CN113023665A - Carbon fiber cloth loaded nano needle-shaped nickel-cobalt double-metal selenide crystal array film and preparation method thereof - Google Patents
Carbon fiber cloth loaded nano needle-shaped nickel-cobalt double-metal selenide crystal array film and preparation method thereof Download PDFInfo
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- CN113023665A CN113023665A CN202110244978.2A CN202110244978A CN113023665A CN 113023665 A CN113023665 A CN 113023665A CN 202110244978 A CN202110244978 A CN 202110244978A CN 113023665 A CN113023665 A CN 113023665A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000004744 fabric Substances 0.000 title claims abstract description 61
- 239000013078 crystal Substances 0.000 title claims abstract description 49
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 45
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 23
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 24
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 18
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000011669 selenium Substances 0.000 claims description 13
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/04—Networks or arrays of similar microstructural devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00111—Tips, pillars, i.e. raised structures
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Analytical Chemistry (AREA)
- Nanotechnology (AREA)
- Computer Hardware Design (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon fiber cloth loaded nanometer needle-shaped nickel-cobalt double-metal selenide crystal array film and a preparation method thereof. The preparation method mainly comprises the following steps: firstly, using soluble nickel salt, soluble cobalt salt and selenium powder as raw materials, namely activated carbon fiber cloth as a substrate, preparing a precursor of the nano needle-shaped nickel-cobalt double-metal selenide film by a hydrothermal method, and then carrying out heat treatment on the precursor under the protection of inert gas to obtain the nano needle-shaped nickel-cobalt double-metal selenide crystal array film. The preparation method of the needle-shaped crystal array film disclosed by the invention has the characteristics of simple process and easiness in operation; the nickel-cobalt double-metal selenide crystal film is directly combined with the activated carbon fiber cloth through the end point of the low-dimensional array, so that the active sites can be increased, and the conductivity and the stability of the material can be improved. The nano needle-shaped nickel-cobalt double-metal selenide crystal array film has wide application prospect in the fields of energy storage, catalysis and the like.
Description
Technical Field
The invention relates to a compound semiconductor film, in particular to a carbon fiber cloth loaded nanometer needle-shaped nickel-cobalt double-metal selenide crystal array film and a preparation method thereof.
Background
The nano selenide is a semiconductor material with excellent performance, and has wide application prospect in the fields of functional materials such as optics, electromagnetism, optoelectronics, nonlinear optics, nonlinear thermology, biomedicine and the like. Transition metal selenides, M, as non-stoichiometric proportionsxSe (M ═ Ni, Co and Mn) has a special electronic configuration, rich unsaturated bonds and a phase stable at room temperature, shows a large number of electrochemically active sites and high-speed charge transfer channels, and becomes a potential energy storage and catalysis material.
At present, transition metal selenides are mainly made of powder materials. Zhao et al prepared a nickel-cobalt selenide nanoparticle as an electrocatalyst for water decomposition by a simple two-step solvothermal method. The cheap and easy-to-prepare electrocatalyst has a current density of 10mV/cm2Exhibits excellent OER activity, and the electrocatalyst also exhibits excellent durability, which can last for 10 hours, under chronoamperometric testing. [ NiCo-selenidide as a novel catalyst for water oxidation [ J ]].Journal of Materials Science,2016,51(8):3724-3734.]
But the nano powder can generate agglomeration phenomenon in the processes of preparation, separation, treatment and storage, which leads to the performance reduction of the nano powder material. The preparation of the nano particles into the low-dimensional array material is an effective way to solve the agglomeration problem. Researchers have therefore begun to focus on the development of transition metal selenide thin film materials. Gong et al use foamed nickel as a substrate and adopt a hydrothermal method to synthesize high-performance Ni on the surface of the foamed nickel0.85The specific capacity of the Se electrode material can reach 1115F/g at most under the condition of 1A/g charge and discharge, and the specific capacity is only reduced by 8.3 percent after 1000 times of cyclic charge and discharge. [ Gong C, Huang M, Zhang J, et al.A. face synthesis of Ni0.85Se on Ni foam for high-performance asymmetry capacitor [ J].Rsc Advances,2015,5(99):81474-81481.]. Abhik Banerjee synthesizes Co with compact self-weaving on conductive carbon fiber paper0.85Se hollow nanowire with area ratio capacitance values of 929.5mF/c and 600mF/cm2The retention Rate reaches 60% [ Abhik, Banerjee, Sumit, et al. Hollow Co0.85Se Nanowire Array on Carbon Fiber Paper for High Rate pseudo-ocapitor[J].ACS Applied Materials&Interfaces,2014,6(21):18844-18852.]。
Selenides containing two or more transition metals exhibit better electrochemical performance than monometallic selenides. Chen et al prepared NiSe-CoSe nanoparticles with different Ni/Co ratios through hydrothermal reaction, the specific capacitance of the NiSe-CoSe nanoparticles can reach 584F/g at a current density of 1A/g, and the capacity of the NiSe-CoSe nanoparticles can still be kept at about 77.3% at a current density of 20A/g.
At present, the research reports of the double transition metal selenide crystal film with the low-dimensional array structure are less common. The low-dimensional array structure directly grows on the surface of the substrate material, so that the process steps of slurry mixing and coating in the traditional electrode preparation process are omitted, and the use of a binder and a conductive agent is avoided. The low-dimensional array structure film provides a high-speed conduction channel for ions and electrons; meanwhile, the gaps among the nano arrays provide sufficient space for volume change in the charging and discharging process, so that the stability of the structure is kept, the electrolyte is fully infiltrated, and the utilization rate of active substances is improved. Various factors enable the double transition metal selenide crystal thin film material to have better electrochemical performance than the traditional material.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a carbon fiber cloth loaded nanometer needle-shaped nickel-cobalt double-metal selenide crystal array film and a preparation method thereof. The preparation method fully utilizes the porous surface of the activated carbon fiber, and provides a large number of nucleation centers for the heterogeneous nucleation crystallization of the crystal on the surface of the activated carbon fiber; by utilizing the strong reduction effect of hydrazine hydrate, selenium element is introduced into the reaction in an ion state, so that the reaction efficiency of the selenium source is improved; optimizing the ratio of nickel to cobalt to form a single phase bimetallic selenide; combining the adjustment of reactant concentration, reaction time and heat treatment parameters, the nickel-cobalt double-metal selenide crystal preferentially crystallizes on the surface of the activated carbon fiber, and then grows anisotropically to form a nanometer needle-like shape.
The invention designs a stable hydrothermal reaction system, and through comprehensive optimization of reaction parameters, the selenium-containing nickel-cobalt bimetallic compound is promoted to form a compact and uniform needle array on the surface of the activated carbon fiber by a one-step method, and the regularity of atomic arrangement is enhanced through subsequent heat treatment to obtain the nickel-cobalt bimetallic selenide compound. The reaction system and parameters accurately control the crystal growth process and promote the formation of anisotropic low-dimensional nano needle-like crystal morphology.
The technical scheme adopted by the invention is as follows:
a carbon fiber cloth loaded nanometer needle-shaped nickel-cobalt double-metal selenide crystal array film comprises: the carbon fiber cloth is loaded with nickel-cobalt double-metal selenide crystals; the nickel-cobalt double-metal selenide crystal is needle-shaped, has the length of 5-10 micrometers and the diameter of 200-300 nanometers, and is densely and uniformly grown on the carbon fiber.
A preparation method of a carbon fiber cloth loaded nanometer needle-shaped nickel-cobalt double-metal selenide crystal array film comprises the following steps:
(1) dissolving soluble nickel salt and soluble cobalt salt in deionized water, and stirring to obtain a uniform solution A;
(2) dissolving selenium powder in a hydrazine hydrate solution, and performing ultrasonic stirring to obtain a uniform solution B;
(3) stirring the solution A by using a magnetic stirrer, dropwise adding the solution B into the vigorously stirred solution A by using a dropper, and continuously stirring for 30min to obtain a uniform solution C;
(4) immersing the activated carbon fiber cloth in the solution C obtained in the step (3) for 5 hours;
(5) transferring the solution soaked in the step (4) and activated carbon fiber cloth into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out closed reaction for 12-24 hours at 150-180 ℃;
(6) after the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber cloth, washing the activated carbon fiber cloth with distilled water and ethanol in sequence, and drying the activated carbon fiber cloth at 60-90 ℃ for 8 hours in vacuum;
(7) and (3) under the protection of argon or nitrogen, carrying out heat treatment on the activated carbon fiber cloth obtained by drying in the step (6) at the temperature of 300-350 ℃ for 1h to obtain the nano needle-shaped nickel-cobalt double-metal selenide crystal array film on the surface of the activated carbon fiber cloth.
In the step 1), the soluble nickel salt is one of nickel nitrate, nickel chloride or nickel acetate; the soluble cobalt salt is one of cobalt nitrate, cobalt chloride or cobalt acetate.
In the step 1), the total molar concentration of the nickel ions and the cobalt ions is 0.10-0.20 mol/L, and the molar concentration ratio of the nickel ions to the cobalt ions is 1: 1.
The selenium content in the solution B in the step 2) is 0.2 mol/L.
In the step 2), the hydrazine hydrate solution is a mixed solution of hydrazine hydrate (the volume percentage of the hydrazine hydrate is 85%) and deionized water in a volume ratio of 1: 1.
In the step 3), the rotating speed of the magnetic stirrer is 2000 r/min.
In the step 4), the activated carbon fiber cloth is obtained by performing heat treatment on natural cotton fiber cloth for 1 hour at 1000 ℃ in a nitrogen atmosphere.
The invention has the beneficial effects that:
1) the film has high specific surface area of low-dimensional material characteristics, is combined with the conductive substrate in an adhesive-free mode, effectively improves the electron transmission efficiency, and greatly improves the application value of the film material in an energy storage device. On the other hand, the degeneracy of the double transition metal d orbit plays a key role in the processes of gain and loss of electrons and bonding, and plays a positive role in improving the catalytic capability of the double transition metal d orbit.
2) The carbon fiber cloth loaded nanometer needle-shaped nickel-cobalt double-metal selenide crystal array film electrode material prepared by the invention is applied to a super capacitor, and test results show that the electrode material of the invention has high-efficiency pseudocapacitance performance and specific capacitance, particularly the nickel-cobalt ratio is 1: the electrochemical performance of the electrode material prepared under the condition of hydrothermal reaction for 12 hours at the temperature of 1,180 ℃ is optimal.
3) The invention utilizes a high-temperature high-pressure wet chemical environment formed by a hydrothermal reaction system, realizes the formation of the nickel-cobalt double-metal selenide into a nanometer needle-shaped appearance by adjusting reaction parameters, and forms a continuous film by densely arranging the nickel-cobalt double-metal selenide on the surface of the activated carbon fiber cloth in an array form. Hydrazine hydrate is selected to reduce a selenium source into an ionic form to enter a solution system, nitrogen on hydrazine molecules is coordinated with a vacant track in a d region of nickel-cobalt ions by utilizing lone pair electrons, and the formation of a low-dimensional needle-shaped appearance is induced in a guiding manner; the porous structure on the surface of the activated carbon fiber provides a large number of nucleation micro-areas for crystallization, reduces the activation energy of crystal nucleation reaction, and leads the crystal to form a film by preferential heterogeneous nucleation; the hydrothermal reaction temperature is adjusted to 170 ℃, the crystal growth speed is controlled, and the low-dimensional anisotropic growth of the crystal to the micron-sized length is facilitated; the amount of nickel and cobalt substances is reasonably proportioned, and heat treatment parameters are finely regulated to form the nickel and cobalt double-metal selenide with a single phase.
4) The hydrothermal synthesis path disclosed by the invention obtains the nano needle-shaped crystal array film through one-step wet chemical reaction, and the preparation process is simple and the conditions are mild. And the subsequent heat treatment at a lower temperature is carried out to obtain a pure phase, so that the method has low energy consumption and low cost and is suitable for industrial production.
Drawings
Figure 1 is the XRD pattern of the product obtained in example 1.
FIG. 2 is an electron micrograph of the product obtained in example 1.
FIG. 3 is an X-ray spectral analysis (EDS) of the product obtained in example 1.
FIG. 4 is a cyclic voltammogram of the product obtained in example 1.
FIG. 5 is a constant current charge and discharge curve diagram of the product obtained in example 1.
FIG. 6 is an AC impedance spectrum of the product obtained in example 1.
FIG. 7 is a graph showing the cycle stability test of the product obtained in example 1.
FIG. 8 is an electron micrograph of a product obtained in example 2.
FIG. 9 is an electron micrograph of a product obtained in example 3.
Detailed Description
The carbon fiber cloth loaded nanometer needle-shaped nickel cobalt double metal selenide crystal array film is characterized in that the diameter of the nanometer needle-shaped nickel cobalt double metal selenide crystal is 200-300 nanometers, the length of the nanometer needle-shaped nickel cobalt double metal selenide crystal is 5-10 micrometers, and the nanometer needle-shaped nickel cobalt double metal selenide crystal array film is formed by dense arrangement in an array form. The nickel-cobalt double-metal selenide crystal film is directly combined with the activated carbon fiber cloth through the end point of the low-dimensional array, so that the active sites can be increased, and the conductivity and the stability of the material can be improved. The nano needle-shaped nickel-cobalt double-metal selenide crystal array film has wide application prospect in the fields of energy storage, catalysis and the like.
Example 1:
0.4759g CoCl2.6H2O and 0.4753g NiCl2.6H2Dissolving O in 20mL of deionized water, and stirring to obtain a uniform mixed solution A, wherein the total molar concentration of nickel ions and cobalt ions is 0.20 mol/L, and the molar concentration ratio of the nickel ions to the cobalt ions is 1: 1. 0.3159g selenium powder is dissolved in 20mL hydrazine hydrate solution to obtain mixed solution B, wherein the selenium content is 0.2 mol/L, and the hydrazine hydrate solution is formed by uniformly mixing 10mL (85%) hydrazine hydrate solution and 10mL deionized water; slowly and dropwise adding the mixed solution B into the mixed solution A which is stirred vigorously, and carrying out ultrasonic treatment for 30min to obtain a uniform solution C; immersing the activated carbon fiber cloth in the solution C for 5 hours; then transferring the solution C together with the activated carbon fiber cloth into a stainless steel autoclave with 85mL of polytetrafluoroethylene lining, and carrying out closed reaction for 12 hours at the temperature of 180 ℃; after the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber cloth, washing the activated carbon fiber cloth by using distilled water and ethanol in sequence, and drying the activated carbon fiber cloth for 8 hours at 90 ℃; under the protection of argon, the dried activated carbon fiber cloth is subjected to heat treatment at 350 ℃ for 1 hour to obtain the nano needle-shaped nickel-cobalt double-metal selenide crystal array film growing on the surface of the activated carbon fiber cloth.
FIG. 1 is the XRD pattern of the product of example 1 showing the characteristic diffraction peaks of the crystalline material and CoNiSe2The standard XRD spectrogram (JCPDS No 70-2851) is matched, the diffraction peak intensity of the sample is larger, and the half-peak width is smaller, which shows that the prepared nano needle-shaped nickel-cobalt double-metal selenide crystal array film sample has higher crystallinity.
FIG. 2 is an electron micrograph of the product of example 1, NiCoSe was formed on the surface of activated carbon fiber2The nanometer needle crystal array film has the advantages that the size of the needles is uniform, the diameter is 200-300 nanometers, the length is 5-10 micrometers, and the needles are densely distributed on the surface of the fiber in an array form.
FIG. 3 is an X-ray energy spectrum analysis (EDS) of the product of example 1, with Ni, Co and Se in each sampleThe atomic contents of the components are 25.46 percent, 29.05 percent and 45.49 percent respectively, and the components basically conform to NiCoSe2The formula ratio.
The electrode material of the nano needle-shaped nickel-cobalt double-metal selenide crystal array film super capacitor prepared by the embodiment is subjected to a three-electrode system test, and fig. 4 is a cyclic voltammogram thereof. At 2 mol. L-1Under the KOH electrolyte, a pair of obvious redox peaks can be seen in a cyclic voltammetry curve obtained by the electrode material, and the redox peaks move to a positive potential and the reduction peaks move to a negative potential along with the increase of the scanning rate, which is mainly caused by the potential jump generated by a galvanic couple layer formed when an electron conductor is contacted with the electrolyte and the increase of the internal resistance of the active material under the high scanning rate, so that the redox peaks are separated. The surface electrode material is 2 mV.s-1To 30 mV. s-1Exhibits good pseudocapacitance behavior at the scan rate of (a). FIG. 5 is a constant current charge/discharge curve picture at 2 mol. L-1With KOH electrolyte, current densities of 2, 5, 10, 20 and 50mA cm-2The composite electrodes exhibited 1513.6, 1421.3, 1254.1, 1102.9 and 967.4F-g-1The high specific capacity of the catalyst shows good electrochemical performance. FIG. 6 is an AC impedance spectrum at 2 mol. L-1In the KOH electrolyte solution (2), the internal resistance of the solution of the composite electrode in the test process is 0.5 omega, and the charge transfer resistance is 2.3 omega. FIG. 7 is a graph showing the test of the cycle stability of the polymer at 10mA cm-2Under the current density, after 1000 charge-discharge cycles, the composite electrode still retains 84.3 percent of the original capacitance value, and shows good cycle stability.
Example 2:
0.2379g CoCl2 .6H2O and 0.2377g NiCl2 .6H2Dissolving O in 20mL of deionized water, and stirring to obtain a uniform mixed solution A, wherein the total molar concentration of nickel ions and cobalt ions is 0.10 mol/L, and the molar concentration ratio of the nickel ions to the cobalt ions is 1: 1. 0.3159g selenium powder is dissolved in 20mL hydrazine hydrate solution to obtain mixed solution B, wherein the selenium content is 0.2 mol/L, and the hydrazine hydrate solution is formed by uniformly mixing 10mL (85%) hydrazine hydrate solution and 10mL deionized water; mixing the solutionSlowly dropwise adding the solution B into the mixed solution A which is stirred vigorously, and carrying out ultrasonic treatment for 30min to obtain a uniform solution C; immersing the activated carbon fiber cloth in the solution C for 5 hours; then transferring the solution C together with the activated carbon fiber cloth into a stainless steel autoclave with 85mL of polytetrafluoroethylene lining, and carrying out closed reaction for 24 hours at the temperature of 150 ℃; after the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber cloth, washing the activated carbon fiber cloth by using distilled water and ethanol in sequence, and drying the activated carbon fiber cloth for 8 hours at the temperature of 60 ℃; and (3) carrying out heat treatment on the dried activated carbon fiber cloth at 300 ℃ for 1 hour under the protection of argon to obtain the nano needle-shaped nickel-cobalt double-metal selenide crystal array film growing on the surface of the activated carbon fiber cloth.
FIG. 8 is an electron micrograph of the product of example 2, NiCoSe2The diameter of the nano needle particles is 100-150 nanometers, the length is 5-10 micrometers, and the nano needle particles are uniformly distributed on the activated carbon fiber.
Example 3:
0.4759g CoCl2.6H2O and 0.4753g NiCl2.6H2Dissolving O in 20mL of deionized water, and stirring to obtain a uniform mixed solution A, wherein the total molar concentration of nickel ions and cobalt ions is 0.20 mol/L, and the molar concentration ratio of the nickel ions to the cobalt ions is 1: 1. 0.3159g selenium powder is dissolved in 20mL hydrazine hydrate solution to obtain mixed solution B, wherein the selenium content is 0.2 mol/L, and the hydrazine hydrate solution is formed by uniformly mixing 10mL (85%) hydrazine hydrate solution and 10mL deionized water; slowly and dropwise adding the mixed solution B into the mixed solution A which is stirred vigorously, and carrying out ultrasonic treatment for 30min to obtain a uniform solution C; immersing the activated carbon fiber cloth in the solution C for 5 hours; then transferring the solution C together with the activated carbon fiber cloth into a stainless steel autoclave with 85mL polytetrafluoroethylene lining, and carrying out closed reaction for 18 hours at the temperature of 165 ℃; after the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber cloth, washing the activated carbon fiber cloth by using distilled water and ethanol in sequence, and drying the activated carbon fiber cloth for 8 hours at 90 ℃; and (3) carrying out heat treatment on the dried activated carbon fiber cloth at 350 ℃ for 1 hour under the protection of nitrogen to obtain the nano needle-shaped nickel-cobalt double-metal selenide crystal array film growing on the surface of the activated carbon fiber cloth.
FIG. 9 is an electron micrograph of the product of example 3, NiCoSe2The diameter of the nano needle particle is 200-300 nanometers, the length is 5-8 micrometers, and the nano needle particle is uniformly distributed on the activated carbon fiber.
Claims (8)
1. A carbon fiber cloth load nanometer needle-like nickel cobalt bimetal selenide crystal array film is characterized in that: the carbon fiber cloth is loaded with nickel-cobalt double-metal selenide crystals; the nickel-cobalt double-metal selenide crystal is needle-shaped, has the length of 5-10 micrometers and the diameter of 200-300 nanometers, and is densely and uniformly grown on the carbon fiber.
2. The preparation method of the carbon fiber cloth-supported nano needle-shaped nickel cobalt double metal selenide crystal array film as claimed in claim 1, which is characterized by comprising the following steps:
(1) dissolving soluble nickel salt and soluble cobalt salt in deionized water, and stirring to obtain a uniform solution A;
(2) dissolving selenium powder in a hydrazine hydrate solution, and performing ultrasonic stirring to obtain a uniform solution B;
(3) stirring the solution A by using a magnetic stirrer, dropwise adding the solution B into the vigorously stirred solution A by using a dropper, and continuously stirring for 30min to obtain a uniform solution C;
(4) immersing the activated carbon fiber cloth in the solution C obtained in the step (3) for 5 hours;
(5) transferring the solution soaked in the step (4) and activated carbon fiber cloth into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out closed reaction for 12-24 hours at 150-180 ℃;
(6) after the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber cloth, washing the activated carbon fiber cloth with distilled water and ethanol in sequence, and drying the activated carbon fiber cloth at 60-90 ℃ for 8 hours in vacuum;
(7) and (3) under the protection of argon or nitrogen, carrying out heat treatment on the activated carbon fiber cloth obtained by drying in the step (6) at the temperature of 300-350 ℃ for 1h to obtain the nano needle-shaped nickel-cobalt double-metal selenide crystal array film on the surface of the activated carbon fiber cloth.
3. The preparation method of the carbon fiber cloth-loaded nano needle-shaped nickel cobalt double metal selenide crystal array film according to claim 2, characterized in that: in the step 1), the soluble nickel salt is one of nickel nitrate, nickel chloride or nickel acetate; the soluble cobalt salt is one of cobalt nitrate, cobalt chloride or cobalt acetate.
4. The preparation method of the carbon fiber cloth-loaded nano needle-shaped nickel cobalt double metal selenide crystal array film according to claim 2, characterized in that: in the step 1), the total molar concentration of the nickel ions and the cobalt ions is 0.10-0.20 mol/L, and the molar concentration ratio of the nickel ions to the cobalt ions is 1: 1.
5. The preparation method of the carbon fiber cloth-loaded nano needle-shaped nickel cobalt double metal selenide crystal array film according to claim 2, characterized in that: the selenium content in the solution B in the step 2) is 0.2 mol/L.
6. The preparation method of the carbon fiber cloth-loaded nano needle-shaped nickel cobalt double metal selenide crystal array film according to claim 2, characterized in that: in the step 2), the hydrazine hydrate solution is a mixed solution of hydrazine hydrate and deionized water in a volume ratio of 1: 1.
7. The preparation method of the carbon fiber cloth-loaded nano needle-shaped nickel cobalt double metal selenide crystal array film according to claim 2, characterized in that: in the step 3), the rotating speed of the magnetic stirrer is 2000 r/min.
8. The preparation method of the carbon fiber cloth-loaded nano needle-shaped nickel cobalt double metal selenide crystal array film according to claim 2, characterized in that: in the step 4), the activated carbon fiber cloth is obtained by performing heat treatment on natural cotton fiber cloth for 1 hour at 1000 ℃ in a nitrogen atmosphere.
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