CN110745871A - Electrode material CuCo of bimetal sulfide super capacitor2S4Preparation method of (1) - Google Patents
Electrode material CuCo of bimetal sulfide super capacitor2S4Preparation method of (1) Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 64
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910016507 CuCo Inorganic materials 0.000 title description 54
- 238000000034 method Methods 0.000 title description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims 4
- 239000000243 solution Substances 0.000 claims 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims 2
- 239000002135 nanosheet Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000002071 nanotube Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910017816 Cu—Co Inorganic materials 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 6
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 5
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- 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
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Abstract
The invention discloses a bimetal sulfide super capacitor electrode material CuCo2S4The preparation method of the supercapacitor electrode material is characterized in that the supercapacitor electrode material is synthesized by a two-step hydrothermal method, the material is in a nanotube cluster structure, the thickness of the tube wall is thin, and the unique structure can provide more active sites for charge and ion transmission, so that excellent electrochemical performance is shown. The preparation method is simple, the production cost is low, the technology is environment-friendly, and the prepared electrode material has high specific capacitance and good electrochemical stability.
Description
Technical Field
The invention relates to preparation of a capacitor electrode material, in particular to a CuCo electrode material of a bimetallic sulfide super capacitor2S4The preparation method of (1).
Background
Although traditional fossil energy has been able to meet the needs of human survival and development for some time, the ever-increasing demands for energy and fossil fuels in humans have also raised environmental pollution problems. In addition, these fuels are non-renewable resources that have been substantially depleted by humans, and it has become important to research and discover efficient, clean, renewable resources. In this process, it becomes very important to produce a stable, mature and safe energy storage system, while the sustainable and renewable resources have the disadvantage of being intermittent and do not guarantee constant supply of electricity outside the grid. Renewable natural energy also has the problem of unbalanced land area distribution, and can not meet the normal requirement of human on energy. To solve these problems, there is a strong need for an efficient energy storage and conversion system to meet the demand of electricity during peak periods of electricity usage. In recent years, electrochemical energy storage and conversion systems such as supercapacitors, lithium ion rechargeable batteries, electrocatalysis and microelectronics have been extensively studied. Compared with a conventional capacitor, the super capacitor has the advantage of high energy density, and has higher energy density and higher power density compared with a battery. The unique electrochemical energy storage mechanism of supercapacitors gives them the ability to store and release large amounts of charge over a short period of time. As a novel energy storage device, the super capacitor is used for erecting a bridge between a battery and a conventional capacitor and is widely concerned by people. Its performance depends to a large extent on the kind of electrode material.
So far, metal sulfide has been widely studied as a good electrode material due to its advantages of high natural abundance, low cost, easy oxidation state change, high electrochemical activity, and the like. Transition metals such as copper, cobalt and the like also show good electrochemical performance as electrode materials, so that the nano material obtained by bimetallic vulcanization has abundant electroactive sites.
Under the contribution of transition metals such as copper, cobalt and the like, the bimetallic sulfide has higher conductivity than corresponding single-component oxides and sulfides, and is more favorable for energy storage and high-efficiency conversion.
Therefore, the research on the preparation method of the novel bimetallic sulfide supercapacitor electrode material is a problem which needs to be solved urgently.
Disclosure of Invention
The invention provides the CuCo electrode material of the bimetallic sulfide super capacitor, which has the advantages of simple preparation method, low production cost, environment-friendly technology, higher specific capacitance and good electrochemical stability2S4The preparation method of (1). In order to achieve the above purpose, the technical scheme of the invention is as follows:
electrode material CuCo of bimetal sulfide super capacitor2S4The preparation method comprises the following steps:
(1) dissolving cobalt chloride hexahydrate, copper chloride dihydrate and urea in deionized water, and uniformly stirring to obtain a precursor solution;
(2) adding the precursor solution prepared in the step (1) into a reaction kettle for hydrothermal reaction;
(3) after the reaction is finished, naturally cooling to room temperature, carrying out centrifugal washing and drying to obtain a precursor product;
(4) dissolving the precursor product obtained in the step (3) and sodium sulfide nonahydrate into deionized water, and uniformly stirring by using a magnetic stirrer;
(5) transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
(6) after the reaction is finished, naturally cooling to room temperature, centrifugally washing with distilled water and drying to obtain CuCo2S4And (3) nano materials.
The precursor solution in the step (1) is as follows: 2-5g of cobalt chloride hexahydrate, 0.75-1.85g of copper chloride dihydrate and 5-12.5g of urea, and dissolving the cobalt chloride hexahydrate, the copper chloride dihydrate and the urea in 320mL of deionized water;
the magnetic stirring time in the step (1) and the step (4) is 30-60 minutes;
the hydrothermal reaction conditions in the step (2) are as follows: placing the mixture in an oven to perform hydrothermal reaction at the temperature of 100 ℃ and 150 ℃ for 6-12 h;
the washing conditions in the step (3) and the step (6) are as follows: washing with deionized water for 3-5 times at 60-80 deg.C for 10-24 hr;
the electrode material CuCo of the bimetallic sulfide supercapacitor according to claim 12S4The preparation method is characterized by comprising the following steps: the amount of the sodium sulfide nonahydrate in the step (4) is 10-15 g.
The hydrothermal reaction conditions in the step (5) are as follows: placing the mixture in an oven to perform hydrothermal reaction at the temperature of 140 ℃ and 180 ℃ for 5-10 h.
Has the positive and beneficial effects that: the preparation method is simple, the production cost is low, the technology is environment-friendly, and the prepared electrode material has high specific capacitance and good electrochemical stability and shows good electrochemical activity. The electrode material synthesized in this experiment was CuCo2S4The electrode material is prepared by a hydrothermal method and the microstructure of the electrode material is characterized, the material is in a nano tube cluster type, and the unique microstructure can further increase the specific surface area of the electrode and active sites for Faraday redox reaction, promote ion diffusion and electron transport, greatly improve the wettability of the electrode and accelerate the electrolyte diffusion. Easy-to-permeate electrolyte and abundant and easy-to-access Faraday redox reaction active sites, so that CuCo2S4The nanotube cluster material has excellent electrochemical performance.
Drawings
FIG. 1 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4An X-ray diffraction pattern of the electrode material;
FIG. 2 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4An X-ray electron energy spectrum of the electrode material;
FIG. 3 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Scanning electron micrographs of the electrode material at different magnifications;
FIG. 4 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Cyclic voltammograms of the electrode material at different scanning rates in a three-electrode system;
FIG. 5 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4A charge-discharge curve diagram of the electrode material under different current densities in a three-electrode system;
FIG. 6 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4A capacitance multiplying power diagram of the electrode material in a three-electrode system;
FIG. 7 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Electrode material in three electrode system electrode cycle chart;
FIG. 8 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4An electrode alternating current impedance diagram of the electrode material in a three-electrode system;
FIG. 9 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4The sweep rate of the electrode material and the active carbon is 50 mV s-1A comparison graph of cyclic voltammograms over time;
FIG. 10 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4V/cyclic voltammograms of AC at different voltages;
FIG. 11 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4v/AC cyclic voltammogram at different sweep rates;
FIG. 12 is a diagram of the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4v/AC constant current discharge curves at different current densities;
FIG. 13 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4// AC capacitance magnification plot;
FIG. 14 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Asymmetric water system composed of electrode material and active carbonTwo-electrode CuCo2S4// cycle chart of AC.
FIG. 15 shows the bimetallic sulfide CuCo prepared in example 1 of the present invention2S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4// AC impedance plot;
Detailed Description
The invention is further described with reference to the following drawings and examples:
example 1
2.4g of cobalt chloride hexahydrate, 0.9g of copper chloride dihydrate and 6g of urea are weighed and dissolved in 150 mL of deionized water, and the mixture is magnetically stirred for 30 minutes to obtain a uniform solution. Then the reaction solution is transferred into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 8 hours at the temperature of 100 ℃. After the reaction is finished, naturally cooling to room temperature, centrifuging for a plurality of times by using deionized water, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the Cu-Co precursor.
Dissolving a Cu-Co precursor and 11g of sodium sulfide nonahydrate in 130mL of deionized water, uniformly stirring by using a magnetic stirrer, transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at 160 ℃. After the reaction is finished, naturally cooling to room temperature, centrifuging for a plurality of times by using distilled water, and drying for 10 hours in vacuum at the temperature of 60 ℃ to obtain CuCo2S4And (3) nano materials.
Example 2
3.6g of cobalt chloride hexahydrate, 1.35g of copper chloride dihydrate and 9g of urea are weighed and dissolved in 250 mL of deionized water, and a uniform solution is obtained after magnetic stirring for 45 minutes. Then the reaction solution is transferred into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 12 hours at the temperature of 150 ℃. After the reaction is finished, naturally cooling to room temperature, centrifuging for a plurality of times by using deionized water, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the Cu-Co precursor.
Dissolving a Cu-Co precursor and 13g of sodium sulfide nonahydrate in 130mL of deionized water, uniformly stirring by using a magnetic stirrer, transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 8 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature, centrifuging for a plurality of times by using distilled water, and then drying in vacuum at 60 ℃ for 10 hour later, CuCo can be obtained2S4And (3) nano materials.
Example 3
5g of cobalt chloride hexahydrate, 1.85g of copper chloride dihydrate and 12.5g of urea are weighed and dissolved in 250 mL of deionized water, and a uniform solution is obtained after magnetic stirring for 60 minutes. Then the reaction solution is transferred into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 12 hours at the temperature of 150 ℃. After the reaction is finished, naturally cooling to room temperature, centrifuging for a plurality of times by using deionized water, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the Cu-Co precursor.
Dissolving a Cu-Co precursor and 15g of sodium sulfide nonahydrate in 130mL of deionized water, uniformly stirring by using a magnetic stirrer, transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 10 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature, centrifuging for a plurality of times by using distilled water, and drying for 10 hours in vacuum at the temperature of 60 ℃ to obtain CuCo2S4And (3) nano materials.
Examples of the experiments
Taking example 1 as an example, the bimetallic sulfide CuCo of the invention2S4And carrying out structural characterization and electrochemical performance test on the electrode material.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The X-ray diffraction pattern of the electrode material is shown in fig. 1. The scanning speed is set to be 10 DEG/min, and the 2 theta angle is changed within the range of 3-90 deg. The figure shows CuCo2S4The material has obvious diffraction peaks near 26.586 degrees, 31.271 degrees, 37.966 degrees, 49.989 degrees, 54.793 degrees and the like, and CuCo2S4The peaks (022), (113), (004), (115) and (044) of (JCPDF cardno.42-1450) correspond to each other.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The X-ray electron energy spectrum of the electrode material is shown in FIG. 2. FIG. 2a shows an enlarged view of the spectral range of Cu2 p; FIG. 2b shows an enlarged view of the spectral range of Co2 p; FIG. 2c shows an enlarged view of the S2 p spectral range. The XPS spectrum of Cu2p has diffraction peaks at the binding energies of 931.88eV and 951.88eV, which respectively correspond to Cu2p3/2And Cu2p1/2(ii) a XPS spectra of Co2p at binding energies of 778.48eV and 79Diffraction peaks at 3.38eV corresponding to Co2p3/2And Co2p1/2(ii) a S2 p is decomposed into three components, centered at binding energies of 160.93eV, 162.01eV, and 163.33eV, respectively. FIG. 2d shows the CuCo prepared2S4A complete XPS survey of the material shows that the major peaks include Cu2p, Co2p, S2 p. According to XPS analysis results, the components of the sample prepared by the experiment are Cu, Co and S.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The scanning electron micrographs of the electrode materials at different magnifications are shown in FIG. 3. The figure shows that the material has a nanotube cluster structure, the thickness of the tube wall is thin, and the unique structure can provide more active sites for the transmission of charges and ions, so that excellent electrochemical performance is necessarily generated.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The cyclic voltammogram of the electrode material at different scan rates in a three-electrode system is shown in fig. 4. Research CuCo by cyclic voltammetry2S4Electrochemical performance of electrode in 0-0.6V range, 6M KOH as electrolyte water solution, and scanning rate of 10 mV s-1To 100 mV s-1In the range of (1), CuCo was tested2S4CV curve of the electrode. As can be seen from fig. 5, a pair of redox peaks are observed on all CV curves, indicating the faradaic behavior of the material, with the anodic and cathodic peaks moving in the lower and higher voltage directions, respectively, as the sweep rate increases.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The charge-discharge curve of the electrode material in a three-electrode system at different current densities is shown in fig. 5. Calculated at a current density of 1 mA cm-2Discharge time was about 2813.4 s, and battery capacity was 5626.8F g-1All constant current charge and discharge curves show better symmetry, indicating remarkable electrochemical reversibility.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The capacitance multiplying power diagram of the electrode material in the three-electrode system is shown in FIG. 6. The battery capacitance gradually decreases with increasing current density because ion diffusion limits its motion at high current density and only the outer surface of the active material can participate in energy storage, thereby reducing the utilization of the active material.
Bimetallic sulfide CuCo prepared in the invention of example 12S4Electrode materials electrode cycling profiles in a three-electrode system are shown in fig. 7. The cycling performance is an important characteristic of the electrode material of the supercapacitor. FIG. 7 is a graph showing the measurement at 10 mA cm-2Current density of CuCo2S4Cycle chart of the electrodes. It can be seen from the figure that at 10 mA cm-2At current density of (2), CuCo2S4The capacitance of the electrode can reach 4204F g-1After 5000 continuous constant current charge and discharge tests, the capacitance of the material is reduced to 3853.8F g-1The coulombic efficiency was about 91.67%. This indicates that CuCo2S4The material has good conductivity and stability.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The electrode ac impedance plot of the electrode material in a three-electrode system is shown in fig. 8. At an open circuit potential of 10-2-105The ac impedance test was performed in the frequency range of Hz. It can be seen from the figure that the pattern is semicircular in the high frequency region and linear in the low frequency region (Warburg resistance). Because the electrode material has a unique tubular structure, CuCo is improved2S4Capacitive properties of nanomaterials.
Bimetallic sulfide CuCo prepared in the invention of example 12S4The sweep rate of the electrode material and the active carbon is 50 mV s-1The cyclic voltammogram versus time is shown in fig. 9. The sweeping speed is 50 mV s-1The voltage range of the active carbon material is-1-0V, CuCo2S4CV curve of the material in the voltage interval of 0-0.6V. We can see that the maximum voltage of the two-electrode system is 1.6V.
Bimetallic sulfide CuCo prepared in the invention of example 12S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4The cyclic voltammogram for a different voltage window// AC is shown in FIG. 10. In FIG. 10a, CuCo changes the highest voltage when the sweep rate is determined2S4The CV curve area of the AC device increases along with the increase of the voltage interval, but the CV curve shape is basically unchanged, which shows that the device has good electrochemical stability in the voltage interval of 0-1.6V. As shown in FIG. 10b, CV curves of the device at 0.6-1.0V, 0.5-1.1V, 0.4-1.2V, 0.3-1.3V, 0.2-1.4V, 0.1-1.5V, and 0-1.6V were measured by varying the voltage interval at a certain sweep rate. The test shows that the CV area gradually increases with increasing voltage range, and the rectangular shape is stable without significant change, which indicates that CuCo2S4The maximum voltage of the AC device can reach 1.6V.
Bimetallic sulfide CuCo prepared in the invention of example 12S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4The cyclic voltammogram at different sweep rates is shown in FIG. 11. As can be seen from the figure, the areas of the CV curves are gradually increased along with the increase of the sweep speed, all the CV curves are similar to rectangles, and no oxidation-reduction peak appears in the potential range of 0-1.6V, which indicates that the device has better rate performance.
Bimetallic sulfide CuCo prepared in the invention of example 12S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4The plot of the galvanostatic discharge at different current densities is shown in FIG. 12. Respectively at a current density of 0.5 mA cm-2、1 mA cm-2、2 mA cm-2、3 mA cm-2、5 mA cm-2、10 mA cm-2、20 mA cm-2To CuCo2S4v/AC constant current discharge test was performed and the specific capacitance of the device at the corresponding current density was calculated. The current density was 0.5 mA cm-2The discharge time is about 348.77 s, and the specific capacitance is 108.99F g calculated based on the total mass of the two electrodes-1Description of two electrodes of asymmetric aqueous CuCo2S4// AC has good electrochemical properties.
Examples of the invention1 bimetallic sulfide CuCo prepared2S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4The capacitance magnification graph of// AC is shown in FIG. 13. For analyzing CuCo2S4Capacitance multiplying Performance at 0.5 mA cm/AC-2、1 mA cm-2、2 mA cm-2、3 mA cm-2、4 mA cm-2、5 mA cm-2、10 mA cm-2、20 mA cm-2The charge and discharge test result under the current density is calculated to obtain the specific capacitance of the capacitor under the corresponding current density, and the maximum specific capacitance is 108.99F g-1。
Bimetallic sulfide CuCo prepared in the invention of example 12S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4The cycle chart of// AC is shown in FIG. 14. At 10 mA cm-2The specific capacitance retention of the device is 84.76% after 5000 cycles of current density.
Bimetallic sulfide CuCo prepared in the invention of example 12S4Asymmetric aqueous two-electrode CuCo consisting of electrode material and activated carbon2S4The AC impedance plot of// AC is shown in FIG. 15. The semi-circle diameter in the figure reflects the charge transfer resistance, the intersection with the solid axis represents the dispersion resistance, and the radius before and after the cycle is smaller, indicating that CuCo2S4// AC has a lower ion transfer resistance. The smaller intercept of the curve intersecting the solid axis is seen in the ac impedance plot, indicating that the device has a lower charge transfer resistance and a lower dispersion resistance.
The preparation method is simple, the production cost is low, the technology is environment-friendly, and the prepared electrode material has high specific capacitance and good electrochemical stability and shows good electrochemical activity. The electrode material synthesized in this experiment was CuCo2S4The electrode material is prepared by a hydrothermal method and the microstructure of the electrode material is characterized, the material is in a nano tube cluster type, and the unique microstructure can further increase the specific surface area of the electrode and active sites for Faraday redox reaction, promote ion diffusion and electron transport, and greatly improve the stability of the electrode materialImprove the wettability of the electrode and accelerate the electrolyte diffusion. Easy-to-permeate electrolyte and abundant and easy-to-access Faraday redox reaction active sites, so that CuCo2S4The nanotube cluster material has excellent electrochemical performance.
Claims (7)
1. Bimetal sulfide supercapacitor electrode material Zn0.76Co0.24The preparation method of S is characterized by comprising the following steps:
(1) dissolving zinc acetate dihydrate and cobalt acetate tetrahydrate in deionized water, and uniformly stirring to obtain a pink mixed solution;
(2) introducing thiourea into the pink mixed solution obtained in the step (1), and continuously stirring to obtain a dark purple solution;
(3) adding the purple solution obtained in the step (2) into a reaction kettle for hydrothermal reaction;
(4) after the reaction is finished, naturally cooling to room temperature, centrifugally washing by using distilled water and ethanol and drying to obtain Zn0.76Co0.24And (4) S nano material.
2. The bimetallic sulfide supercapacitor electrode material Zn according to claim 10.76Co0.24The preparation method of S is characterized by comprising the following steps: the pink solution in the step (1) is as follows: 0.03-0.06g of zinc acetate dihydrate and 0.09-0.18g of cobalt acetate tetrahydrate are dissolved in 30-80mL of deionized water.
3. The bimetallic sulfide supercapacitor electrode material Zn according to claim 10.76Co0.24The preparation method of S is characterized by comprising the following steps: the stirring time in the step (1) is 60-90 minutes.
4. The bimetallic sulfide supercapacitor electrode material Zn according to claim 10.76Co0.24The preparation method of S is characterized by comprising the following steps: in the step (2), 0.08-0.18g of thiourea is used, and the stirring time is 30-60 minutes.
5. The bimetallic sulfide supercapacitor electrode material Zn according to claim 10.76Co0.24The preparation method of S is characterized by comprising the following steps: the hydrothermal reaction conditions in the step (3) are as follows: placing the mixture in an oven to perform hydrothermal reaction at the temperature of 160-200 ℃ for 20-30 h.
6. The bimetallic sulfide supercapacitor electrode material Zn according to claim 10.76Co0.24The preparation method of S is characterized by comprising the following steps: the washing conditions in the step (4) are as follows: washing with deionized water and ethanol for 3-5 times at 60-80 deg.C for 10-24 hr.
7. The bimetallic sulfide supercapacitor electrode material Zn of claim 10.76Co0.24The electrode material prepared by the preparation method of S is characterized in that: the material is in a uniformly dispersed lamellar structure, the thickness of the lamellar is thin, the nanosheets are mutually connected to form a porous structure, and the unique structure can provide more active sites for the transmission of charges and ions.
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