WO2016000614A1 - 一种多孔石墨烯的制备方法 - Google Patents

一种多孔石墨烯的制备方法 Download PDF

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WO2016000614A1
WO2016000614A1 PCT/CN2015/083029 CN2015083029W WO2016000614A1 WO 2016000614 A1 WO2016000614 A1 WO 2016000614A1 CN 2015083029 W CN2015083029 W CN 2015083029W WO 2016000614 A1 WO2016000614 A1 WO 2016000614A1
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Prior art keywords
temperature
intermediate product
acid
treatment
present
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PCT/CN2015/083029
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English (en)
French (fr)
Inventor
祝建勋
刘昭荐
周国栋
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Jinan Shengquan Group Co Ltd
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Jinan Shengquan Group Co Ltd
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Priority to RU2017101597A priority Critical patent/RU2640765C1/ru
Priority to CA2952281A priority patent/CA2952281C/en
Priority to EP15815006.0A priority patent/EP3165507B1/en
Priority to JP2016576090A priority patent/JP6162352B1/ja
Priority to DK15815006.0T priority patent/DK3165507T3/da
Priority to ES15815006T priority patent/ES2699189T3/es
Priority to BR112016030951A priority patent/BR112016030951A2/pt
Priority to KR1020177001403A priority patent/KR101820315B1/ko
Priority to AU2015283392A priority patent/AU2015283392B2/en
Priority to MX2016017361A priority patent/MX353442B/es
Priority to US15/322,043 priority patent/US9790094B2/en
Publication of WO2016000614A1 publication Critical patent/WO2016000614A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • 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
    • 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
    • C01B2204/22—Electronic properties
    • 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

Definitions

  • the present invention relates to the field of graphene technology, and in particular to a method for preparing porous graphene.
  • Graphene is a material of a single-layer sheet structure composed of carbon atoms. Graphene is almost completely transparent, absorbing only 2.3% of light; thermal conductivity is as high as 5300 W/m ⁇ K, higher than that of carbon nanotubes and diamond; graphene has electron mobility at room temperature exceeding 15000 cm 2 /V ⁇ s, exceeding nanometers. Carbon tube or silicon crystal; graphene has a resistivity of only 10 -8 ⁇ m, which is lower than copper or silver, and is the material with the lowest resistivity in the world. Because graphene has the advantages of good transparency, low resistivity, and fast electron migration, it can be used to manufacture transparent touch screens, light panels, and solar cells.
  • the preparation methods of graphene mainly include mechanical stripping method, chemical vapor deposition method, pyrolysis epitaxial growth method, etc.
  • the preparation of graphene by chemical vapor deposition method is simple and easy, and a large-area high-quality graphene can be obtained.
  • Chinese Patent Application No. 200810113596.0 discloses a method for preparing graphene by chemical vapor deposition, in which the substrate with a catalyst is placed in an oxygen-free reactor to bring the temperature of the substrate to 500 ° C.
  • a carbonaceous material is then introduced into the reactor to obtain graphene;
  • the catalyst is a metal or a metal compound; and the carbonaceous material is one of methane, acetylene, ethanol, benzene, toluene and cyclohexane.
  • the preparation method of the graphene provided by the prior art is convenient, simple and easy to operate, and can be used for large-scale production; and the graphene prepared by the method has better quality.
  • the graphene prepared by the prior art has poor conductivity.
  • the object of the present invention is to provide a method for preparing porous graphene, and the porous graphene prepared by the method provided by the invention has better conductivity.
  • the invention provides a preparation method of porous graphene, comprising the following steps:
  • the catalyst comprising one of a manganese chloride, an iron compound, a cobalt compound, and a nickel compound or
  • the first intermediate product is heated from the first temperature to the second temperature and then incubated to obtain a second intermediate product, the first temperature being 20 ° C to 40 ° C,
  • the second temperature is 300 ° C ⁇ 400 ° C;
  • the second intermediate product is heated from the second temperature to the third temperature and then incubated to obtain a third intermediate product;
  • the third temperature is 800 ° C ⁇ 900 ° C;
  • the third intermediate product is heated from the third temperature to the fourth temperature and then incubated to obtain a fourth intermediate product, the fourth temperature is 1100 ° C ⁇ 1300 ° C;
  • the fourth intermediate product is cooled from the fourth temperature to the fifth temperature and then incubated to obtain porous graphene, and the fifth temperature is 900 ° C to 1000 ° C.
  • the biomass carbon source in the step 1) is one or two of cellulose and lignin.
  • the biomass carbon source in the step 1) is cellulose.
  • the cellulose is porous cellulose.
  • the method for preparing the porous cellulose comprises the following steps:
  • biomass resources including one or more of plant and agricultural and forestry waste;
  • the biomass resource in the step A) is agricultural and forestry waste.
  • the agricultural and forestry waste comprises one or more of corn stalk, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalk and reed.
  • the agricultural and forestry waste is a corn cob.
  • the acid in the step A) comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid.
  • the amount of the acid in the step A) is from 3 wt% to 20 wt% of the biomass resource.
  • the temperature of the hydrolysis in the step A) is from 90 ° C to 180 ° C;
  • the hydrolysis time in the step A) is from 10 min to 10 h.
  • the method of salt treatment in the step B) is an acid sulfite treatment or an alkaline sulfite treatment.
  • the pH in the acidic sulfite treatment process is 1 to 7;
  • the amount of the acid in the acidic sulfite treatment process is 4% by weight to 30% by weight of the lignocellulose;
  • the weight percent concentration of the acid in the acidic sulfite treatment results in a liquid to solid ratio of (2-20):1.
  • the temperature of the acidic sulfite treatment is 70 ° C ⁇ 180 ° C;
  • the acid sulfite treatment time is from 1 hour to 6 hours.
  • the pH during the alkaline sulfite treatment is 7 to 14;
  • the amount of alkali used in the alkaline sulfite treatment is 4% by weight to 30% by weight of the lignocellulose;
  • the weight percent concentration of the base in the alkaline sulfite treatment is such that the liquid to solid ratio is (2-20):1.
  • the alkaline sulfite treatment temperature is 70 ° C ⁇ 180 ° C;
  • the alkaline sulfite treatment time is from 1 hour to 6 hours.
  • the method further comprises:
  • the porous cellulose is subjected to a bleaching treatment.
  • the mass ratio of the catalyst to the biomass carbon source in the step 1) is (0.01-2):1.
  • the iron compound in the step 1) comprises one or more of a chloride salt of iron, a cyanide of iron and a ferrite salt;
  • the cobalt compound in the step 1) includes one or more of a cobalt chloride and a cobalt salt;
  • the nickel compound in the step 1) includes one or more of a nickel chloride salt and a nickel acid salt.
  • the catalyst in the step 1) comprises ferric chloride, ferrous chloride, iron nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, iron trihydrate.
  • the protective gas in step 2), the protective gas in step 3), the protective gas in step 4) and the protective gas in step 5) are independently selected from nitrogen and inert gases. One or several.
  • the temperature increase rate of the first intermediate product in the step 2) from the first temperature to the second temperature is 5 ° C / min to 20 ° C / min.
  • the temperature increase rate of the second intermediate product in the step 3) from the second temperature to the third temperature is from 30 ° C / min to 40 ° C / min.
  • the temperature rise of the third intermediate product in the step 4) from the third temperature to the fourth temperature The rate is from 50 ° C / min to 60 ° C / min.
  • the temperature reduction rate of the fourth intermediate product in the step 5) from the fourth temperature to the fifth temperature is from 30 ° C / min to 50 ° C / min.
  • the invention provides a preparation method of porous graphene, comprising the following steps: 1) catalytically treating a biomass carbon source under the action of a catalyst to obtain a first intermediate product, the catalyst comprising a manganese chloride salt And one or more of an iron compound, a cobalt compound and a nickel compound; 2) maintaining the first intermediate product from a first temperature to a second temperature and then holding the heat under a protective gas condition; Obtaining a second intermediate product, the first temperature is 20 ° C ⁇ 40 ° C, the second temperature is 300 ° C ⁇ 400 ° C; 3) under the condition of protective gas, the second intermediate product from the first After the temperature is raised to the third temperature, the temperature is maintained to obtain a third intermediate product; the third temperature is 800 ° C to 900 ° C; 4) the third intermediate product is removed from the third temperature under the condition of a protective gas After the temperature is raised to the fourth temperature, the temperature is maintained to obtain a fourth intermediate product, and the fourth temperature is 1100 ° C to 1300
  • the fifth temperature is 900 ° C to 1000 ° C.
  • the porous graphene prepared by the method provided by the invention has better electrical conductivity.
  • the experimental results show that the porous graphene prepared by the method provided by the invention has a conductivity of up to 40,000 S/m.
  • the porous graphene prepared by the method provided by the invention has a thin layer and a high degree of Sp2 hybridization; and the preparation method of the porous graphene provided by the invention is simple in process, low in energy consumption and low in cost.
  • Example 6 is a Raman spectrum of graphene obtained in Example 6 of the present invention.
  • Example 2 is a TEM image of graphene obtained in Example 6 of the present invention.
  • Example 3 is a transmission electron micrograph of graphene obtained in Example 6 of the present invention.
  • Example 4 is a TEM image of graphene obtained in Example 6 of the present invention.
  • Fig. 5 is a TEM image of graphene obtained in Example 6 of the present invention.
  • the invention provides a preparation method of porous graphene, comprising the following steps:
  • the catalyst comprising one of a manganese chloride, an iron compound, a cobalt compound, and a nickel compound or
  • the first intermediate product is heated from the first temperature to the second temperature and then incubated to obtain a second intermediate product, the first temperature being 20 ° C to 40 ° C,
  • the second temperature is 300 ° C ⁇ 400 ° C;
  • the second intermediate product is heated from the second temperature to the third temperature and then incubated to obtain a third intermediate product;
  • the third temperature is 800 ° C ⁇ 900 ° C;
  • the third intermediate product is heated from the third temperature to the fourth temperature and then incubated to obtain a fourth intermediate product, the fourth temperature is 1100 ° C ⁇ 1300 ° C;
  • the fourth intermediate product is cooled from the fourth temperature to the fifth temperature and then incubated to obtain porous graphene, and the fifth temperature is 900 ° C to 1000 ° C.
  • the porous graphene prepared by the method provided by the invention has better electrical conductivity.
  • the porous graphene prepared by the method provided by the invention has a thin layer and a high degree of Sp2 hybridization; and the preparation method of the porous graphene provided by the invention is simple in process, low in energy consumption and low in cost.
  • the invention catalyzes the biomass carbon source under the action of a catalyst to obtain a first intermediate product, the catalyst comprising one or more of a manganese chloride, an iron compound, a cobalt compound and a nickel compound.
  • the catalyst and biomass carbon source are combined to provide a first intermediate product.
  • the method of the present invention is not particularly limited, and the catalyst and the biomass carbon source may be uniformly stirred by a mixing technique well known to those skilled in the art.
  • the temperature of the mixing is preferably from 20 ° C to 180 ° C, more preferably from 50 ° C to 150 ° C, and most preferably from 80 ° C to 120 ° C.
  • the mixing time is preferably from 2 hours to 10 hours, more preferably from 5 hours to 7 hours.
  • the catalyst comprises one or more of manganese chloride, iron compound, cobalt compound and nickel compound, preferably manganese chloride, iron compound, cobalt compound And one of nickel compounds.
  • the manganese chloride is preferably manganese chloride.
  • the iron compound preferably includes one or more of iron chloride, iron cyanide and ferrite, more preferably iron chloride, ferrous chloride, iron nitrate, One or more of ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide and potassium ferric acid.
  • the cobalt-based compound includes one or more of a cobalt chloride and a cobalt-containing acid salt, and more preferably one or more of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.
  • the nickel-based compound preferably includes one or more of a nickel chloride salt and a nickel-containing acid salt, more preferably one of nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate.
  • the catalyst is preferably ferric chloride, ferrous chloride, iron nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid sulphate.
  • cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate is not particularly limited in the source of the catalyst, and a catalyst of the above kind well known to those skilled in the art can be used, which is commercially available.
  • the biomass carbon source is preferably one or both of cellulose and lignin; more preferably cellulose; most preferably porous cellulose.
  • the method for preparing the porous cellulose preferably comprises the following steps:
  • biomass resources including one or more of plant and agricultural and forestry waste;
  • the present invention preferably hydrolyzes biomass resources in an acid to obtain lignocellulose, which includes one or more of plant and agricultural and forestry waste.
  • the hydrolysis temperature is preferably from 90 ° C to 180 ° C, more preferably from 120 ° C to 150 ° C.
  • the hydrolysis time is preferably from 10 min to 10 h, more preferably from 1 h to 8 h, and most preferably from 3 h to 6 h.
  • the hydrolyzed acid is preferably one or more of sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid, more preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid or acetic acid, most preferably Sulfuric acid, nitric acid or hydrochloric acid.
  • the amount of the acid in the hydrolysis is preferably from 3% by weight to 20% by weight of the biomass resource, more preferably from 5% by weight to 15% by weight, most preferably from 8% by weight to 12% by weight.
  • the biomass resource is preferably agricultural and forestry waste, more preferably corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks and reeds.
  • corn cob preferably corn cob
  • sorghum preferably corn cob
  • beet pulp bagasse
  • furfural residue preferably furfural residue
  • xylose residue preferably wood chips
  • cotton stalks and reeds preferably cotton stalks.
  • the present invention preferably treats the lignocellulose to obtain porous cellulose, and the treatment includes acid treatment, salt treatment or organic solvent treatment; more preferably, the lignocellulose is subjected to salt treatment in the present invention.
  • the salt treatment method is preferably an acidic sulfite treatment or an alkaline sulfite treatment.
  • the pH during the treatment of the acidic sulfurous acid method is preferably from 1 to 7, more preferably from 2 to 5, most preferably from 3 to 4.
  • the temperature of the acidic sulfite treatment is preferably from 70 ° C to 180 ° C, more preferably from 90 ° C to 150 ° C, and most preferably from 100 ° C to 120 ° C.
  • the acid sulfite treatment time is preferably from 1 hour to 6 hours, more preferably from 2 hours to 5 hours, and most preferably from 3 hours to 4 hours.
  • the acid in the acidic sulfite treatment is preferably sulfuric acid.
  • the amount of the acid used in the acidic sulfite treatment is preferably from 4% by weight to 30% by weight, more preferably from 8% by weight to 25% by weight, most preferably from 10% by weight to 20% by weight of the lignocellulose.
  • the concentration by weight of the acid in the acidic sulfite treatment preferably has a liquid-solid ratio of (2 to 20):1, more preferably (4 to 16):1, and most preferably (8 to). 12): 1.
  • the sulfite in the acidic sulfite treatment is preferably calcium sulfite, magnesium sulfite, sodium sulfite or ammonium sulfite, more preferably magnesium sulfite or sodium sulfite.
  • the amount of sulfite used in the acidic sulfite treatment process of the present invention is not particularly limited, and the amount of sulfite in the sulfite pulping process well known to those skilled in the art may be used.
  • the pH during the alkaline sulfite treatment is preferably from 7 to 14, more preferably from 8 to 13, most preferably from 9 to 12.
  • the temperature of the alkaline sulfite treatment is preferably from 70 ° C to 180 ° C, more preferably from 90 ° C to 150 ° C, and most preferably from 100 ° C to 120 ° C.
  • the time of the alkaline sulfite treatment is preferably from 1 hour to 6 hours, more preferably from 2 hours to 5 hours, and most preferably from 3 hours to 4 hours.
  • the base in the alkaline sulfite treatment is preferably calcium hydroxide, sodium hydroxide, ammonium hydroxide or magnesium hydroxide, more preferably sodium hydroxide or magnesium hydroxide.
  • the amount of the base used in the alkaline sulfite treatment is preferably from 4% by weight to 30% by weight, more preferably from 8% by weight to 25% by weight, most preferably from 10% by weight to 20% by weight of the lignocellulose. .
  • the weight percentage concentration of the base in the alkaline sulfite treatment preferably has a liquid-solid ratio of (2 to 20):1, more preferably (4 to 16):1, and most preferably (8). ⁇ 12):1.
  • the sulfite in the alkaline sulfite treatment is preferably calcium sulfite, Magnesium sulfate, sodium sulfite or ammonium sulfite, more preferably magnesium sulfite or sodium sulfite.
  • the amount of sulfite used in the alkaline sulfite treatment process of the present invention is not particularly limited, and the amount of sulfite in the sulfite pulping process well known to those skilled in the art may be used.
  • the present invention preferably further comprises:
  • the porous cellulose is subjected to a bleaching treatment.
  • the method of the bleaching treatment of the present invention is not particularly limited, and a bleaching technique known to those skilled in the art may be employed.
  • the method of bleaching is preferably total chlorine-free bleaching, more preferably hydrogen peroxide bleaching.
  • the concentration of the hydrogen peroxide in the present invention is not particularly limited, and a hydrogen peroxide of a usual concentration may be used.
  • the mass of the hydrogen peroxide is preferably from 1% to 10%, more preferably from 2% to 8% by mass of the porous cellulose.
  • the bleaching temperature of the hydrogen peroxide bleaching is preferably from 60 ° C to 130 ° C, more preferably from 80 ° C to 100 ° C; and the bleaching time of the hydrogen peroxide bleaching is preferably from 1 h to 10 h, more preferably from 2 h to 8 h.
  • the mass ratio of the catalyst to the biomass carbon source is preferably (0.01 to 2):1, more preferably (0.1 to 1):1, and most preferably (0.3 to 0.8):1.
  • the temperature of the catalytic treatment is preferably from 20 ° C to 180 ° C, more preferably from 50 ° C to 150 ° C, and most preferably from 80 ° C to 120 ° C.
  • the catalytic treatment time is preferably from 2 hours to 10 hours, more preferably from 5 hours to 7 hours.
  • the obtained catalytically treated biomass carbon source is preferably dried to obtain a first intermediate product.
  • the temperature at which the catalytically treated biomass carbon source is dried is preferably from 70 ° C to 120 ° C, more preferably from 90 ° C to 100 ° C.
  • the first intermediate product preferably has a water content of ⁇ 10% by weight, more preferably ⁇ 5% by weight.
  • the present invention heats the first intermediate product from the first temperature to the second temperature under a protective gas condition and then incubated to obtain a second intermediate product;
  • the first temperature is 20 ° C ⁇ 40° C.
  • the second temperature is 300° C. to 400° C.
  • the temperature increase rate of the first intermediate product from the first temperature to the second temperature is preferably from 5 ° C / min to 20 ° C / min, more preferably from 10 ° C / min to 15 ° C / min.
  • the first temperature is preferably from 25 ° C to 35 ° C, more preferably from 28 ° C to 32 ° C.
  • the second temperature is preferably 320 ° C to 380 ° C, and more preferably 340 ° C to 360 ° C.
  • the holding time after the first intermediate product is heated from the first temperature to the second temperature is preferably 4 hours to 8 hours, more preferably 5 hours to 6 hours.
  • the protective gas is preferably one or more of nitrogen and an inert gas, more preferably nitrogen.
  • the amount of the protective gas to be introduced is preferably 200 mL/min to 800 mL/min, more preferably 400 mL/min to 600 mL/min.
  • the present invention heats the second intermediate product from the second temperature to the third temperature under a protective gas condition and then incubated to obtain a third intermediate product;
  • the third temperature is 800 ° C. ⁇ 900 °C.
  • the temperature increase rate of the second intermediate product from the second temperature to the third temperature is preferably from 20 ° C / min to 50 ° C / min, more preferably from 30 ° C / min to 40 ° C / min.
  • the third temperature is preferably 820 ° C to 880 ° C, and more preferably 840 ° C to 860 ° C.
  • the holding time after the second intermediate product is heated from the second temperature to the third temperature is preferably from 3.5 hours to 7 hours, more preferably from 5 hours to 6 hours.
  • the type and the amount of the protective gas are the same as the type and the amount of the protective gas described in the above technical solution, and will not be described herein.
  • the protective gas may be the same as or different from the protective gas described in the above aspect.
  • the third intermediate product is heated from the third temperature to the fourth temperature and then incubated under the condition of a protective gas to obtain a fourth intermediate product;
  • the fourth temperature is 1100 ° C. ⁇ 1300 °C.
  • the temperature increase rate of the third intermediate product from the third temperature to the fourth temperature is preferably from 50 ° C / min to 60 ° C / min, more preferably from 54 ° C / min to 58 ° C / min.
  • the fourth temperature is preferably from 1150 ° C to 1250 ° C, more preferably 1200 ° C.
  • the holding time after the third intermediate product is heated from the third temperature to the fourth temperature is preferably 6 hours to 8 hours, more preferably 7 hours.
  • the type and the amount of the protective gas are the same as the type and the amount of the protective gas described in the above technical solution, and will not be described herein.
  • the protective gas may be the same as or different from the protective gas described in the above aspect.
  • the present invention cools the fourth intermediate product from the fourth temperature to the fifth temperature under a protective gas condition, and then heats to obtain porous graphene; the fifth temperature is 900 ° C. 1000 ° C.
  • the temperature drop rate of the fourth intermediate product from the fourth temperature to the fifth temperature is preferably from 30 ° C / min to 50 ° C / min, more preferably from 35 ° C / min to 45 ° C / min.
  • the fifth temperature is preferably 920 ° C to 980 ° C, and more preferably 940 ° C to 960 ° C.
  • the holding time after the fourth intermediate product is cooled from the fourth temperature to the fifth temperature is preferably from 2 hours to 4 hours, more preferably 3 hours.
  • the type and the amount of the protective gas are the same as the type and the amount of the protective gas described in the above technical solution, and will not be described herein.
  • the protective gas It may be the same as or different from the protective gas described in the above technical solution.
  • the present invention preferably cools the product obtained by the fourth heat treatment to obtain porous graphene.
  • the cooling temperature is preferably ⁇ 100 ° C, more preferably 20 ° C to 60 ° C, and most preferably 30 ° C to 40 ° C.
  • the present invention preferably performs the cooling under the conditions of a protective gas.
  • the type and the amount of the protective gas are the same as the type and the amount of the protective gas described in the above technical solution, and will not be described herein.
  • the protective gas may be the same as or different from the protective gas described in the above aspect.
  • the method of cooling is preferably natural cooling.
  • the present invention preferably washes the obtained cooled product to obtain porous graphene.
  • the method of washing is preferably:
  • the second washed product is subjected to a third washing in water to obtain porous graphene.
  • the cooled product is subjected to a first wash in an alkaline solution to provide a first wash product.
  • the mass concentration of the alkaline aqueous solution is preferably from 3% to 55%, more preferably from 10% to 40%, most preferably from 20% to 30%.
  • the temperature of the first washing is preferably from 60 ° C to 120 ° C, more preferably from 80 ° C to 100 ° C.
  • the time of the first washing is preferably from 4 hours to 24 hours, more preferably from 8 hours to 16 hours, and most preferably from 10 hours to 14 hours.
  • the alkaline aqueous solution is preferably an aqueous sodium hydroxide solution or aqueous ammonia.
  • the present invention preferably performs a second washing of the first washed product in an acidic aqueous solution to obtain a second washed product.
  • the mass concentration of the acidic aqueous solution is preferably from 4% to 10%, more preferably from 6% to 8%.
  • the temperature of the second washing is preferably from 70 ° C to 150 ° C, more preferably from 90 ° C to 120 ° C.
  • the second washing time is preferably from 4 hours to 24 hours, more preferably from 8 hours to 16 hours, and most preferably from 10 hours to 14 hours.
  • the acidic aqueous solution is preferably an aqueous hydrochloric acid solution.
  • the present invention preferably performs a third washing of the second washed product in water to obtain porous graphene.
  • the water is preferably distilled water.
  • the method of the third washing is not particularly limited in the present invention, and the third porous washing may be followed by obtaining a porous porous graphene.
  • the present invention preferably dries the obtained washed product to obtain porous graphene.
  • the method for drying the washing product of the present invention is not particularly limited, and the prior art is employed. A well-known drying technology solution is available.
  • the graphene prepared by the present invention was subjected to transmission electron microscopy.
  • the test result showed that the sheet of graphene prepared by the method provided by the invention was thin, and below 10 layers, it was porous graphene.
  • the porous graphene prepared by the present invention was subjected to Raman spectroscopy test, and as a result, the porous graphene Sp2 prepared by the method provided by the present invention has a high degree of hybridization.
  • the conductive properties of the porous graphene prepared by the present invention were tested by using a conductivity tester. The test results showed that the porous graphene prepared by the method provided by the present invention has a conductivity of up to 40,000 S/m.
  • the invention provides a preparation method of porous graphene, comprising the following steps: 1) catalytically treating a biomass carbon source under the action of a catalyst to obtain a first intermediate product, the catalyst comprising a manganese chloride salt And one or more of an iron compound, a cobalt compound and a nickel compound; 2) maintaining the first intermediate product from a first temperature to a second temperature and then holding the heat under a protective gas condition; Obtaining a second intermediate product, the first temperature is 20 ° C ⁇ 40 ° C, the second temperature is 300 ° C ⁇ 400 ° C; 3) under the condition of protective gas, the second intermediate product from the first After the temperature is raised to the third temperature, the temperature is maintained to obtain a third intermediate product; the third temperature is 800 ° C to 900 ° C; 4) the third intermediate product is removed from the third temperature under the condition of a protective gas After the temperature is raised to the fourth temperature, the temperature is maintained to obtain a fourth intermediate product, and the fourth temperature is 1100 ° C to 1300
  • the fifth temperature is 900 ° C to 1000 ° C.
  • the porous graphene prepared by the method provided by the invention has better electrical conductivity.
  • the porous graphene prepared by the method provided by the invention has a thin layer and a high degree of Sp2 hybridization; and the preparation method of the porous graphene provided by the invention is simple in process, low in energy consumption and low in cost.
  • the corn cob is hydrolyzed in sulfuric acid at 90 ° C for 10 min to obtain lignocellulose, the mass of the sulfuric acid being 3% of the mass of the corn cob;
  • the lignocellulose was subjected to an acidic sulfite treatment at 70 ° C for 1 hour to obtain a porous cellulose.
  • the pH of the acidic sulfite treatment was 1, the acid was sulfuric acid, and the sulfite was sulfite.
  • the obtained porous cellulose was subjected to hydrogen peroxide bleaching, the mass of the hydrogen peroxide was 5% by mass of the porous cellulose, the bleaching temperature of the hydrogen peroxide bleaching was 100 ° C, and the bleaching time was 5 h.
  • the corn cob is hydrolyzed in nitric acid for 10 h at 180 ° C to obtain lignocellulose, the mass of the nitric acid being 20% of the mass of the corn cob;
  • the lignocellulose was subjected to an acidic sulfite treatment at 180 ° C for 6 hours to obtain a porous cellulose.
  • the pH of the acidic sulfite treatment was 7, the acid was sulfuric acid, and the sulfite was sulfite.
  • the mass of the sulfuric acid is 30% by mass of the lignocellulose and the liquid to solid ratio is 20 : 1.
  • the porous cellulose was subjected to hydrogen peroxide bleaching, the mass of the hydrogen peroxide being 5% by mass of the porous cellulose, the bleaching temperature of the hydrogen peroxide bleaching being 100 ° C, and the bleaching time being 5 h.
  • the corn cob was hydrolyzed in hydrochloric acid for 5 h at 130 ° C to obtain lignocellulose, the mass of the hydrochloric acid being 10% of the mass of the corn cob;
  • the lignocellulose was subjected to an acidic sulfite treatment at 120 ° C for 4 hours to obtain a porous cellulose.
  • the pH of the acidic sulfite treatment was 3, and the acid was sulfuric acid, sulfite. It is ammonium sulfite having a mass of 18% by mass of the lignocellulose and a liquid to solid ratio of 10 : 1.
  • the porous cellulose was subjected to hydrogen peroxide bleaching, the mass of the hydrogen peroxide being 5% by mass of the porous cellulose, the bleaching temperature of the hydrogen peroxide bleaching being 100 ° C, and the bleaching time being 5 h.
  • the corn cob was hydrolyzed in hydrochloric acid at 150 ° C for 1 h to obtain lignocellulose, the mass of the hydrochloric acid being 15% of the mass of the corn cob;
  • the lignocellulose was subjected to an alkaline sulfite treatment at 70 ° C for 1 hour to obtain a porous cellulose.
  • the pH of the alkaline sulfite treatment was 7, and the alkali was sodium hydroxide.
  • the sulfite is magnesium sulfite having a mass of 4% by mass of the lignocellulose and a liquid to solid ratio of 2 : 1.
  • the porous cellulose was subjected to hydrogen peroxide bleaching, the mass of the hydrogen peroxide being 5% by mass of the porous cellulose, the bleaching temperature of the hydrogen peroxide bleaching being 100 ° C, and the bleaching time being 5 h.
  • the lignocellulose was subjected to an alkaline sulfite treatment at 180 ° C for 6 hours to obtain a porous cellulose.
  • the pH of the alkaline sulfite treatment was 14 and the alkali was magnesium hydroxide.
  • the sulfite is sodium sulfite
  • the mass of the magnesium hydroxide is 30% of the mass of the lignocellulose
  • the liquid The solid ratio is 20:1.
  • the porous cellulose and manganese chloride obtained in Example 1 were subjected to catalytic treatment by stirring at 20 ° C for 2 hours, and the mass ratio of the manganese chloride to the porous cellulose was 0.01:1; the obtained catalytically treated product Drying at 70 ° C gave a first intermediate product having a water content of less than 10% by weight.
  • the first intermediate product was placed in a carbonization furnace, and nitrogen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 200 mL/min, and the first intermediate product was removed at a rate of 5 ° C/min.
  • the cooled fourth intermediate product was washed in an aqueous solution of sodium hydroxide having a mass concentration of 3% at 60 ° C for 4 hours to obtain a first washed product; at 70 ° C, the first washed product was in mass.
  • the mixture was washed in a 4% aqueous hydrochloric acid solution for 4 hours to obtain a second washed product; the second washed product was washed with distilled water until neutral and dried to obtain graphene.
  • FIG. 1 is a Raman spectrum of graphene obtained in Example 6 of the present invention, and FIG. 1 shows that the present invention is implemented.
  • the graphene Sp2 prepared by the method provided in Example 6 was highly hybridized.
  • the graphene prepared in the first embodiment of the present invention was subjected to transmission electron microscopy.
  • the test results are shown in FIGS. 2 to 5.
  • FIG. 2 to FIG. 5 are transmission electron micrographs of graphene obtained in Example 6 of the present invention, and FIG. It can be seen from Fig.
  • the sheet of graphene prepared by the method provided in the sixth embodiment of the invention is relatively thin, and below 10 layers, it is porous graphene.
  • the conductivity of the porous graphene prepared in Example 6 of the present invention was tested by using a conductivity tester. The test results showed that the conductive properties of the porous graphene prepared by the method provided in Example 6 of the present invention were 40,000 S/m.
  • the porous cellulose prepared in Example 2 and ferric nitrate were subjected to catalytic treatment at 180 ° C for 10 hours, and the mass ratio of the ferric nitrate to the porous cellulose was 2:1; the obtained catalytically treated product was Drying at 120 ° C gave a first intermediate product having a water content of less than 5% by weight.
  • the first intermediate product was placed in a carbonization furnace, and the carbon was introduced into the carbon at a flow rate of 800 mL/min.
  • An argon gas is introduced into the furnace as a shielding gas, and the first intermediate product is heated from 20 ° C to 400 ° C at a rate of 20 ° C/min for 8 hours to obtain a second intermediate product; the second intermediate product is obtained.
  • the temperature was raised from 400 ° C to 900 ° C at a rate of 50 ° C / min, and kept for 7 hours to obtain a third intermediate product; the third intermediate product was heated from 900 ° C to 1300 ° C at a rate of 60 ° C / min, and kept for 8 hours.
  • a fourth intermediate product was obtained; the fourth intermediate product was cooled from 1300 ° C to 1000 ° C at a rate of 50 ° C/min for 4 hours; and the cooled fourth intermediate product was cooled to 20 ° C.
  • the cooled fourth intermediate product was washed in an aqueous sodium hydroxide solution having a mass concentration of 55% at 120 ° C for 24 hours to obtain a first washed product; at 150 ° C, the first washed product was in mass.
  • the second washing product was obtained by washing in a 10% aqueous hydrochloric acid solution for 24 hours to obtain a second washing product; the second washing product was washed with distilled water until neutral and dried to obtain graphene.
  • the graphene obtained in the seventh embodiment of the present invention was tested according to the method described in the first embodiment.
  • the result of the detection is that the graphene Sp2 prepared by the method provided in the seventh embodiment of the present invention has a high degree of hybridization; Thin, below 10 layers, is porous graphene; porous graphene has an electrical conductivity of 38000 S/m.
  • the porous cellulose and cobalt sulfate prepared in Example 3 were subjected to catalytic treatment by stirring at 50 ° C for 5 hours, and the mass ratio of the cobalt sulfate to the porous cellulose was 0.1:1; the obtained catalytically treated product was Drying at 90 ° C gives a first intermediate product having a water content of less than 8 wt%.
  • the first intermediate product was placed in a carbonization furnace, and nitrogen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 400 mL/min, and the first intermediate product was at a rate of 10 ° C/min.
  • the third intermediate product is heated from 820 ° C to 1150 ° C at a rate of 54 ° C / min for 7 hours to obtain a fourth intermediate product; the fourth intermediate product is cooled from 1150 ° C at a rate of 35 ° C / min to The temperature was maintained at 920 ° C for 3 hours; the fourth intermediate product after cooling was cooled to 30 ° C.
  • the cooled fourth intermediate product was washed in ammonia water having a mass concentration of 10% at 80 ° C for 8 hours to obtain a first washed product; at 90 ° C, the first washed product was at a mass concentration of 6
  • the aqueous solution of hydrochloric acid was washed for 8 hours to obtain a second washed product; the second washed product was washed with distilled water until neutral and dried to obtain graphene.
  • the graphene obtained in Example 8 of the present invention was tested and inspected.
  • the graphene Sp2 prepared by the method provided in the embodiment 8 of the present invention has a high degree of hybridization; the graphene layer is thin, and under 10 layers, it is porous graphene; the conductive property of the porous graphene is 39000 S/ m.
  • the porous cellulose prepared in Example 4 and nickel acetate were subjected to catalytic treatment at 150 ° C for 7 hours, and the mass ratio of the nickel acetate to the porous cellulose was 1:1; the obtained catalytically treated product was Drying at 100 ° C gives a first intermediate product having a water content of less than 3% by weight.
  • the first intermediate product was placed in a carbonization furnace, and nitrogen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 600 mL/min, and the first intermediate product was at a rate of 15 ° C/min.
  • the third intermediate product is heated from 880 ° C to 1250 ° C at a rate of 58 ° C / min for 6.5 hours to obtain a fourth intermediate product; the fourth intermediate product is cooled from 1250 ° C at a rate of 45 ° C / min to The temperature was maintained at 980 ° C for 2.5 hours; the fourth intermediate product after cooling was cooled to 40 ° C.
  • the cooled fourth intermediate product was washed in an aqueous solution of 40% by mass of sodium hydroxide at 100 ° C for 16 hours to obtain a first washed product; at 120 ° C, the first washed product was in mass
  • the aqueous solution was washed with an aqueous solution of 8% for 16 hours to obtain a second washed product; the second washed product was washed with distilled water until neutral and dried to obtain graphene.
  • Example 9 of the present invention The graphene obtained in Example 9 of the present invention was tested according to the method described in Example 1, and the result was that the graphene Sp2 prepared by the method provided in Example 9 of the present invention had a high degree of hybridization; Thin, below 10 layers, is porous graphene; porous graphene has an electrical conductivity of 38500 S/m.
  • the porous cellulose, potassium ferricyanide and cobalt acetate prepared in Example 5 were subjected to catalytic treatment at 80 ° C for 6 hours, and the mass ratio of the total mass of the potassium ferricyanide and cobalt acetate to the porous cellulose was 0.3:1;
  • the obtained catalytically treated product was dried at 95 ° C to obtain a first intermediate product having a water content of less than 6 wt%.
  • the first intermediate product was placed in a carbonization furnace, and nitrogen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 500 mL/min, and the first intermediate product was at a rate of 12 ° C/min.
  • nitrogen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 500 mL/min, and the first intermediate product was at a rate of 12 ° C/min.
  • the rate is raised from 340 ° C to 840 ° C, and kept for 4 hours to obtain a third intermediate product;
  • the third intermediate product is heated from 840 ° C to 1200 ° C at a rate of 55 ° C / min, and incubated for 7.5 hours to obtain a fourth intermediate a product;
  • the fourth intermediate product was cooled from 1200 ° C to 940 ° C at a rate of 40 ° C/min for 3.5 hours; and the cooled fourth intermediate product was cooled to 50 ° C.
  • the cooled fourth intermediate product was washed in a 20% aqueous solution of sodium hydroxide at 90 ° C for 10 hours to obtain a first washed product; at 100 ° C, the first washed product was in mass
  • the aqueous solution was washed in an aqueous solution of 7% for 10 hours to obtain a second washed product; the second washed product was washed with distilled water until neutral and dried to obtain graphene.
  • the graphene obtained in the tenth embodiment of the present invention was tested according to the method described in the first embodiment.
  • the result of the detection is that the graphene Sp2 prepared by the method provided in the tenth embodiment of the present invention has a high degree of hybridization; Thin, below 10 layers, is porous graphene; porous graphene has an electrical conductivity of 37,000 S/m.
  • the graphene is prepared according to the method disclosed in Chinese Patent Application No. 200810113596.0, and the specific process is as follows:
  • the silicon substrate is sequentially washed with deionized water, ethanol, acetone, and dried, and a layer of zinc sulfide having a thickness of 100 nm is deposited as a catalyst on the surface of the silicon substrate by a vapor deposition technique;
  • the silicon substrate deposited with zinc sulfide is placed in the middle of a clean quartz tube, the quartz tube is placed in an electric furnace, the middle portion of the quartz tube is located in the central portion of the electric furnace, and then 100 sccm of hydrogen and 100 sccm are introduced into the quartz tube. After 60 minutes of argon gas mixture, heating is started;
  • the graphene-deposited substrate was immersed in a 0.1 mol/L hydrochloric acid solution for 60 minutes to remove zinc sulfide, and then washed with deionized water to obtain graphene.
  • the conductive properties of the graphene prepared in Comparative Example 1 of the present invention were tested by using a conductivity tester. The test results showed that the graphene prepared by the method of Comparative Example 1 had an electrical conductivity of 30,000 S/m.
  • the present invention provides a method for preparing porous graphene, including The following steps: 1) catalytically treating the biomass carbon source under the action of a catalyst to obtain a first intermediate product, the catalyst comprising manganese chloride, iron compound, cobalt compound and nickel compound One or several; 2) under the condition of a protective gas, the first intermediate product is heated from the first temperature to the second temperature and then incubated to obtain a second intermediate product, the first temperature being 20 ° C ⁇ 40°C, the second temperature is 300° C. to 400° C.; 3), under the condition of a protective gas, the second intermediate product is heated from the second temperature to the third temperature and then incubated to obtain a third intermediate portion.
  • the third temperature is from 800 ° C to 900 ° C; 4), under the condition of a protective gas, the third intermediate product is heated from the third temperature to the fourth temperature and then incubated to obtain a fourth intermediate product.
  • the fourth temperature is 1100 ° C ⁇ 1300 ° C; 5), under the condition of a protective gas, the fourth intermediate product is cooled from the fourth temperature to the fifth temperature and then incubated to obtain porous graphene, the first The five temperatures are from 900 ° C to 1000 ° C.
  • the porous graphene prepared by the method provided by the invention has better electrical conductivity.
  • the porous graphene prepared by the method provided by the invention has a thin layer and a high degree of Sp2 hybridization; and the preparation method of the porous graphene provided by the invention is simple in process, low in energy consumption and low in cost.

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Abstract

本发明提供了一种多孔石墨烯的制备方法，包括以下步骤：在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物；将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物；将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯。本发明提供的方法制备得到的多孔石墨烯具有较好的导电性能。

Description

一种多孔石墨烯的制备方法 技术领域
本发明涉及石墨烯技术领域，尤其涉及一种多孔石墨烯的制备方法。
背景技术
石墨烯是一种由碳原子构成的单层片状结构的材料。石墨烯几乎是完全透明的，只吸收2.3％的光；导热系数高达5300W/m·K，高于碳纳米管和金刚石；石墨烯常温下的电子迁移率超过15000cm2/V·s，超过纳米碳管或硅晶体；石墨烯的电阻率只有10-8Ω·m，比铜或银更低，为世上电阻率最小的材料。由于石墨烯具有透明性好，电阻率小，电子迁移速度快等优点，可用来制造透明触控屏幕、光板、以及太阳能电池。
目前，石墨烯的制备方法主要有机械剥离法、化学气相沉积法、热解外延生长法等，其中，化学气相沉积法制备石墨烯简单易行，可以得到大面积高质量的石墨烯。如申请号为200810113596.0的中国专利公开了一种化学气相沉积法制备石墨烯的方法，具体过程为：将带有催化剂的衬底放入无氧反应器中，使衬底的温度达到500℃～1200℃，然后向反应器中通入含碳物质，得到石墨烯；所述催化剂为金属或金属化合物；所述含碳物质为甲烷、乙炔、乙醇、苯、甲苯和环己烷中的一种或几种。现有技术提供的这种石墨烯的制备方法操作方便、简便易行，可用于大规模生产；而且这种方法制备得到的石墨烯质量较好。但是，现有技术制备的石墨烯导电性能较差。
发明内容
有鉴于此，本发明的目的在于提供一种多孔石墨烯的制备方法，本发明提供的方法制备得到的多孔石墨烯导电性能较好。
本发明提供了一种多孔石墨烯的制备方法，包括以下步骤：
1)、在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；
2)、在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物，所述第一温度为20℃～40℃，所述第二温度为300℃～400℃；
3)、在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃；
4)、在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物，所述第四温度为1100℃～1300℃；
5)、在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯，所述第五温度为900℃～1000℃。
优选的，所述步骤1)中的生物质碳源为纤维素和木质素中的一种或两种。
优选的，所述步骤1)中的生物质碳源为纤维素。
优选的，所述纤维素为多孔纤维素。
优选的，所述多孔纤维素的制备方法包括以下步骤：
A)、将生物质资源在酸中进行水解，得到木质纤维素，所述生物质资源包括植物和农林废弃物中的一种或几种；
B)、对所述木质纤维素进行处理，得到多孔纤维素，所述处理包括酸处理、盐处理或有机溶剂处理。
优选的，所述步骤A)中的生物质资源为农林废弃物。
优选的，所述农林废弃物包括玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆和芦苇中的一种或几种。
优选的，所述农林废弃物为玉米芯。
优选的，所述步骤A)中的酸包括硫酸、硝酸、盐酸、甲酸、亚硫酸、磷酸和醋酸中的一种或几种。
优选的，所述步骤A)中酸的用量为所述生物质资源的3wt％～20wt％。
优选的，所述步骤A)中水解的温度为90℃～180℃；
所述步骤A)中水解的时间为10min～10h。
优选的，所述步骤B)中盐处理的方法为酸性亚硫酸盐法处理或碱性亚硫酸盐法处理。
优选的，所述酸性亚硫酸盐法处理过程中的pH值为1～7；
所述酸性亚硫酸盐法处理过程中酸的用量为所述木质纤维素的4wt％～30wt％；
所述酸性亚硫酸盐法处理中酸的重量百分浓度使液固比为(2～20)∶1。
优选的，所述酸性亚硫酸盐法处理的温度为70℃～180℃；
所述酸性亚硫酸盐法处理的时间为1小时～6小时。
优选的，所述碱性亚硫酸盐法处理过程中的pH值为7～14；
所述碱性亚硫酸盐法处理过程中碱的用量为所述木质纤维素的4wt％～30wt％；
所述碱性亚硫酸盐法处理中碱的重量百分浓度使液固比为(2～20)∶1。
优选的，所述碱性亚硫酸盐法处理的温度为70℃～180℃；
所述碱性亚硫酸盐法处理的时间为1小时～6小时。
优选的，所述步骤B)得到多孔纤维素后还包括：
将所述多孔纤维素进行漂白处理。
优选的，所述步骤1)中催化剂和生物质碳源的质量比为(0.01～2)∶1。
优选的，所述步骤1)中铁类化合物包括铁的氯化盐、铁的氰化物和含铁酸盐中的一种或几种；
所述步骤1)中钴类化合物包括钴的氯化盐和含钴酸盐中的一种或几种；
所述步骤1)中镍类化合物包括镍的氯化盐和含镍酸盐中的一种或几种。
优选的，所述步骤1)中的催化剂包括氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍中的一种或几种。
优选的，所述步骤2)中的保护性气体、步骤3)中的保护性气体、步骤4)中的保护性气体和步骤5)中的保护性气体独立地选自氮气和惰性气体中的一种或几种。
优选的，所述步骤2)中第一中间产物从第一温度升温至第二温度的升温速率为5℃/min～20℃/min。
优选的，所述步骤3)中第二中间产物从第二温度升温至第三温度的升温速率为30℃/min～40℃/min。
优选的，所述步骤4)中第三中间产物从第三温度升温至第四温度的升温 速率为50℃/min～60℃/min。
优选的，所述步骤5)中第四中间产物从第四温度降温至第五温度的降温速率为30℃/min～50℃/min。
本发明提供了一种多孔石墨烯的制备方法，包括以下步骤：1)、在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；2)、在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物，所述第一温度为20℃～40℃，所述第二温度为300℃～400℃；3)、在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃；4)、在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物，所述第四温度为1100℃～1300℃；5)、在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯，所述第五温度为900℃～1000℃。本发明提供的方法制备得到的多孔石墨烯具有较好的导电性能。实验结果表明，本发明提供的方法制备得到的多孔石墨烯的导电性能最高可达40000S/m。
此外，本发明提供的方法制备得到的多孔石墨烯的片层薄，Sp2杂化程度高；而且本发明提供的多孔石墨烯的制备方法工艺简单、能耗低、成本低。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明实施例6得到的石墨烯的拉曼光谱；
图2为本发明实施例6得到的石墨烯的透射电镜图片；
图3为本发明实施例6得到的石墨烯的透射电镜图片；
图4为本发明实施例6得到的石墨烯的透射电镜图片；
图5为本发明实施例6得到的石墨烯的透射电镜图片。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种多孔石墨烯的制备方法，包括以下步骤：
1)、在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；
2)、在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物，所述第一温度为20℃～40℃，所述第二温度为300℃～400℃；
3)、在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃；
4)、在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物，所述第四温度为1100℃～1300℃；
5)、在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯，所述第五温度为900℃～1000℃。
本发明提供的方法制备得到的多孔石墨烯具有较好的导电性能。此外，本发明提供的方法制备得到的多孔石墨烯的片层薄，Sp2杂化程度高；而且本发明提供的多孔石墨烯的制备方法工艺简单、能耗低、成本低。
本发明在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种。本发明优选将催化剂和生物质碳源进行混合，得到第一中间产物。本发明对所述混合的方法没有特殊的限制，采用本领域技术人员熟知的混合技术方案，将所述催化剂和生物质碳源搅拌均匀即可。在本发明中，所述混合的温度优选为20℃～180℃，更优选为50℃～150℃，最优选为80℃～120℃。在本发明中，所述混合的时间优选为2小时～10小时，更优选为5小时～7小时。
在本发明中，所述催化剂包括锰的氯化物、铁类化合物、钴类化合物和镍类化合物中的一种或几种，优选为锰的氯化物、铁类化合物、钴类化合物 和镍类化合物中的一种。在本发明中，所述锰的氯化物优选为氯化锰。在本发明中，所述铁类化合物优选包括铁的氯化盐、铁的氰化物和含铁酸盐中的一种或几种，更优选为氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾和三草酸合铁酸钾中的一种或几种。在本发明中，所述钴类化合物包括钴的氯化盐和含钴酸盐中的一种或几种，更优选为氯化钴、硝酸钴、硫酸钴和乙酸钴中的一种或几种。在本发明中，所述镍类化合物优选包括镍的氯化盐和含镍酸盐中的一种或几种，更优选为氯化镍、硝酸镍、硫酸镍和乙酸镍中的一种或几种。在本发明中，所述催化剂优选为氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍中的一种或几种。本发明对所述催化剂的来源没有特殊的限制，采用本领域技术人员熟知的上述种类的催化剂即可，可由市场购买获得。
在本发明中，所述生物质碳源优选为纤维素和木质素中的一种或两种；更优选为纤维素；最优选为多孔纤维素。在本发明中，所述多孔纤维素的制备方法优选包括以下步骤：
A)、将生物质资源在酸中进行水解，得到木质纤维素，所述生物质资源包括植物和农林废弃物中的一种或几种；
B)、对所述木质纤维素进行处理，得到多孔纤维素，所述处理包括酸处理、盐处理或有机溶剂处理。
本发明优选将生物质资源在酸中进行水解，得到木质纤维素，所述生物质资源包括植物和农林废弃物中的一种或几种。在本发明中，所述水解的温度优选为90℃～180℃，更优选为120℃～150℃。在本发明中，所述水解的时间优选为10min～10h，更优选为1h～8h，最优选为3h～6h。
在本发明中，所述水解的酸优选为硫酸、硝酸、盐酸、甲酸、亚硫酸、磷酸和醋酸中的一种或几种，更优选为硫酸、硝酸、盐酸、磷酸或醋酸，最优选为硫酸、硝酸或盐酸。在本发明中，所述水解中酸的用量优选为所述生物质资源的3wt％～20wt％，更优选为5wt％～15wt％，最优选为8wt％～12wt％。
在本发明中，所述生物质资源优选为农林废弃物，更优选为玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆和芦苇中的 一种或几种，最优选为玉米芯。
得到木质纤维素后，本发明优选将所述木质纤维素进行处理，得到多孔纤维素，所述处理包括酸处理、盐处理或有机溶剂处理；本发明更优选将所述木质纤维素进行盐处理，得到多孔纤维素。在本发明中，所述盐处理的方法优选为酸性亚硫酸盐法处理或碱性亚硫酸盐法处理。在本发明中，所述酸性亚硫酸法处理过程中的pH值优选为1～7，更优选为2～5，最优选为3～4。在本发明中，所述酸性亚硫酸盐法处理的温度优选为70℃～180℃，更优选为90℃～150℃，最优选为100℃～120℃。在本发明中，所述酸性亚硫酸盐法处理的时间优选为1小时～6小时，更优选为2小时～5小时，最优选为3小时～4小时。
在本发明中，所述酸性亚硫酸盐法处理中的酸优选为硫酸。在本发明中，所述酸性亚硫酸盐法处理过程中酸的用量优选为所述木质纤维素的4wt％～30wt％，更优选为8wt％～25wt％，最优选为10wt％～20wt％。在本发明中，所述酸性亚硫酸盐法处理中酸的重量百分比浓度优选使液固比为(2～20)∶1，更优选为(4～16)∶1，最优选为(8～12)∶1。
在本发明中，所述酸性亚硫酸盐法处理中的亚硫酸盐优选为亚硫酸钙、亚硫酸镁、亚硫酸钠或亚硫酸铵，更优选为亚硫酸镁或亚硫酸钠。本发明对所述酸性亚硫酸盐法处理过程中亚硫酸盐的用量没有特殊的限制，采用本领域技术人员熟知的亚硫酸盐法制浆过程中亚硫酸盐的用量即可。
在本发明中，所述碱性亚硫酸法处理过程中的pH值优选为7～14，更优选为8～13，最优选为9～12。在本发明中，所述碱性亚硫酸盐法处理的温度优选为70℃～180℃，更优选为90℃～150℃，最优选为100℃～120℃。在本发明中，所述碱性亚硫酸盐法处理的时间优选为1小时～6小时，更优选为2小时～5小时，最优选为3小时～4小时。
在本发明中，所述碱性亚硫酸盐法处理中的碱优选为氢氧化钙、氢氧化钠、氢氧化铵或氢氧化镁，更优选为氢氧化钠或氢氧化镁。在本发明中，所述碱性亚硫酸盐法处理过程中碱的用量优选为所述木质纤维素的4wt％～30wt％，更优选为8wt％～25wt％，最优选为10wt％～20wt％。在本发明中，所述碱性亚硫酸盐法处理中碱的重量百分比浓度优选使液固比为(2～20)∶1，更优选为(4～16)∶1，最优选为(8～12)∶1。
在本发明中，所述碱性亚硫酸盐法处理中的亚硫酸盐优选为亚硫酸钙、 亚硫酸镁、亚硫酸钠或亚硫酸铵，更优选为亚硫酸镁或亚硫酸钠。本发明对所述碱性亚硫酸盐法处理过程中亚硫酸盐的用量没有特殊的限制，采用本领域技术人员熟知的亚硫酸盐法制浆过程中亚硫酸盐的用量即可。
得到多孔纤维素后，本发明优选还包括：
将所述多孔纤维素进行漂白处理。
本发明对所述漂白处理的方法没有特殊的限制，采用本领域技术人员熟知的漂白技术方案即可。在本发明中，所述漂白的方法优选为全无氯漂白，更优选为双氧水漂白。本发明对所述双氧水的浓度没有特殊的限制，采用常用浓度的双氧水即可。在本发明中，所述双氧水的质量优选为所述多孔纤维素质量的1％～10％，更优选为2％～8％。在本发明中，所述双氧水漂白的漂白温度优选为60℃～130℃，更优选为80℃～100℃；所述双氧水漂白的漂白时间优选为1h～10h，更优选为2h～8h。
在本发明中，所述催化剂和生物质碳源的质量比优选为(0.01～2)∶1，更优选为(0.1～1)∶1，最优选为(0.3～0.8)∶1。在本发明中，所述催化处理的温度优选为20℃～180℃，更优选为50℃～150℃，最优选为80℃～120℃。在本发明中，所述催化处理的时间优选为2小时～10小时，更优选为5小时～7小时。
将所述生物质碳源进行催化处理后，本发明优选将得到的催化处理后的生物质碳源进行干燥，得到第一中间产物。在本发明中，干燥所述催化处理后的生物质碳源的温度优选为70℃～120℃，更优选为90℃～100℃。在本发明中，所述第一中间产物的含水量优选＜10wt％，更优选＜5wt％。
得到第一中间产物后，本发明在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物；所述第一温度为20℃～40℃，所述第二温度为300℃～400℃。在本发明中，所述第一中间产物从第一温度升温至第二温度的升温速率优选为5℃/min～20℃/min，更优选为10℃/min～15℃/min。在本发明中，所述第一温度优选为25℃～35℃，更优选为28℃～32℃。在本发明中，所述第二温度优选为320℃～380℃，更优选为340℃～360℃。在本发明中，所述第一中间产物从第一温度升温至第二温度后的保温时间优选为4小时～8小时，更优选为5小时～6小时。
在本发明中，所述保护性气体优选为氮气和惰性气体中的一种或几种，更优选为氮气。在本发明中，所述保护性气体的通入量优选为 200mL/min～800mL/min，更优选为400mL/min～600mL/min。
得到第二中间产物后，本发明在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃。在本发明中，所述第二中间产物从第二温度升温至第三温度的升温速率优选为20℃/min～50℃/min，更优选为30℃/min～40℃/min。在本发明中，所述第三温度优选为820℃～880℃，更优选为840℃～860℃。在本发明中，所述第二中间产物从第二温度升温至第三温度后的保温时间优选为3.5小时～7小时，更优选为5小时～6小时。
在本发明中，所述保护性气体的种类和通入量与上述技术方案所述保护性气体的种类和通入量一致，在此不再赘述。在本发明中，所述保护性气体可以和上述技术方案所述的保护性气体相同，也可以不同。
得到第三中间产物后，本发明在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物；所述第四温度为1100℃～1300℃。在本发明中，所述第三中间产物从第三温度升温至第四温度的升温速率优选为50℃/min～60℃/min，更优选为54℃/min～58℃/min。在本发明中，所述第四温度优选为1150℃～1250℃，更优选为1200℃。在本发明中，所述第三中间产物从第三温度升温至第四温度后的保温时间优选为6小时～8小时，更优选为7小时。
在本发明中，所述保护性气体的种类和通入量与上述技术方案所述保护性气体的种类和通入量一致，在此不再赘述。在本发明中，所述保护性气体可以和上述技术方案所述的保护性气体相同，也可以不同。
得到第四中间产物后，本发明在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯；所述第五温度为900℃～1000℃。在本发明中，所述第四中间产物从第四温度降温至第五温度的降温速率优选为30℃/min～50℃/min，更优选为35℃/min～45℃/min。在本发明中，所述第五温度优选为920℃～980℃，更优选为940℃～960℃。在本发明中，所述第四中间产物从第四温度降温至第五温度后的保温时间优选为2小时～4小时，更优选为3小时。
在本发明中，所述保护性气体的种类和通入量与上述技术方案所述保护性气体的种类和通入量一致，在此不再赘述。在本发明中，所述保护性气体 可以和上述技术方案所述的保护性气体相同，也可以不同。
所述第四保温处理完成后，本发明优选将所述第四保温处理得到的产物进行冷却，得到多孔石墨烯。在本发明中，所述冷却的温度优选＜100℃，更优选为20℃～60℃，最优选为30℃～40℃。本发明优选在保护性气体的条件下进行所述冷却。在本发明中，所述保护性气体的种类和通入量与上述技术方案所述保护性气体的种类和通入量一致，在此不再赘述。在本发明中，所述保护性气体可以和上述技术方案所述的保护性气体相同，也可以不同。在本发明中，所述冷却的方法优选为自然冷却。
所述冷却完成后，本发明优选将得到的冷却产物进行洗涤，得到多孔石墨烯。在本发明中，所述洗涤的方法优选为：
将所述冷却产物在碱性水溶液中进行第一洗涤，得到第一洗涤产物；
将所述第一洗涤产物在酸性水溶液中进行第二洗涤，得到第二洗涤产物；
将所述第二洗涤产物在水中进行第三洗涤，得到多孔石墨烯。
本发明优选将所述冷却产物在碱性溶液中进行第一洗涤，得到第一洗涤产物。在本发明中，所述碱性水溶液的质量浓度优选为3％～55％，更优选为10％～40％，最优选为20％～30％。在本发明中，所述第一洗涤的温度优选为60℃～120℃，更优选为80℃～100℃。在本发明中，所述第一洗涤的时间优选为4小时～24小时，更优选为8小时～16小时，最优选为10小时～14小时。在本发明中，所述碱性水溶液优选为氢氧化钠水溶液或氨水。
得到第一洗涤产物后，本发明优选将所述第一洗涤产物在酸性水溶液中进行第二洗涤，得到第二洗涤产物。在本发明中，所述酸性水溶液的质量浓度优选为4％～10％，更优选为6％～8％。在本发明中，所述第二洗涤的温度优选为70℃～150℃，更优选为90℃～120℃。在本发明中，所述第二洗涤的时间优选为4小时～24小时，更优选为8小时～16小时，最优选为10小时～14小时。在本发明中，所述酸性水溶液优选为盐酸水溶液。
得到第二洗涤产物后，本发明优选将所述第二洗涤产物在水中进行第三洗涤，得到多孔石墨烯。在本发明中，所述水优选为蒸馏水。本发明对所述第三洗涤的方法没有特殊的限制，所述第三洗涤后得到中性多孔石墨烯即可。
所述洗涤完成后，本发明优选将得到的洗涤产物进行干燥，得到多孔石墨烯。本发明对干燥所述洗涤产物的方法没有特殊的限制，采用本领域技术 人员熟知的干燥技术方案即可。
对本发明制备得到的石墨烯进行透射电镜测试，测试结果为，本发明提供的方法制备得到的石墨烯的片层较薄，在10层以下，为多孔石墨烯。对本发明制备得到的多孔石墨烯进行拉曼光谱测试，测试结果为，本发明提供的方法制备得到的多孔石墨烯Sp2杂化程度高。采用导电性能测试仪，测试本发明制备得到的多孔石墨烯的导电性能，测试结果为，本发明提供的方法制备得到的多孔石墨烯的导电性能最高可达40000S/m。
本发明提供了一种多孔石墨烯的制备方法，包括以下步骤：1)、在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；2)、在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物，所述第一温度为20℃～40℃，所述第二温度为300℃～400℃；3)、在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃；4)、在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物，所述第四温度为1100℃～1300℃；5)、在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯，所述第五温度为900℃～1000℃。本发明提供的方法制备得到的多孔石墨烯具有较好的导电性能。此外，本发明提供的方法制备得到的多孔石墨烯的片层薄，Sp2杂化程度高；而且本发明提供的多孔石墨烯的制备方法工艺简单、能耗低、成本低。
实施例1
在90℃下，将玉米芯在硫酸中进行10min的水解，得到木质纤维素，所述硫酸的质量为所述玉米芯质量的3％；
在70℃下，对所述木质纤维素进行1小时的酸性亚硫酸盐法处理，得到多孔纤维素，所述酸性亚硫酸盐法处理过程中的pH值为1，酸为硫酸，亚硫酸盐为亚硫酸镁，所述硫酸的质量为所述木质纤维素质量的4％，液固比为2∶1。
将得到的多孔纤维素进行双氧水漂白，所述双氧水的质量为所述多孔纤维素质量的5％，所述双氧水漂白的漂白温度为100℃，漂白时间为5h。
实施例2
在180℃下，将玉米芯在硝酸中进行10h的水解，得到木质纤维素，所述硝酸的质量为所述玉米芯质量的20％；
在180℃下，对所述木质纤维素进行6小时的酸性亚硫酸盐法处理，得到多孔纤维素，所述酸性亚硫酸盐法处理过程中的pH值为7，酸为硫酸，亚硫酸盐为亚硫酸钠，所述硫酸的质量为所述木质纤维素质量的30％，液固比为20∶1。
将所述多孔纤维素进行双氧水漂白，所述双氧水的质量为所述多孔纤维素质量的5％，所述双氧水漂白的漂白温度为100℃，漂白时间为5h。
实施例3
在130℃下，将玉米芯在盐酸中进行5h的水解，得到木质纤维素，所述盐酸的质量为所述玉米芯质量的10％；
在120℃下，对所述木质纤维素进行4小时的酸性亚硫酸盐法处理，得到多孔纤维素，所述酸性亚硫酸盐法处理过程中的pH值为3，酸为硫酸，亚硫酸盐为亚硫酸铵，所述硫酸的质量为所述木质纤维素质量的18％，液固比为10∶1。
将所述多孔纤维素进行双氧水漂白，所述双氧水的质量为所述多孔纤维素质量的5％，所述双氧水漂白的漂白温度为100℃，漂白时间为5h。
实施例4
在150℃下，将玉米芯在盐酸中进行1h的水解，得到木质纤维素，所述盐酸的质量为所述玉米芯质量的15％；
在70℃下，对所述木质纤维素进行1小时的碱性亚硫酸盐法处理，得到多孔纤维素，所述碱性亚硫酸盐法处理过程中的pH值为7，碱为氢氧化钠，亚硫酸盐为亚硫酸镁，所述氢氧化钠的质量为所述木质纤维素质量的4％，液固比为2∶1。
将所述多孔纤维素进行双氧水漂白，所述双氧水的质量为所述多孔纤维素质量的5％，所述双氧水漂白的漂白温度为100℃，漂白时间为5h。
实施例5
在120℃下，将高粱杆在盐酸中进行8h的水解，得到木质纤维素，所述盐酸的质量为所述玉米芯质量的8％；
在180℃下，对所述木质纤维素进行6小时的碱性亚硫酸盐法处理，得到多孔纤维素，所述碱性亚硫酸盐法处理过程中的pH值为14，碱为氢氧化镁，亚硫酸盐为亚硫酸钠，所述氢氧化镁的质量为所述木质纤维素质量的30％，液 固比为20∶1。
实施例6
将实施例1得到的多孔纤维素和氯化锰，在20℃下搅拌2小时进行催化处理，所述氯化锰和多孔纤维素的质量比为0.01∶1；将得到的催化处理后的产物在70℃下干燥，得到含水量低于10wt％的第一中间产物。
将所述第一中间产物置于炭化炉中，以200mL/min的气体通入量向所述碳化炉中通入氮气作为保护气，将所述第一中间产物以5℃/min的速率从25℃升温至300℃，保温4小时，得到第二中间产物；将所述第二中间产物以20℃/min的速率从300℃升温至800℃，保温3.5小时，得到第三中间产物；将所述第三中间产物以50℃/min的速率从800℃升温至1100℃，保温6小时，得到第四中间产物；将所述第四中间产物以30℃/min的速率从1100℃降温至900℃，保温2小时；将所述降温后的第四中间产物冷却至60℃。
在60℃下，将上述冷却后的第四中间产物在质量浓度为3％的氢氧化钠水溶液中洗涤4小时，得到第一洗涤产物；在70℃下，将所述第一洗涤产物在质量浓度为4％的盐酸水溶液中洗涤4小时，得到第二洗涤产物；将所述第二洗涤产物用蒸馏水洗涤至中性后干燥，得到石墨烯。
将本发明实施例1制备得到的石墨烯进行拉曼光谱测试，测试结果如图1所示，图1为本发明实施例6得到的石墨烯的拉曼光谱，由图1可知，本发明实施例6提供的方法制备得到的石墨烯Sp2杂化程度高。对本发明实施例1制备得到的石墨烯进行透射电镜测试，测试结果如图2～图5所示，图2～图5为本发明实施例6得到的石墨烯的透射电镜图片，由图2～图5可以看出，本发明实施例6提供的方法制备得到的石墨烯的片层较薄，在10层以下，为多孔石墨烯。采用导电性能测试仪，测试本发明实施例6制备得到的多孔石墨烯的导电性，测试结果为，本发明实施例6提供的方法制备得到的多孔石墨烯的导电性能为40000S/m。
实施例7
将实施例2制备得到的多孔纤维素和硝酸铁，在180℃下搅拌10小时进行催化处理，所述硝酸铁和多孔纤维素的质量比为2∶1；将得到的催化处理后的产物在120℃下干燥，得到含水量低于5wt％的第一中间产物。
将所述第一中间产物置于炭化炉中，以800mL/min的气体通入量向所述碳 化炉中通入氩气作为保护气，将所述第一中间产物以20℃/min的速率从20℃升温至400℃，保温8小时，得到第二中间产物；将所述第二中间产物以50℃/min的速率从400℃升温至900℃，保温7小时，得到第三中间产物；将所述第三中间产物以60℃/min的速率从900℃升温至1300℃，保温8小时，得到第四中间产物；将所述第四中间产物以50℃/min的速率从1300℃降温至1000℃，保温4小时；将所述降温后的第四中间产物冷却至20℃。
在120℃下，将上述冷却后的第四中间产物在质量浓度为55％的氢氧化钠水溶液中洗涤24小时，得到第一洗涤产物；在150℃下，将所述第一洗涤产物在质量浓度为10％的盐酸水溶液中洗涤24小时，得到第二洗涤产物；将所述第二洗涤产物用蒸馏水洗涤至中性后干燥，得到石墨烯。
按照实施例1所述的方法，对本发明实施例7得到的石墨烯进行检测，检测结果为，本发明实施例7提供的方法制备得到的石墨烯Sp2杂化程度高；石墨烯的片层较薄，在10层以下，为多孔石墨烯；多孔石墨烯的导电性能为38000S/m。
实施例8
将实施例3制备得到的多孔纤维素和硫酸钴，在50℃下搅拌5小时进行催化处理，所述硫酸钴和多孔纤维素的质量比为0.1∶1；将得到的催化处理后的产物在90℃下干燥，得到含水量低于8wt％的第一中间产物。
将所述第一中间产物置于炭化炉中，以400mL/min的气体通入量向所述碳化炉中通入氮气作为保护气，将所述第一中间产物以10℃/min的速率从40℃升温至320℃，保温5小时，得到第二中间产物；将所述第二中间产物以30℃/min的速率从320℃升温至820℃，保温5小时，得到第三中间产物；将所述第三中间产物以54℃/min的速率从820℃升温至1150℃，保温7小时，得到第四中间产物；将所述第四中间产物以35℃/min的速率从1150℃降温至920℃，保温3小时；将所述降温后的第四中间产物冷却至30℃。
在80℃下，将上述冷却后的第四中间产物在质量浓度为10％的氨水中洗涤8小时，得到第一洗涤产物；在90℃下，将所述第一洗涤产物在质量浓度为6％的盐酸水溶液中洗涤8小时，得到第二洗涤产物；将所述第二洗涤产物用蒸馏水洗涤至中性后干燥，得到石墨烯。
按照实施例1所述的方法，对本发明实施例8得到的石墨烯进行检测，检 测结果为，本发明实施例8提供的方法制备得到的石墨烯Sp2杂化程度高；石墨烯的片层较薄，在10层以下，为多孔石墨烯；多孔石墨烯的导电性能为39000S/m。
实施例9
将实施例4制备得到的多孔纤维素和乙酸镍，在150℃下搅拌7小时进行催化处理，所述乙酸镍和多孔纤维素的质量比为1∶1；将得到的催化处理后的产物在100℃下干燥，得到含水量低于3wt％的第一中间产物。
将所述第一中间产物置于炭化炉中，以600mL/min的气体通入量向所述碳化炉中通入氮气作为保护气，将所述第一中间产物以15℃/min的速率从28℃升温至380℃，保温6小时，得到第二中间产物；将所述第二中间产物以40℃/min的速率从380℃升温至880℃，保温6小时，得到第三中间产物；将所述第三中间产物以58℃/min的速率从880℃升温至1250℃，保温6.5小时，得到第四中间产物；将所述第四中间产物以45℃/min的速率从1250℃降温至980℃，保温2.5小时；将所述降温后的第四中间产物冷却至40℃。
在100℃下，将上述冷却后的第四中间产物在质量浓度为40％的氢氧化钠水溶液中洗涤16小时，得到第一洗涤产物；在120℃下，将所述第一洗涤产物在质量浓度为8％的盐酸水溶液中洗涤16小时，得到第二洗涤产物；将所述第二洗涤产物用蒸馏水洗涤至中性后干燥，得到石墨烯。
按照实施例1所述的方法，对本发明实施例9得到的石墨烯进行检测，检测结果为，本发明实施例9提供的方法制备得到的石墨烯Sp2杂化程度高；石墨烯的片层较薄，在10层以下，为多孔石墨烯；多孔石墨烯的导电性能为38500S/m。
实施例10
将实施例5制备得到的多孔纤维素、铁氰化钾和乙酸钴，在80℃下搅拌6小时进行催化处理，所述铁氰化钾和乙酸钴的总质量与多孔纤维素的质量比为0.3∶1；将得到的催化处理后的产物在95℃下干燥，得到含水量低于6wt％的第一中间产物。
将所述第一中间产物置于炭化炉中，以500mL/min的气体通入量向所述碳化炉中通入氮气作为保护气，将所述第一中间产物以12℃/min的速率从35℃升温至340℃，保温7小时，得到第二中间产物；将所述第二中间产物以35℃/min 的速率从340℃升温至840℃，保温4小时，得到第三中间产物；将所述第三中间产物以55℃/min的速率从840℃升温至1200℃，保温7.5小时，得到第四中间产物；将所述第四中间产物以40℃/min的速率从1200℃降温至940℃，保温3.5小时；将所述降温后的第四中间产物冷却至50℃。
在90℃下，将上述冷却后的第四中间产物在质量浓度为20％的氢氧化钠水溶液中洗涤10小时，得到第一洗涤产物；在100℃下，将所述第一洗涤产物在质量浓度为7％的盐酸水溶液中洗涤10小时，得到第二洗涤产物；将所述第二洗涤产物用蒸馏水洗涤至中性后干燥，得到石墨烯。
按照实施例1所述的方法，对本发明实施例10得到的石墨烯进行检测，检测结果为，本发明实施例10提供的方法制备得到的石墨烯Sp2杂化程度高；石墨烯的片层较薄，在10层以下，为多孔石墨烯；多孔石墨烯的导电性能为37000S/m。
比较例1
按照申请号为200810113596.0的中国专利公开的方法制备石墨烯，具体过程为：
将硅衬底依次用去离子水、乙醇、丙酮清洗后烘干，通过气相沉积技术在硅衬底表面沉积一层厚度为100纳米的硫化锌作为催化剂；
将所述沉积有硫化锌的硅衬底置于洁净的石英管中部，将石英管放入电炉中，使石英管的中部位于电炉的中心区域，然后在石英管中通入100sccm的氢气和100sccm的氩气混合气60分钟后，开始加热；
当电炉中心区域的温度高达850℃时，向电炉中通入乙醇作为碳源，反应开始进行；
反应进行20分钟后，停止通入乙醇，同时关闭电炉，继续通入100sccm的氢气和100sccm的氩气的混合气至温度降至室温，得到沉积有石墨烯的衬底；
将所述沉积有石墨烯的衬底放入0.1mol/L的盐酸溶液中浸泡60分钟，除去硫化锌，然后用去离子水洗净烘干，得到石墨烯。
采用导电性能测试仪，测试本发明比较例1制备得到的石墨烯的导电性能，测试结果为，本发明比较例1提供的方法制备得到的石墨烯的导电性能为30000S/m。
由以上实施例可知，本发明提供了一种多孔石墨烯的制备方法，包括以 下步骤：1)、在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；2)、在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物，所述第一温度为20℃～40℃，所述第二温度为300℃～400℃；3)、在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃；4)、在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物，所述第四温度为1100℃～1300℃；5)、在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯，所述第五温度为900℃～1000℃。本发明提供的方法制备得到的多孔石墨烯具有较好的导电性能。此外，本发明提供的方法制备得到的多孔石墨烯的片层薄，Sp2杂化程度高；而且本发明提供的多孔石墨烯的制备方法工艺简单、能耗低、成本低。

Claims (25)

  1. 一种多孔石墨烯的制备方法，包括以下步骤：
    1)、在催化剂的作用下，将生物质碳源进行催化处理，得到第一中间产物，所述催化剂包括锰的氯化盐、铁类化合物、钴类化合物和镍类化合物中的一种或几种；
    2)、在保护性气体的条件下，将所述第一中间产物从第一温度升温至第二温度后保温，得到第二中间产物，所述第一温度为20℃～40℃，所述第二温度为300℃～400℃；
    3)、在保护性气体的条件下，将所述第二中间产物从第二温度升温至第三温度后保温，得到第三中间产物；所述第三温度为800℃～900℃；
    4)、在保护性气体的条件下，将所述第三中间产物从第三温度升温至第四温度后保温，得到第四中间产物，所述第四温度为1100℃～1300℃；
    5)、在保护性气体的条件下，将所述第四中间产物从第四温度降温至第五温度后保温，得到多孔石墨烯，所述第五温度为900℃～1000℃。
  2. 根据权利要求1所述的方法，其特征在于，所述步骤1)中的生物质碳源为纤维素和木质素中的一种或两种。
  3. 根据权利要求2所述的方法，其特征在于，所述步骤1)中的生物质碳源为纤维素。
  4. 根据权利要求3所述的方法，其特征在于，所述纤维素为多孔纤维素。
  5. 根据权利要求4所述的方法，其特征在于，所述多孔纤维素的制备方法包括以下步骤：
    A)、将生物质资源在酸中进行水解，得到木质纤维素，所述生物质资源包括植物和农林废弃物中的一种或几种；
    B)、对所述木质纤维素进行处理，得到多孔纤维素，所述处理包括酸处理、盐处理或有机溶剂处理。
  6. 根据权利要求5所述的方法，其特征在于，所述步骤A)中的生物质资源为农林废弃物。
  7. 根据权利要求6所述的方法，其特征在于，所述农林废弃物包括玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆和芦 苇中的一种或几种。
  8. 根据权利要求7所述的方法，其特征在于，所述农林废弃物为玉米芯。
  9. 根据权利要求5所述的方法，其特征在于，所述步骤A)中的酸包括硫酸、硝酸、盐酸、甲酸、亚硫酸、磷酸和醋酸中的一种或几种。
  10. 根据权利要求5所述的方法，其特征在于，所述步骤A)中酸的用量为所述生物质资源的3wt％～20wt％。
  11. 根据权利要求5所述的方法，其特征在于，所述步骤A)中水解的温度为90℃～180℃；
    所述步骤A)中水解的时间为10min～10h。
  12. 根据权利要求5所述的方法，其特征在于，所述步骤B)中盐处理的方法为酸性亚硫酸盐法处理或碱性亚硫酸盐法处理。
  13. 根据权利要求12所述的方法，其特征在于，所述酸性亚硫酸盐法处理过程中的pH值为1～7；
    所述酸性亚硫酸盐法处理过程中酸的用量为所述木质纤维素的4wt％～30wt％；
    所述酸性亚硫酸盐法处理中酸的重量百分浓度使液固比为(2～20)∶1。
  14. 根据权利要求12所述的方法，其特征在于，所述酸性亚硫酸盐法处理的温度为70℃～180℃；
    所述酸性亚硫酸盐法处理的时间为1小时～6小时。
  15. 根据权利要求12所述的方法，其特征在于，所述碱性亚硫酸盐法处理过程中的pH值为7～14；
    所述碱性亚硫酸盐法处理过程中碱的用量为所述木质纤维素的4wt％～30wt％；
    所述碱性亚硫酸盐法处理中碱的重量百分浓度使液固比为(2～20)∶1。
  16. 根据权利要求12所述的方法，其特征在于，所述碱性亚硫酸盐法处理的温度为70℃～180℃；
    所述碱性亚硫酸盐法处理的时间为1小时～6小时。
  17. 根据权利要求5所述的方法，其特征在于，所述步骤B)得到多孔纤维素后还包括：
    将所述多孔纤维素进行漂白处理。
  18. 根据权利要求1所述的方法，其特征在于，所述步骤1)中催化剂和生物质碳源的质量比为(0.01～2)∶1。
  19. 根据权利要求1所述的方法，其特征在于，所述步骤1)中铁类化合物包括铁的氯化盐、铁的氰化物和含铁酸盐中的一种或几种；
    所述步骤1)中钴类化合物包括钴的氯化盐和含钴酸盐中的一种或几种；
    所述步骤1)中镍类化合物包括镍的氯化盐和含镍酸盐中的一种或几种。
  20. 根据权利要求1所述的方法，其特征在于，所述步骤1)中的催化剂包括氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍中的一种或几种。
  21. 根据权利要求1所述的方法，其特征在于，所述步骤2)中的保护性气体、步骤3)中的保护性气体、步骤4)中的保护性气体和步骤5)中的保护性气体独立地选自氮气和惰性气体中的一种或几种。
  22. 根据权利要求1所述的方法，其特征在于，所述步骤2)中第一中间产物从第一温度升温至第二温度的升温速率为5℃/min～20℃/min。
  23. 根据权利要求1所述的方法，其特征在于，所述步骤3)中第二中间产物从第二温度升温至第三温度的升温速率为30℃/min～40℃/min。
  24. 根据权利要求1所述的方法，其特征在于，所述步骤4)中第三中间产物从第三温度升温至第四温度的升温速率为50℃/min～60℃/min。
  25. 根据权利要求1所述的方法，其特征在于，所述步骤5)中第四中间产物从第四温度降温至第五温度的降温速率为30℃/min～50℃/min。
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AU2015283392A1 (en) 2017-02-02
US9790094B2 (en) 2017-10-17
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MX353442B (es) 2018-01-12
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EP3165507B1 (en) 2018-08-29
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EP3165507A1 (en) 2017-05-10
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