二硒化钨垂直叠层异质结构薄膜的截面扫描电镜照片，其中所有二维材料呈现出高定向、高致密的层状结构特征；(f)使用IMR作为模板制备的图形化的石墨烯薄膜。
具体实施方式
如图1所示，离心浇铸法制备高定向、高致密的二维材料薄膜的流程如下：
采用内表面光滑的圆型管作为浇铸模具，模具高速沿圆周方向(轴向)旋转时，将配置好的含有二维材料的溶液加入到高速旋转的模具中，在离心力的作用下将溶液均匀涂覆在浇铸模具的内表面，在模具带动溶液高速离心旋转的过程中，由于不同液层间的相对运动，液层间存在的现对位移可以形成促进二维材料沿圆周方向层层定向规则排列的剪切力，同时离心力促使二维材料高致密堆积，进而制备出高定向、高致密的二维材料薄膜。
下面，通过实施例对本发明进一步详细阐述。
实施例1
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约1微米，浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割开后从模具上剥离下来，得到氧化石墨烯薄膜，其强度约为90MPa。
实施例2
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约1微米，浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割开后从模具上剥离下来，得到一张氧化石墨烯薄膜，其强度提高到125MPa。
实施例3
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约1微米，浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割开后从模具上剥离下来，得到高定向、高致密的氧化石墨烯薄膜，其强度进一步提高到145MPa。
实施例4
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约1微米，浓度 为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的氧化石墨烯薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到氧化石墨烯薄膜表面，在120℃下进行还原。最后，将薄膜沿轴线切割开后浸入水中将其从模具表面剥离下来，并反复用去离子水冲洗，得到石墨烯薄膜，其强度为170MPa，电导率为220S/cm。
实施例5
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约1微米，浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的氧化石墨烯薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到氧化石墨烯薄膜表面，在120℃下进行还原。最后，将薄膜沿轴线切割开后浸入水中将其从模具表面剥离下来，并反复用去离子水冲洗，得到石墨烯薄膜，其强度提高到250MPa，电导率提高到390S/cm。
实施例6
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约1微米，浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的高定向、高致密的氧化石墨烯薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到氧化石墨烯薄膜表面，在120℃下进行还原。最后，将薄膜沿轴线切割开后浸入水中将其从模具表面剥离下来，并反复用去离子水冲洗，得到高定向、高致密的石墨烯薄膜，其强度进一步提高到290MPa，电导率进一步提高到470S/cm。
实施例7
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(平均片层尺寸约20微米，浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的高定向、高致密的氧化石墨烯薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到氧化石墨烯薄膜表面，在120℃下进行还原。最后，将薄膜沿轴线切割开后浸入水中将其从模具表面剥离下来，并反复用去离子水冲洗，得到高定向、高致密的石墨烯薄膜，其强度进一步提高到600MPa，电导率进一步提高到600S/cm。
实施例8
与实施例1不同之处在于：
本实施例中，采用内径在50mm到1000mm的浇铸模具，浇铸模具为石英玻璃管、陶瓷管、高分子塑料管或金属管，将模具旋转速度设定为500r/min～2500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(浓度为2mg/ml～10mg/ml)连续加入到浇铸模具中，溶液 蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割开后从模具上剥离下来，得到氧化石墨烯薄膜。
实施例9
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿圆周方向切割开后从模具上剥离下来，得到多个高定向、高致密的氧化石墨烯薄膜圆环。
实施例10
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1500r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(浓度为2mg/ml)连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿螺旋线切割，切割时模具的旋转速度为35r/min，切割刀具前进的速度为8mm/min，得到一根完整的高定向、高致密的氧化石墨烯薄膜条带。
实施例11
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1200r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(浓度为5mg/ml)与单壁碳纳米管的十二烷基硫酸钠(SDS)溶液(浓度为1.2wt％)混合，其中氧化石墨烯与单壁碳纳米管的质量比为4:1，然后将混合溶液连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的氧化石墨烯与单壁碳纳米管的复合薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到复合薄膜表面，在120℃下对其中的氧化石墨烯进行还原。最后，将复合薄膜沿轴线切割开后浸入水中将其从模具表面剥离下来，并反复用去离子水冲洗，得到高定向、高致密的石墨烯与单壁碳纳米管的复合薄膜，其密度为1.5g/cm 3，强度为105MPa，电导率为168S/cm，比表面积<1m 2/g，将此杂化薄膜切割成条带作为电极制成的全固态超级电容器的体积容量和质量容量分别为193F/cm 3和128F/g。
实施例12
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1200r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(浓度为5mg/ml)与单壁碳纳米管的SDS溶液(浓度为1.2wt％)混合，其中氧化石墨烯与单壁碳纳米管的质量比为2:1，然后将混合溶液连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的氧化石墨烯与单壁碳纳米管的复合薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到复合薄膜表面，在120℃下对其中的氧化石墨烯进行还原。最后，将复合薄膜沿轴线切割开后浸入水中 将其从模具表面剥离下来，并反复用去离子水冲洗，得到高定向、高致密的石墨烯与单壁碳纳米管的复合薄膜，其密度为1.18g/cm 3，强度为78MPa，电导率为163S/cm，比表面积50m 2/g，将此杂化薄膜切割成条带作为电极制成的全固态超级电容器的体积容量和质量容量分别为224F/cm 3和190F/g。
实施例13
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1200r/min，辅助加热温度设定为80℃。将氧化石墨烯水溶液(浓度为5mg/ml)与单壁碳纳米管的SDS溶液(浓度为1.2wt％)混合，其中氧化石墨烯与单壁碳纳米管的质量比为1:1，然后将混合溶液连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的氧化石墨烯与单壁碳纳米管的复合薄膜。然后，将浓度为10wt％的氢碘酸溶液喷洒到复合薄膜表面，在120℃下对其中的氧化石墨烯进行还原。最后，将复合薄膜沿轴线切割开后浸入水中将其从模具表面剥离下来，并反复用去离子水冲洗，得到高定向、高致密的石墨烯与单壁碳纳米管的复合薄膜，其密度为1.06g/cm 3，强度为47MPa，电导率为158S/cm，比表面积141m 2/g，将此杂化薄膜切割成条带作为电极制成的全固态超级电容器的体积容量和质量容量分别为414F/cm 3和391F/g。
实施例14
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为500r/min，辅助加热温度设定为80℃。本实施例中，溶液为氧化石墨烯水溶液与水溶性聚氨酯的混合溶液；混合溶液中，氧化石墨烯的浓度为10mg/ml，聚氨酯的浓度为10mg/g。将混合溶液一次性加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割后从模具上剥离下来，得到定向氧化石墨烯与聚氨酯的复合薄膜。
实施例15
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为500r/min，辅助加热温度设定为80℃。本实施例中，溶液为氧化石墨烯水溶液与水溶性聚氨酯的混合溶液；混合溶液中，氧化石墨烯的浓度为10mg/ml，聚氨酯的浓度为10mg/g。将混合溶液一次性加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。然后，将复合薄膜沿轴线切割开后从模具表面剥离下来，得到定向氧化石墨烯与聚氨酯的复合薄膜。最后，将该复合薄膜放置在200℃的烘箱中2小时将其还原，其面内和垂直方向的电导率分别为0.3S/m和0.007S/m。
实施例15
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为 1500r/min，辅助加热温度设定为80℃。本实施例中，溶液为氧化石墨烯水溶液与水溶性聚氨酯的混合溶液；混合溶液中，氧化石墨烯的浓度为10mg/ml，聚氨酯的浓度为10mg/g。将混合溶液一次性加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。然后，将复合薄膜沿轴线切割开后从模具表面剥离下来，得到高定向氧化石墨烯与聚氨酯的复合薄膜。最后，将该复合薄膜放置在200℃的烘箱中2小时将其还原，其面内和垂直方向的电导率分别为0.36S/m和0.002S/m。
实施例16
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。本实施例中，使用其它二维纳米材料(如：六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒化钨、黑磷烯、Mxenes、蒙脱土等)水溶液，溶液浓度为1mg/g～10mg/g，将溶液连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割后从模具上剥离下来，得到高定向、高致密的二维材料薄膜。
实施例18
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。本实施例中，使用二维材料(如：石墨烯、氧化石墨烯、氢化石墨烯、氟化石墨烯、六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒化钨、黑磷烯、Mxenes、蒙脱土两种以上两种以上)混合水溶液，溶液浓度为1mg/ml～10mg/ml，将溶液连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿轴线切割后从模具上剥离下来，得到高定向、高致密的混合二维材料的薄膜。
实施例19
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。本实施例中，使用其它二维纳米材料(如：六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒化钨、黑磷烯、Mxenes、蒙脱土等)水溶液，溶液浓度为1mg/ml～10mg/ml，将溶液连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的薄膜。将薄膜沿螺旋线切割，切割时模具的旋转速度为35r/min，切割刀具前进的速度为8mm/min，得到一根完整的高定向、高致密的二维材料的薄膜条带。
实施例20
与实施例1不同之处在于：
本实施例中，采用内径为110mm的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。本实施例中，使用不同的二维材料(如：石墨烯、氧化石墨烯、氢化石墨烯、氟化石墨烯、六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒 化钨、黑磷烯、Mxenes、蒙脱土等)的水溶液，溶液浓度为1mg/ml～10mg/ml，将不同溶液依次连续加入到浇铸模具中，溶液蒸干后制得薄膜厚度为3μm～20μm厚的叠层异质结构薄膜。将薄膜沿轴线切割后从模具上剥离下来，得到高定向、高致密的混合二维材料的薄膜。
实施例21
与实施例1不同之处在于：
本实施例中，采用内径为110mm的表面覆盖有图形化模板的石英玻璃管作为浇铸模具，将模具旋转速度设定为1000r/min，辅助加热温度设定为80℃。本实施例中，使用不同的二维材料(如：石墨烯、氧化石墨烯、氢化石墨烯、氟化石墨烯、六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒化钨、黑磷烯、Mxenes、蒙脱土等)的水溶液，溶液浓度为1mg/ml～10mg/ml，将溶液连续加入到浇铸模具中，溶液蒸干后将图形化的模板去掉，将薄膜沿轴线切割后从模具上剥离下来，得到高定向、高致密的图形化的二维材料的薄膜。
如图2所示，以氧化石墨烯为原料制备的石墨烯薄膜，复制模具内表面特征，为三维立体的管状，呈现出高度定向、高致密的层状结构特征，既可以切割成一张平面膜，也可以沿圆周方向切割成完整连续的带状膜。
如图3所示，采用离心浇铸工艺制备的氧化石墨烯与聚氨酯的复合薄膜，离心浇铸的薄膜均匀贴附在模具的内表面上，可以直接从模具内表面剥离，得到内部的氧化石墨烯高度定向的复合薄膜。
如图4所示，采用离心浇筑工艺可以制备出多种二维材料的薄膜及由不同二维材料薄膜构成的垂直异质结构薄膜，薄膜中二维材料呈现出高度定向、高致密的层状结构特征，并且可以很好实现图形化。
实施例结果表明，本发明方法普适性强，可适于石墨烯等各种二维材料及其复合材料薄膜和叠层异质结构薄膜的制备，极大提高薄膜的电学、热学、力学等性能，可用于高性能导电/导热薄膜、热管理材料、高强度薄膜、电子/光电子器件、致密储能、气体/离子分离膜和质子传输膜等领域。

Claims (10)

  1. 一种高效制备高定向、高致密二维材料薄膜的方法，其特征在于：该方法采用内表面光滑的圆型管作为浇铸模具，模具高速沿圆周方向旋转时将含有二维材料的溶液倒入模具中，利用离心力将溶液均匀涂覆在模具内表面，在离心旋转的过程中，一方面由于液层间的相对运动，形成促使二维材料在溶液中沿圆周方向层层定向规则排列的剪切力，另一方面离心力促使二维材料高致密堆积，进而得到高度定向、高致密的二维材料薄膜。
  2. 按照权利要求1所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，具体步骤如下：
    (1)浇注模具的旋转：将内表面光滑的圆管状模具高速绕轴线旋转，圆管状模具的转速范围为100r/min～50000r/min，形成将溶液均匀粘附在模具内壁上的离心力；
    (2)含二维材料溶液的浇铸：将含有二维材料的溶液加入到上述高速旋转的模具内部，通过离心力使溶液均匀涂覆在模具内壁上，在离心旋转过程中，利用相邻液层的相对运动，促使溶液中的二维材料沿圆周方法层层定向排列，利用离心力使二维材料致密堆积，含有二维材料的溶液浓度范围0.1mg/ml～100mg/ml；
    (3)溶液的蒸干：在离心旋转过程中，采用加热辅助的方式促进浇铸得到的薄膜中溶剂的蒸发；
    (4)薄膜的剥离：采用机械剥离的方法将薄膜从模具内壁剥离下来，得到高度定向、高致密的二维材料的薄膜制品。
  3. 按照权利要求2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，圆管状模具的材质是石英玻璃、陶瓷、高分子、金属之一种或两种及以上的复合，其内径为50mm～1000mm。
  4. 按照权利要求1或2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，采用的二维材料是指厚度在100纳米以下且横向尺寸与厚度比远大于1的材料，包括但不限于石墨烯、氧化石墨烯、氢化石墨烯、氟化石墨烯、六方氮化硼、二硫化钼、二硫化钨、二硒化钼、二硒化钨、黑磷烯、Mxenes之一种或两种及以上复合。
  5. 按照权利要求1或2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，该方法制备二维材料的复合材料薄膜，与二维材料复合的材料为有机高分子材料或无机材料之一种或两种及以上的复合；有机高分子材料包括但不限于聚乙二醇、聚氨酯、聚二甲基硅烷、纳米纤维素、环氧、聚乙烯或天然橡胶，无机材料包括但不限于与前者不同的二维材料、碳纳米管、富勒烯、炭黑、纳米非金属、纳米氧化物或纳米金属。
  6. 按照权利要求1或2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，二维材料或其复合材料的溶液采用连续加料或一次性加料的方式加入到浇铸模具中；在浇铸过程中，含有二维材料的溶液成分和浓度按需改变，进而获得在厚度方向由不同二维材料的薄膜构成的垂直叠层异质结构薄膜或者厚度方向二维材料的含量逐渐变化的梯度复合材料。
  7. 按照权利要求2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，辅助加热温度在25℃～500℃。
  8. 按照权利要求1或2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，得到的二维材料或其复合材料的薄膜直接从模具上剥离下来，对模具没有损伤，重复利用。
  9. 按照权利要求1或2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，得到的二维材料或其复合材料的薄膜呈三维立体的管状，切割成平面膜、环状膜或沿圆周方向切割成完整的带状膜，或通过加捻制备石墨烯纤维。
  10. 按照权利要求1或2所述的高效制备高定向、高致密二维材料薄膜的方法，其特征在于，通过使用模板直接制备图形化的高定向、高致密的二维材料薄膜。
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