CN110950391B - Hollow cubic Ni3S4/CuS2Preparation method and application of electrode material of super capacitor - Google Patents
Hollow cubic Ni3S4/CuS2Preparation method and application of electrode material of super capacitor Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 13
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000013543 active substance Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 80
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
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- 239000007864 aqueous solution Substances 0.000 claims description 32
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- 239000011449 brick Substances 0.000 claims description 24
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- 238000001035 drying Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
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- 238000003860 storage Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 230000002238 attenuated effect Effects 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 239000011796 hollow space material Substances 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal sulfides Chemical class 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
The invention discloses a hollow cubic Ni3S4/CuS2The preparation method and the application of the electrode material of the super capacitor comprise a precursor Cu in the process2O, intermediate Ni (OH)2/CuS2And hollow cubic structure Ni3S4/CuS2The preparation method of (1); the invention synthesizes Cu by a low-temperature-wet chemical method2O cube, and Cu2O cubes as precursors, hollow cubic Ni (OH) synthesized by sacrificial template method2/CuS2Finally hydrothermally sulfurizing to obtain Ni3S4/CuS2A composite material. The preparation method provided by the invention is simple, the synthesis condition is mild and controllable, the repeatability is good, the material cost is low, and the large-scale production and application are easy. Prepared Ni of hollow cubic structure3S4/CuS2The electrode material is used as an electrode active substance of a super capacitor, and has large charge storage capacity and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of capacitors, and particularly relates to hollow cubic Ni3S4/CuS2A preparation method and application of a super capacitor electrode material.
Background
Due to the advantages of high power density, short charging time, long cycle life and the like, research on the super capacitor is widely concerned by researchers. The super capacitor may be classified into an electric double layer capacitor and a pseudo capacitor according to a charge and discharge mechanism. The double-layer capacitor has good cycle performance, the cycle life can reach 10000 circles, but the energy density of the double-layer capacitor is lower. The pseudocapacitive capacitor has a high energy density but poor cycling performance. How to develop supercapacitors with both high energy density and long cycle life has become a matter of diligent research.
Metal sulfides (sulfides such as Co, Ni, Fe, Zn, etc.) are receiving attention because of their good redox reactions, structural flexibility, and low cost, and are expected to be electrode materials for pseudo-capacitors. However, the single-metal and single-structure transition metal sulfides have low conductivity, resulting in low specific capacitance and energy density, and particularly at high rate, such disadvantages are particularly significant, thereby limiting the application of the single-metal and single-structure transition metal sulfides in capacitors. How to improve the conductivity of the material is the key to solve these problems. The greatest initial intention of the composite material is to make up for the deficiencies, synergistically exert the respective advantages of improving the comprehensive performance of the material, for example, utilize the high specific capacitance of transition metal oxides and conductive polymers, utilize the relative large specific area of carbon materials and transition metal sulfides and the stability in the charging and discharging processes, exert the respective advantages of the materials, optimize the comprehensive performance of the material and improve the cost performance of the material so as to realize industrial production.
The porous material with a unique structure can be prepared by a template method. The template method has the advantages of simple operation, good reproducibility and the like. The sacrificial template method is a special type of template method, and is different from the traditional template method in that the sacrificial template method not only serves as particles in a reaction template, but also can serve as reactants to participate in the construction process of a structure. The sacrificial template may directly determine the shape and size of the fabricated material structure and may eventually be partially or completely consumed. The method generally does not need to carry out additional surface functionalization treatment on the template, and is simpler and more efficient.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides hollow cubic Ni3S4/CuS2A preparation method and application of a super capacitor electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
hollow cubic Ni3S4/CuS2Preparation method of super capacitor electrode material with Cu2Synthesis of hollow cubic Ni (OH) from O cubes as precursors by sacrificial template method2/CuS2Then obtaining hollow cubic Ni through one-step hydrothermal vulcanization3S4/CuS2。
Hollow cubic Ni3S4/CuS2The preparation method of the electrode material of the super capacitor comprises the following steps:
S1、Cu2preparing an O precursor template:
aqueous NaOH (10.0 mL, 2.0M) was added dropwise to CuCl2▪2H2Magnetically stirring the mixed solution in an O (100 mL, 0.01M) aqueous solution for 30min, gradually changing the color of the solution into black brown along with the progress of reaction time, then dripping an ascorbic acid (10.0 mL, 0.6M) aqueous solution into the black brown solution, gradually changing the color of the solution into brick red along with the addition of the ascorbic acid, continuously stirring the mixed solution after dripping the ascorbic acid for 3h, finally centrifuging the suspension after reaction to obtain brick red precipitate, washing the precipitate for a plurality of times by deionized water and ethanol, and then drying in vacuum to obtain Cu2O；
S2、Ni(OH)2/CuS2Preparing a nano hollow cubic structure:
PVP (3.33 g) and Cu2O (100 mg) and NiCl2·6H2O (17 mg) is mixed, 100mL of deionized water and ethanol mixed solution with the volume ratio of 1:1 is added into the mixture, and ultrasonic dispersion is carried out for 30min to ensure that the mixture is completely dissolved; then adding Na2S2O3(40.0 mL, 1.0M) aqueous solution was added to the above solution and stirring was continued for 10min with Na2S2O3Adding the solution, wherein the color of the solution gradually changes from brick red to bright green; finally, centrifuging the suspension after reaction to obtain precipitate, washing the precipitate for a plurality of times by using deionized water and ethanol, and then drying in vacuum to obtain Ni (OH) with a hollow cubic structure2/CuS2A nanomaterial;
S3、Ni3S4/CuS2preparing a nano hollow cubic structure:
mixing the Ni (OH) synthesized in step S22/CuS2(1.25 mmol) and thiourea (6.25 mmol) are uniformly dispersed in a mixed solution of ethanol and deionized water (the volume ratio is 1:1, and the total volume is 30 mL); then transferring the mixed solution into a clean reaction kettle, sealing, placing the reaction kettle in a forced air drying oven for hydrothermal reaction, and keeping the temperature at 160 ℃ for 12-36 h; finally, centrifugally collecting the reacted suspension, washing the precipitate for a plurality of times by using ethanol and deionized water, and then drying in vacuum to obtain the hollow cubic Ni3S4/CuS2The powder of (4).
Further, in step S1, an aqueous NaOH solution and CuCl are added2▪2H2The concentrations of O aqueous solution and ascorbic acid aqueous solution were 2M, 0.01M and 0.6M, respectively, NaOH aqueous solution and CuCl2▪2H2The dosage of the O aqueous solution and the ascorbic acid aqueous solution is 10.0mL, 100mL and 10.0mL respectively; in step S1, all reactions were at 55oAnd C, performing in a water bath.
Further, in step S2, PVP and Cu are added2O and NiCl2·6H2The mass of O is 3.33g, 100mg and 17mg respectively, the volume ratio of deionized water to ethanol is 1:1, the total amount of deionized water and ethanol is 100mL, Na2S2O3The concentration of the aqueous solution was 1M, Na2S2O3The dosage of the aqueous solution is 40.0 mL; the whole process of step S2 is completed at room temperature.
Further, in the step S3, Ni (OH)2/CuS2And the dosage of thiourea is 1.25mmol and 6.25mmol respectively, the volume ratio of deionized water to ethanol is 1:1, the total amount of deionized water and ethanol is 30mL, the temperature of the hydrothermal reaction is 160 ℃, and the temperature is kept at 160 ℃ for 12-36 h.
Further, in the steps S1, S2 and S3, the temperature of vacuum drying is 80 ℃, and the drying time is 24 hours.
Hollow cubic Ni prepared based on preparation method3S4/CuS2Use of supercapacitor electrodes, hollow cubic Ni3S4/CuS2Used for manufacturing electrodes.
Further, the preparation method of the electrode comprises the following steps:
hollow cubic Ni3S4/CuS2As an active material, acetylene black is used as a conductive agent, polyvinylidene fluoride is used as a binder, and the weight ratio of the acetylene black to the polyvinylidene fluoride is 8: 1:1, dissolving the mixture in N-methyl pyrrolidone, and grinding the mixture to prepare homogeneous mixed slurry; immersing the foamed nickel cut into the size of 1 × 2cm into the mixed slurry, uniformly coating the mixed slurry on the surface of the foamed nickel, then placing the coated nickel net in a vacuum drying oven for drying, and finally pressing the nickel net into an electrode plate by using a tablet press.
Further, the mass-volume ratio of the active substance to the N-methylpyrrolidone is 20 mg:2.5 mL.
Specifically, the mass of the active substance was 20mg, the volume of N-methylpyrrolidone was 2.5mL, and the amounts of acetylene black and polyvinylidene fluoride were each 2.5 mg.
Further, in the preparation method of the electrode, the temperature of vacuum drying is 80 ℃, the drying time is 12h, the pressure of the tablet press during tabletting is 10MPa, and the duration time is 60 s.
Further, hollow cubic Ni3S4/CuS2The prepared electrode is used for preparing a super capacitor.
Compared with the prior art, the invention has the following beneficial effects:
the invention synthesizes Cu by a low-temperature-wet chemical method2O cube, and Cu2O cubes as precursors, hollow cubic Ni (OH) synthesized by sacrificial template method2/CuS2Finally hydrothermally sulfurizing to obtain Ni3S4/CuS2A composite material. The method can well keep the shape of the precursor and prepare the hollow bimetallic sulfide with a unique structure. The synergistic effect between the two metals of the bimetal sulfide and the enhanced oxidation state can effectively improve the conductivity of the active material, and simultaneously, the unique hollow structure has a great degree of improvementThe specific surface area of the material is increased, which helps to improve the interfacial contact efficiency between the electrode and the electrolyte, and provides sufficient volume expansion space during charge and discharge cycles, effectively improving the charge transfer efficiency and structural stability of the active material. Ni produced by the method3S4/CuS2The electrochemical performance of the electrode in 1mol/L potassium hydroxide alkaline electrolyte is shown as follows: at 1A g-1Has a specific capacity of 888F g at a current density of-1(ii) a At 10A g-1The specific capacity is only attenuated by 17.62 percent when the battery is charged and discharged for 2000 circles under the current density.
Drawings
FIG. 1 is a schematic diagram of Ni preparation of hollow cubic structure3S4/CuS2Scanning electron micrographs relating to materials, in which: a and b are precursors Cu2SEM picture of O; c and d are Ni (OH)2/CuS2SEM picture of (1); e and f are Ni after 12h of vulcanization3S4/CuS2SEM image of (d).
FIG. 2 shows Ni in a hollow cubic structure3S4/CuS2Electrochemical performance test pattern of an electrode, wherein: a is cyclic voltammograms at different vulcanization times; b is constant current charge and discharge curve under different vulcanization time.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
（1）Cu2Preparation of O precursor template
Aqueous NaOH (10.0 mL, 2.0M) was added dropwise to CuCl2▪2H2O (100 mL, 0.01M) in water, and the mixed solution was magnetically stirred for 30 min. As the reaction time progressed, the color of the solution gradually changed to dark brown. An aqueous solution of ascorbic acid (10.0 mL, 0.6M) was then added dropwise to the above dark brown solution, with the addition of ascorbic acid, the color of the solution gradually changed to brick red. The mixed solution after the dripping of the ascorbic acid is continuously stirred for 3 hours, and all the reaction processes are carried out under the condition of water bath at the temperature of 55 ℃. Finally centrifuging the suspension after reaction to obtain a brick red precipitate sample andwashed several times with deionized water and ethanol and dried in vacuum.
（2）Ni(OH)2/CuS2Preparation of nano hollow cubic structure
PVP (3.33 g) and Cu2O (100 mg) and NiCl2·6H2O (17 mg), 100mL of a mixed solution of deionized water and ethanol at a volume ratio of 1:1 was added to the mixture, and ultrasonic dispersion was performed for 30min to completely dissolve the mixture. Then adding Na2S2O3(40.0 mL, 1.0M) aqueous solution was added to the above solution and stirring was continued for 10min with Na2S2O3The color of the solution gradually changes from brick red to bright green. The whole process is carried out at room temperature. Finally, the suspension after the reaction is centrifuged to obtain Ni (OH)2/CuS2The hollow material of (a) is washed with deionized water and ethanol several times and then dried in vacuum.
（3）Ni3S4/CuS2Preparation of nano hollow composite material
Mixing the above-synthesized Ni (OH)2/CuS2(1.25 mmol) and thiourea (6.25 mmol) were uniformly dispersed in a mixed solution of ethanol and deionized water (volume ratio 1:1, total volume 30 mL). And then transferring the mixed solution to a clean reaction kettle, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven for hydrothermal reaction, and preserving the heat for 12 hours at the high temperature of 160 ℃. Finally, centrifuging the suspension after reaction, washing for a plurality of times by using ethanol and deionized water, and obtaining Ni by vacuum drying3S4/CuS2The hollow cubic nano powder.
The electrochemical performance test method comprises the following steps: the test of electrochemical performance is completed in a three-electrode system, and the prepared Ni3S4/CuS2As a working electrode, a platinum sheet was used as a counter electrode, a Saturated Calomel Electrode (SCE) was used as a reference electrode, and the electrolyte was 2M KOH aqueous solution. The electrochemical performance of the electrodes was tested using Cyclic Voltammetry (CV) and constant current charging and discharging (GCD). The cycling stability of the electrodes needs to be performed on a blue test system.
Electrochemical Performance after 12h of vulcanization by the test described aboveNi3S4/CuS2Electrodes at 1A g-1Has a specific capacity of 888F g at a current density of-1(ii) a At 10A g-1The specific capacity is only attenuated by 17.62 percent when the battery is charged and discharged for 2000 circles under the current density.
Example 2
（1）Cu2Preparation of O precursor template
Aqueous NaOH (10.0 mL, 2.0M) was added dropwise to CuCl2▪2H2O (100 mL, 0.01M) in water, and the mixed solution was magnetically stirred for 30 min. As the reaction time progressed, the color of the solution gradually changed to dark brown. An aqueous solution of ascorbic acid (10.0 mL, 0.6M) was then added dropwise to the above dark brown solution, with the addition of ascorbic acid, the color of the solution gradually changed to brick red. The mixed solution after the dripping of the ascorbic acid is continuously stirred for 3 hours, and all the reaction processes are carried out under the condition of water bath at the temperature of 55 ℃. And finally, centrifuging the reacted suspension to obtain a brick red precipitate sample, washing the brick red precipitate sample for a plurality of times by using deionized water and ethanol, and then drying the brick red precipitate sample in vacuum.
（2）Ni(OH)2/CuS2Preparation of nano hollow cubic structure
PVP (3.33 g) and Cu2O (100 mg) and NiCl2·6H2O (17 mg), 100mL of a mixed solution of deionized water and ethanol at a volume ratio of 1:1 was added to the mixture, and ultrasonic dispersion was performed for 30min to completely dissolve the mixture. Then adding Na2S2O3(40.0 mL, 1.0M) aqueous solution was added to the above solution and stirring was continued for 10min with Na2S2O3The color of the solution gradually changes from brick red to bright green. The whole process is carried out at room temperature. Finally, the suspension after the reaction is centrifuged to obtain Ni (OH)2/CuS2The hollow material of (a) is washed with deionized water and ethanol several times and then dried in vacuum.
（3）Ni3S4/CuS2Preparation of nano hollow composite material
Mixing the above-synthesized Ni (OH)2/CuS2(1.25 mmol) and thiourea (6.25 mmol) were uniformly dispersed in ethanol anddeionized water (volume ratio 1:1, total volume 30 mL). And then transferring the mixed solution to a clean reaction kettle, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven for hydrothermal reaction, and preserving the heat for 18 hours at the high temperature of 160 ℃. Finally, centrifuging the suspension after reaction, washing for a plurality of times by using ethanol and deionized water, and obtaining Ni by vacuum drying3S4/CuS2The hollow cubic nano powder.
The electrochemical performance test method comprises the following steps: the test of electrochemical performance is completed in a three-electrode system, and the prepared Ni3S4/CuS2As a working electrode, a platinum sheet was used as a counter electrode, a Saturated Calomel Electrode (SCE) was used as a reference electrode, and the electrolyte was 2M KOH aqueous solution. The electrochemical performance of the electrodes was tested using Cyclic Voltammetry (CV) and constant current charging and discharging (GCD). The cycling stability of the electrodes needs to be performed on a blue test system.
Electrochemical Performance after 18h of sulfurization by the above test, Ni3S4/CuS2Electrodes at 1A g-1Has a specific capacity of 944F g at the current density of (A)-1(ii) a At 10A g-1The specific capacity is attenuated by 32.14 percent after 2000 circles of charge and discharge under the current density.
Example 3
（1）Cu2Preparation of O precursor template
Aqueous NaOH (10.0 mL, 2.0M) was added dropwise to CuCl2▪2H2O (100 mL, 0.01M) in water, and the mixed solution was magnetically stirred for 30 min. As the reaction time progressed, the color of the solution gradually changed to dark brown. An aqueous solution of ascorbic acid (10.0 mL, 0.6M) was then added dropwise to the above dark brown solution, with the addition of ascorbic acid, the color of the solution gradually changed to brick red. The mixed solution after the dripping of the ascorbic acid is continuously stirred for 3 hours, and all the reaction processes are carried out under the condition of water bath at the temperature of 55 ℃. And finally, centrifuging the reacted suspension to obtain a brick red precipitate sample, washing the brick red precipitate sample for a plurality of times by using deionized water and ethanol, and then drying the brick red precipitate sample in vacuum.
（2）Ni(OH)2/CuS2Preparation of nano hollow cubic structure
PVP (3.33 g) and Cu2O (100 mg) and NiCl2·6H2O (17 mg), 100mL of a mixed solution of deionized water and ethanol at a volume ratio of 1:1 was added to the mixture, and ultrasonic dispersion was performed for 30min to completely dissolve the mixture. Then adding Na2S2O3(40.0 mL, 1.0M) aqueous solution was added to the above solution and stirring was continued for 10min with Na2S2O3The color of the solution gradually changes from brick red to bright green. The whole process is carried out at room temperature. Finally, the suspension after the reaction is centrifuged to obtain Ni (OH)2/CuS2The hollow material of (a) is washed with deionized water and ethanol several times and then dried in vacuum.
（3）Ni3S4/CuS2Preparation of nano hollow composite material
Mixing the above-synthesized Ni (OH)2/CuS2(1.25 mmol) and thiourea (6.25 mmol) were uniformly dispersed in a mixed solution of ethanol and deionized water (volume ratio 1:1, total volume 30 mL). And then transferring the mixed solution to a clean reaction kettle, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven for hydrothermal reaction, and preserving the heat for 24 hours at the high temperature of 160 ℃. Finally, centrifuging the suspension after reaction, washing for a plurality of times by using ethanol and deionized water, and obtaining Ni by vacuum drying3S4/CuS2The hollow cubic nano powder.
The electrochemical performance test method comprises the following steps: the test of electrochemical performance is completed in a three-electrode system, and the prepared Ni3S4/CuS2As a working electrode, a platinum sheet was used as a counter electrode, a Saturated Calomel Electrode (SCE) was used as a reference electrode, and the electrolyte was 2M KOH aqueous solution. The electrochemical performance of the electrodes was tested using Cyclic Voltammetry (CV) and constant current charging and discharging (GCD). The cycling stability of the electrodes needs to be performed on a blue test system.
Ni after 24h of vulcanization by electrochemical Performance of the above test3S4/CuS2Electrodes at 1A g-1Specific capacity of 982F g at current density of-1(ii) a At 10A g-1Current density of (2) charge and discharge in 2000 turnsCapacity fade 54.04%.
Example 4
（1）Cu2Preparation of O precursor template
Aqueous NaOH (10.0 mL, 2.0M) was added dropwise to CuCl2▪2H2O (100 mL, 0.01M) in water, and the mixed solution was magnetically stirred for 30 min. As the reaction time progressed, the color of the solution gradually changed to dark brown. An aqueous solution of ascorbic acid (10.0 mL, 0.6M) was then added dropwise to the above dark brown solution, with the addition of ascorbic acid, the color of the solution gradually changed to brick red. The mixed solution after the dripping of the ascorbic acid is continuously stirred for 3 hours, and all the reaction processes are carried out under the condition of water bath at the temperature of 55 ℃. And finally, centrifuging the reacted suspension to obtain a brick red precipitate sample, washing the brick red precipitate sample for a plurality of times by using deionized water and ethanol, and then drying the brick red precipitate sample in vacuum.
（2）Ni(OH)2/CuS2Preparation of nano hollow cubic structure
PVP (3.33 g) and Cu2O (100 mg) and NiCl2·6H2O (17 mg), 100mL of a mixed solution of deionized water and ethanol at a volume ratio of 1:1 was added to the mixture, and ultrasonic dispersion was performed for 30min to completely dissolve the mixture. Then adding Na2S2O3(40.0 mL, 1.0M) aqueous solution was added to the above solution and stirring was continued for 10min with Na2S2O3The color of the solution gradually changes from brick red to bright green. The whole process is carried out at room temperature. Finally, the suspension after the reaction is centrifuged to obtain Ni (OH)2/CuS2The hollow material of (a) is washed with deionized water and ethanol several times and then dried in vacuum.
（3）Ni3S4/CuS2Preparation of nano hollow composite material
Mixing the above-synthesized Ni (OH)2/CuS2(1.25 mmol) and thiourea (6.25 mmol) were uniformly dispersed in a mixed solution of ethanol and deionized water (volume ratio 1:1, total volume 30 mL). Then transferring the mixed solution to a clean reaction kettle, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven for hydrothermal reaction at the temperature of 160 DEG CKeeping the temperature for 30h under the warm condition. Finally, centrifuging the suspension after reaction, washing for a plurality of times by using ethanol and deionized water, and obtaining Ni by vacuum drying3S4/CuS2The hollow cubic nano powder.
The electrochemical performance test method comprises the following steps: the test of electrochemical performance is completed in a three-electrode system, and the prepared Ni3S4/CuS2As a working electrode, a platinum sheet was used as a counter electrode, a Saturated Calomel Electrode (SCE) was used as a reference electrode, and the electrolyte was 2M KOH aqueous solution. The electrochemical performance of the electrodes was tested using Cyclic Voltammetry (CV) and constant current charging and discharging (GCD). The cycling stability of the electrodes needs to be performed on a blue test system.
Ni after 30h of sulfidation by electrochemical Performance of the above test3S4/CuS2Electrodes at 1A g-1Has a specific capacity of 724F g-1(ii) a At 10A g-1The specific capacity is attenuated by 63.45 percent when the battery is charged and discharged for 2000 circles under the current density.
As shown in a and b of FIG. 1, the precursor Cu2The shape of the O is a regular cubic structure; as shown in c and d in FIG. 1, Ni (OH)2/CuS2The shape of the structure is a hollow cubic structure; ni after 12h of sulfidation, as shown by e and f in FIG. 13S4/CuS2The SEM morphology is a hollow cube composed of nanoparticles.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (9)
1. Hollow cubic Ni3S4/CuS2The preparation method of the electrode material of the super capacitor is characterized by comprising the following steps:
S1、Cu2preparing an O precursor template:
dropping NaOH solution into CuCl2 ▪2H2In an aqueous solution of O, mixingMagnetically stirring the solution, gradually changing the color of the solution into black brown along with the progress of reaction time, then dropwise adding an ascorbic acid aqueous solution into the black brown solution, gradually changing the color of the solution into brick red along with the addition of the ascorbic acid, continuously stirring a mixed solution after the dropwise adding of the ascorbic acid, finally centrifuging a suspension after reaction to obtain brick red precipitate, washing the precipitate, and performing vacuum drying to obtain Cu2O；
S2、Ni(OH)2/CuS2Preparing a nano hollow cubic structure:
mixing PVP and Cu2O and NiCl2·6H2O, mixing, namely adding a mixed solution of deionized water and ethanol into the mixture, and performing ultrasonic dispersion to completely dissolve the mixture; then adding Na2S2O3The aqueous solution was added to the above solution and stirring was continued with Na2S2O3Adding the solution, wherein the color of the solution gradually changes from brick red to bright green; finally, centrifuging the suspension after reaction to obtain precipitate, washing the precipitate, and drying in vacuum to obtain the Ni (OH) with a hollow cubic structure2/CuS2A nanomaterial;
S3、Ni3S4/CuS2preparing a nano hollow cubic structure:
mixing the Ni (OH) synthesized in step S22/CuS2Uniformly dispersing the thiourea in a mixed solution of ethanol and deionized water; then transferring the mixed solution into a reaction kettle, sealing, placing the reaction kettle in a drying box for hydrothermal reaction, and keeping the temperature for 12-36 hours; finally, centrifugally collecting and precipitating the reacted suspension, washing the precipitate and then drying the precipitate in vacuum to obtain the hollow cubic Ni3S4/CuS2The powder of (4).
2. Hollow cubic Ni as claimed in claim 13S4/CuS2The preparation method of the electrode material of the super capacitor is characterized in that in the step S1, NaOH aqueous solution and CuCl are adopted2 ▪2H2The concentrations of O aqueous solution and ascorbic acid aqueous solution were 2M, 0.01M and 0.6M, respectively, NaOH aqueous solution and CuCl2 ▪2H2O aqueous solutionAnd the dosage of the ascorbic acid aqueous solution is 10.0mL, 100mL and 10.0mL respectively; in step S1, all reactions were at 55oAnd C, performing in a water bath.
3. Hollow cubic Ni as claimed in claim 13S4/CuS2The preparation method of the electrode material of the super capacitor is characterized in that PVP and Cu are adopted in the step S22O and NiCl2·6H2The mass of O is 3.33g, 100mg and 17mg respectively, the volume ratio of deionized water to ethanol is 1:1, the total amount of deionized water and ethanol is 100mL, Na2S2O3The concentration of the aqueous solution was 1M, Na2S2O3The dosage of the aqueous solution is 40.0 mL; the whole process of step S2 is completed at room temperature.
4. Hollow cubic Ni as claimed in claim 13S4/CuS2The preparation method of the electrode material of the super capacitor is characterized in that in the step S3, Ni (OH)2/CuS2And the dosage of thiourea is 1.25mmol and 6.25mmol respectively, the volume ratio of deionized water to ethanol is 1:1, the total amount of deionized water and ethanol is 30mL, the temperature of the hydrothermal reaction is 160 ℃, and the temperature is kept at 160 ℃ for 12-36 h.
5. Hollow cubic Ni as claimed in claim 13S4/CuS2The preparation method of the supercapacitor electrode material is characterized in that in the steps S1, S2 and S3, the temperature of vacuum drying is 80 ℃, and the drying time is 24 hours.
6. Hollow cubic Ni produced by the production method according to any one of claims 1 to 53S4/CuS2The application of the super capacitor electrode is characterized in that the hollow cubic Ni3S4/CuS2Used for manufacturing electrodes.
7. Hollow cubic Ni produced by the production method according to claim 63S4/CuS2The application of the supercapacitor electrode is characterized in that the preparation method of the electrode comprises the following steps:
hollow cubic Ni3S4/CuS2As an active material, acetylene black is used as a conductive agent, polyvinylidene fluoride is used as a binder, and the weight ratio of the acetylene black to the polyvinylidene fluoride is 8: 1:1, dissolving the mixture in N-methyl pyrrolidone, and grinding the mixture to prepare homogeneous mixed slurry; immersing the foamed nickel cut into the size of 1 × 2cm into the mixed slurry, uniformly coating the mixed slurry on the surface of the foamed nickel, then placing the coated nickel net in a vacuum drying oven for drying, and finally pressing the nickel net into an electrode plate by using a tablet press.
8. Hollow cubic Ni produced by the production method according to claim 73S4/CuS2The application of the supercapacitor electrode is characterized in that the mass-volume ratio of the active substance to the N-methylpyrrolidone is 20 mg:2.5 mL; in the preparation method of the electrode, the temperature of vacuum drying is 80 ℃, the drying time is 12h, the pressure of the tablet press during tabletting is 10MPa, and the duration time is 60 s.
9. Hollow cubic Ni produced by the production method according to claim 7 or 83S4/CuS2The application of the super capacitor electrode is characterized in that the hollow cubic Ni3S4/CuS2The prepared electrode is used for preparing a super capacitor.
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| CN110289177A (en) * | 2019-05-10 | 2019-09-27 | 中国矿业大学 | A kind of hollow cubic nickel hydroxide/curing copper electrode material for super capacitor and its preparation method and application |
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| WO2015174931A1 (en) * | 2014-05-14 | 2015-11-19 | Agency For Science, Technology And Research | A method of forming a porous particle |
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