WO2016197420A1 - Method for preparing doping-type carbon material based on dehalogenation reaction of macromolecule and use of doping-type carbon material in electrochemistry - Google Patents

Method for preparing doping-type carbon material based on dehalogenation reaction of macromolecule and use of doping-type carbon material in electrochemistry Download PDF

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WO2016197420A1
WO2016197420A1 PCT/CN2015/082609 CN2015082609W WO2016197420A1 WO 2016197420 A1 WO2016197420 A1 WO 2016197420A1 CN 2015082609 W CN2015082609 W CN 2015082609W WO 2016197420 A1 WO2016197420 A1 WO 2016197420A1
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carbon material
alkali
earth
doped carbon
metal
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PCT/CN2015/082609
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French (fr)
Chinese (zh)
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孙晓明
张国新
罗华星
李昊远
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北京化工大学
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Priority claimed from CN201510317135.5A external-priority patent/CN104900423B/en
Priority claimed from CN201510316646.5A external-priority patent/CN104891475B/en
Application filed by 北京化工大学 filed Critical 北京化工大学
Publication of WO2016197420A1 publication Critical patent/WO2016197420A1/en

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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
    • H01G11/84—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
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • H01G11/44—Raw materials therefor, e.g. resins or coal

Definitions

  • the invention belongs to the field of preparation methods of doped carbon materials. Specifically, the invention relates to a method for preparing a doped carbon material based on a polymer dehalogenation reaction and an application of the doped carbon material in electrochemistry.
  • Carbon is one of the most closely related elements of human production and living activities. Its diverse electronic orbital properties make it a rich form of bonding and hybridization, making it the only one that can be constructed from a single element from zero-dimensional fullerenes.
  • two types of elemental carbon forms of fullerenes and graphene have won the Nobel Prizes in 1996 and 2010, respectively, which proves the importance of carbon material research.
  • the research on carbon materials and the corresponding production are in full swing, and the carbon materials can be found in many fields, which makes the preparation of carbon materials very important.
  • Chemical vapor deposition that is, the reaction of the gas phase material on the substrate material in the reaction chamber to obtain a thin layer of carbon material
  • the strategy can be used to prepare carbon nanotubes, graphene and three-dimensional graphene.
  • the carbon material prepared by the method has high structure and atomic regularity and can be applied to electrical fields, but its scale is limited.
  • Supercapacitor is an emerging green energy storage device. Compared with the traditional lithium battery energy storage device, it has the advantages of high power density, short charging time and long cycle life, and has broad application prospects.
  • the core of the supercapacitor is the capacitor electrode material, and commonly used capacitor electrode materials include carbon materials, metal (hydrogen) oxides, and the like. Among them, carbon materials have attracted much attention due to their wide range of raw materials, stable physical and chemical properties and good charge and discharge performance.
  • Carbon materials that can be used for capacitors are carbon nanotubes, graphene, activated carbon, carbon fibers, carbon aerosols, and the like. Among them, activated carbon is widely used, and synthetic porous carbon is a kind of activated carbon.
  • the synthesis strategy is consistent with the synthesis strategy of activated carbon, that is, using carbon source under the action of activator to complete the process of pore formation, carbonization and graphitization.
  • synthetic carbon is significantly different from ordinary activated carbon because synthetic carbon has a three-dimensional continuous multi-stage pore structure and the walls of the pores are thin. Therefore, synthetic carbon has attracted the attention of many researchers.
  • the present inventors have found that all materials having a strong basicity (e.g., potassium hydroxide) can form an effective dehalogenation of the halogenated polymer.
  • a strong basicity e.g., potassium hydroxide
  • the carbon chain from which the halogen element is removed has extremely high reactivity, and a dopant can be purposefully added in this process to obtain a doped carbon material.
  • the excess strong base can also activate the prepared carbon material in situ to meet the demand for a large number of micropores.
  • the by-products produced are alkali (earth) metal chlorides, all of which are water-soluble salts, are easy to handle, and have less exhaust gas in by-products, satisfying the environmentally friendly requirements for expanding production.
  • the invention also finds that the halogenated polymer undergoes dehalogenation, hetero atom doping, high temperature graphitization and activation of pores, and a doped carbon material having a rich multi-stage pore structure is obtained.
  • This type of carbon material is used as an electrode material of a supercapacitor or the like, and it is found to have very good capacitance performance, that is, high capacity, high rate characteristics, and high stability. Combined with the wide range of industrial raw materials and low cost, the preparation process is simple, and such doped carbon materials are expected to become carbon materials for supercapacitors and the like having great application value.
  • the invention provides a method for preparing a doped carbon material based on a polymer dehalogenation reaction and an application of the doped carbon material in electrochemistry.
  • a first aspect of the invention relates to a method of preparing a doped carbon material, comprising the steps of:
  • halogenated polymer is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride;
  • the strong base is an alkali (earth) metal hydroxide, an alkali (earth) metal oxide, a zinc oxide, an alkali (earth) metal alkoxide, an alkali (earth) metal sulfide, an alkali (earth) metal amide or Alkali (earth) metal nitride;
  • the strong polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or nitromethylpyrrolidone;
  • the room temperature is 10-40 °C.
  • hetero atom refers to an atom other than a carbon atom and a non-metal element.
  • an oxygen atom for example, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a phosphorus atom, and the like.
  • the concentration of the halogenated polymer dissolved in the mixture can be varied within a wide range on the premise of ensuring the progress of mechanical mixing of the mixture.
  • a heteroatom dopant is also added to the mixture prior to milling, the heteroatom dopant being selected from the group consisting of melamine, ethylenediamine, thiourea, thioacetamide, boric acid, Borane ammonia or triphenylphosphine.
  • the hetero atom dopant may be a plurality of small molecule organic materials containing non-metal elements.
  • the strong base is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium sulfide, zinc oxide, sodium amide or lithium nitride.
  • the grinding is manual or ball milling, the grinding continues The time is not less than 1 minute.
  • the grinding is a low speed ball milling
  • the so-called low speed ball milling means that the speed of the ball mill is no higher than 50 Hz, and the recommended speed range is 10-40 Hz.
  • the strong base is present in a molar amount sufficient to substantially completely remove the halogen atoms in the halogenated polymer.
  • substantially complete removal means that the amount of the cation in the strong base is sufficient to become a metal halide normal salt with all of the halogen atoms in the halogenated polymer.
  • a second aspect of the invention relates to the use of a doped carbon material prepared by the preparation method of the first aspect of the invention in electrochemistry.
  • a third aspect of the invention relates to a method for preparing a doped carbon material, which is a method for preparing a doped carbon material according to the first aspect of the invention, after the end of the grinding, further comprising
  • the doped nanocarbon material is obtained by the step of calcining the mixture in an inert gas, followed by washing and drying.
  • the calcination temperature is from 400 to 900 °C. More preferably, it is 500-800 ° C, further preferably 600-700 ° C.
  • the inert gas may be an inert gas such as argon gas or nitrogen gas.
  • the calcined product can be washed 2-3 times with deionized water, and after drying at 50-100 ° C, the doped nanocarbon material is obtained and used as an electrode material.
  • the grinding is a ball milling and the grinding is for a duration of not less than one hour.
  • the milled mixture may also be dried prior to calcination.
  • the drying temperature may be from 50 to 100 °C.
  • a fourth aspect of the invention relates to the use of a doped carbon material prepared by the preparation method of the third aspect of the invention in a supercapacitor.
  • the doping of the hetero atom can be achieved by three types of hetero atom sources: one is that the strong polar solvent used in the basic embodiment of the present invention itself contains a nitrogen atom or a sulfur atom, and can be used as The nitrogen or sulfur source acts to dope nitrogen or sulfur into the graphitized carbon material.
  • the strong base of the present invention When sodium sulfide, sodium amide or lithium nitride is used, the strong base itself can also function as a nitrogen source or a sulfur source, respectively, to dope nitrogen or sulfur into the graphitized carbon material.
  • heteroatom dopants such as melamine, ethylenediamine, thiourea, thioacetamide, boric acid, borane ammonia or triphenylphosphine, respectively, as a nitrogen source
  • the sulfur source, boron source or phosphorus source acts to dope nitrogen, sulfur, boron or phosphorus into the graphitized carbon material.
  • the reaction mechanism of the present invention is: using a grinding method, utilizing the defunctionalization effect of a strong base on a halogenated molecule, so that the halogen on the halogenated polymer is removed in a strong alkaline environment, and the removed halogen can be as described above.
  • the alkali (earth) metal element contained in the strong base combines to form a metal halide, and the remaining part of the strong base can be combined with the hydrogen element of the halogenated polymer halogen to form water. In this way, a carbon material having a very high carbon content is obtained, and the carbonization process is completed.
  • the doped carbon material which can be used for the supercapacitor can be prepared by annealing and washing and drying the ground product under a high temperature inert atmosphere, wherein the high temperature baking completes the graphitization process of the carbon material.
  • the method of the invention Compared with the other room temperature preparation methods of carbon materials, such as concentrated sulfuric acid dehydration method, the method of the invention has high controllability, and the by-products are liquid water and solid alkali metal halide salts, and no gaseous exhaust gas is generated.
  • This type of reaction can achieve a high degree of reaction completion with low energy input, and the optional energy input method such as mechanical grinding is simple and easy to meet the requirements of actual mass production.
  • the carbon source polyvinylidene chloride (10-30 yuan/kg) and polyvinylidene fluoride (80-100 yuan/kg) are inexpensive, which greatly reduces the cost of the carbon material end product.
  • the method of the invention has low raw material cost, wide source, simple reaction operation, high safety, easy post-treatment, and is easy to be applied to industrial expansion.
  • this strategy has a very high guiding significance for the preparation of new doped carbon materials.
  • implantation regulation and modification in the preparation process a variety of economical and practical carbon materials can be provided for the current hot carbon-based energy materials.
  • the beneficial effects of the invention are as follows: (1) The controllable preparation of the room temperature hetero atom doped carbon material is realized for the first time. (2)
  • the invention can be used as a dehalogenating agent with a large amount of strong bases and dopants, and can try and optimize a large space, and the whole process from the carbon source to the preparation means to the post-treatment process is low in cost, and the reaction can be High reaction completion is achieved with low energy input, and the optional energy input method such as mechanical grinding is simple and easy to meet the requirements of actual large-scale production, and is extremely suitable for industrial expansion.
  • the produced by-product liquid water and solid metal chloride salt are embedded in the carbon matrix material, and after removal, a rich pore structure can be produced, and no gaseous exhaust gas is generated in the reaction by-product, and the environment is friendly.
  • the raw materials are industrial grade materials, which are widely, cheap and easily available. Among them, carbon sources such as polyvinylidene chloride (10-30 yuan/kg) and polyvinylidene fluoride (80-100 yuan/kg) are inexpensive. The cost of the carbon product end product is greatly reduced; and the reaction operation is simple and the reaction controllability is high.
  • the hetero atom introduced in the carbon material prepared by the invention can greatly increase the active site of ion adsorption, and is characterized by a porous carbon material having a large specific surface area, and has very good capacitance performance. .
  • High-resolution transmission electron micrograph, carbon nuclear magnetic resonance, Raman spectrum, X-ray photoelectron spectroscopy and other tests show that the carbon material prepared by the invention has higher carbonization degree, lower functionality, and carbon after calcination.
  • the material has a high degree of graphitization, and the doped carbon material has high capacitance capacity and rate characteristics and low electrochemical impedance when used as a supercapacitor material.
  • Example 1 is a general transmission electron micrograph of a nitrogen-doped carbon material prepared in Example 1.
  • Example 2 is a high-power transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 1.
  • Example 3 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 1.
  • Example 4 is a carbon nuclear magnetic spectrum of the nitrogen-doped carbon material prepared in Example 1.
  • Example 5 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 1.
  • Fig. 6 is a full spectrum of X-ray photoelectron spectroscopy of the nitrogen-doped carbon material prepared in Example 1.
  • Example 7 is a general transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 2.
  • Example 8 is a scanning electron micrograph of a nitrogen-doped carbon material prepared in Example 2.
  • Example 9 is a carbon nuclear magnetic spectrum of the nitrogen-doped carbon material prepared in Example 2.
  • Example 10 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 2.
  • Figure 11 is a full spectrum of X-ray photoelectron spectroscopy of the nitrogen-doped carbon material prepared in Example 2.
  • Figure 12 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 3.
  • Figure 13 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 4.
  • Figure 14 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 5.
  • Figure 15 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 6.
  • Figure 16 is a low power transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 7.
  • Figure 17 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 7.
  • Figure 18 is a BET nitrogen gas absorption desorption test spectrum of the nitrogen-doped carbon material prepared in Example 7.
  • Example 19 is a BET pore size analysis spectrum of the nitrogen-doped carbon material prepared in Example 7.
  • Example 21 is an X-ray photoelectron spectroscopy spectrum of the nitrogen-doped carbon material prepared in Example 7.
  • Fig. 22 is a cyclic voltammetry curve at different sweep speeds of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
  • 23 and 24 are graphs showing constant current charge and discharge curves of different charge and discharge currents of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
  • Fig. 25 is a capacity multiplication curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
  • Fig. 26 is a cycle stability test curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
  • Figure 27 is a transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 8.
  • Example 28 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 8.
  • Example 29 is a BET nitrogen gas absorption desorption test spectrum of the nitrogen-doped carbon material prepared in Example 8.
  • Figure 30 is a BET pore size analysis spectrum of the nitrogen-doped carbon material prepared in Example 8.
  • Example 31 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 8.
  • Example 32 is an X-ray photoelectron spectroscopy spectrum of the nitrogen-doped carbon material prepared in Example 8.
  • Fig. 33 is a graph showing a constant current charge and discharge curve of different charge and discharge currents of a capacitor made of a nitrogen-doped carbon material prepared in Example 8.
  • Figure 34 is a capacity magnification curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 8.
  • Fig. 35 is a cycle stability test curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 8.
  • Example 36 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 9.
  • Example 38 is a capacity magnification curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 9.
  • Example 39 is a scanning electron micrograph of the nitrogen-sulfur doped carbon material prepared in Example 10.
  • Example 40 is a Raman spectrum of the nitrogen-sulfur doped carbon material prepared in Example 10.
  • Example 41 is a capacity magnification curve of a capacitor made of a nitrogen-sulfur-doped carbon material prepared in Example 10.
  • Example 42 is a scanning electron micrograph of the phosphorus-doped carbon material prepared in Example 11.
  • Example 43 is a Raman spectrum of the phosphorus-doped carbon material prepared in Example 11.
  • Example 44 is a capacity magnification curve of a capacitor made of a phosphorus-doped carbon material prepared in Example 11.
  • Example 45 is a scanning electron micrograph of a boron-doped carbon material prepared in Example 12.
  • Figure 46 is a Raman spectrum of the boron-doped carbon material prepared in Example 12.
  • Figure 47 is a capacity magnification curve of a capacitor made of a boron-doped carbon material prepared in Example 12.
  • the resulting product was characterized.
  • the typical TEM images (Fig. 1 and Fig. 2) and scanning electron micrographs (Fig. 3) of the carbon materials prepared by this method show that the apparent carbonaceous morphology of the synthesized carbon material is amorphous and has a certain degree of graphite. The degree of crystallization has a certain continuity in the graphitized region.
  • the 130-133 ppm region peak corresponds to graphitized sp 2 hybrid carbon, and the intensity is high.
  • the Raman spectrum (Fig. 5 and Fig. 10) shows that the synthesized carbon material has a higher degree of graphitization and a graphitized G peak having higher strength.
  • the broad-spectrum spectrum in X-ray photoelectron spectroscopy shows that there are four elements in the heteroatom-doped carbon material, namely C, O, N and Cl, and the corresponding atomic ratios are 75.12%, respectively. , 19.0%, 2.02%, and 3.87%.
  • the N element is derived from the very stable high boiling point and strong polar solvent N,N-dimethylformamide.
  • the Cl element is Cl on the unreacted polyvinylidene chloride.
  • the cause of the residue may be: polydichloroethylene.
  • the particle size of ethylene is relatively large, about 200-300 microns, and the depth of reaction caused by the ball milling method cannot completely complete the reaction of the polyvinylidene chloride deeply buried inside.
  • FIG. 17 A transmission electron micrograph of the specifically obtained doped carbon material is shown in FIG.
  • the abundant hollow structure in the TEM image indicates that the doped carbon material has a rich pore structure.
  • Figure 17 for SEM images.
  • the results of electron microscopy showed that the obtained doped carbon material was a short sheet-like porous amorphous material with a partially twisted graphitized structure.
  • Figure 18 and Figure 19 for the BET specific surface area and pore structure test results.
  • Figure 18 is a BET nitrogen gas absorption desorption test spectrum, and the specific surface area calculated from this curve is 1735 square meters per gram.
  • Fig. 19 is a BET aperture analysis spectrum showing that the main micropores are present at about 2 nm, which is very suitable as a supercapacitor electrode material.
  • Fig. 20 The Raman spectrum is shown in Fig. 20, which clearly shows a strong degree of graphitization, and there are abundant defect sites, which can be used as adsorption sites for the capacitor electrode material.
  • Figure 21 for the X-ray photoelectron spectroscopy.
  • Figure 21 is a full spectrum scan showing that the doped carbon material is composed of three elements, namely carbon (87.91%), nitrogen (5.99%), and oxygen (6.11%).
  • Figure 22-26 for electrochemical capacitance test results.
  • Fig. 22 is a cyclic voltammetry curve of a capacitor made of the doped carbon material at different sweep speeds. The shape of the cyclic voltammetry curve at different sweep speeds shows that the material has excellent charge and discharge performance. 23 and FIG.
  • Fig. 24 are constant current charge and discharge curves of different charging and discharging currents of the capacitor made of the doped carbon material, the capacity under a low charge and discharge current is 328.5 F/g, and the capacity of the super large current charge and discharge, For example, when the capacity is 100 F/g, it is 206 F/g, which shows that it has excellent high-power charge and discharge performance.
  • Fig. 25 is a capacity multiplication curve of a capacitor made of the doped carbon material, which is a modification of Figs. 23 and 24, and more intuitively shows the ultrahigh rate characteristic of the material.
  • Fig. 26 is a cycle stability test curve of a capacitor made of the doped carbon material, which was circulated 5000 times at a large current density (50 A/g) for discharge and discharge.
  • the invention prepares the prepared doped porous carbon material into an electrode according to the following steps, and performs electrochemical performance test:
  • Doped porous carbon material (90% by weight in the electrode), conductive carbon black Super-P (10% by weight in the electrode) and polytetrafluoroethylene dispersion (60% by weight of polytetrafluoroethylene aqueous solution, poly 4)
  • the fluoroethylene dispersion is used in a volume of 0.5 ⁇ l/1 mg relative to the total mass of the doped carbon material and the conductive carbon black to be dissolved in nitrogen nitroformamide to a solid concentration of 1-10 mg/ ML.
  • the mixture is sufficiently ultrasonicated, using foamed nickel as a current collector, the above mixed material is dripped on the surface of the foamed nickel, and the prepared pole piece is dried at 60-120 ° C for 1-6 hours, and then the dried pole piece is placed at Soak in a 6 mol/L potassium hydroxide electrolyte for 0.5-2 hours.
  • the platinum electrode is used as the counter electrode and the saturated calomel electrode is used as the reference electrode.
  • the three-electrode test method is used in a voltage range of 0 to -1.0 volts in a 6 mol/L potassium hydroxide electrolyte at different current densities. Perform a loop test and calculate the unit capacitance value.
  • PVDC polyvinylidene chloride
  • melamine melamine
  • the mixture was treated by ball milling to bring the reactants into full contact.
  • the ball milling rotation frequency was about 30 Hz and the treatment time was 4 hours.
  • vacuum drying at 70 ° C was directly performed.
  • the resulting dried sample was fired under a nitrogen atmosphere at a calcination temperature of 700 °C.
  • the calcined product was washed 3 times with deionized water, and after drying at 60 ° C, a carbon doped material was obtained.
  • FIG. 29 A transmission electron micrograph of the specifically obtained doped carbon material is shown in FIG. See Figure 28 for SEM images. The results of electron microscopy showed that the obtained doped carbon materials were interconnected sheet-like porous amorphous materials. See Figure 29 and Figure 30 for the BET specific surface area and pore structure test results.
  • Figure 29 is a BET nitrogen gas absorption desorption test spectrum, and the specific surface area calculated from this curve is 1593 square meters per gram.
  • Figure 30 is a BET aperture analysis spectrum showing the presence of more microporous structures. The Raman spectrum is shown in Fig.
  • FIG. 31 which clearly shows a strong degree of graphitization, and the defect peak position is higher than the graphitization peak, indicating that it has a rich defect position and can be used as a adsorption site for the capacitor electrode material.
  • Figure 32 for the X-ray photoelectron spectroscopy.
  • Figure 32 is a full spectrum scan showing that the doped carbon material is composed of three elements, namely carbon (77.23%), nitrogen (14.61%), and oxygen (8.16%).
  • Figure 33-35 for electrochemical capacitance test results. Fig.
  • Fig. 33 is a graph showing a constant current charge and discharge curve of different charge and discharge currents of the capacitor made of the doped carbon material, the capacity at a low charge and discharge current is 345.2 F/g, and the capacity of a large current charge and discharge, such as 20 A/g.
  • the capacitance at the time is 217 F/g, which shows that it has excellent high-power charge and discharge performance.
  • Fig. 34 is a capacity multiplication curve of the capacitor made of the doped carbon material, which is a modification of Fig. 33, and more intuitively shows the ultrahigh rate characteristic of the material.
  • Fig. 35 is a cycle stability test curve of the capacitor made of the doped carbon material, which was cycled 1000 times under a large current density (20 A/g) charge and discharge, and its capacity was slightly increased.
  • PVDC carbon source
  • boric acid was used as the boron-doping agent
  • potassium hydroxide was used as the strong alkali dechlorination agent.
  • the three used were 0.64 g, 1.0 g and 1.5 g, respectively, and the above solid matter was added to 10 mL of nitrogen and nitrogen.
  • DMA methyl acetamide
  • the present invention also finds that when polyvinylidene fluoride or polyvinyl chloride is used as a carbon source, and the remaining materials and operation modes are as described in Example 8, a doped carbon material can be obtained, and the obtained doped carbon can be obtained. When used as a supercapacitor material, the material also has high capacitance capacity and rate characteristics and low electrochemical impedance.
  • the reaction mechanism is the same as that of polyvinylidene chloride as a carbon source, and will not be described herein.

Abstract

Provided are a preparation method for a doping-type carbon material and a use of the doping-type carbon material in the electrochemical field. The preparation method comprises the following steps: mixing a halogenated macromolecule, a strong base with a strong polar solvent to obtain a mixture, then grinding the mixture at room temperature, and directly washing and drying same after the grinding is finished, so as to obtain the doping-type carbon material; wherein the halogenated macromolecule is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride; wherein the strong base is an alkali (earth) metal hydroxide, an alkali (earth) metal oxide, zinc oxide, an alkali (earth) metal alkoxide, an alkali (earth) metal sulfide, an alkali (earth) metal amide or an alkali (earth) metal nitride; wherein the strong polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or nitrogen methyl pyrrolidone; and wherein the room temperature is 10°C-40°C. A carbon material of a hierarchical pore structure is obtained by directly calcinating the resulting ground product, and can be used as an electrode material.

Description

一种基于高分子脱卤反应制备掺杂型碳材料的方法及该掺杂型碳材料在电化学中的应用Method for preparing doped carbon material based on polymer dehalogenation reaction and application of the doped carbon material in electrochemistry 技术领域Technical field
本发明属于掺杂型碳材料的制备方法领域。具体涉及一种基于高分子脱卤反应制备掺杂型碳材料的方法及该掺杂型碳材料在电化学中的应用。The invention belongs to the field of preparation methods of doped carbon materials. Specifically, the invention relates to a method for preparing a doped carbon material based on a polymer dehalogenation reaction and an application of the doped carbon material in electrochemistry.
背景技术Background technique
碳元素是与人类生产生活活动最密切相关的元素之一，其多样电子轨道特性使其具有丰富的成键杂化形式，使得其成为唯一的可以完成以单一元素构建从零维富勒烯到一维碳纳米管到二维石墨烯再到三维金刚石及各种多孔碳材料的元素。目前已经有两种单质碳形式富勒烯和石墨烯分别获得1996年和2010年的诺贝尔奖，足以证明碳材料研究的重要性。近些年碳材料的研究及相应的生产进行的如火如荼，可以在众多领域找见碳材料的身影，这也使得碳材料的制备具有非常重要的意义。Carbon is one of the most closely related elements of human production and living activities. Its diverse electronic orbital properties make it a rich form of bonding and hybridization, making it the only one that can be constructed from a single element from zero-dimensional fullerenes. One-dimensional carbon nanotubes to two-dimensional graphene and then to three-dimensional diamond and various porous carbon materials. At present, two types of elemental carbon forms of fullerenes and graphene have won the Nobel Prizes in 1996 and 2010, respectively, which proves the importance of carbon material research. In recent years, the research on carbon materials and the corresponding production are in full swing, and the carbon materials can be found in many fields, which makes the preparation of carbon materials very important.
目前已有很多种碳材料制备的方法见诸报道，所应用的策略可粗略的被总结为以下几个方面。(1)化学气相沉积，即为反应室内使气相物料在基底材料上发生反应得到薄层碳材料，该策略可以用来制备碳纳米管、石墨烯及三维的石墨烯等。该方法所制备的碳材料具有较高的结构及原子规整度，可应用于电学方面，但其规模化有限。(2)热解法，即直接加热反应原料，使其在高温能量输入的情况下发生聚合、重整及去官能团化，最终得到具有较高含碳量的区域石墨化的碳材料，该策略制备的碳材料多为无定型碳材料，但具有丰富的孔道结构及较高的可塑性，但该方法的缺点也较为明显，如可控性相比于化学气相沉积法较差，为保护环境考虑，在去官能团过程中需要严格的尾气废气处理。但这种策略可以很好的为实际生产铺垫。然而这两大类的制备策略均需要较高的能量输入，例如使用高温退火进行碳化及石墨化。如何实现碳材料特别是掺杂型碳材料的低成本、低污染的简单制备具有重大的科学及实际意义。At present, there are many methods for preparing carbon materials, and the applied strategies can be roughly summarized as the following aspects. (1) Chemical vapor deposition, that is, the reaction of the gas phase material on the substrate material in the reaction chamber to obtain a thin layer of carbon material, the strategy can be used to prepare carbon nanotubes, graphene and three-dimensional graphene. The carbon material prepared by the method has high structure and atomic regularity and can be applied to electrical fields, but its scale is limited. (2) Pyrolysis method, that is, directly heating the reaction raw materials to cause polymerization, reforming and de-functionalization in the case of high-temperature energy input, and finally obtaining a graphitized carbon material having a high carbon content, the strategy Most of the carbon materials prepared are amorphous carbon materials, but have rich pore structure and high plasticity, but the disadvantages of this method are also obvious. For example, the controllability is worse than that of chemical vapor deposition, in order to protect the environment. Strict exhaust gas treatment is required in the de-functionalization process. But this strategy can be a good starting point for actual production. However, both types of preparation strategies require high energy input, such as carbonization and graphitization using high temperature annealing. How to realize the low cost and low pollution simple preparation of carbon materials, especially doped carbon materials, has great scientific and practical significance.
超级电容器是一种新兴的绿色储能装置，相对于传统锂电储能装置而言，其具有功率密度高、充电时间短、循环寿命长等优势，应用前景广阔。超级电容器的核心是电容器电极材料，常用的电容器电极材料包括碳材料、金属(氢)氧化物等。其中碳材料因其原料来源广泛、理化性能稳定及良好的充放电性能而倍受关注。可用于电容器的碳材料有碳纳米管、石墨烯、活性炭、碳纤维、碳气溶胶等。其中活性炭包罗广泛，其中合成多孔碳就属于活性炭的一种，其合成策略与活性炭的合成策略一致，即使用碳源在活化剂的作用下，完成造孔、碳化及石墨化过程。但合成碳与普通意义的活性炭有明显区别，因为合成碳拥有三维连续的多级孔结构且孔道的壁较薄，故此，合成碳吸引了众多研究者的目光。Supercapacitor is an emerging green energy storage device. Compared with the traditional lithium battery energy storage device, it has the advantages of high power density, short charging time and long cycle life, and has broad application prospects. The core of the supercapacitor is the capacitor electrode material, and commonly used capacitor electrode materials include carbon materials, metal (hydrogen) oxides, and the like. Among them, carbon materials have attracted much attention due to their wide range of raw materials, stable physical and chemical properties and good charge and discharge performance. Carbon materials that can be used for capacitors are carbon nanotubes, graphene, activated carbon, carbon fibers, carbon aerosols, and the like. Among them, activated carbon is widely used, and synthetic porous carbon is a kind of activated carbon. The synthesis strategy is consistent with the synthesis strategy of activated carbon, that is, using carbon source under the action of activator to complete the process of pore formation, carbonization and graphitization. However, synthetic carbon is significantly different from ordinary activated carbon because synthetic carbon has a three-dimensional continuous multi-stage pore structure and the walls of the pores are thin. Therefore, synthetic carbon has attracted the attention of many researchers.
对于合成碳，碳源及反应方式的选择至关重要，可以决定终产物的形貌、理化性能及最终的电容性能。以往的碳源多集中在生物质(例如CN201410417487、CN201410303083)或碳水化合物(例如CN201410190621、CN201310713624、CN201110290185)，这些碳源具有来源广泛、成本低廉的优势，但制备过程可塑性差、重复性有限；同时，该类碳源丰富的官能度会造成大量的废气(例如一氧 化碳、二氧化碳等)排放，不符合当今环境保护的迫切要求。研究表明(例如CN201310140338)，工业原料聚偏二氯乙烯是一种非常有潜力的碳源，它可以在碳化钙的作用下，完成完全的去官能化，进而得到含碳量非常高的碳材料。For synthetic carbon, the choice of carbon source and reaction mode is critical to determine the morphology, physicochemical properties, and ultimate capacitive properties of the final product. In the past, carbon sources were mostly concentrated in biomass (such as CN201410417487, CN201410303083) or carbohydrates (such as CN201410190621, CN201310713624, CN201110290185). These carbon sources have the advantages of wide source and low cost, but the preparation process has poor plasticity and limited repeatability. The rich functionality of this type of carbon source can cause a large amount of exhaust gas (such as oxygen) The emission of carbon, carbon dioxide, etc. does not meet the urgent requirements of today's environmental protection. Studies have shown (for example, CN201310140338) that industrial raw material polyvinylidene chloride is a very promising carbon source, which can completely de-functionalize under the action of calcium carbide, thereby obtaining carbon materials with very high carbon content. .
本发明发现，所有具有强碱性的物质(例如氢氧化钾)，均可以对卤化高分子形成有效的脱卤。该过程中，脱除掉卤元素的碳链具有极高的反应性，可以在这个过程中，有目的性地加入掺杂剂，即可得到掺杂型碳材料。同时，过量的强碱还可以原位地对所制备的碳材料进行活化，满足对大量微孔的需求。所产生的副产物为碱(土)金属氯化盐，均为水溶性盐，处理容易，且副产物中有较少的废气产生，满足对扩大生产的环境友好的要求。The present inventors have found that all materials having a strong basicity (e.g., potassium hydroxide) can form an effective dehalogenation of the halogenated polymer. In this process, the carbon chain from which the halogen element is removed has extremely high reactivity, and a dopant can be purposefully added in this process to obtain a doped carbon material. At the same time, the excess strong base can also activate the prepared carbon material in situ to meet the demand for a large number of micropores. The by-products produced are alkali (earth) metal chlorides, all of which are water-soluble salts, are easy to handle, and have less exhaust gas in by-products, satisfying the environmentally friendly requirements for expanding production.
本发明同时发现，卤化高分子经历脱卤化、杂原子掺杂、高温石墨化及活化造孔，得到具有丰富的多级孔结构的掺杂型碳材料。将该类碳材料作为超级电容器等的电极材料，发现其具有非常好的电容性能，即高容量、高倍率特性和高稳定性。结合其工业原料来源广泛且价廉、制备过程简单，该类掺杂型碳材料有望成为具有较大应用价值的超级电容器等用碳材料。The invention also finds that the halogenated polymer undergoes dehalogenation, hetero atom doping, high temperature graphitization and activation of pores, and a doped carbon material having a rich multi-stage pore structure is obtained. This type of carbon material is used as an electrode material of a supercapacitor or the like, and it is found to have very good capacitance performance, that is, high capacity, high rate characteristics, and high stability. Combined with the wide range of industrial raw materials and low cost, the preparation process is simple, and such doped carbon materials are expected to become carbon materials for supercapacitors and the like having great application value.
发明内容Summary of the invention
本发明提供了一种基于高分子脱卤反应制备掺杂型碳材料的方法及该掺杂型碳材料在电化学中的应用。The invention provides a method for preparing a doped carbon material based on a polymer dehalogenation reaction and an application of the doped carbon material in electrochemistry.
本发明第一方面涉及一种掺杂型碳材料的制备方法，其包括以下步骤：A first aspect of the invention relates to a method of preparing a doped carbon material, comprising the steps of:
将卤化高分子、强碱与强极性溶剂混合得到混合物，然后在室温下对该混合物进行研磨，研磨结束之后，直接进行清洗和干燥，即得到所述掺杂型碳材料；Mixing a halogenated polymer, a strong base and a strong polar solvent to obtain a mixture, and then grinding the mixture at room temperature, after the completion of the polishing, directly washing and drying to obtain the doped carbon material;
其中所述卤化高分子为聚偏二氟乙烯、聚偏二氯乙烯或聚氯乙烯；Wherein the halogenated polymer is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride;
其中所述强碱为碱(土)金属氢氧化物、碱(土)金属氧化物、氧化锌、碱(土)金属醇盐、碱(土)金属硫化物、碱(土)金属氨基化物或碱(土)金属氮化物；Wherein the strong base is an alkali (earth) metal hydroxide, an alkali (earth) metal oxide, a zinc oxide, an alkali (earth) metal alkoxide, an alkali (earth) metal sulfide, an alkali (earth) metal amide or Alkali (earth) metal nitride;
其中所述强极性溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二甲基亚砜或氮甲基吡咯烷酮；Wherein the strong polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or nitromethylpyrrolidone;
其中所述室温为10-40℃。Wherein the room temperature is 10-40 °C.
其中所述杂原子是指除了碳原子之外的非金属元素的原子。例如氧原子、硫原子、氮原子、硼原子、磷原子，等等。Wherein the hetero atom refers to an atom other than a carbon atom and a non-metal element. For example, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a phosphorus atom, and the like.
其中，在所述混合物中所溶解的所述卤化高分子的浓度在保证该混合物机械混合的可进行性的前提下，可在较大范围内变化。Among them, the concentration of the halogenated polymer dissolved in the mixture can be varied within a wide range on the premise of ensuring the progress of mechanical mixing of the mixture.
在本发明的优选实施方案中，在研磨前还向所述混合物中加入杂原子掺杂剂，所述杂原子掺杂剂选自三聚氰胺、乙二胺、硫脲、硫代乙酰胺、硼酸、硼烷氨或三苯基膦。其中所述杂原子掺杂剂可以为多种含有非金属元素的小分子有机物。In a preferred embodiment of the invention, a heteroatom dopant is also added to the mixture prior to milling, the heteroatom dopant being selected from the group consisting of melamine, ethylenediamine, thiourea, thioacetamide, boric acid, Borane ammonia or triphenylphosphine. The hetero atom dopant may be a plurality of small molecule organic materials containing non-metal elements.
在本发明的优选实施方案中，所述强碱为氢氧化钠、氢氧化钾、氢氧化锂、乙醇钠、硫化钠、氧化锌、氨基钠或氮化锂。In a preferred embodiment of the invention, the strong base is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium sulfide, zinc oxide, sodium amide or lithium nitride.
在本发明的优选实施方案中，所述研磨为手动研磨或球磨，所述研磨的持续 时间不少于1分钟。In a preferred embodiment of the invention, the grinding is manual or ball milling, the grinding continues The time is not less than 1 minute.
在本发明的更优选实施方案中，所述研磨为低速球磨，所谓低速球磨，是指球磨机的转速不高于50Hz，建议使用转速的范围在10-40Hz。In a more preferred embodiment of the invention, the grinding is a low speed ball milling, the so-called low speed ball milling means that the speed of the ball mill is no higher than 50 Hz, and the recommended speed range is 10-40 Hz.
在本发明的优选实施方案中，所述强碱的摩尔量足以将所述卤化高分子中的卤素原子基本完全脱除。基本完全脱除是指强碱中的阳离子的量足以与所述卤化高分子中的全部卤素原子成为金属卤化物正盐。In a preferred embodiment of the invention, the strong base is present in a molar amount sufficient to substantially completely remove the halogen atoms in the halogenated polymer. Substantially complete removal means that the amount of the cation in the strong base is sufficient to become a metal halide normal salt with all of the halogen atoms in the halogenated polymer.
本发明第二方面涉及本发明第一方面所述的制备方法制备的掺杂型碳材料在电化学中的用途。A second aspect of the invention relates to the use of a doped carbon material prepared by the preparation method of the first aspect of the invention in electrochemistry.
本发明第三方面涉及另一种掺杂型碳材料的制备方法，其为在本发明第一方面所述的掺杂型碳材料的制备方法中，在研磨结束之后，还包括将研磨后的混合物在惰性气体中焙烧的步骤，然后再进行清洗和干燥，即得到所述掺杂型纳米碳材料。A third aspect of the invention relates to a method for preparing a doped carbon material, which is a method for preparing a doped carbon material according to the first aspect of the invention, after the end of the grinding, further comprising The doped nanocarbon material is obtained by the step of calcining the mixture in an inert gas, followed by washing and drying.
在本发明的优选实施方案中，所述焙烧的温度为400-900℃。更优选地为500-800℃，进一步优选地为600-700℃。其中，所述惰性气体可以选择氩气、氮气等惰性气体。焙烧产物可以使用去离子水清洗2-3次，50-100℃干燥之后，即得到所述掺杂型纳米碳材料，作为电极材料使用。In a preferred embodiment of the invention, the calcination temperature is from 400 to 900 °C. More preferably, it is 500-800 ° C, further preferably 600-700 ° C. Wherein, the inert gas may be an inert gas such as argon gas or nitrogen gas. The calcined product can be washed 2-3 times with deionized water, and after drying at 50-100 ° C, the doped nanocarbon material is obtained and used as an electrode material.
在本发明的优选实施方案中，所述研磨为球磨，所述研磨的持续时间不少于1小时。In a preferred embodiment of the invention, the grinding is a ball milling and the grinding is for a duration of not less than one hour.
在本发明的优选实施方案中，在焙烧前，还可以将所述研磨后的混合物干燥。优选的，所述干燥的温度可以为50-100℃。In a preferred embodiment of the invention, the milled mixture may also be dried prior to calcination. Preferably, the drying temperature may be from 50 to 100 °C.
本发明第四方面涉及将本发明第三方面所述的制备方法制备的掺杂型碳材料在超级电容器中的用途。A fourth aspect of the invention relates to the use of a doped carbon material prepared by the preparation method of the third aspect of the invention in a supercapacitor.
本发明中，杂原子的掺杂可以通过三种类型的杂原子源来实现：一是本发明的基础实施方案中所使用的强极性溶剂本身就是含有氮原子或硫原子的，可以分别作为氮源或硫源起到向石墨化碳材料中掺杂氮或硫的作用。二是本发明的强碱当使用硫化钠、氨基钠或氮化锂时，该强碱本身也可分别作为氮源或硫源起到向石墨化碳材料中掺杂氮或硫的作用。三是，当在优选实施方案中使用额外的杂原子掺杂剂，例如三聚氰胺、乙二胺、硫脲、硫代乙酰胺、硼酸、硼烷氨或三苯基膦，分别可以作为氮源、硫源、硼源或磷源起到向石墨化碳材料中掺杂氮、硫、硼或磷的作用。当然，也可以组合使用这三种掺杂方式或组合使用各种杂原子源。In the present invention, the doping of the hetero atom can be achieved by three types of hetero atom sources: one is that the strong polar solvent used in the basic embodiment of the present invention itself contains a nitrogen atom or a sulfur atom, and can be used as The nitrogen or sulfur source acts to dope nitrogen or sulfur into the graphitized carbon material. Second, the strong base of the present invention When sodium sulfide, sodium amide or lithium nitride is used, the strong base itself can also function as a nitrogen source or a sulfur source, respectively, to dope nitrogen or sulfur into the graphitized carbon material. Third, when additional heteroatom dopants are used in preferred embodiments, such as melamine, ethylenediamine, thiourea, thioacetamide, boric acid, borane ammonia or triphenylphosphine, respectively, as a nitrogen source, The sulfur source, boron source or phosphorus source acts to dope nitrogen, sulfur, boron or phosphorus into the graphitized carbon material. Of course, it is also possible to use these three doping methods in combination or to use various hetero atom sources in combination.
发明人推测的本发明的反应机理是：使用研磨方式，利用强碱对卤化分子的脱官能团效应，使得卤化高分子上的卤素在强碱性环境下完成脱除，脱除的卤素可以与上述的强碱所含的碱(土)金属元素结合生成卤化金属盐，强碱的剩余部分可与卤化高分子卤素临位的氢元素结合生成水。如此，即得到极高含碳量的碳材料，完成碳化过程。由于脱除官能团后的碳链具有极高的反应性，可以在此过程中选择性的加入掺杂剂，甚至本身强碱和强极性溶剂也可以作为掺杂剂，这更突出本反应策略的简单易行。研磨产物经过高温惰性气氛下退火和清洗干燥，即可制备得到可用于超级电容器的掺杂型碳材料，其中所述高温焙烧完成了碳材料的石墨化过程。 The inventors speculated that the reaction mechanism of the present invention is: using a grinding method, utilizing the defunctionalization effect of a strong base on a halogenated molecule, so that the halogen on the halogenated polymer is removed in a strong alkaline environment, and the removed halogen can be as described above. The alkali (earth) metal element contained in the strong base combines to form a metal halide, and the remaining part of the strong base can be combined with the hydrogen element of the halogenated polymer halogen to form water. In this way, a carbon material having a very high carbon content is obtained, and the carbonization process is completed. Since the carbon chain after removing the functional group has extremely high reactivity, a dopant can be selectively added in the process, and even a strong alkali and a strong polar solvent can be used as a dopant, which highlights the reaction strategy. Simple and easy. The doped carbon material which can be used for the supercapacitor can be prepared by annealing and washing and drying the ground product under a high temperature inert atmosphere, wherein the high temperature baking completes the graphitization process of the carbon material.
本发明的方法相比于其他碳材料的室温制法如浓硫酸脱水法，该反应可控性较高，副产物为液态水及固态碱金属卤化盐，不产生任何气态废气。该类反应可以在低能量输入的情况下达到较高的反应完成度，且可选择的能量输入方式如机械研磨等简单易行，满足实际大规模生产的要求。碳源聚偏二氯乙烯(10-30元/kg)、聚偏二氟乙烯(80-100元/kg)价格低廉，极大降低碳材料终产物的成本。Compared with the other room temperature preparation methods of carbon materials, such as concentrated sulfuric acid dehydration method, the method of the invention has high controllability, and the by-products are liquid water and solid alkali metal halide salts, and no gaseous exhaust gas is generated. This type of reaction can achieve a high degree of reaction completion with low energy input, and the optional energy input method such as mechanical grinding is simple and easy to meet the requirements of actual mass production. The carbon source polyvinylidene chloride (10-30 yuan/kg) and polyvinylidene fluoride (80-100 yuan/kg) are inexpensive, which greatly reduces the cost of the carbon material end product.
综上，本发明的方法原材料成本低廉、来源广泛，反应操作简单、安全性高、后处理易行，极易适用工业扩大生产。同时，该策略对于新型掺杂碳材料的制备也具有非常高的指导意义。通过在制备过程中植入调控和修饰等概念，可以为目前较为火热的碳基能源材料方向提供多种经济实用的碳材料。In summary, the method of the invention has low raw material cost, wide source, simple reaction operation, high safety, easy post-treatment, and is easy to be applied to industrial expansion. At the same time, this strategy has a very high guiding significance for the preparation of new doped carbon materials. Through the concept of implantation regulation and modification in the preparation process, a variety of economical and practical carbon materials can be provided for the current hot carbon-based energy materials.
本发明有益效果在于：(1)首次实现室温杂原子掺杂型碳材料的可控制备。(2)本发明可选作为脱卤剂的强碱和掺杂剂丰富，可尝试及优化空间较大，从碳源到制备手段再到后处理过程的整个流程的成本低廉，该类反应可以在低能量输入的情况下达到较高的反应完成度，且可选择的能量输入方式如机械研磨等简单易行，满足实际大规模生产的要求，极适用于工业扩大生产。(3)生成的副产物液态水和固态氯化金属盐被包埋在碳基体材料中，除去后可以制造丰富的孔道结构，并且反应副产物中不产生任何气态废气，环境友好。(4)原材料为工业级材料，广泛、便宜、易得，其中碳源例如聚偏二氯乙烯(10-30元/kg)、聚偏二氟乙烯(80-100元/kg)价格低廉，极大降低碳材料终产物的成本；并且反应操作简单，反应可控性较高。(5)本发明制备的碳材料中所引入的杂原子可以极大的增加离子吸附的活性位点，测试表征发现其为具有较大的比表面积的多孔碳材料，并具有非常好的电容性能。(6)高分辨透射电镜照片、碳核磁谱、拉曼谱、X射线光电子能谱等测试显示，本发明制备的碳材料具有较高的碳化程度、较低的官能度，经过焙烧后的碳材料具有较高的石墨化程度，该类掺杂型碳材料作为超级电容器材料使用时具有较高的电容容量和倍率特性及较低的电化学阻抗。The beneficial effects of the invention are as follows: (1) The controllable preparation of the room temperature hetero atom doped carbon material is realized for the first time. (2) The invention can be used as a dehalogenating agent with a large amount of strong bases and dopants, and can try and optimize a large space, and the whole process from the carbon source to the preparation means to the post-treatment process is low in cost, and the reaction can be High reaction completion is achieved with low energy input, and the optional energy input method such as mechanical grinding is simple and easy to meet the requirements of actual large-scale production, and is extremely suitable for industrial expansion. (3) The produced by-product liquid water and solid metal chloride salt are embedded in the carbon matrix material, and after removal, a rich pore structure can be produced, and no gaseous exhaust gas is generated in the reaction by-product, and the environment is friendly. (4) The raw materials are industrial grade materials, which are widely, cheap and easily available. Among them, carbon sources such as polyvinylidene chloride (10-30 yuan/kg) and polyvinylidene fluoride (80-100 yuan/kg) are inexpensive. The cost of the carbon product end product is greatly reduced; and the reaction operation is simple and the reaction controllability is high. (5) The hetero atom introduced in the carbon material prepared by the invention can greatly increase the active site of ion adsorption, and is characterized by a porous carbon material having a large specific surface area, and has very good capacitance performance. . (6) High-resolution transmission electron micrograph, carbon nuclear magnetic resonance, Raman spectrum, X-ray photoelectron spectroscopy and other tests show that the carbon material prepared by the invention has higher carbonization degree, lower functionality, and carbon after calcination. The material has a high degree of graphitization, and the doped carbon material has high capacitance capacity and rate characteristics and low electrochemical impedance when used as a supercapacitor material.
附图说明DRAWINGS
图1为实施例1中制备的氮掺杂碳材料的普通透射电镜图。1 is a general transmission electron micrograph of a nitrogen-doped carbon material prepared in Example 1.
图2为实施例1中制备的氮掺杂碳材料的高倍透射电镜图。2 is a high-power transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 1.
图3为实施例1中制备的氮掺杂碳材料的扫描电镜图。3 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 1.
图4为实施例1中制备的氮掺杂碳材料的碳核磁谱图。4 is a carbon nuclear magnetic spectrum of the nitrogen-doped carbon material prepared in Example 1.
图5为实施例1中制备的氮掺杂碳材料的拉曼谱图。5 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 1.
图6为实施例1中制备的氮掺杂碳材料的X射线光电子能谱全谱图。Fig. 6 is a full spectrum of X-ray photoelectron spectroscopy of the nitrogen-doped carbon material prepared in Example 1.
图7为实施例2中制备的氮掺杂碳材料的普通透射电镜图。7 is a general transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 2.
图8为实施例2中制备的氮掺杂碳材料的扫描电镜图。8 is a scanning electron micrograph of a nitrogen-doped carbon material prepared in Example 2.
图9为实施例2中制备的氮掺杂碳材料的碳核磁谱图。9 is a carbon nuclear magnetic spectrum of the nitrogen-doped carbon material prepared in Example 2.
图10为实施例2中制备的氮掺杂碳材料的拉曼谱图。10 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 2.
图11为实施例2中制备的氮掺杂碳材料的X射线光电子能谱全谱图。Figure 11 is a full spectrum of X-ray photoelectron spectroscopy of the nitrogen-doped carbon material prepared in Example 2.
图12为实施例3中制备的氮掺杂碳材料的数码表观谱图。 Figure 12 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 3.
图13为实施例4中制备的氮掺杂碳材料的数码表观谱图。Figure 13 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 4.
图14为实施例5中制备的氮掺杂碳材料的数码表观谱图。Figure 14 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 5.
图15为实施例6中制备的氮掺杂碳材料的数码表观谱图。Figure 15 is a digital apparent spectrum of the nitrogen-doped carbon material prepared in Example 6.
图16为实施例7中制备的氮掺杂碳材料的低倍透射电镜图。Figure 16 is a low power transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 7.
图17为实施例7中制备的氮掺杂碳材料的扫描电镜图。Figure 17 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 7.
图18为实施例7中制备的氮掺杂碳材料的BET氮气吸脱附测试谱图。Figure 18 is a BET nitrogen gas absorption desorption test spectrum of the nitrogen-doped carbon material prepared in Example 7.
图19为实施例7中制备的氮掺杂碳材料的BET孔径分析谱图。19 is a BET pore size analysis spectrum of the nitrogen-doped carbon material prepared in Example 7.
图20为实施例7中制备的氮掺杂碳材料的拉曼图谱。20 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 7.
图21为实施例7中制备的氮掺杂碳材料的X射线光电子能谱图谱。21 is an X-ray photoelectron spectroscopy spectrum of the nitrogen-doped carbon material prepared in Example 7.
图22为实施例7中制备的氮掺杂碳材料制成的电容器的不同扫速下的循环伏安曲线。Fig. 22 is a cyclic voltammetry curve at different sweep speeds of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
图23和图24为实施例7中制备的氮掺杂碳材料制成的电容器的不同的充放电电流的恒流充放电曲线。23 and 24 are graphs showing constant current charge and discharge curves of different charge and discharge currents of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
图25为实施例7中制备的氮掺杂碳材料制成的电容器的容量倍率曲线。Fig. 25 is a capacity multiplication curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
图26为实施例7中制备的氮掺杂碳材料制成的电容器的循环稳定性测试曲线。Fig. 26 is a cycle stability test curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 7.
图27为实施例8中制备的氮掺杂碳材料的透射电镜图。Figure 27 is a transmission electron micrograph of the nitrogen-doped carbon material prepared in Example 8.
图28为实施例8中制备的氮掺杂碳材料的扫描电镜图。28 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 8.
图29为实施例8中制备的氮掺杂碳材料的BET氮气吸脱附测试谱图。29 is a BET nitrogen gas absorption desorption test spectrum of the nitrogen-doped carbon material prepared in Example 8.
图30为实施例8中制备的氮掺杂碳材料的BET孔径分析谱图。Figure 30 is a BET pore size analysis spectrum of the nitrogen-doped carbon material prepared in Example 8.
图31为实施例8中制备的氮掺杂碳材料的拉曼图谱。31 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 8.
图32为实施例8中制备的氮掺杂碳材料的X射线光电子能谱图谱。32 is an X-ray photoelectron spectroscopy spectrum of the nitrogen-doped carbon material prepared in Example 8.
图33为实施例8中制备的氮掺杂碳材料制成的电容器的不同的充放电电流的恒流充放电曲线。Fig. 33 is a graph showing a constant current charge and discharge curve of different charge and discharge currents of a capacitor made of a nitrogen-doped carbon material prepared in Example 8.
图34为实施例8中制备的氮掺杂碳材料制成的电容器的容量倍率曲线。Figure 34 is a capacity magnification curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 8.
图35为实施例8中制备的氮掺杂碳材料制成的电容器的循环稳定性测试曲线。Fig. 35 is a cycle stability test curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 8.
图36为实施例9中制备的氮掺杂碳材料的扫描电镜图。36 is a scanning electron micrograph of the nitrogen-doped carbon material prepared in Example 9.
图37为实施例9中制备的氮掺杂碳材料的拉曼图谱。37 is a Raman spectrum of the nitrogen-doped carbon material prepared in Example 9.
图38为实施例9中制备的氮掺杂碳材料制成的电容器的容量倍率曲线。38 is a capacity magnification curve of a capacitor made of a nitrogen-doped carbon material prepared in Example 9.
图39为实施例10中制备的氮硫掺杂碳材料的扫描电镜图。39 is a scanning electron micrograph of the nitrogen-sulfur doped carbon material prepared in Example 10.
图40为实施例10中制备的氮硫掺杂碳材料的拉曼图谱。40 is a Raman spectrum of the nitrogen-sulfur doped carbon material prepared in Example 10.
图41为实施例10中制备的氮硫掺杂碳材料制成的电容器的容量倍率曲线。41 is a capacity magnification curve of a capacitor made of a nitrogen-sulfur-doped carbon material prepared in Example 10.
图42为实施例11中制备的磷掺杂碳材料的扫描电镜图。42 is a scanning electron micrograph of the phosphorus-doped carbon material prepared in Example 11.
图43为实施例11中制备的磷掺杂碳材料的拉曼图谱。 43 is a Raman spectrum of the phosphorus-doped carbon material prepared in Example 11.
图44为实施例11中制备的磷掺杂碳材料制成的电容器的容量倍率曲线。44 is a capacity magnification curve of a capacitor made of a phosphorus-doped carbon material prepared in Example 11.
图45为实施例12中制备的硼掺杂碳材料的扫描电镜图。45 is a scanning electron micrograph of a boron-doped carbon material prepared in Example 12.
图46为实施例12中制备的硼掺杂碳材料的拉曼图谱。Figure 46 is a Raman spectrum of the boron-doped carbon material prepared in Example 12.
图47为实施例12中制备的硼掺杂碳材料制成的电容器的容量倍率曲线。Figure 47 is a capacity magnification curve of a capacitor made of a boron-doped carbon material prepared in Example 12.
具体实施方式detailed description
实施例1Example 1
将1.00克聚偏二氯乙烯、0.60克氢氧化钾、10毫升N，N-二甲基甲酰胺加入到30毫升的氧化锆球磨罐中，将球磨罐封装好并装备到球磨机上，进行球磨4小时，频率设定为30.0赫兹。反应结束后，加入水停止掉反应，之后采用清洗离心方式除掉可能存在的盐及未反应完全的强碱，离心产物干燥过夜，设定干燥温度为60℃。干燥产物即为目标产物。Add 1.00 g of polyvinylidene chloride, 0.60 g of potassium hydroxide, and 10 ml of N,N-dimethylformamide to a 30 ml zirconia ball mill jar, package the ball mill tank and equip it to a ball mill for ball milling. For 4 hours, the frequency is set to 30.0 Hz. After the end of the reaction, water was added to stop the reaction, and then the salt which may be present and the unreacted strong base were removed by washing and centrifuging, and the centrifuged product was dried overnight to set the drying temperature to 60 °C. The dried product is the target product.
具体数据：透射电镜照片参见图1和图2。扫描电镜照片参见图3。碳核磁谱图参见图4。拉曼谱图参见图5。X射线光电子能谱图谱参见图6。Specific data: See Figure 1 and Figure 2 for transmission electron micrographs. See Figure 3 for SEM images. See Figure 4 for the carbon nuclear magnetic spectrum. See Figure 5 for the Raman spectrum. See Figure 6 for the X-ray photoelectron spectroscopy.
实施例2Example 2
将1.00克聚偏二氯乙烯、0.60克氢氧化钾、10毫升N，N-二甲基甲酰胺加入到研钵中，手动连续研磨五分钟。其他同实施例1。1.00 g of polyvinylidene chloride, 0.60 g of potassium hydroxide, and 10 ml of N,N-dimethylformamide were added to the mortar and manually milled for five minutes. Others are the same as in the first embodiment.
实施例3Example 3
将0.64克聚偏二氟乙烯、0.60克氢氧化钾、10毫升N，N-二甲基甲酰胺加入到30毫升的氧化锆球磨罐中，将球磨罐封装好并装备到球磨机上，进行球磨。其他同实施例1。0.64 g of polyvinylidene fluoride, 0.60 g of potassium hydroxide and 10 ml of N,N-dimethylformamide were added to a 30 ml zirconia ball mill jar, and the ball mill jar was packaged and equipped on a ball mill for ball milling. . Others are the same as in the first embodiment.
实施例4Example 4
将1.00克聚偏二氯乙烯、2.7克九水硫化钠、10毫升N，N-二甲基甲酰胺加入到30毫升的氧化锆球磨罐中，将球磨罐封装好并装备到球磨机上，进行球磨。其他同实施例1。Add 1.00 g of polyvinylidene chloride, 2.7 g of sodium sulfide nonahydrate, and 10 ml of N,N-dimethylformamide to a 30 ml zirconia ball mill jar, package the ball mill tank and equip it on a ball mill. ball milling. Others are the same as in the first embodiment.
实施例5Example 5
将1.00克聚偏二氯乙烯、0.42克氨基钠、10毫升N，N-二甲基甲酰胺加入到30毫升的氧化锆球磨罐中，将球磨罐封装好并装备到球磨机上，进行球磨。其他同实施例1。1.00 g of polyvinylidene chloride, 0.42 g of sodium amide, and 10 ml of N,N-dimethylformamide were placed in a 30 ml zirconia ball mill jar, and the ball mill jar was packaged and equipped on a ball mill for ball milling. Others are the same as in the first embodiment.
实施例6Example 6
将1.00克聚偏二氯乙烯、0.38克氮化锂、10毫升N，N-二甲基甲酰胺加入到30毫升的氧化锆球磨罐中，将球磨罐封装好并装备到球磨机上，进行球磨。其他同实施例1。Add 1.00 g of polyvinylidene chloride, 0.38 g of lithium nitride, and 10 ml of N,N-dimethylformamide to a 30 ml zirconia ball mill jar, package the ball mill tank and equip it to a ball mill for ball milling. . Others are the same as in the first embodiment.
对得到的产物进行表征。该方法制备的碳材料典型的透射电镜照片(图1和图2)和扫描电镜照片(图3)显示，所合成的碳材料的表观形貌为无定形多孔结构，并具有一定程度的石墨化程度，其石墨化区域具有一定连续性。碳核磁谱图(图4和图9)中位于130-133ppm区域峰对应石墨化sp2杂化的碳元素，且强度较高。拉曼图谱(图5和图10)显示所合成的碳材料具有较高的石墨化程度，存在强度较高的石墨化G峰。X光电子能谱中的宽扫谱图(图6和图11)显 示共有4种元素组成该杂原子掺杂碳材料，即为C、O、N和Cl，对应的原子比含量分别为75.12％、19.0％、2.02％和3.87％。N元素来源于非常稳定的高沸点强极性溶剂N，N-二甲基甲酰胺，Cl元素为未反应完全的聚偏二氯乙烯上的Cl，造成残留的原因可能为：聚偏二氯乙烯的颗粒度较大，约为200-300微米，球磨方式所引发的反应深度不能完全使深埋于内部的聚偏二氯乙烯反应完全。The resulting product was characterized. The typical TEM images (Fig. 1 and Fig. 2) and scanning electron micrographs (Fig. 3) of the carbon materials prepared by this method show that the apparent carbonaceous morphology of the synthesized carbon material is amorphous and has a certain degree of graphite. The degree of crystallization has a certain continuity in the graphitized region. In the carbon nuclear magnetic spectrum (Fig. 4 and Fig. 9), the 130-133 ppm region peak corresponds to graphitized sp 2 hybrid carbon, and the intensity is high. The Raman spectrum (Fig. 5 and Fig. 10) shows that the synthesized carbon material has a higher degree of graphitization and a graphitized G peak having higher strength. The broad-spectrum spectrum in X-ray photoelectron spectroscopy (Fig. 6 and Fig. 11) shows that there are four elements in the heteroatom-doped carbon material, namely C, O, N and Cl, and the corresponding atomic ratios are 75.12%, respectively. , 19.0%, 2.02%, and 3.87%. The N element is derived from the very stable high boiling point and strong polar solvent N,N-dimethylformamide. The Cl element is Cl on the unreacted polyvinylidene chloride. The cause of the residue may be: polydichloroethylene. The particle size of ethylene is relatively large, about 200-300 microns, and the depth of reaction caused by the ball milling method cannot completely complete the reaction of the polyvinylidene chloride deeply buried inside.
实施例7Example 7
将2.00克乙醇钠连同1.00克聚偏二氯乙烯和0.50克三聚氰胺一同浸入10毫升氮氮二甲基甲酰胺中，之后加入1.00克氢氧化钾。使用球磨方式处理上述混合物，使反应物充分接触。球磨转动频率约为30Hz，处理时间2小时。处理结束之后，直接进行70℃真空干燥。所得干燥的样品在氮气保护下焙烧，焙烧温度为700℃。焙烧产物使用去离子水清洗3次，60℃干燥之后，即得到掺杂型纳米碳材料。2.00 g of sodium ethoxide was immersed in 10 ml of nitrogen dimethylformamide together with 1.00 g of polyvinylidene chloride and 0.50 g of melamine, followed by the addition of 1.00 g of potassium hydroxide. The above mixture was treated by ball milling to bring the reactants into full contact. The ball mill has a rotation frequency of about 30 Hz and a processing time of 2 hours. After the end of the treatment, vacuum drying at 70 ° C was directly performed. The resulting dried sample was fired under a nitrogen atmosphere at a calcination temperature of 700 °C. The calcined product was washed 3 times with deionized water, and after drying at 60 ° C, a doped nanocarbon material was obtained.
具体得到的掺杂型碳材料的透射电镜照片参见图16。透射电镜照片中丰富的镂空结构表明制得的掺杂型碳材料具有较丰富的孔道结构。扫描电镜照片参见图17。电镜结果表明所得掺杂型碳材料为短小片状多孔无定型材料，且局部有扭曲的石墨化结构。其BET比表面积及孔结构测试结果参见图18和图19。图18为BET氮气吸脱附测试谱图，根据此曲线计算得到的比表面积为1735平方米每克。图19为BET孔径分析谱图，显示主要的微孔存在于2纳米左右，非常适合作为超电容电极材料。拉曼图谱参见图20，清楚的显示有较强的石墨化程度，并且存在丰富的缺陷位，可以作为电容电极材料的吸附位点。X射线光电子能谱图谱参见图21。图21为全谱扫描，显示该掺杂碳材料由三种元素组成，即碳(87.91％)、氮(5.99％)、氧(6.11％)。电化学电容测试结果参见图22-26。图22为由该掺杂型碳材料制成的电容器不同扫速下的循环伏安曲线，不同扫速下的循环伏安曲线的形状相近显示该材料具有优异的充放电性能。图23和图24为由该掺杂型碳材料制成的电容器不同的充放电电流的恒流充放电曲线，低充放电电流下的容量为328.5F/g，而超大电流充放电的容量，如100A/g时的容量为206F/g，显示其大功率充放电性能优异。图25为由该掺杂型碳材料制成的电容器的容量倍率曲线，为图23和图24的变形，更直观的表示出该材料的超高倍率特性。图26为由该掺杂型碳材料制成的电容器的循环稳定性测试曲线，在大电流密度(50A/g)充放电下循环5000次未见容量的衰减。A transmission electron micrograph of the specifically obtained doped carbon material is shown in FIG. The abundant hollow structure in the TEM image indicates that the doped carbon material has a rich pore structure. See Figure 17 for SEM images. The results of electron microscopy showed that the obtained doped carbon material was a short sheet-like porous amorphous material with a partially twisted graphitized structure. See Figure 18 and Figure 19 for the BET specific surface area and pore structure test results. Figure 18 is a BET nitrogen gas absorption desorption test spectrum, and the specific surface area calculated from this curve is 1735 square meters per gram. Fig. 19 is a BET aperture analysis spectrum showing that the main micropores are present at about 2 nm, which is very suitable as a supercapacitor electrode material. The Raman spectrum is shown in Fig. 20, which clearly shows a strong degree of graphitization, and there are abundant defect sites, which can be used as adsorption sites for the capacitor electrode material. See Figure 21 for the X-ray photoelectron spectroscopy. Figure 21 is a full spectrum scan showing that the doped carbon material is composed of three elements, namely carbon (87.91%), nitrogen (5.99%), and oxygen (6.11%). See Figure 22-26 for electrochemical capacitance test results. Fig. 22 is a cyclic voltammetry curve of a capacitor made of the doped carbon material at different sweep speeds. The shape of the cyclic voltammetry curve at different sweep speeds shows that the material has excellent charge and discharge performance. 23 and FIG. 24 are constant current charge and discharge curves of different charging and discharging currents of the capacitor made of the doped carbon material, the capacity under a low charge and discharge current is 328.5 F/g, and the capacity of the super large current charge and discharge, For example, when the capacity is 100 F/g, it is 206 F/g, which shows that it has excellent high-power charge and discharge performance. Fig. 25 is a capacity multiplication curve of a capacitor made of the doped carbon material, which is a modification of Figs. 23 and 24, and more intuitively shows the ultrahigh rate characteristic of the material. Fig. 26 is a cycle stability test curve of a capacitor made of the doped carbon material, which was circulated 5000 times at a large current density (50 A/g) for discharge and discharge.
本发明按如下步骤将制备好的掺杂型多孔碳材料制成电极，并进行电化学性能测试：The invention prepares the prepared doped porous carbon material into an electrode according to the following steps, and performs electrochemical performance test:
将掺杂型多孔碳材料(在电极中占90wt％)、导电炭黑Super-P(在电极中占10wt％)和聚四氟乙烯分散液(为60wt％的聚四氟乙烯水溶液，聚四氟乙烯的分散液的使用体积相对于掺杂型碳材料和导电炭黑的总质量为0.5微升/1毫克)溶入氮氮二甲基甲酰胺中，使固体浓度达到1-10毫克/毫升。将混合物充分超声，采用泡沫镍作为集流体，把上述混合好的材料滴涂在泡沫镍表面，将制作好的极片在60-120℃干燥1-6小时，然后将干燥好的极片在6mol/L的氢氧化钾电解液中浸泡0.5-2小时。以铂电极为对电极、饱和甘汞电极为参比电极，采用三电极测试方法在0～-1.0伏电压范围下，在6摩尔/升的氢氧化钾电解液中、在不同的电流密度下进行循环测试，并计算出单位电容值。Doped porous carbon material (90% by weight in the electrode), conductive carbon black Super-P (10% by weight in the electrode) and polytetrafluoroethylene dispersion (60% by weight of polytetrafluoroethylene aqueous solution, poly 4) The fluoroethylene dispersion is used in a volume of 0.5 μl/1 mg relative to the total mass of the doped carbon material and the conductive carbon black to be dissolved in nitrogen nitroformamide to a solid concentration of 1-10 mg/ ML. The mixture is sufficiently ultrasonicated, using foamed nickel as a current collector, the above mixed material is dripped on the surface of the foamed nickel, and the prepared pole piece is dried at 60-120 ° C for 1-6 hours, and then the dried pole piece is placed at Soak in a 6 mol/L potassium hydroxide electrolyte for 0.5-2 hours. The platinum electrode is used as the counter electrode and the saturated calomel electrode is used as the reference electrode. The three-electrode test method is used in a voltage range of 0 to -1.0 volts in a 6 mol/L potassium hydroxide electrolyte at different current densities. Perform a loop test and calculate the unit capacitance value.
实施例8 Example 8
将1.00克聚偏二氯乙烯(缩写为PVDC)和0.75克三聚氰胺浸入10毫升氮氮二甲基甲酰胺中，之后加入1.70克氧化锌。使用球磨方式处理上述混合物，使反应物充分接触，球磨转动频率约为30Hz，处理时间4小时。处理结束之后，直接进行70℃真空干燥。所得干燥的样品在氮气保护下焙烧，焙烧温度为700℃。焙烧产物使用去离子水清洗3次，60℃干燥之后，即得到掺杂碳材料。1.00 g of polyvinylidene chloride (abbreviated as PVDC) and 0.75 g of melamine were immersed in 10 ml of nitrogen dimethylformamide, followed by the addition of 1.70 g of zinc oxide. The mixture was treated by ball milling to bring the reactants into full contact. The ball milling rotation frequency was about 30 Hz and the treatment time was 4 hours. After the end of the treatment, vacuum drying at 70 ° C was directly performed. The resulting dried sample was fired under a nitrogen atmosphere at a calcination temperature of 700 °C. The calcined product was washed 3 times with deionized water, and after drying at 60 ° C, a carbon doped material was obtained.
具体得到的掺杂型碳材料的透射电镜照片参见图27。扫描电镜照片参见图28。电镜结果表明所得掺杂型碳材料为相互连接的片状多孔无定型材料。其BET比表面积及孔结构测试结果参见图29和图30。图29为BET氮气吸脱附测试谱图，根据此曲线计算得到的比表面积为1593平方米每克。图30为BET孔径分析谱图，显示存在较多的微孔结构。拉曼图谱参见图31，清楚的显示有较强的石墨化程度，缺陷峰位要高于石墨化峰，显示具有丰富的缺陷位，可以作为电容电极材料的吸附位点。X射线光电子能谱图谱参见图32。图32为全谱扫描，显示该掺杂碳材料由三种元素组成，即碳(77.23％)、氮(14.61％)、氧(8.16％)。电化学电容测试结果参见图33-35。图33为该掺杂型碳材料制成的电容器不同的充放电电流的恒流充放电曲线，低充放电电流下的容量为345.2F/g，而超大电流充放电的容量，如20A/g时的电容为217F/g，显示其大功率充放电性能优异。图34为该掺杂型碳材料制成的电容器的容量倍率曲线，为图33的变形，更直观的表示出该材料的超高倍率特性。图35为该掺杂型碳材料制成的电容器的循环稳定性测试曲线，在大电流密度(20A/g)充放电下循环1000次，发现其容量略有升高。A transmission electron micrograph of the specifically obtained doped carbon material is shown in FIG. See Figure 28 for SEM images. The results of electron microscopy showed that the obtained doped carbon materials were interconnected sheet-like porous amorphous materials. See Figure 29 and Figure 30 for the BET specific surface area and pore structure test results. Figure 29 is a BET nitrogen gas absorption desorption test spectrum, and the specific surface area calculated from this curve is 1593 square meters per gram. Figure 30 is a BET aperture analysis spectrum showing the presence of more microporous structures. The Raman spectrum is shown in Fig. 31, which clearly shows a strong degree of graphitization, and the defect peak position is higher than the graphitization peak, indicating that it has a rich defect position and can be used as a adsorption site for the capacitor electrode material. See Figure 32 for the X-ray photoelectron spectroscopy. Figure 32 is a full spectrum scan showing that the doped carbon material is composed of three elements, namely carbon (77.23%), nitrogen (14.61%), and oxygen (8.16%). See Figure 33-35 for electrochemical capacitance test results. Fig. 33 is a graph showing a constant current charge and discharge curve of different charge and discharge currents of the capacitor made of the doped carbon material, the capacity at a low charge and discharge current is 345.2 F/g, and the capacity of a large current charge and discharge, such as 20 A/g. The capacitance at the time is 217 F/g, which shows that it has excellent high-power charge and discharge performance. Fig. 34 is a capacity multiplication curve of the capacitor made of the doped carbon material, which is a modification of Fig. 33, and more intuitively shows the ultrahigh rate characteristic of the material. Fig. 35 is a cycle stability test curve of the capacitor made of the doped carbon material, which was cycled 1000 times under a large current density (20 A/g) charge and discharge, and its capacity was slightly increased.
实施例9Example 9
使用PVDC作为碳源，乙二胺作为掺氮剂，使用氧化镁作为强碱脱氯剂，三者的使用量分别为1.0g、2.0mL和3.0g，将上述固体物质加入到10mL的氮氮二甲基乙酰胺(DMA)中。其他处理方式同实施例8。Using PVDC as a carbon source, ethylenediamine as a nitrogen-doping agent, and magnesium oxide as a strong alkali dechlorination agent, the amounts of the three were 1.0 g, 2.0 mL, and 3.0 g, respectively, and the above solid matter was added to 10 mL of nitrogen and nitrogen. In dimethylacetamide (DMA). Other treatments are the same as in the eighth embodiment.
实施例10Example 10
使用PVDC作为碳源，硫脲作为掺氮和掺硫的试剂，使用氢氧化钠作为强碱脱氯剂，三者的使用量分别为1.0g、1.0g和1.0g，将上述固体物质加入到10mL的氮氮二甲基乙酰胺(DMA)中。其他处理方式同实施例8。Using PVDC as a carbon source, thiourea as a nitrogen-doping and sulfur-doping reagent, using sodium hydroxide as a strong alkali dechlorination agent, the amount of the three used are 1.0g, 1.0g and 1.0g, respectively, and the above solid matter is added to 10 mL of nitrogen nitroacetamide (DMA). Other treatments are the same as in the eighth embodiment.
实施例11Example 11
使用PVDC作为碳源，三苯基膦作为掺磷剂，使用氨基钠作为强碱脱氯剂，三者的使用量分别为1.0g、1.0g和1.0g，将上述固体物质加入到10mL的氮氮二甲基乙酰胺(DMA)中。其他处理方式同实施例8。Using PVDC as a carbon source, triphenylphosphine as a phosphorus-doping agent, and sodium amide as a strong alkali dechlorination agent, the amount of the three used were 1.0 g, 1.0 g, and 1.0 g, respectively, and the above solid matter was added to 10 mL of nitrogen. Nitrodimethyl acetamide (DMA). Other treatments are the same as in the eighth embodiment.
实施例12Example 12
使用PVDC作为碳源，硼酸作为掺硼剂，使用氢氧化钾作为强碱脱氯剂，三者的使用量分别为0.64g、1.0g和1.5g，将上述固体物质加入到10mL的氮氮二甲基乙酰胺(DMA)中。其他处理方式同实施例8。PVDC was used as the carbon source, boric acid was used as the boron-doping agent, and potassium hydroxide was used as the strong alkali dechlorination agent. The three used were 0.64 g, 1.0 g and 1.5 g, respectively, and the above solid matter was added to 10 mL of nitrogen and nitrogen. In methyl acetamide (DMA). Other treatments are the same as in the eighth embodiment.
本发明同时发现，当分别使用聚偏二氟乙烯或聚氯乙烯作为碳源，其余原料及操作方式参照实施例8时，也可制得掺杂型碳材料，并且制得的掺杂型碳材料作为超级电容器材料使用时同样具有较高的电容容量和倍率特性及较低的电化学阻抗，因反应机理等与聚偏二氯乙烯作为碳源时相同，本文不再赘述。 The present invention also finds that when polyvinylidene fluoride or polyvinyl chloride is used as a carbon source, and the remaining materials and operation modes are as described in Example 8, a doped carbon material can be obtained, and the obtained doped carbon can be obtained. When used as a supercapacitor material, the material also has high capacitance capacity and rate characteristics and low electrochemical impedance. The reaction mechanism is the same as that of polyvinylidene chloride as a carbon source, and will not be described herein.

Claims (11)

  1. 一种掺杂型碳材料的制备方法，其特征在于，其包括以下步骤：A method for preparing a doped carbon material, characterized in that it comprises the following steps:
    将卤化高分子、强碱与强极性溶剂混合得到混合物，然后在室温下对该混合物进行研磨，研磨结束之后，直接进行清洗和干燥，即得到所述掺杂型碳材料；Mixing a halogenated polymer, a strong base and a strong polar solvent to obtain a mixture, and then grinding the mixture at room temperature, after the completion of the polishing, directly washing and drying to obtain the doped carbon material;
    其中所述卤化高分子为聚偏二氟乙烯、聚偏二氯乙烯或聚氯乙烯；Wherein the halogenated polymer is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride;
    其中所述强碱为碱(土)金属氢氧化物、碱(土)金属氧化物、氧化锌、碱(土)金属醇盐、碱(土)金属硫化物、碱(土)金属氨基化物或碱(土)金属氮化物；Wherein the strong base is an alkali (earth) metal hydroxide, an alkali (earth) metal oxide, a zinc oxide, an alkali (earth) metal alkoxide, an alkali (earth) metal sulfide, an alkali (earth) metal amide or Alkali (earth) metal nitride;
    其中所述强极性溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二甲基亚砜或氮甲基吡咯烷酮；Wherein the strong polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or nitromethylpyrrolidone;
    其中所述室温为10-40℃。Wherein the room temperature is 10-40 °C.
  2. 根据权利要求1所述的制备方法，其特征在于，在研磨前还向所述混合物中加入杂原子掺杂剂，所述杂原子掺杂剂选自三聚氰胺、乙二胺、硫脲、硫代乙酰胺、硼酸、硼烷氨或三苯基膦。The method according to claim 1, wherein a hetero atom dopant is further added to the mixture prior to grinding, the hetero atom dopant being selected from the group consisting of melamine, ethylenediamine, thiourea, and thio Acetamide, boric acid, borane ammonia or triphenylphosphine.
  3. 根据权利要求1所述的制备方法，其特征在于，所述强碱为氢氧化钠、氢氧化钾、氢氧化锂、乙醇钠、硫化钠、氨基钠或氮化锂。The preparation method according to claim 1, wherein the strong base is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium sulfide, sodium amide or lithium nitride.
  4. 根据权利要求1所述的制备方法，其特征在于，所述研磨为手动研磨或球磨，所述研磨的持续时间不少于1分钟。The preparation method according to claim 1, wherein the grinding is manual grinding or ball milling, and the grinding has a duration of not less than 1 minute.
  5. 根据权利要求1所述的制备方法，其特征在于，所述强碱的摩尔量足以将所述卤化高分子中的卤素原子基本完全脱除。The method according to claim 1, wherein the molar amount of the strong base is sufficient to substantially completely remove the halogen atom in the halogenated polymer.
  6. 根据权利要求2所述的制备方法，其特征在于，所述杂原子是指除了碳原子之外的非金属元素的原子。The production method according to claim 2, wherein the hetero atom means an atom other than a carbon atom.
  7. 根据权利要求2所述的制备方法，其特征在于，所述杂原子是氮、硫、硼、磷或氧。The method according to claim 2, wherein the hetero atom is nitrogen, sulfur, boron, phosphorus or oxygen.
  8. 根据权利要求1-7中任一项所述的制备方法制备的掺杂型碳材料在电化学中的用途。Use of a doped carbon material prepared by the preparation method according to any one of claims 1 to 7 in electrochemistry.
  9. 根据权利要求1所述的制备方法，其特征在于，在研磨结束之后，其还包括将研磨后的混合物在惰性气体中焙烧的步骤，然后再进行清洗和干燥，即得到所述掺杂型纳米碳材料。The preparation method according to claim 1, wherein after the end of the grinding, the step further comprises the step of calcining the ground mixture in an inert gas, followed by washing and drying to obtain the doped nanometer. Carbon material.
  10. 根据权利要求9所述的制备方法，其特征在于，所述焙烧的温度为400-900℃。The production method according to claim 9, wherein the baking temperature is 400 to 900 °C.
  11. 根据权利要求9-10中任一项所述的制备方法制备的掺杂型碳材料在超级电容器中的用途。 Use of a doped carbon material prepared by the preparation method according to any one of claims 9-10 in a supercapacitor.
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CN114436244B (en) * 2021-12-06 2023-10-17 中国地质大学（武汉） Preparation method of graphite diyne
CN115072720A (en) * 2022-07-22 2022-09-20 燕山大学 Oxygen-doped porous carbon electrode material with high pseudocapacitance activity and preparation method thereof
CN115072720B (en) * 2022-07-22 2024-04-02 燕山大学 Oxygen-doped porous carbon electrode material with high pseudocapacitance activity and preparation method thereof
CN115504467A (en) * 2022-10-14 2022-12-23 桂林电子科技大学 Preparation method and application of porous carbon material pretreated based on chlorine-containing organic matter and alkali solution
CN115504467B (en) * 2022-10-14 2023-09-22 桂林电子科技大学 Preparation method and application of pretreatment porous carbon material based on chlorine-containing organic matters and alkali solution

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