WO2016101436A1 - 一种结构可控的三维石墨烯多孔材料制备方法 - Google Patents

一种结构可控的三维石墨烯多孔材料制备方法 Download PDF

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WO2016101436A1
WO2016101436A1 PCT/CN2015/075960 CN2015075960W WO2016101436A1 WO 2016101436 A1 WO2016101436 A1 WO 2016101436A1 CN 2015075960 W CN2015075960 W CN 2015075960W WO 2016101436 A1 WO2016101436 A1 WO 2016101436A1
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dimensional
graphene
porous
metal
template
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闫春泽
史玉升
朱伟
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Huazhong University of Science and Technology
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Priority to US15/614,574 priority patent/US10378113B2/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
    • C23F4/04—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00 by physical dissolution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the invention belongs to the technical field of graphene preparation, and more particularly to a method for preparing a three-dimensional graphene porous material with controllable structure, and is particularly suitable for preparing an effective and precisely controlled three-dimensional graphene porous material by preparing an internal structure and an external shape. product.
  • Graphene is a two-dimensional crystal material composed of a single layer of carbon atoms, which not only has excellent electrical properties (electron mobility at room temperature up to 2 ⁇ 105 cm 2 /V ⁇ s), but also outstanding thermal properties (thermal conductivity) 5000W/m ⁇ K), ultra-high specific surface area (2630m 2 /g) and excellent mechanical properties (Young's modulus up to 1100GPa, breaking strength 125GPa), but also some unique features such as perfect quantum tunneling performance. Because graphene materials have so many unique and excellent properties, they have great application prospects in the fields of electronics, information, energy, materials and biomedicine.
  • CN102674321A discloses a method for depositing a graphene film on a surface of a three-dimensional foamed nickel template by chemical vapor deposition, and obtaining a porous foamy graphene after dissolving the porous metal substrate
  • CN103265022A discloses a spontaneous deposition on a conductive substrate.
  • a method of three-dimensional graphene discloses a method of preparing porous through-three-dimensional graphene using a carbonate or bicarbonate as a template, and the like.
  • the present invention provides a structure controllable method for preparing a three-dimensional graphene porous material, wherein the preparation process thereof and key processes such as the manufacture of a three-dimensional porous metal template and the growth of graphene are provided.
  • the research and design of the other links can effectively overcome the uncontrollable defects of the external shape and internal structure existing in the prior art, and have the characteristics of easy manipulation, short preparation cycle and wide adaptability, so it is especially suitable for large-scale scale. Production of high quality, versatile three-dimensional graphene porous materials.
  • a structure controllable method for preparing a three-dimensional graphene porous material characterized in that the method comprises the following steps:
  • a correspondingly shaped three-dimensional porous metal structure is prepared by an additive manufacturing technique using a metal powder under a protective atmosphere of an inert gas; wherein the metal powder used is selected from the group consisting of nickel and copper. , iron or cobalt, and having an average particle diameter of 5 ⁇ m to 50 ⁇ m, the particle shape of which is spherical or nearly spherical;
  • step (d) growing a graphene film on the metal template obtained in the step (c) by chemical vapor deposition: in the process, first, the metal template is placed in a tube furnace and heated in a mixed atmosphere of inert gas and hydrogen. After heating to 800 ° C to 1000 ° C for 0.5 hour to 1 hour, the carbon source is introduced to continue the reaction, and then cooled to room temperature under a protective atmosphere of an inert gas, thereby producing a raw Three-dimensional graphene grown on the metal template;
  • step (e) arranging an etching solution having a molar concentration of 1 mol/L to 3 mol/L, and immersing the product obtained in the step (d) therein, and refluxing at a temperature of 60 ° C to 90 ° C until the metal template is completely dissolved. And then, after washing and drying, a three-dimensional graphene porous material product is obtained, and the three-dimensional graphene porous material product includes internal structural parameters including pore size, porosity and pore shape, and external shapes thereof are in step (a)
  • the CAD model built is consistent.
  • the CAD model exhibits an ordered periodic porous structure or a randomly arranged interconnected three-dimensional porous structure, and has a unit size of between 0.5 mm and 10 mm.
  • the additive manufacturing technique includes selective laser melting, direct metal laser sintering, or electron beam melting, and the average particle diameter of the metal powder is further controlled to be 10 ⁇ m to 30 ⁇ m.
  • the obtained three-dimensional porous metal structure is heated to 1200 ° C to 1370 ° C under a protective atmosphere of argon gas for about 12 hours, and then cooled to room temperature.
  • the carbon source is selected from the group consisting of styrene, methane or ethane, and the flow rate thereof is controlled to be 0.2 mL/h to 200 mL/h, and the reaction time after the introduction is 0.5 hour. ⁇ 3 hours.
  • the inert gas is argon gas
  • the volume ratio thereof to hydrogen gas is 1:1 to 3:1, and for a mixed atmosphere of argon gas and hydrogen gas
  • the flow rate of argon gas was controlled to be 100 mL/min to 200 mL/min
  • the flow rate of hydrogen gas was controlled to be 180 mL/min to 250 mL/min.
  • the etching solution is selected from one or a mixture of the following: hydrochloric acid, sulfuric acid, nitric acid, and ferric chloride.
  • the preparation method according to the invention has the advantages of wide source of raw materials, environmental protection, low cost and low energy consumption, and has the characteristics of convenient manipulation, short preparation cycle, high yield and high degree of design freedom, and thus is especially suitable for mass production and high quality. Multi-functional three-dimensional graphene porous product with advanced structure.
  • Figure 1 is a process flow diagram of a method of preparing a three-dimensional graphene porous material in accordance with the present invention.
  • CAD software is used to establish a three-dimensional porous unit body having a cell size of 0.5 mm, wherein the unit body array is designed as a periodic porous structure having a porosity of 50% and an ordered arrangement.
  • a pure nickel powder having a particle size distribution in the range of 5 to 20 ⁇ m was screened, and the powder had a nearly spherical surface.
  • a fiber laser was used as the energy source, and the laser power was set to 200 W, the scanning speed was 500 mm/s, the layer thickness was 0.01 mm, and the scanning pitch was 0.08 mm.
  • a three -dimensional porous metal nickel structure having a size of 20 ⁇ 20 ⁇ 10 mm 3 was formed by a selective laser melting (SLM) technique.
  • SLM selective laser melting
  • porous metal nickel structure was placed in a 1370 degree tube furnace, and heat treatment was performed for 10 hours under Ar gas protection.
  • the three-dimensional porous metal nickel structure is subjected to ceramic bead blasting. After the final ultrasonic cleaning, a three-dimensional porous nickel template is obtained;
  • the three-dimensional porous metal nickel template was placed in a tube furnace, and heated to 1000 ° C at 100 ° C / min in a mixed atmosphere of Ar (180 mL / min) and H 2 (200 mL / min); after holding for 30 minutes, the quartz was applied to the quartz. Styrene (0.254 mL/h) was passed through the tube for 1 h; finally, H 2 was turned off, and cooled to room temperature under Ar (50 mL/min) atmosphere to obtain a three-dimensional graphene grown on the surface of the three-dimensional porous metal nickel.
  • porous metal nickel template in which graphene was grown was immersed in a hydrochloric acid solution having a concentration of 3 mol/L, and refluxed at 80 ° C until the three-dimensional porous metal template was completely dissolved, and then washed and dried to obtain a three-dimensional graphene porous structure.
  • the test results show that the three-dimensional graphene completely replicates the shape of the porous metal nickel template.
  • CAD software is used to establish a three-dimensional porous unit body with a cell size of 1 mm, wherein the unit body array is designed as a periodic porous structure with a porosity of 75% and an ordered arrangement.
  • a pure nickel powder having a particle size distribution in the range of 30 to 50 ⁇ m was screened, and the powder had a nearly spherical surface.
  • a fiber laser was used as the energy source, and the laser power was set to 250 W, the scanning speed was 700 mm/s, the layer thickness was 0.02 mm, and the scanning pitch was 0.08 mm.
  • a three -dimensional porous metal nickel structure having a size of 20 ⁇ 20 ⁇ 10 mm 3 was formed by direct metal laser sintering (DMLS) under the protection of argon.
  • DMLS direct metal laser sintering
  • porous metal nickel structure was placed in a 1370 degree tube furnace, and heat treatment was performed for 12 hours under Ar gas protection.
  • the three-dimensional porous metal nickel structure is subjected to ceramic bead blasting. After the final ultrasonic cleaning, a three-dimensional porous nickel template is obtained;
  • the three-dimensional porous metal nickel template was placed in a tube furnace, and heated to 1000 ° C at 100 ° C / min in a mixed atmosphere of Ar (180 mL / min) and H 2 (200 mL / min); after holding for 45 minutes, the quartz was applied to the quartz. Styrene (0.508 mL/h) was introduced into the tube and reacted for 0.5 h. Finally, H 2 was turned off, and cooled to room temperature in an Ar (50 mL/min) atmosphere to obtain a three-dimensional graphene grown on the surface of the three-dimensional porous metal nickel.
  • porous metal nickel template in which graphene was grown was immersed in a hydrochloric acid solution having a concentration of 3 mol/L, and refluxed at 60 ° C until the three-dimensional porous metal template was completely dissolved, and then washed and dried to obtain a three-dimensional graphene porous structure.
  • the test results show that the three-dimensional graphene completely replicates the shape of the porous metal nickel template.
  • CAD software is used to establish a three-dimensional porous unit body with a cell size of 1.5 mm, wherein the unit body array is designed as a periodic porous structure with a porosity of 80% and an ordered arrangement.
  • a pure nickel powder having a particle size distribution in the range of 10 to 30 ⁇ m was screened, and the powder had a nearly spherical surface.
  • a fiber laser was used as the energy source, and the laser power was set to 300 W, the scanning speed was 600 mm/s, the layer thickness was 0.05 mm, and the scanning pitch was 0.1 mm.
  • a three -dimensional porous metal nickel structure having a size of 20 ⁇ 20 ⁇ 10 mm 3 was formed by SLM technique.
  • porous metal nickel structure was placed in a 900 degree tube furnace, and heat treatment was performed for 10 hours under Ar gas protection.
  • the three-dimensional porous metal nickel structure is subjected to ceramic bead blasting. After the final ultrasonic cleaning, a three-dimensional porous nickel template is obtained;
  • the three-dimensional porous metal nickel template was placed in a tube furnace, and heated to 1000 ° C at 100 ° C / min in a mixed atmosphere of Ar (180 mL / min) and H 2 (200 mL / min); after holding for 30 minutes, the quartz was applied to the quartz. Styrene (0.508 mL/h) was introduced into the tube and reacted for 0.5 h. Finally, H 2 was turned off, and cooled to room temperature in an Ar (50 mL/min) atmosphere to obtain a three-dimensional graphene grown on the surface of the three-dimensional porous metal nickel.
  • porous metal nickel template in which graphene was grown was immersed in a hydrochloric acid/sulfuric acid mixed solution having a concentration of 2 mol/L, and refluxed at 90 ° C until the three-dimensional porous metal template was completely dissolved and then washed. After washing and drying, a three-dimensional graphene porous structure is obtained. The test results show that the three-dimensional graphene completely replicates the shape of the porous metal nickel template.
  • CAD software is used to establish a three-dimensional porous structure with a pore size distribution of 1 mm to 3 mm and a porosity of 90%, disorderedly arranged and interconnected.
  • a pure nickel powder having a particle size distribution in the range of 5 to 10 ⁇ m was screened, and the powder had a nearly spherical surface.
  • a fiber laser was used as the energy source, and the vacuum was set to 5.0 ⁇ 10 -2 Pa, the scanning speed was 35 mm/s, the layer thickness was 0.02 mm, and the operating current was 3 mA.
  • a three -dimensional porous metal nickel structure having a size of 20 ⁇ 20 ⁇ 10 mm 3 was formed by electron beam melting (EBM) technique.
  • EBM electron beam melting
  • the porous metal nickel structure was placed in a 1350 degree tube furnace, and after heat treatment for 12 hours under Ar gas protection, it was cooled with the furnace.
  • the three-dimensional porous metal nickel structure is subjected to ceramic bead blasting. After the final ultrasonic cleaning, a three-dimensional porous nickel template is obtained;
  • the three-dimensional porous metal nickel template was placed in a tube furnace, and heated to 1000 ° C at 100 ° C / min in a mixed atmosphere of Ar (200 mL / min) and H 2 (200 mL / min); after 60 minutes of incubation, the quartz was applied to the quartz. Styrene (0.254 mL/h) was introduced into the tube and reacted for 0.5 h. Finally, H 2 was turned off, and cooled to room temperature in an Ar (50 mL/min) atmosphere to obtain a three-dimensional graphene grown on the surface of the three-dimensional porous metal nickel.
  • porous metal nickel template with graphene was immersed in a ferric chloride solution with a concentration of 1 mol/L, and refluxed at 80 ° C until the three-dimensional porous metal template was completely dissolved, and then washed and dried to obtain a three-dimensional graphene porous. structure.
  • the test results show that the three-dimensional graphene completely replicates the shape of the porous metal nickel template.
  • CAD software is used to establish a three-dimensional porous structure with a pore size distribution of 0.5 mm to 2 mm and a porosity of 70%, disorderly arranged and interconnected.
  • pure copper powder having a particle size distribution in the range of 30 to 50 ⁇ m was screened, and the powder had a nearly spherical surface.
  • a fiber laser was used as the energy source, and a fiber laser was used as the energy source.
  • the laser power was set to 300 W, the scanning speed was 600 mm/s, the layer thickness was 0.05 mm, and the scanning pitch was 0.1 mm.
  • a three -dimensional porous metal nickel structure having a size of 20 ⁇ 20 ⁇ 10 mm 3 was formed by SLM technique.
  • the porous metal nickel structure was placed in a 1200-degree tube furnace, and under heat treatment for Ar gas, it was subjected to heat treatment for 12 hours and then cooled with the furnace.
  • the three-dimensional porous metal nickel structure is subjected to ceramic bead blasting. After the final ultrasonic cleaning, a three-dimensional porous nickel template is obtained;
  • the three-dimensional porous metal nickel template was placed in a tube furnace, and heated to 1000 ° C at 100 ° C / min in a mixed atmosphere of Ar (150 mL / min) and H 2 (250 mL / min); after 60 minutes of incubation, to quartz Methane (100 mL/h) was introduced into the tube and reacted for 0.5 h. Finally, H 2 was turned off, and cooled to room temperature in an Ar (50 mL/min) atmosphere to obtain a three-dimensional graphene grown on the surface of the three-dimensional porous metal nickel.
  • porous metal nickel template with graphene was immersed in a ferric chloride solution with a concentration of 1.5 mol/L, and refluxed at 80 ° C until the three-dimensional porous metal template was completely dissolved, and then washed and dried to obtain three-dimensional graphene. porous structure.
  • the test results show that the three-dimensional graphene completely replicates the shape of the porous metal nickel template.
  • CAD software is used to establish a three-dimensional porous unit body with a cell size of 2 mm, wherein the unit body array is designed as a periodic porous structure with a porosity of 50% and an ordered arrangement.
  • a pure nickel powder having a particle size distribution in the range of 20-30 ⁇ m was screened, and the powder had a nearly spherical surface.
  • a fiber laser was used as the energy source, and the laser power was set to 3000 W, the scanning speed was 600 mm/s, the layer thickness was 0.03 mm, and the scanning pitch was 0.08 mm.
  • a three -dimensional porous metal nickel structure having a size of 20 ⁇ 20 ⁇ 10 mm 3 was formed by direct metal laser sintering (DMLS) under the protection of argon.
  • DMLS direct metal laser sintering
  • porous metal nickel structure was placed in a 900 degree tube furnace, and heat treatment was performed for 24 hours under Ar gas protection.
  • the three-dimensional porous metal nickel structure is subjected to ceramic bead blasting. After the final ultrasonic cleaning, a three-dimensional porous nickel template is obtained;
  • the three-dimensional porous metal nickel template was placed in a tube furnace, and heated to 1000 ° C at 100 ° C / min in a mixed atmosphere of Ar (120 mL / min) and H 2 (250 mL / min); after holding for 45 minutes, the quartz was applied to the quartz. Styrene (0.508 mL/h) was introduced into the tube and reacted for 0.5 h. Finally, H 2 was turned off, and cooled to room temperature in an Ar (50 mL/min) atmosphere to obtain a three-dimensional graphene grown on the surface of the three-dimensional porous metal nickel.
  • porous metal nickel template in which graphene was grown was immersed in a hydrochloric acid solution having a concentration of 3 mol/L, and refluxed at 60 ° C until the three-dimensional porous metal template was completely dissolved, and then washed and dried to obtain a three-dimensional graphene porous structure.
  • the test results show that the three-dimensional graphene completely replicates the shape of the porous metal nickel template.

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PCT/CN2015/075960 2014-12-25 2015-04-07 一种结构可控的三维石墨烯多孔材料制备方法 Ceased WO2016101436A1 (zh)

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JP2017530280A JP6518765B2 (ja) 2014-12-25 2015-04-07 構成の制御可能な三次元グラフェン多孔質材料の調製方法
US15/614,574 US10378113B2 (en) 2014-12-25 2017-06-05 Method for preparing three-dimensional porous graphene material

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