CN110890227B - Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof - Google Patents
Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110890227B CN110890227B CN201911261463.2A CN201911261463A CN110890227B CN 110890227 B CN110890227 B CN 110890227B CN 201911261463 A CN201911261463 A CN 201911261463A CN 110890227 B CN110890227 B CN 110890227B
- Authority
- CN
- China
- Prior art keywords
- copper
- cobalt
- nickel
- basic carbonate
- pine needle
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Images
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
- H01G11/22—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and a preparation method and application thereof. The nano composite material is in a pine needle shape and consists of copper hydroxide nano rods and nickel-cobalt-copper basic carbonate nano needles distributed on the nano rods, wherein the nickel-cobalt-copper basic carbonate is a mixture of copper-nickel basic carbonate and copper-cobalt basic carbonate. The preparation method comprises the following steps: and carrying out chemical etching on the foam copper sheet to grow copper hydroxide nanorods, and then growing nickel-cobalt-copper basic carbonate nanoneedles on the copper hydroxide nanorods through a hydrothermal reaction to obtain the pine-needle-shaped nickel-cobalt-copper basic carbonate nanocomposite. The nano composite material has excellent electrochemical performance, higher area specific volume and good rate performance, has excellent electrochemical performance when being used for an asymmetric super capacitor, has super long service life, simple preparation method, easily obtained raw materials and low cost.
Description
Technical Field
The invention belongs to the technical field of inorganic non-metallic composite material synthesis, and particularly relates to a pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material as well as a preparation method and application thereof.
Background
Supercapacitors are currently the hottest energy storage devices, and include two different types of energy storage mechanisms: electrochemical double-layer capacitors and pseudocapacitive capacitors are one of the most promising candidates due to their outstanding advantages of high power density, long lifetime, high power output, etc. With the rapid development of electronic devices and hybrid electric vehicles, assembling supercapacitors with high energy density, rapid charge-discharge performance, higher growth and uplink potential is an effective method for solving the urgent need of the current society for rapidly growing environment-friendly renewable energy devices. At present, more researches are carried out on the viewpoint that the electrode material is reasonably selected and different electrode materials are reasonably matched to have greater development potential and advantages in the aspect of optimizing the performance of the super capacitor. On one hand, reasonably designing an electrode material with high electrochemical capacitance, high electrochemical conductivity, large specific surface area and good average porosity distribution is a good choice for successfully balancing the contradiction between the rate density and the energy density. On the other hand, the electrode materials in different systems are used as composite materials to be used as anode materials to prepare the water-based asymmetric supercapacitor, so that the voltage window is widened, and the energy density and the power density are improved. Thus, a careful and judicious choice of electrode materials is a prerequisite for further improvement and improvement of the deficiencies still present in supercapacitors.
The nickel-cobalt-copper oxide and the hydroxide composite material thereof have the characteristics of high theoretical specific capacitance, low cost, various forms and the like, and become a hot spot of the research on the pseudocapacitance material of the super capacitor in recent years. However, poor electrical conductivity and their structural instability have greatly hindered the development of nickel-cobalt-copper composites in the supercapacitor field. Therefore, the nickel-cobalt composite material with the high-performance novel conductive structure is explored, the actual capacitance of the nickel-cobalt composite material is improved, and the application of the nickel-cobalt composite material in production and life is promoted.
Disclosure of Invention
The invention aims to provide a pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
providing a pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material, wherein the nano composite material is in a pine needle shape and consists of copper hydroxide nano rods and nickel-cobalt-copper basic carbonate nano needles distributed on the nano rods, wherein the nickel-cobalt-copper basic carbonate is copper-nickel basic carbonate (Cu, Ni)2CO3(OH)2And copper cobalt basic carbonate (Cu, Co)2CO3(OH)2The mixture, Cu is +1 valence, and Ni and Co are +3 valence.
According to the scheme, the average diameter length of the copper hydroxide nano rods is 100-500 nm, and the average size length is 6-8 mu m; the average size length of the nanoneedles is 100-500 nm, and the average diameter length is 5-50 nm; the ratio of nickel, cobalt and copper elements is 1: (0.5-2): (1.5 to 3).
According to the scheme, the nano composite material grows on the foam copper sheet in situ.
According to the scheme, the nanocomposite is subjected to cyclic voltammetry redox activation treatment.
The preparation method of the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material comprises the following steps:
1) carrying out chemical etching on the foam copper sheet to prepare a foam copper sheet for growing copper hydroxide nanorods;
2) dissolving a cobalt source, a nickel source, urea and ammonium acetate in distilled water to obtain a mixed solution, placing the foam copper sheet obtained in the step 1) for growing the copper hydroxide nano-rods in the mixed solution for hydrothermal reaction, and growing nickel-cobalt-copper basic carbonate nano-needles on the copper hydroxide nano-rods in situ to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano-composite material, wherein the nickel-cobalt-copper basic carbonate is copper-nickel basic carbonate (Cu, Ni)2CO3(OH)2And copper cobalt basic carbonate (Cu, Co)2CO3(OH)2The mixture, Cu is +1 valence, and Ni and Co are both +3 valence.
According to the scheme, the chemical etching operation in the step 1) is as follows: dissolving ammonium persulfate and sodium hydroxide in deionized water, continuously stirring to form uniform transparent mixed alkaline etching solution, soaking foam copper in the mixed alkaline etching solutionEtching the inside of the solution, chemically etching for 5-30 minutes at the temperature of 10-35 ℃, washing with deionized water, standing and drying to obtain copper hydroxide nanorods; wherein the mass ratio of ammonium persulfate to sodium hydroxide is 1: 0.8-1.6, and the concentration of ammonium persulfate is 1-1.8 mol L-1The concentration of sodium hydroxide is 0.1-0.3 mol L-1。
According to the scheme, in the step 2), the mass ratio of the cobalt source to the nickel source is 1: 0.5-2, the mass ratio of ammonium acetate to urea is 1: 1-4, and the mass ratio of the cobalt source to the urea is 1: 1-8; wherein the cobalt source is cobalt nitrate and the nickel source is nickel nitrate.
According to the scheme, the hydrothermal reaction conditions in the step 2) are as follows: reacting for 60-360 min at 100-140 ℃.
According to the scheme, the method also comprises cyclic voltammetry oxidation-reduction activation treatment, and specifically comprises the following steps: assembling a three-electrode system by taking the foam copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite material obtained in the step 2) as a working electrode, and performing cyclic voltammetry activation treatment on the three-electrode system at 20-60 mV s-1Circulating for 4-8 hours under the scanning speed.
According to the scheme, the method specifically comprises the following steps:
taking the foam copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite obtained in the step 2) as a working electrode, taking a platinum electrode as a counter electrode and a mercury/mercury oxide electrode as a reference electrode to assemble a three-electrode system, and carrying out cyclic voltammetry treatment on the three-electrode system at the temperature of 20-35 ℃ in a potassium hydroxide solution with the molar concentration of 1-3 mol/L, wherein the concentration of s is 20-60 mV-1And circulating for 4-8 hours at the scanning rate to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment.
Provides a super capacitor, which adopts the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material as an anode.
Firstly, chemically etching a copper hydroxide nanorod on a copper foam sheet to grow a copper hydroxide nanorod, and then in the hydrothermal reaction process, gradually adsorbing nickel-cobalt ions in a solution on the surface of the copper hydroxide nanorod, performing ion exchange on part of copper ions on the surface of the copper hydroxide nanorod and the nickel-cobalt ions adsorbed on the surface of the copper hydroxide nanorod, locally adsorbing a layer of nickel-cobalt-copper ions on the surface of the copper hydroxide nanorod, anchoring the nickel-cobalt-copper ions on the surface of the nanorod, and performing in-situ nucleation growth to form the pine-needle-like nickel-cobalt-copper basic carbonate nano composite material.
The pine-needle-shaped nickel-cobalt-copper basic carbonate nanocomposite provided by the invention is beneficial to the transmission of electrons from the copper hydroxide nanorods to the tips of the nano needles, increases the charge capacity of the material for storing charges, reduces the charge transport resistance, accelerates the charge transfer rate, reduces the charge-discharge time of the material, remarkably improves the electrochemical performance of the material, enhances the energy density and power density of a super capacitor assembled by taking the material as an electrode, further generates ion migration and proper bonding rearrangement through cyclic voltammetry redox activation treatment, and can remarkably improve the electrochemical performance of the nanocomposite.
The invention has the beneficial effects that:
1. the pine-needle-shaped nickel-cobalt-copper basic carbonate nano composite material provided by the invention has the advantages of high charge transfer efficiency, low material internal resistance, surface resistance and diffusion resistance, full play of the performance of a nickel-cobalt-copper pseudocapacitance material, excellent electrochemical performance and higher area specific volume (the current density is 2 mAcm)-2When the temperature reaches 6.13Fcm-2) And good rate performance.
2. When the pine needle-shaped nano composite material is used for an asymmetric super capacitor, the area specific volume is large, and the current density is 1mAcm-2Can reach 1.33Fcm-2The energy density and the power density are high, the original 69.2 percent of the area specific volume is still maintained under the circulation condition of 10000 circles, and the service life is long.
3. According to the invention, the copper hydroxide nanorods are grown on the copper foam sheets through chemical etching, and then the nickel-cobalt-copper basic carbonate nanoneedles are grown on the copper hydroxide nanorods in situ through ion exchange and in-situ ion heterogeneous nucleation in the hydrothermal process, and form a pine needle-shaped unique morphology, the preparation process is simple, the operation is convenient, the raw materials are easy to obtain, complex equipment is not needed, the production cost is low, the performance is excellent, and the method is very suitable for large-scale industrial production in practical application.
Drawings
Fig. 1 is a field emission electron microscope image of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1.
Fig. 2 is a transmission electron microscope image of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1.
Fig. 3 is an X-ray diffraction pattern of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1.
Fig. 4 is an XPS full spectrum analysis photograph of the pine needle-shaped nickel cobalt copper basic carbonate nanocomposite material subjected to cyclic voltammetry activation treatment prepared in example 1.
FIG. 5 is a comparison graph of XPS spectra of Cu in the pine needle-like nickel cobalt copper basic carbonate nanocomposite before and after cyclic voltammetry activation treatment prepared in example 1.
FIG. 6 is a comparison graph of XPS spectra of Ni and Co in the needle-like nickel cobalt copper basic carbonate nanocomposite before and after cyclic voltammetry activation prepared in example 1.
FIG. 7 shows the scanning rate of 5mV s of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1-1Increasing to 40mV s-1Time-cyclic voltammetry curve.
FIG. 8 shows that the pine needle-like nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment and prepared in example 1 is 1-20 mA cm-2And (5) testing the charging and discharging performance.
Fig. 9 is an impedance spectrum of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite prepared in example 1 and subjected to cyclic voltammetry activation treatment, wherein an inset in the upper right corner is a partial enlarged view under high frequency conditions.
Fig. 10 is a performance diagram of an asymmetric supercapacitor assembled by taking the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1 as an anode and taking activated carbon as a cathode, wherein a is a comparison diagram of cyclic voltammetry performances of the asymmetric supercapacitor at different scanning rates, and b is a test diagram of charging and discharging performances of the asymmetric supercapacitor at different current densities.
Fig. 11 is a cyclic voltammetry curve diagram of an asymmetric supercapacitor assembled by taking the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment as an anode and taking activated carbon as a cathode, which is prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment specifically comprises the following steps:
1) dissolving 1.8g ammonium persulfate and 2.4g sodium hydroxide in 40ml deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed alkaline etching solution, and adding a solution with the surface area of 4cm2Soaking foamed copper with the thickness of 1mm in the mixed solution, chemically etching for 20 minutes at the temperature of 25 ℃, washing for 3 times by using deionized water, standing and drying at the temperature of 80 ℃ to obtain a foamed copper sheet for growing copper hydroxide nanorods;
2) dissolving 0.58g of cobalt nitrate, 0.29g of nickel nitrate, 0.9g of urea and 0.46g of ammonium acetate in deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed solution, placing the foamed copper sheet of the copper hydroxide nanorod growing obtained in the step 1) in the solution for reaction at 120 ℃ for 240 minutes under the hydrothermal condition, washing with deionized water for 3 times, and standing and drying at 80 ℃ to obtain the pine-needle-shaped nickel-cobalt-copper basic carbonate nano composite material;
3) the area obtained in 2) was 2cm2The foamed copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material is used as a working electrode, a platinum electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode to assemble a three-electrode system, and the molar concentration is 2mol L at the temperature of 25 DEG C-1In potassium hydroxide solution at 50mV s on an electrochemical workstation-1And (3) carrying out cyclic voltammetry on the three-electrode system at a scanning rate for 6.5 hours, washing with deionized water for 3 times, standing at 80 ℃ and drying to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment.
Fig. 1 is a field emission electron microscope image of the cyclic voltammetry activated pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite prepared in example 1, which shows that the prepared nanocomposite consists of nanorods and nanoneedles growing on the nanorods, the average diameter length of the nanorods is about 250nm, and the pine needle-shaped structures are vertically staggered.
Fig. 2 is a transmission electron microscope image of the pine needle-like nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1, which shows that the nanocomposite has a pine needle-like structure, and nanorods have an average diameter of 250nm, an average diameter of about 20nm, and a length of about 500 nm.
FIG. 3 is an X-ray diffraction pattern and a standard spectrum of corresponding components of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite material subjected to cyclic voltammetry activation treatment prepared in example 1, which shows that the material contains copper-nickel basic carbonate (Cu, Ni)2CO3(OH)2And copper cobalt basic carbonate (Cu, Co)2CO3(OH)2。
Fig. 4 is an XPS full spectrum analysis photograph of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite prepared in example 1 and subjected to cyclic voltammetry activation treatment, which confirms the existence of elements C, O, Ni, Co and Cu in the nanocomposite.
Fig. 5 is a comparison graph of XPS spectra of Cu in the pine needle-like nickel-cobalt-copper basic carbonate nanocomposite before and after the cyclic voltammetry activation treatment prepared in example 1, which shows that the content of divalent copper is increased after the cyclic voltammetry activation treatment, and it is confirmed that monovalent copper is oxidized into divalent copper.
Fig. 6 is a comparison graph of XPS spectra of Ni and Co elements in the pine needle-like nickel-cobalt-copper basic carbonate nanocomposite obtained in example 1 before and after cyclic voltammetry activation, where the binding energy of the material after cyclic voltammetry is shifted in a small direction, which indicates that trivalent nickel-cobalt ions are reduced to divalent after cyclic voltammetry.
Preparation and performance test of electrode
The foamed copper sheet of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite material grown with cyclic voltammetry activation treatment prepared in example 1 is used as a working electrode, a platinum electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 2mol/L potassium hydroxide solution is used as electrolyte to assemble a three-electrode system to test the electrochemical performance of the counter electrode, wherein the working electrode tests the cyclic voltammetry curve, the constant current curve and the electrochemical impedance spectrum of an electrode slice in an electrochemical workstation.
FIG. 7 shows the scanning rate of 5mV s of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1-1Increasing to 40mV s-1The charge-discharge capacitance of the material increases along with the increase of the scanning rate of the time-cycle volt-ampere change curve.
FIG. 8 shows that the pine needle-like nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment and prepared in example 1 is 1-20 mA cm-2And (5) testing the charging and discharging performance. From this, the current density of the material at 2mA cm can be calculated-2The specific capacitance is 6.13F cm-2When the current density was increased to 20mA cm-2When the specific volume of the area is still 5.06F cm-2The material is shown to have excellent rate performance.
Fig. 9 is an impedance spectrum of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite prepared in example 1 and subjected to cyclic voltammetry activation treatment, wherein an inset in the upper right corner is a partial enlarged view under high frequency conditions. As shown, these curves consist of quasi-semi-circles and oblique lines, respectively, corresponding to the redox reactions of the interfacial charge transfer process and the diffusion limited process, respectively. In the high-frequency region, the initial values of the semicircle and the X axis are the internal resistance of the material, the diameter of the semicircle is the charge transfer resistance of the material, and the internal resistance of the material and the charge transfer resistance are both small. In the low frequency region, the curves tend to be vertical, showing typical capacitor characteristics.
Fig. 10 is a performance diagram of an asymmetric supercapacitor assembled by taking the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1 as an anode and taking activated carbon as a cathode, wherein a is a comparison diagram of cyclic voltammetry performances of the asymmetric supercapacitor at different scanning rates, and b is a test diagram of charging and discharging performances of the asymmetric supercapacitor at different current densities. From the figure, it can be seen thatThe specific volume of the asymmetric super capacitor is 1mA cm-2The specific area can reach 1.33F cm-2. Meanwhile, the asymmetric capacitor can be calculated to have higher energy density (3.23mWh cm)-2At 15mW cm-2Hour) and higher power density (175mW cm-2At 2.68mWh cm-2Time).
Fig. 11 is a cyclic voltammetry test of an asymmetric supercapacitor assembled by taking the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite subjected to cyclic voltammetry activation treatment prepared in example 1 as an anode and taking activated carbon as a cathode. When the number of circulation turns reaches 10000 turns, the capacitance retention rate still reaches 69.2 percent, and the good cycle service life of the asymmetric super capacitor is shown.
Example 2
A preparation method of pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment specifically comprises the following steps:
1) dissolving 1.8g ammonium persulfate and 1.5g sodium hydroxide in 40ml deionized water, continuously stirring for 20min to form uniform transparent mixed alkaline etching solution with surface area of 4cm2Soaking foamed copper with the thickness of 3mm in the mixed solution, chemically etching for 5 minutes at the temperature of 25 ℃, washing for 3 times by using deionized water, standing and drying at the temperature of 80 ℃ to obtain a foamed copper sheet for growing copper hydroxide nanorods;
2) dissolving 0.58g of cobalt nitrate, 0.29g of nickel nitrate, 1.8g of urea and 0.46g of ammonium acetate in deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed solution, placing the foamed copper sheet of the copper hydroxide nanorod growing obtained by chemical etching in the step 1) in the solution for reaction at 120 ℃ for 360 minutes under the hydrothermal condition, washing with deionized water for 3 times, and standing and drying at 80 ℃ to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material;
3) the area obtained in 2) was 2cm2The foamed copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material is used as a working electrode, a platinum electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode to assemble a three-electrode system, and the molar concentration is 2mol L at the temperature of 25 DEG C-1In potassium hydroxide solution at 50mV s on an electrochemical workstation-1ScanningAnd (3) carrying out cyclic voltammetry on the three-electrode system for 4 hours at a rate, washing the three-electrode system for 3 times by using deionized water, standing and drying the three-electrode system at 80 ℃ to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment.
Preparation and performance test of electrode
The electrochemical performance of a three-electrode system assembled by using the foam copper sheet of the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material grown with cyclic voltammetry activation treatment prepared in example 2 as a working electrode, a platinum electrode as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and 2mol/L potassium hydroxide solution as electrolyte is tested, and the material is 2mA cm-2Specific volume can reach 4.4F cm under current density-2。
Example 3
A preparation method of pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment specifically comprises the following steps:
1) dissolving 1.8g ammonium persulfate and 2.8g sodium hydroxide in 40ml deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed alkaline etching solution, and adding a solution with the surface area of 4cm2Soaking foamed copper with the thickness of 1mm in the mixed solution, chemically etching for 10 minutes at the temperature of 25 ℃, washing for 3 times by using deionized water, standing and drying at the temperature of 80 ℃ to obtain a foamed copper sheet for growing copper hydroxide nanorods;
2) dissolving 0.29g of cobalt nitrate, 0.58g of nickel nitrate, 0.9g of urea and 0.46g of ammonium acetate in deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed solution, placing the foamed copper sheet of the copper hydroxide nanorod growing obtained by chemical etching in the step 1) in the solution for reaction at 120 ℃ for 120 minutes under the hydrothermal condition, washing with deionized water for 3 times, and standing and drying at 80 ℃ to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material;
3) the area obtained in 2) was 2cm2The foamed copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material is used as a working electrode, a platinum electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode to assemble a three-electrode system, and the molar concentration is 1mol L at the temperature of 25 DEG C-1In potassium hydroxide solution on an electrochemical workstation50mV s-1And (3) carrying out cyclic voltammetry on the three-electrode system for 8 hours at a scanning rate, washing with deionized water for 3 times, standing at 80 ℃ and drying to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment.
Preparation and performance test of electrode
The electrochemical performance of a three-electrode system assembled by using the foam copper sheet of the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material grown with cyclic voltammetry activation treatment prepared in example 3 as a working electrode, a platinum electrode as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and 2mol/L potassium hydroxide solution as electrolyte is tested, and the material is 2mA cm-2Specific volume can reach 4.3F cm under current density-2。
Example 4
A preparation method of pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment specifically comprises the following steps:
1) dissolving 1.8g ammonium persulfate and 2.4g sodium hydroxide in 40ml deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed alkaline etching solution, and adding a solution with the surface area of 4cm2Soaking foamed copper with the thickness of 1mm in the mixed solution, chemically etching for 20 minutes at the temperature of 25 ℃, washing for 3 times by using deionized water, standing and drying at the temperature of 80 ℃ to obtain a foamed copper sheet for growing copper hydroxide nanorods;
2) dissolving 0.58g of cobalt nitrate, 0.29g of nickel nitrate, 0.9g of urea and 0.46g of ammonium acetate in deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed solution, placing the foamed copper sheet of the copper hydroxide nanorod growing obtained in the step 1) in the solution for reaction at 100 ℃ for 240 minutes under the hydrothermal condition, washing with deionized water for 3 times, and standing and drying at 80 ℃ to obtain the pine-needle-shaped nickel-cobalt-copper basic carbonate nano composite material;
3) the area obtained in 2) was 2cm2The foamed copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material is used as a working electrode, a platinum electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode to assemble a three-electrode system, and the molar concentration is 1mol L at the temperature of 25 DEG C-1In potassium hydroxide solution of (2), electrochemical workStanding at 50mV s-1And carrying out volt-ampere circulation on the three-electrode system for 8 hours at a scanning rate, washing with deionized water for 3 times, standing at 80 ℃ and drying to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic volt-ampere activation treatment.
Preparation and performance test of electrode
The electrochemical performance of a three-electrode system assembled by using the foam copper sheet of the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material grown with cyclic voltammetry activation treatment prepared in example 3 as a working electrode, a platinum electrode as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and 2mol/L potassium hydroxide solution as electrolyte is tested, and the material is 2mA cm-2The specific volume can reach 3.56F cm under the current density-2。
Comparative example 1
A preparation method of a metal basic carbonate nano composite material subjected to cyclic voltammetry activation treatment specifically comprises the following steps:
1) dissolving 1.8g ammonium persulfate and 2.4g sodium hydroxide in 40ml deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed alkaline etching solution, and adding a solution with the surface area of 4cm2Soaking foamed copper with the thickness of 3mm in the mixed solution, chemically etching for 30 minutes at the temperature of 25 ℃, washing for 3 times by deionized water, standing and drying at the temperature of 80 ℃ to obtain a foamed copper sheet for growing copper hydroxide nanorods;
2) dissolving 0.58g of cobalt nitrate, 0.29g of nickel nitrate, 0.46g of urea and 0.46g of ammonium acetate in deionized water, continuously stirring for 20 minutes to form a uniform and transparent mixed solution, placing the foamed copper sheet of the copper hydroxide nanorod growing obtained by chemical etching in the step 1) in the solution for reaction at 90 ℃ for 240 minutes under the hydrothermal condition, washing with deionized water for 3 times, and standing and drying at 80 ℃ to obtain the metal basic carbonate nano composite material;
3) the area obtained in 2) was 1cm2A copper foam sheet for growing the metal basic carbonate nano composite material is taken as a working electrode, a platinum electrode is taken as a counter electrode, a mercury/mercury oxide electrode is taken as a reference electrode to assemble a three-electrode system, and the three-electrode system is arranged on an electrochemical workstation at 20mV s in a potassium hydroxide solution with the molar concentration of 2mol/L at the temperature of 25 DEG C-1And (3) carrying out cyclic voltammetry on the three-electrode system for 6.5 hours at a scanning rate, washing with deionized water for 3 times, and standing and drying at 80 ℃ to obtain the metal basic carbonate nano composite material subjected to cyclic voltammetry activation treatment.
Preparation and performance test of electrode
The metal basic carbonate nano composite material subjected to cyclic voltammetry activation treatment prepared in comparative example 1 is used as a working electrode, a platinum electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 2mol L of the metal basic carbonate nano composite material is used-1The three-electrode system is assembled by taking the potassium hydroxide solution as electrolyte to test the electrochemical performance of the electrode, wherein the working electrode tests the cyclic voltammetry curve, the constant current curve, the electrochemical impedance spectrum and the cyclic stability of the electrode slice in an electrochemical workstation. The material was at 2mA cm-2Specific volume at current density of 2.04F cm-2。
The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application.
Claims (10)
1. A pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material is characterized in that the nano composite material is in a pine needle shape and consists of copper hydroxide nano rods and nickel-cobalt-copper basic carbonate nano needles distributed on the nano rods, wherein the nickel-cobalt-copper basic carbonate is copper-nickel basic carbonate (Cu, Ni)2CO3(OH)2And copper cobalt basic carbonate (Cu, Co)2CO3(OH)2The mixture, Cu is +1 valence, and Ni and Co are both +3 valence; the nano composite material is prepared by the following method, and the specific steps comprise:
1) carrying out chemical etching on the foam copper sheet to prepare a foam copper sheet for growing copper hydroxide nanorods;
2) dissolving a cobalt source, a nickel source, urea and ammonium acetate in distilled water to obtain a mixed solution, placing the foam copper sheet of the copper hydroxide nanorod growing obtained in the step 1) in the mixed solution for hydrothermal reaction, and growing the nickel-cobalt-copper basic carbonate nanoneedle on the copper hydroxide nanorod in situ to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite.
2. The nanocomposite material according to claim 1, wherein the copper hydroxide nanorods have an average diameter length of 100-500 nm and an average size length of 6-8 μm; the average size length of the nanoneedles is 100-500 nm, and the average diameter length is 5-50 nm; the ratio of nickel, cobalt and copper elements is 1: (0.5-2): (1.5 to 3).
3. The nanocomposite of claim 1, wherein the nanocomposite is grown in situ on a copper foam sheet.
4. The nanocomposite of claim 1, wherein the nanocomposite is subjected to a cyclic voltammetric redox activation process.
5. The preparation method of the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite material of claim 1, which is characterized by comprising the following steps:
1) carrying out chemical etching on the foam copper sheet to prepare a foam copper sheet for growing copper hydroxide nanorods;
2) dissolving a cobalt source, a nickel source, urea and ammonium acetate in distilled water to obtain a mixed solution, placing the foam copper sheet obtained in the step 1) for growing the copper hydroxide nano-rods in the mixed solution for hydrothermal reaction, and growing nickel-cobalt-copper basic carbonate nano-needles on the copper hydroxide nano-rods in situ to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano-composite material, wherein the nickel-cobalt-copper basic carbonate is copper-nickel basic carbonate (Cu, Ni)2CO3(OH)2And copper cobalt basic carbonate (Cu, Co)2CO3(OH)2The mixture, Cu is +1 valence, and Ni and Co are both +3 valence.
6. The production method according to claim 5,
the chemical etching in the step 1) is specifically operated as follows: dissolving ammonium persulfate and sodium hydroxide in deionized water, continuously stirring to form a uniform and transparent mixed alkaline etching solution, soaking foamy copper in the mixed alkaline etching solution, chemically etching for 5-30 minutes at the temperature of 10-35 ℃, washing with deionized water, standing and drying to obtain a copper hydroxide nanorod; wherein the mass ratio of ammonium persulfate to sodium hydroxide is 1: 0.8-1.6, and the concentration of ammonium persulfate is 1-1.8 mol L-1The concentration of sodium hydroxide is 0.1-0.3 mol L-1；
In the step 2), the mass ratio of the cobalt source to the nickel source is 1: 0.5-2, the mass ratio of the ammonium acetate to the urea is 1: 1-4, and the mass ratio of the cobalt source to the urea is 1: 1-8; wherein the cobalt source is cobalt nitrate and the nickel source is nickel nitrate.
7. The preparation method according to claim 5, wherein the hydrothermal reaction conditions in the step 2) are as follows: reacting for 60-360 min at 100-140 ℃.
8. The preparation method according to claim 5, further comprising a cyclic voltammetric redox activation treatment, in particular: assembling a three-electrode system by taking the foam copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite material obtained in the step 2) as a working electrode, and performing cyclic voltammetry activation treatment on the three-electrode system at 20-60 mV s-1Circulating for 4-8 hours under the scanning speed.
9. The preparation method according to claim 8, characterized by comprising the following specific operations:
taking the foam copper sheet growing with the pine needle-shaped nickel-cobalt-copper basic carbonate nanocomposite obtained in the step 2) as a working electrode, taking a platinum electrode as a counter electrode and a mercury/mercury oxide electrode as a reference electrode to assemble a three-electrode system, and carrying out cyclic voltammetry treatment on the three-electrode system at the temperature of 20-35 ℃ in a potassium hydroxide solution with the molar concentration of 1-3 mol/L, wherein the concentration of s is 20-60 mV-1And circulating for 4-8 hours at the scanning rate to obtain the pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material subjected to cyclic voltammetry activation treatment.
10. A supercapacitor, characterized in that the pine needle-like nickel-cobalt-copper basic carbonate nanocomposite material of any one of claims 1 to 4 is used as an anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911261463.2A CN110890227B (en) | 2019-12-10 | 2019-12-10 | Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911261463.2A CN110890227B (en) | 2019-12-10 | 2019-12-10 | Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110890227A CN110890227A (en) | 2020-03-17 |
| CN110890227B true CN110890227B (en) | 2021-09-28 |
Family
ID=69751324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911261463.2A Active CN110890227B (en) | 2019-12-10 | 2019-12-10 | Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110890227B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111540610B (en) * | 2020-05-09 | 2021-03-02 | 中南大学 | Electrode material for super capacitor and preparation method and application thereof |
| CN112467077A (en) * | 2020-11-29 | 2021-03-09 | 西北工业大学 | Universal electrochemical modification preparation method for effectively enhancing electricity storage performance of multiple transition metal oxides |
| CN112735855B (en) * | 2020-12-21 | 2022-04-19 | 吉林大学 | Alkaline nickel-cobalt carbonate and manganese dioxide core-shell structure supercapacitor composite electrode material loaded with foamed nickel and preparation method thereof |
| CN113213554B (en) * | 2021-04-28 | 2023-09-22 | 合肥工业大学 | Sea urchin flower-like Ni 0.3 Co 0.6 Cu 0.1 (CO 3 ) 0.5 Preparation method of (OH) electrode material |
| CN113788516B (en) * | 2021-09-27 | 2022-09-06 | 江南大学 | Application of transition metal carbonate nano material in electrocatalytic reduction reaction of nitrate |
| CN114050058A (en) * | 2021-11-10 | 2022-02-15 | 辽宁大学 | Ternary metal hydroxide electrode material and preparation method and application thereof |
| CN114300280A (en) * | 2021-12-13 | 2022-04-08 | 山东黄海科技创新研究院有限责任公司 | Preparation method of electrode material |
| CN114940517B (en) * | 2022-04-21 | 2024-01-19 | 安徽大学 | FeCoNi basic carbonate electrode material and preparation method thereof |
| CN115888718A (en) * | 2022-10-26 | 2023-04-04 | 福州大学 | Preparation and application of Chinese chestnut-shaped hollow NiCu composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014037602A (en) * | 2012-08-20 | 2014-02-27 | Furukawa Electric Co Ltd:The | Method for producing copper nanowire, copper nanowire and application thereof |
| CN105513831A (en) * | 2015-11-23 | 2016-04-20 | 北京化工大学 | Electrode material in hollow tubular structure, and preparation method for electrode material |
| CN105990044A (en) * | 2016-01-20 | 2016-10-05 | 安徽大学 | Preparation method for flexible solid supercapacitor Cu(OH)2@Ni2(OH)2CO3 multistage nanoarray electrodes |
| CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
| CN108538609A (en) * | 2018-01-02 | 2018-09-14 | 北京化工大学 | A kind of iron Cu oxide/copper base electrode material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008021256A2 (en) * | 2006-08-11 | 2008-02-21 | Aqua Resources Corporation | Nanoplatelet metal hydroxides and methods of preparing same |
| KR20130125124A (en) * | 2012-05-08 | 2013-11-18 | 한국과학기술연구원 | Fabrication method of nanocomposite for lithium secondary battery |
| CN106299296B (en) * | 2016-05-10 | 2020-08-04 | 中国科学院过程工程研究所 | Lithium iron manganese phosphate material with core-shell structure and preparation method and application thereof |
-
2019
- 2019-12-10 CN CN201911261463.2A patent/CN110890227B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014037602A (en) * | 2012-08-20 | 2014-02-27 | Furukawa Electric Co Ltd:The | Method for producing copper nanowire, copper nanowire and application thereof |
| CN105513831A (en) * | 2015-11-23 | 2016-04-20 | 北京化工大学 | Electrode material in hollow tubular structure, and preparation method for electrode material |
| CN105990044A (en) * | 2016-01-20 | 2016-10-05 | 安徽大学 | Preparation method for flexible solid supercapacitor Cu(OH)2@Ni2(OH)2CO3 multistage nanoarray electrodes |
| CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
| CN108538609A (en) * | 2018-01-02 | 2018-09-14 | 北京化工大学 | A kind of iron Cu oxide/copper base electrode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Zn-Ni-Co trimetallic carbonate hydroxide nanothorns branched on Cu(OH)2 nanorods array based on Cu foam for high-performance asymmetric supercapacitors";Ying Liu等;《Journal of Power Sources》;20190717;第437卷;摘要、实验部分和结果讨论部分 * |
| "三维Cu（OH）2纳米管状阵列电极的制备及电化学性能研究";康佳慧;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20190115(第12期);B020-392 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110890227A (en) | 2020-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110890227B (en) | Pine needle-shaped nickel-cobalt-copper basic carbonate nano composite material and preparation method and application thereof | |
| KR101602337B1 (en) | Air electrode for lithium air battery and method of making the same | |
| CN102709058B (en) | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors | |
| CN105529192B (en) | A kind of preparation method of copper quantum dot/absorbent charcoal composite material applied to ultracapacitor | |
| CN111540610B (en) | Electrode material for super capacitor and preparation method and application thereof | |
| CN104701036A (en) | Research of super-capacitor electrode material based on graded flowerlike NiCo2O4 | |
| CN109267047B (en) | Preparation method of flexible cloth electrode based on nickel-manganese hydroxide | |
| CN106098397B (en) | NiSe-Ni for supercapacitor3Se2Three-dimensional pine needle shape nano material and preparation method thereof | |
| CN112830523B (en) | Molybdenum-doped cobaltosic oxide for super capacitor and preparation method thereof | |
| CN109411238B (en) | Layered double hydroxide composite electrode material and preparation method and application thereof | |
| He et al. | Bouquet‐Like NiCo2O4@ CoNi2S4 Arrays for High‐Performance Pseudocapacitors | |
| CN111689523A (en) | Chromium metal doped-MnO2Preparation method of nanosheet | |
| Li et al. | Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material | |
| CN111268745A (en) | NiMoO4@Co3O4Core-shell nano composite material, preparation method and application | |
| CN109637824B (en) | CoFe for super capacitor2S4Nano-sheet/foamed nickel composite material and preparation method thereof | |
| CN108281292B (en) | Preparation method and application of Ni-Co-S nanoneedle array | |
| CN111333129B (en) | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor | |
| CN113496823B (en) | Symmetric hybrid supercapacitor and application thereof | |
| Park et al. | Facile preparation of nanoflake MnNi 2 O 4–PbS nanoparticle composites on Ni foam as advanced electrode materials for supercapacitors | |
| CN106710891B (en) | A kind of NiCo2O4The preparation method of/absorbent charcoal composite material | |
| CN110931268B (en) | Oxygen-sulfur doped Ni-Mo bimetallic material for super capacitor and preparation method thereof | |
| CN114300276B (en) | Ni-Fe-S@NiCo 2 O 4 Nano-NF composite material and preparation method and application thereof | |
| CN111326351A (en) | Cu for capacitor2Preparation method of O/NiO material | |
| CN111128559B (en) | Preparation method of fabric-based metal/metal hydroxide flexible composite material | |
| CN111341567B (en) | 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |