CN115974074A - Method for preparing nitrogen-containing porous carbon material by utilizing cockroaches - Google Patents
Method for preparing nitrogen-containing porous carbon material by utilizing cockroaches Download PDFInfo
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing a nitrogen-containing porous carbon material by utilizing cockroaches and application thereof. The nitrogen-containing porous carbon material is applied to the field of energy storage of super capacitor electrodes and the field of pollutant adsorption. The porous carbon has the characteristics of low preparation cost, excellent electrochemical performance, high pore density and large specific surface area.
Description
The application is a divisional application with the application date of 2019, 05 and 30, and the application number of 201910464653.8, and the invention name of "a method for preparing nitrogen-containing porous carbon material by utilizing cockroaches and application thereof".
Technical Field
The invention relates to a method for preparing a nitrogen-containing porous carbon material and application thereof, in particular to a method for preparing a nitrogen-containing porous carbon material by utilizing cockroaches and application thereof.
Background
The porous carbon material is the best choice for high-performance electrode materials due to its low cost, high conductivity, good chemical stability and long cycle life, and can provide large active sites for electrochemical reactions and short diffusion paths for ion transport. Among various porous carbon materials, biomass-derived porous carbon is gradually and widely applied to electrode materials of energy storage devices due to the advantages of huge availability, rapid regeneration, environmental protection and the like. Porous carbon with high specific surface area is usually prepared from different natural or synthetic carbon-rich precursors by chemical/physical activation and subsequent carbonization in an inert atmosphere.
Currently, the introduction of heteroatoms such as N, O, P, S or B into carbon substrates (a) k.y.park, et al, journal of Physical Chemistry C,2012,116,16848-16853, (B) y.a.huang, f.yang, z.xu and j.shen, journal of colloid & Interface Science,2011,363, 193-198) is considered as an effective strategy to improve their electrochemical activity, catalytic behavior and adsorption performance. Among these different heteroatom-doped carbons, N-doped carbon has attracted much attention because of its excellent conductivity, oxidation stability, and adsorption wettability. The lone pair of electrons of N can remarkably adjust the electron donor-acceptor characteristics of the carbon material, and the combination with the graphite pi bond of carbon distorts the carbon structure, so that more defects and available active sites are generated, and the electrochemical performance of a lithium ion battery and a supercapacitor is improved. Nitrogen-doped porous Carbon materials have previously been prepared by post-treating nitrogen-doping (k.gong, f.du, z.xia, m.durtock and dl.dai, science,2009,323, 760-764) with Carbon and expensive and toxic nitrogen-containing compounds (such as urea, ammonia and acrylonitrile), or by direct carbonization of biomass precursors or nitrogen-containing compounds (such as polypyrrole) to yield nitrogen-doped porous Carbon materials (Fiset E, rufford TE, carbon,2015, 81. The renewable biomass has low cost benefit, simple synthesis process and high natural utilization rate of C and N, and is favorable for synthesizing carbon materials required by industry at low price and high efficiency to a great extent.
In previous research, plant precursors were used as precursors to prepare porous carbon materials containing heteroatoms such as O, N, S, P, etc. by carbonization and activation. For example, various porous Carbon Materials such as tobacco stems (Kleszyk P, ratajczak P, et al, carbon,2015, 81. Yong-Qing ZHao (Journal of Power Sources,2016,307, 391-400.) et al activate tobacco leaves with KOH to obtain nitrogen-doped porous carbon materials, and apply to electrode materials of lithium ion batteries and supercapacitors. The method has the advantages of wide raw material source, environmental protection, economy, simple preparation process and the like, and has absolute feasibility.
Disclosure of Invention
The invention aims to provide a method for preparing a nitrogen-containing porous carbon material by utilizing cockroaches and application thereof. The method provided by the invention has the characteristics of low porous carbon preparation cost, excellent electrochemical performance, high pore density and large specific surface area.
The technical scheme of the invention is as follows: a method for preparing a nitrogen-containing porous carbon material by utilizing cockroaches comprises the steps of pre-carbonizing the cockroaches, mixing and grinding the cockroaches with potassium hydroxide, adding pure water, grinding the mixture into paste, drying, dehydrating, carbonizing the paste, and cleaning and drying the paste to obtain the nitrogen-containing porous carbon material.
The method for preparing the nitrogen-containing porous carbon material by utilizing the cockroaches specifically comprises the following steps:
(1) Sequentially washing cockroach with ethanol and pure water, and drying to obtain product A;
(2) Placing the product A in a heating furnace, preserving heat for 0.5-2h at 400-500 ℃, and pre-carbonizing to obtain a product B;
(3) Mixing the product B with potassium hydroxide, grinding into powder, adding pure water, and further grinding into paste to obtain product C;
(4) Vacuum drying the product C, taking out, placing in a heating furnace, keeping the temperature at 600-900 deg.C for 1-3h, and carbonizing to obtain product D;
(5) And cooling the product D to room temperature, taking out, sequentially washing with hydrochloric acid and pure water, and drying in vacuum to obtain the nitrogen-containing porous carbon material.
In the method for preparing the nitrogen-containing porous carbon material by utilizing the cockroaches, the drying in the step (1) is freeze drying, the drying temperature is-58 ℃, and the drying time is 24-48 hours.
In the method for preparing the nitrogen-containing porous carbon material by utilizing the cockroaches, in the step (2), the temperature is increased to 400-500 ℃ at the speed of 5-10 ℃/min, and argon with the flow rate of 100-200ml/min is introduced into the heating furnace in the processes of temperature increase and heat preservation.
In the method for preparing the nitrogen-containing porous carbon material by utilizing the cockroaches, in the step (3), the mixing mass ratio of the product B to the potassium hydroxide is 1.
In the method for preparing the nitrogen-containing porous carbon material by using the cockroaches, in the step (3), the product B is mixed with the potassium hydroxide and then ground for 5-15min, and then pure water is added according to the mass ratio of the product B to the pure water of 1-3 and ground into paste.
In the method for preparing the nitrogen-containing porous carbon material by utilizing the cockroaches, in the step (4), the vacuum drying temperature is 80-100 ℃, and the drying time is 4-8h.
In the step (4), after drying, the nitrogen-containing porous carbon material is placed in a heating furnace, the temperature is raised to 600-900 ℃ at the speed of 5-10 ℃/min, and argon with the flow of 100-200ml/min is introduced into the heating furnace in the processes of temperature raising and heat preservation.
In the method for preparing the nitrogen-containing porous carbon material by utilizing cockroaches, in the step (5), the hydrochloric acid is 2M hydrochloric acid, and is washed for 1-10h and then is washed to be neutral by pure water; the vacuum drying temperature is 80-120 ℃, and the drying time is 10-12h.
The application of the nitrogen-containing porous carbon material prepared by the method for preparing the nitrogen-containing porous carbon material by utilizing cockroaches in the fields of energy storage of electrodes of super capacitors and adsorption of pollutants.
The invention has the advantages of
1. According to the invention, the porous carbon is prepared by improving the process and taking the cockroach as a carbon source, and the preparation cost of the porous carbon is greatly reduced by means of the characteristics of strong breeding capacity, wide sources, low price and environmental friendliness of the cockroach.
2. As the cockroach provides abundant C, N and O elements, the process of the invention is combined to fully activate pore-forming, and the electrical property of the activated carbon is improved (mainly reflected in the aspects of high power density, short charging time, long cycle life and the like); meanwhile, the porous carbon material also has the advantages of high pore density and large specific surface area.
Drawings
FIG. 1 is an SEM image of carbon materials CR-800, CR-KOH-700, CR-KOH-800, and CR-KOH-900 prepared under different conditions;
FIG. 2 is a TEM image of carbon materials CR-800, CR-KOH-700, CR-KOH-800, and CR-KOH-900 prepared under different conditions;
FIG. 3 is the XRD and Raman spectra of carbon materials CR-800, CR-KOH-800 prepared by direct carbonization of cockroaches and activation method;
FIG. 4 is XRD and Raman spectra of nitrogen-containing porous carbon materials CR-KOH-700, CR-KOH-800 and CR-KOH900 prepared at different activation temperatures;
FIG. 5 is a BET diagram of carbon materials CR-800, CR-KOH-800 prepared by direct carbonization of cockroaches and activation;
FIG. 6 is a BET diagram of nitrogen-containing porous carbon materials CR-KOH-700, CR-KOH-800 and CR-KOH900 prepared at different activation temperatures;
FIG. 7 is an XPS plot of carbon materials CR-800, CR-KOH-700, CR-KOH-800, CR-KOH-900 prepared under different conditions;
FIG. 8 is a graph showing electrochemical performance (CV, GCD, EIS, rate capability) of carbon materials CR-800 and CR-KOH-800 prepared by direct carbonization of cockroaches and activation;
FIG. 9 is a diagram of electrochemical performances (CV, GCD, EIS, rate capability) of nitrogen-containing porous carbon materials CR-KOH-700, CR-KOH-800 and CR-KOH900 prepared at different activation temperatures;
FIG. 10 shows electrochemical performances (CV, GCD, EIS) of carbon-containing porous carbon CR-KOH-800 prepared by an activation method at 800 ℃ in a 1M Na2SO4 electrolyte;
FIG. 11 shows adsorption experiments of carbon-containing porous carbon CR-KOH-800 prepared by 800 ℃ activation method on methylene blue with different concentrations.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Inventive example 1
To illustrate the scope of the present invention, we prepared nitrogen-containing porous carbon materials by using different activation temperatures.
(1) 1 part of cockroach is washed clean by ethanol and pure water in turn, and is frozen and dried for 48 hours at the temperature of minus 58 ℃ to obtain a product A;
(2) Placing the product A in a tubular furnace with argon atmosphere, heating to 500 ℃ at the rate of 5 ℃/min and the argon flow of 200ml/min, and pre-carbonizing for 2h to obtain a product B;
(3) Mixing the product B with potassium hydroxide (C/KOH =1 = 4) and grinding for 10min, then adding pure water according to the mass ratio of 1;
(4) Vacuum drying product C at 90 deg.C for 6h, placing in a tubular furnace under argon atmosphere, activating at different temperatures (700 deg.C, 800 deg.C, 900 deg.C) for 2h, with heating rate of 5 deg.C/min and argon flow of 200ml/min to obtain product D;
(5) And (3) stirring and washing the product D with 2M HCl for 10h, washing with pure water for 3 times until the pH is =7, and performing vacuum drying at 110 ℃ for 12h to obtain three nitrogen-containing porous carbon materials which are respectively named as CR-KOH-700, CR-KOH-800 and CR-KOH-900. The surface topography of the three target products is shown in fig. 1-2; XRD and Raman are shown in fig. 4, indicating that as the activation temperature increases, the degree of disorder of the material increases; the specific surface area and pore size distribution are shown in FIG. 6, indicating that CR-KOH-800 has the largest specific surface area and pore volume; electrochemical properties are shown in FIG. 9, indicating that CR-KOH-800 has the best electrochemical properties.
Inventive example 2
To illustrate the scope of the present invention, we prepared nitrogen-containing porous carbon materials by using different activation temperatures.
(1) 1 part of cockroach is washed clean by ethanol and pure water in sequence, and freeze drying is carried out for 24 hours at the temperature of minus 58 ℃ to obtain a product A;
(2) Putting the product A in a tubular furnace in argon atmosphere, heating to 400 ℃ at the heating rate of 10 ℃/min and the argon flow of 100ml/min, and pre-carbonizing for 0.5h to obtain a product B;
(3) Mixing the product B with potassium hydroxide (C/KOH = 1) and grinding for 5min, then adding pure water according to the mass ratio of 1;
(4) Vacuum drying the product C at 80 deg.C for 4h, placing in a tubular furnace under argon atmosphere, activating at 600 deg.C for 1h, heating at 10 deg.C/min, and argon flow at 100ml/min to obtain product D;
(5) And (3) stirring and washing the D product for 1h by using 2MHCl, washing the D product for 3 times by using pure water until the pH is =7, and drying the D product for 10h in vacuum at 80 ℃ to obtain the nitrogen-containing porous carbon material.
Inventive example 3
To illustrate the scope of the present invention, we prepared nitrogen-containing porous carbon materials by using different activation temperatures.
(1) Washing 1 part of cockroach with ethanol and pure water in sequence, and freeze-drying at-58 ℃ for 36h to obtain a product A;
(2) Putting the product A in a tubular furnace in argon atmosphere, heating at a rate of 8 ℃/min and an argon flow of 150ml/min, and heating to 450 ℃ for pre-carbonization for 1h to obtain a product B;
(3) Mixing the product B with potassium hydroxide (C/KOH = 1) and grinding for 15min, then adding pure water according to the mass ratio of 1;
(4) Vacuum drying the product C at 100 deg.C for 8h, placing in a tubular furnace under argon atmosphere, activating at 600 deg.C for 3h at different temperatures, with heating rate of 10 deg.C/min and argon flow of 150ml/min to obtain product D;
(5) And (3) washing the D product with 2MHCl for 15h under stirring, washing the D product with pure water for 3 times until the pH is =7, and performing vacuum drying at 120 ℃ for 11h to obtain the nitrogen-containing porous carbon material.
Comparative example
(1) 1 part of cockroach is cleaned by ethanol and pure water, and freeze drying is carried out to obtain a product A;
(2) Carbonizing the product A in a tubular furnace in argon atmosphere at the temperature rise rate of 5 ℃/min and the argon flow rate of 200ml/min for 2h at 800 ℃ to obtain a product B;
(3) Product C was washed with 2MHCl with stirring for 12h, 3 times with pure water to pH =7, and dried under vacuum at 110 ℃ for 12h to give product C, which was named CR-800. The surface morphology, XRD and Raman, specific surface area, pore size distribution and electrochemical properties are respectively shown in figures 1-2, 3, 5 and 8, and the results show that almost no pore structure exists in direct carbonization, and the electrochemical properties of the activated carbon material are greatly increased.
Experimental example 1
We performed electrochemical tests on carbon materials using different electrolytes.
(1) Soaking the electrode plate and the diaphragm in 1M Na 2 SO 4 Neutralizing for 4h;
(2) After soaking, according to the cathode shell, the elastic sheet, the gasket, the working electrode plate and the 1MNa 2 SO 4 Electrolyte, separator, 1M Na 2 SO 4 Sequentially loading the working electrode plate, the gasket and the positive electrode shell, and packaging by using a sealing machine at the pressure of 8 MPa;
(3) Electrochemical performance was tested on an electrochemical workstation after resting for 4 h. The test results are shown in FIG. 10, and the results show that the carbon material prepared by the invention is applied to alkaline KOH and neutral Na 2 SO 4 Has good electrochemical performance.
Experimental example 2
The adsorption test of the CR-KOH-800 nitrogen-containing porous carbon material on methylene blue dye is carried out, and the application range of the carbon material prepared by the method is illustrated.
(1) Preparing 1600mg/L MB solution, and diluting the MB solution into 200mg/L, 400mg/L, 600mg/L, 800mg/L, 1000mg/L, 1200mg/L, 1400mg/L and 1600mg/L MB solution with different concentrations;
(2) Adding 5.0mg of CR-KOH-800 into 5ml of MB solution, and shaking for 12 hours by using a shaking table to reach an adsorption balance state;
(3) And testing the ultraviolet absorption spectrum of the solution, and calculating to obtain the concentration of the solute remained in the solution after adsorption balance according to a standard curve formula. The adsorption isotherm was plotted with the remaining solute concentration as abscissa and the equilibrium adsorption amount as ordinate (fig. 11). Due to the ultrahigh specific surface area, the large pore volume and the high-level nitrogen-oxygen doping of the carbon material, the equilibrium adsorption capacity of the carbon material reaches the ultrahigh 1012.1mg/L, and the carbon material has great potential in the application of adsorption and degradation of industrial pollutants.
Experimental example 3
(1) Taking 8 parts of the products of the example 1 and the comparative example and 1 part of acetylene black to fully grind to obtain a product A;
(2) Dispersing 1 part of polytetrafluoroethylene in 1ml of ethanol, adding the polytetrafluoroethylene into the product A, and quickly grinding to obtain a pasty mixture product B;
(3) Rolling the product B to a sheet by using a glass rod, pressing the sheet on a foamed nickel circular sheet with the diameter of 12mm, and then tabletting by using a tabletting machine to obtain a product C;
(4) Vacuum drying the product C at 90 ℃ for 12h to obtain a product D of the pole piece;
(5) And (5) placing the product D in a 2032 coin cell with 6M KOH electrolyte, standing for 12h, and then carrying out electrochemical test. The electrochemical test comprises: constant current charge and discharge test, alternating current impedance test, cyclic voltammetry and the like. Test results show that the nitrogen-containing porous carbon material prepared by utilizing the cockroach precursor has excellent electrochemical properties, and the maximum specific capacitance reaches 324.88F/g.
Claims (7)
1. A method for preparing a nitrogen-containing porous carbon material by utilizing cockroaches is characterized by specifically comprising the following steps:
(1) Sequentially washing cockroach with ethanol and pure water, and drying to obtain product A;
(2) Putting the product A into a heating furnace, and preserving heat for 0.5-2h at 400-500 ℃ for pre-carbonization to obtain a product B;
(3) Mixing the product B with potassium hydroxide, grinding into powder, adding pure water, and further grinding into paste to obtain product C;
(4) Vacuum drying the product C, taking out, placing in a heating furnace, preserving heat at 800 ℃ for 2h, and carbonizing to obtain a product D;
(5) Cooling the product D to room temperature, taking out, sequentially washing with hydrochloric acid and pure water, and then carrying out vacuum drying to obtain the nitrogen-containing porous carbon material;
and (3) mixing the product B and the potassium hydroxide according to the mass ratio of 1-5.
2. The method for preparing a nitrogen-containing porous carbon material by cockroaches according to claim 1, wherein: the drying in the step (1) is freeze drying, wherein the freeze drying temperature is-58 ℃ and the time is 24-48h.
3. The method for preparing a nitrogen-containing porous carbon material by using cockroaches as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the temperature is raised to 400-500 ℃ at the speed of 5-10 ℃/min, and argon with the flow rate of 100-200ml/min is introduced into the heating furnace in the processes of temperature rise and heat preservation.
4. The method for preparing a nitrogen-containing porous carbon material by cockroaches according to claim 1, wherein: in the step (3), the product B and potassium hydroxide are mixed and ground for 5-15min, and then pure water is added according to the mass ratio of the product B to the pure water of 1-3 and ground into paste.
5. The method for preparing a nitrogen-containing porous carbon material by using cockroaches as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the temperature of vacuum drying is 80-100 ℃, and the drying time is 4-8h.
6. The method for preparing a nitrogen-containing porous carbon material by cockroaches according to claim 1, wherein: in the step (4), the temperature is raised to 800 ℃ at the speed of 5-10 ℃/min, and argon with the flow rate of 100-200ml/min is introduced into the heating furnace in the processes of temperature rise and heat preservation.
7. The method for preparing a nitrogen-containing porous carbon material by using cockroaches as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the hydrochloric acid is 2M hydrochloric acid, and is washed for 1-10h and then is washed to be neutral by pure water; the vacuum drying temperature is 80-120 ℃, and the drying time is 10-12h.
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