WO2015000152A1 - Procédé de préparation d'un composite de particules de graphène/nano-carbone - Google Patents

Procédé de préparation d'un composite de particules de graphène/nano-carbone Download PDF

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Publication number
WO2015000152A1
WO2015000152A1 PCT/CN2013/078770 CN2013078770W WO2015000152A1 WO 2015000152 A1 WO2015000152 A1 WO 2015000152A1 CN 2013078770 W CN2013078770 W CN 2013078770W WO 2015000152 A1 WO2015000152 A1 WO 2015000152A1
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Prior art keywords
graphene
carbon
spray
suspension
nano
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PCT/CN2013/078770
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English (en)
Chinese (zh)
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王要兵
洪茂椿
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中国科学院福建物质结构研究所
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Priority to PCT/CN2013/078770 priority Critical patent/WO2015000152A1/fr
Publication of WO2015000152A1 publication Critical patent/WO2015000152A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to the field of graphene materials, in particular to a method for preparing a graphene/nanocarbon particle composite material, and to the application of a mesene/nanoparticle composite material in a supercapacitor. Background technique
  • graphene materials can be used as electrode materials in supercapacitors and lithium ion batteries. So far, graphite has been prepared.
  • the oxidation-reduction method is a method capable of preparing graphene in a large amount and having a high yield, and the whole process involves oxidizing graphite into graphite oxide, and further vaporizing graphite to peel off under external force.
  • Graphene oxide chemically or thermally reduced to graphene. Chemical reduction is a relatively simple method of reducing graphene, which is beneficial to the composite of graphene and other substances.
  • the graphene after reduction is easily agglomerated, resulting in loss of some functions and difficulty in processing, which is not conducive to industrialization.
  • Graphene research has become a hot research topic in current materials.
  • Graphene is also a kind of carbon material. It has the same properties as carbon materials in many aspects, but at the same time it exists in a two-dimensional structure, so it has unique properties, graphene. And the application of nano carbon particles is particularly extensive. Based on the above reasons, in order to take advantage of these two different materials, we have proposed a new method for preparing graphene/nano-particle materials. Summary of the invention
  • the present invention provides a method for preparing a graphene composite material loaded with carbon nanoparticles, comprising the following steps:
  • step 5) The powder obtained in the step 4) is subjected to reduction treatment, and after the reduction is completed, it is cooled to room temperature in a reducing atmosphere, washed and dried to finally obtain a graphene composite material loaded with carbon nanoparticles.
  • the graphite raw material used in the present invention may be a graphite flake such as natural flake graphite, graphite powder, ketjen black or the like.
  • nanocarbon particles in the present invention are not particularly referred to as spherical particles, but refer to other carbon materials having a nanometer size in addition to graphene.
  • the nanocarbon particles used in the present invention may be carbon 60, carbon black, acetylene black, ketjen black, carbon nanotubes, carbon nanofibers or a combination thereof.
  • the nanocarbon particles have a size of 2 to 100 nm, preferably 10 to 80 nm, more preferably 20 to 60 nm, and most preferably 20 to 50 nm; in the case of spherical carbon particles, the size means an average diameter; In the case of carbon, the size refers to the average thickness; in the case of carbon nanofibers, the size refers to the diameter of the fiber; in the case of other shapes, it refers to between any two points on the surface of the material. The longest straight line distance.
  • the method of preparing graphene oxide by graphite oxide is an improved Hummers method, which is well known to those skilled in the art, for example, see JACS, 1958, 80, 1339.
  • the surfactant for dispersing the nano carbon particles may be any surfactant capable of uniformly dispersing carbon nanoparticles and graphene oxide, uniformly mixing, and being water-washed after high temperature, including but not limited to anionic surfactants. , cationic surfactant, zwitterionic surfactant, nonionic surfactant and special surfactant, wherein the anionic surfactants are: sulfate type, carboxylate type, sulfonate type and phosphate
  • the cationic surfactants are: quaternary ammonium salt type, imidazolium salt type and pyridinium salt type; wherein the zwitterionic surfactants are: acid type, betaine type, pyrazoline type, etc.;
  • the ionic surfactants are: polyoxyethylene, phenolyl alcohol amine, sorbitan fatty acid ester, amine oxide, alkyl glycoside and the like.
  • the special surfactant contains a fluorocarbon surfactant (for example, C 2 F 5 (OCF 2 CF(CF 3 )) 2 OC 2 F 4 S0 3 Na), a silicon-containing surfactant, a Gemini surfactant, and the like.
  • the surfactant is usually used in an amount of 0.001 to 30 g/L, preferably 0.01 to 10 g/L, and most preferably 0.1 to 5 g/L.
  • the nanocarbon particles are used in an amount of from 1 to 50%, preferably from 1 to 20%, most preferably from 5 to 15%, based on the mass of the graphene oxide.
  • the spray drying technique used in the present invention may be a centrifugal spray, an ultrasonic spray, a jet spray or a pressure spray technique or a combination thereof.
  • Spray drying equipment is well known to those skilled in the art.
  • Pressure spray techniques are preferred.
  • the size of the carbon nanoparticle-loaded graphene composite may be affected by parameters such as the concentration of the raw material, the temperature of the inlet, the temperature of the outlet, and the centrifugal speed (or pressure). Therefore, in the spray drying process, parameters such as the concentration of the raw material, the spray pressure, the inlet air temperature, the outlet temperature, and the centrifugal speed (or pressure) are preferably optimized to obtain the desired size, structure, and desired electrical properties.
  • Composite material is preferably optimized to obtain the desired size, structure, and desired electrical properties.
  • the inventors have found through long-term studies that spray drying can be carried out under the following process conditions to obtain an oxyalkylene graphene/carbon nanoparticle composite having the desired size, structure and particularly good electrical properties: under pressure
  • the spray pressure is l-10 MPa, preferably 4-6 MPa
  • the inlet air temperature is 120-200 ° C, preferably 140-160 ° C
  • the outlet temperature is 80-120 ° C, preferably 90-100 ° C
  • the centrifugal speed is from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm.
  • the resulting powder was subjected to a reduction treatment under a reducing atmosphere.
  • the reducing agent used in the reduction treatment is preferably a reducing gas including, but not limited to, hydrogen, or a mixed gas of hydrogen and an inert gas.
  • the volume ratio of hydrogen to inert gas is from 1:100 to 30:100, preferably from 5:100 to 20:100, more preferably 10 : 100-20:100, most preferably 10:100-15:100.
  • the inert gas is argon, nitrogen, helium or neon.
  • the reduction treatment time is from 1 to 10 hours, preferably from 2 to 4 hours.
  • the temperature of the reduction treatment is from 600 to 1200 ° C, preferably from 600 to 800 ° C.
  • the reduction treatment is usually carried out in a tube furnace. Specific tube furnaces are well known to those skilled in the art.
  • the inventors have found through long-term intensive studies that the spray-dried powder is first pre-heat treated under an inert atmosphere, and then the powder is cooled to room temperature, followed by reduction under a reducing atmosphere. By reacting, a carbon nanoparticle-loaded graphene composite material having particularly excellent properties can be obtained.
  • low temperature pretreatment is beneficial to the decomposition of reactive groups.
  • the pore structure is formed, and the later reduction treatment is advantageous for improving the conductivity of the graphene material and further stabilizing the structure.
  • the present invention is directed to a method of preparing a graphene composite loaded with carbon nanoparticles, comprising the steps of:
  • step 5) The powder obtained in the step 4) is placed under an inert gas atmosphere, preheated, and then cooled to room temperature, followed by reduction in a reducing atmosphere, and after reduction, cooling to a reducing atmosphere At room temperature, it is washed and dried to finally produce a graphene composite loaded with carbon nanoparticles.
  • the preheat treatment temperature is usually 300 to 500 ° C, preferably 320 to 400 ° C, and most preferably 350 to 400 ° C; the preheat treatment time is usually 1 to 12 hours, preferably 2-4 hours.
  • the inert gas used in the inert atmosphere is argon, nitrogen, helium or neon.
  • the reduction treatment is carried out at a temperature of from 600 to 1200 ° C, preferably from 600 to 800 ° C; and the reduction treatment is usually carried out for from 1 to 10 hours, preferably from 2 to 4 hours.
  • the preheating and reduction treatments of the present invention are generally carried out in a tube furnace, which may be carried out in the same tube furnace or in a different tube furnace, but preferably in the same tube furnace. Specific tube furnaces are well known to those skilled in the art.
  • the present invention relates to an embodiment in which the powder obtained after drying is placed in a tube furnace with an inert gas and slowly heated to a temperature of 300 to 500 ° C for 10 to 12 hours at 10 ° C / mi, and then the powder is further Cooling to room temperature with the furnace; then introducing a mixed gas of hydrogen and an inert gas into the tubular furnace (for example, hydrogen, or a volume ratio of 1:100-30:100), wherein the inert gas is argon gas, nitrogen gas , helium or helium) 5-10m i, control the flow rate of reducing gas to 60mL / min, the air in the tube furnace is discharged to form a reducing atmosphere, and then the temperature is raised to 600-1200 ° C, at this temperature Keep heating for l-10h, after the reduction is completed, cool to room temperature under reducing atmosphere, and repeatedly wash with distilled water and absolute ethanol to remove residual surfactant and its residue after high temperature conversion (such as inorganic salt), the final system A graphene
  • the carbon nanoparticle graphene composite of the present invention can be used as a supercapacitor material, a catalyst carrier or Infrared optical material.
  • the nano carbon particles can be well dispersed between the sheets of graphene, a synergistic effect can be exerted; in the composite material prepared by the method, both of them
  • the composite not only prevents the agglomeration of the graphene sheets, but also prevents the agglomeration between the carbon particles, effectively increasing the specific surface area of the composite, thereby improving the capacitance performance thereof; and the conductivity of the graphene sheets and the carbon nanoparticles are high.
  • the resulting composite material also has a higher conductivity;
  • the composite material prepared by the method has a high specific surface area and has wide application prospects in the field of supercapacitors;
  • Figure 1 is a particle obtained by spray drying in Example 1.
  • Fig. 2 is a graph showing the charge and discharge curves of the supercapacitor prepared in Example 1. detailed description
  • the invention provides a graphene/nano carbon particle composite material and a preparation method thereof, firstly, the natural flake graphite is oxidized into graphene oxide, the surfactant dissolves the nano particles to form a suspension, and the graphene oxide nano carbon particles are obtained by mixing.
  • the suspension is stirred at room temperature, and after mixing uniformly, the mixed suspension is spray-dried, the solvent is removed to obtain a powder, and the powder is placed in a tube furnace protected by an inert gas to be heated and reduced.
  • the invention provides a process for preparing a graphene composite material loaded with carbon nanoparticles as follows: natural flake graphite ⁇ graphene oxide ⁇ graphene oxide suspension ⁇ carbon nanoparticle and graphene mixed suspension ⁇ graphene/nanocarbon Granular composites.
  • the present invention relates to the following aspects:
  • a method for preparing a graphene/nano carbon particle composite material comprising the steps of:
  • nanocarbon particles are selected from the group consisting of carbon 60, carbon black, aceton black, ketjen black, carbon nanotubes, carbon nanofibers, or a combination thereof.
  • nanocarbon particles have a size of from 2 to 100 nm, preferably from 10 to 80 nm, more preferably from 20 to 60 nm, and most preferably from 20 to 50 nm.
  • step 4 employs a centrifugal spray, an ultrasonic spray, a gas spray or a pressure spray technique, or a combination thereof.
  • the spray drying is carried out by a pressure spray technique, wherein the spray pressure is l-10 MPa, preferably 4-6 MPa; the inlet air temperature is 120-200 ° C, preferably 140-160 ° C; and the outlet temperature is 80 -120 ° C, preferably 90-100 ° C.
  • the reducing atmosphere is hydrogen or a mixed gas of hydrogen and an inert gas.
  • the method according to any one of 1-8, wherein the reduction treatment in a) and b) of step 5) is from 1 to 10 hours, preferably from 2 to 4 hours.
  • the preheating temperature is 300-500 ° C, preferably 320-400 ° C, most preferably 350 ° C;
  • the preheat treatment time is 1-12 hours, preferably 2-4 hours.
  • a graphene/nanocarbon particle composite obtained by the method of any of 1-11.
  • Example 1 The preparation process of the present invention is further illustrated by the following examples, and the embodiments of the present invention are not intended to limit the scope of the present invention. Any modifications and variations made on the basis of the present invention are within the scope of the present invention.
  • Example 1
  • the dried sample was added to 0 ° C, 230 mL of concentrated sulfuric acid, 60 g of potassium permanganate was added, the temperature of the mixture was kept below 20 ° C, and then kept in an oil bath at 35 ° C for 2 h, then slowly added 920 mL.
  • Deionized water After 15 minutes, add 2.8 L of deionized water (containing 50 mL of 30% hydrogen peroxide), then the color of the mixture turned bright yellow, filtered while hot, and washed with 5 L of 10% hydrochloric acid. After drying under vacuum at 60 ° C for 48 hours, graphene oxide was obtained, which was added to deionized water and stirred to obtain a suspension.
  • the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. / Acetonitrile electrolyte, sealed injection port, get super capacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • Ketjen black ECP600JD (Switzerland, Temco ECP600JD, particle size 20 nm) was added to 500 mL of deionized water together with 5 g of surfactant dodecyltetraethyl quaternary ammonium salt. The ultrasonic power was dispersed for 100 min for 30 min, thereby obtaining a uniform suspension of Ketchen Black ECP600JD.
  • the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. / Acetonitrile electrolyte, sealed injection port, get super capacitor.
  • the electrochemical performance of charge and discharge, cyclic voltammetry, and lifetime was tested.
  • the capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. / Acetonitrile electrolyte, sealed injection port, get super capacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. /acetonitrile electrolyte, Seal the injection port to get a supercapacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • Example 5 Example 5:
  • the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. / Acetonitrile electrolyte, sealed injection port, get super capacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. / Acetonitrile electrolyte, sealed injection port, get super capacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Comparative Example 1
  • Example 7 A graphene/nanocarbon particle composite was prepared similarly to the procedure of Example 6, and a supercapacitor was prepared according to the procedure of Example 6 (6), and its capacity, pressure resistance, rate performance and life were measured. The results are summarized in Table 1. in. The difference from Example 6 was that, at the time of spray drying, a spray pressure of 3 MPa, an inlet air temperature of 200 ° C, and an outlet air temperature of 90 ° C were employed.
  • Example 7 A graphene/nanocarbon particle composite was prepared similarly to the procedure of Example 6, and a supercapacitor was prepared according to the procedure of Example 6 (6), and its capacity, pressure resistance, rate performance and life were measured. The results are summarized in Table 1. in. The difference from Example 6 was that, at the time of spray drying, a spray pressure of 3 MPa, an inlet air temperature of 200 ° C, and an outlet air temperature of 90 ° C were employed.
  • Example 7
  • a graphene/nanocarbon particle composite was prepared in a manner similar to that of Example 6, and a supercapacitor was prepared according to the procedure of the procedure (6) of Example 1, and the capacity, pressure resistance, rate performance and life were measured.
  • the results are summarized in Table 1. in.
  • the difference from Example 1 is that after spray drying, 2 g of the obtained powder is slowly heated to 800 ° C at 10 ° C / mi in a tube furnace having a volume ratio of 20:100 hydrogen and an inert gas. After maintaining the temperature for 5 h, after the reduction, the mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
  • the graphene/nanocarbon particle composite prepared by the present invention has better electrical properties.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un composite de particules de graphène/nano-carbone. Le procédé comprend : 1) l'oxydation de graphite pour préparer du graphène oxydé, et l'addition du graphène oxydé obtenu à de l'eau pour préparer une suspension liquide; 2) l'addition de particules de nano-carbone dans une solution d'eau avec un agent tensioactif pour obtenir une suspension liquide des particules de nano-carbone; 3) le mélange de la suspension liquide du graphène oxydé avec la suspension liquide des particules de nano-carbone, afin d'obtenir une suspension liquide mélangée; 4) la réalisation d'un séchage par pulvérisation sur la suspension liquide mélangée de manière uniforme pour obtenir une poudre; et 5) la réalisation d'un traitement de réduction sur la poudre obtenue à l'étape 4), ou la mise en place de la poudre obtenue à l'étape 4) dans une atmosphère de gaz inerte, le préchauffage de la poudre, et ensuite la réalisation d'une réaction de réduction sous une atmosphère réductrice, afin de préparer finalement le composite de graphène chargé des particules de nano-carbone. La présente invention concerne également le composite de particules de graphène/nano-carbone obtenu par l'utilisation du procédé selon la présente invention, et les applications du composite de particules de graphène/nano-carbone utilisé comme matériau pour supercondensateurs, un support pour catalyseur ou un matériau optique infrarouge.
PCT/CN2013/078770 2013-07-03 2013-07-03 Procédé de préparation d'un composite de particules de graphène/nano-carbone WO2015000152A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10770734B2 (en) 2015-08-14 2020-09-08 Lg Chem, Ltd. Lithium air battery and manufacturing method therefor

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Publication number Priority date Publication date Assignee Title
US10770734B2 (en) 2015-08-14 2020-09-08 Lg Chem, Ltd. Lithium air battery and manufacturing method therefor

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