CN104831307A - Preparation method of micro/nano graphene sheet - Google Patents

Preparation method of micro/nano graphene sheet Download PDF

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Publication number
CN104831307A
CN104831307A CN201510243280.3A CN201510243280A CN104831307A CN 104831307 A CN104831307 A CN 104831307A CN 201510243280 A CN201510243280 A CN 201510243280A CN 104831307 A CN104831307 A CN 104831307A
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micro
preparation
graphene film
nano graphene
nano
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CN104831307B (en
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曾宇乔
李晨骏
朱建峰
陈佳熠
陈友明
郭俊楠
张旭海
邵起跃
谈荣生
蒋建清
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals

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  • Inorganic Chemistry (AREA)
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Abstract

The invention provides a preparation method of a micro/nano graphene sheet, which comprises the following steps: by using a graphite plate as a positive pole, an inert metal plate or graphite plate as a negative pole and ultrapure water or a benzene hexacarbonic acid solution as a electrolyte, carrying out electrolysis on graphite to obtain a micro/nano carbon material with the diameter of 10-500nm; and drying by distillation, and carrying out heat treatment at 400-600 DEG C in an argon or nitrogen atmosphere for 30-120 minutes to obtain the micro/nano graphene sheet with the thickness of 5-10nm. The method is simple in technique and convenient for operation, and is green and environment-friendly. The prepared graphene sheet has small diameter size.

Description

A kind of preparation method of micro-nano graphene film
Technical field
The present invention relates to a kind of preparation method of micro-nano graphene film, particularly a kind of preparation method of graphene film that can be used for plastics enhancing, sensing, catalysis, cell negative electrode material and the neighborhood such as stealthy, belongs to field of nano material preparation.
Background technology
Grapheme material has the performances such as excellent electroconductibility, thermal conductivity and superstrength, is expected in plastic material enhancings, sensing, photoelectricity, battery electrode, catalysis and the neighborhood acquisition widespread use such as stealthy.Preparing grapheme material on a large scale mainly contains two kinds at present: one is by the large stretch of graphene film of chemical gaseous phase depositing process growing high-quality on copper or nickel substrate; Another kind prepares graphene powder by oxidation reduction process.Although the former can obtain the complete Graphene of high quality, cost is high, is only limitted to require harsh semiconductor industry application.And the latter due to technique relatively simple, cost is low, can be mass-produced, but because a large amount of chemical feedstocks of needs is for graphite oxidation and Graphene reduction, therefore can produce a large amount of chemical waste fluid, environmental pollution is larger.
Summary of the invention
Goal of the invention: the object of the invention is for the deficiencies in the prior art, provides a kind of novel preparation method receiving micro-graphene film.
Technical scheme: the preparation method of a kind of micro-nano graphene film provided by the invention, comprise the following steps: take graphite cake as anode, inert metal plate or graphite cake be negative electrode, ultrapure water or mellitic acid solution is electrolytic solution, electrolysis is implemented to graphite, the micro-nano carbon material of diameter between 10-500nm scope can be obtained in the electrolytic solution; Evaporate to dryness, thermal treatment 30-120min at 400-600 DEG C in argon gas or nitrogen atmosphere, obtains the micro-nano graphene film that thickness is 5-10nm.
As preferably, anode graphite plate features is: ash≤50ppm, volume density>=1.5g/cm 3, granularity < 500um.
Preferred as another kind, the spacing between adjacent anode graphite cake and negative electrode inert metal plate or graphite cake is 1-10mm.
Preferred as another kind, ultrapure water resistivity is at more than 18M Ω; The concentration of mellitic acid sodium is 0.1-2mol/L.
Preferred as another kind, electrolytic condition is: at voltage 4-50V, current density 0-300mA/cm 2, electrolysis time is 4-96h.
Beneficial effect: as compared to prior art (chemical Vapor deposition process and oxidation reduction process), the present invention has following outstanding advantage:
(1) technique is simple, convenient operation, environmental protection.This technique does not need the expensive vacuum deposition system needed for chemical vapour deposition technique, does not need the copper of special processing or nickel growth substrate and 800-100 DEG C of high growth temperature environment, does not have flammable explosive gas to discharge; Also there will not be produce in oxidation reduction process metallic pollution, toxic gas and blast hidden danger.Grapheme material can be obtained by comparatively simple electrochemistry and thermal treatment process.
(2) graphene film that the present invention obtains has less diameter dimension: chemical vapour deposition is at present mainly for the preparation of large-area graphene; And Graphene diameter prepared by oxidation reduction process is generally micron millimeter rank (this is because the particle size of graphite raw material is larger), further acquisition diameter is that the Graphene of nano-grade size is more difficult.This technology makes diameter be that the generation of micro/nano level graphene film becomes possibility by electrochemistry and thermal treatment.
Accompanying drawing explanation
Carbon material shape appearance figure in carbon liquid before Fig. 1 thermal treatment;
The pattern of the graphene film obtained after Fig. 2 thermal treatment and high resolution fine structure thereof.
Embodiment
Before description material of the present invention, method, be to be understood that this disclosure is not limited to described concrete grammar and material, because these can change.Will also be understood that the object of term as used in this specification just in order to describe these specific forms or embodiment, instead of be intended to limit this scope.Unless otherwise defined, as used herein all technology or the term of science there is the identical implication usually understood with those of ordinary skill in the art.
Take graphite cake as anode, its ash≤50ppm, volume density>=1.5g/cm 3, granularity < 500um.Its cathode electrode plate adopts inert metal plate or graphite cake; Spacing between adjacent anode graphite cake and negative plate is 1-10mm.Electrolytic solution is ultrapure water or the 0.1-2mol/L mellitic acid solution acidic solution that resistivity is greater than 18M Ω.During electrolysis, voltage 4-50V, current density 0-300mA/cm 2, the time is 4 hours-96 hours.Evaporation mode is utilized to be removed by water in solution after electrolysis.Finally by solid matter 400-600 DEG C of condition thermal treatment 30-120 minute in argon gas or nitrogen atmosphere.
Provide the specific embodiment utilizing preparation method of the present invention to prepare nanometer grade diameter grapheme material below.
Embodiment 1
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density >=1.5g/cm3, granularity < 500um; Cathode electrode plate employing thickness is the titanium plate of 10mm, length 700mm, width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 3mm.Electrolytic solution is the ultrapure water of resistivity at more than 18M Ω.Power supply selects rectification DC power supply.
After switching on power, voltage control is at 4V, and current density controls at 0-200mA/cm 2, after 96 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 120min under nitrogen atmosphere 400 DEG C of conditions, acquisition diameter is about the graphene film between 10-100nm thickness 5-10nm.
Embodiment 2
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density >=1.5g/cm3, granularity < 500um; Cathode electrode plate adopts thickness to be 10mm, length 700mm, the titanium plate of width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 3mm.Electrolytic solution is 0.1mol/L mellitic acid solution.Power supply selects rectification DC power supply.
After switching on power, voltage control is at 4V, and current density controls at 100-200mA/cm 2, after 48 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 120min under nitrogen atmosphere 400 DEG C of conditions, acquisition diameter is about the graphene film between 50 – 1000nm thickness 5-10nm.
Embodiment 3
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density>=1.5g/cm 3, granularity < 500um; Cathode electrode plate adopts thickness to be 10mm, length 700mm, the titanium plate of width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 3mm.Electrolytic solution is the ultrapure water of resistivity at more than 18M Ω.Power supply selects rectification DC power supply.
After switching on power, voltage control is at 50V, and current density controls at 0-300mA/cm 2, after 48 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 30min under nitrogen atmosphere 600 DEG C of conditions, acquisition diameter is about the graphene film between 50-500nm thickness 5-10nm.
Embodiment 4
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density>=1.5g/cm 3, granularity < 500um; Cathode electrode plate adopts thickness to be 10mm, length 700mm, the titanium plate of width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 3mm.Electrolytic solution is 2mol/L mellitic acid solution.Power supply selects rectification DC power supply.
After switching on power, voltage control is at 50V, and current density controls at 200-300mA/cm 2, after 6 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 30min under nitrogen atmosphere 400 DEG C of conditions, acquisition diameter is about the graphene film between 100 – 1500nm thickness 5-10nm.
Embodiment 5
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density>=1.5g/cm 3, granularity < 500um; Cathode electrode plate adopts thickness to be 10mm, length 700mm, the titanium plate of width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 3mm.Electrolytic solution is 2mol/L mellitic acid solution.Power supply selects the pulse power.
After switching on power, voltage control is at 50V, and current density controls at 200-300mA/cm 2, frequency is 10kHz.After 6 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 30min under nitrogen atmosphere 400 DEG C of conditions, acquisition diameter is about the graphene film between 100 – 1500nm thickness 5-10nm.
Embodiment 6
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density >=1.5g/cm3, granularity < 500um; Cathode electrode plate employing thickness is the titanium plate of 10mm, length 700mm, width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 1mm.Electrolytic solution is the ultrapure water of resistivity at more than 18M Ω.Power supply selects rectification DC power supply.
After switching on power, voltage control is at 20V, and current density controls at 0-200mA/cm 2, after 60 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 60min under nitrogen atmosphere 500 DEG C of conditions, acquisition diameter is about the graphene film between 10-100nm thickness 5-10nm.
Embodiment 7
Anode electrode plate employing thickness is the graphite cake of 80mm, length 700mm, width 700mm, ash≤50ppm, volume density >=1.5g/cm3, granularity < 500um; Cathode electrode plate employing thickness is the titanium plate of 10mm, length 700mm, width 700mm; Spacing between adjacent anode graphite cake and negative electrode inert metal plate is 10mm.Electrolytic solution is the ultrapure water of resistivity at more than 18M Ω.Power supply selects rectification DC power supply.
After switching on power, voltage control is at 30V, and current density controls at 0-200mA/cm 2, after 4 hours, obtain micro-nano carbon particle colloidal sols.At 80 DEG C, after evaporating water, solid matter is heated 90min under nitrogen atmosphere 500 DEG C of conditions, acquisition diameter is about the graphene film between 10-100nm thickness 5-10nm.

Claims (6)

1. the preparation method of a micro-nano graphene film, it is characterized in that: comprise the following steps: take graphite cake as anode, inert metal plate or graphite cake be negative electrode, ultrapure water or mellitic acid solution is electrolytic solution, electrolysis is implemented to graphite, the micro-nano carbon material of diameter between 10-500nm scope can be obtained in the electrolytic solution; Evaporate to dryness, thermal treatment 30-120min at 400-600 DEG C in argon gas or nitrogen atmosphere, obtains the micro-nano graphene film that thickness is 5-10nm.
2. the preparation method of a kind of micro-nano graphene film according to claim 1, is characterized in that: anode graphite plate features is: ash≤50ppm, volume density>=1.5g/cm 3, granularity < 500um.
3. the preparation method of a kind of micro-nano graphene film according to claim 1, is characterized in that: the spacing between adjacent anode graphite cake and negative electrode inert metal plate or graphite cake is 1-10mm.
4. the preparation method of a kind of micro-nano graphene film according to claim 1, is characterized in that: ultrapure water resistivity is at more than 18M Ω.
5. the preparation method of a kind of micro-nano graphene film according to claim 1, is characterized in that: the concentration of mellitic acid sodium is 0.1-2mol/L.
6. the preparation method of a kind of micro-nano graphene film according to claim 1, is characterized in that: electrolytic condition is: at voltage 4-50V, current density 0-300mA/cm 2, electrolysis time is 4-96h.
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN106337192A (en) * 2016-10-03 2017-01-18 上海库儿科技有限公司 Method for preparing nanocarbon solution with conductive carbon fibers as electrode
CN107601488A (en) * 2017-09-08 2018-01-19 深圳大学 A kind of preparation method of graphene oxide
CN109971527A (en) * 2019-04-19 2019-07-05 宁波石墨烯创新中心有限公司 Modified graphene material, lubricating oil containing modified graphene material and preparation method thereof
CN110698683A (en) * 2019-09-27 2020-01-17 广西师范大学 One-dimensional dysprosium polymer and preparation method thereof
CN110804189A (en) * 2019-09-27 2020-02-18 广西师范大学 Three-dimensional lutetium polymer and preparation method thereof
CN111647901A (en) * 2020-05-15 2020-09-11 湖北省哈福生物化学有限公司 Black hole liquid and preparation method and use method thereof
CN113170702A (en) * 2020-08-18 2021-07-27 山西大同大学 Multi-season morchella planting method and application thereof

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CN101469431A (en) * 2007-12-24 2009-07-01 清华大学 Method for preparing nano oxidized graphite particle or flake graphite and benzene hexacarbonic acid simultaneously
CN102465309A (en) * 2010-11-10 2012-05-23 海洋王照明科技股份有限公司 Preparation method of graphene
CN103794792A (en) * 2014-02-28 2014-05-14 江苏丽港科技有限公司 Method for preparing nano carbon sphere materials for negative electrode of lithium ion battery
CN104707599A (en) * 2015-03-03 2015-06-17 江苏丽港科技有限公司 Preparation method for palladium-carbon composite catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101469431A (en) * 2007-12-24 2009-07-01 清华大学 Method for preparing nano oxidized graphite particle or flake graphite and benzene hexacarbonic acid simultaneously
CN102465309A (en) * 2010-11-10 2012-05-23 海洋王照明科技股份有限公司 Preparation method of graphene
CN103794792A (en) * 2014-02-28 2014-05-14 江苏丽港科技有限公司 Method for preparing nano carbon sphere materials for negative electrode of lithium ion battery
CN104707599A (en) * 2015-03-03 2015-06-17 江苏丽港科技有限公司 Preparation method for palladium-carbon composite catalyst

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106337192A (en) * 2016-10-03 2017-01-18 上海库儿科技有限公司 Method for preparing nanocarbon solution with conductive carbon fibers as electrode
CN107601488A (en) * 2017-09-08 2018-01-19 深圳大学 A kind of preparation method of graphene oxide
CN109971527A (en) * 2019-04-19 2019-07-05 宁波石墨烯创新中心有限公司 Modified graphene material, lubricating oil containing modified graphene material and preparation method thereof
CN109971527B (en) * 2019-04-19 2021-09-07 宁波石墨烯创新中心有限公司 Modified graphene material, lubricating oil containing modified graphene material and preparation method of lubricating oil
CN110698683A (en) * 2019-09-27 2020-01-17 广西师范大学 One-dimensional dysprosium polymer and preparation method thereof
CN110804189A (en) * 2019-09-27 2020-02-18 广西师范大学 Three-dimensional lutetium polymer and preparation method thereof
CN110698683B (en) * 2019-09-27 2021-08-24 广西师范大学 One-dimensional dysprosium polymer and preparation method thereof
CN110804189B (en) * 2019-09-27 2021-11-02 广西师范大学 Three-dimensional lutetium polymer and preparation method thereof
CN111647901A (en) * 2020-05-15 2020-09-11 湖北省哈福生物化学有限公司 Black hole liquid and preparation method and use method thereof
CN111647901B (en) * 2020-05-15 2023-08-25 湖北省哈福生物化学有限公司 Black hole liquid and preparation method and application method thereof
CN113170702A (en) * 2020-08-18 2021-07-27 山西大同大学 Multi-season morchella planting method and application thereof

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