CN115424875A - Cu loaded nano Cu x O material and preparation method and application thereof - Google Patents

Cu loaded nano Cu x O material and preparation method and application thereof Download PDF

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Publication number
CN115424875A
CN115424875A CN202211030993.8A CN202211030993A CN115424875A CN 115424875 A CN115424875 A CN 115424875A CN 202211030993 A CN202211030993 A CN 202211030993A CN 115424875 A CN115424875 A CN 115424875A
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copper
gallium
preparation
nano
alloy layer
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张弛
李振瀚
林坚彬
梁萍
杨广俊
周子龙
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Wuyi University
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Wuyi University
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Priority to PCT/CN2023/077434 priority patent/WO2024040889A1/en
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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
    • H01G11/84—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
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/46—Metal oxides
    • 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

Abstract

The invention discloses Cu loaded nano Cu x O material and a preparation method and application thereof. Wherein, the Cu loads the nanometer Cu x The preparation method of the O material comprises the following steps: applying gallium to the surface of Cu, and reacting to form a copper-gallium alloy layer; performing dealloying on the copper-gallium alloy layer to obtain a porous Cu base material; carrying out constant-pressure electrochemical oxidation on the porous Cu substrate to obtain nano Cu x And (3) O material. The Cu provided by the invention loads the nanometer Cu x The preparation method of the O material is simple and convenient to operate, does not need toxic organic reagents in the preparation process, and is green and environment-friendly. Cu-supported nano Cu prepared by the method x O material realizes higher specific capacitance and specific capacitance retention rate and simultaneously has a ringEnvironmental friendliness and low cost.

Description

Cu loaded nano Cu x O material and preparation method and application thereof
Technical Field
The invention relates to the technical field of conductive materials, in particular to Cu loaded nano Cu x O material and a preparation method and application thereof.
Background
In recent years, rapid development of economy has made the contradiction between the high demand of human beings for fossil fuels and the limited reserves thereof more prominent, and the development of energy storage devices with high specific power, high specific energy, high safety and low cost is urgent. In many applications, efficient and practical energy storage and conversion devices such as solar cells, lithium ion batteries, fuel cells, supercapacitors, etc. are being developed and applied. The super capacitor has the advantages of high specific power, long cycle life, perfect theoretical research and the like, and is widely concerned by a plurality of researchers.
The electrode material is the heart and brain of the super capacitor, and the overall performance of the whole device is good and bad. Cobalt oxide, ruthenium oxide and the like are electrode materials used by most commercial supercapacitors, but the electrode materials prepared by the method have the defects of high cost of raw materials, environmental pollution and the like. For example, high surface area carbon materials can cost $ 50 to $ 100 per kilogram, resulting in higher electrode material costs. The rare metal ruthenium is not only high in cost, but also has certain toxicity and has adverse effects on the environment.
Cu x O has the advantages of high theoretical capacity, no toxicity, low cost, simple preparation process and the like, and is one of candidate materials as the electrode material of the super capacitor. The disadvantage is poor conductivity, resulting in a very different actual and theoretical specific capacity. Therefore, it is necessary to develop Cu having more excellent properties x And (3) O material.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a method for preparing Cu-loaded nano Cu x The method for preparing the O material has the advantages of simple and convenient operation, mild reaction conditions, good process stability, environmental protection, and good electrical property, low cost and environmental protection of the prepared productHas the advantages of being beneficial to large-scale industrial popularization and application. The invention is realized by the following method:
in one aspect, the invention provides a Cu-loaded nano Cu x The preparation method of the O material comprises the following steps:
applying gallium to the surface of Cu, and reacting to form a copper-gallium alloy layer;
performing dealloying on the copper-gallium alloy layer to obtain a porous Cu base material;
carrying out constant-pressure electrochemical oxidation on the porous Cu base material to obtain nano Cu x And O material.
Specifically, cu supports nanometer Cu x The preparation method of the O material comprises the following steps:
coating liquid gallium on the surface of a Cu base material, and carrying out solid-phase diffusion reaction to form a copper-gallium alloy layer on the surface of the Cu base material;
performing dealloying on the copper-gallium alloy layer to obtain a porous Cu base material;
carrying out constant-pressure electrochemical oxidation on the porous Cu base material for growing nano Cu on the surface of the porous Cu base material x O。
The liquid metal gallium has low melting point and low toxicity, has good fluidity at room temperature, is easy to coat on the surface of the metal foil, has the advantages of safety and simple preparation, is also liquid metal at room temperature and Hg which has toxicity and is unsafe, and other replaceable metals comprise Mg, al and the like, but the melting points of the elements are higher, heat treatment is required to be carried out at high temperature, and the preparation process is more complex.
Nano Cu prepared in the invention x O is in the form of nano-ribbon or sheet, wherein Cu x O is Cu 2 A mixture of O and CuO. In the experiment, the concentration ratio of copper atoms to oxygen atoms is close to Cu when the electrooxidation time is 15min 2 The concentration ratio of two atoms in O and the concentration ratio of the copper atom to the oxygen atom approaches 1And (4) forming.
Further, the gallium is liquid gallium, and the Cu is a copper foil 9-100 μm thick.
The prepared copper foil loaded copper oxide self-supporting structure can be used for preparing a self-supporting electrode, so that the purpose of physical weight reduction is realized, and meanwhile, the flexible and bendable characteristic of the copper foil is also beneficial to the design of a flexible super capacitor.
Further, gallium is applied to the surface of Cu, and solid phase diffusion reaction is carried out for 1-8h at 100-500 ℃ to form a copper-gallium alloy layer.
Specifically, gallium is applied in an amount of 0.001-0.01g/cm 2 。
Specifically, liquid gallium is coated on the surface of the copper foil, and solid phase diffusion reaction is carried out for 1-8h at 100-500 ℃ to form a copper-gallium alloy layer on the surface of the copper foil.
In the aspect of preparing a copper-gallium alloy layer, the conventional technical route of smelting-rapid solidification is mostly adopted in the conventional preparation alloy, the alloy smelting process involves higher temperature, and a large-area amorphous film or amorphous block is difficult to generate.
Specifically, the solid phase reaction temperature is 150-450 ℃, 200-400 ℃, 250-350 ℃ or 300-350 ℃; more specifically, the solid phase reaction temperature is about 100 ℃, about 150 ℃, about 200 ℃, about 250 ℃, about 300 ℃, about 350 ℃, about 400 ℃, about 450 ℃ or about 500 ℃. Preferably, the solid phase diffusion reaction temperature is 100-150 ℃.
Specifically, the time of the solid phase diffusion reaction is 2-7h, 3-6h or 4-5h; more specifically, the time for the solid phase diffusion reaction is about 1h, about 1.5h, about 2h, about 2.5h, about 3h, about 3.5h, about 4h, about 4.5h, about 5h, about 5.5h, about 6h, about 6.5h, about 7h, about 7.5h, or about 8h. Preferably, the solid phase diffusion reaction time is 6-8h.
Further, the thickness of the copper-gallium alloy layer is 1-20 μm.
Specifically, the thickness of the copper-gallium alloy layer is 5-15 μm or 10-15 μm; more specifically, the copper gallium alloy layer has a thickness of about 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, or 20 μm.
Further, with HNO 3 And (4) treating the copper-gallium alloy layer by using the solution to perform dealloying.
Through experiments, HNO 3 The solution can well complete the dealloying process, and hydrochloric acid, sulfuric acid and the like are difficult to complete the dealloying process. The corrosion rate of HF is faster, but on one hand, the risk of HF is higher, and on the other hand, the faster dealloying speed can cause the rapid diffusion of Cu, cause the size coarsening or the corrosion of a copper substrate, and further influence the structure and the performance of a final product. Thus, HNO is preferably employed in the present invention 3 The copper-gallium alloy layer is solution processed.
Specifically, HNO is used 3 Solution etching of the copper-gallium alloy layer to remove the alloy, HNO 3 The concentration of the solution is 0.2-0.4M, and the corrosion time is 3-5 h.
The porous Cu is prepared by the dealloying method, so that the use of a binder and a conductive agent in the preparation process of the electrode material can be avoided, the contact resistance between the active material and a current collector is reduced, the light weight can be realized, and the electrode performance is improved to a great extent.
HNO for corrosion 3 The solution concentration should not be too high or the etching time should not be too long to reduce or avoid corrosion of the Cu substrate.
Further, at a temperature of 25-80 deg.C, with HNO 3 The solution corrodes the copper-gallium alloy layer, and the corrosion temperature is not more than 80 ℃.
Furthermore, the method also comprises the steps of washing the product after the alloy is removed with water and then carrying out vacuum drying after the product is washed with water.
Further, the pore size of the porous Cu substrate obtained after dealloying is 100nm-5 μm.
Further, the potential of the constant-voltage electrochemical oxidation is 0.6-2V, and the time of the constant-voltage electrochemical oxidation is 15min-5h.
Specifically, the potential of the constant-voltage electrochemical oxidation is 0.8-1.5V, 1-1.2V or 1-1.1V; more specifically, the potential of the constant-voltage electrochemical oxidation is about 0.6V, 0.8V, 1V, 1.2V, 1.4V, 1.6V, 1.8V, or 2V.
In the invention, the constant-voltage electrochemical oxidation is realized by adopting a two-electrode system, wherein the working electrode adopts the porous Cu base material. Specifically, in a two-electrode system, a carbon rod is used as a reference electrode and a counter electrode.
Further, in the constant-voltage electrochemical oxidation, at least one of KOH or NaOH is used as an electrolyte. Preferably, the concentration of the electrolyte is 0.1-1M.
Furthermore, the method also comprises the steps of washing the product after constant-pressure electrochemical oxidation with water and drying the product in vacuum after washing with water.
In another aspect, the invention provides the Cu-supported nano Cu prepared by the preparation method in the previous aspect x And O material.
Further, the Cu supports the nano Cu x The aperture of the O material is 100nm-5 μm. The porous copper prepared by the invention presents typical bicontinuous ligaments under the scale of 1 mu m, different sizes of nanoscale gaps exist among different ligaments, and the nanoscale ligaments and pores can present the characteristics of surface effect, small-size effect, quantum size effect, macroscopic quantum tunneling effect and the like which are only possessed by a nano material.
In one aspect, the invention provides an electrode comprising the Cu-supported nanocu of the preceding aspect x And O material.
Specifically, the Cu of the invention loads the nanometer Cu x The O material can be directly used as the positive electrode of the super capacitor, so that an additional conductive agent and a binder are avoided.
In another aspect, the invention provides the Cu-loaded nano Cu x Use of an O material for the preparation of a capacitor device.
Specifically, the Cu of the invention loads nano Cu x The O material is used for the positive electrode of the asymmetric super capacitor, and the negative electrode is active carbon.
The Cu provided by the invention loads the nanometer Cu x The preparation method of the O material at least has the following effects:
the Cu provided by the invention loads the nanometer Cu x The preparation method of the O material has simple and convenient operation, does not need toxic organic reagent in the preparation process, and is green and cyclicAnd (4) preserving.
In the method provided by the invention, the pore size of the porous Cu substrate can be regulated and controlled by adjusting the technological parameters of solid-phase diffusion reaction, dealloying or constant-pressure electrochemical oxidation, such as setting different temperatures and times for the procedures or selecting different potentials in the electrochemical oxidation process, so that the nano Cu is influenced x And (4) growing O. In the electrochemical oxidation process, compared with cyclic voltammetry, the potentiostatic method can realize obviously better specific capacitance and specific capacitance retention rate.
Cu-loaded nano Cu prepared by the method of the invention x The O material realizes higher specific capacitance and specific capacitance retention rate, and has the advantages of environmental friendliness and low cost. The invention takes the porous copper foil as the base material, which is beneficial to nano Cu x And O is grown, so that the aim of improving the electrical property is better fulfilled.
In the present invention, the term "about" means ± 5% around the point value.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an SEM image of a porous copper foil prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of copper-supported nano-copper oxide prepared in example 1 of the present invention;
FIG. 3 is an SEM cross-sectional view of copper-supported nano-copper oxide prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a sample of copper-supported nanoporous copper foil electro-oxidized for 15min in example 4 of the invention;
FIG. 5 is an SEM image of a sample of copper-loaded nanoporous copper foil that was electro-oxidized for 5h in example 4 of the invention;
FIG. 6 is an SEM image of a sample of pure copper electro-oxidized for 2h in comparative example 1 of the present invention;
FIG. 7 is an XRD pattern of the copper gallium alloy and the dealloyed porous copper foil prepared in example 1;
FIG. 8 is an XRD pattern of samples of example 3 at different heat treatment temperatures;
FIG. 9 is an XRD pattern of samples of example 4 at different electrooxidation times;
FIG. 10 is a graph of samples at 0.4mA cm for different electrooxidation times for examples 1 and 4 -2 A GCD curve of (1);
FIG. 11 is a GCD curve of the sample electro-oxidized for 2h in example 1 at different current densities;
FIG. 12 shows the voltage at 100mV of the working electrode obtained by electrooxidation for 2h in example 1 -1 Cycling performance measured under conditions;
FIG. 13 is a GCD curve for different current densities for the O-Cu-2h// AC asymmetric supercapacitor of example 2;
FIG. 14 is a Ragon plot of an O-Cu-2h// AC asymmetric supercapacitor;
FIG. 15 is a graph of the stability of the device after 10000 cycles of O-Cu-2h// AC asymmetric supercapacitor.
Detailed Description
The embodiments of the present invention will be described in detail below, and the embodiments described below with reference to the accompanying drawings are exemplary only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention.
Wherein the materials used in the present invention are commercially available unless otherwise specified, and the methods used are conventional in the art unless otherwise specified.
Example 1
Cu loaded nano Cu x The preparation method of the O material comprises the following steps:
(1) And preparing the copper-gallium alloy by utilizing intermetallic solid-phase diffusion reaction. The copper foil (with the thickness of 50 mu m) is firstly washed by deionized water, then is wiped by absolute ethyl alcohol to remove impurities, is dried and is fixed on the paper. Coating liquid metal gallium on the outer surface of the copper foil, wherein the coating amount is 0.01g/cm 2 And standing for 10min after the coating is completely carried out. And (3) putting the sample into a vacuum drying oven, and carrying out heat treatment at 150 ℃ for 8h to form the copper-gallium alloy on the surface of the copper foil.
(2) Preparing the copper foil with the copper-gallium alloy layer prepared in the step (1) into a porous copper foil through a chemical dealloying method. Selection of 0.2M HNO 3 The solution was dealloyed at 40 c for 4 hours to remove gallium, and then the etched copper foil was rinsed with deionized water, followed by vacuum drying.
(3) And (3) preparing the copper-loaded nano copper oxide from the porous copper foil prepared in the step (2) by a constant-pressure oxidation method. Adopting a two-electrode system, using a carbon rod as a reference electrode and a counter electrode, using a porous copper foil as a working electrode, namely the two-electrode system, selecting 1M KOH as an electrolyte, carrying out electrochemical oxidation for 2h under a constant potential of 1V, and growing nano Cu on the surface of the porous copper foil in situ x O (as Cu) x O @ Cu). And after the reaction is finished, washing the mixture by using deionized water, drying the mixture, and placing the dried mixture in a vacuum drying tank for later use.
Example 2
In this embodiment, an asymmetric supercapacitor is prepared by assembling the nano copper oxide electrode prepared in embodiment 1 as a positive electrode, activated carbon as a negative electrode, 1M KOH as an electrolyte, and a fibrous paper as a separator.
Example 3
Example 3 the same procedure as in example 1 was repeated except that the solid phase diffusion reaction time in step (1) was 1 hour and the solid phase diffusion reaction temperatures were 100 ℃, 200 ℃, 300 ℃, 400 ℃ and 500 ℃, respectively.
Example 4
Example 4 compares with example 1, the other steps are the same, except that the electrochemical oxidation process in step (3) is: the electrooxidation time was set at 1V constant potential for 15min and 5h, respectively.
Comparative example 1
The copper-supported nanocopper oxide was prepared by a constant pressure oxidation method using an untreated pure copper foil with the same thickness as in example 1. A two-electrode system is adopted, a carbon rod is used as a reference electrode and a counter electrode, a copper foil is used as a working electrode, namely the two-electrode system, 1M KOH is selected as electrolyte, and the electrolyte is subjected to electro-oxidation for 2 hours under a constant potential of 1V. And after the reaction is finished, washing the mixture by using deionized water, drying the mixture, and placing the dried mixture in a vacuum drying tank for later use.
Performance test
Microscopic morphology analysis
Surface topography analysis was performed using a field emission Scanning Electron Microscope (SEM).
Fig. 1 is an SEM image of the porous copper foil prepared in example 1, and it can be seen that a three-dimensional bicontinuous ligament structure is formed on the surface of the copper foil.
FIG. 2 is an SEM photograph of the copper-supported nano-copper oxide obtained in example 1, and it can be seen that the surface of the copper foil is nano-flaky Cu x And covering by O.
FIG. 3 is an SEM cross-sectional view of the copper-supported nano-copper oxide prepared in example 1, and it can be seen that nano-flake Cu is coated on the surface of the copper foil x O is about 9.5 μm thick.
Fig. 4 and 5 are SEM images of the copper-supported nano copper oxide prepared in example 4, and it can be seen that the surface of the copper foil is covered with the nano flaky and needle shaped copper oxide.
Fig. 6 is an SEM image of copper-supported nano copper oxide prepared in comparative example 1, and it can be seen that pure copper foil without three-dimensional bicontinuous ligament structure is not favorable for surface copper oxide growth.
X-ray diffraction (XRD) analysis
Phase composition analysis was performed using X-ray diffraction (XRD).
Fig. 7 is an XRD pattern of the copper-gallium alloy prepared in example 1 and the dealloyed porous copper foil, and from fig. 7, a diffraction peak corresponding to the copper-gallium alloy is clearly seen, demonstrating that a copper-gallium alloy phase is grown on the surface.
Fig. 8 is an XRD pattern of copper-supported nano copper oxide prepared in example 1 at different heat treatment temperatures. It can be seen that Ga is formed at 100 and 200 deg.C 4 The Cu phase, but with further increase in temperature, other unknown phases appeared.
Figure 9 is an XRD pattern of copper supported nano-copper oxide at different electrooxidation times prepared in example 4. It can be seen that the peak position at 36.5 ° 2 θ is associated with Cu 2 O, and samples of different oxidation times show different peaks at this peak position. As the oxidation time increases, the corresponding characteristic peak at this peak position becomes weaker.
Analysis of electrochemical Properties
Electrochemical performance testing methodThe method comprises the following steps: adopting a standard three-electrode system, and sequentially selecting 0.2, 0.4, 0.6, 0.8 and 1mA cm at a potential range of 0-0.5V (vs. Ag/AgCl) -2 The constant current charge and discharge test (CP test) was performed.
FIG. 10 is a graph of the results of samples prepared in examples 1 and 4 at 0.4mA/cm 2 The constant current charge-discharge curve is obtained by testing under the current density. From left to right, samples with electrooxidation time of 15min, 30min, 1h, 5h and 2h are sequentially arranged. It can be seen that the zone lines exhibit a quasi-linear shape, indicating a pseudo-capacitive nature, where O-Cu-2h has the largest capacitance.
FIG. 11 shows the samples prepared in example 1 at 0.2, 0.4, 0.6, 0.8, 1mA cm -2 Constant current charge and discharge curve at current density (from right to left). As the area current density used becomes smaller, the slope of the charge-discharge curve decreases and the charge-discharge time increases, and the larger the corresponding area specific capacitance, the more excellent energy storage characteristics are exhibited.
FIG. 12 shows the passage of 100mV for example 2 -1 12000 cycles of the CV cycle of (1) were performed. After cycling, the area capacitance dropped from an initial value of 0.171 to 0.162Fcm -2 94.71% of the initial capacitance remains.
FIG. 13 shows samples prepared in example 2 at 2, 3, 4, 5, 6, 7mA cm -2 Constant current charge and discharge curve (from right to left) at current density of (d). The GCD curve exhibits nonlinear characteristics, manifested as a faraday process. Wherein the maximum area specific capacitance is 2mA cm -2 Is obtained when reaching 0.60F cm -2 . When the current density increased to 7mA cm -2 When the area specific capacitance is reduced to 0.52F cm -2 。
Fig. 14 is a Ragone plot of an asymmetric supercapacitor calculated from the GCD curve. The energy density of the device is 20.86 to 24.20Wh kg -1 (0.26 to 0.30Wh cm -2 ) In the range of 2.14 to 0.65kW kg -1 (26.49 to 8.08W cm -2 ) The power density of (a). Energy density and others based on Cu x The super capacitor of O is competitive. For example, 3D Cu 2 The energy density of the O @ Cu nanoneedle array electrode is 26Wh kg -1 The power density is 1.8kW kg -1 . With 3D nano-junctionsForm Cu x When the power density is 3mW cm, the all-solid-state supercapacitor with the O-modified foamy copper as the electrode -2 At an energy density of 25. Mu. Wh cm -2 。
FIG. 15 is a graph of the stability of the device after 10000 cycles of O-Cu-2h// AC asymmetric supercapacitor. After cycling, the area capacitance dropped from an initial value of 0.357 to 0.227Fcm -2 Only 63.59% of the original capacitance remains.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.

Claims (10)

  1. Cu loaded nano Cu x The preparation method of the O material is characterized by comprising the following steps:
    applying gallium to the surface of Cu, and reacting to form a copper-gallium alloy layer;
    performing dealloying on the copper-gallium alloy layer to obtain a porous Cu base material;
    carrying out constant-pressure electrochemical oxidation on the porous Cu base material to obtain nano Cu x And (3) O material.
  2. 2. The method according to claim 1, wherein the gallium is liquid gallium, and the Cu is a copper foil 9 to 100 μm thick.
  3. 3. The method of claim 1, wherein the gallium is applied to the Cu surface and reacted at 100-500 ℃ for 1-8h to form the copper-gallium alloy layer.
  4. 4. The production method according to claim 3, wherein the thickness of the copper-gallium alloy layer is 1 to 20 μm.
  5. 5. The method of claim 1, wherein HNO is used 3 And (4) treating the copper-gallium alloy layer by using the solution to remove the alloy.
  6. 6. The production method according to claim 1, wherein the pore size of the porous Cu substrate obtained after dealloying is 100nm to 5 μm.
  7. 7. The method of claim 1, wherein the potential of the constant-voltage electrochemical oxidation is 0.6-2V, and the time of the constant-voltage electrochemical oxidation is 15min-5h.
  8. 8. Cu-supported nano Cu prepared by the preparation method of any one of claims 1 to 7 x And O material.
  9. 9. An electrode comprising the Cu-supported nanocu of claim 8 x And (3) O material.
  10. 10. The Cu-supported nanocu of claim 8 x Use of an O material for the preparation of a capacitor device.
CN202211030993.8A 2022-08-26 2022-08-26 Cu loaded nano Cu x O material and preparation method and application thereof Pending CN115424875A (en)

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WO2024040889A1 (en) * 2022-08-26 2024-02-29 五邑大学 Cu-loaded nano-cuxo material, preparation method therefor, and application thereof

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CN107871627A (en) * 2016-09-28 2018-04-03 南京大学 Foam copper supports high capacitance flexible electrode material of CuO nanometer sheet and preparation method thereof
CN108295854B (en) * 2018-01-30 2019-06-14 河北工业大学 A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method
CN109888167A (en) * 2019-02-21 2019-06-14 三峡大学 A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material
CN113881939A (en) * 2021-10-25 2022-01-04 昆明理工大学 Method for preparing nano porous copper by dealloying
CN115424875A (en) * 2022-08-26 2022-12-02 五邑大学 Cu loaded nano Cu x O material and preparation method and application thereof

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WO2024040889A1 (en) * 2022-08-26 2024-02-29 五邑大学 Cu-loaded nano-cuxo material, preparation method therefor, and application thereof

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