CN107301921B - A kind of preparation method of three-dimensional Activated Graphite alkene nanometer sheet - Google Patents

A kind of preparation method of three-dimensional Activated Graphite alkene nanometer sheet Download PDF

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CN107301921B
CN107301921B CN201710453837.5A CN201710453837A CN107301921B CN 107301921 B CN107301921 B CN 107301921B CN 201710453837 A CN201710453837 A CN 201710453837A CN 107301921 B CN107301921 B CN 107301921B
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nanometer sheet
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graphite alkene
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CN107301921A (en
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李泽胜
李泊林
梁琪君
李德豪
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Guangdong University of Petrochemical Technology
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    • 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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of preparation methods of three-dimensional Activated Graphite alkene nanometer sheet.The preparation method includes the selection and pre-treatment of S1. carbon source；S2. the selection of activator, three-dimensional structure template and catalyst precursor；S3. presoma mixed processing；S4. heat treatment is covered；S5. product post-processes.The present invention uses carbon source of the widely used polyol-based non-ionic surfactant as graphene nanometer sheet, largely reduces the preparation cost of material；Activator, three-dimensional structure template and catalyst precursor are used as simultaneously using cheap alkali metal hydroxide, synthesis step is radically simplified and reduces the preparation cost of material；Using heat treatment technics is covered, in common Muffle furnace, that is, implementable, suitable large-scale production.Preparation process of the present invention is simple, easy to industrialized production.

Description

A kind of preparation method of three-dimensional Activated Graphite alkene nanometer sheet
Technical field
The present invention relates to a kind of preparation method of graphene nanometer sheet in energy storage material and application more particularly to a kind of three-dimensionals The preparation method and applications of Activated Graphite alkene nanometer sheet.
Background technique
Lithium ion battery and supercapacitor are two kinds of important class of electrochemical energy accumulating device.The former passes through electrification Reaction storage energy is learned, higher energy density can be shown；And the latter can be provided by electric double layer process storage energy Higher power density.Supercapacitor also has many advantages, such as that non-maintaining, the service life is long, has been widely used in many portable electrics Sub- equipment.It is always long-term main struggle mesh in exploitation high energy supercapacitor for electric vehicle, specific capacitance high electrode material Mark.Active carbon is a kind of most common supercapacitor (double layer capacitor) electrode material, have porous structure, low price and The advantages that can be mass.However, the specific surface area of conventional carbon is small, conductivity is low, and chemical stability is insufficient, prevent its from Meet the newest stored energy application requirement of long period, high reliability and high-energy density.
Two-dimensional graphene material has become the electrochemical energy storage electrode material of a new generation by excellent physicochemical characteristics. The surface-active site of height exposure and the unique electronic structure of graphene, class graphene (such as ultra-thin carbon nanosheet), can be lithium Ion battery and supercapacitor provide high capacity.Three-dimensional grapheme structure as graphene nanometer sheet (three made of being connected with each other Tie up structure), by its unique structure and in the form of sustainable energy storage in show tempting application prospect.Novel three-dimensional stone Black alkene structure has in electro-chemical systems there are two advantage: (i) the network structure of connected graphene nanometer sheet can prevent stone Black alkene nanometer sheet aggregation, the macroporous structure (ii) interconnected provide advantageous channel for electron transmission and ion diffusion.Therefore, three-dimensional Graphene-structured can significantly improve the specific capacitance of supercapacitor.
In view of the excellent performance of three-dimensional grapheme material and wide prospect, the efficient of synthesis three-dimensional grapheme material is explored Synthetic method has important scientific meaning and practical value.Currently, the preparation method of three-dimensional grapheme material mainly has two Kind: (1) using graphene oxide as presoma be mutually related three-dimensional grapheme knot is obtained by hydrothermal reduction and self assembling process Structure；(2) the three of self-supporting are obtained by chemical vapor deposition and removing template process using nickel foam as three-dimensional template and catalytic substrate Tie up graphene-structured.Obviously, above-mentioned multistep preparation process is cumbersome and energy consumption is higher, is difficult to realize three-dimensional grapheme material Mass production.In particular, structure is complicated and expensive for device therefor, great difficulty is brought to the exploitation of subsequent material Topic.In consideration of it, the industrialization for pushing three-dimensional grapheme material will be played to Guan Chong by developing cheap, the simple preparation method of one kind The effect wanted.
Summary of the invention
The purpose of the present invention is overcoming the shortcomings of the prior art, a kind of system of three-dimensional Activated Graphite alkene nanometer sheet is provided The step of Preparation Method, the current three-dimensional Activated Graphite alkene nanometer piece preparation method of solution is faced, is complicated, equipment is expensive, it is numerous to operate The problems such as trivial, difficult batch production.
Above-mentioned purpose of the invention is achieved by the following technical programs:
A kind of preparation method of three-dimensional Activated Graphite alkene nanometer sheet, includes the following steps:
S1. carbon source select and pre-treatment: select polyol-based non-ionic surfactant for carbon source, and carried out with solvent Dissolution and dilution；
S2. activator, three-dimensional structure template and catalyst precursor select: select alkali metal hydroxide simultaneously as Activator, three-dimensional structure template and catalyst precursor；
S3. presoma mixed processing: by the alkali metal of nonionic surfactant and step S2 after step S1 pre-treatment Hydroxide carries out high-speed stirred mixing and vacuum drying；
S4. it covers heat treatment: mixture obtained by step S3 is placed in graphite crucible, adjust sample volume and sample The volume of air of top, closes the lid, and is heat-treated with the burial of charcoal carbon dust；
S5. product post-processes: the product after step S4 heat treatment being collected, clean, wash, filter, is drying to obtain Three-dimensional Activated Graphite alkene nanometer sheet.
The present invention uses carbon source of the widely used polyol-based non-ionic surfactant as graphene nanometer sheet, very The preparation cost of material is reduced in big degree；Activator (alkali metal hydrogen is used as using cheap alkali metal hydroxide simultaneously Material specific surface area can be improved in the chemical activation of oxide), (alkali metal hydroxide is in the high temperature process for three-dimensional structure template The percarbonate particle of generation can be used as three-dimensional structure template) and catalyst (alkali metal hydroxide generates after air oxidation Alkali metal oxide can be used as graphited catalyst) presoma, radically simplifying synthesis step and reduces material The preparation cost of material；Using heat treatment technics is covered, in common Muffle furnace, that is, implementable, suitable large-scale production.
Preferably, polyol-based non-ionic surfactant described in S1 is sorbitan fatty acid ester, polyoxyethylene mistake One or both of water Span.
Dissolution described in S1 and dilution solvent for use include one of distilled water, ethyl alcohol, acetone or a variety of.
Preferably, alkali metal hydroxide described in step S2 be one of sodium hydroxide, potassium hydroxide, lithium hydroxide or Two or more mixing.
Preferably, the mass ratio of nonionic surfactant and alkali metal hydroxide described in step S3 is 1:0.5 ~ 3.0.
Preferably, the temperature of heat treatment described in step S4 is 600 ~ 900 DEG C, and heating time is 30 min ~ 120min, heating Speed is 1 ~ 10 DEG C/min.
Preferably, sample volume is the 20% of crucible total volume in graphite crucible described in step S4, the air body above sample Product is the 20% ~ 80% of crucible total volume.
Preferably, removal of impurities described in step S5 refers to using salt acid soak products therefrom, the concentration of hydrochloric acid used is 0.5 ~ 2mol/L, soaking time are 0.5 ~ 2h.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention uses carbon source of the polyol-based non-ionic surfactant as graphene nanometer sheet, largely On reduce the preparation cost of material.
(2) present invention is used as the activator (chemistry of alkali metal hydroxide using cheap alkali metal hydroxide simultaneously Activation material specific surface area can be improved), the three-dimensional structure template (carbonate that alkali metal hydroxide generates in the high temperature process Particle can be used as three-dimensional structure template) and catalyst (the alkali metal oxidation that alkali metal hydroxide generates after air oxidation Object can be used as graphited catalyst) presoma, it radically simplifies synthesis step and reduces the preparation cost of material.
(3) the cover heat treatment technics that the present invention uses belongs to non-inert gas heat treatment technics, in common Muffle furnace It is i.e. implementable, it is suitble to large scale preparation, solves the step of current three-dimensional Activated Graphite alkene nanometer sheet is faced complicated, equipment and hold high It is expensive, cumbersome, difficult the problems such as producing in batches.
Detailed description of the invention
Fig. 1 is the schematic diagram that the present invention prepares three-dimensional Activated Graphite alkene nanometer sheet device therefor device: 1 Muffle furnace, 2 wood Charcoal carbon dust, 3 graphite crucibles, 4 air, 5 samples.
Fig. 2 is the X ray diffracting spectrum of three-dimensional Activated Graphite alkene nanometer sheet prepared by embodiment 1.
Fig. 3 is the scanning electron microscope diagram piece of three-dimensional Activated Graphite alkene nanometer sheet prepared by embodiment 1.
Fig. 4 is that the cyclic voltammetric of three-dimensional Activated Graphite alkene nanometer sheet electrode material for super capacitor prepared by embodiment 1 is bent Line, 50,100,200,500,1000 mV/s of sweep speed.
Fig. 5 is the constant current charge-discharge of three-dimensional Activated Graphite alkene nanometer sheet electrode material for super capacitor prepared by embodiment 1 Curve, current density 1,2,3,4,5A/g.
Specific embodiment
Explanation is further expalined to the present invention with attached drawing combined with specific embodiments below, description is more specific and detailed Carefully, but it cannot be understood as limitations on the scope of the patent of the present invention, as long as using the shape of equivalent substitution or equivalent transformation Formula technical solution obtained should all include within the scope of protection of the claims of the present invention.
Embodiment 1
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 800 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 800nm, and thickness is about 20nm, material specific surface area are 2360 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 205 F g-1.Fig. 2 is the X-ray diffracting spectrum of 1 material prepared of embodiment.Fig. 3 is 1 material prepared of embodiment Scanning electron microscope image.Fig. 4 is the cyclic voltammetry curve of 1 material prepared of embodiment.Fig. 5 is prepared by embodiment 1 The constant current charge-discharge curve of material.
Embodiment 2
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 100g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 800 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 600nm, and thickness is about 30nm, material specific surface area are 1870 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 169 F g-1。
Embodiment 3
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 300g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 800 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 500nm, and thickness is about 25nm, material specific surface area are 2250 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 194 F g-1。
Embodiment 4
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 20% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 800 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 500nm, and thickness is about 40nm, material specific surface area are 2420 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 202 F g-1。
Embodiment 5
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 80% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 800 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 900nm, and thickness is about 15nm, material specific surface area are 1990 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 184 F g-1。
Embodiment 6
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 600 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 700nm, and thickness is about 30nm, material specific surface area are 1910 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 186 F g-1。
Embodiment 7
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 900 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally by resulting catalysis Product is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional work Property graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 600nm, and thickness is about 30nm, material specific surface area are 2060 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 189 F g-1。
Embodiment 8
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Sample upper air volume is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, is placed in Muffle furnace and carries out heat Processing, the temperature of heat treatment are 800 DEG C, heating time 30min, and heating rate is 5 DEG C/min.Finally resulting catalysis is produced Object is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, is filtered, drying and obtain three-dimensional activity Graphene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 800nm, and thickness is about 20nm, material specific surface area are 2160 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 201 F g-1。
Embodiment 9
100g sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, adds 200g hydroxide Potassium carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, after charging Volume of air above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, and Muffle furnace progress is placed in Heat treatment, the temperature of heat treatment are 800 DEG C, heating time 120min, and heating rate is 5 DEG C/min.Finally urged resulting Change product to be collected, and be 1h with 1mol/L hydrochloric acid soaking time, then is washed with distilled water, filters, drying and obtain three-dimensional Activated Graphite alkene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 700nm, and thickness is about 20nm, material specific surface area are 2190 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 198 F g-1。
Embodiment 10
100g polyoxyethylene sorbitan fatty acid ester is dissolved with 500ml distilled water and dilution is handled, is added 200g potassium hydroxide carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite of a volume Crucible, the volume of air after charging above sample are the 50% of total volume, cover graphite lid, are buried, be placed in charcoal carbon dust Muffle furnace is heat-treated, and the temperature of heat treatment is 800 DEG C, heating time 60min, and heating rate is 5 DEG C/min.Finally will Resulting catalysate is collected, and is 1h with 1mol/L hydrochloric acid soaking time, then be washed with distilled water, filter, dry i.e. Three-dimensional Activated Graphite alkene nanometer sheet is made.
The three-dimensional Activated Graphite alkene nanometer sheet prepared by the above method, wherein graphene width is about 900nm, and thickness is about 10nm, material specific surface area are 2490 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Compare under current density Capacity is 224 F g-1。
Embodiment 11
100g polyoxyethylene sorbitan fatty acid ester is dissolved with 500ml ethyl alcohol and dilution is handled, adds 50g hydrogen Sodium oxide molybdena carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, is filled Volume of air after material above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, is placed in Muffle furnace It is heat-treated, the temperature of heat treatment is 600 DEG C, heating time 100min, and heating rate is 1 DEG C/min.Finally by gained Catalysate be collected, and be 2h with 0.5mol/L hydrochloric acid soaking time, then be washed with distilled water, filter, drying and make Obtain three-dimensional Activated Graphite alkene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet material prepared by the above method, wherein graphene width is about 2000nm, thick Degree is about 200nm, material specific surface area 795m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Electric current is close Spending lower specific capacity is 86F g-1。
Embodiment 12
100g polyoxyethylene sorbitan fatty acid ester 500ml acetone solution and dilution are handled, 50g hydrogen is added Lithia carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, is filled Volume of air after material above sample is the 50% of total volume, covers graphite lid, is buried with charcoal carbon dust, is placed in Muffle furnace It is heat-treated, the temperature of heat treatment is 900 DEG C, heating time 60min, and heating rate is 10 DEG C/min.Finally by gained Catalysate be collected, and be 0.5h with 2mol/L hydrochloric acid soaking time, then be washed with distilled water, filter, drying and make Obtain three-dimensional Activated Graphite alkene nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet material prepared by the above method, wherein graphene width is about 3000 nm, thick Degree is about 250 nm, and material specific surface area is 887 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Electric current Specific capacity is 82F g under density-1。
Comparative example 1
100g polyoxyethylene sorbitan fatty acid ester 500ml acetone solution and dilution are handled, 50g hydrogen is added Lithia carries out high-speed stirred mixing and vacuum drying.Resulting mixture is placed in the adjustable graphite crucible of a volume, is filled Volume of air after material above sample is the 50% of total volume, covers graphite lid, is placed in Muffle furnace and is heat-treated, at heat The temperature of reason is 900 DEG C, heating time 60min, and heating rate is 10 DEG C/min.Finally resulting catalysate is received Collection, and is 0.5h with 2mol/L hydrochloric acid soaking time, then is washed with distilled water, filters, drying and obtain three-dimensional Activated Graphite alkene Nanometer sheet.
The three-dimensional Activated Graphite alkene nanometer sheet material prepared by the above method, wherein graphene width is about 5000 nm, thick Degree is about 2000 nm, and material specific surface area is 150 m2 g-1；Applied to the electrode material of supercapacitor, in 1 A g-1Electric current Specific capacity is 17 F g under density-1。

Claims (7)

1. a kind of preparation method of three-dimensional Activated Graphite alkene nanometer sheet, which comprises the steps of:
S1. carbon source select and pre-treatment: select polyol-based non-ionic surfactant for carbon source, and dissolved with solvent And dilution；
S2. activator, three-dimensional structure template and catalyst precursor select: selecting alkali metal hydroxide simultaneously as activating Agent, three-dimensional structure template and catalyst precursor；
S3. presoma mixed processing: by the alkali of polyol-based non-ionic surfactant and step S2 after step S1 pre-treatment Metal hydroxides is mixed and is dried in vacuo；
S4. it covers heat treatment: mixture obtained by step S3 is placed in graphite crucible, adjust above sample volume and sample Volume of air, close the lid, with charcoal carbon dust burial be heat-treated；
S5. product post-processes: the product after step S4 heat treatment being collected, clean, wash, filter, is drying to obtain three-dimensional Activated Graphite alkene nanometer sheet；
Polyol-based non-ionic surfactant described in step S1 is sorbitan fatty acid ester, polyoxyethylene sorbitan One or both of aliphatic ester.
2. the preparation method of three-dimensional Activated Graphite alkene nanometer sheet according to claim 1, which is characterized in that molten described in step S1 Agent is one of distilled water, ethyl alcohol, acetone or a variety of.
3. the preparation method of three-dimensional Activated Graphite alkene nanometer sheet according to claim 1, which is characterized in that alkali described in step S2 Metal hydroxides is the mixing of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide.
4. the preparation method of three-dimensional Activated Graphite alkene nanometer sheet according to claim 1, which is characterized in that more described in step S3 The mass ratio of first alcohol type nonionic surfactant and alkali metal hydroxide is 1:0.5 ~ 3.0.
5. the preparation method of three-dimensional Activated Graphite alkene nanometer sheet according to claim 1, which is characterized in that heat described in step S4 The temperature of processing is 600 ~ 900 DEG C, and heating time is 30 min ~ 120min, and heating rate is 1 ~ 10 DEG C/min.
6. the preparation method of three-dimensional Activated Graphite alkene nanometer sheet according to claim 1, which is characterized in that stone described in step S4 Sample volume is the 20% of crucible total volume in black crucible, and the volume of air above sample is the 20% ~ 80% of crucible total volume.
7. the preparation method of three-dimensional Activated Graphite alkene nanometer sheet according to claim 1, which is characterized in that removed described in step S5 Miscellaneous to refer to that, using salt acid soak products therefrom, the concentration of hydrochloric acid used is 0.5 ~ 2mol/L, soaking time is 0.5 ~ 2h.
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