WO2018001206A1 - Graphene-based hierarchical porous capacitive carbon and preparation method therefor, and capacitor - Google Patents

Graphene-based hierarchical porous capacitive carbon and preparation method therefor, and capacitor Download PDF

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WO2018001206A1
WO2018001206A1 PCT/CN2017/090053 CN2017090053W WO2018001206A1 WO 2018001206 A1 WO2018001206 A1 WO 2018001206A1 CN 2017090053 W CN2017090053 W CN 2017090053W WO 2018001206 A1 WO2018001206 A1 WO 2018001206A1
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graphene
preparing
temperature
based multi
stage pore
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PCT/CN2017/090053
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French (fr)
Chinese (zh)
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唐一林
张金柱
罗华星
郑应福
刘顶
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济南圣泉集团股份有限公司
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Publication of WO2018001206A1 publication Critical patent/WO2018001206A1/en

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the present invention relates to the field of capacitor materials, and in particular to a graphene-based multi-stage pore capacitor carbon, a preparation method thereof, and a capacitor.
  • Supercapacitors have the characteristics of high power density, long cycle life and clean and safe. This ideal energy storage device has attracted people's attention.
  • Carbon materials have become the most promising electrode materials in supercapacitor applications due to their high electrical conductivity, large specific surface area and low cost.
  • Activated carbon is the most widely used carbon material in many carbon materials because of its simple preparation (usually divided into two stages of low temperature pre-carbonization and high-temperature activation) and abundant raw materials (the raw materials are usually divided into two types, coconut shell and middle Phase asphalt).
  • Activated carbon-based supercapacitors have been widely used in various fields of social life, including electronic products, large machinery, and transportation.
  • the commercial device-type supercapacitor has an energy density of only 6 wh/kg, which is far from meeting the needs of miniaturization and intelligent development of electronic and mechanical products. Therefore, the increase in energy density is the current development direction of supercapacitors.
  • the electric double layer area capacity is 20 ⁇ F/cm 2
  • the activated carbon has a specific surface area of 2000-3000 m 2 /g, and the specific capacitance value should be above 400 F/g.
  • the pores of the activated carbon material are mainly micropores, on the one hand, the single pore structure increases the internal charge transport resistance of the material, and the conductivity of the material decreases; on the other hand, the electrolyte cannot sufficiently wet the material, resulting in the activated carbon up to 3000 m 2 /g.
  • the specific surface area utilization rate is reduced, so the specific capacitance of activated carbon in water-based electrolyte is only 100-180F/g (Japanese Cola Li company activated carbon specific capacitance value 100F / g, South Korea PCT activated carbon specific capacitance value 160F / g, China Nanjing Kikang activated carbon specific capacitance The value is 130F/g, Shanghai Heda carbon activated carbon capacitor value is 180F/g). Therefore, the direction of the modified activated carbon should be to prepare an activated carbon material having a multi-stage pore structure.
  • Graphene has an extremely high theoretical specific surface area, excellent electrical conductivity and electron mobility, and extremely low electrical resistivity.
  • Graphene is considered to be the most probable electrode material for replacing activated carbon. In reality, however, the application of graphene as an electrode material is far less optimistic than one would expect.
  • the reduced graphene material prepared by the activation of graphene prepared by Rodney S. Ruoff et al. has a specific surface area of up to 3000 m 2 /g, but its specific capacity is only 150 F/g (0.8 A/g) (Science, 2011, 332). , 1537-1541). This is because the simple pursuit of high specific surface area, the complete two-dimensional structure of graphene is severely damaged, and the electrical conductivity is drastically reduced. Therefore, the application of pure graphene in supercapacitors still has a long way to go.
  • the graphene oxide prepared by the oxidation method also has two-dimensional properties, and is more water-soluble, and is more easily used as a carrier in combination with a biomass precursor.
  • Shanghai Jiaotong University invented a graphene oxide-coated carbon microsphere.
  • a method of preparing a graphene-coated carbon microsphere material (CN 102544459 A). The invention prepares carbon microspheres by using hydrothermal method using glucose, sucrose and starch as carbon sources under acidic conditions, adding dry carbon microspheres to the graphene oxide dispersion, filtering and drying to obtain graphene oxide coated carbon microparticles.
  • the ball product is thermally reduced in a gas-protected atmosphere and naturally cooled to room temperature to obtain a three-dimensional product of graphene-coated carbon microspheres.
  • the method constructs a three-dimensional system and improves the conduction rate of electrons, but still does not solve the problem that the internal charge transfer distance of the activated carbon material is long and the charge transfer resistance is large.
  • the Shanxi Institute of Coal Chemistry of the Chinese Academy of Sciences applied for a patent for a graphene-based porous carbon material and its method and application (CN 104477878 A), which combines graphene with biomass carbon source cellulose.
  • a supercapacitor electrode material with multi-stage pore structure was obtained.
  • the material exhibited excellent supercapacitance performance, and the specific capacitance reached 285F/g at a current density of 1A/g. .
  • the invention still does not fully exert the effects of cellulose and graphene, and the specific capacitance value needs to be improved.
  • the object of the present invention is to provide a method for preparing graphene-based multi-stage pore capacitor carbon, which can inhibit the stacking and agglomeration of graphene to a greater extent, increase specific surface area and porosity, and increase specific surface area. Utilization and specific capacitance.
  • Another object of the present invention is to provide a graphene-based multi-stage pore capacitor carbon which has a higher specific capacitance, a higher stability, and is easier to store.
  • the present invention provides the following technical solutions:
  • a method for preparing graphene-based multi-stage pore capacitor carbon comprises the following steps:
  • the water-soluble sugar and the graphene-like substance are hydrothermally reacted, the crosslinking agent is added during the reaction, the activator is added after the reaction, and then the carbonization reaction is carried out to obtain the product;
  • the crosslinking agent is a nitrogen-containing blowing agent, and the activator is selected from one or more of potassium hydroxide, sodium hydroxide, zinc chloride, and phosphoric acid;
  • the graphene-based material includes graphene, One or more of graphene oxide and graphene derivatives.
  • the present invention adopts water-soluble sugar to hydrothermally react with graphene materials, so that the sugar can be fully intercalated into the two-dimensional structure of graphene, and the graphite is suppressed to the utmost extent.
  • the problem of curling, stacking, agglomeration and the like between the ene plate layers makes the graphene spontaneously produce a macroporous structure; and the graphene can cover the sugar to improve the overall strength and stability of the material.
  • the present invention introduces a nitrogen-containing blowing agent, which can produce a gas under hydrothermal conditions, can produce mesopores on the already grown graphene-based carbon material skeleton, and secondly can introduce nitrogen doping, which greatly improves Specific surface area utilization and specific capacitance.
  • the final addition of the activator can further etch the three-dimensional carbon skeleton by carbonization to further pore formation.
  • the present invention increases the specific area and utilization of graphene by various means, so that the specific capacitance reaches 313 F/g or more, and at the same time enhances the mechanical stability of the material.
  • the above preparation method can be further improved to achieve more technical effects, such as:
  • the graphene-based substance is preferably graphene oxide having a C and O atom molar ratio of 2 to 6:1, and the C and O atom molar ratio is preferably 3-5:1, more preferably 2-4:1.
  • the graphene oxide of the present invention may be a product of oxidation of graphene prepared by partial reduction crosslinking, or may be a product of oxidation of graphene prepared by PECVD.
  • the mass ratio of the water-soluble sugar to the graphene-based substance is from 20 to 200:1; preferably from 20 to 50:1.
  • the mass ratio of the activator to the graphene-based substance is from 50 to 150:1, more preferably from 60 to 100:1, still more preferably from 70 to 90:1.
  • the excessive incorporation of the water-soluble sugar not only reduces the strength of the material, but also increases the difficulty of the electric resistance and the carbonization reaction.
  • the problems of agglomeration and curling of the graphene cannot be sufficiently suppressed. It has been verified that when it is added in an amount of 20 to 200 times that of the graphene-based substance, it can exert a large positive effect, more preferably 20-50 times.
  • the blowing agent is selected from one or more of ethylenediamine, melamine, hexamethylenediamine, and urea.
  • the main function of the cross-linking agent has two points. Therefore, in order to reduce the adverse effect of the cross-linking agent on the capacitor carbon, a small-molecule foaming agent should be selected, and a reagent of a chemical foaming mechanism should be selected to avoid introducing impurities. . More preferred are ethylenediamine and melamine.
  • the graphene-based substance and the water-soluble sugar mixed solution are warmed in a range of 25 to 75 ° C.
  • the foaming agent is gradually added dropwise during the warm bath.
  • the bath time is from 1 to 4 h, preferably from 2 to 3 h.
  • the water soluble sugar is selected from the group consisting of monosaccharides and/or polysaccharides.
  • the polysaccharide has a large molecular weight and is more stably intercalated into the graphene, and the starch is optimal; the monosaccharide has a small molecular weight and is more easily intercalated into the graphene.
  • the monosaccharide is selected from one or more of glucose, xylose, and sucrose; and the polysaccharide is selected from one or more of starch, chitosan, and cyclodextrin.
  • carbon sources such as carbon nanotubes
  • Class substances to reduce material costs.
  • the amount of carbon nanotubes added is from 1 to 10% by weight of the graphene-based substance.
  • the mass ratio of the blowing agent to the graphene-based substance is preferably from 5 to 30:1.
  • the strength of the material is lowered, taking into consideration various factors, and it is preferably 5 to 30 times, more preferably 5 to 20 times, more preferably 5 to 10 times the graphene-based substance.
  • the temperature of the hydrothermal reaction is 140-220 ° C, at which the intercalation rate is faster and the effect is better, more preferably 160-220 ° C.
  • the hydrothermal reaction is preferably carried out in a high pressure polytetrafluoroethylene hydrothermal reactor, although other reaction vessels may be employed.
  • the temperature of the hydrothermal reaction is preferably 4-15 h at a temperature of 140-220 ° C, preferably 6 h.
  • the graphene-based substance and the sugar are ultrasonically mixed uniformly to facilitate the reaction.
  • the graphene-based substance is first ultrasonically obtained to obtain a uniform aqueous graphene solution, and then water-soluble sugar is added to the aqueous graphene solution, and ultrasonically mixed again.
  • the solvent can be removed by suction filtration, and then an activator is added to carbonize to increase the reaction efficiency.
  • the activator is preferably added as a solution to facilitate mixing with the graphene.
  • the carbonization reaction is activated at a preset temperature for 1-2 hours under the protection of an inert gas atmosphere, and then cooled and cooled, followed by washing with dilute hydrochloric acid and deionized water in order, followed by drying to obtain a material of better quality.
  • the predetermined temperature of the carbonization reaction is preferably 550 to 1000 ° C, and the etching rate and the etching effect can be balanced at this temperature, and more preferably 650 to 800 ° C.
  • the graphene-based substance mentioned in the present invention is graphene made of cellulose as a raw material, and the graphene is oxidized to obtain graphene oxide.
  • the method for preparing graphene from cellulose as a raw material comprises: mixing cellulose and ferrous chloride, drying after catalytic treatment to obtain a precursor; and obtaining a crude product by temperature-programming the precursor; Got it.
  • the cellulose and the ferrous chloride are mixed at a mass ratio of 1-3:1; the cellulose and the ferrous chloride ion are coordinated, and the precursor is obtained by high temperature deoxidation, and the cellulose and the chloride are verified.
  • the iron is mixed at a mass ratio of 1-3:1, the reaction is more complete, preferably the mass ratio of cellulose to ferrous chloride is 1-2:1; preferably the mass ratio is 1:1.
  • the temperature of the catalytic treatment is from 100 to 200 ° C, preferably from 120 to 180 ° C; preferably from 140 to 160 ° C; and the time of the catalytic treatment is from 2 to 6 h, preferably from 3 to 5 h, preferably 4 h. At this temperature, the deoxidation rate is faster and the effect is better.
  • the temperature programming comprises: heating the precursor to 150-200 ° C at a heating rate of 1-5 ° C / min, holding for 2-3 h, and then raising the temperature to 300-500 ° C at a heating rate of 10-20 ° C / min, After 3-4 h of heat preservation, the temperature was raised to 1000-1400 ° C at a heating rate of 10-20 ° C / min, and the crude product was obtained after 3-4 h of heat preservation. Since the heating rate has a great influence on the crystallite structure of the fiber, the multiple temperature rising and holding heat of the present invention respectively heats at a lower rate at different heating rates, and then heats up at a higher rate, so that the precursor is repeatedly performed. Pre-carbonization, carbon fiber has better mechanical properties.
  • the precursor is heated to 160-180 ° C at a temperature increase rate of 2-4 ° C / min, and incubated for 2-3 h, after which The heating rate of 13-17 ° C / min is raised to 350-450 ° C, 3-4 hr, and then heated to 1100-1300 ° C at a heating rate of 3-17 ° C / min, after 3-4 h of heat to obtain a crude product;
  • the precursor is heated to 170 ° C at a heating rate of 3 ° C / min, held for 2 h, then heated to 400 ° C at a heating rate of 15 ° C / min, held for 3 h, and then heated at a heating rate of 15 ° C / min After 1200 ° C, the crude product was obtained after 3 h of heat preservation.
  • washing the crude product comprises washing the crude product with a sodium hydroxide solution having a concentration of 8-12% at a temperature of 55-65 ° C, followed by pickling with a concentration of 2-6 wt% hydrochloric acid, and then washing with water. .
  • the cellulose may be an existing commercially available cellulose, which may be obtained by extraction from corn cob, corn stover, sorghum straw, soybean straw or wheat straw.
  • the cellulose is preferably extracted from the wheat straw by the following method. Specifically, the preparation method of the cellulose comprises:
  • the wheat straw is cooked by the first organic acid under the action of the first catalyst, and the first solid is separated;
  • the second solid is washed with water to obtain a water washing slurry, and the water washing slurry is subjected to solid-liquid separation and collecting solids, that is, obtained;
  • the first organic acid comprises acetic acid and formic acid in a mass ratio of 1:12;
  • the second organic acid comprises acetic acid and formic acid in a mass ratio of 1:12;
  • the first catalyst and the second catalyst are both hydrogen peroxide.
  • the total acid concentration of the first organic acid is 80-90 wt%, preferably 80-85 wt%, more preferably 80 wt%;
  • the solid-liquid mass ratio of the wheat straw to the first organic acid Is 1:10-12, preferably 1:10-11, more preferably 1:10;
  • the first catalyst is added in an amount of from 1 to 3% by weight of wheat straw, preferably from 1 to 2% by weight, more preferably 1% by weight;
  • the reaction temperature of the first organic acid cooking is 120-150 ° C, and the reaction time is 30-50 min.
  • the total acid concentration of the second organic acid is 70-79 wt%, preferably 72-77 wt%; more preferably 75 wt%; solid-liquid mass ratio of wheat straw to second organic acid Is 1:7-9; preferably 1:8-9, more preferably 1:9; the second catalyst is added in an amount of 8-10% by weight of wheat straw; preferably 8-9 wt%, more preferably 8 wt%;
  • the second organic acid wash has a wash temperature of 90-100 ° C and a wash time of 1-2 h.
  • the present invention also provides a graphene-based multi-stage pore capacitor carbon obtained by the above-mentioned preparation method of graphene-based multi-stage pore capacitor carbon.
  • the graphene-based multi-stage pore capacitor carbon produced by the invention has various uses, and is most widely used in batteries and capacitors, and the invention is not limited thereto. Accordingly, the present invention also provides a capacitor as an example of the above-described graphene-based multi-stage pore capacitor carbon as a capacitor material.
  • the technical effects of the present invention include, for example:
  • the material is widely used, especially for capacitors.
  • the graphene-based substance can be obtained by the following method, but is not limited to the following methods:
  • the treated wheat straw is cooked using the first organic acid solution of formic acid and acetic acid having a total acid concentration of 80% by weight, and the acetic acid in the first organic acid solution of the present embodiment
  • the mass ratio to formic acid is 1:12, and 1 wt% of hydrogen peroxide (H 2 O 2 ), which is the raw material of wheat straw, is added as the first catalyst before the feedstock is added, and the reaction temperature is controlled at 120 ° C for 30 min.
  • the ratio is 1:10, and the obtained reaction liquid is subjected to the first solid-liquid separation;
  • the first solid obtained by the first solid-liquid separation is added to a second organic acid solution having a total acid concentration of 75 wt% of formic acid and acetic acid, wherein the total acid concentration is 75 wt% of the second organic acid solution.
  • 8wt% of hydrogen peroxide (H 2 O 2 ) is used as the second catalyst, and the mass ratio of acetic acid to formic acid is 1:12, the control temperature is 90 ° C, the washing time is 1 h, and the solid-liquid mass ratio is added. 1:9, and the reaction liquid is subjected to a second solid-liquid separation;
  • step (3) collecting the liquid obtained by the first and second solid-liquid separation, performing high-temperature and high-pressure evaporation at 120 ° C, 301 kPa until evaporation to dryness, and condensing the obtained formic acid and acetic acid vapor back to the reaction kettle of the step (1). Used as a cooking liquor for the cooking of step (1);
  • step (5) collecting the liquid obtained by the third solid-liquid separation, performing water and acid distillation, and returning the obtained mixed acid solution to the reaction vessel of the step (1) for use as a cooking liquid for the cooking of the step (1).
  • Water is used in step (5) to act as water for washing;
  • the precursor was heated to 170 ° C at a rate of 3 ° C / min, kept for 2 h, then programmed to 400 ° C, held for 3 h, then heated to 1200 ° C, after 3 h to obtain a crude product;
  • the heating rate of the heating is 15 ° C / min;
  • Preparation Example 2 The difference between Preparation Example 2 and Preparation Example 1 is that in the first organic acid cooking, the total acid concentration of the first organic acid is 90% by weight, and the solid-liquid mass ratio of the wheat straw to the first organic acid is 1:12, first The catalyst was added in an amount of 3 wt% of the wheat straw, the reaction temperature of the first organic acid cooking was 150 ° C, and the reaction time was 50 min.
  • the total acid concentration of the second organic acid is 79 wt%
  • the solid-liquid mass ratio of the wheat straw to the second organic acid is 1:7
  • the second catalyst is added in an amount of 10 wt% of the wheat straw
  • the second organic acid wash had a wash temperature of 100 ° C and a wash time of 2 h.
  • Preparation Example 3 The difference between Preparation Example 3 and Preparation Example 1 is that in the first organic acid cooking, the total acid concentration of the first organic acid is 85 wt%, and the solid-liquid mass ratio of the wheat straw to the first organic acid is 1:11, first The catalyst was added in an amount of 2% by weight of wheat straw; the reaction temperature of the first organic acid cooking was 120 ° C, and the reaction time was 30 min.
  • the total acid concentration of the second organic acid is 72 wt%; the solid-liquid mass ratio of the wheat straw to the second organic acid is 1:8; the second catalyst is added in an amount of 9 wt% of the wheat straw;
  • the second organic acid wash had a wash temperature of 90 ° C and a wash time of 1 h.
  • Preparation Example 4 differs from Preparation Example 1 in that cellulose and ferrous chloride were mixed at a mass ratio of 3:1; the temperature of the catalytic treatment was 100 ° C; and the time of the catalytic treatment was 6 h.
  • Preparation Example 5 differs from Preparation Example 1 in that cellulose and ferrous chloride were mixed at a mass ratio of 2:1. Catalysis The treated temperature was 180 ° C; the catalytic treatment time was 3 h.
  • Preparation Example 6 The difference between Preparation Example 6 and Preparation Example 1 is that the parameters for temperature programming are different.
  • the precursor was heated to 150 ° C at a heating rate of 1 ° C / min, kept for 2 h, then heated to 300 ° C at a heating rate of 10 ° C / min, held for 3 h, and then heated at a heating rate of 10 ° C / min To 1000 ° C, after 3 h of heat preservation, a crude product was obtained.
  • Preparation Example 7 The difference between Preparation Example 7 and Preparation Example 1 is that the parameters for temperature programming are different.
  • the precursor was heated to 200 ° C at a heating rate of 5 ° C / min, kept for 3 h, then heated to 500 ° C at a heating rate of 20 ° C / min, held for 4 h, and then heated at a heating rate of 20 ° C / min At 1400 ° C, the crude product was obtained after 4 h of incubation.
  • Preparation Example 8 differs from Preparation Example 1 in that the parameters for temperature programming are different.
  • the precursor was heated to 160 ° C at a heating rate of 2 ° C / min, held for 2 h, then heated to 350 ° C at a heating rate of 13 ° C / min, held for 3 h, and then heated at a heating rate of 13 ° C / min Up to 1100 ° C, after 3 h of heat preservation, the crude product was obtained;
  • Preparation Example 9 The difference between Preparation Example 9 and Preparation Example 1 is that the parameters for temperature programming are different.
  • the precursor was heated to 180 ° C at a heating rate of 4 ° C / min, kept for 3 h, and then heated to 450 ° C at a heating rate of 17 ° C / min, held for 4 h, and then heated at a heating rate of 17 ° C / min At 1300 ° C, the crude product was obtained after 4 h of incubation.
  • Preparation Example 10 The difference between Preparation Example 10 and Preparation Example 1 was that the parameters for washing the crude product were different.
  • the crude product was washed with a sodium hydroxide solution having a concentration of 8% at a temperature of 55 to 65 ° C, followed by pickling with a hydrochloric acid having a concentration of 2 wt%, and then washed with water.
  • Preparation Example 11 differs from Preparation Example 1 in that the parameters for washing the crude product are different.
  • the crude product was washed with a sodium hydroxide solution having a concentration of 12% at a temperature of 55 to 65 ° C, followed by pickling with a hydrochloric acid having a concentration of 6 wt%, and then washed with water.
  • a method for preparing a three-dimensional graphene-based capacitor carbon having a multi-stage pore structure comprises the following steps:
  • the multi-dimensional graphene-based capacitor carbon was uniformly mixed with 80 g of KOH, and activated at 650 ° C for 1 hour under the protection of an inert gas atmosphere, naturally cooled to room temperature, and the product was taken out, washed with 5% diluted hydrochloric acid and deionized water, and dried.
  • a three-dimensional graphene-based capacitor carbon having a multi-stage pore structure of a high specific surface area of an electrode material is obtained.
  • the graphene-based substance used in Examples 2 to 9 was graphene oxide A having a C/O ratio of 3.5:1.
  • Example 1 The difference from Example 1 is that the graphene-based substance is graphene oxide A.
  • Example 2 The difference from Example 2 was that the amount of starch used was different, and the amount of starch added was 20 g.
  • Example 2 The difference from Example 2 was that the amount of starch used was different, and the amount of starch added was 200 g.
  • Example 2 The difference from Example 2 is that the starch is replaced with chitosan.
  • Example 2 The difference from Example 2 is that the starch is replaced with a cyclodextrin.
  • Example 2 The difference from Example 2 is that the starch is replaced with glucose.
  • Example 2 The difference from Example 2 was that the starch was replaced with glucose and starch, both in an amount of 100 g.
  • Example 2 The difference from Example 2 is that the hydrothermal reaction temperature is different and is 180 °C.
  • Example 2 The difference from Example 2 is that the graphene-based substance is graphene oxide A and the C/O ratio is 2:1.
  • Example 2 The difference from Example 2 is that the graphene-based substance is graphene oxide A and has a C/O ratio of 6:1.
  • Example 2 The difference from Example 2 is that the graphene-based substance is graphene oxide A and has a C/O ratio of 5:1.
  • Example 2 The difference from Example 2 is that the graphene-based substance is graphene oxide A and has a C/O ratio of 4:1.
  • the graphene-based substance is a graphene derivative, that is, nitrogen-doped graphene oxide (refer to the preparation method of Example 1 of CN103359708A).
  • Example 2 The difference from Example 2 was that the activator KOH was added in an amount of 50 g.
  • Example 2 The difference from Example 2 was that the activator KOH was added in an amount of 100 g.
  • Example 2 The difference from Example 2 was that the activator KOH was added in an amount of 150 g.
  • Example 2 The difference from Example 2 was that a warm bath was carried out before the hydrothermal reaction at a temperature of 25 ° C, during which a blowing agent was added, and the blowing agent time was 2.5 h.
  • Example 2 The difference from Example 2 was that a warm bath was carried out before the hydrothermal reaction at a temperature of 25 ° C, during which a blowing agent was added, and the blowing agent time was 4 h.
  • Example 2 The difference from Example 2 is that the graphene-based substance (i.e., graphene oxide A) is added in an amount of 0.5 g and 0.5 g of carbon nanotubes.
  • the graphene-based substance i.e., graphene oxide A
  • Example 2 The difference from Example 2 was that the graphene-based substance (i.e., graphene oxide A) was added in an amount of 0.95 g and the carbon nanotubes were 0.05 g.
  • the graphene-based substance i.e., graphene oxide A
  • the prepared active material solution was uniformly dropped on a foamed nickel area of 1 cm 2 using a 200 ⁇ l pipette, and dried in an oven.
  • the electrode sheet is placed on a tablet press to obtain a pole piece for supercapacitance.
  • the Shanghai Chenhua 660e electrochemical workstation was used to test the supercapacitor performance of the electrode material.
  • the electrolyte solution was a 6 mol/L KOH solution.
  • the test technique used constant current charge and discharge.
  • Control group Application Publication No. CN 104477878 A Example 6.
  • Test Example 2 Example 2, Example 10, Example 11, Example 12, and Example 13 were used as Test Examples 1-5.
  • Comparative Example 1 The graphene-based substance used was graphene oxide A, and its C/O ratio was 1:1;
  • Comparative Example 2 The graphene-based substance used was graphene oxide A having a C/O ratio of 18:1.
  • Test Example 4 (corresponding to Example 12) 5:1 315
  • Test Example 5 (corresponding to Example 13) 4:1 317 Comparative example 1 1:1 267 Comparative example 2 18:1 208
  • Test Example 3 Example 4, Example 8 was used as Test Example 6-8, the mass ratio of the water-soluble sugar to the graphene-based substance of Test Example 9 was 50:1;
  • Comparative Example 3 the mass ratio of the water-soluble sugar to the graphene-based substance used was 10:1;
  • Comparative Example 4 The mass ratio of the water-soluble sugar to the graphene-based substance used was 300:1. Table 3: Different water soluble sugars
  • Mass ratio Specific capacitance Material properties Test Example 6 20:1 320 Good strength, low electrical resistance, easy carbonization reaction, less graphene agglomeration Test Example 7 200:1 225 Better strength, lower electrical resistance, easier carbonization reaction, less graphene agglomeration Test Example 8 200:1 285 Better strength, lower electrical resistance, easier carbonization reaction, less graphene agglomeration Test Example 9 50:1 315 Good strength, low electrical resistance, easy carbonization reaction, less graphene agglomeration Comparative example 3 10:1 215 Insufficient inhibition of graphene agglomeration and curling Comparative example 4 300:1 196 Low material strength, high electrical resistance, and increased difficulty in carbonization
  • the mass ratio of the water-soluble sugar to the graphene-like substance is in the range of 20-200:1, so that the water-soluble sugar and the graphene-like substance undergo hydrothermal reaction, and the water-soluble sugar is sufficiently intercalated.
  • the problems of curling, stacking, agglomeration and the like between the graphene sheets are suppressed to the maximum, so that the graphene spontaneously generates a macroporous structure; and the graphene can be covered with sugar to improve the overall strength of the material.
  • stability excessive incorporation of water-soluble sugar not only reduces the strength of the material, but also increases the difficulty of resistance and carbonization reaction. When the blending is too small, the problems of agglomeration and curling of graphene cannot be sufficiently suppressed.
  • Test Example 15 Example 15, Example 16, Example 17 was used as Test Example 10-12, the mass ratio of activator to graphene in Test Example 13 was 80:1;
  • Comparative Example 5 mass ratio of activator to graphene-based substance used was 10:1;
  • Comparative Example 6 The mass ratio of the activator to the graphene-based substance used was 200:1.
  • the mass ratio of the activator to the graphene-like substance is in the range of 50-150:1, and the activator can etch the three-dimensional carbon skeleton through the carbonization reaction to further form pores, thereby improving
  • the specific surface area is beneficial to enhance the strength of the material.
  • the activator is too little, the activator has a low degree of etching on the three-dimensional carbon skeleton, and the degree of pore formation is weak, resulting in a small specific surface area, and when the activator is excessively incorporated, the activator etches the three-dimensional carbon skeleton.
  • the degree is large, although the specific surface area is increased, but the pores are large, which tends to cause a decrease in material strength. Therefore, it is preferred that the activator is incorporated in an amount of 50 to 150 times that of the graphene-based substance.
  • the material is widely used, especially for capacitors.

Abstract

Provided are a graphene-based hierarchical porous capacitive carbon and a preparation method therefor, and a capacitor. The preparation method comprises the following steps of: performing a hydrothermal reaction on a water-soluble sugar and a graphene substance, wherein a cross-linking agent is added during the reaction, and an activator is added after the completion of the reaction, and a carbonization reaction is then performed so as to obtain the product. The cross-linking agent is a nitrogen-containing foaming agent, and the activator is selected from one or more of potassium hydroxide, sodium hydroxide, zinc chloride and phosphoric acid. By means of the method, the stacking and agglomeration of graphene can be inhibited to a greater extent, the specific surface area and porosity are improved, and at the same time, the utilization rate of the specific surface area and the specific capacitance are improved.

Description

一种石墨烯基多级孔电容炭及其制备方法、及电容器Graphene-based multi-stage pore capacitor carbon, preparation method thereof and capacitor
本申请要求于2016年06月27日提交中国专利局的申请号为2016104895927、名称为“一种石墨烯基多级孔电容炭及其制备方法、及电容器”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。The present application claims priority to Chinese Patent Application No. 2016104895927, entitled "A Graphene-Based Multi-Level Pore Capacitor Charcoal and Its Preparation Method, and Capacitor", which is filed on June 27, 2016, The entire contents are incorporated herein by reference.
技术领域Technical field
本发明涉及电容材料技术领域，尤其是涉及一种石墨烯基多级孔电容炭及其制备方法、及电容器。The present invention relates to the field of capacitor materials, and in particular to a graphene-based multi-stage pore capacitor carbon, a preparation method thereof, and a capacitor.
背景技术Background technique
随着全球经济的飞速发展和社会人口的急剧增长，化石燃料的日渐枯竭和生态环境的逐渐恶化成为了当今社会亟待解决的问题。因此寻找一种高效、环保、可再生的新能源以及更高效的能源存储和转换技术，成为了解决上述问题的根本途径。因此，锂电池、超级电容器、太阳能电池技术都得到了快速的发展。With the rapid development of the global economy and the rapid growth of the social population, the depletion of fossil fuels and the gradual deterioration of the ecological environment have become an urgent problem to be solved in today's society. Therefore, finding an efficient, environmentally friendly, renewable new energy source and more efficient energy storage and conversion technology has become a fundamental way to solve the above problems. Therefore, lithium batteries, supercapacitors, and solar cell technologies have all developed rapidly.
超级电容器具有功率密度高、循环寿命长以及清洁安全的特点，这种理想的储能装置已经引起了人们的关注。Supercapacitors have the characteristics of high power density, long cycle life and clean and safe. This ideal energy storage device has attracted people's attention.
碳材料由于具有高的导电性、大的比表面积和廉价的优点，在超级电容器应用中已经成为最有前途的电极材料。活性炭是众多碳材料中应用于超电容最广泛的碳材料，原因在于其制备简单(通常分为低温预碳化和高温活化两个阶段)、原料丰富(原料通常分为两种，椰壳和中间相沥青)。活性炭基超级电容器已经广泛应用于社会生活的各个领域，包括电子产品、大型机械、交通工具等。但是，商业化器件型超级电容器能量密度只有6wh/kg，已经远远不能满足电子、机械产品微型化、智能化发展的需要。因此，能量密度的提高是超级电容器目前发展的方向。按照双电层理论，双电层面积容量为20μF/cm2，理论上活性炭高达2000-3000m2/g的比表面积，比电容值应该在400F/g以上。但是由于活性炭材料的孔以微孔为主，一方面单一的孔结构使得材料内部电荷传输电阻增加，材料的导电性下降；另一方面电解液不能充分浸润材料，导致活性炭高达3000m2/g的比表面积利用率降低，因此活性炭在水系电解液比电容只有100-180F/g(日本可乐丽公司活性炭比电容值100F/g，韩国PCT活性炭比电容值160F/g，中国南京吉仓活性炭比电容值130F/g，上海合达炭素活性炭电容值180F/g)。因此改良活性炭的方向应该是制备具有多级孔结构活性炭材料。Carbon materials have become the most promising electrode materials in supercapacitor applications due to their high electrical conductivity, large specific surface area and low cost. Activated carbon is the most widely used carbon material in many carbon materials because of its simple preparation (usually divided into two stages of low temperature pre-carbonization and high-temperature activation) and abundant raw materials (the raw materials are usually divided into two types, coconut shell and middle Phase asphalt). Activated carbon-based supercapacitors have been widely used in various fields of social life, including electronic products, large machinery, and transportation. However, the commercial device-type supercapacitor has an energy density of only 6 wh/kg, which is far from meeting the needs of miniaturization and intelligent development of electronic and mechanical products. Therefore, the increase in energy density is the current development direction of supercapacitors. According to the electric double layer theory, the electric double layer area capacity is 20 μF/cm 2 , theoretically, the activated carbon has a specific surface area of 2000-3000 m 2 /g, and the specific capacitance value should be above 400 F/g. However, since the pores of the activated carbon material are mainly micropores, on the one hand, the single pore structure increases the internal charge transport resistance of the material, and the conductivity of the material decreases; on the other hand, the electrolyte cannot sufficiently wet the material, resulting in the activated carbon up to 3000 m 2 /g. The specific surface area utilization rate is reduced, so the specific capacitance of activated carbon in water-based electrolyte is only 100-180F/g (Japanese Cola Li company activated carbon specific capacitance value 100F / g, South Korea PCT activated carbon specific capacitance value 160F / g, China Nanjing Kikang activated carbon specific capacitance The value is 130F/g, Shanghai Heda carbon activated carbon capacitor value is 180F/g). Therefore, the direction of the modified activated carbon should be to prepare an activated carbon material having a multi-stage pore structure.
石墨烯具有超高的理论比表面积、优异的导电率和电子迁移率、极低的电阻率，因此 Graphene has an extremely high theoretical specific surface area, excellent electrical conductivity and electron mobility, and extremely low electrical resistivity.
石墨烯被认为是最有可能替代活性炭的超电容电极材料。然而事实上，石墨烯作为电极材料的应用效果远不如人们预期的那样乐观。2011年，Rodney S.Ruoff等人制备的石墨烯经过活化处理制备的还原石墨烯材料比表面积高达3000m2/g，但是其比容量只有150F/g(0.8A/g)(Science，2011，332，1537-1541)。这是因为单纯的追求高比表面积，石墨烯完整的二维结构被破坏严重，导电性急剧下降。因此单纯的石墨烯应用在超电容还有很长一段路要走。然而，使用氧化法制备的氧化石墨烯同样具备二维属性，且水溶性更好，更容易作为载体与生物质前驱体相结合，如上海交通大学发明了一种氧化石墨烯包覆碳微球制备石墨烯包覆碳微球材料的方法(CN 102544459 A)。该发明在酸性条件下，利用水热法以葡萄糖、蔗糖、淀粉为碳源制备碳微球，将干燥碳微球加入到氧化石墨烯分散液中，过滤干燥后得到氧化石墨烯包覆碳微球产物，在气体保护氛围下，对材料进行热还原，自然冷却至室温得到石墨烯包覆碳微球三维产物。该方法构建了一种三维体系，改善了电子的传导速率，但仍然没有解决活性炭材料内部电荷传输距离长、电荷传输电阻大的问题。另外，中国科学院山西煤炭化学研究所申请了一项名称为一种石墨烯基多孔炭材料及制法和应用的发明专利(CN 104477878 A)，该发明将石墨烯与生物质碳源纤维素相结合进行自组装，然后经过后期KOH活化处理得到了具有多级孔结构的超电容电极材料，该材料表现出了优良的超电容性能，在1A/g电流密度下比电容值达到了285F/g。但是，该发明仍然没有充分发挥纤维素和石墨烯的作用，比电容值有待提高。Graphene is considered to be the most probable electrode material for replacing activated carbon. In reality, however, the application of graphene as an electrode material is far less optimistic than one would expect. In 2011, the reduced graphene material prepared by the activation of graphene prepared by Rodney S. Ruoff et al. has a specific surface area of up to 3000 m 2 /g, but its specific capacity is only 150 F/g (0.8 A/g) (Science, 2011, 332). , 1537-1541). This is because the simple pursuit of high specific surface area, the complete two-dimensional structure of graphene is severely damaged, and the electrical conductivity is drastically reduced. Therefore, the application of pure graphene in supercapacitors still has a long way to go. However, the graphene oxide prepared by the oxidation method also has two-dimensional properties, and is more water-soluble, and is more easily used as a carrier in combination with a biomass precursor. For example, Shanghai Jiaotong University invented a graphene oxide-coated carbon microsphere. A method of preparing a graphene-coated carbon microsphere material (CN 102544459 A). The invention prepares carbon microspheres by using hydrothermal method using glucose, sucrose and starch as carbon sources under acidic conditions, adding dry carbon microspheres to the graphene oxide dispersion, filtering and drying to obtain graphene oxide coated carbon microparticles. The ball product is thermally reduced in a gas-protected atmosphere and naturally cooled to room temperature to obtain a three-dimensional product of graphene-coated carbon microspheres. The method constructs a three-dimensional system and improves the conduction rate of electrons, but still does not solve the problem that the internal charge transfer distance of the activated carbon material is long and the charge transfer resistance is large. In addition, the Shanxi Institute of Coal Chemistry of the Chinese Academy of Sciences applied for a patent for a graphene-based porous carbon material and its method and application (CN 104477878 A), which combines graphene with biomass carbon source cellulose. Combined with self-assembly, and then through the late KOH activation treatment, a supercapacitor electrode material with multi-stage pore structure was obtained. The material exhibited excellent supercapacitance performance, and the specific capacitance reached 285F/g at a current density of 1A/g. . However, the invention still does not fully exert the effects of cellulose and graphene, and the specific capacitance value needs to be improved.
发明内容Summary of the invention
本发明的目的在于提供一种石墨烯基多级孔电容炭的制备方法，所述的制备方法能更大程度地抑制石墨烯的堆叠和团聚，提高比表面积和孔隙率，同时提高比表面积的利用率和比电容。The object of the present invention is to provide a method for preparing graphene-based multi-stage pore capacitor carbon, which can inhibit the stacking and agglomeration of graphene to a greater extent, increase specific surface area and porosity, and increase specific surface area. Utilization and specific capacitance.
本发明的另一目的在于提供一种石墨烯基多级孔电容炭，所述的电容炭比电容高，稳定性强，更容易保存。Another object of the present invention is to provide a graphene-based multi-stage pore capacitor carbon which has a higher specific capacitance, a higher stability, and is easier to store.
本发明的又一目的在于提供一种电容器，所述的电容器能量密度大，比电容值高。It is still another object of the present invention to provide a capacitor which has a high energy density and a higher specific capacitance value.
为了解决上述技术问题，本发明提供了以下技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
一种石墨烯基多级孔电容炭的制备方法，包括下列步骤：A method for preparing graphene-based multi-stage pore capacitor carbon comprises the following steps:
使水溶性糖与石墨烯类物质发生水热反应，反应过程中加入交联剂，反应结束后加入活化剂，再进行碳化反应，即得产品；The water-soluble sugar and the graphene-like substance are hydrothermally reacted, the crosslinking agent is added during the reaction, the activator is added after the reaction, and then the carbonization reaction is carried out to obtain the product;
所述交联剂为含氮的发泡剂，所述活化剂选自氢氧化钾、氢氧化钠、氯化锌、磷酸中的一种或多种；所述石墨烯类物质包括石墨烯、氧化石墨烯、石墨烯衍生物中的一种或多种。 The crosslinking agent is a nitrogen-containing blowing agent, and the activator is selected from one or more of potassium hydroxide, sodium hydroxide, zinc chloride, and phosphoric acid; the graphene-based material includes graphene, One or more of graphene oxide and graphene derivatives.
与现有技术相比，本发明采用的是水溶性的糖，以便与石墨烯类物质发生水热反应，这样既可以使糖充分插层到石墨烯的二维结构中，最大程度地抑制石墨烯片层间的卷曲、堆叠、团聚等问题，使石墨烯自发产生大孔结构；又可以使石墨烯覆盖糖，以提高材料的整体强度和稳定性。Compared with the prior art, the present invention adopts water-soluble sugar to hydrothermally react with graphene materials, so that the sugar can be fully intercalated into the two-dimensional structure of graphene, and the graphite is suppressed to the utmost extent. The problem of curling, stacking, agglomeration and the like between the ene plate layers makes the graphene spontaneously produce a macroporous structure; and the graphene can cover the sugar to improve the overall strength and stability of the material.
其次，本发明引入含氮的发泡剂，一是可以在水热条件下产生气体，能够在已经成长的石墨烯基碳材料骨架上制造介孔；二是可以引入氮掺杂，极大提高比表面积的利用率和比电容。Secondly, the present invention introduces a nitrogen-containing blowing agent, which can produce a gas under hydrothermal conditions, can produce mesopores on the already grown graphene-based carbon material skeleton, and secondly can introduce nitrogen doping, which greatly improves Specific surface area utilization and specific capacitance.
第三，最后加入活化剂可以进一步通过碳化反应对三维碳骨架进行刻蚀，以进一步造孔。Third, the final addition of the activator can further etch the three-dimensional carbon skeleton by carbonization to further pore formation.
综上，本发明通过多种手段增大了石墨烯的比面积及其利用率，使比电容达到313F/g以上，同时增强了材料的机械稳定性。In summary, the present invention increases the specific area and utilization of graphene by various means, so that the specific capacitance reaches 313 F/g or more, and at the same time enhances the mechanical stability of the material.
上述制备方法还可以进一步改进，以达到更多的技术效果，例如：The above preparation method can be further improved to achieve more technical effects, such as:
所述石墨烯类物质优选为C、O原子摩尔比为2-6:1的氧化石墨烯，C、O原子摩尔比优选为3-5:1，再优选为2-4:1。The graphene-based substance is preferably graphene oxide having a C and O atom molar ratio of 2 to 6:1, and the C and O atom molar ratio is preferably 3-5:1, more preferably 2-4:1.
本发明所述的氧化石墨烯可以是部分还原交联制备的石墨烯经氧化后的产物，亦可以是PECVD法制备的石墨烯经氧化后的产物。优选地，所述水溶性糖与所述石墨烯类物质的质量比为20-200:1；优选为20-50:1。The graphene oxide of the present invention may be a product of oxidation of graphene prepared by partial reduction crosslinking, or may be a product of oxidation of graphene prepared by PECVD. Preferably, the mass ratio of the water-soluble sugar to the graphene-based substance is from 20 to 200:1; preferably from 20 to 50:1.
优选的，活化剂与石墨烯类物质质量比50-150:1，再优选60-100:1，再优选70-90:1。Preferably, the mass ratio of the activator to the graphene-based substance is from 50 to 150:1, more preferably from 60 to 100:1, still more preferably from 70 to 90:1.
水溶性糖掺入过多既降低材料的强度，又增加电阻及碳化反应的难度，掺入过少时不能充分抑制石墨烯的团聚、卷曲等问题。经验证，当其加入量为石墨烯类物质的20-200倍时，能发挥较大的正面作用，更优选20-50倍。The excessive incorporation of the water-soluble sugar not only reduces the strength of the material, but also increases the difficulty of the electric resistance and the carbonization reaction. When the blending is too small, the problems of agglomeration and curling of the graphene cannot be sufficiently suppressed. It has been verified that when it is added in an amount of 20 to 200 times that of the graphene-based substance, it can exert a large positive effect, more preferably 20-50 times.
所述的发泡剂选自乙二胺、三聚氰胺、己二胺，尿素中的一种或多种。如上文所述交联剂的主要作用有两点，因此为了降低交联剂对电容炭的不利影响，宜选用小分子的发泡剂，更宜选化学发泡机理的试剂，以避免引入杂质。更优选乙二胺、三聚氰胺。The blowing agent is selected from one or more of ethylenediamine, melamine, hexamethylenediamine, and urea. As mentioned above, the main function of the cross-linking agent has two points. Therefore, in order to reduce the adverse effect of the cross-linking agent on the capacitor carbon, a small-molecule foaming agent should be selected, and a reagent of a chemical foaming mechanism should be selected to avoid introducing impurities. . More preferred are ethylenediamine and melamine.
优选的，水热反应前，将石墨烯类物质和水溶性糖混合溶液在25-75℃的范围内温浴，优选的，所述发泡剂在温浴过程中逐渐滴加。Preferably, before the hydrothermal reaction, the graphene-based substance and the water-soluble sugar mixed solution are warmed in a range of 25 to 75 ° C. Preferably, the foaming agent is gradually added dropwise during the warm bath.
优选的，温浴时间为1-4h，优选2-3h。Preferably, the bath time is from 1 to 4 h, preferably from 2 to 3 h.
所述的水溶性糖选自单糖和/或多糖。多糖分子量大，更能稳定地插层到石墨烯中，以淀粉为最优；单糖分子量小，更容易插层到石墨烯中。The water soluble sugar is selected from the group consisting of monosaccharides and/or polysaccharides. The polysaccharide has a large molecular weight and is more stably intercalated into the graphene, and the starch is optimal; the monosaccharide has a small molecular weight and is more easily intercalated into the graphene.
所述单糖选自葡萄糖，木糖、蔗糖中的一种或多种；所述多糖选自淀粉、壳聚糖、环糊精的一种或多种。The monosaccharide is selected from one or more of glucose, xylose, and sucrose; and the polysaccharide is selected from one or more of starch, chitosan, and cyclodextrin.
在上述水热反应过程中还可以加入其它的碳源，例如碳纳米管，可以替代部分石墨烯 类物质，以降低材料成本。优选的，碳纳米管加入量为石墨烯类物质的1-10wt％。In the above hydrothermal reaction process, other carbon sources, such as carbon nanotubes, may be added, which may replace part of graphene. Class substances to reduce material costs. Preferably, the amount of carbon nanotubes added is from 1 to 10% by weight of the graphene-based substance.
所述发泡剂与所述石墨烯类物质的质量比优选为5-30:1。发泡剂量过多时会降低材料的强度，兼顾多种因素，优选为石墨烯类物质的5-30倍，更优选5-20倍，更优选5-10倍。The mass ratio of the blowing agent to the graphene-based substance is preferably from 5 to 30:1. When the foaming amount is too large, the strength of the material is lowered, taking into consideration various factors, and it is preferably 5 to 30 times, more preferably 5 to 20 times, more preferably 5 to 10 times the graphene-based substance.
所述水热反应的温度为140-220℃，在该温度下，插层速率更快，效果更佳，更优选160-220℃。The temperature of the hydrothermal reaction is 140-220 ° C, at which the intercalation rate is faster and the effect is better, more preferably 160-220 ° C.
水热反应优选在高压聚四氟乙烯水热反应釜中进行，当然也可以采用其它反应容器。在140-220℃温度下，所述水热反应的时间优选为4-15h，以6h为优。The hydrothermal reaction is preferably carried out in a high pressure polytetrafluoroethylene hydrothermal reactor, although other reaction vessels may be employed. The temperature of the hydrothermal reaction is preferably 4-15 h at a temperature of 140-220 ° C, preferably 6 h.
在进行水热反应时，先将石墨烯类物质和糖超声混合均匀，更利于反应的进行。优选地，先对石墨烯类物质进行超声得到均一的石墨烯水溶液，接着向石墨烯水溶液中加入水溶性糖，再次超声混合。In the hydrothermal reaction, the graphene-based substance and the sugar are ultrasonically mixed uniformly to facilitate the reaction. Preferably, the graphene-based substance is first ultrasonically obtained to obtain a uniform aqueous graphene solution, and then water-soluble sugar is added to the aqueous graphene solution, and ultrasonically mixed again.
水热反应结束后，可以先通过抽滤除去溶剂，再加入活化剂碳化，以提高反应效率。After the hydrothermal reaction is completed, the solvent can be removed by suction filtration, and then an activator is added to carbonize to increase the reaction efficiency.
活化剂优选以溶液形式加入，便于与石墨烯混匀。The activator is preferably added as a solution to facilitate mixing with the graphene.
碳化反应在惰性气体氛围保护下以预设温度活化1-2h后，冷却降温，接着用稀盐酸和去离子水依次洗涤，再干燥，获得质量更优的材料。The carbonization reaction is activated at a preset temperature for 1-2 hours under the protection of an inert gas atmosphere, and then cooled and cooled, followed by washing with dilute hydrochloric acid and deionized water in order, followed by drying to obtain a material of better quality.
所述碳化反应的预设温度优选为550-1000℃，此温度下刻蚀速率和刻蚀效果能达到平衡，更优选650-800℃。The predetermined temperature of the carbonization reaction is preferably 550 to 1000 ° C, and the etching rate and the etching effect can be balanced at this temperature, and more preferably 650 to 800 ° C.
本发明提及的石墨烯类物质是以纤维素为原料制成的石墨烯，该石墨烯经氧化后可得到氧化石墨烯。The graphene-based substance mentioned in the present invention is graphene made of cellulose as a raw material, and the graphene is oxidized to obtain graphene oxide.
具体地，以纤维素为原料制成石墨烯具体包括：混合纤维素和氯化亚铁，经催化处理后干燥，得到前驱体；将前驱体经程序升温处理后得到粗品；粗品经洗涤后即得。Specifically, the method for preparing graphene from cellulose as a raw material comprises: mixing cellulose and ferrous chloride, drying after catalytic treatment to obtain a precursor; and obtaining a crude product by temperature-programming the precursor; Got it.
其中，纤维素和氯化亚铁以质量比为1-3：1进行混合；纤维素和氯化亚铁离子配位，经高温脱氧，得到前驱体，经验证，当纤维素与氯化亚铁以质量比为1-3：1进行混合时，反应更完全，优选纤维素与氯化亚铁的质量比为1-2:1；优选质量比为1:1。Wherein, the cellulose and the ferrous chloride are mixed at a mass ratio of 1-3:1; the cellulose and the ferrous chloride ion are coordinated, and the precursor is obtained by high temperature deoxidation, and the cellulose and the chloride are verified. When the iron is mixed at a mass ratio of 1-3:1, the reaction is more complete, preferably the mass ratio of cellulose to ferrous chloride is 1-2:1; preferably the mass ratio is 1:1.
进一步地，催化处理的温度为100-200℃，优选为120-180℃；优选为140-160℃；催化处理的时间为2-6h，优选为3-5h，优选为4h。在该温度下，脱氧速度更快，效果更佳。Further, the temperature of the catalytic treatment is from 100 to 200 ° C, preferably from 120 to 180 ° C; preferably from 140 to 160 ° C; and the time of the catalytic treatment is from 2 to 6 h, preferably from 3 to 5 h, preferably 4 h. At this temperature, the deoxidation rate is faster and the effect is better.
进一步地，程序升温包括：以1-5℃/min的升温速率将前驱体升温至150-200℃，保温2-3h，之后以10-20℃/min的升温速率升温至300-500℃，保温3-4h，之后以10-20℃/min的升温速率升温至1000-1400℃，保温3-4h后得到粗品。由于升温速率对纤维的微晶结构影响很大，本发明的多次升温保温分别以不同的升温速率，先以较低的速率进行升温，之后以较高的速率升温，使得前驱体进行多次预炭化，碳纤维的力学性能较佳。Further, the temperature programming comprises: heating the precursor to 150-200 ° C at a heating rate of 1-5 ° C / min, holding for 2-3 h, and then raising the temperature to 300-500 ° C at a heating rate of 10-20 ° C / min, After 3-4 h of heat preservation, the temperature was raised to 1000-1400 ° C at a heating rate of 10-20 ° C / min, and the crude product was obtained after 3-4 h of heat preservation. Since the heating rate has a great influence on the crystallite structure of the fiber, the multiple temperature rising and holding heat of the present invention respectively heats at a lower rate at different heating rates, and then heats up at a higher rate, so that the precursor is repeatedly performed. Pre-carbonization, carbon fiber has better mechanical properties.
优选地；以2-4℃/min的升温速率将前驱体升温至160-180℃，保温2-3h，之后以 13-17℃/min的升温速率升温至350-450℃，保温3-4h，之后以3-17℃/min的升温速率升温至1100-1300℃，保温3-4h后得到粗品；Preferably, the precursor is heated to 160-180 ° C at a temperature increase rate of 2-4 ° C / min, and incubated for 2-3 h, after which The heating rate of 13-17 ° C / min is raised to 350-450 ° C, 3-4 hr, and then heated to 1100-1300 ° C at a heating rate of 3-17 ° C / min, after 3-4 h of heat to obtain a crude product;
更优选地；以3℃/min的升温速率将前驱体升温至170℃，保温2h，之后以15℃/min的升温速率升温至400℃，保温3h，之后以15℃/min的升温速率升温至1200℃，保温3h后得到粗品。More preferably; the precursor is heated to 170 ° C at a heating rate of 3 ° C / min, held for 2 h, then heated to 400 ° C at a heating rate of 15 ° C / min, held for 3 h, and then heated at a heating rate of 15 ° C / min After 1200 ° C, the crude product was obtained after 3 h of heat preservation.
进一步地，洗涤粗品包括将粗品于温度为55-65℃条件下，经浓度为8-12％的氢氧化钠溶液碱洗、接着经浓度为2-6wt％的盐酸酸洗后，再进行水洗。Further, washing the crude product comprises washing the crude product with a sodium hydroxide solution having a concentration of 8-12% at a temperature of 55-65 ° C, followed by pickling with a concentration of 2-6 wt% hydrochloric acid, and then washing with water. .
纤维素可以为现有的经市售购买的纤维素，可以是通过从玉米芯、玉米秸秆、高粱秸秆、大豆秸秆或小麦秸秆中经提取得到。本发明实施例中，纤维素优选从小麦秸秆中经以下方法提取得到，具体地，纤维素的制备方法包括：The cellulose may be an existing commercially available cellulose, which may be obtained by extraction from corn cob, corn stover, sorghum straw, soybean straw or wheat straw. In the embodiment of the present invention, the cellulose is preferably extracted from the wheat straw by the following method. Specifically, the preparation method of the cellulose comprises:
小麦秸秆在第一催化剂的作用下经第一有机酸蒸煮后，分离取第一固体；The wheat straw is cooked by the first organic acid under the action of the first catalyst, and the first solid is separated;
将所述第一固体在第二催化剂的作用下经第二有机酸洗涤后，分离取第二固体；以及After the first solid is washed by the second organic acid under the action of the second catalyst, the second solid is separated;
将所述第二固体进行水洗，获得水洗浆，将所述水洗浆进行固液分离并收集固体，即得；The second solid is washed with water to obtain a water washing slurry, and the water washing slurry is subjected to solid-liquid separation and collecting solids, that is, obtained;
其中，第一有机酸包括质量比为1:12的乙酸与甲酸；第二有机酸包括质量比为1:12的乙酸与甲酸；第一催化剂和第二催化剂均为过氧化氢。Wherein, the first organic acid comprises acetic acid and formic acid in a mass ratio of 1:12; the second organic acid comprises acetic acid and formic acid in a mass ratio of 1:12; the first catalyst and the second catalyst are both hydrogen peroxide.
进一步地，在第一有机酸蒸煮中，第一有机酸的总酸浓度为80-90wt％，优选为80-85wt％，更优选为80wt％；小麦秸秆与第一有机酸的固液质量比为1:10-12，优选为1:10-11，更优选为1:10；第一催化剂的加入量为小麦秸秆的1-3wt％，优选为1-2wt％，更优选为1wt％；第一有机酸蒸煮的反应温度为120-150℃，反应时间为30-50min。Further, in the first organic acid cooking, the total acid concentration of the first organic acid is 80-90 wt%, preferably 80-85 wt%, more preferably 80 wt%; the solid-liquid mass ratio of the wheat straw to the first organic acid Is 1:10-12, preferably 1:10-11, more preferably 1:10; the first catalyst is added in an amount of from 1 to 3% by weight of wheat straw, preferably from 1 to 2% by weight, more preferably 1% by weight; The reaction temperature of the first organic acid cooking is 120-150 ° C, and the reaction time is 30-50 min.
进一步地，在第二有机酸洗涤中，第二有机酸的总酸浓度为70-79wt％，优选为72-77wt％；更优选为75wt％；小麦秸秆与第二有机酸的固液质量比为1:7-9；优选为1:8-9，更优选为1:9；第二催化剂的加入量为小麦秸秆的8-10wt％；优选为8-9wt％，更优选为8wt％；第二有机酸洗涤的洗涤温度为90-100℃，洗涤时间为1-2h。本发明还提供了一种石墨烯基多级孔电容炭，其采用上述提及的石墨烯基多级孔电容炭的制备方法制得。Further, in the second organic acid washing, the total acid concentration of the second organic acid is 70-79 wt%, preferably 72-77 wt%; more preferably 75 wt%; solid-liquid mass ratio of wheat straw to second organic acid Is 1:7-9; preferably 1:8-9, more preferably 1:9; the second catalyst is added in an amount of 8-10% by weight of wheat straw; preferably 8-9 wt%, more preferably 8 wt%; The second organic acid wash has a wash temperature of 90-100 ° C and a wash time of 1-2 h. The present invention also provides a graphene-based multi-stage pore capacitor carbon obtained by the above-mentioned preparation method of graphene-based multi-stage pore capacitor carbon.
本发明制得的石墨烯基多级孔电容炭有多种用途，以电池、电容器方面的应用为最广，本发明对此并不做限制。据此，本发明还提供了一种电容器作为示范例，该电容器是以上述石墨烯基多级孔电容炭为电容材料。The graphene-based multi-stage pore capacitor carbon produced by the invention has various uses, and is most widely used in batteries and capacitors, and the invention is not limited thereto. Accordingly, the present invention also provides a capacitor as an example of the above-described graphene-based multi-stage pore capacitor carbon as a capacitor material.
与现有技术相比，本发明的技术效果例如包括是：Compared with the prior art, the technical effects of the present invention include, for example:
(1)限制了糖的种类，以水热反应来对石墨烯类物质改性，提高孔的多级结构，提高比表面积；(1) Limiting the type of sugar, modifying the graphene-like substance by hydrothermal reaction, increasing the multi-stage structure of the pores, and increasing the specific surface area;
(2)引入氮元素，提高比电容； (2) Introducing nitrogen element to increase specific capacitance;
(3)材料用途广泛，尤其适用于电容器。(3) The material is widely used, especially for capacitors.
具体实施方式detailed description
下面将结合具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。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。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。The technical solutions of the present invention will be clearly and completely described below in conjunction with the specific embodiments, but those skilled in the art will understand that the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments, only The invention is illustrated and should not be construed as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention. Those who do not specify the specific conditions in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained by commercially available purchase.
下文所述的C/O比均指摩尔比。The C/O ratios described below all refer to the molar ratio.
制备例1：Preparation Example 1:
石墨烯类物质可通过下述方法制得，但不限于以下方法：The graphene-based substance can be obtained by the following method, but is not limited to the following methods:
先制备纤维素：First prepare cellulose:
(1)将小麦秸杆粉碎预处理后，使用总酸浓为80wt％的甲酸和乙酸的第一有机酸液对处理后的小麦秸杆进行蒸煮，本实施例的第一有机酸液中乙酸与甲酸的质量比为1:12，并在加入原料前加入占小麦秸杆原料1wt％的过氧化氢(H2O2)作为第一催化剂，控制反应温度120℃，反应30min，固液质量比为1:10，并将得到的反应液进行第一次固液分离；(1) After pulverizing and pretreating the wheat straw, the treated wheat straw is cooked using the first organic acid solution of formic acid and acetic acid having a total acid concentration of 80% by weight, and the acetic acid in the first organic acid solution of the present embodiment The mass ratio to formic acid is 1:12, and 1 wt% of hydrogen peroxide (H 2 O 2 ), which is the raw material of wheat straw, is added as the first catalyst before the feedstock is added, and the reaction temperature is controlled at 120 ° C for 30 min. The ratio is 1:10, and the obtained reaction liquid is subjected to the first solid-liquid separation;
(2)将第一次固液分离得到的第一固体加入总酸浓为75wt％的甲酸和乙酸的第二有机酸液进行酸洗涤，其中上述总酸浓为75wt％的第二有机酸液中加入了占小麦秸杆原料8wt％的过氧化氢(H2O2)作为第二催化剂且乙酸与甲酸的质量比为1:12，控制温度为90℃，洗涤时间1h，固液质量比为1:9，并将反应液进行第二次固液分离；(2) The first solid obtained by the first solid-liquid separation is added to a second organic acid solution having a total acid concentration of 75 wt% of formic acid and acetic acid, wherein the total acid concentration is 75 wt% of the second organic acid solution. 8wt% of hydrogen peroxide (H 2 O 2 ) is used as the second catalyst, and the mass ratio of acetic acid to formic acid is 1:12, the control temperature is 90 ° C, the washing time is 1 h, and the solid-liquid mass ratio is added. 1:9, and the reaction liquid is subjected to a second solid-liquid separation;
(3)收集第一次和第二次固液分离得到的液体，于120℃，301kPa下进行高温高压蒸发，直至蒸干，将得到的甲酸和乙酸蒸气冷凝回流至步骤(1)的反应釜中作为蒸煮液，用于步骤(1)的蒸煮；(3) collecting the liquid obtained by the first and second solid-liquid separation, performing high-temperature and high-pressure evaporation at 120 ° C, 301 kPa until evaporation to dryness, and condensing the obtained formic acid and acetic acid vapor back to the reaction kettle of the step (1). Used as a cooking liquor for the cooking of step (1);
(4)收集第二次固液分离得到的第二固体，并进行水洗，控制水洗温度为80℃，水洗浆浓为6wt％，并将得到的水洗浆进行第三次固液分离；(4) collecting the second solid obtained by the second solid-liquid separation, and washing with water, controlling the water washing temperature to be 80 ° C, the water washing slurry is 6 wt%, and the obtained water washing slurry is subjected to a third solid-liquid separation;
(5)收集第三次固液分离得到的液体，进行水、酸精馏，得到的混合酸液回用于步骤(1)的反应釜中作为蒸煮液用于步骤(1)的蒸煮，得到的水回用于步骤(5)作用水洗用水；(5) collecting the liquid obtained by the third solid-liquid separation, performing water and acid distillation, and returning the obtained mixed acid solution to the reaction vessel of the step (1) for use as a cooking liquid for the cooking of the step (1). Water is used in step (5) to act as water for washing;
(6)收集第三次固液分离得到的第三固体并进行筛选得到所需的细浆纤维素。(6) Collecting the third solid obtained by the third solid-liquid separation and screening to obtain the desired fine cellulose.
然后以上文制备的纤维素为原料制备石墨烯：Then the cellulose prepared above is used as a raw material to prepare graphene:
(1)按质量比1:1混合纤维素和氯化亚铁，在150℃下搅拌进行催化处理4h，干燥至前驱体水分含量10wt％，得到前驱体； (1) mixing cellulose and ferrous chloride according to a mass ratio of 1:1, stirring at 150 ° C for catalytic treatment for 4 h, drying to a precursor moisture content of 10 wt%, to obtain a precursor;
(2)N2气氛中，以3℃/min速率将前驱体升温至170℃，保温2h，之后程序升温至400℃，保温3h，之后升温至1200℃，保温3h后得到粗品；所述程序升温的升温速率为15℃/min；(2) In a N 2 atmosphere, the precursor was heated to 170 ° C at a rate of 3 ° C / min, kept for 2 h, then programmed to 400 ° C, held for 3 h, then heated to 1200 ° C, after 3 h to obtain a crude product; The heating rate of the heating is 15 ° C / min;
(3)55-65℃下，将粗品经过浓度为10％的氢氧化钠溶液、4wt％的盐酸酸洗后，水洗得到生物质石墨烯，记为石墨烯A。(3) The crude product was acid-washed at a concentration of 10% sodium hydroxide solution and 4 wt% hydrochloric acid at 55-65 ° C, and washed with water to obtain biomass graphene, which was designated as graphene A.
氧化石墨烯AGraphene oxide A
(1)取1g石墨烯A转移至圆底烧瓶，加入98％硫酸25mL，再加入25mL磷酸，冰水浴下冷却磁力搅拌，往三口烧瓶缓慢加入7g高锰酸钾，冰水浴保持温度在20℃以下，搅拌30分钟。(1) 1 g of graphene A was transferred to a round bottom flask, 25 mL of 98% sulfuric acid was added, 25 mL of phosphoric acid was added, and magnetic stirring was carried out under ice-cold cooling. 7 g of potassium permanganate was slowly added to the three-necked flask, and the temperature was kept at 20 ° C in an ice water bath. The mixture was stirred for 30 minutes.
(2)开启加热，使温度保持在50℃，反应10小时。(2) Turn on the heating to maintain the temperature at 50 ° C and react for 10 hours.
(3)冷却至室温，冰水浴下缓慢加水稀释。(3) Cool to room temperature and slowly dilute with water in an ice water bath.
(4)将反应物倒出，逐滴加入30％过氧化氢溶液，直到溶液变成金黄色且无气泡冒出，继续反应半个小时。(4) The reaction was poured out, and a 30% hydrogen peroxide solution was added dropwise until the solution turned golden yellow and no bubbles appeared, and the reaction was continued for half an hour.
(5)用5％稀盐酸离心洗涤数次，直到用硝酸钡饱和溶液检测上清液无沉淀产生，这时说明硫酸根离子已经被洗涤干净。最后用去离子水离心洗涤数次，直至上清液pH值为7(pH计测量)，放置于真空干燥箱50℃烘干备用。(5) Centrifugation with 5% dilute hydrochloric acid for several times until no precipitation was detected in the supernatant with a saturated solution of cerium nitrate, indicating that the sulfate ions had been washed. Finally, it was washed with deionized water several times until the pH of the supernatant was 7 (measured by a pH meter), and placed in a vacuum oven at 50 ° C for drying.
制备例2Preparation Example 2
制备例2与制备例1的区别在于：在第一有机酸蒸煮中，第一有机酸的总酸浓度为90wt％，小麦秸秆与第一有机酸的固液质量比为1:12，第一催化剂的加入量为小麦秸秆的3wt％，第一有机酸蒸煮的反应温度为150℃，反应时间为50min。在第二有机酸洗涤中，第二有机酸的总酸浓度为79wt％，小麦秸秆与第二有机酸的固液质量比为1:7；第二催化剂的加入量为小麦秸秆的10wt％；第二有机酸洗涤的洗涤温度为100℃，洗涤时间为2h。The difference between Preparation Example 2 and Preparation Example 1 is that in the first organic acid cooking, the total acid concentration of the first organic acid is 90% by weight, and the solid-liquid mass ratio of the wheat straw to the first organic acid is 1:12, first The catalyst was added in an amount of 3 wt% of the wheat straw, the reaction temperature of the first organic acid cooking was 150 ° C, and the reaction time was 50 min. In the second organic acid washing, the total acid concentration of the second organic acid is 79 wt%, the solid-liquid mass ratio of the wheat straw to the second organic acid is 1:7; the second catalyst is added in an amount of 10 wt% of the wheat straw; The second organic acid wash had a wash temperature of 100 ° C and a wash time of 2 h.
制备例3Preparation Example 3
制备例3与制备例1的区别在于：在第一有机酸蒸煮中，第一有机酸的总酸浓度为85wt％，小麦秸秆与第一有机酸的固液质量比为1:11，第一催化剂的加入量为小麦秸秆的2wt％；第一有机酸蒸煮的反应温度为120℃，反应时间为30min。在第二有机酸洗涤中，第二有机酸的总酸浓度为72wt％；小麦秸秆与第二有机酸的固液质量比为1:8；第二催化剂的加入量为小麦秸秆的9wt％；第二有机酸洗涤的洗涤温度为90℃，洗涤时间为1h。The difference between Preparation Example 3 and Preparation Example 1 is that in the first organic acid cooking, the total acid concentration of the first organic acid is 85 wt%, and the solid-liquid mass ratio of the wheat straw to the first organic acid is 1:11, first The catalyst was added in an amount of 2% by weight of wheat straw; the reaction temperature of the first organic acid cooking was 120 ° C, and the reaction time was 30 min. In the second organic acid washing, the total acid concentration of the second organic acid is 72 wt%; the solid-liquid mass ratio of the wheat straw to the second organic acid is 1:8; the second catalyst is added in an amount of 9 wt% of the wheat straw; The second organic acid wash had a wash temperature of 90 ° C and a wash time of 1 h.
制备例4Preparation Example 4
制备例4与制备例1的区别在于：纤维素和氯化亚铁以质量比为3：1进行混合；催化处理的温度为100℃；催化处理的时间为6h。Preparation Example 4 differs from Preparation Example 1 in that cellulose and ferrous chloride were mixed at a mass ratio of 3:1; the temperature of the catalytic treatment was 100 ° C; and the time of the catalytic treatment was 6 h.
制备例5Preparation Example 5
制备例5与制备例1的区别在于：纤维素和氯化亚铁以质量比为2：1进行混合。催化 处理的温度为180℃；催化处理的时间为3h。Preparation Example 5 differs from Preparation Example 1 in that cellulose and ferrous chloride were mixed at a mass ratio of 2:1. Catalysis The treated temperature was 180 ° C; the catalytic treatment time was 3 h.
制备例6Preparation Example 6
制备例6与制备例1的区别在于：程序升温的参数不同。本制备例中以1℃/min的升温速率将前驱体升温至150℃，保温2h，之后以10℃/min的升温速率升温至300℃，保温3h，之后以10℃/min的升温速率升温至1000℃，保温3h后得到粗品。The difference between Preparation Example 6 and Preparation Example 1 is that the parameters for temperature programming are different. In the preparation example, the precursor was heated to 150 ° C at a heating rate of 1 ° C / min, kept for 2 h, then heated to 300 ° C at a heating rate of 10 ° C / min, held for 3 h, and then heated at a heating rate of 10 ° C / min To 1000 ° C, after 3 h of heat preservation, a crude product was obtained.
制备例7Preparation Example 7
制备例7与制备例1的区别在于：程序升温的参数不同。本制备例中以5℃/min的升温速率将前驱体升温至200℃，保温3h，之后以20℃/min的升温速率升温至500℃，保温4h，之后以20℃/min的升温速率升温至1400℃，保温4h后得到粗品。The difference between Preparation Example 7 and Preparation Example 1 is that the parameters for temperature programming are different. In the preparation example, the precursor was heated to 200 ° C at a heating rate of 5 ° C / min, kept for 3 h, then heated to 500 ° C at a heating rate of 20 ° C / min, held for 4 h, and then heated at a heating rate of 20 ° C / min At 1400 ° C, the crude product was obtained after 4 h of incubation.
制备例8Preparation Example 8
制备例8与制备例1的区别在于：程序升温的参数不同。本制备例中以2℃/min的升温速率将前驱体升温至160℃，保温2h，之后以13℃/min的升温速率升温至350℃，保温3h，之后以13℃/min的升温速率升温至1100℃，保温3h后得到粗品；Preparation Example 8 differs from Preparation Example 1 in that the parameters for temperature programming are different. In the preparation example, the precursor was heated to 160 ° C at a heating rate of 2 ° C / min, held for 2 h, then heated to 350 ° C at a heating rate of 13 ° C / min, held for 3 h, and then heated at a heating rate of 13 ° C / min Up to 1100 ° C, after 3 h of heat preservation, the crude product was obtained;
制备例9Preparation Example 9
制备例9与制备例1的区别在于：程序升温的参数不同。本制备例中以4℃/min的升温速率将前驱体升温至180℃，保温3h，之后以17℃/min的升温速率升温至450℃，保温4h，之后以17℃/min的升温速率升温至1300℃，保温4h后得到粗品。The difference between Preparation Example 9 and Preparation Example 1 is that the parameters for temperature programming are different. In the preparation example, the precursor was heated to 180 ° C at a heating rate of 4 ° C / min, kept for 3 h, and then heated to 450 ° C at a heating rate of 17 ° C / min, held for 4 h, and then heated at a heating rate of 17 ° C / min At 1300 ° C, the crude product was obtained after 4 h of incubation.
制备例10Preparation Example 10
制备例10与制备例1的区别在于：洗涤粗品的参数不同。本制备例中将所述粗品于温度为55-65℃条件下，经浓度为8％的氢氧化钠溶液碱洗、接着经浓度为2wt％的盐酸酸洗后，再进行水洗。The difference between Preparation Example 10 and Preparation Example 1 was that the parameters for washing the crude product were different. In the preparation example, the crude product was washed with a sodium hydroxide solution having a concentration of 8% at a temperature of 55 to 65 ° C, followed by pickling with a hydrochloric acid having a concentration of 2 wt%, and then washed with water.
制备例11Preparation Example 11
制备例11与制备例1的区别在于：洗涤粗品的参数不同。本制备例中将所述粗品于温度为55-65℃条件下，经浓度为12％的氢氧化钠溶液碱洗、接着经浓度为6wt％的盐酸酸洗后，再进行水洗。Preparation Example 11 differs from Preparation Example 1 in that the parameters for washing the crude product are different. In the preparation example, the crude product was washed with a sodium hydroxide solution having a concentration of 12% at a temperature of 55 to 65 ° C, followed by pickling with a hydrochloric acid having a concentration of 6 wt%, and then washed with water.
实施例1Example 1
一种具有多级孔结构的三维石墨烯基电容炭的制备方法，包括如下步骤：A method for preparing a three-dimensional graphene-based capacitor carbon having a multi-stage pore structure comprises the following steps:
(1)将1g由上述制备例1-11中任意一制备例制备的石墨烯A溶于水中，超声得到均一分散的石墨烯水溶液；(1) 1 g of the graphene A prepared by the preparation of any of the above Preparation Examples 1 to 11 is dissolved in water, and ultrasonically obtained to obtain a uniformly dispersed graphene aqueous solution;
(2)加入25g可溶性淀粉，搅拌，超声，得到混和均一的溶液；(2) adding 25 g of soluble starch, stirring, and sonicating to obtain a homogeneous solution;
(3)将上述混合溶液加入到高压聚四氟乙烯水热反应釜中，将温度设置为160℃进行反应，温度达到160℃开始逐渐添加5g己二胺，并开启搅拌，完毕后关闭搅拌，水热反应6 小时；自然冷却至室温，将反应釜内固液混合物进行抽滤洗涤，得到多维石墨烯基电容炭；(3) The above mixed solution is added to a high-pressure polytetrafluoroethylene hydrothermal reaction kettle, and the temperature is set to 160 ° C to carry out the reaction. When the temperature reaches 160 ° C, 5 g of hexamethylenediamine is gradually added, and stirring is started, and the stirring is turned off after completion. Hydrothermal reaction 6 Hour; naturally cooled to room temperature, the solid-liquid mixture in the reaction vessel was subjected to suction filtration to obtain a multi-dimensional graphene-based capacitor carbon;
(4)将多维石墨烯基电容炭与80gKOH混合均匀，并在惰性气体氛围保护下650℃高温活化1小时，自然冷却至室温，取出产物，用5％稀盐酸和去离子水洗涤，干燥，得到可用于电极材料的高比表面积的多级孔结构的三维石墨烯基电容炭。(4) The multi-dimensional graphene-based capacitor carbon was uniformly mixed with 80 g of KOH, and activated at 650 ° C for 1 hour under the protection of an inert gas atmosphere, naturally cooled to room temperature, and the product was taken out, washed with 5% diluted hydrochloric acid and deionized water, and dried. A three-dimensional graphene-based capacitor carbon having a multi-stage pore structure of a high specific surface area of an electrode material is obtained.
实施例2至9所用的石墨烯类物质为氧化石墨烯A，其C/O比为3.5:1。The graphene-based substance used in Examples 2 to 9 was graphene oxide A having a C/O ratio of 3.5:1.
实施例2Example 2
与实施例1的区别在于石墨烯类物质为氧化石墨烯A。The difference from Example 1 is that the graphene-based substance is graphene oxide A.
实施例3Example 3
与实施例2的区别在于淀粉用量不同，淀粉加入量为20g。The difference from Example 2 was that the amount of starch used was different, and the amount of starch added was 20 g.
实施例4Example 4
与实施例2的区别在于淀粉用量不同，淀粉加入量为200g。The difference from Example 2 was that the amount of starch used was different, and the amount of starch added was 200 g.
实施例5Example 5
与实施例2的区别在于将淀粉替换为壳聚糖。The difference from Example 2 is that the starch is replaced with chitosan.
实施例6Example 6
与实施例2的区别在于将淀粉替换为环糊精。The difference from Example 2 is that the starch is replaced with a cyclodextrin.
实施例7Example 7
与实施例2的区别在于将淀粉替换为葡萄糖。The difference from Example 2 is that the starch is replaced with glucose.
实施例8Example 8
与实施例2的区别在于将淀粉替换为葡萄糖和淀粉，两者用量均为100g。The difference from Example 2 was that the starch was replaced with glucose and starch, both in an amount of 100 g.
实施例9Example 9
与实施例2的区别在于水热反应温度不同，为180℃。The difference from Example 2 is that the hydrothermal reaction temperature is different and is 180 °C.
实施例10Example 10
与实施例2的区别在于石墨烯类物质为氧化石墨烯A且C/O比为2:1。The difference from Example 2 is that the graphene-based substance is graphene oxide A and the C/O ratio is 2:1.
实施例11Example 11
与实施例2的区别在于石墨烯类物质为氧化石墨烯A且C/O比为6:1。The difference from Example 2 is that the graphene-based substance is graphene oxide A and has a C/O ratio of 6:1.
实施例12Example 12
与实施例2的区别在于石墨烯类物质为氧化石墨烯A且C/O比为5:1。The difference from Example 2 is that the graphene-based substance is graphene oxide A and has a C/O ratio of 5:1.
实施例13Example 13
与实施例2的区别在于石墨烯类物质为氧化石墨烯A且C/O比为4:1。The difference from Example 2 is that the graphene-based substance is graphene oxide A and has a C/O ratio of 4:1.
实施例14Example 14
与实施例2的区别在于石墨烯类物质为石墨烯衍生物，即氮掺杂的氧化石墨烯(参考CN103359708A实施例1的制备方法)。 The difference from Example 2 is that the graphene-based substance is a graphene derivative, that is, nitrogen-doped graphene oxide (refer to the preparation method of Example 1 of CN103359708A).
实施例15Example 15
与实施例2的区别在于活化剂KOH加入量为50g。The difference from Example 2 was that the activator KOH was added in an amount of 50 g.
实施例16Example 16
与实施例2的区别在于活化剂KOH加入量为100g。The difference from Example 2 was that the activator KOH was added in an amount of 100 g.
实施例17Example 17
与实施例2的区别在于活化剂KOH加入量为150g。The difference from Example 2 was that the activator KOH was added in an amount of 150 g.
实施例18Example 18
与实施例2的区别在于水热反应前进行温浴，温度为25℃，在此过程中加入发泡剂，发泡剂时间为2.5h。The difference from Example 2 was that a warm bath was carried out before the hydrothermal reaction at a temperature of 25 ° C, during which a blowing agent was added, and the blowing agent time was 2.5 h.
实施例19Example 19
与实施例2的区别在于水热反应前进行温浴，温度为25℃，在此过程中加入发泡剂，发泡剂时间为4h。The difference from Example 2 was that a warm bath was carried out before the hydrothermal reaction at a temperature of 25 ° C, during which a blowing agent was added, and the blowing agent time was 4 h.
实施例20Example 20
与实施例2的区别在于石墨烯类物质(即氧化石墨烯A)加入量为0.5g，碳纳米管0.5g。The difference from Example 2 is that the graphene-based substance (i.e., graphene oxide A) is added in an amount of 0.5 g and 0.5 g of carbon nanotubes.
实施例21Example 21
与实施例2的区别在于石墨烯类物质(即氧化石墨烯A)加入量为0.95g，碳纳米管0.05g。The difference from Example 2 was that the graphene-based substance (i.e., graphene oxide A) was added in an amount of 0.95 g and the carbon nanotubes were 0.05 g.
实验experiment
检测上文所有实施例所得材料的性能，结果如下表1所示。The properties of the materials obtained in all the above examples were examined, and the results are shown in Table 1 below.
检测方法：Detection method:
取5mg活性材料分散于1mL乙醇中，然后再加入0.8mg的导电石墨(本发明的电容炭或者对照品)，摇匀，再加入1μL聚四氟乙烯溶液(60％，阿拉丁试剂)，摇匀，超声一段时间直到样品分散均匀。剪一块大小为5cm×1cm的泡沫镍，并标记出1cm×1cm的地方，在乙醇中超声10min，更换乙醇然后再超声20分钟，取出置于80℃烘箱烘干。用200微升的移液枪将配制好的活性材料溶液逐滴均匀滴在泡沫镍上面积为1cm2的地方，放入烘箱中干燥。将电极片放在压片机上压片得到超电容用极片。使用上海辰华660e电化学工作站测试电极材料超电容性能，电解液为6mol/L的KOH溶液,测试技术使用恒流充放电。5 mg of the active material was dispersed in 1 mL of ethanol, and then 0.8 mg of conductive graphite (capacitor carbon of the present invention or a control) was added, shaken, and then 1 μL of a polytetrafluoroethylene solution (60%, Aladdin reagent) was added, and shaken. Evenly, soon for a while until the sample is evenly dispersed. Cut a piece of foamed nickel with a size of 5 cm × 1 cm, and mark a place of 1 cm × 1 cm, sonicate in ethanol for 10 min, replace the ethanol and then ultrasonically for 20 minutes, and take it out and dry it in an oven at 80 °C. The prepared active material solution was uniformly dropped on a foamed nickel area of 1 cm 2 using a 200 μl pipette, and dried in an oven. The electrode sheet is placed on a tablet press to obtain a pole piece for supercapacitance. The Shanghai Chenhua 660e electrochemical workstation was used to test the supercapacitor performance of the electrode material. The electrolyte solution was a 6 mol/L KOH solution. The test technique used constant current charge and discharge.
对照组：申请公布号CN 104477878 A实施例6。Control group: Application Publication No. CN 104477878 A Example 6.
表1本发明的电容炭的性能Table 1 Performance of the capacitor carbon of the present invention
  比表面积(m2/g)Specific surface area (m 2 /g) 比电容(F/g)Specific capacitance (F/g)
实施例1Example 1 18101810 313313
实施例2Example 2 22102210 323323
实施例3Example 3 22002200 320320
实施例4Example 4 14601460 225225
实施例5Example 5 21502150 308308
实施例6Example 6 21602160 310310
实施例7Example 7 22302230 315315
实施例8Example 8 15601560 285285
实施例9Example 9 18001800 316316
实施例10Example 10 20102010 298298
实施例11Example 11 20502050 304304
实施例12Example 12 21202120 315315
实施例13Example 13 21402140 317317
实施例14Example 14 21402140 315315
实施例15Example 15 20502050 312312
实施例16Example 16 20502050 313313
实施例17Example 17 20002000 303303
实施例18Example 18 23002300 330330
实施例19Example 19 22302230 318318
实施例20Example 20 24002400 340340
实施例21Example 21 24202420 345345
对照组Control group 16001600 302302
对比实验Comparative Experiment
第一：氧化石墨烯的C、O原子摩尔比的选择First: the choice of the molar ratio of C and O atoms of graphene oxide
试验例：以实施例2、实施例10、实施例11、实施例12以及实施例13作为试验例1-5，Test Example: Example 2, Example 10, Example 11, Example 12, and Example 13 were used as Test Examples 1-5.
对比例1：所用的石墨烯类物质为氧化石墨烯A，其C/O比为1:1；Comparative Example 1: The graphene-based substance used was graphene oxide A, and its C/O ratio was 1:1;
对比例2：所用的石墨烯类物质为氧化石墨烯A，其C/O比为18:1。Comparative Example 2: The graphene-based substance used was graphene oxide A having a C/O ratio of 18:1.
表2：不同C、O原子摩尔比的对比实验结果Table 2: Comparative experimental results of different C and O atom molar ratios
  C/OC/O 比电容(F/g)Specific capacitance (F/g)
试验例1(对应实施例2)Test Example 1 (corresponding to Example 2) 3.5:13.5:1 323323
试验例2(对应实施例10)Test Example 2 (corresponding to Example 10) 2:12:1 298298
试验例3(对应实施例11)Test Example 3 (corresponding to Example 11) 6:16:1 304304
试验例4(对应实施例12)Test Example 4 (corresponding to Example 12) 5:15:1 315315
试验例5(对应实施例13)Test Example 5 (corresponding to Example 13) 4:14:1 317317
对比例1Comparative example 1 1:11:1 267267
对比例2Comparative example 2 18:118:1 208208
从表2可以明显看出，较低的C/O比，有利于提高石墨烯电极的导电性，从而提高比电容，这是基于经发明人研究发现，选用C/O比较小的氧化石墨烯A作为石墨烯类物质，由于C/O较小，石墨烯层的团聚减少，有利于电解质进入电极材料内部，石墨烯电极的导电性增强，比电容显著提高。It can be clearly seen from Table 2 that the lower C/O ratio is beneficial to increase the conductivity of the graphene electrode and thereby increase the specific capacitance. This is based on the discovery by the inventors that the smaller C/O graphene oxide is selected. As a graphene-based substance, since the C/O is small, the agglomeration of the graphene layer is reduced, which facilitates the entry of the electrolyte into the electrode material, and the conductivity of the graphene electrode is enhanced, and the specific capacitance is remarkably improved.
第二：水溶性糖与石墨烯类物质的质量比的选择Second: the choice of the mass ratio of water-soluble sugar to graphene
试验例：以实施例3、实施例4、实施例8作为试验例6-8，试验例9的水溶性糖与石墨烯类物质的质量比为50:1；Test Example: Example 3, Example 4, Example 8 was used as Test Example 6-8, the mass ratio of the water-soluble sugar to the graphene-based substance of Test Example 9 was 50:1;
对比例3：所用的水溶性糖与石墨烯类物质的质量比为10:1；Comparative Example 3: the mass ratio of the water-soluble sugar to the graphene-based substance used was 10:1;
对比例4：所用的水溶性糖与石墨烯类物质的质量比为300:1。表3：不同水溶性糖Comparative Example 4: The mass ratio of the water-soluble sugar to the graphene-based substance used was 300:1. Table 3: Different water soluble sugars
与石墨烯类物质的质量比的对比实验结果Comparison of experimental results with mass ratio of graphene
  质量比Mass ratio 比电容Specific capacitance 材料性能Material properties
试验例6Test Example 6 20:120:1 320320 强度佳，电阻小，碳化反应容易，石墨烯团聚少Good strength, low electrical resistance, easy carbonization reaction, less graphene agglomeration
试验例7Test Example 7 200:1200:1 225225 强度较佳，电阻小，碳化反应比较容易，石墨烯团聚少Better strength, lower electrical resistance, easier carbonization reaction, less graphene agglomeration
试验例8Test Example 8 200:1200:1 285285 强度较佳，电阻小，碳化反应比较容易，石墨烯团聚少Better strength, lower electrical resistance, easier carbonization reaction, less graphene agglomeration
试验例9Test Example 9 50:150:1 315315 强度佳，电阻小，碳化反应容易，石墨烯团聚少Good strength, low electrical resistance, easy carbonization reaction, less graphene agglomeration
对比例3Comparative example 3 10:110:1 215215 不能充分抑制石墨烯团聚和卷曲Insufficient inhibition of graphene agglomeration and curling
对比例4Comparative example 4 300:1300:1 196196 材料强度低，电阻大，碳化反应难度加大Low material strength, high electrical resistance, and increased difficulty in carbonization
从表3可以明显看出，水溶性糖与石墨烯类物质的质量比在20-200:1的范围内，以便水溶性糖与石墨烯类物质发生水热反应，便于水溶性糖充分插层到石墨烯的二维结构中，最大程度地抑制石墨烯片层间的卷曲、堆叠、团聚等问题，使石墨烯自发产生大孔结构；又可以使石墨烯覆盖糖，以提高材料的整体强度和稳定性，水溶性糖掺入过多既降低材料的强度，又增加电阻及碳化反应的难度，掺入过少时不能充分抑制石墨烯的团聚、卷曲等问题。It can be clearly seen from Table 3 that the mass ratio of the water-soluble sugar to the graphene-like substance is in the range of 20-200:1, so that the water-soluble sugar and the graphene-like substance undergo hydrothermal reaction, and the water-soluble sugar is sufficiently intercalated. In the two-dimensional structure of graphene, the problems of curling, stacking, agglomeration and the like between the graphene sheets are suppressed to the maximum, so that the graphene spontaneously generates a macroporous structure; and the graphene can be covered with sugar to improve the overall strength of the material. And stability, excessive incorporation of water-soluble sugar not only reduces the strength of the material, but also increases the difficulty of resistance and carbonization reaction. When the blending is too small, the problems of agglomeration and curling of graphene cannot be sufficiently suppressed.
第三：活化剂与石墨烯类物质的质量比的选择 Third: the choice of mass ratio of activator to graphene
试验例：以实施例15、实施例16、实施例17作为试验例10-12，试验例13的活化剂与石墨烯类物质质量比为80:1；Test Example: Example 15, Example 16, Example 17 was used as Test Example 10-12, the mass ratio of activator to graphene in Test Example 13 was 80:1;
对比例5：所用的活化剂与石墨烯类物质的质量比为10:1；Comparative Example 5: mass ratio of activator to graphene-based substance used was 10:1;
对比例6：所用的活化剂与石墨烯类物质的质量比为200:1。Comparative Example 6: The mass ratio of the activator to the graphene-based substance used was 200:1.
表4：不同活化剂与石墨烯类物质的质量比的对比实验结果Table 4: Comparative experimental results of mass ratios of different activators to graphenes
Figure PCTCN2017090053-appb-000001
Figure PCTCN2017090053-appb-000001
从表4可以明显看出，活化剂与石墨烯类物质的质量比在50-150:1的范围内，能够使活化剂通过碳化反应对三维碳骨架进行刻蚀，以进一步造孔，从而提高了比表面积，有利于增强材料的强度。当活化剂的掺入过少时，活化剂对三维碳骨架的刻蚀程度低，造孔程度弱，导致比表面积小，而当活化剂的掺入过多时，活化剂对三维碳骨架的刻蚀程度大，虽然比表面积得以增大，但是孔隙多，容易导致材料强度降低，因此优选活化剂的掺入量为石墨烯类物质的50-150倍。It can be clearly seen from Table 4 that the mass ratio of the activator to the graphene-like substance is in the range of 50-150:1, and the activator can etch the three-dimensional carbon skeleton through the carbonization reaction to further form pores, thereby improving The specific surface area is beneficial to enhance the strength of the material. When the activator is too little, the activator has a low degree of etching on the three-dimensional carbon skeleton, and the degree of pore formation is weak, resulting in a small specific surface area, and when the activator is excessively incorporated, the activator etches the three-dimensional carbon skeleton. The degree is large, although the specific surface area is increased, but the pores are large, which tends to cause a decrease in material strength. Therefore, it is preferred that the activator is incorporated in an amount of 50 to 150 times that of the graphene-based substance.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, and are not intended to be limiting; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that The technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features may be equivalently replaced; and the modifications or substitutions do not deviate from the technical solutions of the embodiments of the present invention. range.
工业实用性Industrial applicability
(1)限制了糖的种类，以水热反应来对石墨烯类物质改性，提高孔的多级结构，提高比表面积；(1) Limiting the type of sugar, modifying the graphene-like substance by hydrothermal reaction, increasing the multi-stage structure of the pores, and increasing the specific surface area;
(2)引入氮元素，提高比电容；(2) Introducing nitrogen element to increase specific capacitance;
(3)材料用途广泛，尤其适用于电容器。 (3) The material is widely used, especially for capacitors.

Claims (20)

  1. 一种石墨烯基多级孔电容炭的制备方法，其特征在于，包括下列步骤：A method for preparing graphene-based multi-stage pore capacitor carbon, comprising the steps of:
    使水溶性糖与石墨烯类物质发生水热反应，反应过程中加入发泡剂，反应结束后加入活化剂，再进行碳化反应，即得产品；The water-soluble sugar is hydrothermally reacted with the graphene substance, and the foaming agent is added during the reaction, and after the reaction is completed, the activator is added, and then the carbonization reaction is carried out to obtain the product;
    所述发泡剂为含氮的发泡剂；所述活化剂选自氢氧化钾、氢氧化钠、氯化锌、磷酸中的一种或多种；所述石墨烯类物质包括石墨烯、氧化石墨烯、石墨烯衍生物中的一种或多种。The blowing agent is a nitrogen-containing blowing agent; the activator is selected from one or more of potassium hydroxide, sodium hydroxide, zinc chloride, and phosphoric acid; the graphene-based material includes graphene, One or more of graphene oxide and graphene derivatives.
  2. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述石墨烯类物质为C、O原子摩尔比为2-6:1的氧化石墨烯，C、O原子摩尔比优选为3-5:1，再优选为2-4:1；The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the graphene-based substance is graphene oxide having a molar ratio of C to O of 2-6:1, C, O. The atomic molar ratio is preferably 3-5:1, more preferably 2-4:1;
    优选地，所述水溶性糖与所述石墨烯类物质的质量比为20-200:1；优选为20-50：1；Preferably, the mass ratio of the water-soluble sugar to the graphene-like substance is 20-200:1; preferably 20-50:1;
    优选的，所述活化剂与所述石墨烯类物质质量比50-150:1，再优选60-100:1，再优选70-90:1。Preferably, the mass ratio of the activator to the graphene-based substance is 50-150:1, more preferably 60-100:1, still more preferably 70-90:1.
  3. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述发泡剂选自乙二胺、三聚氰胺、己二胺，尿素、三聚氰胺中的一种或多种；The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the foaming agent is one or more selected from the group consisting of ethylenediamine, melamine, hexamethylenediamine, urea, and melamine. ;
    优选的，水热反应前，将石墨烯类物质和水溶性糖混合溶液在25-75℃的范围内温浴，优选的，所述发泡剂在温浴过程中逐渐滴加。Preferably, before the hydrothermal reaction, the graphene-based substance and the water-soluble sugar mixed solution are warmed in a range of 25 to 75 ° C. Preferably, the foaming agent is gradually added dropwise during the warm bath.
  4. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述水溶性糖选自单糖和/或多糖；所述单糖选自葡萄糖，木糖、蔗糖中的一种或多种；所述多糖选自淀粉、壳聚糖、环糊精的一种或多种。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the water-soluble sugar is selected from the group consisting of monosaccharides and/or polysaccharides; and the monosaccharide is selected from the group consisting of glucose, xylose and sucrose. One or more; the polysaccharide is selected from one or more of starch, chitosan, and cyclodextrin.
  5. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，在所述水热反应过程中还加入碳纳米管，优选的，碳纳米管加入量为石墨烯类物质的1-10wt％。The method for preparing graphene-based multi-stage pore capacitor carbon according to claim 1, wherein carbon nanotubes are further added during the hydrothermal reaction, and preferably, the amount of carbon nanotubes added is graphene. 1-10wt%.
  6. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述发泡剂与所述石墨烯类物质的质量比为5-30:1；优选地，5-20:1；更优选地，5-10:1。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein a mass ratio of the foaming agent to the graphene-based substance is 5-30:1; preferably, 5- 20:1; more preferably, 5-10:1.
  7. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述水热反应的温度为140-220℃；优选160-220℃；所述水热反应的时间优选为4-15h。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the hydrothermal reaction temperature is 140-220 ° C; preferably 160-220 ° C; and the hydrothermal reaction time is preferably It is 4-15h.
  8. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述碳化反应包括在惰性气体氛围保护下以预设温度活化1-2h后，冷却降温。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the carbonization reaction comprises cooling at a preset temperature for 1-2 hours under the protection of an inert gas atmosphere, and cooling and cooling.
  9. 根据权利要求8所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述 碳化反应的预设温度为550-1000℃；优选650-800℃。The method for preparing graphene-based multi-stage pore capacitor carbon according to claim 8, wherein The preset temperature of the carbonization reaction is 550-1000 ° C; preferably 650-800 ° C.
  10. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述石墨烯类物质和所述水溶性糖超声混合均匀，再进行所述水热反应；优选地，先对所述石墨烯类物质进行超声得到均一的石墨烯水溶液，接着向所述石墨烯水溶液中加入所述水溶性糖，再次超声混合。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the graphene-based substance and the water-soluble sugar are ultrasonically mixed uniformly, and then the hydrothermal reaction is performed; preferably, The graphene-based substance is first ultrasonically obtained to obtain a uniform aqueous graphene solution, and then the water-soluble sugar is added to the graphene aqueous solution, and ultrasonically mixed again.
  11. 根据权利要求1所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述石墨烯类物质是以纤维素为原料制成的石墨烯，以纤维素制成石墨烯具体包括：混合所述纤维素和氯化亚铁，经催化处理后干燥，得到前驱体；将所述前驱体经程序升温处理后得到粗品；所述粗品经洗涤后即得。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 1, wherein the graphene-based material is graphene made of cellulose as a raw material, and graphene made of cellulose is specifically included. Mixing the cellulose and ferrous chloride, and drying after catalytic treatment to obtain a precursor; the precursor is subjected to a temperature-programmed treatment to obtain a crude product; and the crude product is obtained after washing.
  12. 根据权利要求11所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述纤维素和所述氯化亚铁以质量比为1-3：1进行混合；优选质量比为1-2:1；优选质量比为1:1。The method for preparing a graphene-based multi-stage pore capacitor carbon according to claim 11, wherein the cellulose and the ferrous chloride are mixed at a mass ratio of 1-3:1; preferably the mass ratio is 1-2:1; the preferred mass ratio is 1:1.
  13. 根据权利要求11-12任一项所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述催化处理的温度为100-200℃，优选为120-180℃；优选为140-160℃；所述催化处理的时间为2-6h，优选为3-5h，优选为4h。The method for preparing graphene-based multi-stage pore capacitor carbon according to any one of claims 11 to 12, wherein the temperature of the catalytic treatment is 100-200 ° C, preferably 120-180 ° C; preferably 140 -160 ° C; the catalytic treatment time is 2-6 h, preferably 3-5 h, preferably 4 h.
  14. 根据权利要求11-13任一项所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述程序升温包括：以1-5℃/min的升温速率将所述前驱体升温至150-200℃，保温2-3h，之后以10-20℃/min的升温速率升温至300-500℃，保温3-4h，之后以10-20℃/min的升温速率升温至1000-1400℃，保温3-4h后得到所述粗品；The method for preparing a graphene-based multi-stage pore capacitor carbon according to any one of claims 11 to 13, wherein the temperature rising comprises: heating the precursor at a temperature increase rate of 1-5 ° C / min Increasing to 150-200 ° C, holding for 2-3 h, then raising the temperature to 300-500 ° C at a heating rate of 10-20 ° C / min, holding for 3-4 h, then raising the temperature to 1000-1400 at a heating rate of 10-20 ° C / min °C, after 3-4h incubation, the crude product is obtained;
    优选地；以2-4℃/min的升温速率将所述前驱体升温至160-180℃，保温2-3h，之后以13-17℃/min的升温速率升温至350-450℃，保温3-4h，之后以13-17℃/min的升温速率升温至1100-1300℃，保温3-4h后得到所述粗品；Preferably, the precursor is heated to 160-180 ° C at a temperature increase rate of 2-4 ° C / min, held for 2-3 h, and then heated to 350-450 ° C at a temperature increase rate of 13-17 ° C / min, heat preservation 3 -4h, after which the temperature is raised to 1100-1300 ° C at a heating rate of 13-17 ° C / min, and the crude product is obtained after 3-4 hours of incubation;
    更优选地；以3℃/min的升温速率将所述前驱体升温至170℃，保温2h，之后以15℃/min的升温速率升温至400℃，保温3h，之后以15℃/min的升温速率升温至1200℃，保温3h后得到所述粗品。More preferably; the precursor is heated to 170 ° C at a temperature increase rate of 3 ° C / min, held for 2 h, then heated to 400 ° C at a heating rate of 15 ° C / min, held for 3 h, then raised at 15 ° C / min The temperature was raised to 1200 ° C, and the crude product was obtained after 3 h of heat preservation.
  15. 根据权利要求11-14任一项所述的石墨烯基多级孔电容炭的制备方法，其特征在于，洗涤所述粗品包括将所述粗品于温度为55-65℃条件下，经浓度为8-12％的氢氧化钠溶液碱洗、接着经浓度为2-6wt％的盐酸酸洗后，再进行水洗。The method for preparing a graphene-based multi-stage pore capacitor carbon according to any one of claims 11 to 14, wherein washing the crude product comprises subjecting the crude product to a temperature of 55-65 ° C at a concentration of The 8-12% sodium hydroxide solution was washed with alkali, followed by pickling with a concentration of 2-6 wt% hydrochloric acid, followed by washing with water.
  16. 根据权利要求11-15任一项所述的石墨烯基多级孔电容炭的制备方法，其特征在于，所述纤维素的制备方法包括：The method for preparing a graphene-based multi-stage pore capacitor carbon according to any one of claims 11 to 15, wherein the method for preparing the cellulose comprises:
    小麦秸秆在第一催化剂的作用下经第一有机酸蒸煮后，分离取第一固体；The wheat straw is cooked by the first organic acid under the action of the first catalyst, and the first solid is separated;
    将所述第一固体在第二催化剂的作用下经第二有机酸洗涤后，分离取第二固体；以及 将所述第二固体进行水洗，获得水洗浆，将所述水洗浆进行固液分离并收集固体，即得；After the first solid is washed by the second organic acid under the action of the second catalyst, the second solid is separated; The second solid is washed with water to obtain a water washing slurry, and the water washing slurry is subjected to solid-liquid separation and collecting solids, that is, obtained;
    其中，所述第一有机酸包括质量比为1:12的乙酸与甲酸；所述第二有机酸包括质量比为1:12的乙酸与甲酸；所述第一催化剂和所述第二催化剂均为过氧化氢。Wherein the first organic acid comprises acetic acid and formic acid in a mass ratio of 1:12; the second organic acid comprises acetic acid and formic acid in a mass ratio of 1:12; both the first catalyst and the second catalyst are It is hydrogen peroxide.
  17. 根据权利要求16所述的石墨烯基多级孔电容炭的制备方法，其特征在于，在所述第一有机酸蒸煮中，所述第一有机酸的总酸浓度为80-90wt％，优选为80-85wt％，更优选为80wt％；The method for preparing graphene-based multi-stage pore capacitor carbon according to claim 16, wherein in the first organic acid cooking, the total acid concentration of the first organic acid is 80-90 wt%, preferably 80-85 wt%, more preferably 80 wt%;
    所述小麦秸秆与所述第一有机酸的固液质量比为1:10-12，优选为1:10-11，更优选为1:10；The solid-liquid mass ratio of the wheat straw to the first organic acid is 1:10-12, preferably 1:10-11, more preferably 1:10;
    所述第一催化剂的加入量为所述小麦秸秆的1-3wt％，优选为1-2wt％，更优选为1wt％；The first catalyst is added in an amount of 1-3 wt%, preferably 1-2 wt%, more preferably 1 wt% of the wheat straw;
    所述第一有机酸蒸煮的反应温度为120-150℃，反应时间为30-50min。The reaction temperature of the first organic acid cooking is 120-150 ° C, and the reaction time is 30-50 min.
  18. 根据权利要求16所述的石墨烯基多级孔电容炭的制备方法，其特征在于，在所述第二有机酸洗涤中，所述第二有机酸的总酸浓度为70-79wt％，优选为72-77wt％；更优选为75wt％；The method for preparing graphene-based multi-stage pore capacitor carbon according to claim 16, wherein in the second organic acid washing, the total acid concentration of the second organic acid is 70-79 wt%, preferably Is 72-77 wt%; more preferably 75 wt%;
    所述小麦秸秆与所述第二有机酸的固液质量比为1:7-9；优选为1:8-9，更优选为1:9；The solid-liquid mass ratio of the wheat straw to the second organic acid is 1:7-9; preferably 1:8-9, more preferably 1:9;
    所述第二催化剂的加入量为所述小麦秸秆的8-10wt％；优选为8-9wt％，更优选为8wt％；The second catalyst is added in an amount of 8-10% by weight of the wheat straw; preferably 8-9 wt%, more preferably 8 wt%;
    所述第二有机酸洗涤的洗涤温度为90-100℃，洗涤时间为1-2h。The second organic acid washing has a washing temperature of 90-100 ° C and a washing time of 1-2 h.
  19. 一种石墨烯基多级孔电容炭，其特征在于，采用权利要求1-18任一项所述的石墨烯基多级孔电容炭的制备方法制得。A graphene-based multistage pore capacitor carbon obtained by the method for preparing a graphene-based multi-stage pore capacitor carbon according to any one of claims 1 to 18.
  20. 一种电容器，其特征在于，以权利要求19所述的石墨烯基多级孔电容炭为电容材料。 A capacitor characterized by comprising the graphene-based multi-stage pore capacitor carbon according to claim 19 as a capacitor material.
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CN113651320A (en) * 2021-10-19 2021-11-16 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) Method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite material
CN115116763A (en) * 2022-07-11 2022-09-27 武汉工程大学 Cyano-rich porous carbon, preparation method thereof and application of cyano-rich porous carbon as electrode material of supercapacitor

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012193100A (en) * 2011-03-16 2012-10-11 Ind Technol Res Inst Porous carbon material, and manufacturing method thereof
CN103626151A (en) * 2013-11-28 2014-03-12 复旦大学 Preparation method of graphene/carbon composite material
CN103723716A (en) * 2013-12-23 2014-04-16 北京化工大学 Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof
CN103898782A (en) * 2012-12-25 2014-07-02 济南圣泉集团股份有限公司 Technology for extracting cellulose from biomass raw materials
CN104003374A (en) * 2014-05-04 2014-08-27 昆明理工大学 Preparation method of graphene-based nanocomposite material having three-dimensional porous structure
CN104724699A (en) * 2015-03-04 2015-06-24 黑龙江大学 Method for preparing biomass graphene employing cellulose as raw material
CN105185599A (en) * 2015-10-16 2015-12-23 中国科学院福建物质结构研究所 Super-capacitor carbon composite material, preparation method therefor, and application of super-capacitor carbon composite material
CN105590757A (en) * 2014-11-18 2016-05-18 中国科学院宁波材料技术与工程研究所 Carbon nanotube/graphene composite gel and preparation method thereof
CN106467299A (en) * 2016-06-27 2017-03-01 济南圣泉集团股份有限公司 A kind of graphene-based multi-stage porous electric capacity charcoal and preparation method thereof and capacitor

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012193100A (en) * 2011-03-16 2012-10-11 Ind Technol Res Inst Porous carbon material, and manufacturing method thereof
CN103898782A (en) * 2012-12-25 2014-07-02 济南圣泉集团股份有限公司 Technology for extracting cellulose from biomass raw materials
CN103626151A (en) * 2013-11-28 2014-03-12 复旦大学 Preparation method of graphene/carbon composite material
CN103723716A (en) * 2013-12-23 2014-04-16 北京化工大学 Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof
CN104003374A (en) * 2014-05-04 2014-08-27 昆明理工大学 Preparation method of graphene-based nanocomposite material having three-dimensional porous structure
CN105590757A (en) * 2014-11-18 2016-05-18 中国科学院宁波材料技术与工程研究所 Carbon nanotube/graphene composite gel and preparation method thereof
CN104724699A (en) * 2015-03-04 2015-06-24 黑龙江大学 Method for preparing biomass graphene employing cellulose as raw material
CN105185599A (en) * 2015-10-16 2015-12-23 中国科学院福建物质结构研究所 Super-capacitor carbon composite material, preparation method therefor, and application of super-capacitor carbon composite material
CN106467299A (en) * 2016-06-27 2017-03-01 济南圣泉集团股份有限公司 A kind of graphene-based multi-stage porous electric capacity charcoal and preparation method thereof and capacitor

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019211521A1 (en) 2018-04-30 2019-11-07 Teknologian Tutkimuskeskus Vtt Oy Production of graphene structures
CN109467082A (en) * 2018-12-18 2019-03-15 济南大学 A kind of preparation method being graphitized the derivative carbon electrode material of porous corncob
CN111268673A (en) * 2020-02-11 2020-06-12 西安理工大学 Preparation method of supercapacitor electrode material taking foamed nickel as template
CN112863891A (en) * 2020-07-04 2021-05-28 山东八三石墨新材料厂 Preparation method of carbon material for super capacitor
CN112366097A (en) * 2020-12-14 2021-02-12 山东精工电子科技有限公司 Preparation method of all-carbon electrode for improving performance of graphene-based supercapacitor
CN112366097B (en) * 2020-12-14 2022-05-03 山东精工电子科技有限公司 Preparation method of all-carbon electrode for improving performance of graphene-based supercapacitor
CN112723343A (en) * 2020-12-30 2021-04-30 安徽工程大学 Method for directly preparing high-quality graphene from biomass
CN113184848A (en) * 2021-04-22 2021-07-30 合肥工业大学 Method for preparing biomass porous carbon for supercapacitor based on shaddock peel
CN113593924A (en) * 2021-07-28 2021-11-02 哈尔滨万鑫石墨谷科技有限公司 Carbon nitride-graphene composite material and preparation method and application thereof
CN113694890A (en) * 2021-08-16 2021-11-26 厦门大学 Preparation method and application of cotton-based activated carbon fiber
CN113620287A (en) * 2021-08-17 2021-11-09 上海赛普瑞特生物科技有限公司 Nitrogen-doped capacitance carbon using lignin as precursor of carbon and adopting 'inner leaching-outer wrapping' technology and preparation method thereof
CN113620287B (en) * 2021-08-17 2023-06-09 上海赛普瑞特生物科技有限公司 Nitrogen-doped capacitor carbon taking lignin as precursor of carbon and adopting 'inner soaking-outer wrapping' technology and preparation method thereof
CN113620348A (en) * 2021-08-26 2021-11-09 徐州润锋新材料有限公司 Porous ferroferric oxide powder and preparation method thereof
CN113830762A (en) * 2021-09-29 2021-12-24 中钢集团鞍山热能研究院有限公司 Nitrogen-doped porous carbon material with microstructure easy to regulate and control, and preparation method and application thereof
CN113830762B (en) * 2021-09-29 2023-09-12 中钢集团鞍山热能研究院有限公司 Nitrogen-doped porous carbon material with microstructure easy to regulate and control, and preparation method and application thereof
CN113830764A (en) * 2021-11-09 2021-12-24 四川金汇能新材料股份有限公司 Melamine-doped porous carbon material and preparation method and application thereof
CN114804098A (en) * 2022-03-18 2022-07-29 广东省农业科学院作物研究所 Method for preparing porous activated carbon by adopting waste tobacco straws
CN114804098B (en) * 2022-03-18 2024-02-06 广东省农业科学院作物研究所 Method for preparing porous activated carbon from waste tobacco straw
CN114700036A (en) * 2022-03-25 2022-07-05 华南理工大学 Modified tobacco stem-based biomass hierarchical pore carbon and preparation method and application thereof
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