CN110189925B - Preparation method and application of one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material - Google Patents
Preparation method and application of one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 89
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011258 core-shell material Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 title abstract description 6
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 7
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000007514 bases Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 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 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a preparation method and application of a one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material, wherein the preparation method comprises the following steps: MnO of monomer2The @ C nanowire, the nickel source, the persulfate and the alkaline compound are subjected to contact reaction in water to prepare one-dimensional MnO2@C@Ni(OH)2Core-shell nanowire composites. The one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material has an ultralong one-dimensional morphology structure and excellent electrochemical performance, so that the composite material can be applied to electrode materials of super capacitors, and meanwhile, the preparation method is simple in process and low in cost.
Description
Technical Field
The invention relates to a core-shell nanowire composite material, in particular to a preparation method and application of a one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material.
Background
As the demand for next-generation electrochemical storage devices continues to increase, supercapacitors are considered to be one of the most potentially valuable energy storage devices, exhibiting high charge-discharge efficiency, long cycle life and ultra-high power density. Capacitors can be classified into two types according to the energy storage mechanism: one is a non-faraday double layer capacitor and the other is a faraday pseudocapacitor, typically composed of a transition metal oxide. Among these transition metal oxides, MnO2Is particularly valuable for research purposes because of its high theoretical specific capacity (theoretical pseudocapacitance of 1370F g-1) Small voltage hysteresis and environmentFriendly and the like. However, poor conductivity and large volume changes during charge and discharge greatly limit their performance in rate capability and cycling stability.
Disclosure of Invention
The invention aims to provide a preparation method and application of a one-dimensional manganese dioxide @ carbon @ nickel hydroxide core-shell nanowire composite material.
In order to achieve the above object, the present invention provides a one-dimensional MnO2@C@Ni(OH)2A method of preparing a core-shell nanowire composite, comprising: MnO of monomer2The @ C nanowire, the nickel source, the persulfate and the alkaline compound are subjected to contact reaction in water to prepare one-dimensional MnO2@C@Ni(OH)2Core-shell nanowire composites.
The invention also provides a one-dimensional MnO2@C@Ni(OH)2Core-shell nanowire composite, the one-dimensional MnO2@C@Ni(OH)2The core-shell nanowire composite material is prepared by the preparation method.
The invention further provides a one-dimensional MnO as described above2@C@Ni(OH)2Use of a core-shell nanowire composite in a supercapacitor.
In the technical scheme, the characteristics of high theoretical specific capacity, excellent electrochemical activity and low cost of the nickel hydroxide nanosheet are utilized, so that the nickel hydroxide nanosheet and the monomer MnO are enabled to be formed2@ C nanowire composite to form one-dimensional MnO2@C@Ni(OH)2A core-shell nanowire composite; the core-shell structure nano composite material enlarges the specific surface area, provides more sites for surface oxidation-reduction reaction, and accelerates the transmission speed of ions or electrons. (ii) a The one-dimensional MnO2@C@Ni(OH)2The core-shell nanowire composite material has the properties of large specific capacitance and good cycling stability, and can be used as an electrode material of a super capacitor; in particular toOne-dimensional MnO at 1A/g current density2@C@Ni(OH)2The specific capacitance of the core-shell nanowire composite material can reach 1595.4F/g; after 4000 cycles, one-dimensional MnO2@C@Ni(OH)2The capacitance of the core-shell nanowire composite material can still be kept relatively stable, which shows that one-dimensional MnO is2@C@Ni(OH)2The core-shell nanowire composite material has good stability.
In addition, the preparation method has the advantages of simple operation, low cost, mild condition and environmental protection, and further can be popularized in a large range.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows a one-dimensional MnO prepared in example 12Scanning Electron Microscope (SEM) image of @ C nanowire composite material at 30K magnification
FIG. 2 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2A Scanning Electron Microscope (SEM) image at 6K magnification of the core-shell nanowire composite;
FIG. 3 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2Transmission Electron Microscopy (TEM) images of core-shell nanotube composites;
FIG. 4 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2An X-ray diffraction (XRD) pattern of the core-shell nanowire composite;
FIG. 5 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2Alternating current impedance curves of the core-shell nanowire composite material before and after 6000 cycles of circulation;
FIG. 6 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2Cyclic voltammograms of core-shell nanowire composites;
FIG. 7 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2A constant current charge-discharge curve diagram of the core-shell nanowire composite material under different current densities;
FIG. 8 shows a one-dimensional MnO prepared in example 12@C@Ni(OH)2The core-shell nanowire composite material has the current density of 60 mV.s-1Cyclic-specific capacitance plots of time.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a one-dimensional MnO2@C@Ni(OH)2A method of preparing a core-shell nanowire composite, comprising: MnO of monomer2The @ C nanowire, the nickel source, the persulfate and the alkaline compound are subjected to contact reaction in water to prepare one-dimensional MnO2@C@Ni(OH)2Core-shell nanowire composites.
In the above preparation method, monomer MnO2The dosage of the @ C nanowire, the nickel source and the persulfate can be selected in a wide range, but in order to enable the prepared core-shell nano hollow tube composite material to have more excellent electrochemical performance and stability, the monomer MnO is preferably selected2The dosage ratio of the @ C nanowire to the nickel source to the persulfate is 15 mg: 0.25-0.5 mmol: 0.02-0.04 mmol;
in the above-mentioned production method, the amount of water to be used can be selected within a wide range, but in order to enable sufficient contact between the reactants and thereby improve the reaction rate and yield, it is preferable that monomer MnO is used2The dosage ratio of the @ C nanowire to the water is 15 mg: 80-200 mL.
In the above preparation method, the amount of the basic compound may be selected within a wide range, but in order to obtain a core-shell nano hollow tube composite material having more excellent electrochemical properties and stability, preferably, the monomer MnO is used2The dosage ratio of the @ C nanowire to the alkaline compound is 15 mg: 0.01-0.05 mg.
In the above production method, the kind of the basic compound may be selected from a wide range, but from the viewpoint of cost, it is preferable that the basic compound is selected from at least one of ammonia water, sodium hydroxide, and potassium hydroxide. More preferably, the basic compound is provided by an aqueous ammonia solution of 10-30% by weight, relative to 15mg of monomeric MnO2@ C nanowire, the dosage of ammonia water solution is 0.15 mL.
In the above-mentioned contact reaction, the conditions of the contact reaction can be selected within a wide range, but in order to further improve the reaction yield and rate, it is preferable that the contact reaction satisfies the following requirements: the reaction temperature is 15-20 ℃, and the reaction time is 0.5-1 h.
In the above preparation method, monomer MnO2The specification of the @ C nanowire can be selected in a wide range, but in order to enable the prepared core-shell nanowire composite material to have more excellent electrochemical performance and stability, the monomer MnO is2The @ C nanowire satisfies the following conditions: the diameter is 40-60nm, and the length is 1-2 μm.
In the above method, the specific kinds of the nickel source and the persulfate may be selected within a wide range, but in order to further improve the reaction yield and rate, preferably, the nickel source is selected from at least one of nickel sulfate hexahydrate, nickel nitrate, nickel chloride and nickel acetate; the persulfate is at least one selected from potassium persulfate, ammonium persulfate and sodium persulfate.
In the present invention, monomer MnO2The @ C nanowire can be a commercial product or can be prepared by self to further improve the monomer MnO2Activity of @ C nanowire, preferably monomeric MnO2The @ C nanowire is prepared by the following method: mixing KMnO4、NH4Cl and water as 0.6 mmol: 0.6-0.8 mmol: the dosage of 30-50mL is higher than 190 ℃ at 170 DEG CPerforming hydrothermal reaction for 20-30h to obtain MnO2A nanowire monomer; then the obtained MnO is added2Magnetically stirring the nanowire monomer, 1-1.5mmol of glucose and 30-50mL of water at 15-35 ℃ for 10-15h, then drying in vacuum for 20-30h, and finally annealing in nitrogen at 440-2@ C nanowire.
The invention also provides a one-dimensional MnO2@C@Ni(OH)2Core-shell nanowire composite, the one-dimensional MnO2@C@Ni(OH)2The core-shell nanowire composite material is prepared by the preparation method.
In the above core-shell nanowire composites, the specific specifications of the core-shell nanowire composites may be varied within a wide range, but in order to further improve the one-dimensional MnO2@C@Ni(OH)2Electrochemical performance and stability of core-shell nanowire composites, preferably, one-dimensional MnO2@C@Ni(OH)2The core-shell nanowire composite material satisfies the following conditions: the diameter is 90-110nm, and the outside of the thread layer is wrapped with the nano-sheet.
The invention further provides a one-dimensional MnO as described above2@C@Ni(OH)2Use of a core-shell nanowire composite in a supercapacitor.
The present invention will be described in detail below by way of examples.
Preparation example 1
The monomer MnO2The @ C nanowire is prepared by the following method: taking 15ml of KMnO4Aqueous solution (0.04mol/L) and 15ml of NH4Pouring a Cl aqueous solution (0.04mol/L) into a 50ml polytetrafluoroethylene stainless steel autoclave, magnetically stirring for 30 minutes, sealing, placing in an oven at 180 ℃ for reaction for 24 hours, and cooling to 25 ℃ after the reaction is finished; taking out the product, and sequentially cleaning with deionized water and absolute ethyl alcohol for three times to obtain MnO2And (4) a nanowire monomer.
Taking all the MnO prepared above2Placing the nanowire monomer and 30ml of glucose solution (0.04mol/L) in a 50ml beaker, placing the beaker at 25 ℃ and magnetically stirring the beaker for 12 hours, washing the beaker once by using deionized water, and placing the beaker in a vacuum drying oven to dry the beaker for 24 hours; finally, nitrogen at 450 deg.CAnnealing in gas for 2h, after the reaction is finished, gradually cooling to 25 ℃, taking out the product to obtain MnO2@ C nanowire, resulting monomeric MnO2@ C nanowire; by the monomer MnO in FIG. 12The electron scan of the @ C nanowire reveals: monomer MnO2The @ C nanowire is approximately 50nm in diameter and approximately 1 μm in length.
Example 1
0.25mmol of nickel sulfate hexahydrate, 0.02mmol of potassium persulfate and 0.15ml of 10 weight percent ammonia water are dissolved in 160ml of deionized water, and the monomer MnO prepared is2Adding and mixing the @ C nanowire (15mg), uniformly stirring, then reacting the mixed system at 15 ℃ for 0.5h, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃.
Example 2
The procedure is as in example 1, except that the mixture is reacted at 20 ℃ for 0.5 h.
Example 3
The procedure is as in example 1, except that the mixed system is reacted at 15 ℃ for 1 h.
Example 4
The procedure is as in example 1, except that the mixed system is reacted at 20 ℃ for 1 h.
Example 5
0.5mmol of nickel sulfate hexahydrate, 0.04mmol of potassium persulfate and 0.3ml of 10 weight percent ammonia water are dissolved in 80ml of deionized water, and the monomer MnO prepared is2Adding and mixing the @ C nanowire (15mg), uniformly stirring, then reacting the mixed system at 15 ℃ for 0.5h, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃.
Example 6
0.25mmol of nickel sulfate hexahydrate, 0.02mmol of potassium persulfate and 0.15ml of 30 weight percent ammonia water are dissolved in 160ml of deionized water, and the monomer MnO prepared is2Adding and mixing the @ C nanowire (15mg), uniformly stirring, then reacting the mixed system at 15 ℃ for 0.5h, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain the product。
Example 7
The procedure is as in example 1, except that nickel sulfate hexahydrate is replaced by an equimolar amount of nickel nitrate.
Example 8
The procedure is as in example 1, except that nickel sulfate hexahydrate is replaced by an equimolar amount of nickel acetate.
Detection example 1
1) The product obtained in example 1 was subjected to morphology analysis by a Scanning Electron Microscope (SEM), and the results are shown in fig. 1 and 2, indicating that the prepared product was a one-dimensional nanostructure.
2) The composition of the product obtained in example 1 was analyzed by a Transmission Electron Microscope (TEM), and the result is shown in FIG. 3, which indicates that the product is a one-dimensional heterostructure.
3) The product obtained in example 1 was examined by X-ray diffraction (XRD), and the results are shown in FIG. 4, whereby MnO having a spectrum corresponding to that of JCPDS Standard card No.42-1316 was obtained2Diffraction Peak, Ni (OH) corresponding to JCPDS Standard card No.03-01772The diffraction peaks of the two are completely coincident; this XRD pattern is sufficient to demonstrate that the product is MnO2@C@Ni(OH)2A composite material.
Detection example 2
The instrument used in the following tests was CHI660E electrochemical workstation (manufactured by Shanghai Chenghua instruments, Inc.). The following tests all used a three-electrode system in which the one-dimensional MnO prepared in example 1 was used2@C@Ni(OH)2The core-shell nanowire composite, the acetylene black, and the Polytetrafluoroethylene (PTFE) were mixed according to a 6: 2: 2, preparing a working electrode by weight mixing, and respectively taking a platinum wire electrode and a Saturated Calomel Electrode (SCE) as a counter electrode and a reference electrode; 3mol/L KOH solution was used as an electrolyte.
1) Electrochemical impedance spectroscopy test
The detection result of the electrochemical impedance spectroscopy is shown in figure 5; the alternating-current impedance spectrum is divided into a high-frequency region part and a low-frequency region part and consists of a semicircular arc of the high-frequency region and an inclined straight line of the low-frequency region. FIG. 5 shows a one-dimensional MnO at the intersection of the impedance spectrum of the middle and high frequency region and the real axis2@C@Ni(OH)2The internal resistance of the core-shell nanowire composite electrode comprises the resistance of an active material, the resistance of an electrolyte and the contact resistance of the active material and the electrolyte, MnO2@C@Ni(OH)2The impedance spectrum of (a) presents a similar semicircular shape in a high-frequency region and a linear shape in a low-frequency region; apparently, in MnO2@C@Ni(OH)2The intercept of the axis in the high frequency range of the core-shell electrode is small, indicating a low internal resistance. In addition, MnO is mixed2@C@Ni(OH)2The semi-circle diameter of the core-shell electrode is small, which shows that the electrode has the lowest interface charge transfer resistance and the simplest and fastest electrode transmission in the electrochemical process, so that the core-shell nanowire composite material electrode can be used as an electrode material of a supercapacitor.
2) Cyclic Voltammetry (CV) test
Respectively at 2mV s-1、4mV·s-1、6mV·s-1、8mV·s-1And 10 mV. s-1Scanning at the scanning rate of (2) to obtain the one-dimensional MnO in example 12@C@Ni(OH)2The cyclic voltammetry curve of the core-shell nanowire composite material is shown in FIG. 6, and the potential range of the curve is 0-0.5V. And even at 10mV · s-1The CV curve does not change greatly at the scanning rate of (2), and the synthesized electrode material is known to have the characteristic of pseudo capacitance.
3) Constant current charge-discharge (CP) test
Respectively at 1 A.g-1、2A·g-1、3A·g-1、4A·g-1And 5 A.g-1Constant current charge-discharge detection is carried out to obtain the one-dimensional MnO in the embodiment 12@C@Ni(OH)2The constant current charge-discharge curve of the core-shell nanowire composite material under different current densities is shown in fig. 7. Wherein the ordinate of the curve, namely the voltage range, is 0-0.5V. The specific capacitance at different current densities was calculated by the following formula. Calculating specific capacitance, i.e. one-dimensional MnO, from a charge-discharge diagram2@C@Ni(OH)2In the core-shell nanowire material, the ratio of the core-shell nanowire material is 1 A.g-1Specific capacitance under current density is 1595.4F g-1Description of one-dimensional MnO2@C@Ni(OH)2The core-shell nanowire material has excellent storage capacityThe performance of (c).
Wherein, the capacitance calculation formula is as follows: cmI is the current magnitude, t is the discharge time, Δ V is the potential difference, and m is the mass of the sample on the working electrode plate.
4) Cycle performance detection
At 60mV · s-14000 cycles at a current density of (2) to obtain a one-dimensional MnO of example 12@C@Ni(OH)2The result of the cycle curve of the core-shell nanowire composite material is shown in fig. 8, the final capacity is compared with the initial capacity, and the final capacity is similar to the initial capacity after 4000 cycles, which shows that one-dimensional MnO is formed2@C@Ni(OH)2The core-shell nanowire material has excellent stability.
The products of examples 2 to 8 were examined in the same manner as in example 1-2, and the examination results were substantially identical to those of example 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. One-dimensional MnO2@C@Ni(OH)2The preparation method of the core-shell nanowire composite material is characterized by comprising the following steps: MnO of monomer2The @ C nanowire, the nickel source, the persulfate and the alkaline compound are subjected to contact reaction in water to prepare the one-dimensional MnO2@C@Ni(OH)2A core-shell nanowire composite;
wherein, the monomer MnO2The dosage ratio of the @ C nanowire to the nickel source to the persulfate is 15 mg: 0.25-0.5 mmol: 0.02-0.04 mmol.
2. The production method according to claim 1, wherein the monomer MnO2The dosage ratio of the @ C nanowire to the water is 15 mg: 80-200 mL.
3. The production method according to claim 1, wherein the monomer MnO2The dosage ratio of the @ C nanowire to the alkaline compound is 15 mg: 0.01-0.05 mg.
4. The production method according to claim 1, wherein the basic compound is at least one selected from the group consisting of ammonia water, sodium hydroxide, and potassium hydroxide.
5. The production method according to claim 1, wherein the basic compound is provided from a 10 to 30 wt% aqueous ammonia solution with respect to 15mg of the monomer MnO2@ C nanowire, the dosage of ammonia water solution is 0.15 mL.
6. The production method according to claim 1, wherein the contact reaction satisfies the following requirements: the reaction temperature is 15-20 ℃, and the reaction time is 0.5-1 h.
7. The production method according to claim 1, wherein the monomer MnO2The @ C nanowire satisfies the following conditions: the diameter is 40-60nm, and the length is 1-2 μm.
8. The production method according to claim 1, wherein the nickel source is selected from at least one of nickel sulfate hexahydrate, nickel nitrate, nickel chloride, and nickel acetate; the persulfate is at least one selected from potassium persulfate, ammonium persulfate and sodium persulfate.
9. According to the rightThe method according to claim 1, wherein said monomer MnO is2The @ C nanowire is prepared by the following method: mixing KMnO4、NH4Cl and water as 0.6 mmol: 0.6-0.8 mmol: the dosage of 30-50mL is more than that of the hydrothermal reaction at the temperature of 170-190 ℃ for 20-30h to prepare MnO2A nanowire monomer; then the obtained MnO is added2Magnetically stirring the nanowire monomer, 1-1.5mmol of glucose and 30-50mL of water at 15-35 ℃ for 10-15h, then drying in vacuum for 20-30h, and finally annealing in nitrogen at 440-2@ C nanowire.
10. One-dimensional MnO2@C@Ni(OH)2Core-shell nanowire composite, characterized in that said one-dimensional MnO is2@C@Ni(OH)2The core-shell nanowire composite material is prepared by the preparation method of any one of claims 1 to 9.
11. The one-dimensional MnO of claim 102@C@Ni(OH)2Core-shell nanowire composite, wherein the one-dimensional MnO is2@C@Ni(OH)2The core-shell nanowire composite material satisfies the following conditions: the diameter is 90-110nm, and the outside of the thread layer is wrapped with the nano-sheet.
12. A one-dimensional MnO as claimed in claim 10 or 112@C@Ni(OH)2Use of a core-shell nanowire composite in a supercapacitor.
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