CN106128790A - A kind of preparation method of Graphene electrode material for super capacitor - Google Patents

A kind of preparation method of Graphene electrode material for super capacitor Download PDF

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Publication number
CN106128790A
CN106128790A CN201610815461.3A CN201610815461A CN106128790A CN 106128790 A CN106128790 A CN 106128790A CN 201610815461 A CN201610815461 A CN 201610815461A CN 106128790 A CN106128790 A CN 106128790A
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graphene
super capacitor
electrode material
preparation
quantum dot
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陈爱英
王静雯
王现英
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses the preparation method of a kind of Graphene electrode material for super capacitor, at nano-porous gold film surface deposited graphite alkene material, described deposition process uses electrochemical cyclic voltammetry, the concentration of described grapheme material is 0.02g/L 0.5g/L, during using electrochemical cyclic voltammetry deposited graphite alkene material, deposition window is 0 2V voltage, cycle-index 50 600 times, sweep speed 10 200mVs‑1.The electrode material for super capacitor of the present invention has high specific capacitance and good structural stability, cyclical stability.It is up to 864 F/g than electric capacity, circulates the ratio electric capacity still keeping 90% for 2000 times.It is applicable to the power supply occasion of high stability, high power density.

Description

A kind of preparation method of Graphene electrode material for super capacitor
Technical field
The invention belongs to materialogy field, relate to a kind of ultracapacitor, specifically a kind of electrode of super capacitor The preparation method of material.
Background technology
Ultracapacitor is one of electrochemical energy storage technology of most application prospect.At present, the research weight of ultracapacitor Point is to improve energy density and power density, and development has the electrode material of high-specific surface area, high conductivity and structural stability Material.Comparing traditional Carbon Materials, Graphene has the highest electric conductivity, great specific surface area and substantial amounts of interlayer structure, Lamella both sides all can be enriched with electric charge and form the diffusion of electric double layer and beneficially electrolyte, are preferable electrode of super capacitor materials Material.The Graphene ultracapacitor prepared with Graphene has the features such as high-power, fast charging and discharging and cyclical stability are strong. Although separately as electrode material for super capacitor, but can there is a techniques below difficult problem in Graphene: (1) its theoretical specific capacity is only There are 329 F/g, limit the large-scale application of this material;(2) in graphene-based electrode production process, stacking it is susceptible to existing As, affect grapheme material dispersibility in the electrolyte and surface wettability, cause grapheme material specific surface area and from Electron conductivity declines.Therefore, effectively minimizing graphene sheet layer is assembled and stacking is to build newly to obtain good volumetric capacitance The key of the graphene-based ultracapacitor of type.
For super capacitor material, vital characteristic is specific surface area and electric conductivity.Nano-porous gold has double The features such as continuous print internal structure, high-specific surface area and good electric conductivity, have the physics of uniqueness, chemical property, are good Support materials.By controlling size and the distribution of nano aperture, can further improve specific surface area.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of Graphene electrode material for super capacitor Preparation method, the preparation method of described this Graphene electrode material for super capacitor to solve of the prior art super Capacitor electrode material is prone to the technical problem stacked, electric conductivity is not good enough.
The invention provides the preparation method of a kind of electrode material for super capacitor, deposit at nano-porous gold film surface Grapheme material, described deposition process uses electrochemical cyclic voltammetry, and the concentration of described grapheme material is 0.02g/ L-0.5g/L, during using electrochemical cyclic voltammetry deposited graphite alkene material, deposition window is 0-2V voltage, circulation Number of times 50-600 time, sweep speed 10-200mVs-1
Further, described grapheme material is selected from graphene oxide, graphene quantum dot, nitrogen-doped graphene or nitrogen Doped graphene quantum dot.
Further, Graphene or nitrogen-doped graphene are monolayer or multilayer oxygen functionalized graphene;Graphene quantum dot Or nitrogen-doped graphene quantum dot granular size is 2-10nm.
Further, also including a process that electrode material for super capacitor carries out heat treatment, heat treatment temperature is 100-500oC, heat treatment time 20-120 minute.
Further, during using electrochemical cyclic voltammetry deposited graphite alkene material, in electrolyte solution Adding dispersant, the mass percent concentration of described dispersant is 0.05%-1%.
Further, described dispersant is Polyethylene Glycol, vitamin C or citric acid.
The nano-porous gold of the present invention has three-dimensional porous structure, and the capillarity in bending hole wall and hole can reduce graphite The gathering of alkene material and stacking.Using graphene oxide and graphene quantum dot is parent material, utilizes the cyclic voltammetry can be real Existing single-layer graphene or the deposition of individual particle graphene quantum dot.Form the combination electrode material of monomolecular dispersion.
The nano-porous gold of the present invention has good electric conductivity, is characterized with three-dimensional porous structure, can improve specific surface Long-pending.Grapheme material is deposited on nanoporous gold surface, still retains the three-dimensional continuous aperture gap structure of nano-porous gold, loose structure Allow electrolyte ion that quickly diffusion and transfer occur in composite construction, thus carry out reversible absorption in electrode material surface With desorbing, and then increase substantially ratio electric capacity and the charge-discharge velocity of electrode material.
The present invention controls grapheme material sinking on NPG thin film by controlling cycle-index, cycle rate and voltage Accumulated amount and distribution.The graphene/nanometer porous gold composite construction electrode material for super capacitor of above-mentioned gained is good owing to having Energy storage capability, high specific capacitance and good cyclical stability, therefore can be as efficient, the combination electrode material of lightweight.
The electrode material for super capacitor of the present invention, due to load grapheme material, utilizes fine particle interphase interaction Power completes interface diffusion and combines so that it is have good structural stability.Simultaneously because between nano-porous gold and Graphene Cooperative effect make composite electrode have the ratio electric capacity bigger than simple Graphene and nano-porous gold.
The present invention compares with prior art, and its technological progress is significant.Electrode of super capacitor prepared by the present invention Material has high specific capacitance and good structural stability, cyclical stability.It is up to 864 F/g than electric capacity, circulates 2000 times Still keep the ratio electric capacity of 90%.It is applicable to the power supply occasion of high stability, high power density.The present invention is at nanoporous golden watch Face deposited graphite alkene material, it is achieved that the ion migration resistance that porosity is high, effective ratio area is big and low, solves Graphene A base electrode material technology difficult problem.And the method technique of the present invention is simple, structure-controllable, environmental protection.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the graphene quantum dot prepared by embodiment 1/nanoporous metal/composite material.
Fig. 2 is that embodiment 1 gained graphene quantum dot/nano-porous gold combination electrode material is at 0.5 M Na2SO4Solution In cyclic voltammetry curve.
Fig. 3 is the TEM figure of the graphene oxide prepared by embodiment 2/nanoporous metal/composite material.
Fig. 4 is that embodiment 2 gained graphene oxide/nano-porous gold combination electrode material is at 0.5 M Na2SO4In solution Cyclic voltammetry curve.
Fig. 5 is the TEM figure of embodiment 3 gained nitrogen-doped graphene quantum dot/nano-porous gold sandwich.
Fig. 6 is the composition measurement of embodiment 3 gained nitrogen-doped graphene quantum dot/nano-porous gold sandwich EDX schemes.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is expanded on further, elaboration below is merely to explain Advantages of the present invention and technical scheme, do not limit the invention.
Embodiment 1
Graphene quantum dot/nano-porous gold composite construction electrode material for super capacitor, its method system as follows For forming:
(1) take nanoporous gold thin film, clean twice with deionized water, take out with copper sheet.
(2) being placed in graphene quantum dot aqueous solution by NPG thin film, concentration is 0.02g/L, adds mass concentration and is 0.05%PEG.Using three-electrode system, utilize cyclic voltammetry deposited graphite alkene quantum dot, voltage window is 0-1V voltage, follows Ring number of times 50 times, sweep speed 20mVs-1.Obtain graphene quantum dot/nano-porous gold composite construction electrode of super capacitor material Material.
Use transmission electron microscope that above-mentioned graphene quantum dot/nanoporous metal/composite material is tested, see attached Fig. 1.It will be seen from figure 1 that graphene quantum dot individual particle spherical in shape is distributed on nano-porous gold hole wall, granular size is 3- 8nm.Nanoporous gold thin film porous is evenly distributed, and still remains with three-dimensional continuous aperture gap structure after load graphene quantum dot.
Graphene quantum dot/nanoporous the metal/composite material of above-mentioned gained is carried out capacitive property test, with Graphene Quantum dot/nano-porous gold is working electrode, with saturated calomel electrode as reference electrode, with platinized platinum for electrode, with 0.5M's Na2SO4Solution is electrolyte, surveys capacitance curve result as shown in Figure 2.823 F/g are reached than electric capacity.Power density reaches 228 kW/ kg.More than 90% is still kept than electric capacity after circulating 3000 times.
Embodiment 2
Graphene oxide/nano-porous gold composite construction electrode material for super capacitor, prepared by its method as follows Form:
(1) take nanoporous gold thin film, clean twice with deionized water, take out with copper sheet.
(2) being placed in graphene oxide water solution by NPG thin film, concentration is 0.5g/L.Using three-electrode system, utilization follows Ring voltammetry deposited oxide grapheme material, voltage window is 0-2V voltage, cycle-index 500 times, sweep speed 200mVs-1。 Obtain graphene oxide/nano-porous gold composite construction electrode material for super capacitor.
(3) graphene oxide prepared by/nano-porous gold composite construction electrode material for super capacitor is 500oC, heat Process 120 minutes.
Use transmission electron microscope that above-mentioned graphene oxide/nanoporous metal/composite material is tested, see accompanying drawing 3.From figure 3, it can be seen that Graphene is lamellar structure is deposited in nanoporous gold surface.The distribution of nanoporous gold thin film porous is all Even, still remain with three-dimensional continuous aperture gap structure after load graphene oxide.
Graphene oxide/nanoporous the metal/composite material of above-mentioned gained is carried out capacitive property test, with graphite oxide Alkene/nano-porous gold is working electrode, with saturated calomel electrode as reference electrode, with platinized platinum for electrode, with the Na of 0.5M2SO4 Solution is electrolyte, and the cyclic voltammetry under this three-electrode system surveys capacitance curve result as shown in Figure 4.Reach than electric capacity 423 F/g.Power density reaches 59 kW/kg.More than 90% is still kept than electric capacity after circulating 4000 times.
Embodiment 3
Nitrogen-doped graphene quantum dot/nano-porous gold composite construction electrode material for super capacitor, it is as follows Method is prepared from:
(1) take nanoporous gold thin film, clean twice with deionized water, take out with copper sheet.
(2) being placed in by NPG thin film in nitrogen-doped graphene quantum dot aqueous solution, concentration is 0.1g/L, adds mass concentration It it is 0.05% vitamin C.Using three-electrode system, utilize cyclic voltammetry deposited graphite alkene quantum dot, voltage window is 0-1.6V Voltage, cycle-index 200 encloses, sweep speed 100mVs-1.Obtain nitrogen-doped graphene quantum dot/nano-porous gold composite construction Electrode material for super capacitor.
Use transmission electron microscope that above-mentioned nitrogen-doped graphene quantum dot/nanoporous metal/composite material is surveyed Examination, is shown in accompanying drawing 5.From fig. 5, it can be seen that nitrogen-doped graphene quantum dot individual particle spherical in shape is distributed in nano-porous gold hole wall On, granular size is 4-9nm.Nanoporous gold thin film porous is evenly distributed, and still retains after load nitrogen-doped graphene quantum dot There is three-dimensional continuous aperture gap structure.Nitrogen-doped graphene quantum dot/nano-porous gold sample surfaces EDX composition measurement result is shown in accompanying drawing 6.Wherein, doping N content is 2.6%.
Nitrogen-doped graphene quantum dot/nanoporous the metal/composite material of above-mentioned gained is carried out capacitive property test, with Nitrogen-doped graphene quantum dot/nano-porous gold is working electrode, with saturated calomel electrode as reference electrode, with platinized platinum for electricity Pole, with the Na of 0.5M2SO4Solution is electrolyte, and the ratio electric capacity recorded reaches 864 F/g.Power density reaches 120 kW/kg.Circulation More than 90% is still kept than electric capacity after 2000 times.
Embodiment 4
Nitrogen-doped graphene/nano-porous gold composite construction electrode material for super capacitor, its method system as follows For forming:
(1) take nanoporous gold thin film, clean twice with deionized water, take out with copper sheet.
(2) being placed in nitrogen-doped graphene aqueous solution by NPG thin film, concentration is 0.3g/L.Use three-electrode system, utilize Cyclic voltammetry deposition nitrogen-doped graphene, voltage window is 0-1V voltage, cycle-index 600 times, sweep speed 50mVs-1.I.e. Obtain nitrogen-doped graphene/nano-porous gold composite construction electrode material for super capacitor.
(3) nitrogen-doped graphene prepared by/nano-porous gold composite construction electrode material for super capacitor is 200oC, Heat treatment 30 minutes.
Nitrogen-doped graphene/nanoporous the metal/composite material of above-mentioned gained is carried out capacitive property test, with N doping Graphene/nanometer porous gold is working electrode, with saturated calomel electrode as reference electrode, with platinized platinum for electrode, with 0.5M's Na2SO4Solution is electrolyte, and the ratio electric capacity recorded reaches 514 F/g.Power density reaches 71 kW/kg.Than electricity after circulating 2000 times Hold and still keep more than 90%.
Foregoing is only the basic explanation under present inventive concept, and according to technical scheme made any etc. Effect conversion, all should belong to protection scope of the present invention.

Claims (6)

1. the preparation method of a Graphene electrode material for super capacitor, it is characterised in that: at nano-porous gold film surface Deposited graphite alkene material, described deposition process uses electrochemical cyclic voltammetry, and the concentration of described grapheme material is 0.02g/L-0.5g/L, during using electrochemical cyclic voltammetry deposited graphite alkene material, deposition window is 0-2V electricity Pressure, cycle-index 50-600 time, sweep speed 10-200mVs-1
The preparation method of a kind of Graphene electrode material for super capacitor the most as claimed in claim 1, it is characterised in that: described Grapheme material is selected from graphene oxide, graphene quantum dot, nitrogen-doped graphene or nitrogen-doped graphene quantum dot.
The preparation method of a kind of Graphene electrode material for super capacitor the most as claimed in claim 2, it is characterised in that: graphite Alkene or nitrogen-doped graphene are monolayer or multilayer oxygen functionalized graphene;Graphene quantum dot or nitrogen-doped graphene quantum dot Grain size is 2-10nm.
The preparation method of a kind of Graphene electrode material for super capacitor the most as claimed in claim 1, it is characterised in that: also wrap Including a process that electrode material for super capacitor carries out heat treatment, heat treatment temperature is 100-500oC, heat treatment time 20-120 minute.
The preparation method of a kind of Graphene electrode material for super capacitor the most as claimed in claim 1, it is characterised in that: adopting During electrochemical cyclic voltammetry deposited graphite alkene material, electrolyte solution adds dispersant, described dispersion The mass percent concentration of agent is 0.05%-1%.
The preparation method of a kind of Graphene electrode material for super capacitor the most as claimed in claim 5, it is characterised in that: described Dispersant be Polyethylene Glycol, vitamin C or citric acid.
CN201610815461.3A 2016-09-08 2016-09-08 A kind of preparation method of Graphene electrode material for super capacitor Pending CN106128790A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108364800A (en) * 2018-01-22 2018-08-03 上海理工大学 A kind of electrode material for super capacitor and preparation method thereof of nitrogen-doped graphene quantum dot/graphene
CN110415989A (en) * 2019-08-07 2019-11-05 哈尔滨师范大学 A kind of method that electrodeposition process prepares the super capacitor material of cobaltous selenide
CN111261418A (en) * 2020-01-21 2020-06-09 江苏大学 Method for preparing high-purity graphene film, electrode and capacitor
CN113643905A (en) * 2021-08-23 2021-11-12 武夷学院 Preparation method and application of graphene grafted polymer electrode material

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Publication number Priority date Publication date Assignee Title
CN102051651A (en) * 2011-01-11 2011-05-11 湖南大学 Preparation method of graphene film
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Publication number Priority date Publication date Assignee Title
CN102051651A (en) * 2011-01-11 2011-05-11 湖南大学 Preparation method of graphene film
CN103578771A (en) * 2012-07-18 2014-02-12 海洋王照明科技股份有限公司 Graphene thin film and preparation method and application thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108364800A (en) * 2018-01-22 2018-08-03 上海理工大学 A kind of electrode material for super capacitor and preparation method thereof of nitrogen-doped graphene quantum dot/graphene
CN110415989A (en) * 2019-08-07 2019-11-05 哈尔滨师范大学 A kind of method that electrodeposition process prepares the super capacitor material of cobaltous selenide
CN111261418A (en) * 2020-01-21 2020-06-09 江苏大学 Method for preparing high-purity graphene film, electrode and capacitor
CN113643905A (en) * 2021-08-23 2021-11-12 武夷学院 Preparation method and application of graphene grafted polymer electrode material
CN113643905B (en) * 2021-08-23 2022-11-22 武夷学院 Preparation method and application of nitrogen-doped graphene oxide grafted polymer electrode material

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Application publication date: 20161116