WO2017190629A1 - 一种石墨烯材料及其制备方法 - Google Patents

一种石墨烯材料及其制备方法 Download PDF

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WO2017190629A1
WO2017190629A1 PCT/CN2017/082266 CN2017082266W WO2017190629A1 WO 2017190629 A1 WO2017190629 A1 WO 2017190629A1 CN 2017082266 W CN2017082266 W CN 2017082266W WO 2017190629 A1 WO2017190629 A1 WO 2017190629A1
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cellulose
preparation
graphene
catalyst
starch
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French (fr)
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张金柱
郑应福
刘京才
刘顶
刘晓敏
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济南圣泉集团股份有限公司
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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
    • 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
    • C01B2204/02—Single layer 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
    • C01B2204/04—Specific amount of layers or specific thickness
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • the invention relates to the field of graphene preparation, in particular to a graphene material and a preparation method thereof.
  • Graphene has attracted much attention as a new type of carbon material. It has a very high specific surface area and is the thinnest, strongest, and most conductive and thermally conductive material found. At present, there are mainly three methods for synthesizing graphene: chemical vapor deposition (CVD), solvent stripping, and oxidation-reduction.
  • CVD chemical vapor deposition
  • the CVD method is a method in which a gas containing a carbon source is introduced into a high-temperature vacuum reaction chamber, a carbon source is cracked at a high temperature, and graphene is grown on a metal base (nickel, copper, etc.) in a large area.
  • the reaction conditions required for this method are harsh, the requirements for equipment are high, and the long production cycle is not conducive to industrialization.
  • the graphite particles are dispersed in an organic solvent, and the solvent molecules are intercalated into the graphite by ultrasonic or the like to obtain the graphene by peeling off the graphite.
  • the graphene produced by this method is uncontrollable in size and has a low yield, which limits industrial applications.
  • the oxidation-reduction method oxidizes flake graphite, and then removes the oxygen-containing group by chemical reduction, and finally obtains graphene.
  • This method requires a large amount of strong oxidant (concentrated sulfuric acid, potassium permanganate, etc.), has a high risk, and exerts great pressure on the environment, which is not conducive to industrialization.
  • Chinese Patent Publication No. CN103787321A discloses "a self-supporting graphene material and a preparation method thereof", which forms a three-dimensional self-supporting structure from graphene grown on a substrate, and is prepared by heat-treating, washing and filtering the starch. Drying; mixing the dried product with a base, sintering treatment under anaerobic conditions, washing, and drying to obtain self-supporting graphene, but the method The scale of preparation of graphene is only at the gram level.
  • FIG. 1 Chinese Patent Publication No. CN104724699A discloses a method for preparing biomass graphene by using cellulose as a raw material, and the specific preparation method is as follows: Step 1: Preparation of a catalyst solution; Step 2: Coordination of cellulose with catalyst ions, high temperature deoxidation, Precursor; Step 3: Heat treatment; Step 4: Acid treatment, drying; that is, graphene is obtained.
  • the graphene prepared by the method has uniform morphology and has a single layer or a multi-layer two-dimensional layer structure with a size of 0.5-2 ⁇ m and an electrical conductivity of 25000-45000 S/m. However, the preparation scale of the graphene is only in the gram grade.
  • the present invention produces high quality graphene on the basis of overcoming the shortcomings of various current methods for producing graphene.
  • the invention proposes a method for preparing graphene by using biomass such as corn starch as a raw material.
  • the method has the advantages of safe and environmentally friendly raw materials, simple preparation process, stable quality controllable product, short production period and high output, and can realize industrialization.
  • Starch is a rich natural sugar resource and a natural resource for renewable and biodegradable.
  • Various kinds of crops have rich sources of starch, and at the same time, a large amount of wastes with high starch content (such as corn processing, rice processing, potato processing, etc.) are produced during the processing of agricultural and sideline products.
  • the stock of corn in China is very heavy, and the price of corn is falling.
  • the method for preparing graphene by using corn starch as raw material has the advantages of simple process, low cost, high output, strong production safety, controllable quality, industrialized production, and large-scale digestion of corn, which can relieve the national finances and help farmers. Increase income, get more in one fell swoop.
  • a first object of the present invention is to prepare a graphene material by preparing a graphene material by mixing cellulose and a starchy substance, and the obtained graphene material has stable properties, good specific surface area, and dispersibility. Ok, it can achieve large-scale applications.
  • a second object of the present invention is to provide a graphene material obtained by the above production method.
  • a method for preparing a graphene material comprising the steps of:
  • the invention adopts cellulose as a skeleton, and at the same time that cellulose is carbonized to form a graphene structure, starch and/or starch sugar are simultaneously carbonized on the cellulose skeleton to form a graphene-like structure and a carbon microsphere structure and adhere to the graphene structure.
  • the surface or part is embedded inside to obtain a graphene material, which has a graphene structure, has a high specific surface area, and has good activity, good water solubility, easy dispersion, and difficulty in agglomeration.
  • the cellulose has a purity of 95% or more.
  • Agricultural and forestry waste is an important member of waste and an important biomass resource.
  • the cellulose is prepared from agricultural and forestry waste.
  • the preparation method can be prepared according to the prior art.
  • the cellulose prepared by the following agricultural and forestry wastes can react better with the first substance under the conditions of the catalyst, and the finally obtained graphene has excellent performance.
  • the cellulose is prepared from any one or more of corn cob, sorghum, corn stalk, cotton stalk, wood chips, beet pulp, furfural slag, and reed.
  • the preparation method of cellulose can be prepared by using the prior art.
  • the starch comprises any one or more of corn starch, potato starch, and tapioca starch.
  • starch sugar includes any one or more of glucose, maltose, sucrose, and fructose.
  • the first substance in the following ratio is reacted with cellulose to form a synthetic material.
  • the graphene produced is more excellent in performance.
  • the first substance and the cellulose are in a weight ratio of 1:0.1 to 1:10, preferably 1:1 to 1: 5 mixed.
  • the first substance is mixed with the cellulose in a weight ratio of 1:1 to 1:3.
  • the catalyst is FeCl 2 , FeCl 3 , K 3 [Fe(CN) a mixture of any one or more of 6 ], K 4 [Fe(CN) 6 ], NiCl 2 ;
  • the weight ratio of the catalyst to the total weight of the cellulose and the first substance is from 1:0.5 to 1:2.
  • the weight ratio of the catalyst to the total weight of the cellulose and the first substance may be 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, and the like.
  • the weight ratio of the catalyst to the total weight of the cellulose and the first substance is from 1:0.5 to 1:1.5, more preferably from 1:10 to 1:1.2.
  • the hydrothermal condition is 160-200 ° C for 2-10 h, in order to achieve a better synthesis effect, preferably, in the step (a), the reaction is carried out under hydrothermal conditions of 160-200 ° C. 5-8 hours to form a synthetic material.
  • the reaction is carried out under hydrothermal conditions at 160 ° C for 8 hours to form a composite; in some embodiments, the reaction is carried out under hydrothermal conditions at 180 ° C for 7 hours to form a composite; in some embodiments, The reaction was carried out under hydrothermal conditions at 190 ° C for 6 hours to form a synthetic material; in some embodiments, the reaction was carried out under hydrothermal conditions at 200 ° C for 5 hours to form a synthetic material, and the like.
  • the drying is carried out at a temperature of 80 to 120 ° C; the temperature of the composition can further stabilize the structure of the composition.
  • the gas used in the protective atmosphere is any one of nitrogen, argon and hydrogen.
  • the protective atmosphere used does not contain other gases.
  • the washing is mainly for removing metal impurities and removing other residues to reduce the impurities of the graphene material.
  • the washing comprises the following steps:
  • the acid used for the pickling is any one of hydrochloric acid, sulfuric acid, and phosphoric acid having a mass concentration of 3% to 10%. That is to say, the acid used for pickling may be hydrochloric acid having a mass concentration of 3% to 10%, sulfuric acid having a mass concentration of 3% to 10%, or phosphoric acid having a mass concentration of 3% to 10%.
  • the mass concentration refers to the mass concentration of the acid in the total liquid after dilution of various acids with water.
  • the acid used for pickling may be hydrochloric acid having a mass concentration of 3%, hydrochloric acid having a mass concentration of 5%, hydrochloric acid having a mass concentration of 7%, hydrochloric acid having a mass concentration of 8%, hydrochloric acid having a mass concentration of 10%, etc.
  • the acid used for pickling may be sulfuric acid having a mass concentration of 3%, sulfuric acid having a mass concentration of 5%, sulfuric acid having a mass concentration of 7%, sulfuric acid having a mass concentration of 8%, and a mass concentration of 10 % of sulfuric acid, etc.; similarly, the acid used for pickling may be a phosphoric acid having a mass concentration of 3%, a phosphoric acid having a mass concentration of 5%, a phosphoric acid having a mass concentration of 7%, and a phosphoric acid having a mass concentration of 8%. Phosphoric acid having a mass concentration of 10% or the like.
  • the gradient heating carbonization is: 250-C-450 ° C heat preservation 2.5-3.5 h, 550 ° C-800 ° C heat preservation 1.5-2.5 h , 800 ° C -1000 ° C insulation 1.5-2.5h.
  • the gradient heating carbonization is: 350 ° C for 3.5 h, 550 ° C for 2.5 h, 800 ° C for 2.5 h; in some embodiments, the gradient heating carbonization is: 300 ° C for 3 h, 600 ° C for 2 h In some embodiments, the gradient heating carbonization is: 350 ° C for 3 h, 700 ° C for 1.5 h, 950 ° C for 1.5 h; in some embodiments 450 ° C for 2.5 h, 800 ° C for 1.5 h , 1000 ° C insulation 1.5h, and so on.
  • starch and/or its sugar and cellulose may be mixed with starch and cellulose, starch or starch sugar may be mixed with cellulose, or starch sugar may be mixed with cellulose.
  • the graphene material provided by the invention has excellent dispersing performance, wherein the dispersing property can be used by Zeta electric Characterization, which is an important indicator of the stability of colloidal dispersions.
  • Zeta electric Characterization is an important indicator of the stability of colloidal dispersions.
  • the graphene material prepared by the invention has an absolute value of zeta potential of more than 20 mV.
  • cellulose is used as a skeleton, and while the cellulose is carbonized to form a graphene structure, starch and/or starch sugar are simultaneously carbonized on the cellulose skeleton to form a graphene-like structure and a carbon microsphere structure and adhere thereto.
  • the graphene structure is partially or partially embedded inside to obtain a graphene material, which has a graphene structure, has a high specific surface area, and has good activity, good water solubility, easy dispersion, and difficulty in agglomeration. .
  • the present invention also defines the types and addition ratios of the respective raw materials, and further defines the reaction conditions of the respective steps and the subsequent washing process to stabilize the properties of the produced graphene materials.
  • the graphene material prepared by the invention has a two-dimensional sheet structure of single layer or multiple layers (up to ten layers), the specific surface area is above 200 m 2 /g, and the absolute value of the zeta potential is above 20 mV. .
  • the method for preparing graphene material by using biomass as raw material according to the invention has simple process, low cost, high output, strong production safety, controllable quality, green environmental protection, and the preparation scale has reached the kilogram level. Industrial production can be achieved.
  • Example 1 is an SEM image of a graphene material according to Example 3 of the present invention.
  • Example 2 is an SEM image of a graphene material according to Example 4 of the present invention.
  • a method for preparing a graphene material comprising the steps of:
  • Corn starch (2kg) and cellulose having a purity of 95% or more are mixed at a weight ratio of 1:0.1 to obtain a first mixture, and the cellulose is made of a high mast, a corn stalk, and a cotton stalk;
  • the catalyst is FeCl 2
  • the weight ratio of the catalyst to the first mixture is 1:0.5
  • the reaction was carried out under hydrothermal conditions of 200 ° C for 3 hours to form a synthetic material
  • the composite was dried at a temperature of 120 ° C until the water content was 9.5%.
  • the gradient heating was carried out under a protective atmosphere of nitrogen. The gradient heating was: 250 ° C for 3.5 h, 550 ° C for 2 h, 900 ° C for 1.5 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a concentration of 3% hydrochloric acid at a temperature of 80 ° C for 5 h, then washed with water until neutral, and then dried at 100 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 200 m 2 /g and a zeta potential of -50 mV.
  • a method for preparing a graphene material comprising the steps of:
  • the reaction was carried out under hydrothermal conditions of 160 ° C for 10 hours to form a synthetic material
  • the composite is dried at a temperature of 80 ° C to a water content of 9.2% or less, and subjected to a gradient heating carbonization under a protective atmosphere of argon gas.
  • the gradient temperature is: 300 ° C for 2.5 h, 600 ° C Insulation for 2h, 800 ° C for 2h, carbonization and cooling to obtain carbonized materials;
  • the carbonized material is first washed with sulfuric acid having a mass concentration of 10% at a temperature of 30 ° C for 8 hours, then washed with water until neutral, and then dried at 70 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 250 m 2 /g and a zeta potential of -45 mV.
  • a method for preparing a graphene material comprising the steps of:
  • starch Mixing starch (2 kg) and starch sugar (2 kg) with cellulose having a purity of 95% or more in a weight ratio of 1:1 to obtain a first mixture, the starch being a mixture of potato starch (1 kg) and tapioca starch (1 kg).
  • Starch sugar is a mixture of glucose (1kg) and sucrose (1kg), which is prepared from high masts, cornstalks, cotton rods, wood chips and reeds;
  • the catalyst is a mixture of FeCl 3 , K 4 [Fe(CN) 6 ], NiCl 2 (the weight ratio of the three catalysts is 1:1:1), the weight ratio of the catalyst to the first mixture is 1:1;
  • the reaction was carried out under hydrothermal conditions at 180 ° C for 6 hours to form a synthetic material
  • the temperature of the composite material was dried at 100 ° C, and the water content was 9.7%.
  • the gradient temperature was carbonized under a protective atmosphere of nitrogen.
  • the gradient temperature was 350 ° C for 3.5 h, 600 ° C for 2.5 h, and 1000 ° C for 1.5 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a mass concentration of 10% phosphoric acid at a temperature of 50 ° C for 6 h, then washed with water until neutral, and then dried at 110 ° C to obtain a graphene material.
  • the obtained graphene material was scanned by an electron microscope, and the results are shown in Fig. 1. It can be seen from Fig. 1 that the carbon microsphere structure in the obtained graphene material is attached to the graphene sheet structure, and some are embedded therein, and are integrated.
  • the graphene material was determined to have a specific surface area of 500 m 2 /g and a zeta potential of -30 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Corn starch (1.5kg), potato starch (1kg) and cellulose with a purity of 95% or more were mixed at a weight ratio of 1:3 to obtain a first mixture.
  • the cellulose was prepared from corn cob, wood chips, beet pulp and furfural residue. get;
  • the catalyst is a mixture of FeCl 2 , K 3 [Fe(CN) 6 ] (weight ratio of the two catalysts is 1:1), the weight ratio of the catalyst to the first mixture is 1:1.2;
  • the reaction was carried out under hydrothermal conditions of 170 ° C for 5 hours to form a synthetic material
  • the temperature of the composite was dried at 100 ° C, and the water content was 9.3%.
  • the gradient heating was carried out under a protective atmosphere of argon. The gradient heating was: 350 ° C for 2.5 h, 700 ° C for 2 h, 800 ° C for 2.5 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with sulfuric acid having a concentration of 3% for 5 hours at a temperature of 60 ° C, then washed with water to neutrality, and then dried at 80 ° C to obtain a graphene material.
  • the obtained graphene material was scanned by an electron microscope, and the results are shown in Fig. 2. It can be seen from Fig. 2 that the carbon microsphere structure in the obtained graphene material is attached to the graphene sheet structure, and some are embedded in it, and are integrated.
  • the specific surface area of graphene was determined to be 600 m 2 /g, and the zeta potential was -27 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Glucose (1 kg), maltose (1 kg), sucrose (1 kg), fructose (1 kg) and cellulose having a purity of 95% or more are mixed at a weight ratio of 1:5 to obtain a first mixture, and the cellulose is composed of corn cob and sorghum. Preparation of rods, cornstalks, cotton rods, and wood chips;
  • the catalyst is a mixture of FeCl 2 , K 3 [Fe(CN) 6 ], NiCl 2 (the weight ratio of the three catalysts is 1:1:1), the weight ratio of the catalyst to the first mixture is 1:1;
  • the reaction was carried out under hydrothermal conditions of 170 ° C for 8 hours to form a synthetic material
  • the carbonized material is first washed with a 10% hydrochloric acid at a temperature of 80 ° C for 5 h, then washed with water until neutral, and then dried at 110 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 700 m 2 /g and a zeta potential of -25 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Corn starch (1 kg), potato starch (1 kg), maltose (1 kg), sucrose (1 kg), fructose (1 kg) and cellulose having a purity of 95% or more are mixed at a weight ratio of 1:7 to obtain a first mixture;
  • Cellulose is prepared from high mast, furfural residue and reed;
  • the catalyst is NiCl 2 , the weight ratio of the catalyst to the first mixture is 1:1.2;
  • the reaction was carried out under hydrothermal conditions of 160 ° C for 8 hours to form a synthetic material
  • the temperature of the composite material is dried at 100 ° C, and the water content is 9.2%.
  • the gradient heating is carried out under a protective atmosphere of hydrogen.
  • the gradient heating is: 400 ° C for 3 h, 700 ° C for 2 h, 1000 ° C for 2 h, after carbonization. Cooling to obtain a carbonized material;
  • the carbonized material was first washed with a mass concentration of 3% phosphoric acid at a temperature of 80 ° C for 5 h, then washed with water until neutral, and then dried at 110 ° C to obtain the graphene material.
  • the specific surface area of graphene was determined to be 750 m 2 /g, and the zeta potential was -23 mV.
  • a method for preparing a graphene material comprising the steps of:
  • cellulose is prepared from corn cob, cotton rod, wood chips, beet pulp, furfural residue;
  • the catalyst is a mixture of K 3 [Fe(CN) 6 ] and NiCl 2 (the weight ratio of the two catalysts is 1:1.5), the weight ratio of the catalyst to the first mixture is 1:1;
  • the reaction was carried out under hydrothermal conditions at 180 ° C for 6 hours to form a synthetic material
  • the temperature of the composite was dried at 100 ° C, and the water content was 9.8%.
  • the gradient heating was carried out under a protective atmosphere of nitrogen. The gradient heating was: 450 ° C for 2.5 h, 700 ° C for 1.5 h, 900 ° C for 1.5 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a hydrochloric acid having a concentration of 5% at a temperature of 50 ° C for 6 hours, then washed with water until neutral, and then dried at 80 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 800 m 2 /g and a zeta potential of -20 mV.
  • a method for preparing a graphene material comprising the steps of:
  • the tapioca starch (2 kg) and the cellulose having a purity of 95% or more are mixed at a weight ratio of 1:3 to obtain a first mixture; the cellulose is prepared from cotton stalks, wood chips, and furfural slag;
  • the catalyst is a mixture of K 3 [Fe(CN) 6 ] and NiCl 2 (the weight ratio of the two catalysts is 2:1), the weight ratio of the catalyst to the first mixture is 1:1;
  • the reaction was carried out under hydrothermal conditions at 180 ° C for 5 hours to form a synthetic material
  • the temperature of the composite material is dried at 100 ° C, and the water content is 10% or less, and the temperature is increased by carbonization under a protective atmosphere of nitrogen.
  • the gradient temperature is 350 ° C for 3 h, 700 ° C for 2.5 h, and 1000 ° C for 2 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with sulfuric acid having a concentration of 7% at a temperature of 50 ° C for 6 hours, then washed with water to neutrality, and then dried at 80 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 400 m 2 /g and a zeta potential of -25 mV.
  • a method for preparing a graphene material comprising the steps of:
  • the catalyst is K 4 [Fe(CN) 6 ], the weight ratio of the catalyst to the first mixture is 1:1.8;
  • the reaction was carried out under hydrothermal conditions at 200 ° C for 2 hours to form a synthetic material
  • the composite was dried at a temperature of 110 ° C to a water content of 9.5%, and subjected to a gradient heating carbonization under a protective atmosphere of nitrogen.
  • the gradient heating was: 250 ° C for 3.5 h, 550 ° C for 2.5 h, 800 ° C for 2.5. h, after carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a hydrochloric acid having a mass concentration of 7% at a temperature of 50 ° C for 7 hours, then washed with water until neutral, and then dried at 70 ° C to obtain a graphene material.
  • the specific surface area of the graphene material was determined to be 552 m 2 /g, and the zeta potential was -32 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Glucose (2kg) and cellulose having a purity of 95% or more are mixed at a weight ratio of 1:2.5 to obtain a first mixture, and the cellulose is prepared from corn cob, beet pulp and furfural slag as raw materials;
  • the catalyst is FeCl 3 , the weight ratio of the catalyst to the first mixture is 1:0.8;
  • the reaction was carried out under hydrothermal conditions at 180 ° C for 7 hours to form a synthetic material
  • the composite was dried at a temperature of 100 ° C to a water content of 9.5%, and subjected to a gradient heating carbonization under a protective atmosphere of argon.
  • the gradient heating was: 300 ° C for 3 h, 600 ° C for 2 h, 900 ° C for 2 h, After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a hydrochloric acid having a concentration of 8% at a temperature of 40 ° C for 6 hours, then washed with water until neutral, and then dried at 100 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 581 m 2 /g and a zeta potential of -30 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Corn starch (2kg) and glucose (1kg) were mixed with cellulose having a purity of 95% or more at a weight ratio of 1:2 to obtain a first mixture.
  • the cellulose was prepared from high stalks, corn stalks, cotton stalks, wood chips and reeds. get;
  • the catalyst is NiCl 2 , the weight ratio of the catalyst to the first mixture is 1:1.5;
  • the reaction was carried out under hydrothermal conditions at 190 ° C for 6 hours to form a synthetic material
  • the temperature of the composite material was dried at 80 ° C, and the water content was 9.7%.
  • the gradient temperature was carbonized under a protective atmosphere of nitrogen.
  • the gradient heating was 350 ° C for 3 h, 70 ° C for 1.5 h, 950 ° C for 1.5 h, carbonization. After cooling to obtain a carbonized material;
  • the carbonized material is first washed with sulfuric acid having a concentration of 5% at a temperature of 60 ° C for 6 hours, then washed with water until neutral, and then dried at 90 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 624 m 2 /g and a zeta potential of -29 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Sucrose (2kg) and fructose (1kg) are mixed with cellulose having a purity of 95% or more at a weight ratio of 1:1.5 to obtain a first mixture, and the cellulose is prepared from corn cob, wood chips, beet pulp, and furfural residue;
  • the catalyst is added, and the catalyst is a mixture of K 3 [Fe(CN) 6 ] and K 4 [Fe(CN) 6 ] (the weight ratio of the two catalysts is 1:1), and the weight ratio of the catalyst to the first mixture is 1: 1.1;
  • the reaction was carried out under hydrothermal conditions of 200 ° C for 5 hours to form a synthetic material
  • the temperature of the composite is dried at 100 ° C, and the water content is 9.3%.
  • the gradient heating is carried out under a protective atmosphere of argon. The gradient heating is: 450 ° C for 2.5 h, 800 ° C for 1.5 h, 1000 ° C for 1.5. h, after carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a phosphoric acid having a concentration of 7% for 5 hours at a temperature of 70 ° C, then washed with water until neutral, and then dried at 100 ° C to obtain a graphene material.
  • the specific surface area of graphene was determined to be 575 m 2 /g, and the zeta potential was -34 mV.
  • oxidized crosslinked starch is placed in a tube furnace under the protection of an inert gas (nitrogen) at 500 ° C for heat treatment, and is kept at 500 ° C for 4 h. After completion of the reaction, the mixture was washed 6 times with hydrochloric acid and water, respectively, and filtered, and the obtained black powder was dried in a blast oven.
  • an inert gas nitrogen
  • a method for preparing a graphene material comprising the steps of:
  • Corn starch (2kg) and cellulose having a purity of 95% or more are mixed at a weight ratio of 1:20 to obtain a first mixture, and the cellulose is made of a high mast, a corn stalk, and a cotton stalk;
  • the catalyst is NiCl 2 , the weight ratio of the catalyst to the first mixture is 1:1.2;
  • the reaction was carried out under hydrothermal conditions of 200 ° C for 3 hours to form a synthetic material
  • the composite was dried at a temperature of 100 ° C to a water content of 9.5%, and subjected to a gradient heating carbonization under a protective atmosphere of nitrogen.
  • the gradient heating was: 250 ° C for 3.5 h, 550 ° C for 2 h, 900 ° C for 1.5 h.
  • the carbonized material is first washed with a concentration of 3% hydrochloric acid at a temperature of 80 ° C for 5 h, then washed with water until neutral, and then dried at 100 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 180 m 2 /g and a zeta potential of -17 mV.
  • a method for preparing a graphene material comprising the steps of:
  • the reaction was carried out under hydrothermal conditions at 165 ° C for 8 hours to form a synthetic material
  • the composite is dried at a temperature of 80 ° C to a water content of 9.2% or less, and subjected to a gradient heating carbonization under a protective atmosphere of argon gas.
  • the gradient temperature is: 300 ° C for 2.5 h, 600 ° C Insulation for 2h, 800 ° C for 2h, carbonization and cooling to obtain carbonized materials;
  • the carbonized material is first washed with sulfuric acid having a mass concentration of 10% at a temperature of 30 ° C for 8 hours, then washed with water until neutral, and then dried at 70 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 174 m 2 /g and a zeta potential of -15 mV.
  • a method for preparing a graphene material comprising the steps of:
  • Glucose (2 kg) and cellulose having a purity of 95% or more are mixed at a weight ratio of 1:3 to obtain a first mixture, and the cellulose is prepared from a high mast, a corn stalk, a cotton stalk, wood chips, and reed;
  • the catalyst is FeCl 3 , the weight ratio of the catalyst to the first mixture is 1:1;
  • the reaction was carried out under hydrothermal conditions at 130 ° C for 8 hours to form a synthetic material
  • the temperature of the composite material was dried at 110 ° C, and the water content was 9.7%.
  • the gradient temperature was carbonized under a protective atmosphere of nitrogen.
  • the gradient temperature was 350 ° C for 3.5 h, 600 ° C for 2.5 h, and 1000 ° C for 1.5 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with a mass concentration of 10% phosphoric acid at a temperature of 50 ° C for 6 h, then washed with water until neutral, and then dried at 110 ° C to obtain a graphene material.
  • the graphene material was determined to have a specific surface area of 186 m 2 /g and a zeta potential of -14 mV.
  • a method for preparing a graphene material comprising the steps of:
  • the tapioca starch (2kg) and the cellulose having a purity of 95% or more are mixed at a weight ratio of 1:2 to obtain a first mixture; the cellulose is prepared from a high mast, a furfural residue, and a reed;
  • the catalyst is K 3 [Fe(CN) 6 ], the weight ratio of the catalyst to the first mixture is 1:1.1;
  • the reaction was carried out under 185 ° C hydrothermal conditions for 6 hours to form a synthetic material
  • the temperature of the composite material was dried at 100 ° C, and the water content was 9.2%.
  • the gradient temperature was carbonized under a protective atmosphere of nitrogen.
  • the gradient heating was: 200 ° C for 2 h, 400 ° C for 1.5 h. Heated at 600 ° C for 2.5 h, carbonized and cooled to obtain a carbonized material;
  • the carbonized material was first washed with a phosphoric acid having a concentration of 3% for 5 hours at a temperature of 80 ° C, then washed with water until neutral, and then dried at 80 ° C to obtain the graphene material.
  • the graphene had a specific surface area of 170 m 2 /g and a zeta potential of -10 mV.
  • a method for preparing a graphene material comprising the steps of:
  • the tapioca starch (1 kg) and the fructose (1 kg) are mixed with the cellulose having a purity of 95% or more at a weight ratio of 1:1.5 to obtain a first mixture, and the cellulose is prepared from corn cob, wood chips, beet pulp, and furfural residue;
  • the catalyst is NiCl 2 , the weight ratio of the catalyst to the first mixture is 1:1;
  • the reaction was carried out under 175 ° C hydrothermal conditions for 6.5 hours to form a synthetic material
  • the temperature of the composite was dried at 100 ° C, and the water content was 9.3%.
  • the gradient heating was carried out under a protective atmosphere of argon. The gradient heating was: 350 ° C for 2.5 h, 700 ° C for 2 h, 800 ° C for 2.5 h. After carbonization, cooling to obtain a carbonized material;
  • the carbonized material is first washed with hydrochloric acid having a concentration of 0.5% at a temperature of 25 ° C for 7 hours, then washed with water until neutral, and then dried at 110 ° C to obtain a graphene material.
  • the graphene had a specific surface area of 178 m 2 /g and a zeta potential of -13 mV.
  • the graphene material prepared according to the method disclosed by the present invention has a high specific surface area, and also has good activity, good water solubility, easy dispersion, and difficulty in agglomeration.
  • the weight ratio of the first substance to the cellulose, the catalyst and the cellulose and the first Total weight of matter are determined by the weight ratio, the hydrothermal conditions, the gradient heating carbonization conditions, and the concentration of the acid used in the pickling process falling within the preferred conditions described herein. The higher value indicates that the graphene prepared under the preferred conditions of the present invention has better dispersion properties.
  • the method for preparing graphene material by using biomass as raw material has simple process, low cost, high output, strong production safety, controllable quality, green environmental protection, and the preparation scale has reached kilogram level, and industrialization can be realized. produce.

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Abstract

一种石墨烯材料及其制备方法，制备方法包括以下步骤：将第一物质与纤维素混合，加入催化剂，在水热条件下反应形成合成料，第一物质为淀粉、淀粉糖中的任一种或两种；将合成料干燥至含水量为10％以下，在保护性气氛下梯度升温碳化，得到碳化料；碳化料洗涤，得到所述石墨烯材料。这种石墨烯材料性能稳定，具有良好的比表面积，分散性能好。

Description

一种石墨烯材料及其制备方法
本申请要求于2016年5月4日提交中国知识产权局、申请号为CN201610288888.2、名称为“一种石墨烯材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及石墨烯制备领域，具体而言，涉及一种石墨烯材料及其制备方法。
背景技术
石墨烯作为一种新型碳材料备受关注，它具有极高的比表面积，是目前发现的最薄、强度最大、导电导热性能最好的材料。目前合成石墨烯的方法主要有三种：化学气相沉积法(CVD)、溶剂剥离法和氧化-还原法。CVD法是将含有碳源的气体引入高温真空反应室内，使碳源在高温下裂解，在金属底座(镍、铜等)上大面积生长石墨烯的方法。这种方法所需反应条件苛刻，对设备的要求较高，且生产周期长不利于产业化。溶剂剥离法是将石墨颗粒分散在有机溶剂中，利用超声等方法使溶剂分子对石墨插层，实现对石墨的剥离得到石墨烯。这种方法生产的石墨烯尺寸不可控，且产率较低，限制了工业上的应用。氧化-还原法是将鳞片石墨氧化，再通过化学还原的方法去除含氧基团，最后得到石墨烯。这种方法需要大量的强氧化剂(浓硫酸、高锰酸钾等)，有较高的危险性，并且对环境造成了很大的压力，不利于产业化。
中国专利公开号CN103787321A公开了“一种自支撑石墨烯材料及其制备方法”，该石墨烯材料由生长在基体上的石墨烯形成三维自支撑结构，其制备方法是将淀粉热处理，洗涤，过滤干燥；再将干燥后的产物与碱混合，在无氧条件下烧结处理后，洗涤，烘干，得到自支撑石墨烯,但该方法 石墨烯的制备规模仅在克级别。
中国专利公开号CN104724699A公开了“纤维素为原料制备生物质石墨烯的方法”，其具体制备方法为：步骤一：催化剂溶液的配制；步骤二：纤维素与催化剂离子配位、高温脱氧，得到前驱体；步骤三：热处理；步骤四：酸处理、干燥；即得到石墨烯。该方法制备的石墨烯形貌均一，具有单层或多层二维层状结构，尺寸为0.5～2μm，导电性为25000～45000S/m，但该方法石墨烯的制备规模仅在克级别。
现有技术只是一味地突出强调制备缺陷少的石墨烯，或者说性能好的石墨烯，但是都忽略了如何才能大规模应用。
发明内容
本发明在克服目前各种生产石墨烯方法的缺点的基础上，生产出高质量的石墨烯。本发明提出了利用玉米淀粉等生物质为原料制备石墨烯的方法。本方法原料安全环保，制备工艺简单，产品可控质量稳定，生产周期短产量高，能够实现产业化。淀粉是自然界丰富的糖类资源,属可再生和生物降解的天然资源。各类农作物淀粉来源丰富,同时农副产品加工过程中产生大量淀粉含量很高的废弃物(如玉米加工、大米加工、薯类加工等过程),目前我国玉米库存积压很重，玉米价格下跌，如何有效开发和利用淀粉始终是一个热门话题。以玉米淀粉为原料制备石墨烯的方法，工艺简单、成本低、产量高、生产安全性强、质量可控，可以实现工业化生产，并且大量消化玉米，能够给国家财政减轻负担，又能帮助农民增收，一举多得。
本发明的第一目的在于一种石墨烯材料的制备方法，该方法通过以纤维素与淀粉类物质混合进行制备石墨烯材料，得到的石墨烯材料性能稳定，具有良好的比表面积，且分散性好，能够实现大规模应用。
本发明的第二目的在于提供所述的制备方法制得的石墨烯材料。
为了实现本发明的上述目的，特采用以下技术方案：
一种石墨烯材料的制备方法，包括以下步骤：
(a)、将第一物质与纤维素混合，加入催化剂，在水热条件下反应形成合成料，所述第一物质为淀粉、淀粉糖中的任一种或两种；
(b)、将所述合成料干燥至含水量为10％以下，在保护性气氛下梯度升温碳化，得到碳化料；
(c)、所述碳化料洗涤，得到所述石墨烯材料。
本发明以纤维素为骨架，在纤维素碳化形成石墨烯结构的同时，淀粉和/或淀粉糖在纤维素骨架上同时进行碳化，形成类石墨烯结构和碳微球结构并附着于石墨烯结构表面或部分嵌入内部，得到石墨烯材料，该石墨烯材料兼具了石墨烯结构，并且具有较高的比表面积，并且还具有很好的活性，水溶性好，易于分散，不易团聚。为了使纤维素与淀粉或其糖复合制得的石墨烯性能更为稳定和优良，优选地，在步骤(a)中，所述纤维素的纯度为95％以上。
农林废弃物是废弃物的重要成员，是一种重要的生物质资源，为了将农林废弃物变废为宝，优选地，所述纤维素由农林废弃物制备得到。制备方法根据现有的技术制备即可。
经验证，采用以下农林废弃物制得的纤维素与第一物质在催化剂的条件下，能更好的反应，最终制得的石墨烯性能优良。具体地，所述纤维素由玉米芯、高粱杆、玉米杆、棉花杆、木屑、甜菜渣、糠醛渣、芦苇中的任一种或几种制备得到。纤维素的制备方法采用现有的技术制备即可。
进一步地，在步骤(a)中，所述淀粉包括玉米淀粉、马铃薯淀粉、木薯淀粉中的任一种或多种。
进一步地，所述淀粉糖包括葡萄糖、麦芽糖、蔗糖、果糖中的任一种或多种。
经验证，采用以下配比的第一物质与纤维素进行反应，形成的合成料 制得的石墨烯性能更为优良，优选地，在步骤(a)中，所述第一物质与所述纤维素以重量比为1:0.1-1:10，优选为1:1-1:5混合。
更优选地，所述第一物质与所述纤维素以重量比为1:1-1:3混合。
为了使淀粉和/或其糖与纤维素更好的复合，增加形成的合成料的性能，进一步地，在步骤(a)中，所述催化剂为FeCl2、FeCl3、K3[Fe(CN)6]、K4[Fe(CN)6]、NiCl2中的任一种或几种的混合物；
所述催化剂与所述纤维素和所述第一物质总重量的重量比为1:0.5-1:2。如催化剂与纤维素和第一物质总重量的重量比可以为1:0.5、1:0.6、1:0.8、1:1、1:1.2、1:1.5、1:1.8、1:2等等。
优选地，所述催化剂与所述纤维素和所述第一物质总重量的重量比为1:0.5-1:1.5，更优选为1:1.0-1:1.2。
优选地，步骤(a)中，水热条件为160-200℃反应2-10h，为了达到更好的合成效果，优选地，在步骤(a)中，在160-200℃水热条件下反应5-8小时，形成合成料。如在一些实施例中，在160℃水热条件下反应8小时，形成合成料；在一些实施例中，在180℃水热条件下反应7小时，形成合成料；在一些实施例中，在190℃水热条件下反应6小时，形成合成料；在一些实施例中，在200℃水热条件下反应5小时，形成合成料，等等。
优选地，在步骤(b)中，所述干燥采用的温度为80-120℃；该温度条件下能进一步稳定合成料的结构。
优选地，所述保护性气氛所用的气体为氮气、氩气以及氢气中的任一种。所用的保护性气氛中不含有其他气体。
洗涤主要是为了去除金属杂质，并将其他残余物清除干净，减少石墨烯材料杂质，优选地，在步骤(c)中，所述洗涤包括以下步骤：
先在30-80℃的温度下进行酸洗5-8h,然后水洗至中性，再在 70-110℃下烘干即得所述石墨烯材料；
所述酸洗采用的酸为：质量浓度均为3％-10％的盐酸、硫酸以及磷酸中的任一种。也就是说，酸洗采用的酸可以为质量浓度为3％-10％的盐酸，也可以为质量浓度为3％-10％的硫酸，也可以为质量浓度为3％-10％的磷酸。其中，质量浓度是指各种酸用水稀释后，酸在总液体中的质量浓度。
如酸洗采用的酸可以为质量浓度为3％的盐酸，可以为质量浓度为5％的盐酸，质量浓度为7％的盐酸，质量浓度为8％的盐酸，质量浓度为10％的盐酸等等；同样地，酸洗采用的酸可以为质量浓度为3％的硫酸，可以为质量浓度为5％的硫酸，质量浓度为7％的硫酸，质量浓度为8％的硫酸，质量浓度为10％的硫酸等等；同样地，酸洗采用的酸可以为质量浓度为3％的磷酸，可以为质量浓度为5％的磷酸，质量浓度为7％的磷酸，质量浓度为8％的磷酸，质量浓度为10％的磷酸等等。
经验证，上述种类的酸洗涤效果好。
为了制得的石墨烯材料性能稳定，分散效果好，优选地，在步骤(b)中，梯度升温碳化为：250℃-450℃保温2.5-3.5h，550℃-800℃保温1.5-2.5h，800℃-1000℃保温1.5-2.5h。
如在一些实施例中，梯度升温碳化为：250℃保温3.5h，550℃保温2.5h，800℃保温2.5h；在一些实施例中，梯度升温碳化为：300℃保温3h，600℃保温2h，900℃保温2h；在一些实施例中，梯度升温碳化为：350℃保温3h，700℃保温1.5h，950℃保温1.5h；在一些实施例中450℃保温2.5h，800℃保温1.5h，1000℃保温1.5h，等等。
本发明中，淀粉和/或其糖与纤维素即可以为淀粉与纤维素混合，也可以为淀粉和淀粉糖与纤维素混合，也可以为淀粉糖与纤维素混合。
本发明提供的石墨烯材料分散性能优良，其中分散性能可以用Zeta电 位来进行表征，它是表征胶体分散系稳定性的重要指标。一般来说，Zeta电位的绝对值越大，其分散性能越稳定。本发明制备的石墨烯材料其Zeta电位的绝对值均在20mV以上。
与现有技术相比，本发明的有益效果为：
(1)本发明以纤维素为骨架，在纤维素碳化形成石墨烯结构的同时，淀粉和/或淀粉糖在纤维素骨架上同时进行碳化，形成类石墨烯结构和碳微球结构并附着于石墨烯结构表面或部分嵌入内部，得到石墨烯材料，该石墨烯材料兼具了石墨烯结构，并且具有较高的比表面积，并且还具有很好的活性，水溶性好，易于分散，不易团聚。
(2)本发明还限定了各原料的种类以及添加比例，还进一步限定了各步骤的反应条件以及后续洗涤的过程，以使制得的石墨烯材料性能稳定。
(3)本发明制备得到的石墨烯材料，具有单层或者多层(可达十几层)的二维片状结构，比表面积在200m2/g以上，Zeta电位的绝对值均在20mV以上。
(4)本发明所述的以生物质为原料制备石墨烯材料的方法，工艺简单、成本低、产量高、生产安全性强、质量可控、绿色环保，并且该制备规模已达到千克级别，可以实现工业化生产。
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，以下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。
图1为本发明实施例3石墨烯材料的SEM图；
图2为本发明实施例4石墨烯材料的SEM图。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明 的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
一种石墨烯材料的制备方法，包括以下步骤：
将玉米淀粉(2kg)与纯度为95％以上的纤维素以重量比为1:0.1混合，得到第一混合物，纤维素由高粱杆、玉米杆、棉花杆为原料制成；
加入催化剂，催化剂为FeCl2，催化剂与第一混合物的重量比为1:0.5；
在200℃水热条件下反应3小时，形成合成料；
将合成料在温度为120℃条件下干燥，至含水量为9.5％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为：250℃保温3.5h，550℃保温2h，900℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在80℃的温度下用质量浓度为3％的盐酸洗5h,然后水洗至中性，再在100℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为200m2/g，Zeta电位-50mV。
实施例2
一种石墨烯材料的制备方法，包括以下步骤：
将麦芽糖(2kg)与纯度为95％以上的纤维素以重量比为1:0.5混合，得到第一混合物；纤维素由玉米芯、甜菜渣、糠醛渣制备得到；
加入催化剂K3[Fe(CN)6]，催化剂与第一混合物的重量比为1:2；
在160℃水热条件下反应10小时，形成合成料；
将合成料在温度为80℃条件下干燥，至含水量为9.2％以下，在保护性气氛氩气条件下进行梯度升温碳化，梯度升温为：300℃保温2.5h，600℃ 保温2h，800℃保温2h，碳化后冷却得到碳化料；
碳化料先在30℃的温度下用质量浓度为10％的硫酸洗8h,然后水洗至中性，再在70℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为250m2/g，Zeta电位-45mV。
实施例3
一种石墨烯材料的制备方法，包括以下步骤：
将淀粉(2kg)和淀粉糖(2kg)与纯度为95％以上的纤维素以重量比为1:1混合，得到第一混合物，淀粉为马铃薯淀粉(1kg)和木薯淀粉(1kg)的混合物，淀粉糖为葡萄糖(1kg)和蔗糖(1kg)的混合物，纤维素由高粱杆、玉米杆、棉花杆、木屑和芦苇制备得到；
加入催化剂，催化剂为FeCl3、K4[Fe(CN)6]、NiCl2(三种催化剂的重量比为1:1:1)的混合物，催化剂与第一混合物的重量比为1:1；
在180℃水热条件下反应6小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.7％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为350℃保温3.5h，600℃保温2.5h，1000℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在50℃的温度下用质量浓度为10％的磷酸洗6h,然后水洗至中性，再在110℃下烘干即得石墨烯材料。
将制得的石墨烯材料采用电子显微镜扫描，结果如图1所示。从图1可以看出，制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为500m2/g，Zeta电位-30mV。
实施例4
一种石墨烯材料的制备方法，包括以下步骤：
将玉米淀粉(1.5kg)、马铃薯淀粉(1kg)与纯度为95％以上的纤维素以重量比为1:3混合，得到第一混合物，纤维素由玉米芯、木屑、甜菜渣、糠醛渣制备得到；
加入催化剂，催化剂为FeCl2、K3[Fe(CN)6](两种催化剂的重量比为1:1)的混合物，催化剂与第一混合物的重量比为1:1.2；
在170℃水热条件下反应5小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.3％，在保护性气氛氩气下进行梯度升温碳化，梯度升温为：350℃保温2.5h，700℃保温2h，800℃保温2.5h，碳化后冷却得到碳化料；
碳化料先在60℃的温度下用质量浓度为3％的硫酸洗5h,然后水洗至中性，再在80℃下烘干即得石墨烯材料。
将制得的石墨烯材料采用电子显微镜扫描，结果如图2所示。从图2可以看出，制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯的比表面积为600m2/g，Zeta电位-27mV。
实施例5
一种石墨烯材料的制备方法，包括以下步骤：
将葡萄糖(1kg)、麦芽糖(1kg)、蔗糖(1kg)、果糖(1kg)与纯度为95％以上的纤维素以重量比为1:5混合，得到第一混合物，纤维素由玉米芯、高粱杆、玉米杆、棉花杆、木屑制备得到；
加入催化剂，催化剂为FeCl2、K3[Fe(CN)6]、NiCl2(三种催化剂的重量比为1:1:1)的混合物，催化剂与第一混合物的重量比为1:1；
在170℃水热条件下反应8小时，形成合成料；
将合成料温度为120℃条件下干燥，至含水量为9.5％，在保护性气 氛氢气下进行梯度升温碳化，梯度升温为：400℃保温3h，700℃保温2h，900℃保温2h，碳化后冷却得到碳化料；
碳化料先在80℃的温度下用质量浓度为10％的盐酸洗5h,然后水洗至中性，再在110℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为700m2/g，Zeta电位-25mV。
实施例6
一种石墨烯材料的制备方法，包括以下步骤：
将玉米淀粉(1kg)、马铃薯淀粉(1kg)、麦芽糖(1kg)、蔗糖(1kg)、果糖(1kg)与纯度为95％以上的纤维素以重量比为1:7混合，得到第一混合物；纤维素由高粱杆、糠醛渣、芦苇制备得到；
加入催化剂，催化剂为NiCl2，催化剂与第一混合物的重量比为1:1.2；
在160℃水热条件下反应8小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.2％，在保护性气氛氢气下进行梯度升温碳化，梯度升温为：400℃保温3h，700℃保温2h，1000℃保温2h，碳化后冷却得到碳化料；
碳化料先在80℃的温度下用质量浓度为3％的磷酸洗5h,然后水洗至中性，再在110℃下烘干即得所述石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯的比表面积为750m2/g，Zeta电位-23mV。
实施例7
一种石墨烯材料的制备方法，包括以下步骤：
将玉米淀粉(1kg)、果糖(1kg)与纯度为95％以上的纤维素以重量比 为1:10混合，得到第一混合物；纤维素由玉米芯、棉花杆、木屑、甜菜渣、糠醛渣制备得到；
加入催化剂，催化剂为K3[Fe(CN)6]和NiCl2(两种催化剂的重量比为1:1.5)的混合物，催化剂与第一混合物的重量比为1:1；
在180℃水热条件下反应6小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.8％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为：450℃保温2.5h，700℃保温1.5h，900℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在50℃的温度下用质量浓度为5％的盐酸洗6h,然后水洗至中性，再在80℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为800m2/g，Zeta电位-20mV。
实施例8
一种石墨烯材料的制备方法，包括以下步骤：
将木薯淀粉(2kg)与纯度为95％以上的纤维素以重量比为1:3混合，得到第一混合物；纤维素由棉花杆、木屑、糠醛渣制备得到；
加入催化剂，催化剂为K3[Fe(CN)6]和NiCl2(两种催化剂的重量比为2:1)的混合物，催化剂与第一混合物的重量比为1:1；
在180℃水热条件下反应5小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为10％以下，在保护性气氛氮气下进行梯度升温碳化，梯度升温为：350℃保温3h，700℃保温2.5h，1000℃保温2h，碳化后冷却得到碳化料；
碳化料先在50℃的温度下用质量浓度为7％的硫酸洗6h,然后水洗至中性，再在80℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为400m2/g，Zeta电位-25mV。
实施例9
一种石墨烯材料的制备方法，包括以下步骤：
将马铃薯淀粉(2kg)和果糖(2kg)与纯度为95％以上的纤维素以重量比为1:5混合，得到第一混合物，纤维素由高粱杆、玉米杆、棉花杆为原料制成；
加入催化剂，催化剂为K4[Fe(CN)6]，催化剂与第一混合物的重量比为1:1.8；
在200℃水热条件下反应2小时，形成合成料；
将合成料在温度为110℃条件下干燥，至含水量为9.5％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为：250℃保温3.5h，550℃保温2.5h，800℃保温2.5h，碳化后冷却得到碳化料；
碳化料先在50℃的温度下用质量浓度为7％的盐酸洗7h,然后水洗至中性，再在70℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为552m2/g，Zeta电位-32mV。
实施例10
一种石墨烯材料的制备方法，包括以下步骤：
将葡萄糖(2kg)与纯度为95％以上的纤维素以重量比为1:2.5混合，得到第一混合物，纤维素由玉米芯、甜菜渣、糠醛渣为原料制成；
加入催化剂，催化剂为FeCl3，催化剂与第一混合物的重量比为1:0.8；
在180℃水热条件下反应7小时，形成合成料；
将合成料在温度为100℃条件下干燥，至含水量为9.5％，在保护性气氛氩气下进行梯度升温碳化，梯度升温为：300℃保温3h，600℃保温2h，900℃保温2h，碳化后冷却得到碳化料；
碳化料先在40℃的温度下用质量浓度为8％的盐酸洗6h,然后水洗至中性，再在100℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为581m2/g，Zeta电位-30mV。
实施例11
一种石墨烯材料的制备方法，包括以下步骤：
将玉米淀粉(2kg)和葡萄糖(1kg)与纯度为95％以上的纤维素以重量比为1:2混合，得到第一混合物，纤维素由高粱杆、玉米杆、棉花杆、木屑和芦苇制备得到；
加入催化剂，催化剂为NiCl2，催化剂与第一混合物的重量比为1:1.5；
在190℃水热条件下反应6小时，形成合成料；
将合成料温度为80℃条件下干燥，至含水量为9.7％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为350℃保温3h，70℃保温1.5h，950℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在60℃的温度下用质量浓度为5％的硫酸洗6h,然后水洗至中性，再在90℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯材料的比表面积为624m2/g，Zeta电位-29mV。
实施例12
一种石墨烯材料的制备方法，包括以下步骤：
将蔗糖(2kg)和果糖(1kg)与纯度为95％以上的纤维素以重量比为1:1.5混合，得到第一混合物，纤维素由玉米芯、木屑、甜菜渣、糠醛渣制备得到；
加入催化剂，催化剂为K3[Fe(CN)6]和K4[Fe(CN)6](两种催化剂的重量比为1:1)的混合物，催化剂与第一混合物的重量比为1:1.1；
在200℃水热条件下反应5小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.3％，在保护性气氛氩气下进行梯度升温碳化，梯度升温为：450℃保温2.5h，800℃保温1.5h，1000℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在70℃的温度下用质量浓度为7％的磷酸洗5h,然后水洗至中性，再在100℃下烘干即得石墨烯材料。
采用电子显微镜扫描，可以看到制得的石墨烯材料中碳微球结构附着于石墨烯片层结构上，有的镶嵌于其中，浑然一体。
经测定，石墨烯的比表面积为575m2/g，Zeta电位-34mV。
对比实施例1
根据申请号为CN201410029985.0公开的一种自支撑石墨烯材料及其制备方法，将5g的氧化交联淀粉放入管式炉中惰性气体(氮气)保护下500℃热处理，在500℃保温4h，反应完全后，将混合物分别用盐酸与水洗涤6次并过滤，所得到的黑色粉末于鼓风烘箱中干燥。
将1g干燥后的产物和5g氢氧化铁加适量水混合均匀，用惰性气体保护/掩埋下950℃烧结、保温0.5h处理，烧结结束后自然冷却至室温，将所得黑色粉末分别用盐酸与水洗涤5次，在鼓风干燥箱中干燥得到即得到自支撑石墨烯材料。经测定，由此制备得到的石墨烯的比表面积为600m2/g，Zeta电位-5mV。
对比实施例2
根据申请号为CN201410781644.9公开的石墨烯的制备方法，将1g硫酸铁和10g氯化钠溶于500ml去离子水中，将10g纤维素接枝丙烯腈水解产物与上述溶液混合后，与50g氢氧化钾混合，在氮气气氛下，900℃处理10h，然后将产物依次用稀盐酸和去离子水清洗后烘干，得到石墨烯。经测定，由此制备得到的石墨烯的比表面积为500m2/g，Zeta电位-10mV。
对比实施例3
一种石墨烯材料的制备方法，包括以下步骤：
将玉米淀粉(2kg)与纯度为95％以上的纤维素以重量比为1:20混合，得到第一混合物，纤维素由高粱杆、玉米杆、棉花杆为原料制成；
加入催化剂，催化剂为NiCl2，催化剂与第一混合物的重量比为1:1.2；
在200℃水热条件下反应3小时，形成合成料；
将合成料在温度为100℃条件下干燥，至含水量为9.5％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为：250℃保温3.5h，550℃保温2h，900℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在80℃的温度下用质量浓度为3％的盐酸洗5h,然后水洗至中性，再在100℃下烘干即得石墨烯材料。
经测定，石墨烯材料的比表面积为180m2/g，Zeta电位-17mV。
对比实施例4
一种石墨烯材料的制备方法，包括以下步骤：
将马铃薯淀粉(2kg)与纯度为95％以上的纤维素以重量比为1:2.5混合，得到第一混合物；纤维素由玉米芯、甜菜渣、糠醛渣制备得到；
加入催化剂K4[Fe(CN)6]，催化剂与第一混合物的重量比为1:4；
在165℃水热条件下反应8小时，形成合成料；
将合成料在温度为80℃条件下干燥，至含水量为9.2％以下，在保护性气氛氩气条件下进行梯度升温碳化，梯度升温为：300℃保温2.5h，600℃ 保温2h，800℃保温2h，碳化后冷却得到碳化料；
碳化料先在30℃的温度下用质量浓度为10％的硫酸洗8h,然后水洗至中性，再在70℃下烘干即得石墨烯材料。
经测定，石墨烯材料的比表面积为174m2/g，Zeta电位-15mV。
对比实施例5
一种石墨烯材料的制备方法，包括以下步骤：
将葡萄糖(2kg)与纯度为95％以上的纤维素以重量比为1:3混合，得到第一混合物，纤维素由高粱杆、玉米杆、棉花杆、木屑和芦苇制备得到；
加入催化剂，催化剂为FeCl3，催化剂与第一混合物的重量比为1:1；
在130℃水热条件下反应8小时，形成合成料；
将合成料温度为110℃条件下干燥，至含水量为9.7％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为350℃保温3.5h，600℃保温2.5h，1000℃保温1.5h，碳化后冷却得到碳化料；
碳化料先在50℃的温度下用质量浓度为10％的磷酸洗6h,然后水洗至中性，再在110℃下烘干即得石墨烯材料。
经测定，石墨烯材料的比表面积为186m2/g，Zeta电位-14mV。
对比实施例6
一种石墨烯材料的制备方法，包括以下步骤：
将木薯淀粉(2kg)与纯度为95％以上的纤维素以重量比为1:2混合，得到第一混合物；纤维素由高粱杆、糠醛渣、芦苇制备得到；
加入催化剂，催化剂为K3[Fe(CN)6]，催化剂与第一混合物的重量比为1:1.1；
在185℃水热条件下反应6小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.2％，在保护性气氛氮气下进行梯度升温碳化，梯度升温为：200℃保温2h，400℃保温1.5h， 600℃保温2.5h，碳化后冷却得到碳化料；
碳化料先在80℃的温度下用质量浓度为3％的磷酸洗5h,然后水洗至中性，再在80℃下烘干即得所述石墨烯材料。
经测定，石墨烯的比表面积为170m2/g，Zeta电位-10mV。
对比实施例7
一种石墨烯材料的制备方法，包括以下步骤：
将木薯淀粉(1kg)和果糖(1kg)与纯度为95％以上的纤维素以重量比为1:1.5混合，得到第一混合物，纤维素由玉米芯、木屑、甜菜渣、糠醛渣制备得到；
加入催化剂，催化剂为NiCl2，催化剂与第一混合物的重量比为1:1；
在175℃水热条件下反应6.5小时，形成合成料；
将合成料温度为100℃条件下干燥，至含水量为9.3％，在保护性气氛氩气下进行梯度升温碳化，梯度升温为：350℃保温2.5h，700℃保温2h，800℃保温2.5h，碳化后冷却得到碳化料；
碳化料先在25℃的温度下用质量浓度为0.5％的盐酸洗7h，然后水洗至中性，再在110℃下烘干即得石墨烯材料。
经测定，石墨烯的比表面积为178m2/g，Zeta电位-13mV。
根据本发明公开的方法所制备的石墨烯材料具有高的比表面积，并且还具有很好的活性，水溶性好，易于分散，不易团聚。
与现有技术专利申请CN201410029985.0(对比实施例1)和CN201410781644.9(对比实施例2)所公开的石墨烯材料制备方法相比，根据本发明公开的制备方法及其优选条件所制备的石墨烯的Zeta电位绝对值显著提高，表明其分散性能显著优于现有技术。与使用本发明所公开的方法并且在非优选条件下制备的石墨烯(对比实施例3-7)相比较可知，当第一物质与纤维素的重量比、催化剂与所述纤维素和第一物质总重 量的重量比、水热条件、梯度升温碳化条件以及在酸洗过程中所使用的酸的浓度落入本发明所述的优选条件范围内时，所制备的石墨烯的比表面积和Zeta电位绝对值更高，表明在本发明的优选条件下制备得到的石墨烯的分散性能更优。
本发明所述的以生物质为原料制备石墨烯材料的方法，工艺简单、成本低、产量高、生产安全性强、质量可控、绿色环保，并且该制备规模已达到千克级别，可以实现工业化生产。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (20)

  1. 一种石墨烯材料的制备方法，其特征在于，包括以下步骤：
    (a)、将第一物质与纤维素混合，加入催化剂，在水热条件下反应形成合成料，所述第一物质为淀粉、淀粉糖中的任一种或两种；
    (b)、将所述合成料干燥至含水量为10％以下，在保护性气氛下梯度升温碳化，得到碳化料；
    (c)、所述碳化料洗涤，得到所述石墨烯材料。
  2. 根据权利要求1所述的制备方法，其特征在于，在步骤(a)中，所述纤维素的纯度为95％以上。
  3. 根据权利要求1或2所述的制备方法，其特征在于，在步骤(a)中，所述纤维素优选由农林废弃物制备得到。
  4. 根据权利要求1-3中任一项所述的制备方法，其特征在于，在步骤(a)中，所述纤维素优选由玉米芯、高粱杆、玉米杆、棉花杆、木屑、甜菜渣、糠醛渣、芦苇中的任一种或几种制备得到。
  5. 根据权利要求1-4中任一项所述的制备方法，其特征在于，在步骤(a)中，所述淀粉包括玉米淀粉、马铃薯淀粉、木薯淀粉中的任一种或多种。
  6. 根据权利要求1-5中任一项所述的制备方法，其特征在于，在步骤(a)中，所述淀粉糖包括葡萄糖、麦芽糖、蔗糖、果糖中的任一种或多种。
  7. 根据权利要求1-6中任一项所述的制备方法，其特征在于，在步骤(a)中，所述第一物质与所述纤维素以重量比为1:0.1-1:10混合。
  8. 根据权利要求1-7中任一项所述的制备方法，其特征在于，在步骤(a)中，所述第一物质与所述纤维素以重量比为1:1-1:5混合。
  9. 根据权利要求1-8中任一项所述的制备方法，其特征在于，在步骤(a)中，所述第一物质与所述纤维素以重量比为1:1-1:3混合。
  10. 根据权利要求1-9中任一项所述的制备方法，其特征在于，在步骤(a)中，所述催化剂为FeCl2、FeCl3、K3[Fe(CN)6]、K4[Fe(CN)6]、NiCl2中的任一种或几种的混合物；
  11. 根据权利要求1-10中任一项所述的制备方法，其特征在于，在步骤(a)中，所述催化剂与所述纤维素和第一物质总重量的重量比为1:0.5-1:2。
  12. 根据权利要求1-11中任一项所述的制备方法，其特征在于，在步骤(a)中，所述催化剂与所述纤维素和第一物质总重量的重量比为1:0.5-1:1.5。
  13. 根据权利要求1-12中任一项所述的制备方法，其特征在于，在步骤(a)中，所述催化剂与所述纤维素和第一物质总重量的重量比为1:1.0-1:1.2。
  14. 根据权利要求1-13中任一项所述的制备方法，其特征在于，在步骤(a)中，水热条件为160-200℃反应2-10h，形成合成料。
  15. 根据权利要求1-14中任一项所述的制备方法，其特征在于，在步骤(a)中，水热条件为160-200℃反应5-8h，形成合成料。
  16. 根据权利要求1-15中任一项所述的制备方法，其特征在于，在步骤(b)中，所述干燥采用的温度为80-120℃。
  17. 根据权利要求1-16中任一项所述的制备方法，其特征在于，在步骤(b)中，所述保护性气氛所用的气体为氮气、氩气以及氢气中的任一种。
  18. 根据权利要求1-17中任一项所述的制备方法，其特征在于，在步骤(c)中，所述洗涤包括以下步骤：
    先在30-80℃的温度下进行酸洗5-8h,然后水洗至中性，再在70-110℃下烘干即得所述石墨烯；
    所述酸洗采用的酸为：质量浓度均为3％-10％的盐酸、硫酸以及磷酸中的任一种。
  19. 根据权利要求1-18中任一项所述的制备方法，其特征在于，在步骤(b)中，梯度升温碳化为：250℃-450℃保温2.5-3.5h，550℃-800℃保温1.5-2.5h，800℃-1000℃保温1.5-2.5h。
  20. 权利要求1-19中任一项所述的制备方法制得的石墨烯材料。
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