CN114203457B - NiCo 2 S 4 Preparation method of/MC - Google Patents
NiCo 2 S 4 Preparation method of/MC Download PDFInfo
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- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 87
- 240000008042 Zea mays Species 0.000 claims abstract description 35
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 35
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 35
- 235000005822 corn Nutrition 0.000 claims abstract description 35
- 239000002071 nanotube Substances 0.000 claims abstract description 15
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000010902 straw Substances 0.000 claims abstract description 9
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 8
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 8
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical group [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a NiCo 2 S 4 A preparation method of/MC belongs to the technical field of super capacitors. The invention loads NiCo on the surface of biomass-based mesoporous carbon 2 S 4 The nano tube not only maintains good stability and conductivity of the porous carbon electrode, but also can solve the problem of lower specific capacitance of the carbon electrode material in the application of the double-layer capacitor. The invention loads Ni-Co by a two-step hydrothermal method and obtains NiCo on the surface of the corn straw-based mesoporous carbon after vulcanization 2 S 4 A nanotube. The invention loads NiCo with nano tubular structure on corn straw-based mesoporous carbon 2 S 4 The method comprises the steps of carrying out a first treatment on the surface of the The corn stalk based mesoporous carbon has larger specific surface area and proper pore structure can be NiCo 2 S 4 The MC provides a substrate, not only can effectively improve the nano NiCo 2 S 4 Can also enhance NiCo 2 S 4 Conductivity of/MC. Synthesized NiCo 2 S 4 The MC not only has larger specific surface area and rich pore structure, but also has more redox active sites.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a NiCo 2 S 4 Corn stalk based mesoporous carbon (NiCo) 2 S 4 MC).
Background
The super capacitor has the advantages of high charge and discharge speed, good cycle stability, high power density, low cost, environmental friendliness and the like, and is considered as an energy storage device with wide application prospect. For an electric double layer capacitor, it stores energy by electrostatic adsorption of ions between the electrode/electrolyte interface. Porous carbon is one of the most common electrode materials for electric double layer capacitors, and has good stability and conductivity. These porous structures promote the transfer and diffusion of electrolyte ions on the one hand and also reduce the volume change during charge and discharge cycles on the other hand, so that the porous carbon electrode material has excellent rate performance and cycle stability, but is affected by the pore structure, which has a low specific capacitance. The pseudocapacitor stores energy through a rapid and reversible surface redox reaction. Transition metal compounds and conductive polymers are two major pseudocapacitive electrode materials. Among them, transition metal compounds are widely used in supercapacitors due to their high theoretical capacitance and high electrochemical activity in various oxidation states. The transition metal sulfide is more suitable for being used as an electrode material for providing a pseudo capacitor due to the advantages of good conductivity, more redox sites, large specific capacitance and the like. In addition, binary metal sulfides exhibit lower kinetic energy barriers than elementary metal sulfides, with better electrochemical performance, since the introduction of other metal ions can enhance charge transfer between different ions and provide an electronic structure that facilitates faradaic reactions.
NiCo is currently 2 S 4 Has become an electrode material which is widely studied. Heretofore, many nanostructured NiCo have been synthesized 2 S 4 And further studied the influence of these different structures on electrochemical properties, such as hollow spheres, nanowires, nanoplatelets, etc. However, most NiCo 2 S 4 Nanostructures tend to randomly grow into bulk structures (e.g., flower-like or sphere-like), have a small specific surface area, and are chemically unstable. And thus is easily damaged by oxidation-reduction reactions during long-term charge/discharge, resulting in undesirable electrochemical performance. Therefore, it is necessary to prepare an electrode material having a high specific capacitance, good rate performance and cycle stability.
Disclosure of Invention
The invention provides NiCo 2 S 4 Preparation method of/MC, the method of the invention loads NiCo on the surface of biomass-based mesoporous carbon 2 S 4 The nano tube not only maintains good stability and conductivity of the porous carbon electrode, but also can solve the problem of lower specific capacitance of the carbon electrode material in the application of the double-layer capacitor.
The invention loads Ni-Co by a two-step hydrothermal method and obtains nano tubular NiCo on the surface of the corn straw-based mesoporous carbon after vulcanization 2 S 4 。
NiCo of the invention 2 S 4 The preparation method of the MC is carried out according to the following steps:
step one, adding Ni (NO) into deionized water 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 The preparation method comprises the steps of (1) carrying out ultrasonic treatment on O and urea until the O and the urea are fully dissolved, then adding corn stalk-based Mesoporous Carbon (MC), dispersing uniformly, then carrying out heat preservation at 140 ℃ for 5 hours, naturally cooling to room temperature, repeatedly washing with absolute ethyl alcohol and deionized water in sequence, and then drying at 80 ℃ until the weight is constant to obtain a Ni-Co/MC precursor;
step two, firstly adding Na into deionized water 2 S·9H 2 O, fully mixing, adding the Ni-Co/MC precursor obtained in the step one, carrying out ultrasonic treatment until uniformity is obtained after mixing, then carrying out heat preservation at 160 ℃ for 8 hours, naturally cooling to room temperature, taking out precipitate, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and finally drying at 80 ℃ until constant weight is obtained to obtain NiCo 2 S 4 /MC。
Further defined, the corn stalk based Mesoporous Carbon (MC) in step one is prepared by:
step 1, taking corn straw as a raw material, cleaning the raw material, drying the raw material to constant weight, and crushing the raw material;
step 2, KMnO 4 Adding the solid into deionized water, and fully stirring; adding crushed corn stalks, continuously stirring for a certain time to fully and uniformly mix, and then drying to constant weight;
and 3, placing the raw materials treated in the step 2 into a quartz boat, placing the quartz boat into a tube furnace protected by inert gas, performing carbonization treatment, cooling the quartz boat to room temperature along with the furnace, soaking carbonized products in HCl solution to remove redundant oxides, washing the carbonized products with deionized water to be neutral, and drying the carbonized products at 105 ℃ to obtain the corn stalk-based Mesoporous Carbon (MC).
Further defined, in step 2, the corn stover is combined with KMnO 4 The mass ratio of (2) is 1:1.5.
Further defined, the inert gas in step 3 is nitrogen.
Further defined, the carbonization treatment in step 3 is continuous heating at 700 ℃ for 2 hours.
Further defined, the concentration of HCl solution in step 3 is 1M.
Further defined, in the first step, mesoporous carbon and NiCo are prepared according to the basis of corn straw 2 S 4 The mass ratio of (1) is (0.5-2): 1, adding the corn stalk-based mesoporous carbon prepared in the step three.
Further defined, 0.5mol Ni (NO) was added to 30mL deionized water in step one 3 ) 2 ·6H 2 O、1.0molCo(NO 3 ) 2 ·6H 2 O and 1.5mol urea, 6.0mol Na is firstly added into 30mL deionized water 2 S·9H 2 O。
According to NiCo 2 S 4 The stoichiometric ratio of each atom in the alloy is Ni (NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O and Na 2 S·9H 2 O。
NiCo prepared by the method 2 S 4 Corn stalk based mesoporous carbon is used as supercapacitor electrode material.
The invention loads NiCo with nano tubular structure on corn straw-based mesoporous carbon 2 S 4 The method comprises the steps of carrying out a first treatment on the surface of the The corn stalk based mesoporous carbon has larger specific surface area and proper pore structure can be NiCo 2 S 4 The MC provides a substrate, which not only can effectively improve NiCo 2 S 4 Can also enhance NiCo 2 S 4 Conductivity of/MC. Synthesized NiCo 2 S 4/ MC not only has larger specific surface area and rich pore structure, but also has more redox active sites.
MC in the invention can promote NiCo 2 S 4 Electrochemical performance of/MC. Due to the high specific surface area MC and the high specific capacitance NiCo 2 S 4 Is NiCo 2 S 4 The MC shows better electrochemical performance, and the specific capacitance is 1802.9F/g at the current density of 0.5A/g. NiCo 2 S 4 The MC possesses better multiplying power characteristics (81.3%) and cycle stability (91.6%).
The assembled super capacitor is used for investigating the practical application potential, and when MC and NiCo are used 2 S 4 When the mass ratio of the NiCo to the catalyst is 1:1, the NiCo prepared by the method of the invention 2 S 4 The energy density of the/MC was 47.5Wh/kg (power density 374.9W/kg). Even at higher power densities (15005.9W/kg), the energy density is as high as 31.4Wh/kg. NiCo 2 S 4 High performance of/M// MC, indicating such NiCo 2 S 4 The MC is an ideal supercapacitor electrode material.
Drawings
FIG. 1 shows MC, niCo 2 S 4 And NiCo 2 S 4 A is a SEM morphology diagram of MC in FIG. 1, a is a SEM morphology diagram of MC-0.5, and b is NiCo 2 S 4 SEM topography, c is NiCo 2 S 4 SEM topography of/MC-0.5, d being NiCo 2 S 4 SEM image of MC-0.5 high magnification;
FIG. 2 is NiCo 2 S 4 EDS diagram of high multiple SEM, TEM, HRTEM of MC-1 and C, ni, co and S elements, a being NiCo 2 S 4 NiCo in MC-1 2 S 4 Nanotube SEM, b is NiCo 2 S 4 NiCo in MC-1 2 S 4 Nanotube TEM, c and d are NiCo 2 S 4 NiCo in MC-1 2 S 4 HRTEM of the nanotube, wherein e is C, f is Ni, g is Co, h is S element in NiCo 2 S 4 EDS analysis chart in MC-1, i is NiCo 2 S 4 Total EDS profile of MC-1;
FIG. 3 is MC, niCo 2 S 4 And NiCo 2 S 4 Specific surface area and pore size distribution curve of MC, a is N 2 An adsorption and desorption curve, b is a pore size distribution curve;
FIG. 4 NiCo under a three electrode system 2 S 4 And NiCo 2 S 4 Electrochemical performance curve of/MC,ais NiCo 2 S 4 CV curves of different scanning rates of MC-1, b being NiCo 2 S 4 GCD curves of different current densities of MC-1, c being NiCo 2 S 4 And NiCo 2 S 4 The cycle curve of/MC-1, d is NiCo 2 S 4 MC-1 dependence of log (i) to log (v) at different scan rates, e being NiCo 2 S 4 PerMC-1 has a CV curve of 5mV/s, the shaded portion contributes to the surface control capacitance, and f is NiCo 2 S 4 Ratio of capacitance contributions of MC-1 at different scan rates;
FIG. 5 is NiCo 2 S 4 Electrochemical performance curve of MC-1// MC asymmetric super capacitor, wherein a is MC and NiCo 2 S 4 CV curve of MC-1 at 5mV/s, b being NiCo 2 S 4 CV curve of MC-1// MC at different scanning rates, c being NiCo 2 S 4 GCD curves of different current densities of/MC-1// MC, d being NiCo 2 S 4 Ragone relation diagram of/MC-1// MC, e is NiCo 2 S 4 Cycle performance curves of/MC-1// MC.
Detailed Description
The following examples employ the following chemical reagents, as shown in Table 1
TABLE 1 reagents
The main equipment used is shown in table 2.
Table 2 apparatus
Example 1: niCo of the invention 2 S 4 The preparation method of the MC is carried out according to the following steps:
step one, taking corn stalks as a base raw material, naturally airing, removing leaves, cutting into sections, cleaning the corn stalks, drying the corn stalks to constant weight at 45 ℃, performing industrial analysis and element analysis as shown in table 3, and then performing crushing treatment;
TABLE 3 Industrial analysis and elemental analysis
Step two, KMnO 4 Adding the solid into 100ml deionized water, stirring thoroughly to obtain 0.03g/ml KMnO 4 A solution; adding crushed corn stalks, continuously stirring for a certain time to fully and uniformly mix, and then drying to constant weight; in the second step, the substrate raw material and KMnO 4 The mass ratio of (2) to (3).
Step three, putting the corn stalks treated in the step two into a quartz boat, and then putting the corn stalks into N 2 Carbonizing in a gas-shielded tube furnace for 2h at 700 ℃, cooling to room temperature along with the furnace, soaking in HCl solution with the concentration of 1M to remove oxides, washing with deionized water to neutrality (pH=7), and drying at 105 ℃ to obtain corn stalk-based Mesoporous Carbon (MC);
step four, adding 30mL deionized water into the reaction kettle, and adding 0.5mmol Ni (NO) 3 ) 2 ·6H 2 O、1mmol Co(NO 3 ) 2 ·6H 2 O and 1.5mmol urea, ultrasonic treating and stirring to disperse for 30min, then adding 30mg of corn stalk-based Mesoporous Carbon (MC) prepared in the third step, MC and NiCo 2 S 4 The mass ratio of (2) is 1:1, the mixture is subjected to ultrasonic treatment and stirring and dispersing for 30min, then the mixture is subjected to heat preservation at 140 ℃ for 5h, naturally cooled to room temperature, taken out, repeatedly washed with absolute ethyl alcohol and deionized water in sequence, and dried to constant weight at 80 ℃ to obtain a Ni-Co/MC precursor;
step five, adding 6mol Na into 30mL deionized water 2 S·9H 2 O is fully provided withMixing, adding the Ni-Co/MC precursor obtained in the step four, carrying out ultrasonic treatment until uniformity is obtained after mixing, then carrying out heat preservation for 8 hours under a Teflon lining autoclave at 160 ℃, naturally cooling to room temperature, taking out precipitate, washing with deionized water and absolute ethyl alcohol in sequence, and finally drying at 80 ℃ until constant weight is obtained to obtain NiCo 2 S 4 /MC-1。
Example 2: the present example differs from example 1 in that 15mg of the corn stalk based Mesoporous Carbon (MC) prepared in step three, MC and NiCo were added in step four 2 S 4 The mass ratio of (2) is 0.5:1. Labeled NiCo 2 S 4 MC-0.5. Other steps and parameters were the same as in example 1.
Example 3: the present example differs from example 1 in that 60mg of the corn stalk based Mesoporous Carbon (MC) prepared in step three, MC and NiCo were added in step four 2 S 4 The mass ratio of (2) to (1). Labeled NiCo 2 S 4 MC-2. Other steps and parameters were the same as in example 1.
The MC surface of the invention is an obvious mesoporous structure; and NiCo 2 S 4 The displayed sea urchin-shaped structure is composed of a plurality of nanotubes pointing to the center of the sphere, and the tubular structure not only can increase the contact area between the electrode material and the electrolyte, but also is convenient for the infiltration of the electrolyte and enhances the electrochemical performance.
NiCo in the present invention 2 S 4 The nanotubes are formed by a two-step hydrothermal reaction: first, the CO produced by hydrolysis of urea in an initial hydrothermal reaction 3 2- And OH (OH) - With Ni 2+ And Co 2+ The reaction produces NiCo with uniform sea urchin-like structure 2 (CO 3 ) 1.5 (OH) 3 A precursor; subsequently, niCo 2 (CO 3 ) 1.5 (OH) 3 CO in (b) 3 2- And OH (OH) - Anionic quilt S 2- Further substitution, because the cobalt ions and nickel ions diffuse out at a rate higher than S 2- The rate of ion in-diffusion is fast, and NiCo is formed in the next hydrothermal process by Kirkendall effect 2 S 4 A nanotube. When MC is of small mass, niCo 2 S 4 Is easier to be on a carbon meterSurface agglomeration, with the increase of MC mass, can improve the dispersibility of growth, effectively prevent NiCo 2 S 4 Is not limited, and is not limited. MC is added without adding NiCo 2 S 4 The morphology of (a) is influenced and still presents a tubular structure, and NiCo of such a structure 2 S 4 the/MC may provide enough active sites to enhance its electrochemical performance.
NiCo 2 S 4 The high multiple SEM, TEM, HRTEM of MC-1 and EDS of the C, ni, co and S elements are shown in FIG. 2. From FIGS. 2 a-b, niCo is clearly seen 2 S 4 Is a hollow nano tubular structure, and the thickness of the tube wall is about 21nm. From FIG. 2c, it can be seen that NiCo 2 S 4 Has high crystallinity, and lattice fringes with lattice spacing of 0.33nm and 0.28nm respectively correspond to NiCo 2 S 4 The (220) and (311) planes. Further visualization of NiCo by EDS analysis 2 S 4 C, ni, co and S present in the MC are uniformly dispersed. The atomic contents of Ni, co and S elements were 6.33%, 15.33% and 22.28%, respectively, which are similar to NiCo 2 S 4 The stoichiometric ratio of 1:2:4 of the atoms is basically consistent, indicating that NiCo 2 S 4 Evenly distributed over the MC. In NiCo 2 S 4 The valence of this mixture of Ni and Co is due to part of Ni 2+ And Co 2+ As a result of being sulfided during the hydrothermal reaction, this provides more active sites to promote redox reactions as compared to the single metal sulfide. NiCo of the invention 2 S 4 The surface of the MC has carbon oxygen functional groups and Ni 2+ 、Ni 3+ 、Co 2+ 、Co 3+ And S is 2- Ions.
The MC of the invention does not affect NiCo 2 S 4 Is a lattice structure of (a) and (b). The porous carbon skeleton of MC can well disperse NiCo 2 S 4 Nanotubes, and effectively improve NiCo 2 S 4 Agglomeration of nanotubes to enable NiCo 2 S 4 Still can keep better crystallinity.
MC、NiCo 2 S 4 And NiCo 2 S 4 Specific surface area/MC and pore size distribution curve 3 and Table 4。NiCo 2 S 4 The MC has a large specific surface area and a sufficient mesoporous structure, can be used for diffusion and transfer of electrolyte ions, further provides sufficient contact between a chemical reaction active site and an electrolyte solution, and shows better electrochemical performance.
TABLE 4 MC, niCo 2 S 4 And NiCo 2 S 4 Specific surface area and pore size characteristics of MC
NiCo 2 S 4 And NiCo 2 S 4 As shown in FIG. 4a-f, the electrochemical performance test result of the MC has higher specific surface area and rich pore structure, and can effectively disperse nano-tubular NiCo 2 S 4 Increasing the active sites in the redox process. The presence of MC can also limit NiCo during continuous charge and discharge 2 S 4 Can enhance the stability of the electrode structure. NiCo with rough surface and hollow structure 2 S 4 The nanotubes facilitate diffusion of electrolyte ions, reduce ion transport resistance and provide additional electroactive sites. And, the nanotube structure has a larger surface area by exposing the inner wall and the outer wall to electrochemical reaction, thereby better utilizing the electrode material. The addition of MC can improve NiCo 2 S 4 Poor conductivity, causing NiCo 2 S 4 The MC-1 has high conductivity, is favorable for the transmission and diffusion of electrolyte ions, and ensures the rapid transfer of electrons in the charge storage process.
NiCo 2 S 4 Electrochemical performance curves of the/MC-1// MC asymmetric supercapacitor are shown in FIG. 5 and Table 5.
TABLE 5 NiCo 2 S 4 MC-1 and NiCo reported previously 2 S 4 Performance comparison of base electrodes
As can be seen from FIG. 5 and Table 5, MC and NiCo 2 S 4 Is NiCo 2 S 4 MC-1 shows better electrochemical performance, and the specific capacitance is 1802.9F/g at the current density of 0.5A/g. With NiCo 2 S 4 Compared with NiCo 2 S 4 MC-1 also possesses better rate characteristics (81.3%) and cycle performance (91.6%).
The above results indicate that NiCo 2 S 4 MC-1 is an ideal supercapacitor electrode material.
Claims (7)
1. NiCo 2 S 4 The preparation method of the MC is characterized by comprising the following steps:
step one, adding Ni (NO) into deionized water 3 ) 2 ·6H 2 O、 Co(NO 3 ) 2 ·6H 2 The preparation method comprises the steps of (1) carrying out ultrasonic treatment on O and urea until the O and the urea are fully dissolved, then adding corn straw-based mesoporous carbon MC, dispersing uniformly, then preserving heat at 140 ℃ for 5h, naturally cooling to room temperature, repeatedly washing with absolute ethyl alcohol and deionized water in sequence, and then drying at 80 ℃ to constant weight to obtain a Ni-Co/MC precursor;
step two, firstly adding Na into deionized water 2 S·9H 2 O, fully mixing, adding the Ni-Co/MC precursor obtained in the step one, carrying out ultrasonic treatment until uniformity is obtained after mixing, then carrying out heat preservation at 160 ℃ for 8h, naturally cooling to room temperature, taking out precipitate, washing with absolute ethyl alcohol and deionized water in sequence, and finally drying at 80 ℃ until constant weight is obtained to obtain NiCo 2 S 4 /MC；
Wherein NiCo 2 S 4 The sea urchin-like structure shown is composed of a number of nanotubes pointing towards the centre of the sphere, the nanotubes having a rough surface and a hollow structure;
step one, mesoporous carbon and NiCo are prepared according to the basis of corn straw 2 S 4 The mass ratio of (1) is (0.5-2): 1, adding corn stalk based mesoporous carbon in proportion.
2. The method of claim 1, wherein the corn stalk based mesoporous carbon MC in step one is prepared by:
step 1, taking corn straw as a raw material, cleaning the raw material, drying the raw material to constant weight, and crushing the raw material;
step 2, KMnO 4 Adding the solid into deionized water, and fully stirring; adding crushed corn stalks, continuously stirring for a certain time to fully and uniformly mix, and then drying to constant weight;
and 3, placing the corn stalks treated in the step 2 into a quartz boat, placing the quartz boat into a tube furnace protected by inert gas, performing carbonization treatment, cooling the quartz boat to room temperature along with the furnace, soaking carbonized products in HCl solution to remove redundant oxides, washing the carbonized products with deionized water to be neutral, and drying the carbonized products at 105 ℃ to obtain the corn stalk-based mesoporous carbon MC.
3. The method of claim 2, wherein the corn stalks and KMnO in step 2 are selected from the group consisting of 4 The mass ratio of (2) is 1:1.5.
4. The method according to claim 2, wherein the inert gas in step 3 is nitrogen.
5. The production method according to claim 2, characterized in that the carbonization treatment in step 3 is continuous heating at 700 ℃ for 2h.
6. The process according to claim 2, wherein the concentration of the HCl solution in step 3 is 1M.
7. NiCo prepared by the method of any one of claims 1-6 2 S 4 the/MC is used as supercapacitor electrode material.
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