WO2024040889A1 - Nanomatériau de cuxo chargé de cu, son procédé de préparation et son application - Google Patents

Nanomatériau de cuxo chargé de cu, son procédé de préparation et son application Download PDF

Info

Publication number
WO2024040889A1
WO2024040889A1 PCT/CN2023/077434 CN2023077434W WO2024040889A1 WO 2024040889 A1 WO2024040889 A1 WO 2024040889A1 CN 2023077434 W CN2023077434 W CN 2023077434W WO 2024040889 A1 WO2024040889 A1 WO 2024040889A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
preparation
gallium
cuxo
nano
Prior art date
Application number
PCT/CN2023/077434
Other languages
English (en)
Chinese (zh)
Inventor
张弛
李振瀚
林坚彬
梁萍
杨广俊
周子龙
Original Assignee
五邑大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 五邑大学 filed Critical 五邑大学
Publication of WO2024040889A1 publication Critical patent/WO2024040889A1/fr

Links

Classifications

    • 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

Definitions

  • the present invention relates to the technical field of conductive materials, and in particular to Cu-loaded nano-Cu x O materials and their preparation methods and applications.
  • Electrode materials are the "heart and brain" of supercapacitors, which are related to the overall performance of the entire device. Cobalt oxide, ruthenium oxide, etc. are the electrode materials used in most commercial supercapacitors. However, the electrode materials prepared therefrom also have defects such as high raw material cost and non-environmental protection. For example, the cost of carbon materials with high specific surface area can reach 50 to 100 US dollars per kilogram, resulting in high electrode material costs. The rare metal ruthenium is not only expensive, but also has certain toxicity and has adverse effects on the environment.
  • Cu x O has the advantages of high theoretical capacity, non-toxicity, low cost, and simple preparation process. It is one of the candidate materials as supercapacitor electrode material. Its disadvantage is poor electrical conductivity, resulting in a large gap between its actual specific capacity and its theoretical specific capacity. Therefore, it is necessary to develop C x O materials with better performance.
  • the present invention aims to solve at least one of the above technical problems existing in the prior art.
  • the present invention provides a method for preparing Cu- loaded nano-Cu
  • the advantages of environmental friendliness are conducive to large-scale promotion and application in industry.
  • the present invention is realized by the following methods:
  • the present invention provides a method for preparing Cu-loaded nano-Cu x O materials, which includes the following steps:
  • the porous Cu substrate is subjected to constant voltage electrochemical oxidation to obtain nano-C x O materials.
  • the preparation method of Cu-loaded nano-Cu x O material includes the following steps:
  • the porous Cu substrate is subjected to constant voltage electrochemical oxidation to grow nanometer Cu x O on the surface of the porous Cu substrate.
  • Liquid metal gallium has a low melting point and low toxicity. It has good fluidity at room temperature and can be easily coated on the surface of metal foil. It has the advantages of safety and simple preparation. Hg is also a liquid metal at room temperature, but Hg It is toxic and unsafe. Other alternative metals include Mg and Al, but these elements have higher melting points and require heat treatment in a high-temperature environment, and the preparation process is complicated.
  • the nanometer CxO prepared in the present invention is in the shape of nanoribbons and sheets, wherein CuxO is a mixture of Cu2O and CuO. It was found in the experiment that when the electrooxidation time is 15 minutes, the concentration ratio of copper atoms to oxygen atoms is close to the concentration ratio of the two atoms in Cu 2 O, and as the electrooxidation time increases, the concentration ratio of copper atoms to oxygen atoms will decrease. Approaching 1:1, even when the electro-oxidation time reaches 5 hours, this ratio will decrease, indicating that higher valence copper may appear.
  • the electro-oxidation time limited in the present invention corresponds to the above valence composition of Cu.
  • the gallium is liquid gallium
  • the Cu is a copper foil with a thickness of 9-100 ⁇ m.
  • Preparing a self-supporting structure of copper foil loaded with copper oxide can be used to prepare self-supporting electrodes to achieve weight reduction.
  • the flexible and bendable characteristics of copper foil are also helpful for the design of flexible supercapacitors.
  • gallium is applied to the Cu surface, and a solid-phase diffusion reaction is performed at 100-500°C for 1-8 hours to form a copper-gallium alloy layer.
  • the applied amount of gallium is 0.001-0.01g/cm 2 .
  • liquid gallium is coated on the surface of the copper foil, and a solid-phase diffusion reaction is performed at 100-500°C for 1-8 hours to form a copper-gallium alloy layer on the surface of the copper foil.
  • the solid phase reaction temperature is 150-450°C, 200-400°C, 250-350°C or 300-350°C; more specifically, the solid phase reaction temperature is about 100°C, about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, about 450°C, or about 500°C.
  • the solid phase diffusion reaction temperature is 100-150°C.
  • the time of the solid phase diffusion reaction is 2-7h, 3-6h or 4-5h; more specifically, the time of 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.
  • the solid phase diffusion reaction time is 6-8 hours.
  • the thickness of the copper gallium alloy layer is 1-20 ⁇ m.
  • the thickness of the copper gallium alloy layer is 5-15 ⁇ m or 10-15 ⁇ m; more specifically, the thickness of the copper gallium alloy layer is Approximately 1 ⁇ m, 3 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m or 20 ⁇ m.
  • the copper gallium alloy layer is treated with HNO 3 solution for dealloying.
  • the present invention preferably uses HNO 3 solution to treat the copper-gallium alloy layer.
  • HNO 3 solution is used to corrode the copper-gallium alloy layer to dealloy it.
  • the HNO 3 solution concentration is 0.2-0.4M, and the etching time is 3h-5h.
  • the present invention uses a dealloying method to prepare porous Cu, which can eliminate the use of binders and conductive agents in the preparation process of electrode materials, reduce the contact resistance between active materials and current collectors, and not only achieve lightweighting, but also reduce the weight to a large extent. Improved electrode performance.
  • the concentration of HNO3 solution used for corrosion should not be too high, or the corrosion time should not be too long, in order to reduce or avoid corrosion of the Cu substrate.
  • HNO 3 solution to corrode the copper gallium alloy layer at a temperature of 25-80°C.
  • the corrosion temperature should not exceed 80°C.
  • the present invention also includes the steps of washing the dealloyed product with water and vacuum drying after washing.
  • the pore size of the porous Cu substrate obtained after dealloying is 100 nm-5 ⁇ m.
  • the potential of the constant voltage electrochemical oxidation is 0.6-2V
  • the time of the constant voltage electrochemical oxidation is 15min-5h.
  • 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.
  • the constant voltage electrochemical oxidation is implemented using a two-electrode system, in which the working electrode uses the above-mentioned porous Cu substrate.
  • the working electrode uses the above-mentioned porous Cu substrate.
  • carbon rods are used as the reference electrode and counter electrode.
  • the electrolyte concentration is 0.1-1M.
  • the present invention also includes the steps of washing the product after constant voltage electrochemical oxidation with water and vacuum drying after washing.
  • the present invention provides a Cu-loaded nano-C x O material prepared by the preparation method of the aforementioned aspect.
  • the pore size of the Cu-loaded nano-C x O material is 100 nm-5 ⁇ m.
  • the porous copper prepared by the present invention exhibits typical bicontinuous ligaments at a scale of 1 ⁇ m. There are nanoscale gaps of different sizes between different ligaments. Nanoscale ligaments and pores can exhibit surface effects and small size effects that are unique to nanomaterials. , quantum size effect, macroscopic quantum tunneling effect and other characteristics.
  • the present invention provides an electrode, which electrode includes the Cu-supported nano -CuxO material of the aforementioned aspect.
  • the Cu-loaded nano-Cu x O material of the present invention can be directly used as the positive electrode of a supercapacitor, thereby avoiding the need to add additional conductive agents and binders.
  • the present invention provides the application of the above-mentioned Cu-supported nano-Cu x O material in the preparation of capacitive devices.
  • the Cu-loaded nano-Cu x O material of the present invention is used as the positive electrode of an asymmetric supercapacitor, and the negative electrode is activated carbon.
  • the preparation method of Cu-loaded nano-Cu x O material provided by the invention is easy to operate, does not require the use of toxic organic reagents during the preparation process, and is green and environmentally friendly.
  • the process parameters of solid phase diffusion reaction, dealloying or constant voltage electrochemical oxidation can be adjusted, for example, by setting different temperatures and times for these processes, or by selecting different potentials in the electrochemical oxidation process. Then the pore size of the porous Cu substrate is controlled, thereby affecting the growth of nano-Cu x O.
  • the potentiostatic method can achieve significantly better specific capacitance and specific capacitance retention than cyclic voltammetry.
  • the Cu-loaded nano-Cu x O material prepared by the method of the present invention achieves high specific capacitance and specific capacitance retention rate, and has the advantages of environmental friendliness and low cost.
  • the present invention uses porous copper foil as the base material, which is beneficial to the growth of nanometer Cu x O, thereby better achieving the purpose of improving electrical properties.
  • the term "about” means ⁇ 5% around the point value.
  • Figure 1 is an SEM image of the porous copper foil prepared in Example 1 of the present invention.
  • Figure 2 is an SEM image of copper-supported nano-copper oxide prepared in Example 1 of the present invention.
  • Figure 3 is an SEM cross-sectional view of the copper-supported nano-copper oxide prepared in Example 1 of the present invention.
  • Figure 4 is an SEM image of a sample of copper-loaded nanoporous copper foil electrooxidized for 15 minutes in Example 4 of the present invention
  • Figure 5 is an SEM image of a sample of copper-loaded nanoporous copper foil electrooxidation for 5 hours in Example 4 of the present invention
  • Figure 6 is an SEM image of the pure copper electrooxidation sample for 2 hours in Comparative Example 1 of the present invention.
  • Figure 7 is an XRD pattern of the copper-gallium alloy prepared in Example 1 and the porous copper foil after dealloying;
  • Figure 8 is the XRD pattern of the sample at different heat treatment temperatures in Example 3.
  • Figure 9 is the XRD pattern of the sample under different electrooxidation times in Example 4.
  • Figure 10 is the GCD curve of the sample at 0.4mA cm -2 under different electrooxidation times in Example 1 and Example 4;
  • Figure 11 is the GCD curve of the sample electrooxidized for 2 hours under different current densities in Example 1;
  • Figure 12 shows the cycle performance measured under the condition of 100mV -1 using the sample electrooxidized for 2h in Example 1 as the working electrode;
  • Figure 13 is the GCD curve of the O-Cu-2h//AC asymmetric supercapacitor under different current densities in Example 2;
  • Figure 14 is the Ragone diagram of O-Cu-2h//AC asymmetric supercapacitor
  • Figure 15 shows the stability curve of the O-Cu-2h//AC asymmetric supercapacitor device after 10,000 cycles.
  • the preparation method of Cu-loaded nano-Cu x O material includes the following steps:
  • step (2) Use the copper foil with the copper-gallium alloy layer prepared in step (1) to prepare a porous copper foil through a chemical dealloying method.
  • a 0.2M HNO 3 solution was selected for dealloying at 40°C, and the etching time was 4 h to remove gallium.
  • the etched copper foil was then rinsed with deionized water and then dried in a vacuum.
  • step (3) Prepare copper-supported nano-copper oxide by using the porous copper foil prepared in step (2) through a constant pressure oxidation method.
  • a two-electrode system is used.
  • the carbon rod is used as the reference electrode and the counter electrode, and the porous copper foil is used as the working electrode, that is, a two-electrode system.
  • the electrolyte is 1M KOH, which is electrochemically oxidized at a constant potential of 1V for 2 hours.
  • Nano-sized Cu x O (denoted as Cu x O@Cu) is grown on site. After the reaction is completed, rinse with deionized water, dry and place in a vacuum drying tank for later use.
  • an asymmetric supercapacitor was prepared.
  • the nano-copper oxide electrode prepared in Example 1 was used as the positive electrode, activated carbon was used as the negative electrode, 1M KOH was used as the electrolyte, and fiber paper was used as the separator to form a supercapacitor.
  • Example 3 Compared with Example 1, the other steps of Example 3 are the same. The difference is that the solid-phase diffusion reaction time in step (1) is 1 hour, and the temperatures of the solid-phase diffusion reaction are 100°C, 200°C, 300°C, and 400°C respectively. and 500°C.
  • Example 4 Compared with Example 1, the other steps of Example 4 are the same. The difference is that the electrochemical oxidation process in step (3) is: the electrooxidation time is set to 15 minutes and 5 hours respectively at a constant potential of 1V.
  • untreated pure copper foil was used to prepare copper-loaded nano-copper oxide through a constant voltage oxidation method.
  • a two-electrode system was used.
  • the carbon rod was used as the reference electrode and the counter electrode, and the copper foil was used as the working electrode, that is, a two-electrode system.
  • the electrolyte was 1M KOH, and the electrolyte was oxidized at a constant potential of 1V for 2 hours. After the reaction is completed, rinse with deionized water, dry and place in a vacuum drying tank for later use.
  • Figure 1 is an SEM image of the porous copper foil prepared in Example 1. It can be seen that a three-dimensional bicontinuous ligament structure is formed on the surface of the copper foil.
  • Figure 2 is an SEM image of the copper-supported nano-copper oxide prepared in Example 1. It can be seen that the surface of the copper foil is covered with nanosheet-like C x O.
  • Figure 3 is an SEM cross-sectional view of the copper-supported nano-copper oxide prepared in Example 1. It can be seen that the nanosheet-shaped C x O covered on the surface of the copper foil is about 9.5 ⁇ m thick.
  • Figures 4 and 5 are SEM images of the copper-supported nano-copper oxide prepared in Example 4. It can be seen that the surface of the copper foil is covered with nano-sheet and needle-shaped copper oxide.
  • Figure 6 is an SEM image of the copper-loaded nano-copper oxide prepared in Comparative Example 1. It can be seen that pure copper foil without a three-dimensional bicontinuous ligament structure is not conducive to the growth of surface copper oxide.
  • Phase composition analysis was performed using X-ray diffraction (XRD).
  • Figure 7 is an XRD pattern of the copper gallium alloy prepared in Example 1 and the porous copper foil after dealloying. From Figure 7, obvious diffraction peaks corresponding to the copper gallium alloy can be seen, proving that the copper gallium alloy phase grows on the surface.
  • Figure 8 is an XRD pattern of the copper-loaded nano-copper oxide prepared in Example 1 at different heat treatment temperatures. It can be seen that the Ga 4 Cu phase is generated at 100 and 200°C, but as the temperature further increases, other unknown phases appear.
  • Figure 9 is an XRD pattern of copper-loaded nano-copper oxide prepared in Example 4 under different electrooxidation times. It can be seen that the peak position at 2 ⁇ of 36.5° corresponds to the standard card of Cu 2 O, and samples with 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.
  • Electrochemical performance test method Use a standard three-electrode system, and select current densities of 0.2, 0.4, 0.6, 0.8, and 1mA cm -2 in the 0-0.5V (vs.Ag/AgCl) potential range for constant current charge and discharge tests. (CP test).
  • Figure 10 is a constant current charge and discharge curve tested at a current density of 0.4 mA/cm 2 for the samples prepared in Example 1 and Example 4. From left to right, there are samples with electrooxidation times of 15min, 30min, 1h, 5h, and 2h. It can be seen that the zone lines show a quasi-linear shape, indicating pseudocapacitive properties, with O-Cu-2h having the largest capacitance.
  • Figure 11 shows the constant current charge and discharge curves of the sample prepared in Example 1 at current densities of 0.2, 0.4, 0.6, 0.8, and 1 mA cm -2 (from right to left). As the current density of the used area becomes smaller, the slope of the charge-discharge curve decreases, the charge-discharge time increases, and the corresponding area specific capacitance is larger, showing better energy storage characteristics.
  • Figure 12 is a cycle performance diagram of Example 2 performed 12,000 times through a CV cycle of 100 mV -1 . After cycling, the area capacitance dropped from the initial value of 0.171 to 0.162Fcm -2 , retaining 94.71% of the initial capacitance.
  • Figure 13 shows the constant current charge and discharge curves of the sample prepared in Example 2 at current densities of 2, 3, 4, 5, 6 and 7 mA cm -2 (from right to left).
  • the GCD curve exhibits nonlinear characteristics, manifesting as a Faraday process.
  • the maximum area specific capacitance is obtained at 2mA cm -2 , reaching 0.60F cm -2 .
  • the area specific capacitance drops to 0.52F cm -2 .
  • Figure 14 is the Ragone diagram of the asymmetric supercapacitor calculated based on the GCD curve.
  • the energy density of the device is in the range of 20.86 to 24.20Wh kg -1 (0.26 to 0.30Wh cm -2 ), corresponding to a power density of 2.14 to 0.65kW kg -1 (26.49 to 8.08W cm -2 ).
  • the energy density is competitive with some other Cu x O based supercapacitors.
  • the energy density of the 3D Cu2O@Cu nanoneedle array electrode is 26Wh kg -1 and the power density is 1.8kW kg -1 .
  • An all-solid-state supercapacitor using 3D nanostructured Cu x O modified copper foam as an electrode has an energy density of 25 ⁇ Wh cm -2 when the power density is 3mW cm -2 .
  • Figure 15 shows the stability curve of the O-Cu-2h//AC asymmetric supercapacitor device after 10,000 cycles. After cycling, the area capacitance dropped from the initial value of 0.357 to 0.227Fcm -2 , retaining only 63.59% of the initial capacitance.

Abstract

Un nanomatériau de CuxO chargé de Cu, son procédé de préparation et son application sont divulgués. Le procédé de préparation du nanomatériau de CuxO chargé de Cu comprend les étapes consistant à : appliquer du gallium sur une surface de Cu, et assurer une réaction pour former une couche d'alliage cuivre-gallium ; désallier la couche d'alliage cuivre-gallium pour obtenir un matériau de base de Cu poreux ; réaliser une oxydation électrochimique à pression constante sur le matériau de base de Cu poreux pour obtenir un nanomatériau de CuxO. Le procédé de préparation fourni du nanomatériau de CuxO chargé de Cu est simple et pratique à utiliser, le procédé de préparation ne nécessite pas l'utilisation de réactifs organiques toxiques, et le processus de préparation est écologique et respectueux de l'environnement. Le nanomatériau de CuxO chargé de Cu préparé permet d'assurer une capacité spécifique et un taux de rétention de capacité spécifique relativement élevés, et présente également les avantages d'un respect de l'environnement et d'un faible coût.
PCT/CN2023/077434 2022-08-26 2023-02-21 Nanomatériau de cuxo chargé de cu, son procédé de préparation et son application WO2024040889A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211030993.8A CN115424875A (zh) 2022-08-26 2022-08-26 Cu负载纳米CuxO材料及其制备方法和应用
CN202211030993.8 2022-08-26

Publications (1)

Publication Number Publication Date
WO2024040889A1 true WO2024040889A1 (fr) 2024-02-29

Family

ID=84201067

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/077434 WO2024040889A1 (fr) 2022-08-26 2023-02-21 Nanomatériau de cuxo chargé de cu, son procédé de préparation et son application

Country Status (2)

Country Link
CN (1) CN115424875A (fr)
WO (1) WO2024040889A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115424875A (zh) * 2022-08-26 2022-12-02 五邑大学 Cu负载纳米CuxO材料及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103871752A (zh) * 2014-03-19 2014-06-18 山东大学 一种氧化铜基非对称型超级电容器及其制备方法
US20150072236A1 (en) * 2013-04-19 2015-03-12 CellMotive Co. Ltd. Metal Foam for Electrode of Secondary Lithium Battery, Preparing Method Thereof, and Secondary Lithium Battery Including the Metal Foam
CN107871627A (zh) * 2016-09-28 2018-04-03 南京大学 泡沫铜担载CuO纳米片的高电容柔性电极材料及其制备方法
CN108295854A (zh) * 2018-01-30 2018-07-20 河北工业大学 一种多级孔纳米多孔铜负载氧化亚铜纳米线复合材料及其制备方法
CN109888167A (zh) * 2019-02-21 2019-06-14 三峡大学 一种铜基自支撑CuO-Cu2O复合阵列钠离子负极材料的制备方法
CN113881939A (zh) * 2021-10-25 2022-01-04 昆明理工大学 一种去合金化制备纳米多孔铜的方法
CN115424875A (zh) * 2022-08-26 2022-12-02 五邑大学 Cu负载纳米CuxO材料及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150072236A1 (en) * 2013-04-19 2015-03-12 CellMotive Co. Ltd. Metal Foam for Electrode of Secondary Lithium Battery, Preparing Method Thereof, and Secondary Lithium Battery Including the Metal Foam
CN103871752A (zh) * 2014-03-19 2014-06-18 山东大学 一种氧化铜基非对称型超级电容器及其制备方法
CN107871627A (zh) * 2016-09-28 2018-04-03 南京大学 泡沫铜担载CuO纳米片的高电容柔性电极材料及其制备方法
CN108295854A (zh) * 2018-01-30 2018-07-20 河北工业大学 一种多级孔纳米多孔铜负载氧化亚铜纳米线复合材料及其制备方法
CN109888167A (zh) * 2019-02-21 2019-06-14 三峡大学 一种铜基自支撑CuO-Cu2O复合阵列钠离子负极材料的制备方法
CN113881939A (zh) * 2021-10-25 2022-01-04 昆明理工大学 一种去合金化制备纳米多孔铜的方法
CN115424875A (zh) * 2022-08-26 2022-12-02 五邑大学 Cu负载纳米CuxO材料及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI ZHENHAN, LIN JIANBIN, HE XIN, XIN YUE, LIANG PING, ZHANG CHI: "CuxO-Modified Nanoporous Cu Foil as a Self-Supporting Electrode for Supercapacitor and Oxygen Evolution Reaction", NANOMATERIALS, MDPI, vol. 12, no. 12, 1 June 2022 (2022-06-01), pages 2121, XP093142325, ISSN: 2079-4991, DOI: 10.3390/nano12122121 *

Also Published As

Publication number Publication date
CN115424875A (zh) 2022-12-02

Similar Documents

Publication Publication Date Title
Huang et al. High performance asymmetric supercapacitor based on hierarchical flower-like NiCo2S4@ polyaniline
Swain et al. Construction of three-dimensional MnO2/Ni network as an efficient electrode material for high performance supercapacitors
Yu et al. Mesoporous NiCo2O4 nanoneedles grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation
Zhang et al. Electrochemical reduction of graphene oxide films: Preparation, characterization and their electrochemical properties
CN105513831B (zh) 一种中空管状结构电极材料及其制备方法
Lo et al. Synthesis of Ni (OH) 2 nanoflakes on ZnO nanowires by pulse electrodeposition for high-performance supercapacitors
Jiang et al. Electrochemical fabrication of Ni (OH) 2/Ni 3D porous composite films as integrated capacitive electrodes
Shu et al. One-step phosphating synthesis of CoP nanosheet arrays combined with Ni 2 P as a high-performance electrode for supercapacitors
Zhang et al. High energy density PbO2/activated carbon asymmetric electrochemical capacitor based on lead dioxide electrode with three-dimensional porous titanium substrate
Zhang et al. Hierarchical CuCo 2 O 4 nanowire@ NiCo 2 O 4 nanosheet core/shell arrays for high-performance supercapacitors
Guo et al. TiO2 nanowire arrays on titanium substrate as a novel binder-free negative electrode for asymmetric supercapacitor
Miao et al. Facile microwave-assisted synthesis of cobalt diselenide/reduced graphene oxide composite for high-performance supercapacitors
CN110911174A (zh) 一种NiCo-LDH纳米材料的制备方法及其应用
Zeng et al. Electrodeposition of hierarchical manganese oxide on metal nanoparticles decorated nanoporous gold with enhanced supercapacitor performance
CN110129825B (zh) 一种高效Ni/Ni(OH)2析氢电极及其制备方法
Yi et al. The electrochemical performance of deposited manganese oxide-based film as electrode material for electrochemical capacitor application
CN107045948B (zh) NaxMnO2正极材料、制备方法及其应用
Deng et al. Hierarchical NiCoO2@ Ni3S2 core/shell nanoflakes arrays with superior capacitive performances for energy storage
CN109904004B (zh) 一种SiC纳米线阵列薄膜的制备方法及其在超级电容器电极中的应用
Zhou et al. Tailored synthesis of nano-corals nickel-vanadium layered double hydroxide@ Co2NiO4 on nickel foam for a novel hybrid supercapacitor
WO2024040889A1 (fr) Nanomatériau de cuxo chargé de cu, son procédé de préparation et son application
KR20120032286A (ko) 이산화망간／탄소나노튜브／종이를 기반으로 하는 수퍼캐패시터 전극 및 그 제조 방법
Zhou et al. MnO2/ZnO porous film: Electrochemical synthesis and enhanced supercapacitor performances
Wu et al. Redox sculptured dual-scale porous nickel-iron foams for efficient water oxidation
Yang et al. Bi 2 S 3 nanorods modified with Co (OH) 2 ultrathin nanosheets to significantly improve its pseudocapacitance for high specific capacitance

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23855986

Country of ref document: EP

Kind code of ref document: A1