CN109994323A - Amorphous gallium nitride/Graphene electrodes material, preparation method and supercapacitor - Google Patents

Amorphous gallium nitride/Graphene electrodes material, preparation method and supercapacitor Download PDF

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CN109994323A
CN109994323A CN201910255731.3A CN201910255731A CN109994323A CN 109994323 A CN109994323 A CN 109994323A CN 201910255731 A CN201910255731 A CN 201910255731A CN 109994323 A CN109994323 A CN 109994323A
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gallium nitride
graphene
amorphous
preparation
substrate
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黄鹏
袁国栋
王军喜
李晋闽
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Institute of Semiconductors of CAS
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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
    • H01G11/24—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
    • 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
    • H01G11/84—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

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  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

A kind of amorphous gallium nitride/Graphene electrodes material, preparation method and supercapacitor.Wherein, amorphous gallium nitride/Graphene electrodes material preparation method includes: to form graphene on a substrate；And the composite material of amorphous state gallium nitride and graphene is prepared on the substrate for be formed with graphene using pulsed laser deposition.The preparation method effectively avoids component segregation, avoids the use of gallium metal, does not need high temperature, compatible with subsequent preparation process, is a kind of method of efficient controllable preparation high-quality gallium nitride base electrode material.Amorphous gallium nitride/Graphene electrodes material passes through the synergistic effect using two kinds of materials, the validity of the electrode as double layer capacitor is also ensured while realizing two kinds of material advantages and being combined, have both high capacity and good stable circulation characteristic, specific capacitance with higher, has a good application prospect.

Description

Amorphous gallium nitride/Graphene electrodes material, preparation method and supercapacitor
Technical field
The disclosure belongs to field of new energy technologies, be related to a kind of amorphous gallium nitride/Graphene electrodes material, preparation method and Supercapacitor.
Background technique
While energy consumption provides necessary guarantee for current social development, preceding institute also is brought not to ball ecological environment Some pressure.For this purpose, the whole world is made joint efforts, the good situation based on fossil energy, supplemented by emerging green energy resource is formd. At the same time, the discontinuity of the concentration consumption patterns and new green energy of fossil energy, is still energy technology and urgently solves Certainly the problem of.
Supercapacitor (also referred to as electrochemical capacitor) is a kind of efficient energy management and memory device, can be in the short time Interior progress collection of energy and controlled release have in the strategic emerging field such as rail traffic, modern communications, aerospace, national defence Broad application prospect.Supercapacitor be different from traditional electrochmical power source, be one kind between traditional capacitor and battery, Power supply with property relies primarily on electric double layer and redox fake capacitance charge storage electric energy.It is stored up in supercapacitor It can not chemically react in the process, energy storage is reversible.
There are the following problems for current existing supercapacitor: the capacitance of double layer capacitor is limited by material structure, The space that performance is further promoted is limited；In oxidation-reduction type electrochemical capacitor (pseudocapacitors), polymer electrode and containing miscellaneous The electrochemical stability of the materials such as the nanoporous carbon of the carbon material of atom and Electrostatic Absorption hydrogen is poor；Transition group metallic oxide electricity The structure of pole material in charge and discharge process by destroy so as to cause cycle performance decline.
Therefore, it needs to propose a kind of electrode material for super capacitor for having both high capacity and good stable circulation characteristic.
Summary of the invention
(1) technical problems to be solved
Present disclose provides a kind of amorphous gallium nitride/Graphene electrodes material, preparation method and supercapacitors, at least Part solves technical problem set forth above.
(2) technical solution
According to one aspect of the disclosure, a kind of preparation method of amorphous gallium nitride/Graphene electrodes material is provided, it should Preparation method includes: to form graphene on a substrate；And using pulsed laser deposition on the substrate for being formed with graphene Prepare the composite material of amorphous state gallium nitride and graphene.
In some embodiments of the present disclosure, amorphous is prepared on the substrate for be formed with graphene using pulsed laser deposition In the step of composite material of state gallium nitride and graphene, using gallium nitride ceramic target as gallium source, swashed using high energy pulse Light evaporates gallium nitride target, the plasma comprising gallium, nitrogen is generated, using plasma in the substrate for being formed with graphene On deposition the composite material of amorphous state gallium nitride and graphene is prepared.
In some embodiments of the present disclosure, high energy pulse laser is 248nm laser.
In some embodiments of the present disclosure, in the step of forming graphene on a substrate, comprising: utilize chemical gaseous phase It is deposited on substrate and directly forms graphene；Alternatively, utilizing graphite oxide reduction method, mechanical stripping method, electrochemical reducing, outer Prolong after graphene is prepared in one of crystal growth, liquid phase stripping method, pyrolysis method or method of cutting carbon nanotubes and shifts To a substrate.
A kind of amorphous gallium nitride/Graphene electrodes material another aspect of the present disclosure provides, amorphous nitridation Gallium/Graphene electrodes material are as follows: the composite material of amorphous state gallium nitride and graphene.
In some embodiments of the present disclosure, cyclic process of the amorphous gallium nitride/Graphene electrodes material in charge and discharge The phase transformation of amorphous state to crystalline state occurs for middle gallium nitride.
In some embodiments of the present disclosure, the amorphous gallium nitride/Graphene electrodes material is appointed using what the disclosure was mentioned A kind of preparation method is prepared.
According to the another aspect of the disclosure, a kind of supercapacitor is provided, the electrode material of the supercapacitor is Any amorphous gallium nitride/Graphene electrodes material that the disclosure is mentioned.
It in some embodiments of the present disclosure, is tested under three-electrode system, wherein 1 mole of KCl is electrolyte, graphite Alkene film is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, and potential window is -0.9V~-0.3V, is followed Ring volt-ampere is tested from 10mVs-1To 100mVs-1, constant current charge-discharge test is from 0.5mAcm-2To 1mAcm-2, described non- Brilliant gallium nitride/Graphene electrodes material specific capacitance is better than 2.5 μ Fcm-2。
(3) beneficial effect
It can be seen from the above technical proposal that amorphous gallium nitride/Graphene electrodes material, preparation method that the disclosure provides And supercapacitor, it has the advantages that
1, by the synergistic effect using two kinds of materials, a kind of amorphous state gallium nitride/Graphene electrodes material is proposed, in reality Show and also ensured the validity of the electrode as double layer capacitor while two kinds of material advantages are combined, on the one hand, Gallium nitride material has good electro-chemical activity, and amorphous structure is conducive to diffusion speed of the electrolyte ion in solid phase Rate reduces its diffusion length, and the phase transition process of amorphous state to crystalline state can be released effectively structure change generation in cyclic process Stress, to improve its cyclical stability；On the other hand, there is good electric conductivity with the compound grapheme material of gallium nitride, Ionic mobility is effectively improved, and graphene-structured has big specific surface area, promotes the migration of electrolyte ion, minimized Electrolyte ion makes material more effectively contact and react with electrolyte ion in the diffusion rate of material internal, can get more High specific capacity；GaN/ grapheme material micro-structure small electric double layer capacitance structure easy to form after compound improves electricity The validity of pole material.Therefore, amorphous state gallium nitride/graphene composite material is a kind of high performance new electrode materials, simultaneous Have high capacity and good stable circulation characteristic, specific capacitance with higher (is better than 2.5 μ Fcm-2), there is good application Prospect.
2, composite material is prepared by using pulsed laser deposition (PLD), using gallium nitride ceramic target as gallium source, benefit With high energy pulse laser evaporation gallium nitride target, the plasma comprising gallium, nitrogen is generated, is being formed with using plasma The composite material of amorphous state gallium nitride and graphene is prepared in deposition on the substrate of graphene.Component segregation effectively is avoided, The use for avoiding gallium metal avoids causing during the preparation process since the fusing point of gallium in Solid Gallium source is very low (~30 DEG C) The problem of material gallium is poisoned, and subsequent technique is directly endangered；Simultaneously this method can reduce reaction temperature (substrate heating temperature~ 500 DEG C), with conventional metal organic vapor phase epitaxy method (MOCVD), the methods of hydride vapour phase epitaxy method (HVPE) needs (~1000 DEG C) cracking gallium sources of hot environment are compared, and high temperature is not needed, compatible with subsequent preparation process, are a kind of efficient controllable The method for preparing high-quality gallium nitride base electrode material.
Detailed description of the invention
Fig. 1 is amorphous gallium nitride/Graphene electrodes material preparation method schematic diagram shown in one embodiment of the disclosure.
Fig. 2 is amorphous gallium nitride/Graphene electrodes material preparation method flow chart shown in one embodiment of the disclosure.
Fig. 3 A is the Raman map for the graphene that step S21 shown in one embodiment of the disclosure is prepared.
Fig. 3 B is the compound of the amorphous state gallium nitride that is prepared of step S22 and graphene shown in one embodiment of the disclosure The Raman map of material.
Fig. 4 is the compound of the amorphous state gallium nitride that is prepared of step S22 and graphene shown in one embodiment of the disclosure (a) low power SEM spectrum and (b) high power SEM spectrum of material.
Fig. 5 A- Fig. 5 B is that amorphous gallium nitride/Graphene electrodes material cyclic voltammetric shown in one embodiment of the disclosure is surveyed Try curve.
Fig. 5 C is the relation curve of the specific capacitance that obtains according to Fig. 5 A and Fig. 5 B test result calculations with scan speed change.
Fig. 5 D is that amorphous gallium nitride/Graphene electrodes material constant current charge-discharge test shown in one embodiment of the disclosure is bent Line.
[symbol description]
1- substrate；2- graphene；
3- gallium nitride ceramic target；4-PLD chamber.
Specific embodiment
The energy storage mechanism of supercapacitor can be divided into two kinds: 1, double layer capacitor (EDLC), using separation of charge Mode realizes that energy is converted.It mainly include active carbon, carbon aerogels, carbon nanotube, activated carbon fibre and graphene etc..Because its Capacitance is only related with the relevant aggregation of electrostatic charge electrode potential on interface, is limited by material structure, double layer capacitor The space that can be further promoted is limited；2, oxidation-reduction type electrochemical capacitor (pseudocapacitors), by electrode material surface Quick faraday's redox reaction occurs to store charge.Specifically include that transition group metallic oxide, conducting polymer are rich Nanoporous carbon etc. containing heteroatomic carbon material and Electrostatic Absorption hydrogen.Wherein, conducting polymer has high electrical conductivity, current potential The advantages of window, capacitance, mainly has polyaniline (PANI), polypyrrole (PPy) and polythiophene (PTh) and its growth etc..It is poly- The main problem for closing object electrode is that counter ion adulterates and shrinks, expands caused by deionization doping in cyclic process, influences it Although electrochemical stability still cannot fundamentally overcome modified using modes such as doping.Containing heteroatomic carbon material and quiet The materials such as the nanoporous carbon of Electro Sorb hydrogen, it may have higher theoretical capacity.However, electrode reaction is by chemistry affect, Cause the stability of electrode reaction poor, there are also a certain distance from practical application.Its table of transition metal oxide electrode material Quick redox reaction is passed through in face, shows very strong fake capacitance behavior.It mainly include ruthenium-oxide (RuO2), manganese oxide (MnOx), nickel oxide (NiO), cobaltosic oxide (Co3O4) etc..Compared with traditional carbon material, transition group metallic oxide can be provided Higher energy density and specific capacity, it is with better electrochemical stability compared with conducting polymer, and has preparation The advantages such as method degree of controllability height, green, cheap.However oxidation-reduction process generates destruction to the structure of material, leads to cyclicity It can decline, while the resistivity of transition group metallic oxide is higher, influences its high rate performance.
The method for improving electrode material for super capacitor focuses primarily upon following both direction, and one of direction is to prepare Composite material reduces particle size using the synergistic effect of storeroom, charge-conduction, raising material specific surface area etc. is promoted to mention High electrochemical performance；Another direction is the control of material microscopic appearance, and the specific surface of material is improved using the dimensional effect of material, Reduce electrolyte in the diffusion rate of material internal, to obtain better specific capacity.In the application, by using gallium nitride with The synergistic effect of two kinds of materials of graphene proposes a kind of amorphous state gallium nitride/Graphene electrodes material, is realizing two kinds of materials The validity of the electrode as double layer capacitor is also ensured while advantage is combined, on the one hand, gallium nitride material tool There is good electro-chemical activity, and amorphous structure is conducive to diffusion rate of the electrolyte ion in solid phase, reduces its expansion Distance is dissipated, the phase transition process of amorphous state to crystalline state can be released effectively the stress of structure change generation in cyclic process, to mention Its high cyclical stability；On the other hand, there is good electric conductivity with the compound grapheme material of gallium nitride, effectively improves ion Mobility, and graphene-structured has big specific surface area, promotes the migration of electrolyte ion, minimizes electrolyte ion and exists The diffusion rate of material internal makes material more effectively contact and react with electrolyte ion, can get higher specific capacity；It is multiple GaN/ grapheme material micro-structure small electric double layer capacitance structure easy to form after conjunction, improves the effective of electrode material Property.Therefore, amorphous state gallium nitride/graphene composite material is a kind of high performance new electrode materials, has both high capacity and good Good stable circulation characteristic, has a good application prospect.
On the other hand, the mainstream preparation method of gallium nitride material can be divided into gaseous state gallium source and Solid Gallium according to gallium source at present Source.Method using gaseous state gallium source includes metal organic vapor phase epitaxy method (MOCVD), hydride vapour phase epitaxy method (HVPE) and Molecular beam epitaxy etc., these methods generally require in (~1000 DEG C) cracking gallium sources of hot environment, and general metal electrode is such as It is difficult to keep stablizing in this high temperature and chemical activity environment, and dystectic metal, such as tungsten, tantalum, hardness is high, and subsequent The preparation process of electrode is incompatible.In method using Solid Gallium source, since the fusing point of gallium is very low (~30 DEG C), prepared The poisoning of material gallium is easily caused in journey, directly endangers subsequent technique.
Therefore, the defects and limitations based on above-mentioned preparation method, the application propose a kind of heavy by using laser pulse The method for accumulating (PLD) to prepare the composite material of amorphous state gallium nitride and graphene, using gallium nitride ceramic target as gallium source, benefit With high energy pulse laser evaporation gallium nitride target, the plasma comprising gallium, nitrogen is generated, is being formed with using plasma The composite material of amorphous state gallium nitride and graphene is prepared in deposition on the substrate of graphene.This method can be avoided effectively Component segregation avoids the use of gallium metal, avoids preparing since the fusing point of gallium in Solid Gallium source is very low (~30 DEG C) The problem of causing material gallium to be poisoned in journey, directly endangering subsequent technique；This method can reduce reaction temperature (silicon simultaneously Temperature~500 DEG C), with conventional metal organic vapor phase epitaxy method (MOCVD), the methods of hydride vapour phase epitaxy method (HVPE) It needs to compare in (~1000 DEG C) cracking gallium sources of hot environment, does not need high temperature, it is compatible with subsequent preparation process, it is a kind of efficient Controllable preparation high-quality gallium nitride base electrode material method.
For the purposes, technical schemes and advantages of the disclosure are more clearly understood, below in conjunction with specific embodiment, and reference The disclosure is further described in attached drawing.
In first exemplary embodiment of the disclosure, a kind of amorphous gallium nitride/Graphene electrodes material is provided Preparation method.
Fig. 1 is amorphous gallium nitride/Graphene electrodes material preparation method schematic diagram shown in one embodiment of the disclosure.Figure 2 be amorphous gallium nitride/Graphene electrodes material preparation method flow chart shown in one embodiment of the disclosure.
Shown in referring to Figures 1 and 2, amorphous gallium nitride/Graphene electrodes material preparation method of the disclosure, comprising:
Step S11: graphene is formed on a substrate；
In step S11, graphene 2 is formed on a substrate 1, comprising: using chemical vapor deposition (CVD) in substrate It is upper directly to form graphene；Alternatively, utilizing graphite oxide reduction method, mechanical stripping method, electrochemical reducing, epitaxial crystal growth Method, liquid phase stripping method, pyrolysis method or cutting carbon nanotubes etc., which are prepared after graphene is prepared in one of method of graphene, to be turned It moves on a substrate.
Graphene is directly formed on substrate preferably by chemical vapor deposition in the present embodiment.
In one example, using chemical vapor deposition, directly specific step is as follows for formation graphene on substrate:
1, copper foil substrate is cleaned up；
2, copper foil is put into CVD, is vacuumized；
3, it is passed through gas (carbon sources such as methane, ethylene) purging, and is heated to 600 DEG C；
Step S12: using pulsed laser deposition (PLD) on the substrate for be formed with graphene prepare amorphous state gallium nitride with The composite material of graphene；
Shown in referring to Fig.1, in step S12, gallium source is used as using gallium nitride ceramic target 3, is steamed using high energy pulse laser Gallium nitride ceramic target 3 is sent out, the plasma comprising gallium, nitrogen is generated, it is corresponding after the concentration of plasma reaches a certain level Plasma plume brightness is generated in PLD chamber 4, and plasma plume brightness is illustrated with triangle in Fig. 1, includes nitridation in plasma Gallium molecule, gallium atom, nitrogen-atoms, gallium ion and Nitrogen ion, it is enterprising in the substrate 1 for being formed with graphene 2 using plasma Row deposition obtains the composite material of amorphous state gallium nitride and graphene.Wherein, in the present embodiment, the high energy pulse laser of selection is 248nm laser.
In one example, amorphous state nitridation is prepared on the substrate for be formed with graphene using pulsed laser deposition (PLD) Specific step is as follows for the composite material of gallium and graphene:
1, the substrate of the first one-step growth is packed into PLD chamber, is evacuated to 10-7pa；
2, lead to nitrogen ionization；
3, silicon is to 500 DEG C；
4, it deposits 2 hours；
5, deposition terminates, natural cooling, takes out sample.
In second exemplary embodiment of the disclosure, a kind of electrode material is provided, which is amorphous nitrogen Change gallium/Graphene electrodes material, the amorphous gallium nitride/Graphene electrodes material are as follows: amorphous state gallium nitride and graphene it is compound Material.
Amorphous state occurs for the amorphous gallium nitride/Graphene electrodes material gallium nitride in the cyclic process of charge and discharge to crystalline state Phase transformation.
The amorphous gallium nitride of the present embodiment/Graphene electrodes material preparation method as described in one embodiment is prepared into It arrives.
Raman and SEM characterization have been carried out to amorphous gallium nitride/Graphene electrodes material pattern and property of the present embodiment.
4, after reacting 1 hour, natural cooling simultaneously takes out sample.
Fig. 3 A is the Raman map for the graphene that step S21 shown in one embodiment of the disclosure is prepared.Fig. 3 B is this The Raman map of the composite material of amorphous state gallium nitride and graphene that step S22 shown in one embodiment is prepared is disclosed.
The characteristic peak of graphite can be obviously observed from Fig. 3 A and Fig. 3 B, and can't see the characteristic peak of gallium nitride, As it can be seen that gallium nitride is amorphous state in finally formed composite material.
Fig. 4 is the compound of the amorphous state gallium nitride that is prepared of step S22 and graphene shown in one embodiment of the disclosure (a) low power SEM spectrum and (b) high power SEM spectrum of material.
From finding out that the surface topography of the composite material is integrally uniform in (a) low power SEM spectrum in Fig. 4, (b) high power in Fig. 4 SEM spectrum shows that the composite material being prepared has big specific surface area, is conducive to improve ion-exchanging efficiency.
On the one hand, gallium nitride material has good electro-chemical activity, and amorphous structure is conducive to electrolyte ion Diffusion rate in solid phase reduces its diffusion length, and the phase transition process of amorphous state to crystalline state can be released effectively in cyclic process The stress for putting structure change generation, to improve its cyclical stability；On the other hand, have with the compound grapheme material of gallium nitride Have good electric conductivity, effectively improve ionic mobility, and graphene-structured has big specific surface area, promote electrolyte from The migration of son minimizes electrolyte ion in the diffusion rate of material internal, contacts material more effectively with electrolyte ion And reaction, it can get higher specific capacity；GaN/ grapheme material micro-structure small electric double layer easy to form after compound Capacitance structure improves the validity of electrode material.
In the third exemplary embodiment of the disclosure, a kind of supercapacitor, the electricity of the supercapacitor are provided Pole material is any amorphous gallium nitride/Graphene electrodes material that the disclosure is mentioned.
Fig. 5 A- Fig. 5 B is that amorphous gallium nitride/Graphene electrodes material cyclic voltammetric shown in one embodiment of the disclosure is surveyed Try curve.Fig. 5 C is the relation curve of the specific capacitance that obtains according to Fig. 5 A and Fig. 5 B test result calculations with scan speed change. Fig. 5 D is amorphous gallium nitride/Graphene electrodes material constant current charge-discharge test curve shown in one embodiment of the disclosure.
In the present embodiment, the composite material of amorphous state gallium nitride and graphene (as electrode, is subjected to electro-chemical test. It is tested under three-electrode system, wherein 1 mole of KCl is electrolyte, and graphene film is working electrode, and platinized platinum is to electrode, saturation Calomel electrode is reference electrode, and potential window is -0.9V~-0.3V, and cyclic voltammetry is from 10mVs-1To 100mVs-1, Constant current charge-discharge test is from 0.5mAcm-2To 1mAcm-2, in conjunction with Fig. 5 A- Fig. 5 D it is found that working as the scanning of cyclic voltammetry Speed is from 10mVs-1To 100mVs-1When even variation, sampled point is 10 in the present embodiment, by the counted specific capacitance of CV For 6.18 μ Fcm-2、4.88μF·cm-2、4.18μF·cm-2、3.83μF·cm-2、3.51μF·cm-2、3.24μF·cm-2、 3.03μF·cm-2、2.85μF·cm-2、2.71μF·cm-2、2.63μF·cm-2, it is seen then that the amorphous gallium nitride/Graphene electrodes The specific capacitance of material is better than 2.5 μ Fcm-2.The result shows that amorphous state gallium nitride/graphene composite material is a kind of high performance New electrode materials have both high capacity and good stable circulation characteristic, and the electrode material as supercapacitor has preferable Application prospect.
In conclusion present disclose provides a kind of amorphous gallium nitride/Graphene electrodes material, preparation method and super capacitors Device prepares amorphous state gallium nitride and graphene by using pulsed laser deposition (PLD) on the substrate for be formed with graphene Composite material, preparation method effectively avoid component segregation, avoid the use of gallium metal, do not need high temperature, with subsequent preparation process It is compatible, it is a kind of method of efficient controllable preparation high-quality gallium nitride base electrode material, amorphous state gallium nitride and graphene Composite material is as a kind of electrode material, and the amorphous gallium nitride/Graphene electrodes material has both high capacity and good circulation is steady Determine characteristic, has a good application prospect.
It unless there are known entitled phase otherwise anticipates, the numerical parameter in this specification and appended claims is approximation, energy Enough bases pass through the resulting required characteristic changing of content of this disclosure.Specifically, all be used in specification and claim The middle content for indicating composition, the number of reaction condition etc., it is thus understood that repaired by the term of " about " in all situations Decorations.Under normal circumstances, the meaning expressed refers to include by specific quantity ± 10% variation in some embodiments, some ± 5% variation in embodiment, ± 1% variation in some embodiments, in some embodiments ± 0.5% variation.
Furthermore word "comprising" or " comprising " do not exclude the presence of element or step not listed in the claims.Positioned at member Word "a" or "an" before part does not exclude the presence of multiple such elements.
Particular embodiments described above has carried out further in detail the purpose of the disclosure, technical scheme and beneficial effects Describe in detail it is bright, it is all it should be understood that be not limited to the disclosure the foregoing is merely the specific embodiment of the disclosure Within the spirit and principle of the disclosure, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the disclosure Within the scope of shield.

Claims (9)

1. a kind of amorphous gallium nitride/Graphene electrodes material preparation method characterized by comprising
Graphene is formed on a substrate；And
The composite material of amorphous state gallium nitride and graphene is prepared on the substrate for be formed with graphene using pulsed laser deposition.
2. preparation method according to claim 1, which is characterized in that described to be formed with graphite using pulsed laser deposition In the step of preparing the composite material of amorphous state gallium nitride and graphene on the substrate of alkene, using gallium nitride ceramic target as gallium Source is generated the plasma comprising gallium, nitrogen, is existed using plasma using high energy pulse laser evaporation gallium nitride target The composite material of amorphous state gallium nitride and graphene is prepared in the deposition being formed on the substrate of graphene.
3. preparation method according to claim 2, which is characterized in that the high energy pulse laser is 248nm laser.
4. preparation method according to claim 2, which is characterized in that described the step of forming graphene on a substrate In, comprising:
Graphene is directly formed on substrate using chemical vapor deposition；Alternatively,
Utilize graphite oxide reduction method, mechanical stripping method, electrochemical reducing, epitaxial crystal growth method, liquid phase stripping method, hot tearing One of solution or the method for cutting carbon nanotubes are transferred on a substrate after graphene is prepared.
5. a kind of amorphous gallium nitride/Graphene electrodes material, which is characterized in that the amorphous gallium nitride/Graphene electrodes material are as follows: The composite material of amorphous state gallium nitride and graphene.
6. amorphous gallium nitride according to claim 5/Graphene electrodes material, which is characterized in that the amorphous gallium nitride/stone The phase transformation of amorphous state to crystalline state occurs for black alkene electrode material gallium nitride in the cyclic process of charge and discharge.
7. amorphous gallium nitride according to claim 5/Graphene electrodes material, which is characterized in that the amorphous gallium nitride/stone Black alkene electrode material is prepared using preparation method described in any one of Claims 1-4.
8. a kind of supercapacitor, which is characterized in that the electrode material of the supercapacitor is any one of claim 5 to 7 The amorphous gallium nitride/Graphene electrodes material.
9. supercapacitor according to claim 8, which is characterized in that tested under three-electrode system, wherein 1 mole KCl is electrolyte, and graphene film is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, potential window For -0.9V~-0.3V, cyclic voltammetry is from 10mVs-1To 100mVs-1, constant current charge-discharge test is from 0.5mAcm-2 To 1mAcm-2, the amorphous gallium nitride/Graphene electrodes material specific capacitance is better than 2.5 μ F.cm-2。
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Application publication date: 20190709