CN114566395A - Preparation method of biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material - Google Patents
Preparation method of biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 61
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 61
- 239000002028 Biomass Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 241000196252 Ulva Species 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910003266 NiCo Inorganic materials 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- 229940078494 nickel acetate Drugs 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229940045136 urea Drugs 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 5
- 239000004917 carbon fiber Substances 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 241000196253 Ulva prolifera Species 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
Abstract
A preparation method of a biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material relates to a preparation method of a metal oxide/carbon-based composite material. It is to solve the existing Co3O4The specific capacitance of the porous carbon fiber electrode material of the @ enteromorpha is low. The method comprises the following steps: firstly, preparing a biomass derived carbon substrate by using enteromorpha; secondly, preparing a metal oxide/carbon material; and thirdly, preparing the nitrogen-sulfur double-doped metal oxide/carbon-based composite material. The capacitance of the composite material is 1Ag at the current density‑1At the time of 1600Fg‑1When the current density is from 1Ag‑1Increased to 50Ag‑1Time, capacitance protectorThe retention rate reaches 65.8 percent. The asymmetric super capacitor assembled by the composite material has no obvious polarization under the voltage window of 1.5V and 1.48KW kg‑1The energy density of the power density reaches 73.6Whkg‑1And can be used in the fields of marine ecological protection and energy storage.
Description
Technical Field
The invention relates to a preparation method of a metal oxide/carbon-based composite material.
Background
In recent years, with the vigorous development of the breeding industry, the problem of flooding of enteromorpha prolifera is accompanied, and certain influence is caused on the ecological environment. The research of the biomass-derived carbon material makes the recycling of the enteromorpha possible. As the enteromorpha has a single-layer cell tubular structure, the material obtained after freeze drying and carbonization is easy to obtain ideal specific surface area and pore size, thereby obtaining ideal electrochemical performance and being widely explored. Chinese patent with application number CN201610803690.3 discloses a Co3O4A preparation method of a @ enteromorpha porous carbon fiber super-capacity electrode material comprises the step of compounding Co with enteromorpha porous carbon serving as a substrate3O4Compounding the prepared enteromorpha porous carbon fiber with Co nanowires in a hydrothermal mode, and preparing Co through high-temperature oxidation3O4@ @ enteromorpha porous carbon fiber. The specific capacitance per unit mass is less than or equal to 1200Fg-1. The low specific capacitance limits the application of the material.
Disclosure of Invention
The invention aims to solve the problem of using Co3O4The technical problem of low specific capacitance of the porous carbon fiber electrode material of the Enteromorpha @ is solved, and the preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material is provided.
The preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material comprises the following steps:
firstly, preparing a biomass-derived carbon substrate: washing the enteromorpha with water, and freeze-drying with a freeze dryer to obtain freeze-dried enteromorpha; then putting the freeze-dried enteromorpha into a heating furnace, and carrying out nitrogen protection at the temperature of 3-7 ℃ for min-1Heating to 700-900 ℃ at the heating rate, keeping for 1-5 hours, sequentially washing the product with 1M HCl and deionized water, and drying in vacuum to obtain the biomass derived carbon substrate; marking as C;
two, metal oxide/carbon material NiCo2O4Preparation of-C: mixing a biomass derived carbon substrate with nickel acetate, cobalt acetate, urea and hexadecyl trimethyl ammonium chloride, transferring the mixture into a Teflon high-pressure kettle, heating the mixture to 100-140 ℃, keeping the mixture for 4-6 hours, taking out a product, sequentially washing the product with ethanol and deionized water, drying the product in vacuum, putting the product into a tubular furnace, heating the product to 250-450 ℃ in an air atmosphere, keeping the temperature for 3-5 hours, and obtaining a metal oxide/carbon material; is denoted as NiCo2O4-C；
N, S-NiCo composite material of metal oxide/carbon base with double doping of nitrogen and sulfur2O4Preparation of-C: putting the mixture of the metal oxide/carbon material and thiourea into a tube furnace, heating to 400-600 ℃, and annealing for 2-4 h to obtain the N, S-NiCo double-doped metal oxide/carbon-based composite material2O4-C。
Further, the vacuum drying in the step one is carried out for 8 to 14 hours under the conditions that the temperature is 60 ℃ and the vacuum degree is-0.08 to-0.098 MPa.
Further, in step two, the ratio of the mass of the biomass-derived carbon substrate to the sum of the amounts of the nickel acetate and cobalt acetate species is 1 g: (2-8) mmol;
further, in the second step, the molar ratio of nickel acetate to cobalt acetate is 1: (1-3);
further, in step two, the ratio of the mass of the biomass-derived carbon substrate to the amount of the substance of urea is 1 g: (2-10) mmol;
further, in step two, the ratio of the mass of biomass-derived carbon substrate to the amount of the mass of cetyltrimethylammonium chloride is 1 g: (0.5-3) mmol;
furthermore, in the second step, the vacuum drying is carried out for 10 to 14 hours under the conditions that the temperature is 50 to 70 ℃ and the vacuum degree is-0.08 to-0.098 MPa;
furthermore, in the third step, the mass ratio of the metal oxide/carbon material to the thiourea is 1: (4-6).
The preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material comprises the steps of calcining a biomass material enteromorpha to generate an interconnected sheet structure, reacting the sheet structure with a metal compound to generate the metal oxide/nitrogen-doped carbon-based composite material, and finally reacting with thiourea at a high temperature to generate the nitrogen-sulfur double-doped metal oxide/carbon-based composite material.
The capacitance of the nitrogen-sulfur double-doped metal oxide/carbon-based composite material has the current density of 1Ag-1When it reaches 1600F.g-1Good rate capability and current density from 1Ag-1Increased to 50Ag-1The capacity retention rate reached 65.8%. The asymmetric supercapacitor assembled with the material does not have obvious polarization under the voltage window of 1.5V. The asymmetric super capacitor is 1.48KW kg-1Can exhibit 73.6Wh kg at a power density of-1And an energy density of 30.798KW kg-1Can exhibit 42.755Wh kg at a power density of-1The invention provides a way for the application of the enteromorpha biomass material in the field of energy storage, and can be used in the fields of marine ecological protection and energy storage.
Drawings
FIG. 1 is a scanning electron micrograph of a biomass-derived carbon substrate C-800 obtained in step one of example 1;
FIG. 2 is a scanning electron micrograph of comparative biomass-derived nitrogen-doped carbon substrate NC-800 from step one of example 1;
FIG. 3 is a scanning electron micrograph of NiCo double hydroxide/activated carbon NiCo-LDH-C-800 obtained in step two of example 1;
FIG. 4 shows a metal oxide/carbon material NiCo obtained in step two of example 12O4-scanning electron micrographs of C-800;
FIG. 5 is a N, S-NiCo double-doped metal oxide/carbon-based composite material obtained in step three of example 12O4-scanning electron micrographs of C-800;
FIG. 6 is an X-ray diffraction pattern of the material prepared in example 1;
FIG. 7 is an XPS spectrum of the material prepared in example 1;
FIG. 8 is a BET plot of the material prepared in example 1;
FIG. 9 is a pore size distribution plot for the material prepared in example 1;
FIG. 10 is a graph of rate performance of the material prepared in example 1 at different current densities;
FIG. 11 is a N, S-NiCo composite material with a nitrogen-sulfur double-doped metal oxide/carbon matrix2O4-C-800 is the anode and the biomass-derived nitrogen-doped carbon substrate NC-800 is the cathode of the working window tuning scheme of the asymmetric supercapacitor assembled;
FIG. 12 is a N, S-NiCo composite material with a nitrogen-sulfur double-doped metal oxide/carbon matrix2O4-the energy density of the asymmetric supercapacitor assembled with the anode of C-800 and the cathode of the biomass-derived nitrogen-doped carbon material NC-800 is plotted as a function of the power density;
FIG. 13 is a N, S-NiCo composite N, S-NiCo material prepared in example 22O4-scanning electron micrographs of C-800.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: the preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material of the embodiment comprises the following steps:
firstly, preparing a biomass-derived carbon substrate: washing Enteromorpha with deionized water for 10 times, placing into freeze drying machine, and drying at high temperatureFreeze drying at-55 deg.C under vacuum degree of 10Pa for 2 days to obtain lyophilized Enteromorpha prolifera; putting 4.5 g of freeze-dried enteromorpha into a heating furnace, and carrying out heating at 5 ℃ for min under the protection of nitrogen-1Heating the product to 800 ℃ at the heating rate, keeping the temperature for 2 hours, sequentially washing the product with 1M HCl and deionized water, putting the product into a vacuum drying oven, and keeping the product for 12 hours under the conditions that the temperature is 60 ℃ and the vacuum degree is-0.09 MPa to obtain a biomass-derived carbon substrate used as a comparison; is marked as C-800;
in the step, the vacuum degree of the freeze dryer is 10Pa as absolute pressure, and the vacuum degree of the vacuum drying box is-0.09 MPa as relative pressure.
Simultaneously preparing a biomass-derived nitrogen-doped carbon material as a comparison, namely uniformly mixing 4.5 g of freeze-dried enteromorpha prolifera and 6g of ammonium citrate, putting the mixture into a heating furnace, and performing nitrogen protection at 5 ℃ for min-1Heating the mixture to 800 ℃ at the heating rate, keeping the temperature for 2 hours, sequentially washing the product with 1M HCl and deionized water, putting the product into a vacuum drying oven, and keeping the product for 12 hours under the conditions that the temperature is 60 ℃ and the vacuum degree is-0.09 MPa to obtain the biomass derived nitrogen-doped carbon material; marking as NC-800;
two, metal oxide/carbon material NiCo2O4Preparation of-C: 0.239g (0.9643mmol) of nickel acetate, 0.32g (1.929mmol) of cobalt acetate, 0.139g (2.314mmol) of urea and 0.165g (0.514mmol) of cetyltrimethylammonium chloride are put into 30mL of deionized water and stirred for 10 minutes, then 0.45g of biomass-derived carbon substrate C-800 is added, after uniform mixing, the mixture is transferred into a Teflon autoclave and subjected to 5 ℃ for min-1Heating to 120 ℃ at the heating rate, keeping the temperature for 5 hours, taking out the product, sequentially cleaning the product with ethanol and deionized water, then putting the product into a vacuum drying oven, and keeping the product for 12 hours under the conditions that the temperature is 60 ℃ and the vacuum degree is-0.09 MPa to obtain the nickel-cobalt double hydroxide/activated carbon, which is marked as NiCo-LDH-C-800; 0.6139g of the obtained nickel cobalt double hydroxide/activated carbon is put into a tube furnace and heated to 350 ℃ for 4 hours in the air atmosphere to obtain a metal oxide/carbon material; is denoted as NiCo2O4-C-800；
N, S-NiCo composite material of metal oxide/carbon base with double doping of nitrogen and sulfur2O4Preparation of C-800: 0.1180g of metal oxide/carbon material NiCo2O4Mixture of-C-800 and 0.5023g of thiourea, placed in a tube furnace at 2 ℃ for min-1Heating to 400 ℃ at the speed of (1) and keeping the temperature for 3 hours for annealing to obtain the N, S-NiCo double-doped metal oxide/carbon-based composite material2S4-C-800。
The scanning electron micrograph of the biomass-derived carbon substrate C-800 obtained in the first step is shown in FIG. 1, and it can be seen from FIG. 1 that C-800 is an interconnected sheet structure.
The scanning electron micrograph of the biomass-derived nitrogen-doped carbon material NC-800 obtained in the first step as a comparison is shown in fig. 2, and it can be seen from fig. 2 that the NC-800 structure is changed into a sheet structure stacked one on another layer by layer.
The scanning electron micrograph of the nickel cobalt double hydroxide/activated carbon NiCo-LDH-C obtained in the second step is shown in FIG. 3, and it can be seen from FIG. 3 that many spherical particles are found to grow on the surface of the activated carbon.
The metal oxide/carbon material NiCo obtained in the second step2O4The scanning electron micrograph of-C-800 is shown in FIG. 4, and it can be seen from FIG. 4 that the oxidized metal oxide/carbon material NiCo2O4The surface of the C-800 laminate becomes smooth and a few nanoplates grow on the surface.
The N, S-NiCo composite material N, S-NiCo with the nitrogen and sulfur double-doped metal oxide/carbon base obtained in the third step2O4The scanning electron micrograph of-C-800 is shown in FIG. 5, and it can be seen from FIG. 5 that the material surface is a lamellar structure with a large number of defects, and a large number of particles are present on the surface, and the sulfur on the surface is successfully doped.
The material prepared in each step of example 1, biomass-derived carbon substrate C-800, biomass-derived nitrogen-doped carbon material NC-800 as a comparison, nickel cobalt double hydroxide/activated carbon NiCo-LDH-C-800, metal oxide/carbon material NiCo2O4-C-800, N, S-NiCo double-doped metal oxide/carbon-based composite material2O4The X-ray diffraction test of-C-800 gave the X-ray diffraction pattern shown in FIG. 6, as can be seen from FIG. 6,the diffraction peak of NC-800 shifts to a lower diffraction degree than C-800, indicating that the lattice spacing of N-doped crystal is enlarged, resulting in an overall leftward shift of its peak. While in NiCo-LDH-C-800, NiCo2O4The main peak of-C-800 may represent NiCo2O4Successful synthesis of, and N, S-NiCo2O4The main peak of-C-800 can be represented by successful doping of elemental sulfur.
The material prepared in each step of example 1, biomass-derived carbon substrate C-800, biomass-derived nitrogen-doped carbon material NC-800 as a comparison, nickel cobalt double hydroxide/activated carbon NiCo-LDH-C-800, metal oxide/carbon material NiCo2O4-C-800, N, S-NiCo double-doped metal oxide/carbon-based composite material2O4The XPS spectrum of-C-800 is shown in FIG. 7, and the peaks of C, N, O, Ni, Co, S elements are shown in FIG. 7, indicating that C-800, NC-800, NiCo-LDH-C-800, NiCo2O4-C-800，N,S-NiCo2O4Successful synthesis of C-800.
The material prepared in each step of example 1, biomass-derived carbon substrate C-800, biomass-derived nitrogen-doped carbon material NC-800 as a comparison, nickel cobalt double hydroxide/activated carbon NiCo-LDH-C-800, metal oxide/carbon material NiCo2O4-C-800, N, S-NiCo double-doped metal oxide/carbon-based composite material2O4The BET plot of-C-800 is shown in FIG. 8, the corresponding pore size distribution is shown in FIG. 9, and it can be seen from FIGS. 8 and 9 that the specific surface area of NC-800 is 683.2m2g-1The average pore diameter is 12.5 nm; the specific surface area of NiCo-LDH-C-800 was 573.3m2g-1The average pore diameter is 7.67 nm; n, S-NiCo2O4Specific surface area of-C-800 of 465.9m2g-1The average pore diameter is 5.4 nm; the specific surface areas of the active carbon particles are all higher than that of the active carbon C-800, and the specific surface area of the active carbon C-800 is 378.9m2g-1The average pore diameter is 8.43nm, which proves that the modified activated carbon can effectively improve the specific surface area, further enlarge the contact area with electrolyte and an electrode, and improve the electrochemical performance. Following the addition of the metallic elements and the corresponding heat treatment,the specific surface area of the material is larger and larger, and the pore size distribution mainly comprising multiple mesopores is presented, which is beneficial to the full contact of the material and electrolyte ions and is beneficial to improving the specific capacitance and the conductivity of the material.
Example 1 the material prepared by the steps of example 1, biomass-derived carbon substrate C-800, comparative biomass-derived nitrogen-doped carbon material NC-800, metal oxide/carbon material NiCo2O4-C-800, N, S-NiCo double-doped metal oxide/carbon-based composite material2O4The rate performance curve of-C-800 at different current densities is shown in FIG. 10, and it can be seen from FIG. 10 that C-800, NC-800 and NiCo2O4-C-800 and N, S-NiCo2O4Capacitance of-C-800 at current density from 1Ag-1Are respectively 150, 300, 1300, 1600F.g-1Current density of 1Ag-1Increased to 50Ag-1When is, C-800, NC-800, NiCo2O4-C-800 and N, S-NiCo2O4The capacitance retention rates of-C-800 are respectively 50%, 57%, 65.4% and 65.8%, and comparison shows that nitrogen-sulfur double doping can improve an ion diffusion channel so as to improve the rate capability and specific capacitance of the material.
N, S-NiCo composite material of metal oxide/carbon base with double doping of nitrogen and sulfur2O4The asymmetric supercapacitor assembled with-C-800 as the anode and the biomass-derived nitrogen-doped carbon material NC-800 as the cathode tested the operating window of the device, and as can be seen from fig. 11, the asymmetric supercapacitor did not develop significant polarization at a voltage window of 1.5V. FIG. 12 is a graph of energy density as a function of power density for an asymmetric ultracapacitor, as seen in FIG. 12 at 1.48KW kg-1Can exhibit 73.6Wh kg at a power density of-1And an energy density of 30.798KW kg-1Can exhibit 42.755Wh kg at a power density of-1The energy density of the enteromorpha prolifera biomass material provides a road for the application of the enteromorpha prolifera biomass material in the field of energy storage.
Example 2: the preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material comprises the following steps:
firstly, preparing a biomass-derived carbon substrate: washing Enteromorpha prolifera with deionized water for 10 times, placing into a freeze dryer, and freeze-drying at-55 deg.C under vacuum degree of 10Pa for 2 days to obtain lyophilized Enteromorpha prolifera; then 4.5 g of freeze-dried enteromorpha is put into a heating furnace and is heated for 5 min under the protection of nitrogen-1Heating the product to 900 ℃ at the heating rate, keeping the temperature for 1.5 hours, sequentially cleaning the product with 1M HCl and deionized water, putting the product into a vacuum drying oven, and keeping the product for 12 hours under the conditions that the temperature is 60 ℃ and the vacuum degree is-0.09 MPa to obtain the biomass derived carbon substrate; is marked as C-900;
two, metal oxide/carbon material NiCo2O4Preparation of-C: 0.239g (0.9643mmol) of nickel acetate, 0.16g (0.9643mmol) of cobalt acetate, 0.139g (2.314mmol) of urea and 0.165g (0.514mmol) of hexadecyltrimethylammonium chloride are put into 30mL of deionized water and stirred for 10 minutes, then 0.45g of biomass-derived carbon substrate C-900 is added, after uniform mixing, the mixture is transferred into a Teflon autoclave and the temperature is kept for 5 ℃ for min-1Heating to 140 ℃ at the heating rate, keeping the temperature for 3 hours, taking out the product, sequentially cleaning the product with ethanol and deionized water, putting the product into a vacuum drying oven, and keeping the product for 12 hours under the conditions that the temperature is 60 ℃ and the vacuum degree is-0.09 MPa to obtain the nickel-cobalt double hydroxide/activated carbon, which is marked as NiCo-LDH-C-900; 0.6139g of the obtained nickel cobalt double hydroxide/activated carbon is put into a tube furnace and heated to 450 ℃ for 4 hours in the air atmosphere to obtain a metal oxide/carbon material; is marked as NiCo2O4-C-900；
N, S-NiCo composite material of metal oxide/carbon base with double doping of nitrogen and sulfur2O4Preparation of C-900: 0.1180g of NiCo, a metal oxide/nitrogen-doped carbon material2O4Mixture of-C-900 and 0.5023g of thiourea, placed in a tube furnace at 2 ℃ for min-1Heating to 500 ℃ at the speed of (1) and keeping the temperature for 3 hours for annealing to obtain the N, S-NiCo double-doped metal oxide/carbon-based composite material2O4-C-900。
The N, S-NiCo composite material N, S-NiCo with double doped nitrogen and sulfur obtained in the embodiment2O4-C-The scanning electron micrograph of 900 is shown in FIG. 13. As can be seen in FIG. 13, N, S-NiCo2O4C-900 is a layer, with a large number of particles present on the surface.
The N, S-NiCo composite material N, S-NiCo double-doped with nitrogen and sulfur obtained in the example was tested2O4The results of the rate performance curves of-C-900 at different current densities show that N, S-NiCo2O4-C-900 at a current density of 1Ag-1The specific capacitance can reach 1200F g-1Increased to 50Ag-1The capacity retention was 62%.
Claims (8)
1. The preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material is characterized by comprising the following steps of:
firstly, preparing a biomass-derived carbon substrate: washing the enteromorpha with water, and freeze-drying with a freeze dryer to obtain freeze-dried enteromorpha; then putting the freeze-dried enteromorpha into a heating furnace, and carrying out nitrogen protection at the temperature of 3-7 ℃ for min-1Heating to 700-900 ℃ at the heating rate, keeping for 1-5 hours, sequentially washing the product with 1M HCl and deionized water, and drying in vacuum to obtain the biomass derived carbon substrate;
two, metal oxide/carbon material NiCo2O4Preparation of-C: mixing a biomass derived carbon substrate with nickel acetate, cobalt acetate, urea and hexadecyl trimethyl ammonium chloride, transferring the mixture into a Teflon high-pressure kettle, heating the mixture to 100-140 ℃, keeping the mixture for 4-6 hours, taking out a product, sequentially washing the product with ethanol and deionized water, drying the product in vacuum, putting the product into a tubular furnace, heating the product to 250-450 ℃ in an air atmosphere, keeping the temperature for 3-5 hours, and obtaining a metal oxide/carbon material;
n, S-NiCo composite material of metal oxide/carbon base with double doping of nitrogen and sulfur2O4Preparation of-C: and (3) putting the mixture of the metal oxide/carbon material and thiourea into a tube furnace, heating to 400-600 ℃, and annealing for 2-4 h to obtain the nitrogen-sulfur double-doped metal oxide/carbon-based composite material.
2. The method for preparing a biomass-derived nitrogen and sulfur double-doped metal oxide/carbon-based composite material according to claim 1, wherein the vacuum drying in the step one is performed at 60 ℃ and at a vacuum degree
Vacuum drying for 8-14 hours under the condition of-0.08 to-0.098 MPa.
3. The method for preparing a biomass-derived nitrogen and sulfur double-doped metal oxide/carbon-based composite material according to claim 1 or 2, wherein in the second step, the ratio of the mass of the biomass-derived carbon substrate to the sum of the amounts of the nickel acetate and cobalt acetate is 1 g: (2-8) mmol.
4. The method for preparing a biomass-derived nitrogen-sulfur double doped metal oxide/carbon-based composite material according to claim 1 or 2, wherein in the second step, the molar ratio of nickel acetate to cobalt acetate is 1: (1-3).
5. The method for preparing a biomass-derived nitrogen-sulfur double doped metal oxide/carbon based composite material according to claim 1 or 2, wherein in step two, the ratio of the mass of the biomass-derived carbon substrate to the amount of the substance of urea is 1 g: (2-10) mmol.
6. The method for preparing a biomass-derived nitrogen-sulfur double doped metal oxide/carbon based composite material according to claim 1 or 2, wherein in step two, the ratio of the mass of the biomass-derived carbon substrate to the amount of the substance of cetyltrimethylammonium chloride is 1 g: (0.5 to 3) mmol.
7. The preparation method of the biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material as claimed in claim 1 or 2, wherein in the second step, the vacuum drying is performed for 10-14 hours at a temperature of 50-70 ℃ and a vacuum degree of-0.08-0.098 MPa.
8. The preparation method of the biomass-derived nitrogen and sulfur double-doped metal oxide/carbon-based composite material according to claim 1 or 2, wherein in the third step, the mass ratio of the metal oxide/carbon material to the thiourea is 1: (4-6).
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