CN110577207B - Preparation method of nitrogen and phosphorus co-doped carbon nanosheet - Google Patents

Preparation method of nitrogen and phosphorus co-doped carbon nanosheet Download PDF

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CN110577207B
CN110577207B CN201910709484.XA CN201910709484A CN110577207B CN 110577207 B CN110577207 B CN 110577207B CN 201910709484 A CN201910709484 A CN 201910709484A CN 110577207 B CN110577207 B CN 110577207B
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phosphorus
nitrogen
dopo
phenylenediamine
terephthalaldehyde
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CN110577207A (en
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袁丛辉
蔡其鹏
戴李宗
毛杰
李云同
柳君
苗芮
陈国荣
罗伟昂
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Xiamen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • H01G11/24—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 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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

The invention discloses a preparation method of nitrogen-phosphorus co-doped carbon nanosheets, which comprises the steps of calcining P-phenylenediamine and DOPO serving as a nitrogen source and a phosphorus source at a high temperature, introducing nitrogen atoms and phosphorus atoms into a skeleton of a carbon material, and using the nitrogen atoms and the phosphorus atoms as an electrode material of a supercapacitor, wherein the reaction rate of condensation polymerization of pure P-phenylenediamine and terephthalaldehyde is relatively slow, because an imine bond formed by an aldehyde-amine reaction is a dynamic reversible bond, and usually a catalyst needs to be heated or added to promote the reaction, and the imine bond of a P-H bond in the DOPO has relatively high reaction activity and can be converted into an irreversible C-N single bond, so that the reaction rate of a polymer is greatly improved.

Description

Preparation method of nitrogen and phosphorus co-doped carbon nanosheet
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a preparation method of nitrogen and phosphorus co-doped carbon nanosheets.
Background
In recent years, super capacitors have been receiving increasing attention due to their ultra-fast charge and discharge characteristics, high energy density, and excellent electrochemical stability. In the electrode materials of various super capacitors, the carbon material is widely applied to the super capacitors due to the characteristics of large specific surface area, excellent chemical stability, adjustable pores and the like. However, pure carbon materials have limited their use in supercapacitors due to their highly hydrophobic nature and lack of active sites. And heteroatom doping is an effective means for improving the surface wettability and electrochemical activity of the carbon material. In a supercapacitor, the introduction of heteroatoms into the carbon skeleton can improve the conductivity of the material and form more defects, and the defects can promote the accumulation of charges during charge transfer, thereby providing additional faradaic pseudocapacitance and finally improving the capacitance performance of the material.
Wang Yang et al [ Yang W, Yang W, Kong L, et al, phosphorous-doped 3D structural protein carbon for high-performance supercapacitors: a balanced structure for pore structure and chemical composition [ J ]. Carbon, 2018, 127: 557 567. the phosphorus-doped porous carbon material is prepared by taking glucose, manganese nitrate and sodium hypophosphite as materials, has a multi-level pore structure of micropores, mesopores and macropores, and the introduction of phosphorus provides more electrochemical active sites, thereby greatly improving the capacitance performance of the material.
Cheng Zhu et al [ Zhu C, Wang M, Yang G, et al.N, P dual-jointed hole carbon spheres for high-performance supercapacitors [ J].Journal of Solid State Electrochemistry，2017，21(12)：3631-3640.]Using phenolic resin to coat silicon dioxide as a precursor, calcining at high temperature, etching a silicon dioxide template by hydrofluoric acid to form hollow carbon spheres, and finally using micromolecule NH4H2PO4 as activator, and introducing two kinds of impurity including nitrogen and phosphorus after calcining at high temperatureAnd finally obtaining the nitrogen-phosphorus doped hollow carbon spheres. Compared with a pure hollow carbon sphere, the introduction of nitrogen and phosphorus heteroatoms greatly improves the conductivity of the carbon sphere, and the capacitive performance is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-phosphorus co-doped carbon nanosheet.
The technical scheme of the invention is as follows:
a preparation method of nitrogen and phosphorus co-doped carbon nanosheets comprises the following steps:
(1) ultrasonically dissolving p-phenylenediamine and DOPO in a mixed solvent consisting of ethanol and dichloromethane;
(2) dissolving terephthalaldehyde in ethanol by ultrasonic waves;
(3) dropwise adding the material obtained in the step (2) into the material obtained in the step (1) at the temperature of 20-50 ℃ while stirring, and then stirring for reaction for 6-24 hours;
(4) centrifuging the material obtained in the step (3) to obtain a precipitate;
(5) washing the precipitate with lower alcohol for several times, and vacuum drying to obtain p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor;
(6) and heating the p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor to the temperature of 700-900 ℃ in the inert gas atmosphere, and then preserving heat for 1-6h to obtain the nitrogen-phosphorus co-doped carbon nanosheet.
In a preferred embodiment of the present invention, the molar ratio of p-phenylenediamine, DOPO and terephthalaldehyde is 1-100:2-200: 1-100.
In a preferred embodiment of the present invention, the volume ratio of ethanol to dichloromethane in the mixed solvent is 0.8-1.2: 0.8-1.2.
Further preferably, the volume ratio of ethanol to dichloromethane in the mixed solvent is 1: 1.
In a preferred embodiment of the present invention, the power of the ultrasonic dissolution is 40-50W, and the time is 10-20 min.
Further preferably, the power of ultrasonic dissolution is 45W.
In a preferred embodiment of the present invention, the dropping time in the step (3) is 0.5 to 1 hour.
In a preferred embodiment of the invention, the lower alcohol is methanol or ethanol.
In a preferred embodiment of the present invention, the temperature of the vacuum drying is 40 to 60 ℃ and the time is 12 to 24 hours.
In a preferred embodiment of the invention, the inert gas is argon.
The invention has the beneficial effects that: DOPO is often applied to the flame retardant field, and few reports report that DOPO is taken as a phosphorus source to be introduced into a carbon material skeleton, the invention uses p-phenylenediamine and DOPO as nitrogen source and phosphorus source, after high temperature calcination, nitrogen atom and phosphorus atom are introduced into the skeleton of carbon material, the reaction rate of the pure p-phenylenediamine and the terephthalaldehyde is slow when the material is used as an electrode material of a super capacitor, this is because the imine bond formed by the reaction of the aldehyde amine is a dynamically reversible bond, and usually requires heat or an additional catalyst to promote the reaction, the P-H bond in DOPO has higher reaction activity to imine bond, can convert dynamic reversible imine bond into irreversible C-N single bond, therefore, the reaction rate of the polymer is greatly improved, and the lamellar structure is favorable for the permeation and infiltration of the electrolyte and is favorable for improving the capacitive performance of the electrolyte.
Drawings
FIG. 1 is an infrared spectrum of a phenylenediamine-terephthalaldehyde-DOPO polymer precursor prepared in examples 1 to 3 of the present invention.
Fig. 2 is a transmission electron microscope image of the nitrogen and phosphorus co-doped carbon nanosheet prepared in embodiments 1 to 3 of the present invention.
Fig. 3 is a constant current charge and discharge curve of the nitrogen and phosphorus co-doped nanosheets calcined at different temperatures in examples 1 to 3 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1:
(1) ultrasonically dissolving 60mg of p-phenylenediamine and 120mg of DOPO in 60mL of mixed solvent consisting of ethanol and dichloromethane (the volume ratio of the ethanol to the dichloromethane is 1: 1);
(2) dissolving 34mg of terephthalaldehyde in 60mL of ethanol by ultrasonic waves;
(3) dropwise adding the material obtained in the step (2) into the material obtained in the step (1) at 25 ℃ while stirring, wherein the dropwise adding time is 0.5-1h, and stirring for reaction for 12h after the dropwise adding is finished;
(4) centrifuging the material obtained in the step (3) to obtain a precipitate;
(5) washing the precipitate with ethanol for 3 times, and vacuum drying at 60 deg.C for 12h to obtain p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor;
(6) placing the p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor into a porcelain ark, placing the porcelain ark into a tube furnace, heating to 700 ℃ under the argon atmosphere, preserving heat for 2h, and cooling to room temperature to obtain the nitrogen-phosphorus co-doped carbon nanosheet (CNP-700);
the ultrasonic dissolving power is 45W, and the time is 10-20 min.
Example 2:
in the steps (1) to (5), the carbon nanosheet (CNP-800) co-doped with nitrogen and phosphorus is obtained by heating to 800 ℃ in the step (6) as in the example 1.
Example 3:
heating to 900 ℃ in the step (6) in the same manner as in the example 1 in the steps (1) to (5) to obtain nitrogen-phosphorus co-doped carbon nanosheet (CNP-900).
Fig. 1 is an infrared spectrum of a p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor prepared in examples 1 to 3, showing: 1446cm-1、1193cm-1And 1044cm-1Respectively is a P-Ph bond, and the stretching vibration absorption peaks of a P ═ O bond and a P-C bond show that DOPO is successfully introduced; furthermore, at 1693cm-1A characteristic absorption peak for the C ═ O bond appeared, indicating that a portion of the aldehyde groups still remained unreacted.
Fig. 2 is a transmission electron microscope image of the nitrogen and phosphorus co-doped nanosheets prepared in embodiments 1 to 3 of the present invention, and the electron microscope image shows that the prepared nitrogen and phosphorus co-doped carbon material exhibits an obvious lamellar structure.
Fig. 3 is a constant current charge and discharge curve of the nitrogen and phosphorus co-doped nanosheet calcined at different temperatures in embodiments 1 to 3 of the present invention, where the curve indicates that the nitrogen and phosphorus co-doped nanosheet obtained after carbonization at 700 ℃ has a capacity of 88F/g, the nitrogen and phosphorus co-doped nanosheet obtained after carbonization at 800 ℃ has a capacity of 101F/g, and the nitrogen and phosphorus co-doped nanosheet obtained after carbonization at 900 ℃ has a capacity of 145F/g, which also indicates that the prepared nitrogen and phosphorus co-doped nanosheet has excellent capacitance performance.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (10)

1. A preparation method of nitrogen and phosphorus co-doped carbon nanosheets is characterized by comprising the following steps: the method comprises the following steps:
(1) ultrasonically dissolving p-phenylenediamine and DOPO in a mixed solvent consisting of ethanol and dichloromethane;
(2) dissolving terephthalaldehyde in ethanol by ultrasonic waves;
(3) dropwise adding the material obtained in the step (2) into the material obtained in the step (1) at the temperature of 20-50 ℃ while stirring, and then stirring for reaction for 6-24 hours;
(4) centrifuging the material obtained in the step (3) to obtain a precipitate;
(5) washing the precipitate with lower alcohol for several times, and vacuum drying to obtain p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor;
(6) and heating the p-phenylenediamine-terephthalaldehyde-DOPO polymer precursor to the temperature of 700-900 ℃ in the inert gas atmosphere, and then preserving the heat for 1-6h to obtain the nitrogen-phosphorus co-doped carbon nanosheet.
2. The method of claim 1, wherein: the molar ratio of the p-phenylenediamine to the DOPO to the terephthalaldehyde is 1-100:2-200: 1-100.
3. The method of claim 1, wherein: in the mixed solvent, the volume ratio of the ethanol to the dichloromethane is 0.8-1.2: 0.8-1.2.
4. The method of claim 3, wherein: in the mixed solvent, the volume ratio of ethanol to dichloromethane is 1: 1.
5. The method of claim 1, wherein: the ultrasonic dissolving power is 40-50W, and the time is 10-20 min.
6. The method of claim 5, wherein: the power of ultrasonic dissolution was 45W.
7. The method of claim 1, wherein: the dripping time in the step (3) is 0.5-1 h.
8. The method of claim 1, wherein: the lower alcohol is methanol or ethanol.
9. The method of claim 1, wherein: the vacuum drying temperature is 40-60 deg.C, and the drying time is 12-24 h.
10. The method of claim 1, wherein: the inert gas is argon.
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CN113035583B (en) * 2021-03-01 2022-02-22 齐鲁工业大学 Super capacitor based on gel polymer electrolyte and preparation method thereof
CN113845107B (en) * 2021-10-29 2024-03-15 哈尔滨工业大学 Method for preparing porous carbon nano-sheet by utilizing two-dimensional covalent organic framework pyrolysis
CN114455569B (en) * 2022-02-11 2023-05-02 齐鲁工业大学 Phosphorus-doped nitrogen-rich porous carbon nano sheet and preparation method and application thereof

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