CN110415988B - Graphene quantum dot nanotube GO/YCoO with AAO template as support3Preparation of nano array electrode material - Google Patents
Graphene quantum dot nanotube GO/YCoO with AAO template as support3Preparation of nano array electrode material Download PDFInfo
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- 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
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- 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
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Abstract
Graphene quantum dot nanotube GO/YCoO with AAO template as support3The preparation of the nano array electrode material comprises the following steps; preparing a pore-diameter-controllable nano porous array AAO template by adopting a two-step anodic oxidation method; step (2), etching and stripping a Staudenmai method by an electrochemical stripping method to obtain graphene GO nano-sheets; dialyzing the filtrate filtered by a polytetrafluoroethylene extraction filter membrane to obtain a graphene GO quantum dot solution; depositing graphene GO quantum dots in the pore channels of the AAO template by adopting an electrochemical deposition method to form an AAO/GO quantum dot nanotube array; and (4): depositing YCoO in the AAO/GO quantum dot nano array tube obtained in the step (3) by using a vacuum spin coating method3Sol precursor array; step (5) calcining AAO/GO/YCoO obtained in step (4)3Converting sol precursor into AAO/GO/YCoO3Nanotube array to form nanotube array of coaxial heterostructure AAO/GO/YCoO3An electrode material. The invention has the characteristics of improved energy density and excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of nano material preparation and electrochemical energy storage, in particular to a graphene quantum dot nanotube GO/YCoO taking an AAO template as a support3And (3) preparing the nano array electrode material.
Background
The aluminum anodic oxidation AAO film has the excellent performances of stability, high temperature resistance, good insulativity, uniform hole distribution, high hole density and the like, has simple preparation process and wide application range of materials for preparing products, and can be used for preparing the productsA plurality of one-dimensional nanostructure materials with different materials and different shapes are produced. The porous AAO is used as a template, the nano material is prepared by the growth of the confinement effect, the method is very economical, effective and convenient, and the template can be used for growing uniform and orderly nano arrays. The electrode material for preparing the nano array based on the AAO template is widely applied to the preparation of the electrode material of the super capacitor. Wang et al synthesized nickel hydroxide nanowires using porous anodic aluminum oxide as a template by a coordination precipitation-decomposition method. The nano-wire is made into an electrode at 6 mol.L-1In the KOH electrolyte solution, the performance of the super capacitor is researched by utilizing cyclic voltammetry and constant current charging and discharging technologies, the nanowire electrode has good super capacitance performance, and when the current density is 5mA cm–2When the specific capacity of the single electrode reaches 833Fg–1. Chen and the like successfully synthesize the electrode material gamma-MnO of the super capacitor in a porous alumina AAO template by adopting a chemical deposition and 500 ℃ heat treatment method2A nanotube. The specific electrochemical capacity can reach 566Fg–1And the electrochemical specific capacity can be kept above 90% after the cycle is carried out for 1000 times.
The appearance of the electrode material can be controllably prepared by adopting the AAO template, the specific surface area of the electrode is increased, so that the electrode is fully contacted with electrolyte, and the potential of the prepared material as the electrode can be better explored.
Graphene GO is a novel two-dimensional atomic crystal composed of a monoatomic layer in which carbon atoms are hybridized and connected by sp2, and is the thinnest two-dimensional material at present; as a novel carbon material, graphene has the advantages of stable physical structure, large specific surface area, good conductivity, excellent physical and chemical properties, and potential application prospects in the fields of chemical and energy materials, microelectronics, information, physics and the like. The GO-based composite material obtained by modifying or compounding GO by using other conductive substances has become a hot point of research on electrode materials of super capacitors. Graphene GO has 2630m2.g-1Large specific surface area, excellent ionic conductivity and carrier transport ability (electron mobility 2X 10)5cm2.V-1s-1) So that the advantage of the GO stone in energy storage is obvious, and the GO stone is also a GO stoneThe reason why graphene is useful for a supercapacitor.
The quasi-zero-dimensional graphene GO quantum dot nano material has unique physical and chemical properties because the movement of electrons in all directions is limited and the quantum dot local effect is obvious. Compared with the traditional semiconductor quantum dot, the graphene quantum dot is resistant to strong acid, strong alkali and photo-corrosion and has a stable structure; adjustable band gap width; surface functionalization is easy to realize; the thickness can be as thin as a single atom, the chemical stability is good, and the like, and the material is an environment-friendly quantum dot material without containing high-toxicity metal elements. The preparation of the graphene quantum dots is mainly divided into a bottom-up expansion method and a top-down reduction method. A graphene GO quantum dot reduction method preparation technology relates to 11 methods such as a hydrothermal method, a stripping method, a strong acid oxidation method, a solvothermal method, an electrochemical method, electron beam irradiation, an ozone method, a hydrogen method, a gas-thermal method, a magnetron sputtering technology and irradiation. The stripping method and the hydrothermal method are main techniques of the graphene quantum dot shrinking method preparation technology. Techniques such as electrochemical methods, strong acid oxidation methods, solvothermal methods, and the like have also been developed.
The graphene-metal oxide composite material is used as a supercapacitor electrode material, so that on one hand, the high intrinsic conductivity of graphene provides a rapid transmission channel for electrons, and the charge-discharge rate of the material is greatly improved; on the other hand, the metal oxide electrode is reversible in chemistry and structure due to oxidation and reduction reactions, and has good electronic conductivity; the metal oxide is relatively susceptible to electron and proton transitions in the hydrated oxide lattice structure, thereby causing insertion and extraction of protons, providing higher capacitance to the electrode through redox reactions. Therefore, the metal oxide electrode can cause a reversible process of the pseudo capacitor and enable the electrode to react to penetrate into the electrode, energy is stored in a three-dimensional space, and specific energy is improved. In addition, the metal oxide and the graphene are compounded, so that the agglomeration of the graphene can be effectively avoided, the effective contact area of the electrolyte and the electrode material is increased, and the capacitance performance of the material is improved. The metal oxide compounded with graphene at present mainly comprises RuO2、MnO2、Co3O4NiO, etc.
ABO3The perovskite material has wide application in the aspects of fuel cells, catalysts, high-temperature superconductivity and the like due to unique ferroelectric, piezoelectric, magnetic and charge transport properties. The perovskite nanotube researched at present is mainly titanate nanotube, mainly inspects ferroelectric and electromagnetic properties and photocatalytic properties in the aspect of performance, and reports on electrochemical energy storage research are less. The study of perovskite nanotube arrays is still in its infancy, with less study of cobaltate nanotube arrays and YCoO3Nanotube arrays have been less studied, which makes it difficult to form nanotubes due to the particularities of the perovskite crystal structure. In view of the fact that arrays of metal oxide nanotubes, carbon nanotubes, non-metal oxide nanotubes, etc. all show excellent performance in the aspects of adsorption, catalyst carrier, gas sensitive material, etc., perovskite YCoO with good performance is used3The prepared nanotube array can improve the electrochemical performance of the nanotube array and can be completely new applied to the aspect of energy storage of electrode materials of super capacitors. At present, the method for preparing the nanotube array (hard template method, soft template method, hydrothermal synthesis method and the like) is not applied to perovskite YCoO3In the preparation of nanotube arrays. In conclusion, the invention determines a super capacitor electrode material AAO/GO/YCoO3A method for preparing a nano array tube.
Disclosure of Invention
The invention aims to provide a graphene quantum dot nanotube GO/YCoO taking an AAO template as a support3Preparation of nano array electrode material by changing electrode material structure and using GO/YCoO3The synergistic effect of the components enables the energy density of the final product to be improved and the comprehensive performance to be excellent. In order to achieve the purpose, the invention adopts the technical scheme that:
graphene quantum dot nanotube GO/YCoO with AAO template as support3The preparation of the nano array electrode material comprises the following steps;
step (1):
preparing a pore diameter controllable nano porous array AAO template by adopting a two-step anodic oxidation method, wherein the pore diameter range is 30-100 nm;
step (2):
stripping graphene GO nano sheets prepared by a Staudenmaier method by an electrochemical method; filtering the filtrate by using a polytetrafluoroethylene filter membrane, and dialyzing to obtain a graphene GO quantum dot solution, wherein the filtrate is a phosphate buffer solution containing graphene GO quantum dots;
and (3):
depositing graphene GO quantum dots in the pore channels of the AAO template by adopting an electrochemical deposition method to form an AAO/GO quantum dot nanotube array;
and (4):
depositing YCoO in the AAO/GO quantum dot nano array tube obtained in the step (3) by using a vacuum spin coating method3Sol precursor array;
and (5):
calcining AAO/GO/YCoO obtained in the step (4)3Converting sol precursor into AAO/GO/YCoO3Nanotube array to form nanotube array of coaxial heterostructure AAO/GO/YCoO3An electrode material.
And (3) filtering polytetrafluoroethylene after electrochemical etching of graphene GO nanosheets by using a phosphate electrolyte in the step (2), dialyzing the filtrate to obtain a graphene GO quantum dot solution, and then electrochemically depositing GO quantum dots in AAO template nanopores.
The YCoO in the step (4) and the step (5)3The main steps of nanotube deposition in the AAO/GO quantum dot nanotube are as follows: (1) YCoO3Preparing a sol precursor; (2) deposition of YCoO in AAO/GO quantum dot nanotubes by vacuum spin coating3A sol precursor; (3) calcination of AAO/GO/YCoO3The sol precursor is converted into a coaxial heterostructure AAO/GO/YCoO3An array of nanotubes.
Said (1) YCoO3Preparing a sol precursor:
the Co and Y salts were dissolved in deionized water at a 1:1 molar ratio, clarified by stirring, and then mixed with (0.4-0.6M) citric acid, Co salt: y salt: the citric acid is in a molar ratio of 1:1:2, stirring is carried out for 30-60min at 60-90 ℃ until the citric acid is uniform, ammonia water is slowly dripped to adjust the pH value of the solution to be 6-7, the solution is continuously stirred in the process so as to be uniformly mixed, when the pH value of the solution is adjusted to be 6-7, sol particles are weakly electropositive, and the inner wall of the AAO/GO template is electronegative.
The (2) depositing YCoO in the AAO/GO quantum dot nanotube by a vacuum spin coating method3Sol precursor:
YCoO obtained in step (1)3Adding a dispersing agent into the sol precursor, and dispersing YCoO by ultrasonic oscillation3Sol precursor, dispersant and YCoO3The mass ratio of (A) to (B) is 8-12: 1, placing the AAO/GO quantum dot nanotube array in a closed container, ensuring the vacuum degree of the closed container at the internal pressure of 0.01-0.05MPa, and dropwise adding YCoO to the surface of an AAO template3Ultrasonically dipping a sol precursor for 10-30min, then homogenizing glue at low speed of 200-400r/min for 10-30s in a rotary film coating machine, then homogenizing glue at high speed of 2500-3500r/min for 60s, drying for 10-30min in a drying oven at 80-150 ℃, and ultrasonically soaking and vacuum spin coating can effectively improve YCoO in the AAO/GO quantum dot nanotube3Filling degree of sol precursor, preparing highly ordered nanotube array, repeating the above steps of ultrasonic dipping, spin coating and vacuum drying for 2-6 times, and performing YCoO3The sol precursor is deposited on the wall of the AAO/GO quantum dot nanotube.
The dispersant can be one or a mixture of several of ethyl cellulose, sodium dodecyl sulfate or methyl amyl alcohol.
The (3) coaxial heterostructure AAO/GO/YCoO3Formation of nanotube array electrode material:
the AAO/GO/YCoO dried in the step (2) in vacuum3The sol precursor is firstly pretreated for 4 hours in a muffle furnace at the temperature of 300 ℃ and 500 ℃ at a low heating rate, citric acid organic matters are burnt at the temperature of 300 ℃ and nitrate is subjected to decomposition reaction at the temperature of about 400 ℃, then the sol precursor is calcined for 48 to 96 hours at the temperature of 900 ℃ and 1000 ℃, and the sol precursor is naturally cooled to the room temperature after water and a dispersing agent are removed.
In the whole process, the AAO/GO quantum dot nanotube template is used as a micro channel, YCoO3The sol precursor nanotube is transformed into a heterostructure AAO/GO/YCoO under the conditions of nucleation, growth and calcination heat treatment in the GO quantum dot nanotube3An array of nanotubes.
YCoO3Precursor sol formation YCoO3The main reactions that occur with nanotube arrays are:
the invention has the beneficial effects that:
the invention forms the nano array according to the sequence of the steps (3), (4) and (5), and finally forms AAO/GO/YCoO3Nanotube array electrode material with coaxial heterostructure for maximum exertion of YCoO3And the volume change compatibility of the electrode is improved under the synergistic effect of the GO quantum dot nanotube.
The coaxial heterostructure AAO/GO/YCoO prepared by the invention3The nanotube array electrode structure can well reduce the thickness of graphene, effectively prevent the agglomeration of graphene oxide and realize the stripping of the graphene oxide; AAO/GO/YCoO3The coaxial heterogeneous nanotube array structure can be backed to form parallel connection of capacitors, so that the capacitance performance of the electrode material is further improved; the structure has large specific surface area, AAO/GO/YCoO3Good contact and synergy between the materials helps to improve the energy density of the capacitor.
Nanostructured ABO in the invention3The perovskite type metal oxide array is deposited on the surface of the graphene GO quantum dot nanotube, and the structure and mechanical properties of the graphene GO quantum dot nanotube limit the nano-structure ABO in the oxidation-reduction process3The mechanical deformation of the perovskite metal oxide avoids the damage of the electrode material and obtains better stability. In addition, the deposited graphene GO quantum nanotube array has stress relaxation property, and the structural damage of the capacitor material in the charging and discharging process is reduced.
The invention exerts the excellent conductivity and volume compatibility of graphene GO quantum dots, and utilizes the multiple effects of capillary force and hydrostatic pressure in the vacuum spin coating and dipping processes to effectively improve YCoO3The deposition rate and filling degree of the AAO/GO quantum dot nanotube are improved under the condition of not reducing power density and cycle lifeThe energy density of the electrode material is determined. The performance indexes are as follows: the specific capacity is more than or equal to 370F/g, the energy density is more than or equal to 60Wh/kg, and the capacity retention rate is more than or equal to 90 percent after 1000 cycles.
Drawings
FIG. 1 shows a coaxial heterostructure AAO/GO/YCoO3XRD patterns of nanotube nanoarrays.
FIG. 2 is YCoO deposited in AAO/GO nanotubes3EDS spectrum.
FIG. 3 shows a coaxial heterostructure AAO/GO/YCoO3Nanotube array CV curve.
FIG. 4 shows a coaxial heterostructure AAO/GO/YCoO3Nanotube array GCD curve.
Detailed Description
At present, the capacitor electrode material formed by compounding graphene and metal oxide becomes a hot point of research, but the research on the formation of the supercapacitor electrode material by compounding graphene with a few layers and a metal oxide nano array is not much. While the structure of the electrode material is critical to the performance of the capacitor. Therefore, the invention considers the large specific surface area and size effect of the nano material, the excellent conductivity and large volume compatibility of the graphene and the perovskite ABO3On the basis of the physical and chemical properties such as large specific capacitance and the like of the nano-structure metal oxide, the graphene GO quantum dot nanotube is designed and prepared by using an AAO template, and perovskite YCoO is deposited in the graphene GO quantum dot nanotube by using an ultrasonic dispersion auxiliary vacuum spin coating method3Obtaining coaxial heterostructure AAO/GO/YCoO3Nanotube array composite electrode, graphene quantum dot nanotube with good conductivity and YCoO with larger composite specific capacitance3The method for preparing the electrode material used by the novel potential energy storage super capacitor with high energy density and high power density lays a foundation for realizing the industrialization of a new generation of graphene composite nano metal oxide electrode material with higher energy density and longer service life, and provides a powerful technical support for the promotion of products in related industriesThe method is expected to bring good economic and social benefits when being used on the super capacitor.
The present invention will be described in further detail with reference to the accompanying drawings.
The invention relates to a coaxial heterogeneous nanotube array electrode material AAO/GO/YCoO for a symmetrical electrochemical supercapacitor3The preparation method comprises the following main process steps:
(1) preparing a pore diameter controllable nano porous array AAO template by adopting a two-step anodic oxidation method, wherein the pore diameter range is 30-100 nm; (2) etching and stripping the graphene GO nanosheets by using an electrochemical stripping method; dialyzing the filtrate filtered by a polytetrafluoroethylene extraction filter membrane to obtain a graphene GO quantum dot solution; (3) depositing graphene GO quantum dots in the pore channels of the AAO template by an electrochemical deposition method to form an AAO/GO quantum dot nanotube array; (4) depositing YCoO in AAO/GO quantum dot nano array tube by vacuum spin coating method3Sol precursor array; (5) calcination of AAO/GO/YCoO3Converting sol precursor into AAO/GO/YCoO3Nanotube array to form nanotube array of coaxial heterostructure AAO/GO/YCoO3An electrode material. Coaxial heterostructure AAO/GO/YCoO3The XRD pattern of the nanotube array is shown in fig. 1. FIG. 1 shows that AAO/GO/YCoO can be formed by the above process steps3A coaxial heterogeneous nanotube array structure. In the preparation method, the pore size of the AAO template influences YCoO3The preparation of the nanotube should control YCoO while ensuring the large-size aperture of the template3Mass of sol particles. Formation of nanotube arrays AAO/GO/YCoO3The order of the carbon nanotubes determines the coaxial heterostructure of the formed nanotube array electrode, thereby affecting the electrochemical performance of the nanotube array electrode.
The GO quantum dots are effectively embedded in the AAO template by an electrochemical method to form the GO quantum nanotube array. The phenomenon that the graphene sheets are stacked in a mixed and disorderly mode is reduced, the number of layers of the graphene is reduced by dispersing the graphene, double electric layers are formed on the surface of the AAO, the nano array GO/AAO structure well prevents the graphene oxide from agglomerating, the graphene oxide is peeled off, the thickness of the graphene is reduced, the specific surface area of an electrode is increased, the transport capacity of electronic ions is improved, and the specific capacitance is increased.
The invention uses a vacuum spin coating method to deposit YCoO in an AAO/GO nano tube array3Array, forming nano AAO/GO/YCoO3Coaxial heterogeneous nanotube array electrode materials. YCoO deposited in AAO/GO nanotubes3The EDS spectrum is shown in FIG. 2. FIG. 2 shows YCoO3Deposited in an AAO/GO nanotube array. YCoO3Loaded on graphene GO quantum dot nanotubes, further preventing graphene layer agglomeration, YCoO3The nanotubes are inserted between graphene layers to form a large-area conductive network, and an electron transmission channel is formed in the composite material, and simultaneously AAO/GO/YCoO3The coaxial heterogeneous nanotube sandwich structure can be backed to form the parallel connection of the capacitor, so that the heterostructure of graphene GO quantum dots and metal oxide with a nanostructure is formed, the synergistic effect of the graphene GO quantum dots and the metal oxide with the nanostructure is exerted, and the organic unification of the non-Faraday effect and the Faraday effect of the pseudo capacitor of the electrochemical electric double-layer capacitor is realized. The compatibility of the electrode material is improved, and the electrochemical performance of the coaxial heterogeneous nanotube array electrode material is improved. Coaxial heterostructure AAO/GO/YCoO3The nanotube array CV curve is shown in FIG. 3. From FIG. 3, it can be seen that AAO/GO/YCoO3The area enclosed by the CV curves is larger than the area enclosed by the CV curves of AAO/GO and AAO, which shows that the area enclosed by the CV curves of AAO/GO/YCoO is larger than the area enclosed by the CV curves of AAO/GO and AAO3The specific capacitance of the nanotube array is larger than that of AAO and AAO/GO.
The coaxial heterogeneous nanotube array AAO/GO/YCoO of the invention3The electrode material has excellent stability. Nanostructured YCoO3The array is deposited on the surface of graphene oxide, and the structure and mechanical properties of the graphene oxide limit the nano-structure YCoO in the oxidation-reduction process3The mechanical deformation of the electrode avoids the damage of the electrode material and obtains better stability. In addition, the nano array deposited with the graphene quantum dots has stress relaxation property, and the structural damage of the capacitor material in the charging and discharging process is reduced. Coaxial heterostructure AAO/GO/YCoO3The GCD curve of the nanotube array is shown in fig. 4. FIG. 4 shows a coaxial heterogeneous nanotube array AAO/GO/YCoO3The electrode material has excellent stability.
The method effectively avoids the defect of difficult ion and electron transmission caused by the irregular orientation of the graphene sheets relative to the current collector and the parallel lamination in the traditional design, and fully utilizes the good conductivity in the surface of the graphene quantum dot tube to prepare the coaxial heterostructure nano array AAO/GO/YCoO3The tubular electrode sandwich structure further exerts the high conductivity of the graphene quantum dots in the same plane, and improves the metal oxide compatibility.
Coaxial heterostructure AAO/GO/YCoO constructed by the invention3The energy density of the electrode material of the nanotube array super capacitor is high. The electrode material constructed by the invention exerts the excellent conductivity and volume compatibility of graphene GO quantum dots, and utilizes the multiple actions of capillary force and hydrostatic pressure in the vacuum spin coating and dipping processes to effectively improve YCoO3The deposition rate and the filling degree of the AAO/GO quantum dot nanotube improve the energy density of the electrode material under the condition of not reducing the power density and the cycle life. The performance indexes are as follows: the specific capacity is more than or equal to 370F/g, the energy density is more than or equal to 60Wh/kg, and the capacity retention rate is more than or equal to 90 percent after 1000 cycles
The invention relates to a coaxial heterogeneous nanotube array AAO/GO/YCoO3The 4 main steps included in the preparation process of the electrode material have good universality. Other anodic oxidation templates are also suitable; adapted for removing YCoO3Other perovskite metal oxides than perovskite metal oxides; is suitable for other carbon materials (graphite, graphyne, carbon nano tube, carbon nano paper and the like) except GO; the method is suitable for the composition of the heterostructure of the perovskite metal oxide and the carbon material, and has good universality.
Example 1:
step (1):
preparing a nano array AAO template with a hole diameter of 30nm and double-sided through holes: preparing a double-sided through hole nano array AAO template according to a conventional aluminum anodic oxidation method, wherein the method comprises the steps of pretreating an aluminum plate; polishing; two-step anodic oxidation process; and (6) reaming.
Step (2):
preparing graphene used for forming a GO quantum dot nanotube array by a Staudenmaier method: 5g of graphite is added into a 500mL round-bottom flask, 45mL of concentrated nitric acid and 87.5mL of concentrated sulfuric acid are added under the condition of ice-water bath, 55g of potassium chlorate is added in batches, and the mixture is reacted for 120 hours at room temperature after being subjected to ice-water bath for 2 hours. After the reaction was completed, an excess amount of distilled water was added, filtered, and the cake was washed with hydrochloric acid and water to neutrality. Vacuum drying at 60 deg.C. Graphene obtained by thermal reduction in a muffle furnace at 950 ℃ is the Staudenmaier method GO. The GO prepared by the Staudenmaier method is used for electrochemical stripping to form GO quantum dots.
Preparing graphene GO quantum dots:
(1) firstly, preparing graphene GO by a pretreatment Staudenmaier method: the prepared GO is used as an anode and a cathode, and is electrolyzed at a constant potential of 5V by a direct current stabilized voltage supply in a sulfuric acid aqueous solution with the concentration of 0.05 mol/L for 0.5h, the size of sulfate ions is larger than the interval between graphene layers, so that the graphene GO can be effectively intercalated and separated, and the graphene on the surfaces of the anode and the cathode can expand. And secondly, electrolyzing water molecules at a constant potential of 1.25V to generate hydroxyl and oxygen free radicals, and chemically cutting and cutting the graphene to generate oxygen-containing functional groups.
(2) The pretreated graphene GO film is directly used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and a phosphate buffer solution (PH is 6.8) is used as an electrolyte. Performing cyclic voltammetry scanning on the graphene film, wherein the voltage range is-3-3V, and the scanning rate is 0.2Vs-1. Along with the increase of the number of scanning circles, the graphene film is constantly etched, and graphene GO quantum dots are constantly generated in electrolyte.
(3) And removing residues in the solution by using a polytetrafluoroethylene suction filtration membrane with the pore diameter of 30 nm. And (3) dialyzing the filtrate with the residues removed from the solution in a dialysis bag with the molecular weight cutoff of 2000Da for 48h at room temperature to obtain the graphene quantum dot dispersion liquid.
And (3):
preparing a graphene GO quantum dot nanotube array by an electrochemical method:
one side of the AAO template is plated with gold, the AAO template is used as a working electrode, a platinum wire is used as a counter electrode, and graphene GO quantum dot solution is used as electrodeposition electrolyte. A positive voltage of 3V was applied to the gold plated AAO template for 3 hours of deposition. The graphene GO quantum dot solution is used as a working electrode, a platinum wire is used as a counter electrode, and the graphene GO quantum dot solution is used as an electrodeposition electrolyte. A positive voltage of 3V was applied to the gold plated AAO template for 3 hours of deposition. And (2) freeze-drying for 24h at-70 ℃ under the vacuum degree of 4Pa, wherein the graphene oxide sheet layer is driven to curl by the formation of ice crystals in the freeze-drying process, and the sheet layer is curled due to nonuniform stress caused by one part of the graphene oxide sheet layer in the ice and the other part of the graphene oxide sheet layer outside the ice in the freeze-drying process. And (3) washing the surface with deionized water, and then annealing at 150 ℃ for 3h to obtain the AAO/GO graphene quantum dot nanotube array in the AAO template. The frozen AAO/GO graphene quantum dot nanotube array shows good structural stability and a high specific surface area, and is beneficial to improving the specific capacitance.
And (4):
depositing YCoO in vacuum spin coating method AAO/GO/template3Nano-array
(1)YCoO3Preparation of sol precursors
0.2M Y(NO3)3And 0.2MCo (NO)3)2Dissolving in deionized water, and stirring for clarifying. They were then mixed with 0.4M citric acid and stirred at 90 ℃ until homogeneous. Slowly dropwise adding ammonia water to adjust the pH value of the solution to be 6-7, and continuously stirring the solution in the process to uniformly mix the solution. When the pH value of the solution is adjusted to 6-7, the sol particles are weakly electropositive, and the inner wall of the AAO template is electronegative. Therefore, electrostatic interaction is generated between the sol particles and the inner wall of the AAO template, so that the sol ions enter and are adsorbed on the inner wall of the template, and the sol particles are favorably converted into gel ions through a concentration reaction and then form the nanotube.
(2) Deposition of YCoO in AAO/GO quantum dot nanotubes by vacuum spin coating3Sol precursor:
for increasing YCoO3Fluidity of sol precursor to YCoO3Adding a dispersing agent into the sol precursor, and dispersing YCoO by ultrasonic oscillation3Sol precursor, dispersant and YCoO3The mass ratio of (A) to (B) is 8: 1. the added dispersing agent can be one or a mixture of several of ethyl cellulose, sodium dodecyl sulfate or methyl amyl alcohol. Placing an AAO/GO quantum dot nanotube array inThe internal pressure of the closed container is 0.01MPa, so that the vacuum degree of the closed container is ensured. Dripping YCoO to the surface of the AAO template3Ultrasonically dipping the sol precursor for 30min, then homogenizing the sol for 10s at a low speed of 400r/min in a rotary film coating machine, then homogenizing the sol for 60s at a high speed of 2500r/min, and drying for 30min in a drying oven at 80 ℃. Ultrasonic soaking and vacuum spin coating can effectively improve YCoO in AAO/GO quantum dot nano-tube3And preparing the highly ordered nanotube array by the filling degree of the sol precursor. The above process of ultrasonic dipping, spin coating under vacuum and vacuum drying was repeated 2 times. YCoO3The sol precursor is deposited on the wall of the AAO/GO quantum dot nanotube.
And (5):
(3) coaxial heterostructure AAO/GO/YCoO3And forming the nanotube array electrode material.
Subjecting the vacuum-dried AAO/GO/YCoO3The sol precursor is first pre-treated in a muffle furnace at low temperature raising rate to 300 deg.c for 4 hr, the citric acid organic matter burns at 300 deg.c and nitrate decomposes at 400 deg.c, and the sol precursor is then calcined at 900 deg.c for 96 hr to eliminate water and ethanol and cooled naturally to room temperature, and during the whole process, AAO/GO template is used as one micro channel and YCoO/GO template is used as one micro channel3The sol precursor nanotube forms and grows in the channel and is converted into nested AAO/GO/YCoO under calcination3An array of nanotubes. Spin coating YCoO by vacuum3Precursor sol formation YCoO3The main reactions that occur with nanotube arrays are:
construction with coaxial heterostructure AAO/GO/YCoO3The nanotube array is a super capacitor of electrode materials.
With AAO/GO/YCoO3The nano-array is a capacitor symmetrical electrode, 1M NaSO4Is electrolyte and polytetrafluoroethylene is diaphragm to assemble a symmetrical super capacitor. With AAO/GO/YCoO3The nano array is a working electrode, the platinum electrode is a counter electrode, and the calomel electrode SCE is a reference electrode to form a three-electrode system. Electrochemical workstation using Chenhua CHI660EAnd testing the electrochemical performance of the nested AAO/GO/YCoO3 nano array as an electrode material.
Example 2
Step (1): a nano-array AAO template with a pore diameter of 100nm and double-sided through holes is prepared, and the implementation steps are the same as those of example 1.
Step (2): preparation method of graphene for forming GO quantum dot nanotube array, Staudenmai and embodiment 1
Preparing graphene GO quantum dots:
(1) firstly, preparing graphene GO by a pretreatment Staudenmaier method: the prepared GO is used as an anode and a cathode, and the constant potential of a direct current stabilized power supply is electrolyzed at 18V in a sulfuric acid aqueous solution with the concentration of 0.8 mol/L, the electrolysis time is 4h, the size of sulfate ions is larger than the interval between graphene layers, so that the graphene GO can be effectively intercalated and separated, and the graphene on the surfaces of the anode and the cathode can expand. And secondly, electrolyzing water molecules at a constant potential of 1.5V to generate hydroxyl and oxygen free radicals, and chemically cutting and cutting the graphene to generate oxygen-containing functional groups.
(2) The pretreated graphene GO film is directly used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and a phosphate buffer solution (PH is 6.8) is used as an electrolyte. Performing cyclic voltammetry scanning on the graphene film, wherein the voltage range is-3-3V, and the scanning rate is 0.5Vs-1. Along with the increase of the number of scanning circles, the graphene film is constantly etched, and graphene GO quantum dots are constantly generated in electrolyte.
(3) And removing residues in the solution by using a polytetrafluoroethylene suction filtration membrane with the pore diameter of 100 nm. And (3) dialyzing the filtrate with the residues removed from the solution in a dialysis bag with the molecular weight cutoff of 12000Da for 72h at room temperature to obtain the graphene quantum dot dispersion liquid.
And (3):
preparing a graphene GO quantum dot nanotube array by an electrochemical method:
one side of the AAO template is plated with gold, the AAO template is used as a working electrode, a platinum wire is used as a counter electrode, and graphene GO quantum dot solution is used as electrodeposition electrolyte. A positive voltage of 6V was applied to the gold plated AAO template for 5 hours of deposition. The graphene GO quantum dot solution is used as a working electrode, a platinum wire is used as a counter electrode, and the graphene GO quantum dot solution is used as an electrodeposition electrolyte. A positive voltage of 6V was applied to the gold plated AAO template for 5 hours of deposition. And (2) freeze-drying for 48h at-70 ℃ under the vacuum degree of 4Pa, wherein the graphene oxide sheet layer is driven to curl by the formation of ice crystals in the freeze-drying process, and the sheet layer is curled due to nonuniform stress caused by one part of the graphene oxide sheet layer in the ice and the other part of the graphene oxide sheet layer outside the ice in the freeze-drying process. And (3) washing the surface with deionized water, and then annealing at 150 ℃ for 3h to obtain the AAO/GO graphene quantum dot nanotube array in the AAO template. The frozen AAO/GO graphene quantum dot nanotube array shows good structural stability and a high specific surface area, and is beneficial to improving the specific capacitance.
And (4):
depositing YCoO in vacuum spin coating method AAO/GO/template3Nano-array
(1)YCoO3Preparation of sol precursors
0.3M Y(NO3)3And 0.3MCo (NO)3)2Dissolving in deionized water, and stirring for clarifying. They were then mixed with 0.6M citric acid and stirred at 90 ℃ until homogeneous. Slowly dropwise adding ammonia water to adjust the pH value of the solution to be 6-7, and continuously stirring the solution in the process to uniformly mix the solution. When the pH value of the solution is adjusted to 6-7, the sol particles are weakly electropositive, and the inner wall of the AAO template is electronegative. Therefore, electrostatic interaction is generated between the sol particles and the inner wall of the AAO template, so that the sol ions enter and are adsorbed on the inner wall of the template, and the sol particles are favorably converted into gel ions through a concentration reaction and then form the nanotube.
(2) Deposition of YCoO in AAO/GO quantum dot nanotubes by vacuum spin coating3Sol precursor:
for increasing YCoO3Fluidity of sol precursor to YCoO3Adding a dispersing agent into the sol precursor, and dispersing YCoO by ultrasonic oscillation3Sol precursor, dispersant and YCoO3The mass ratio of (A) to (B) is 12: 1. the added dispersing agent can be one or a mixture of several of ethyl cellulose, sodium dodecyl sulfate or methyl amyl alcohol. Placing the AAO/GO quantum dot nanotube array in a closed containerIn the container, the internal pressure is 0.05MPa, and the vacuum degree of the closed container is ensured. Dripping YCoO to the surface of the AAO template3Ultrasonically dipping the sol precursor for 30min, then homogenizing the sol for 30s at a low speed of 200r/min in a rotary film coating machine, then homogenizing the sol for 60s at a high speed of 3500r/min, and drying for 10min at the temperature of 150 ℃ in a drying oven. Ultrasonic soaking and vacuum spin coating can effectively improve YCoO in AAO/GO quantum dot nano-tube3And preparing the highly ordered nanotube array by the filling degree of the sol precursor. The above-described processes of ultrasonic dipping, spin coating under vacuum and vacuum drying were repeated 6 times. YCoO3The sol precursor is deposited on the wall of the AAO/GO quantum dot nanotube.
And (5):
(3) coaxial heterostructure AAO/GO/YCoO3And forming the nanotube array electrode material.
Subjecting the vacuum-dried AAO/GO/YCoO3The sol precursor is first pre-treated in a muffle furnace at low temperature raising rate to 500 deg.c for 4 hr, the citric acid organic matter burns at 300 deg.c and nitrate decomposes at 400 deg.c, and the sol precursor is then calcined at 1000 deg.c for 48 hr to eliminate water and ethanol and cooled naturally to room temperature, and during the whole process, AAO/GO template is used as one micro channel and YCoO/GO template is used as one micro channel3The sol precursor nanotube forms and grows in the channel and is converted into nested AAO/GO/YCoO under calcination3An array of nanotubes. Spin coating YCoO by vacuum3Precursor sol formation YCoO3The main reactions that occur with nanotube arrays are:
construction with coaxial heterostructure AAO/GO/YCoO3The nanotube array is a super capacitor of electrode materials.
With AAO/GO/YCoO3The nano-array is a capacitor symmetrical electrode, 1M NaSO4Is electrolyte and polytetrafluoroethylene is diaphragm to assemble a symmetrical super capacitor. A three-electrode system is formed by taking an AAO/GO/YCoO3 nano array as a working electrode, a platinum electrode as a counter electrode and a calomel electrode SCE as a reference electrode. Testing of nested AA Using Chenghua CHI660E electrochemical workstationAnd the O/GO/YCoO3 nano-array is the electrochemical performance of the electrode material.
Example 3.
Step (1): a nano array AAO template with a pore diameter of 70nm and double-sided through holes is prepared, and the implementation steps are the same as those of example 1.
Step (2): preparation method of graphene for forming GO quantum dot nanotube array, Staudenmai and embodiment 1
Preparing graphene GO quantum dots:
(1) firstly, preparing graphene GO by a pretreatment Staudenmaier method: the prepared GO is used as an anode and a cathode, a constant potential of 10V is electrolyzed by a direct current stabilized power supply in a sulfuric acid aqueous solution with the concentration of 0.4 mol/L, the electrolysis time is 2h, the size of sulfate ions is larger than the interval between graphene layers, and the graphene GO can be effectively intercalated and separated, so that the graphene on the surfaces of the anode and the cathode expands. And secondly, electrolyzing water molecules at a constant potential of 1.35V to generate hydroxyl and oxygen free radicals, and chemically cutting and cutting the graphene to generate oxygen-containing functional groups.
(2) The pretreated graphene GO film is directly used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and a phosphate buffer solution (PH is 6.8) is used as an electrolyte. Performing cyclic voltammetry scanning on the graphene film, wherein the voltage range is-3-3V, and the scanning rate is 0.3Vs-1. Along with the increase of the number of scanning circles, the graphene film is constantly etched, and graphene GO quantum dots are constantly generated in electrolyte.
(3) And removing residues in the solution by using a polytetrafluoroethylene suction filtration membrane with the pore diameter of 70 nm. And (3) dialyzing the filtrate with the residues removed from the solution in a dialysis bag with the molecular weight cutoff of 7000Da for 60 hours at room temperature to obtain the graphene quantum dot dispersion liquid.
And (3):
preparing a graphene GO quantum dot nanotube array by an electrochemical method:
one side of the AAO template is plated with gold, the AAO template is used as a working electrode, a platinum wire is used as a counter electrode, and graphene GO quantum dot solution is used as electrodeposition electrolyte. A positive voltage of 4V was applied to the gold plated AAO template for a deposition duration of 4 hours. The graphene GO quantum dot solution is used as a working electrode, a platinum wire is used as a counter electrode, and the graphene GO quantum dot solution is used as an electrodeposition electrolyte. A positive voltage of 4V was applied to the gold plated AAO template for 3 hours of deposition. And (2) freeze-drying for 36h at-70 ℃ under the vacuum degree of 4Pa, wherein the graphene oxide sheet layer is driven to curl by the formation of ice crystals in the freeze-drying process, and the sheet layer is curled due to nonuniform stress caused by one part of the graphene oxide sheet layer in the ice and the other part of the graphene oxide sheet layer outside the ice in the freeze-drying process. And (3) washing the surface with deionized water, and then annealing at 150 ℃ for 3h to obtain the AAO/GO graphene quantum dot nanotube array in the AAO template. The frozen AAO/GO graphene quantum dot nanotube array shows good structural stability and a high specific surface area, and is beneficial to improving the specific capacitance.
And (4):
depositing YCoO in vacuum spin coating method AAO/GO/template3Nano-array
(1)YCoO3Preparation of sol precursors
0.25M Y(NO3)3And 0.25MCo (NO)3)2Dissolving in deionized water, and stirring for clarifying. They were then mixed with 0.5M citric acid and stirred at 90 ℃ until homogeneous. Slowly dropwise adding ammonia water to adjust the pH value of the solution to be 6-7, and continuously stirring the solution in the process to uniformly mix the solution. When the pH value of the solution is adjusted to 6-7, the sol particles are weakly electropositive, and the inner wall of the AAO template is electronegative. Therefore, electrostatic interaction is generated between the sol particles and the inner wall of the AAO template, so that the sol ions enter and are adsorbed on the inner wall of the template, and the sol particles are favorably converted into gel ions through a concentration reaction and then form the nanotube.
(2) Deposition of YCoO in AAO/GO quantum dot nanotubes by vacuum spin coating3Sol precursor:
for increasing YCoO3Fluidity of sol precursor to YCoO3Adding a dispersing agent into the sol precursor, and dispersing YCoO by ultrasonic oscillation3Sol precursor, dispersant and YCoO3The mass ratio of (A) to (B) is 10: 1. the added dispersing agent can be one or a mixture of several of ethyl cellulose, sodium dodecyl sulfate or methyl amyl alcohol. Placing the AAO/GO quantum dot nanotube array in a closed containerThe pressure is 0.03MPa, and the vacuum degree of the closed container is ensured. Dripping YCoO to the surface of the AAO template3Ultrasonically dipping a sol precursor for 30min, then homogenizing the sol for 20s at a low speed of 300r/min in a rotary film coating machine, then homogenizing the sol for 60s at a high speed of 3000r/min, and drying for 20min in a drying oven at 110 ℃. Ultrasonic soaking and vacuum spin coating can effectively improve YCoO in AAO/GO quantum dot nano-tube3And preparing the highly ordered nanotube array by the filling degree of the sol precursor. The above-described processes of ultrasonic dipping, spin coating under vacuum and vacuum drying were repeated 4 times. YCoO3The sol precursor is deposited on the wall of the AAO/GO quantum dot nanotube.
And (5):
(3) coaxial heterostructure AAO/GO/YCoO3And forming the nanotube array electrode material.
Subjecting the vacuum-dried AAO/GO/YCoO3The sol precursor is first pre-treated in a muffle furnace at low temperature raising rate to 400 deg.c for 4 hr, the citric acid organic matter burns at 300 deg.c and nitrate decomposes at 400 deg.c, and the sol precursor is then calcined at 950 deg.c for 72 hr to eliminate water and ethanol and cooled naturally to room temperature, and during the whole process, AAO/GO template is used as one micro channel and YCoO is used as one micro channel3The sol precursor nanotube forms and grows in the channel and is converted into nested AAO/GO/YCoO under calcination3An array of nanotubes. Spin coating YCoO by vacuum3Precursor sol formation YCoO3The main reactions that occur with nanotube arrays are:
construction with coaxial heterostructure AAO/GO/YCoO3The nanotube array is a super capacitor of electrode materials.
With AAO/GO/YCoO3The nano-array is a capacitor symmetrical electrode, 1M NaSO4Is electrolyte and polytetrafluoroethylene is diaphragm to assemble a symmetrical super capacitor. With AAO/GO/YCoO3The nano array is a working electrode, the platinum electrode is a counter electrode, and the calomel electrode SCE is a reference electrode to form a three-electrode system. Testing of nested AAO/GO with Chenhua CHI660E electrochemical workstation/YCoO3The nano-array is the electrochemical performance of the electrode material.
Claims (7)
- Graphene quantum dot nanotube GO/YCoO with AAO template as support3The preparation of the nano array electrode material is characterized by comprising the following steps;step (1):preparing a pore-diameter-controllable nano porous array AAO template by adopting a two-step anodic oxidation method;step (2):stripping graphene GO nano sheets prepared by a Staudenmaier method by an electrochemical method; dialyzing the filtrate filtered by a polytetrafluoroethylene extraction filter membrane to obtain a graphene GO quantum dot solution;and (3):depositing graphene GO quantum dots in the pore channels of the AAO template by adopting an electrochemical deposition method to form an AAO/GO quantum dot nanotube array;and (4):depositing YCoO in the AAO/GO quantum dot nano array tube obtained in the step (3) by using a vacuum spin coating method3Sol precursor array;and (5):calcining AAO/GO/YCoO obtained in the step (4)3Converting sol precursor into AAO/GO/YCoO3Nanotube array to form nanotube array of coaxial heterostructure AAO/GO/YCoO3An electrode material.
- 2. The AAO template-based graphene quantum dot nanotube GO/YCoO of claim 13The preparation method of the nano-array electrode material is characterized in that in the step (2) and the step (3), polytetrafluoroethylene is filtered after graphene GO nanosheets are electrochemically etched by using a phosphate electrolyte, filtrate is dialyzed to obtain a graphene GO quantum dot solution, and then GO quantum dots are electrochemically deposited in AAO template nanopores.
- 3. The AAO template-based graphene quantum dot nanotube GO/YCoO of claim 13Nano array electricityThe preparation of the pole material is characterized in that in the step (2):preparing graphene used for forming a GO quantum dot nanotube array by a Staudenmaier method: adding 5g of graphite into a 500mL round-bottom flask, adding 45mL of concentrated nitric acid and 87.5mL of concentrated sulfuric acid under the condition of ice-water bath, adding 55g of potassium chlorate in batches, reacting for 120h at room temperature after 2h of ice-water bath, adding excessive distilled water after the reaction is finished, filtering, washing a filter cake to be neutral by using hydrochloric acid and water, carrying out vacuum drying at 60 ℃, carrying out thermal reduction in a muffle furnace at 950 ℃ to obtain graphene which is GO by a Staudenmaier method, and preparing GO by the Staudenmier method for electrochemical stripping to form GO quantum dots;preparing graphene GO quantum dots:(1) firstly, preparing graphene GO by a pretreatment Staudenmaier method: the prepared GO is used as an anode and a cathode, and is electrolyzed at a constant potential of 5-18V by a direct current stabilized power supply in a sulfuric acid aqueous solution with the concentration of 0.05-0.8 mol/L for 0.5-4h, the size of sulfate ions is larger than the spacing between graphene layers, so that graphene GO can be effectively intercalated and separated, graphene on the surfaces of the anode and the cathode is expanded, then water molecules are electrolyzed at a constant potential of 1.25-1.5V at an oxygen evolution potential to generate hydroxyl and oxygen free radicals, and the graphene is chemically cut to generate oxygen-containing functional groups;(2) directly taking a pretreated graphene GO thin film as a working electrode, a platinum wire as a counter electrode, an Ag/AgCl electrode as a reference electrode, and a phosphate buffer solution PH (6.8) as electrolyte, performing cyclic voltammetry scanning on the graphene thin film, wherein the voltage range is-3-3V, the scanning rate is 0.5Vs-1, the graphene thin film is continuously etched along with the increase of the number of scanning turns, and graphene GO quantum dots are continuously generated in the electrolyte;(3) and removing residues in the solution by adopting a polytetrafluoroethylene extraction and filtration membrane with the pore diameter of 100nm, and dialyzing the filtrate from which the residues are removed in a dialysis bag with the molecular weight cutoff of 2000-12000Da at room temperature for 48-72h to obtain the graphene quantum dot dispersion liquid.
- 4. The AAO template-based graphene quantum dot nanotube GO/YCoO of claim 13Preparation of nano array electrode materialThe preparation method is characterized in that graphene GO quantum dots are deposited in the pore channels of the AAO template by adopting an electrochemical deposition method in the step (3) to form the AAO/GO quantum dot nanotube array:gold is plated on one surface of an AAO template, the AAO template is used as a working electrode, a platinum wire is used as a counter electrode, graphene GO quantum dot solution is used as electrodeposition electrolyte, a positive voltage of 3-6V is applied to the gold-plated AAO template, deposition is continuously carried out for 3-5 hours, freeze drying is carried out for 48 hours at-70 ℃ and under the vacuum degree of 4Pa, the graphene oxide lamella is driven to curl by formation of ice crystals in the freeze drying process, the lamella curls due to uneven stress caused by the fact that one part of the graphene oxide lamella is in ice and the other part of the graphene oxide lamella is out of the ice in the freeze drying process, the surface is washed by deionized water, and annealing is carried out for 3 hours at 150 ℃, so that an AAO/GO graphene quantum dot nanotube array is obtained in the AAO template.
- 5. The AAO template-based graphene quantum dot nanotube GO/YCoO of claim 13The preparation of nano array electrode material is characterized by that YCoO3Preparing a sol precursor:dissolving Co salt and Y salt in a molar ratio of 1:1 in deionized water, stirring for clarification, and then mixing with 0.4-0.6M citric acid, wherein the ratio of Co salt: y salt: the citric acid is in a molar ratio of 1:1:2, stirring is carried out for 30-60min at 60-90 ℃ until the citric acid is uniform, ammonia water is slowly dripped to adjust the pH value of the solution to be 6-7, the solution is continuously stirred in the process so as to be uniformly mixed, when the pH value of the solution is adjusted to be 6-7, sol particles are weakly electropositive, and the inner wall of the AAO/GO template is electronegative;deposition of YCoO in AAO/GO quantum dot nanotubes by vacuum spin coating3Sol precursor:to the obtained YCoO3Adding a dispersing agent into the sol precursor, and dispersing YCoO by ultrasonic oscillation3Sol precursor, dispersant and YCoO3The mass ratio of (A) to (B) is 8-12: 1, placing the AAO/GO quantum dot nanotube array in a closed container, ensuring the vacuum degree of the closed container at the internal pressure of 0.01-0.05MPa, and dropwise adding YCoO to the surface of an AAO template3Ultrasonic soaking the sol precursor for 10-30min, and thenThen, the gel is homogenized at low speed of 200-400r/min for 10-30s and at high speed of 3500r/min for 60s in a rotary coating machine, and the gel is dried in a drying oven at 80-150 ℃ for 10-30min, and the YCoO in the AAO/GO quantum dot nanotube can be effectively improved by ultrasonic soaking and vacuum spin coating3Filling degree of sol precursor, preparing highly ordered nanotube array, repeating the above steps of ultrasonic dipping, spin coating and vacuum drying for 2-6 times, and performing YCoO3The sol precursor is deposited on the wall of the AAO/GO quantum dot nanotube;coaxial heterostructure AAO/GO/YCoO3Formation of nanotube array electrode material:subjecting the vacuum-dried AAO/GO/YCoO3The sol precursor is firstly pretreated for 4 hours in a muffle furnace at the temperature of 300 ℃ and 500 ℃ at a low heating rate, citric acid organic matters are burnt at the temperature of 300 ℃ and nitrate is subjected to decomposition reaction at the temperature of about 400 ℃, then the sol precursor is calcined for 48 to 96 hours at the temperature of 900 ℃ and 1000 ℃, and the sol precursor is naturally cooled to the room temperature after water and a dispersing agent are removed.
- 6. The AAO template-based graphene quantum dot nanotube GO/YCoO of claim 53The preparation method of the nano array electrode material is characterized in that the dispersing agent can be one or a mixture of several of ethyl cellulose, sodium dodecyl sulfate or methyl amyl alcohol.
- 7. The AAO template-based graphene quantum dot nanotube GO/YCoO of claim 13The preparation of the nano array electrode material is characterized in that the pore diameter range of the controllable nano porous array AAO template in the step (1) is 30nm-100 nm.
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