CN114724866A - Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof - Google Patents

Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof Download PDF

Info

Publication number
CN114724866A
CN114724866A CN202210236104.7A CN202210236104A CN114724866A CN 114724866 A CN114724866 A CN 114724866A CN 202210236104 A CN202210236104 A CN 202210236104A CN 114724866 A CN114724866 A CN 114724866A
Authority
CN
China
Prior art keywords
nise
solution
vanadium
adhesive
doped nickel
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.)
Pending
Application number
CN202210236104.7A
Other languages
Chinese (zh)
Inventor
张莉
夏京京
陈雅琼
张颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai University of Medicine and Health Sciences
Original Assignee
Shanghai University of Medicine and Health Sciences
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 Shanghai University of Medicine and Health Sciences filed Critical Shanghai University of Medicine and Health Sciences
Priority to CN202210236104.7A priority Critical patent/CN114724866A/en
Publication of CN114724866A publication Critical patent/CN114724866A/en
Pending legal-status Critical Current

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
    • H01G11/84—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
    • 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
    • H01G11/24—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
    • 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 vanadium-doped nickel selenide nano array material without an adhesive and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing a solution: dissolving vanadyl acetylacetonate and selenium powder to obtain a uniform mixed solution; (2) reaction preparation: putting the pretreated foam nickel into the mixed solution for hydrothermal reaction; (3) and (3) post-reaction treatment: and washing the foamed nickel after the hydrothermal reaction, and drying to constant weight to obtain the vanadium-doped nickel selenide nano array material without the adhesive, wherein the material is used as the positive electrode material of the super capacitor. Compared with the prior art, the invention has the advantages of higher specific capacitance, excellent rate capability, simple and controllable operation method, direct use of the electrode material without further processing, lower cost, no environmental pollution and the like.

Description

Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof
Technical Field
The invention relates to the field of electrochemical materials, in particular to a vanadium-doped nickel selenide nano array material without an adhesive and a preparation method and application thereof.
Background
Nowadays, environmental problems and energy crisis problems are becoming more serious due to the excessive use of conventional energy sources such as fossil fuels. There is a pressing need to explore and develop energy conversion and storage devices that are environmentally friendly and efficient. Supercapacitors (SCs), also known as Electrochemical Capacitors (ECs), have the advantages of environmental protection, good stability, wide operating voltage, high power density, etc., as compared to rechargeable batteries, and thus have received much attention from researchers in the field of electrochemical energy storage. Supercapacitors (SCs), as a new type of energy storage device, are considered to play an important role in solving the energy crisis and environmental pollution problems.
As is well known, SCs consist of electrodes, separators, collectors, and electrolytes. Where the electrode material plays a crucial role in SCs. Based on the energy storage mechanism, the SCs are generally classified into electric double-layer capacitors (EDLCs) and Pseudo Capacitors (PCs). The former stores energy through reversible electrostatic accumulation of ions on the surface of an electrode, and the latter stores energy by relying on a rapid and highly reversible redox reaction on an electrode material. The pseudocapacitance electrode material has a specific capacity two orders of magnitude higher than that of the electric double layer capacitance material. Therefore, researchers are gradually looking to explore and synthesize pseudocapacitance electrode materials with better electrochemical performance.
Common pseudocapacitive electrode materials are Transition Metal Oxides (TMOs), Transition Metal Sulfides (TMSs), and transition metal selenides. Oxygen, sulfur and selenium are elements of the same group of the sixth main group of the periodic table of elements. Wherein the element selenium has better metal performance, lower electronegativity and higher electronic conductivity (1 × 10)-3S·m-1) The conductivity and stability of the electrode material can be effectively improved. Among the numerous transition metal selenides, nickel selenide (NiSe) stands out because it has a different oxidation state, possibly at oxygenConversion is easily performed in the redox reaction, and has good conductivity to perform charge transfer. Vanadium is also an important member of the transition metal family, having a plurality of oxidation states (V)2+、V3+、V4+、V5+) The method is very beneficial to the generation of oxidation-reduction reaction, thereby greatly improving the specific capacitance of the electrode material.
However, the nanomaterials aggregate easily, which inevitably impairs the electrochemical performance of the electrode material. Meanwhile, the synthesized solid powder material needs to be added with a binder material to be fixed on the foamed nickel, which undoubtedly weakens the electrochemical performance of the electrode material again. Therefore, the design and synthesis of non-adhesive nanomaterials with higher electrochemical performance are receiving more and more attention.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an adhesive-free vanadium-doped nickel selenide nano array material which has higher specific capacitance, excellent rate capability, simple and controllable operation method, lower cost and no environmental pollution, can be directly used without further processing of an electrode material and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention adopts a simple one-step hydrothermal method to prepare a vanadium-doped nickel selenide nano array (V-NiSe/NF) electrode material on foamed nickel, obtains nickel selenide nano array (V-NiSe/NF) materials with different vanadium doping amounts by adjusting the using amount of a vanadium source and the hydrothermal temperature, and then takes the nickel selenide nano array (V-NiSe/NF) materials as the anode of a super capacitor, and has higher specific capacitance, and the specific scheme is as follows:
a preparation method of a vanadium doped nickel selenide nano array material without an adhesive comprises the following steps:
(1) preparing a solution: dissolving vanadyl acetylacetonate and selenium powder to obtain a uniform mixed solution;
(2) reaction preparation: putting the pretreated foam nickel into the mixed solution for hydrothermal reaction;
(3) and (3) post-reaction treatment: and washing the foamed nickel after the hydrothermal reaction, and drying to constant weight to obtain the vanadium-doped nickel selenide nano array material without the adhesive, namely the V-NiSe/NF material.
Furthermore, the mass ratio of the nickel foam, the vanadyl acetylacetonate and the selenium powder is (30-35): (0-50): (10-15), and 0 is not selected.
Furthermore, the mass ratio of the vanadyl acetylacetonate to the selenium powder is (20-40) to (10-15).
Further, the specific steps of the step (1) are as follows:
adding vanadyl acetylacetonate into absolute ethyl alcohol, stirring until the vanadyl acetylacetonate is dissolved to form a light blue transparent uniform solution, and marking the solution as A solution;
adding selenium powder into a hydrazine hydrate solution, stirring until the selenium powder is dissolved to form a dark red transparent uniform solution, and marking as a B solution;
and transferring the solution A to the solution B, and continuously stirring to obtain a uniform mixed solution.
Further, the pretreatment mode of the foamed nickel is as follows: and ultrasonically cleaning the foamed nickel for multiple times by using hydrochloric acid, deionized water and absolute ethyl alcohol to remove oxides and impurities on the surface of the foamed nickel, and finally drying for later use.
Further, the temperature of the hydrothermal reaction is 120-160 ℃, and the time is 2-4 h.
Further, the temperature of the hydrothermal reaction is 120-140 ℃.
Binderless vanadium-doped nickel selenide nano array material prepared by using method
The application of the vanadium-doped nickel selenide nano array material without the adhesive is used as a positive electrode material of a super capacitor.
Further, the application process is as follows: the obtained V-NiSe/NF material is directly used as a positive electrode without further treatment to be applied to a three-electrode system, wherein V-NiSe/NF is used as an active working electrode, a Pt wire is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 3M potassium hydroxide (KOH) is used as electrolyte.
Most of materials synthesized by the prior art are solid powder samples, and in order to test the electrochemical performance of the materials, the materials need to be subjected to slurry coating treatment, and a bonding agent PVDF needs to be added in the process, so that the solid powder is firmly adhered to a conductive substrate, and the problem of large-area sample falling in the test process is solved. But PVDF is a fluoroplastic and is not conducive to electron transport. Its addition greatly affects the electrochemical performance of the material. The technology of the application adopts a one-step hydrothermal method to directly grow the electrode material on the conductive substrate nickel foam. The synthesis process is simple and needs no adhesive. The stability of the electrode is improved, the conductivity of the electrode is improved, and the electrochemical performance of the material is improved.
Drawings
FIG. 1 is a microstructure characterization of the product V-NiSe/NF-0 obtained in example 1;
FIG. 2 is a graph showing the electrochemical properties of the product V-NiSe/NF-0 obtained in example 1;
FIG. 3 is a microstructure characterization of the product V-NiSe/NF-1 obtained in example 2;
FIG. 4 is a graph showing the electrochemical properties of the product V-NiSe/NF-1 obtained in example 2;
FIG. 5 is a microstructure characterization plot of the product V-NiSe/NF-2 obtained in example 3;
FIG. 6 is a graph showing the electrochemical properties of the product V-NiSe/NF-2 obtained in example 3;
FIG. 7 is a microstructure characterization plot of the product V-NiSe/NF-3 obtained in example 4;
FIG. 8 is a graph showing the electrochemical properties of the product V-NiSe/NF-3 obtained in example 4;
FIG. 9 is a microstructure characterization chart of the product V-NiSe/NF-2(1) obtained in example 5;
FIG. 10 is a graph showing the electrochemical properties of the product V-NiSe/NF-2(1) obtained in example 5;
FIG. 11 is a microstructure characterization plot of the product V-NiSe/NF-2(3) obtained in example 6;
FIG. 12 is a graph showing the electrochemical properties of the product V-NiSe/NF-2(3) obtained in example 6;
FIG. 13 is a graph comparing the constant current discharge of various samples under different conditions;
FIG. 14 is a graph of electrochemical performance characterization in a two-electrode system.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a vanadium-doped nickel selenide nano array material without an adhesive. The preparation method relates to a one-step hydrothermal method, successfully prepares the vanadium-doped nickel selenide nano array material without the adhesive, and has higher specific capacitance when being used as the positive electrode material of the super capacitor.
In the technical scheme, the V-NiSe/NF-2 serving as the positive electrode material has excellent specific capacitance performance when being applied to the super capacitor. Preferably, the synthesized V-NiSe/NF-0 material is used as a positive electrode material for a super capacitor for comparison.
In the technical scheme, the V-NiSe/NF-2 serving as the positive electrode material has excellent specific capacitance performance when being applied to the super capacitor. Preferably, the synthesized V-NiSe/NF-1 material is used as a positive electrode material for a super capacitor for comparison.
In the technical scheme, the V-NiSe/NF-2 serving as the positive electrode material has excellent specific capacitance performance when being applied to the super capacitor. Preferably, the synthesized V-NiSe/NF-3 material is used as a positive electrode material for a super capacitor for comparison.
In the technical scheme, the V-NiSe/NF-2 serving as the positive electrode material has excellent specific capacitance performance when applied to the super capacitor. Preferably, the synthesized V-NiSe/NF-2(1) material is used as a positive electrode material for a super capacitor for comparison.
In the technical scheme, the V-NiSe/NF-2 serving as the positive electrode material has excellent specific capacitance performance when being applied to the super capacitor. Preferably, the synthesized V-NiSe/NF-2(3) material is used as a positive electrode material for a super capacitor for comparison.
The products marked by the labels V-NiSe/NF-0, V-NiSe/NF-1, V-NiSe/NF-2 and V-NiSe/NF-3 have the unique difference that vanadyl acetylacetonate with different mass is added, and the added quantity is 0mg, 10mg, 30mg and 50mg in sequence. The products marked by the above labels V-NiSe/NF-2(1) and V-NiSe/NF-2(3) have the only difference that the hydrothermal temperature is different and is 120 ℃ and 160 ℃ in sequence.
The electrochemical performance of the super capacitor is characterized mainly by test means such as Cyclic Voltammetry (CV), constant current charging and discharging (GCD) and impedance spectroscopy (EIS). The key performance indexes include specific capacity, energy density, power density and cycling stability. The most important parameter is the specific capacity representing the energy storage capacity of the supercapacitor.
Example 1
1. Pretreating foamed nickel:
taking a piece of 1cm × 2cm foamed nickel (model: KSH-1011, thickness of 1mm, about 35mg), sequentially using 3mol L- 1And (3) ultrasonically cleaning the HCl solution, the deionized water and the absolute ethyl alcohol for multiple times in an ultrasonic instrument to remove oxides and impurities on the surface of the HCl solution, the deionized water and the absolute ethyl alcohol. Finally, the mixture is put into an oven to be dried for standby at 60 ℃.
2. Preparing a V-NiSe/NF-0 material:
(1) preparing a solution: 15mg of selenium powder is added into 10mL of hydrazine hydrate solution and stirred until the solution is dissolved, so that a dark red transparent uniform solution is formed.
(2) Reaction preparation: transferring the solution into a reaction kettle with a Teflon coating, putting the pretreated foamed nickel into the kettle, transferring the kettle into an oven for reaction at the reaction temperature of 140 ℃ for 3 hours.
(3) And (3) post-reaction treatment: and (3) repeatedly washing the foamed nickel obtained in the step (2) by using deionized water and absolute ethyl alcohol for multiple times, and putting the washed foamed nickel into a vacuum drying oven at the temperature of 50-70 ℃ for drying until the weight is constant to obtain the V-NiSe/NF-0 material.
(4) And (4) performance testing: and (3) taking the product obtained in the step 2- (3) as a positive electrode material to be applied to three-electrode performance tests.
FIGS. 1(a) and (b) are scanning electron micrographs at different magnifications of the product V-NiSe/NF-0 obtained in example 1; FIG. 1(c) is an X-ray powder diffraction pattern of the product V-NiSe/NF-0 obtained in example 1; the low and high power scanning electron micrographs of V-NiSe/NF-0 are shown in FIGS. 1(a) and (b); it can be seen that the sparse and disordered needles are not uniformly distributed on the foam nickel skeleton. The X-ray powder diffraction pattern of V-NiSe/NF-0 is shown in figure 1(c), except that strong peaks at 44.5 degrees, 51.8 degrees and 76.4 degrees belong to the characteristic peak of simple nickel, and other peaks are consistent with NiSe (JCPDS No. 02-0892).
FIGS. 2(a) and (b) are the cyclic voltammogram and galvanostatic charge-discharge plot of the product V-NiSe/NF-0 obtained in example 1; FIGS. 2(c) and (d) are a graph of the rate capability and the impedance of the product V-NiSe/NF-0 obtained in example 1; the cyclic voltammogram of V-NiSe/NF-0 is shown in FIG. 2 (a); the constant current charge-discharge diagram of V-NiSe/NF-0 is shown in FIG. 2 (b); the graph of the rate performance of V-NiSe/NF-0 is shown in FIG. 2 (c); the impedance plot of V-NiSe/NF-0 is shown in FIG. 2 (d); as can be seen from FIGS. 2(b) and 2(c), V-NiSe/NF-0 applied to three electrodes as an electrode material at a current density of 1A g-1The specific capacitance of the material only reaches 572F g-1(ii) a FIG. 2(c) shows that V-NiSe/NF-0 has a good rate capability (70%) when applied to three electrodes as an electrode material;
FIG. 2(d) shows the impedance spectrum of V-NiSe/NF-0 as the electrode material applied to three electrodes, from which a semicircle with a diameter of charge transfer resistance (denoted as R) is observed in the high frequency regionct) (ii) a In the low frequency region, a straight line with small slope appears, the part of the straight line is attributed to the diffusion impedance (marked as W) of the electrolyte, and the intercept of the high frequency region and the real axis represents the internal resistance (marked as R) of the electrodes) (ii) a Through analysis, the radius of the high-frequency region is larger, which shows that the resistance of the V-NiSe/NF-0 electrode material is larger; is located at lowThe slope of the straight line in the frequency region is small, the internal resistance of the electrode is large, and the dynamic process is slow, so that the electrode material is not a particularly ideal electrode material of the super capacitor.
Example 2
1. Pretreating foamed nickel:
a1 cm X2 cm piece of nickel foam (type: KSH-1011, thickness 1mm, about 35mg) was sequentially charged with 3mol L- 1And (3) ultrasonically cleaning the HCl solution, the deionized water and the absolute ethyl alcohol for multiple times in an ultrasonic instrument to remove oxides and impurities on the surface of the HCl solution, the deionized water and the absolute ethyl alcohol. Finally, the mixture is put into an oven to be dried for standby at 60 ℃.
2. Preparing a V-NiSe/NF-1 material:
(1) preparing a solution: vanadyl acetylacetonate, 10mg in mass, was added to 20mL of absolute ethanol and stirred to dissolve, forming a pale blue, transparent and homogeneous solution, denoted as solution a. 15mg of selenium powder is added into 10mL of hydrazine hydrate solution and stirred until the solution is dissolved, so that a dark red transparent uniform solution is formed and is marked as a B solution. And transferring the solution A to the solution B, and continuously stirring for 30min to obtain a uniform solution.
(2) Reaction preparation: transferring the solution into a reaction kettle with a Teflon coating, putting the pretreated foamed nickel into the kettle, transferring the kettle into an oven for reaction at the reaction temperature of 140 ℃ for 3 hours.
(3) And (3) post-reaction treatment: and (3) repeatedly washing the foamed nickel obtained in the step (2) by using deionized water and absolute ethyl alcohol for multiple times, and putting the washed foamed nickel into a vacuum drying oven at the temperature of 50-70 ℃ for drying until the weight is constant to obtain the V-NiSe/NF-1 material.
(4) And (3) performance testing: and (3) taking the product obtained in the step 2- (3) as a positive electrode material to be applied to three-electrode performance tests.
FIGS. 3(a) and (b) are scanning electron micrographs at different magnifications of the product V-NiSe/NF-1 obtained in example 2; FIGS. 3(c), (d) are the X-ray powder diffraction pattern and EDS pattern of the product V-NiSe/NF-1 obtained in example 2; the low-power and high-power scanning electron micrographs of V-NiSe/NF-1 are shown in FIGS. 3(a) and (b); it can be seen that the V-NiSe/NF-1 is a fine needle-shaped nano array which is uniformly distributed on the foam nickel framework. The X-ray powder diffraction pattern of V-NiSe/NF-1 is shown in FIG. 3(c), except that three strong peaks at 44.5 DEG, 51.8 DEG and 76.4 DEG belong to the characteristic peaks of elemental nickel, and the other peaks coincide with NiSe (JCPDS No. 02-0892). The EDS diagram of V-NiSe/NF-1 is shown in FIG. 3(d), and it can be seen that there are three elements of Ni, Se and V in the sample. Wherein the content of the V element is 1.53 percent;
FIGS. 4(a) and (b) are the cyclic voltammogram and galvanostatic charge-discharge plot of the product V-NiSe/NF-1 obtained in example 2; FIGS. 4(c), (d) are the rate performance graph and impedance graph of the product V-NiSe/NF-1 obtained in example 2; the cyclic voltammogram of V-NiSe/NF-1 is shown in FIG. 4 (a); the constant current charge-discharge diagram of V-NiSe/NF-1 is shown in FIG. 4 (b); the multiplying power performance graph of V-NiSe/NF-1 is shown in a figure 4 (c); the impedance plot of V-NiSe/NF-1 is shown in FIG. 4 (d); as can be seen from FIGS. 4(b) and 4(c), when V-NiSe/NF-1 was applied to three electrodes as an electrode material, the current density was 1A g-1The specific capacitance of the material reaches 1241F g-1(ii) a FIG. 4(c) shows that V-NiSe/NF-1 has good rate capability (46.4%) when applied to three electrodes as an electrode material;
FIG. 4(d) shows an impedance spectrum of V-NiSe/NF-1 as an electrode material applied to three electrodes, from which it can be observed that the radius of the semicircle appearing in the high frequency region is relatively small, indicating that the resistance of the V-NiSe/NF-1 electrode material is small; however, the slope of the straight line in the low frequency region is smaller, which indicates that the diffusion resistance of the electrolyte is larger, and indicates that the electrode material is not the optimal electrode material of the supercapacitor.
Example 3
1. V-NiSe/NF-2 was prepared as in example 2, except that the amount of vanadyl acetylacetonate was changed to 30 mg.
2. And (3) performance testing: and (3) taking the product obtained in the step (1) as an electrode material to be applied to a three-electrode performance test.
FIGS. 5(a), (b) are scanning electron micrographs at different magnifications of the product V-NiSe/NF-2 obtained in example 3; FIGS. 5(c), (d) are X-ray powder diffractogram and EDS chart of V-NiSe/NF-2 obtained in example 3; the low-power and high-power scanning electron micrographs of V-NiSe/NF-2 are shown in FIGS. 5(a) and (b), and it can be seen that V-NiSe/NF-2 is a needle-shaped array with a diameter of about 50nm uniformly distributed on a carbon skeleton; the X-ray powder diffraction pattern of V-NiSe/NF-2 is shown in FIG. 5(c), except that three strong peaks at 44.5 DEG, 51.8 DEG and 76.4 DEG belong to the characteristic peaks of elemental nickel. Other peaks are consistent with NiSe (JCPDS No. 02-0892);
FIGS. 6(a) and (b) are the cyclic voltammogram and galvanostatic charge-discharge plot of the product V-NiSe/NF-2 obtained in example 3; FIGS. 6(c) and (d) are a graph of rate capability and impedance of the product V-NiSe/NF-2 obtained in example 3; the EDS diagram of V-NiSe/NF-2 is shown in figure 5(d), and it can be seen that the sample contains three elements of Ni, Se and V, wherein the content of the element V is 2.55%; the cyclic voltammogram of V-NiSe/NF-2 is shown in FIG. 6 (a); the constant current charge-discharge diagram of V-NiSe/NF-2 is shown in FIG. 6 (b); the rate performance graph of V-NiSe/NF-2 is shown in FIG. 6 (c); the impedance plot of V-NiSe/NF-2 is shown in FIG. 6 (d); as can be seen from FIGS. 6(b) and 6(c), when V-NiSe/NF-2 was applied as an electrode material to three electrodes, the current density was 1A g-1The specific capacitance of the material reaches 1580F g-1(ii) a FIG. 6(c) shows that V-NiSe/NF-2 has a better rate capability (45.1%) when applied to three electrodes as an electrode material;
FIG. 6(d) shows an impedance spectrum of V-NiSe/NF-2 as an electrode material applied to three electrodes, from which it can be observed that the semi-circle radius appearing in the high frequency region and the intercept with the x solid axis are small, which indicates that the charge transfer resistance and the electrode internal resistance of the V-NiSe/NF-2 electrode material are small; the slope of the line in the low frequency region is larger, indicating that the kinetic process of the electrode material is faster. The electrochemical performance of the material is superior to V-NiSe/NF-0, V-NiSe/NF-1 and V-NiSe/NF-3, and the material is the most ideal electrode material of the super capacitor.
Example 4
1. V-NiSe/NF-3 was prepared according to the procedure in example 2, except that vanadyl acetylacetonate was changed to 50 mg.
2. And (3) performance testing: and (3) taking the product obtained in the step (1) as an electrode material to be applied to a three-electrode performance test.
FIGS. 7(a), (b) are scanning electron micrographs at different magnifications of the product V-NiSe/NF-3 obtained in example 4; FIGS. 7(c), (d) are the X-ray powder diffraction pattern and EDS pattern of the product V-NiSe/NF-3 obtained in example 4; the macroscopic and macroscopic scanning electron micrographs of V-NiSe/NF-3 are shown in FIGS. 7(a) and (b), and it can be seen that V-NiSe/NF-3 is a needle-like array with a diameter of about 100nm uniformly distributed on the carbon skeleton; the X-ray powder diffraction pattern of V-NiSe/NF-3 is shown in FIG. 7(c), except that three strong peaks at 44.5 DEG, 51.8 DEG and 76.4 DEG belong to the characteristic peaks of elemental nickel. The other peaks correspond to NiSe (JCPDS No. 02-0892). The EDS diagram of V-NiSe/NF-3 is shown in FIG. 7(d), and it can be seen that there are three elements of Ni, Se and V in the sample. Wherein the content of the V element is 3.25 percent;
FIGS. 8(a) and (b) are the cyclic voltammogram and galvanostatic charge-discharge plot of the product V-NiSe/NF-3 obtained in example 4; FIGS. 8(c) and (d) are a graph of the rate capability and the impedance of the product V-NiSe/NF-3 obtained in example 4; the cyclic voltammogram of V-NiSe/NF-3 is shown in FIG. 8 (a); the constant current charge-discharge diagram of V-NiSe/NF-3 is shown in FIG. 8 (b); the multiplying power performance graph of V-NiSe/NF-3 is shown in a figure 8 (c); the impedance plot of V-NiSe/NF-3 is shown in FIG. 8 (d); as can be seen from FIGS. 8(b) and 8(c), when V-NiSe/NF-3 was applied as an electrode material to three electrodes, the current density was 1A g-1The specific capacitance of the material is up to 1217F g-1(ii) a FIG. 8(c) shows that the rate performance of V-NiSe/NF-3 applied to three electrodes as an electrode material is general (32.8%);
FIG. 8(d) is a graph showing the impedance spectrum of V-NiSe/NF-3 as an electrode material applied to three electrodes, from which it can be observed that the radius of the semicircle appearing in the high frequency region is larger, indicating that the resistance of the V-NiSe/NF-3 electrode material is larger; the internal resistance of the electrode is higher, but the slope of the straight line in a low-frequency region is lower, which indicates that the diffusion resistance of the electrolyte is higher; the electrochemical performance of the electrode material is only superior to that of V-NiSe/NF-0, and the electrode material is not a particularly ideal electrode material of a super capacitor.
Example 5
1. V-NiSe/NF-2(1) was prepared as in example 3, except that the hydrothermal temperature was changed to 120 ℃.
2. And (3) performance testing: and (3) taking the product obtained in the step (1) as an electrode material to be applied to a three-electrode performance test.
FIGS. 9(a) and (b) are scanning electron micrographs at different magnifications of the product V-NiSe/NF-2(1) obtained in example 5; FIGS. 9(c), (d) are the X-ray powder diffraction pattern and EDS pattern of the product V-NiSe/NF-2(1) obtained in example 5; scanning electron micrographs of V-NiSe/NF-2(1) under and under high magnification are shown in FIGS. 9(a) and (b); it can be seen that the V-NiSe/NF-2(1) is a fine needle array uniformly distributed on the foam nickel skeleton. The X-ray powder diffraction pattern of V-NiSe/NF-2(1) is shown in FIG. 9(c), except that three strong peaks at 44.5 degrees, 51.8 degrees and 76.4 degrees belong to the characteristic peaks of elemental nickel, and other peaks are consistent with NiSe (JCPDS No. 02-0892). The EDS diagram of V-NiSe/NF-3 is shown in FIG. 9(d), and it can be seen that there are three elements of Ni, Se and V in the sample. Wherein the content of the V element is 1.92 percent;
FIGS. 10(a), (b) are the cyclic voltammogram and galvanostatic charge-discharge plot of the product V-NiSe/NF-2(1) obtained in example 5; FIGS. 10(c) and (d) are the rate performance diagram and impedance diagram of the product V-NiSe/NF-2(1) obtained in example 5; the cyclic voltammogram of V-NiSe/NF-2(1) is shown in FIG. 10 (a); the constant current charge-discharge diagram of V-NiSe/NF-2(1) is shown in FIG. 10 (b); the rate performance graph of V-NiSe/NF-2(1) is shown in figure 10 (c); the impedance diagram of V-NiSe/NF-2(1) is shown in FIG. 10 (d); as can be seen from FIGS. 10(b) and 10(c), when V-NiSe/NF-2(1) was applied to three electrodes as an electrode material, the current density was 1A g-1The specific capacitance of the material reaches 1265F g-1(ii) a FIG. 10(c) shows that the rate performance of V-NiSe/NF-2(1) applied to three electrodes as an electrode material is general (37.5%);
FIG. 10(d) shows the impedance spectrum of V-NiSe/NF-2(1) as the electrode material applied to three electrodes, from which it can be observed that the semi-circle radius appearing in the high frequency region is relatively small, which indicates that the charge transfer resistance of the V-NiSe/NF-2(1) electrode material is small; the slope of the straight line in the low-frequency region is smaller, which shows that the dynamic process of the electrode material is slower, and the electrochemical performance of the electrode material is superior to V-NiSe/NF-0, V-NiSe/NF-3 and V-NiSe/NF-2(3) and inferior to V-NiSe/NF-1 and V-NiSe/NF-2.
Example 6
1. V-NiSe/NF-2(3) was prepared as in example 3, except that the hydrothermal temperature was changed to 160 ℃.
2. And (3) performance testing: and (3) taking the product obtained in the step (1) as an electrode material to be applied to a three-electrode performance test.
FIGS. 11(a) and (b) are scanning electron micrographs at different magnifications of the product V-NiSe/NF-2(3) obtained in example 6; FIGS. 12(c), (d) are the X-ray powder diffraction pattern and EDS pattern of the product V-NiSe/NF-2(3) obtained in example 6; scanning electron micrographs of V-NiSe/NF-2(3) under and under magnification are shown in FIGS. 11(a) and (b); it can be seen that V-NiSe/NF-2(3) is an array of needles about 150nm in diameter distributed on the nickel foam skeleton. The X-ray powder diffraction pattern of V-NiSe/NF-2(3) is shown in FIG. 11(c), except that three strong peaks at 44.5 degrees, 51.8 degrees and 76.4 degrees belong to the characteristic peaks of elemental nickel, and other peaks are consistent with NiSe (JCPDS No. 02-0892). The EDS diagram of V-NiSe/NF-2(3) is shown in FIG. 11(d), and it can be seen that there are three elements of Ni, Se and V in the sample. Wherein the content of the V element is 3.39%;
FIGS. 12(a) and (b) are the cyclic voltammograms and constant current charge-discharge plots of the product V-NiSe/NF-2(3) obtained in example 6; FIGS. 12(c) and (d) are the rate performance diagram and impedance diagram of the product V-NiSe/NF-2(3) obtained in example 6; the cyclic voltammogram of V-NiSe/NF-2(3) is shown in FIG. 12 (a); the constant current charge-discharge diagram of V-NiSe/NF-2(3) is shown in figure 12 (b); the rate performance graph of V-NiSe/NF-2(3) is shown in figure 12 (c); the impedance diagram of V-NiSe/NF-2(3) is shown in FIG. 12 (d); as can be seen from FIGS. 12(b) and 12(c), when V-NiSe/NF-2(3) is used as the anode material of the three-electrode, the current density is 1A g-1The specific capacitance of the material reaches 821F g-1(ii) a From FIG. 12(c), it can be seen that V-NiSe/NF-2(3) has poor rate performance (26.3%) when applied to three electrodes as the anode material of the electrode;
FIG. 12(d) shows the impedance spectrum of V-NiSe/NF-2(3) as the electrode material applied to three electrodes, from which it can be observed that the semi-circle radius appearing in the high frequency region is larger, indicating that the resistance of the V-NiSe/NF-2(3) electrode material is larger; and the slope of the line in the low frequency region is smaller, indicating that the kinetic process of V-NiSe/NF-2(3) is slower. The electrochemical performance of the material is poor, and the material is not a particularly ideal electrode material of a super capacitor.
Example 7
The performance of V-NiSe/NF electrode materials with different vanadium contents is compared:
FIG. 13(a) is a graph of V-NiSe/NF electrode materials of different vanadium content at a current density of 1A g in a three-electrode system-1A constant current discharge diagram of time; as can be seen from FIG. 13(a), the V-NiSe/NF-2 electrode material has the highest performance compared with the V-NiSe/NF-0, V-NiSe/NF-1 and V-NiSe/NF-3 electrode materialsSpecific capacitance.
The performance of the V-NiSe/NF electrode material at the hydrothermal temperature is compared:
FIG. 13(b) is a graph of V-NiSe/NF electrode material at different hydrothermal temperatures in a three-electrode system at a current density of 1A g-1A constant current discharge diagram of time; as can be seen from FIG. 13(b), the V-NiSe/NF-2 electrode material has the highest specific capacitance compared with the V-NiSe/NF-2(1) and V-NiSe/NF-2(3) electrode materials.
Example 8
The performance of the asymmetric supercapacitor assembled by using V-NiSe/NF-2 as a positive electrode and activated carbon as a negative electrode is shown as follows:
fig. 14(a), 14(b) and 14(c) are cyclic voltammograms of the device at different scanning speeds, and charge-discharge curves and rate performance graphs at different current densities, respectively. As can be seen from FIG. 14(c), the device was operated at a current density of 1A g-1When the specific capacitance is 149.8F g-1And when the current density rises to 10A g-1In this case, the better rate performance (49.4%) is maintained. Such excellent electrochemical performance is expected to be practically applied in the field of energy storage.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method of a vanadium doped nickel selenide nano array material without an adhesive is characterized by comprising the following steps:
(1) preparing a solution: dissolving vanadyl acetylacetonate and selenium powder to obtain a uniform mixed solution;
(2) reaction preparation: putting the pretreated foam nickel into the mixed solution for hydrothermal reaction;
(3) and (3) post-reaction treatment: and washing the foamed nickel after the hydrothermal reaction, and drying to constant weight to obtain the vanadium-doped nickel selenide nano array material without the adhesive.
2. The method for preparing the adhesive-free vanadium-doped nickel selenide nano-array material as claimed in claim 1, wherein the mass ratio of the foamed nickel, the vanadyl acetylacetonate and the selenium powder is (30-35): 0-50): 10-15.
3. The method for preparing the adhesive-free vanadium-doped nickel selenide nano-array material as claimed in claim 2, wherein the mass ratio of the vanadyl acetylacetonate to the selenium powder is (20-40) to (10-15).
4. The preparation method of the adhesive-free vanadium-doped nickel selenide nanoarray material according to claim 1, wherein the specific steps of the step (1) are as follows:
adding vanadyl acetylacetonate into anhydrous ethanol, and stirring until the vanadyl acetylacetonate is dissolved to form a light blue transparent uniform solution, namely solution A;
adding selenium powder into a hydrazine hydrate solution, stirring until the selenium powder is dissolved to form a dark red transparent uniform solution, and marking as a B solution;
and transferring the solution A to the solution B, and continuously stirring to obtain a uniform mixed solution.
5. The preparation method of the adhesive-free vanadium-doped nickel selenide nano-array material as claimed in claim 1, wherein the pretreatment mode of the foamed nickel is as follows: and ultrasonically cleaning the foamed nickel for multiple times by using hydrochloric acid, deionized water and absolute ethyl alcohol, and finally drying for later use.
6. The method for preparing the adhesive-free vanadium-doped nickel selenide nano-array material as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120 ℃ and 160 ℃ for 2-4 h.
7. The method as claimed in claim 6, wherein the hydrothermal reaction temperature is 120-140 ℃.
8. An adhesive-free vanadium doped nickel selenide nanoarray material prepared by the method of any one of claims 1 to 7.
9. The use of the binderless vanadium doped nickel selenide nanoarray material of claim 8 as a positive electrode material for a supercapacitor.
10. The application of the binderless vanadium doped nickel selenide nanoarray material of claim 9, wherein the application process comprises: the obtained V-NiSe/NF material is directly used as a positive electrode without further treatment to be applied to a three-electrode system, wherein V-NiSe/NF is used as an active working electrode, a Pt wire is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 3M potassium hydroxide (KOH) is used as electrolyte.
CN202210236104.7A 2022-03-11 2022-03-11 Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof Pending CN114724866A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210236104.7A CN114724866A (en) 2022-03-11 2022-03-11 Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210236104.7A CN114724866A (en) 2022-03-11 2022-03-11 Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114724866A true CN114724866A (en) 2022-07-08

Family

ID=82237322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210236104.7A Pending CN114724866A (en) 2022-03-11 2022-03-11 Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114724866A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107818873A (en) * 2017-10-10 2018-03-20 安阳师范学院 Cellular nickelous selenide nano-chip arrays electrode material and preparation method thereof
CN108987120A (en) * 2018-07-23 2018-12-11 哈尔滨工业大学 A method of nickel hydroxide is mixed by etching manganese and prepares ultra-thin porous nickelous selenide nano-chip arrays
CN109686592A (en) * 2019-01-04 2019-04-26 安阳师范学院 Two nickelous selenide nano-array electrode material of white beech mushroom shape and preparation method thereof
CN109802118A (en) * 2019-01-22 2019-05-24 南京大学 A kind of preparation method of the rechargeable magnesium battery based on two selenizing vanadium anodes
CN110136975A (en) * 2019-05-13 2019-08-16 华侨大学 A kind of preparation method and applications of amorphous tetrathio cobalt molybdate/nickelous selenide nano-chip arrays composite material
CN110165174A (en) * 2019-05-18 2019-08-23 福建师范大学 A kind of preparation method and application of selenizing vanadium-nitrogen with high performance/sulphur codope carbon complex kalium ion battery negative electrode material
CN110280275A (en) * 2019-06-17 2019-09-27 安徽师范大学 A kind of Fe doping four three nanosized nickel rods of selenizing/nanometer sheet hierarchical array structural material, preparation method and applications
CN112064060A (en) * 2020-09-21 2020-12-11 陕西科技大学 Nickel selenide/nickel iron substrate material and preparation method and application thereof
US20210090819A1 (en) * 2019-10-08 2021-03-25 University Of Electronic Science And Technology Of China Method for preparing super capacitor electrode material Ni doped CoP3/foam nickel
CN113470983A (en) * 2020-03-30 2021-10-01 天津大学 Nickel selenide-nickelous diselenide nanorod composite material and preparation method and application thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107818873A (en) * 2017-10-10 2018-03-20 安阳师范学院 Cellular nickelous selenide nano-chip arrays electrode material and preparation method thereof
CN108987120A (en) * 2018-07-23 2018-12-11 哈尔滨工业大学 A method of nickel hydroxide is mixed by etching manganese and prepares ultra-thin porous nickelous selenide nano-chip arrays
CN109686592A (en) * 2019-01-04 2019-04-26 安阳师范学院 Two nickelous selenide nano-array electrode material of white beech mushroom shape and preparation method thereof
CN109802118A (en) * 2019-01-22 2019-05-24 南京大学 A kind of preparation method of the rechargeable magnesium battery based on two selenizing vanadium anodes
CN110136975A (en) * 2019-05-13 2019-08-16 华侨大学 A kind of preparation method and applications of amorphous tetrathio cobalt molybdate/nickelous selenide nano-chip arrays composite material
CN110165174A (en) * 2019-05-18 2019-08-23 福建师范大学 A kind of preparation method and application of selenizing vanadium-nitrogen with high performance/sulphur codope carbon complex kalium ion battery negative electrode material
CN110280275A (en) * 2019-06-17 2019-09-27 安徽师范大学 A kind of Fe doping four three nanosized nickel rods of selenizing/nanometer sheet hierarchical array structural material, preparation method and applications
US20210090819A1 (en) * 2019-10-08 2021-03-25 University Of Electronic Science And Technology Of China Method for preparing super capacitor electrode material Ni doped CoP3/foam nickel
CN113470983A (en) * 2020-03-30 2021-10-01 天津大学 Nickel selenide-nickelous diselenide nanorod composite material and preparation method and application thereof
CN112064060A (en) * 2020-09-21 2020-12-11 陕西科技大学 Nickel selenide/nickel iron substrate material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Meng et al. Highly conductive NiSe2 nanostructures for all-solid-state battery–supercapacitor hybrid devices
Lu et al. Improved electrochemical stability of NixCo2x (OH) 6x/NiCo2O4 electrode material
Ye et al. In-situ growth of Se-doped NiTe on nickel foam as positive electrode material for high-performance asymmetric supercapacitor
CN105513819A (en) Ni-Co double metal hydroxide nanometer sheet / N-doped carbon fiber hybrid material and preparation method thereof
CN102299306A (en) Nano-silicon composite lithium ion battery cathode material with poly (3,4-ethylenedioxythiophene) as coating and carbon source and preparation method thereof
Yan et al. Hierarchically porous carbon derived from wheat straw for high rate lithium ion battery anodes
Zhang et al. Preparation of MnO2 electrodes coated by Sb-doped SnO2 and their effect on electrochemical performance for supercapacitor
CN111689523B (en) Metallic chromium doped delta-MnO2Preparation method of nanosheet
Wang et al. Design bifunctional nitrogen doped flexible carbon sphere electrode for dye-sensitized solar cell and supercapacitor
CN110690057A (en) Nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material and preparation method and application thereof
CN108630445B (en) method for preparing supercapacitor carbon material from alkali-activated nitrogen-containing heterocyclic metal complex and application thereof
Tang et al. Enhancement in electrochemical performance of nitrogen-doped hierarchical porous carbon-based supercapacitor by optimizing activation temperature
Liu et al. Heterogeneous cobalt polysulfide leaf-like array/carbon nanofiber composites derived from zeolite imidazole framework for advanced asymmetric supercapacitors
Zeng et al. Asymmetric supercapacitors based on high capacitance Ni6MnO8 and graphene
Tong et al. Co2NiO4 nanoneedle networks for high performance pseudocapacitor
CN112490017A (en) Preparation method and application of NiCo-LDH nano material
CN111268745A (en) NiMoO4@Co3O4Core-shell nano composite material, preparation method and application
CN105206845B (en) One-step synthesis method has the S of excellent ORR and lithium electrical property, the meso-porous carbon material method of N synergies
He et al. Homogeneous coating of carbon nanotubes with tailored N-doped carbon layers for improved electrochemical energy storage
CN108597899A (en) NiSe for ultracapacitor2-Ni2O3Nanocomposite and preparation method thereof
He et al. Hierarchical tubular porous carbon derived from mulberry branches for long-life lead-carbon battery
Ji et al. High-performance MoO3 nanoplate electrode for asymmetric supercapacitor with long-term electrochemical stability
CN114724866A (en) Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof
Dai et al. Facile hydrothermal synthesis and their electrochemical performance of NiCo2O4 nanosheets
Yuan et al. High-voltage aqueous symmetric electrochemical capacitor based on Ru 0.7 Sn 0.3 O 2· nH 2 O electrodes in 1 M KOH

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