CN115784206A - Mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere and preparation method and application thereof - Google Patents
Mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
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- 238000005406 washing Methods 0.000 claims description 13
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 12
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 12
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 12
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 10
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- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 8
- 229920000428 triblock copolymer Polymers 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 claims description 6
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 claims description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229920002025 Pluronic® F 88 Polymers 0.000 claims description 2
- 229920002057 Pluronic® P 103 Polymers 0.000 claims description 2
- 229920002066 Pluronic® P 65 Polymers 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
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- 238000006555 catalytic reaction Methods 0.000 abstract description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
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- 239000000843 powder Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
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- 239000011807 nanoball Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 1
- -1 lithium-sulfur ion Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere and a preparation method and application thereof. Compared with the prior art, the method is simple, the wet method is used for preparation, the raw materials are easy to obtain, the method is suitable for large-scale production, and the method has wide application prospects in a plurality of fields such as separation, environment, energy, catalysis and the like.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres and a preparation method, a preparation method and application thereof.
Background
Lithium ion batteries, which are commercialized batteries, have the advantages of stable discharge voltage, high energy density, long cycle life, high voltage, wide working temperature range, low self-discharge, and the like, and are currently widely used in various aspects of production and life (including large-scale energy storage of portable electronic devices, aerospace, hybrid power and electric vehicles, and smart grids). However, the existing commercial lithium ion battery has limited specific capacity and high cost, and cannot meet the increasing demand of human for energy. Therefore, it is urgent to find a new form of rechargeable lithium secondary battery having a high energy density while reducing the battery cost. Among the family of rechargeable lithium secondary batteries, lithium sulfur secondary batteries are due to their high theoretical capacity (1672 mA h g) -1 ) And high specific energy density (2600W h kg) -1 ) But is of great interest. The discharge of a lithium sulfur battery is subject to a solid-to-liquid-to-solid conversion process. This complex phase transition is different from other battery systems, making the study of lithium sulfur batteries difficult. Researchers have thought to compound sulfur with other materials to alleviate these problems with the sulfur anode. Carbon materials have become widely used as positive electrode carrier materials for lithium-sulfur batteries by researchers due to their high conductivity and high adsorption of sulfur, mainly because of: 1) The carbon material has small volume change (graphite is 9%) in the charging and discharging processes, and can buffer the volume expansion of sulfur; 2) The carbon material also has higher coulombic efficiency, better cycle performance and higher conductivity, and can relieve the influence of the defects of poor sulfur cycle performance and the like; 3) The carbon material has excellent adsorption to polysulfides, and can reduce the dissolution thereof in an electrolyte. Among them, the mesoporous carbon material is considered as an ideal choice for preparing the anode material of the new generation lithium-sulfur secondary battery due to adjustable pore channels, large specific surface area, high pore volume and uniform pore size. Compared with microporous materials such as activated carbon and the like, the porous material has larger pore diameter, the surface is more easily soaked by electrolyte, the internal ion migration resistance of the material is smaller, and the electrochemical performance of the material on a lithium-sulfur secondary battery is better; compared with materials such as macroporous carbon, the uniform pore size and the pore canal in ordered connection are more favorable for the rapid transmission of electrolyte ions. However, the large-scale synthesis of the compounds is still limited due to the complicated or expensive method used in the synthesis production.
Disclosure of Invention
The invention aims to provide mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres, a preparation method and application thereof, wherein the preparation method is simple and easy to control.
The purpose of the invention can be realized by the following technical scheme: a preparation method of mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres comprises the steps of using dopamine hydrochloride as a carbon source and a nitrogen source, using amphiphilic triblock copolymer PEO-PPO-PEO as a template agent, using organic micromolecules of methyl phenol as a structure directing agent, using organic micromolecules of methyl benzene as a pore-expanding agent, using inorganic base as a catalyst, using a mixed solution of alcohol and water as a solvent, firstly preparing polydopamine nanospheres, then removing the template agent in the material through roasting, and carbonizing the polydopamine nanospheres simultaneously to obtain the mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres.
The method is simple, the wet method is used for preparation, the raw materials are easy to obtain, the method is suitable for large-scale production, and the method has wide application prospects in a plurality of fields such as separation, environment, energy, catalysis and the like.
Preferably, the preparation method of the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere comprises the following specific steps of:
(1) Firstly, adding a certain amount of dopamine hydrochloride, an amphiphilic triblock copolymer PEO-PPO-PEO surfactant and a methylphenol organic small molecular structure directing agent into a mixed system of alcohol and water, and stirring for dissolving to obtain a transparent solution;
(2) Adding a certain amount of methylbenzene organic micromolecule pore-enlarging agent into the transparent solution prepared in the step (1), and stirring to obtain a colloidal solution;
(3) Adding a certain amount of inorganic base substances into the colloidal solution prepared in the step (2), further reacting, and centrifugally washing to obtain a multilayer spiral chiral nano polydopamine nanosphere with a mesoporous structure;
(4) And (4) roasting the polydopamine nanospheres prepared in the step (3) in an inert atmosphere to finally obtain the mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres.
Preferably, the inert atmosphere is selected from nitrogen or argon.
Preferably, the reaction temperature in the step (3) is 20-80 ℃.
Preferably, the amphiphilic triblock copolymer PEO-PPO-PEO surfactant is selected from Pluronic P123 (EO) 20 PO 70 EO 20 )、Pluronic P103(EO 17 PO 56 EO 17 )、Pluronic P85(EO 26 PO 39 EO 26 )、Pluronic P65(EO 20 PO 30 EO 20 )、Pluronic L121(EO 5 PO 70 EO 5 )、Pluronic F127(EO 106 PO 70 EO 106 )、Pluronic F88(EO 100 PO 39 EO 100 )、Pluronic F98(EO 123 PO 47 EO 123 )、Pluronic F108(EO 132 PO 50 EO 132 )、B50-6600(EO 39 BO 47 EO 39 )、B70-4600(EO 15 BO 45 EO 15 )、B40-1900(EO 13 BO 11 EO 13 )、B20-3800(EO 34 BO 11 EO 34 ) One or more of them.
Preferably, the organic small molecule of methyl benzene is selected from one or more of 2,4, 6-trimethylphenol, 2,3, 5-trimethylphenol, 3, 5-dimethylphenol, 2, 5-dimethylphenol, 3, 6-dimethylphenol, 3-methylphenol and phenol.
Preferably, the organic small molecule of methylbenzene is selected from one or more of dimethylbenzene, mesitylene and fatty acid.
Preferably, the inorganic base is one or more selected from sodium hydroxide, potassium hydroxide, ammonia water, ethylenediamine and calcium hydroxide.
Preferably, the alcohol comprises one or more of ethanol, ethylene glycol, glycerol, methanol, butanol and pentanol.
Preferably, the roasting temperature range is 350-1200 ℃, the temperature rising speed is 0.5-10 ℃/min, and the time range is 1-9h.
Preferably, the mass ratio of the carbon source to the surfactant is 1.
The mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres prepared by the preparation method have mesoporous channels and have multilayer spiral structures and structural chiral characteristics.
Preferably, the diameter of the nanosphere is 50-210nm, and the specific surface area is 200-800m 2 Per g, pore volume of 0.10-0.96cm 3 Per g, aperture of 3-15nm, 1-7 layers, and nitrogen content of 2-10%.
The mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres have uniform and adjustable particle size (50-210 nm) and large specific surface area (200-800 m) 2 Per gram) and pore volume (0.10-0.96 cm) 3 The pore size is uniform and adjustable (3.0-15.0 nm), and the nitrogen content is adjustable (2-10%). The specific surface area, the pore volume and the nitrogen content can be regulated and controlled through roasting conditions.
The mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres are used as electrode materials of lithium-sulfur batteries and show excellent electrochemical performance.
Compared with the prior art, the invention has the following advantages:
1. the method is simple to operate, easy to repeat, easy to control reaction conditions and easy to industrialize;
2. the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere material has a multilayer spiral structure, has the structural chiral characteristic, and has the advantages of high specific surface area, large pore volume, uniform pore diameter, adjustable size cavity and adjustable wall thickness;
3. the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material has uniform and adjustable multilayer spiral mesoporous channels, and the existence of the channels is beneficial to the storage of substances and the transmission of electrolyte, and is beneficial to the storage of sulfur and the transmission of electrolyte when being applied to an electrode material of a lithium-sulfur ion battery, so that the performance of the battery is improved;
4. when the nanosphere is applied to a lithium-sulfur battery electrode material, the nanosphere shows higher battery capacity and excellent rate performance, and after the nanosphere is circulated for 1000 circles under the current density of 0.1C, the specific capacity of the nanosphere is still stable at 985mAh/g;
5. the invention has wide and cheap raw material sources, is beneficial to industrial production, and has wide application prospects in various fields of environment, energy, catalysis and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph and a high-resolution transmission electron microscope (HRTEM) photograph of a mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composite material of the present invention having a particle size of 210nm and 5 helical layers, wherein (a) and (b) are Scanning Electron Microscope (SEM) photographs, (c) is a Transmission Electron Microscope (TEM) photograph, and (d) is a high-resolution transmission electron microscope (HRTEM) photograph, obtained in example 1.
FIG. 2 is an optical photograph of a clear solution during the reaction, obtained in example 1.
FIG. 3 is an optical photograph of a colloidal solution during the reaction, obtained in example 1.
Fig. 4 is a CD map of a mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composite material having a particle size of 210nm and 5 helical layers according to the present invention, which is obtained in example 1.
Fig. 5 shows a nitrogen adsorption/desorption isotherm (a) and a pore size distribution (b) of a mesoporous multilayer helical chiral nitrogen-doped carbon nanoball composite material of the present invention, which has a particle diameter of 210nm and 5 helical layers, obtained in example 1.
Fig. 6 shows XPS survey (a) and N1s fitting survey (b) of mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composites of the present invention having a particle size of 210nm and 5 helical layers, obtained in example 1.
Fig. 7 is a thermogravimetric curve of the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 210nm and the number of spiral layers of 5 according to the present invention, which is obtained from example 1.
Fig. 8 is an infrared spectrum of the polydopamine nanosphere having a particle size of 210nm and 5 spiral layers and the corresponding mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material, which is obtained in example 1.
Fig. 9 is a raman spectrum of a mesoporous multilayer helical chiral nitrogen-doped carbon nanoball composite material of the present invention, which has a particle size of 210nm and 5 spiral layers, obtained in example 1.
Fig. 10 is an XRD spectrum of the mesoporous multilayer helical chiral nitrogen-doped carbon nanoball composite material of the present invention, which has a particle size of 210nm and 5 spiral layers, obtained from example 1.
Fig. 11 is a scanning electron micrograph and a high-resolution transmission electron micrograph of the mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composite material of the present invention having a particle size of 190nm and 7 helical layers, obtained in example 2.
Fig. 12 is a scanning electron micrograph and a high-resolution transmission electron micrograph of the mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composite material of the present invention having a particle size of 160nm and 4 helical layers, which were obtained in example 3.
Fig. 13 is a scanning electron micrograph and a high-resolution transmission electron micrograph of the mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composite material of the present invention having a particle size of 150nm and 3 helical layers, which were obtained in example 4.
Fig. 14 is a scanning electron micrograph and a high-resolution transmission electron micrograph of the mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere composite material of the present invention having a particle size of 140nm and 2 helical layers, which were obtained in example 5.
Fig. 15 is a scanning electron micrograph and a high-resolution transmission electron micrograph of a mesoporous multilayer helical chiral nitrogen-doped carbon nanoball composite material of the present invention, which has a particle size of 120nm and a number of helical layers of 1 layer, obtained in example 6.
Fig. 16 is a graph showing electrochemical properties of a mesoporous multilayer spiral chiral nitrogen-doped carbon nanoball composite material of the present invention, which has a particle size of 210nm and 5 spiral layers, as an electrode for a lithium-sulfur battery, and is obtained in example 7.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
Example 1
Synthesizing the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 210nm and 5 spiral layers:
1.0g of F127, 1.0g of dopamine hydrochloride and 5g of 2,4, 6-trimethylphenol were dissolved in a mixed solution of 25ml of ethanol and 75ml of deionized water, and stirred to obtain a uniform transparent solution, and an optical photograph is shown in FIG. 2. Thereafter, 5g of 1,3, 5-trimethylbenzene was added thereto, and the solvent was gradually changed from a colorless solution to a colloidal solution, and the optical photograph thereof is shown in FIG. 3. The above colloidal solution was stirred for a further 12h and then 3ml of an aqueous ammonia solution was added dropwise thereto, whereupon the solution rapidly turned brown in color. The reaction was continued for 24h, and then the solution was subjected to centrifugal alcohol washing and washing, followed by freeze-drying to obtain a solid. And (3) placing the prepared brown solid powder in a tube furnace, roasting for 2h at 350 ℃ in the nitrogen atmosphere, then continuously heating to 900 ℃ and roasting for 5h, wherein the heating rate is 5 ℃/min, and finally obtaining the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 210nm and 5 spiral layers. The scanning electron micrograph and the high-resolution transmission electron micrograph are shown in figure 1, the CD spectrum is shown in figure 4, the nitrogen adsorption curve and the pore size distribution are shown in figure 5, the XPS full spectrum and the N1s energy spectrum are shown in figure 6, the thermogravimetric curve is shown in figure 7, the infrared spectrum is shown in figure 8, the Raman spectrum is shown in figure 9, and the XRD spectrum is shown in figure 10.
The prepared mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material has the BET specific surface area of 650m 2 Per g, pore volume of 0.65cm 3 Per g, pore diameter of 3.9nm, average particle sizeThe diameter is 210nm.
Example 2
Synthesizing the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 190nm and 7 spiral layers:
1.0g of F108, 1.0g of dopamine hydrochloride and 5g of 2,3, 5-trimethylphenol were dissolved in a mixed solution of 50ml of ethylene glycol and 50ml of deionized water, and stirred to obtain a uniform and transparent solution. Thereafter, 5g of 1,3, 5-trimethylbenzene was added thereto, and the solvent gradually changed from a colorless solution to a colloidal solution. The above colloidal solution was stirred for a further 6h and then 2ml of ethylenediamine solution were added dropwise thereto, whereupon the solution rapidly turned brown in color. The reaction was continued for 24h, and then the solution was subjected to centrifugal alcohol washing and washing, followed by freeze-drying to obtain a solid. And (3) placing the prepared brown solid powder in a tube furnace, roasting for 2h at 350 ℃ in the nitrogen atmosphere, then continuously heating to 900 ℃ and roasting for 6h, wherein the heating rate is 2 ℃/min, and finally obtaining the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 190nm and 7 spiral layers. The scanning electron micrograph and the high-resolution transmission electron micrograph are shown in FIG. 11.
Example 3
The synthesis of the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 160nm and 4 spiral layers:
1.0g of P123, 1.0g of dopamine hydrochloride and 5g of 3, 5-dimethylphenol were dissolved in a mixed solution of 50ml of methanol and 50ml of deionized water, and stirred to obtain a uniform and transparent solution. Thereafter, 5g of 1,3, 5-trimethylbenzene was added thereto, and the solvent gradually changed from a colorless solution to a colloidal solution. The above colloidal solution was stirred for a further 8h and then 3ml of aqueous ammonia solution was added dropwise thereto, whereupon the solution rapidly turned brown in color. The reaction was continued for 12h, and then the solution was subjected to centrifugal alcohol washing and washing, followed by freeze-drying to obtain a solid. And (3) placing the prepared brown solid powder in a tube furnace, roasting at 350 ℃ for 2h in the nitrogen atmosphere, then continuously heating to 900 ℃ and roasting for 4h at the heating rate of 3 ℃/min, and finally obtaining the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 160nm and 4 layers of spiral layers. The scanning electron micrograph and the high-resolution transmission electron micrograph are shown in FIG. 12.
Example 4
Synthesis of mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with particle size of 150nm and 3 spiral layers:
1.0g of F127, 1.0g of dopamine hydrochloride and 8g of 2,4, 6-trimethylphenol were dissolved in a mixed solution of 50ml of ethylene-propylene-triol and 50ml of deionized water, and stirred to obtain a uniform and transparent solution. Then, 10g1,3, 5-trimethylbenzene was added thereto, and the solvent gradually changed from a colorless solution to a colloidal solution. The colloidal solution was stirred for a further 8h and then 1ml of aqueous ammonia solution was added dropwise thereto, whereupon the solution rapidly turned brown in color. The reaction was continued for 12h, and then the solution was subjected to centrifugal alcohol washing and water washing, followed by freeze-drying to obtain a solid. And (3) placing the prepared brown solid powder in a tube furnace, roasting at 350 ℃ for 2h in the nitrogen atmosphere, then continuously heating to 900 ℃ and roasting for 8h, wherein the heating rate is 1 ℃/min, and finally obtaining the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 150nm and 3 spiral layers. The scanning electron micrograph and the high-resolution transmission electron micrograph are shown in FIG. 13.
Example 5
Synthesizing the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 140nm and 2 spiral layers:
1.0g of F68, 1.0g of dopamine hydrochloride and 5g of 3-methylphenol were dissolved in a mixed solution of 25ml of pentanol and 75ml of deionized water, and stirred to obtain a uniform and transparent solution. Thereafter, 5g of 1,3, 5-trimethylbenzene was added thereto, and the solvent gradually changed from a colorless solution to a colloidal solution. The above colloidal solution was stirred for a further 12h and then 3ml of an aqueous ammonia solution was added dropwise thereto, whereupon the solution rapidly turned brown in color. The reaction was continued for 24h, and then the solution was subjected to centrifugal alcohol washing water, followed by freeze-drying to obtain a solid. And (3) placing the prepared brown solid powder in a tube furnace, roasting for 2h at 350 ℃ in the nitrogen atmosphere, then continuously heating to 900 ℃ and roasting for 5h, wherein the heating rate is 5 ℃/min, and finally obtaining the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 140nm and 2 spiral layers. The scanning electron micrograph and the high-resolution transmission electron micrograph are shown in FIG. 14.
Example 6
Synthesizing the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 120nm and 1 spiral layer:
1.0g of F127, 1.0g of dopamine hydrochloride and 5g of 2,4, 6-trimethylphenol were dissolved in a mixed solution of 25ml of ethanol and 75ml of deionized water, and stirred to obtain a uniform transparent solution. Thereafter, 5g of 1, 3-dimethylbenzene was added thereto, and the solvent gradually changed from a colorless solution to a colloidal solution. The above colloidal solution was stirred for a further 12h and then 3ml of 1M sodium hydroxide solution were added dropwise thereto, whereupon the solution quickly turned brown in color. The reaction was continued for 4h, and then the solution was subjected to centrifugal alcohol washing and water washing, followed by freeze-drying to obtain a solid. And (3) placing the prepared brown solid powder in a tube furnace, roasting for 2h at 350 ℃ in the nitrogen atmosphere, then continuously heating to 900 ℃ and roasting for 5h, wherein the heating rate is 5 ℃/min, and finally obtaining the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 120nm and 1 layer of spiral layers. The scanning electron micrograph and the high-resolution transmission electron micrograph are shown in FIG. 15.
Example 7
The mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 210nm and 5 spiral layers is used as an electrode material of a lithium-sulfur battery:
firstly, the polydopamine nanospheres obtained in the first embodiment are roasted at 600-800 ℃ to obtain the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere composite material with the particle size of 210nm and 5 spiral layers. Then mixing and heating the lithium sulfur battery electrode material and sublimed sulfur in a high-pressure reaction kettle, finally using the lithium sulfur battery electrode material as an electrode material of the lithium sulfur battery, and still stabilizing the specific capacity of the lithium sulfur battery electrode material at 985mAh/g after the lithium sulfur battery electrode material is circulated for 1000 circles under the current density of 0.1C. The cycle and magnification curves are shown in fig. 16.
The preparation method comprises the steps of firstly preparing polydopamine nanospheres by using a solvent method, namely using dopamine hydrochloride as a carbon source and a nitrogen source, using a commercial amphiphilic triblock copolymer PEO-PPO-PEO as a template agent, using organic micromolecules of methyl phenol as a structure directing agent, using organic micromolecules of methyl benzene as a pore-expanding agent, using an inorganic base as a catalyst, and using a mixed solution of alcohol and water as a solvent, removing the template agent in the material by roasting, and carbonizing the polydopamine nanospheres to obtain the mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres. The obtained nitrogen-doped carbon nanosphere composite material shows a mesoporous multilayer spiral structure and has structural chiral characteristics. In addition, the material also has larger specific surface area, higher pore volume, uniform pore diameter and adjustable nitrogen content. The present invention adopts a novel synthesis method of colloidal solution. The method has the advantages of simple operation, easy repetition, easily controlled reaction conditions, easy industrialization and the like.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A preparation method of mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres is characterized in that dopamine hydrochloride is used as a carbon source and a nitrogen source, amphiphilic triblock copolymer PEO-PPO-PEO is used as a template agent, organic small molecules of methyl phenol are used as a structure directing agent, organic small molecules of methyl benzene are used as a pore expanding agent, inorganic base is used as a catalyst, a mixed solution of alcohol and water is used as a solvent, polydopamine nanospheres are prepared firstly, then the template agent in a material is removed through roasting, and meanwhile the polydopamine nanospheres are carbonized, so that the mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres are obtained.
2. The preparation method of the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere according to claim 1, comprising the following steps:
(1) Firstly, adding a certain amount of dopamine hydrochloride, an amphiphilic triblock copolymer PEO-PPO-PEO surfactant and a methylphenol organic small molecular structure directing agent into a mixed system of alcohol and water, and stirring for dissolving to obtain a transparent solution;
(2) Adding a certain amount of methylbenzene organic micromolecule pore-expanding agent into the transparent solution prepared in the step (1), and stirring to obtain a colloidal solution;
(3) Adding a certain amount of inorganic base substances into the colloidal solution prepared in the step (2), further reacting, and centrifugally washing to obtain a multilayer spiral chiral nano polydopamine nanosphere with a mesoporous structure;
(4) And (4) roasting the polydopamine nanospheres prepared in the step (3) in an inert atmosphere to finally obtain the mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres.
3. The preparation method of the mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere according to claim 1, wherein the amphiphilic triblock copolymer PEO-PPO-PEO surfactant is selected from one or more of Pluronic P123, pluronic P103, pluronic P85, pluronic P65, pluronic L121, pluronic F127, pluronic F88, pluronic F98, pluronic F108, B50-6600, B70-4600, B40-1900 and B20-3800.
4. The method for preparing mesoporous multilayer helical chiral nitrogen-doped carbon nanospheres according to claim 1, wherein the methylbenzene organic small molecule is selected from one or more of 2,4, 6-trimethylphenol, 2,3, 5-trimethylphenol, 3, 5-dimethylphenol, 2, 5-dimethylphenol, 3, 6-dimethylphenol, 3-methylphenol and phenol;
the organic small molecule of the methylbenzene is selected from one or more of dimethylbenzene, mesitylene and fatty acid.
5. The method for preparing the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere according to claim 1, wherein the inorganic base is one or more selected from sodium hydroxide, potassium hydroxide, ammonia water, ethylenediamine and calcium hydroxide;
the alcohol comprises one or more of ethanol, ethylene glycol, glycerol, methanol, butanol and pentanol.
6. The method for preparing mesoporous multilayer spiral chiral nitrogen-doped carbon nanospheres according to claim 1, wherein the roasting temperature range is 350-1200 ℃, the temperature rise speed is 0.5-10 ℃/min, and the time range is 1-9h.
7. The preparation method of the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere according to claim 1, wherein the mass ratio of dopamine hydrochloride to amphiphilic triblock copolymer PEO-PPO-PEO is 1.
8. A mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere is characterized in that the mesoporous multilayer spiral chiral nitrogen-doped carbon nanosphere is prepared by the preparation method of any one of claims 1-7, has a mesoporous pore channel, and has a multilayer spiral structure and structural chiral characteristics.
9. The mesoporous multilayer helical chiral nitrogen-doped carbon nanosphere according to claim 8, wherein the nanosphere has a diameter of 50-210nm and a specific surface area of 200-800m 2 Per g, pore volume of 0.10-0.96cm 3 Per g, aperture of 3-15nm, 1-7 layers, and nitrogen content of 2-10%.
10. Use of the mesoporous multilayer helical chiral nitrogen-doped carbon nanospheres as claimed in claim 8, wherein said nanospheres are used as electrode material of lithium-sulfur battery.
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| CN110894067A (en) * | 2019-12-20 | 2020-03-20 | 复旦大学 | Hollow mesoporous carbon sphere and preparation method thereof |
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| LIANG PENG ET AL.: "Spiral self-assembly of lamellar micelles into multi-shelled hollow nanospheres with unique chiral architecture", SCIENCE ADVANCES, vol. 7, no. 45, pages 1 - 10 * |
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