CN111591988A - Porous carbon prepared from nitrogen source modified enteromorpha and preparation method and application thereof - Google Patents
Porous carbon prepared from nitrogen source modified enteromorpha and preparation method and application thereof Download PDFInfo
- Publication number
- CN111591988A CN111591988A CN202010519113.8A CN202010519113A CN111591988A CN 111591988 A CN111591988 A CN 111591988A CN 202010519113 A CN202010519113 A CN 202010519113A CN 111591988 A CN111591988 A CN 111591988A
- Authority
- CN
- China
- Prior art keywords
- enteromorpha
- nitrogen source
- porous carbon
- temperature
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- 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
Abstract
The invention discloses porous carbon prepared from nitrogen source modified enteromorpha and a preparation method and application thereof, and the porous carbon comprises the following steps: washing, drying, crushing and sieving the enteromorpha to obtain enteromorpha powder; mixing enteromorpha powder with a nitrogen source to obtain a nitrogen source modified enteromorpha precursor; carbonizing a nitrogen source modified enteromorpha precursor in an inert atmosphere; washing the carbonized product, and soaking in a chemical activating agent solution; and heating and activating under a protective atmosphere after dipping to obtain the product. The nitrogen-containing substance is introduced into the precursor to modify enteromorpha, so that the prepared porous carbon material has a three-dimensional open structure, hierarchical pore channels, a large specific surface area and a high pore volume. Therefore, the electrochemical performance of the porous carbon material is improved, and the high-quality utilization of the enteromorpha is realized.
Description
Technical Field
The invention belongs to the technical field of porous carbon materials and electrochemical capacitors, and particularly relates to porous carbon prepared from nitrogen source modified enteromorpha and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The carbonaceous porous material with high specific surface area, large pore volume and developed pore structure has high conductivity and good thermochemical stability, so that the carbonaceous porous material is widely applied to the aspects of gas adsorption, catalysis, energy storage and the like. Coal, biomass extracts, domestic wastes, industrial wastes and the like have potential to be used as raw materials for preparing porous carbon, wherein the biomass materials are widely concerned by researchers due to the advantages of rich varieties, low price and easy availability. Generally speaking, although porous carbon directly prepared by taking biomass as a precursor can present good performance, research shows that the potential of biomass raw materials can be further exploited by carrying out certain treatment on the raw materials so as to obtain a porous carbon material with higher performance. For example, by removing minerals from the feedstock, the specific surface area of the product can be increased; the microstructure of the product can be changed by adjusting the composition of the raw materials (for example, adding calcium-containing substances and the like); the addition of certain compounds to the feedstock enables the introduction of targeted elements (e.g., nitrogen, phosphorus, sulfur, etc.).
Enteromorpha prolifera, also called Enteromorpha prolifera and Enteromorpha prolifera, belongs to Enteromorpha of Ulvaceae of Chlorophyta and is a natural wild enteromorpha prolifera living in offshore mud flatThe green algae has strong natural reproduction capability. In recent years, due to global climate change, water eutrophication and other reasons, green tide frequency of enteromorpha prolifera of marine macroalgae is outbreak, a large amount of enteromorpha prolifera is floated and gathered to the shore to block a navigation channel, and meanwhile, a large amount of oxygen is consumed during rotting and breeding after the enteromorpha prolifera is accumulated in a large amount, odor is emitted, an ocean ecosystem is damaged, and the development of coastal fishery and tourism is seriously threatened. The basic method for treating the enteromorpha is to process the enteromorpha into food or animal feed, but still cannot consume a large amount of enteromorpha, and the aim of pollution treatment cannot be achieved. The enteromorpha prolifera has the composition structure characteristics, so that the enteromorpha prolifera has potential application in other fields, such as production of antibacterial drugs, bio-oil and lactic acid, carbon dioxide capture, heavy metal removal, preparation of porous carbon and the like. Xie Tian and the like take enteromorpha as raw materials and are pretreated by freeze drying and ZnCl2The activated prepared porous carbon is used for a super capacitor (RSC Adv,2015,5(21): 16575) -16581), the preparation method has a complicated flow, the specific surface area of the obtained porous carbon is low, and the mass specific capacitance of the prepared super capacitor is low. Patent CN107651687A discloses a method for preparing a carbon material rich in pyridine nitrogen by using enteromorpha as a carbon source, performing high-pressure hydrothermal carbonization synthesis on a mixed solution formed by the carbon source and a solvent to obtain a carbide, heating the carbide, melamine and potassium hydroxide according to a certain ratio in a nitrogen atmosphere, cooling, washing and drying.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide porous carbon prepared from nitrogen source modified enteromorpha and a preparation method and application thereof. The nitrogen-containing substance is introduced into the precursor to modify enteromorpha, so that the prepared porous carbon material has a three-dimensional open structure, hierarchical pore channels, a large specific surface area and a high pore volume. Therefore, the electrochemical performance of the porous carbon material is improved, and the high-quality utilization of the enteromorpha is realized.
In order to achieve the above object, one or more embodiments of the present invention disclose the following technical solutions:
in a first aspect, the invention provides a preparation method of porous carbon prepared from nitrogen source modified enteromorpha, which comprises the following steps:
washing, drying, crushing and sieving the enteromorpha to obtain enteromorpha powder;
fully mixing the enteromorpha powder with a nitrogen source to obtain a nitrogen source modified enteromorpha precursor;
carbonizing a nitrogen source modified enteromorpha precursor in an inert atmosphere;
washing the carbonized product, and soaking in a chemical activating agent solution;
and heating and activating under a protective atmosphere after dipping to obtain the product.
In a second aspect, the invention provides porous carbon prepared by the preparation method.
In a third aspect, the present invention provides the use of the above porous carbon in the preparation of a supercapacitor.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
(1) the composition of the precursor and the distribution condition of each component are optimized by mixing the enteromorpha powder and the nitrogen source, so that the composition of the precursor is richer and more uniformly distributed.
(2) The nitrogen source can adjust the pore structure and the element composition of the carbon material obtained from the enteromorpha, so that the prepared porous carbon has more excellent pore structure, surface chemical property and internal molecular structure, and the electrochemical performance of the porous carbon material is favorably improved.
(3) The carbonized product impregnated with the chemical activating agent is heated, so that impurities in the carbonized product can be removed, the ash content in the carbonized product can be reduced, the porosity of the carbonized product can be improved, the pore-forming effect can be optimized, and the performance of the porous carbon can be further improved; the washing process can remove metal compounds, and is favorable for improving the performance stability of the porous carbon.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope photograph of the porous carbon prepared in example 8.
FIG. 2 shows the nitrogen adsorption and desorption curves of the porous carbon prepared in example 8.
FIG. 3 is a scanning electron microscope photograph of the porous carbon prepared in example 9.
FIG. 4 is a graph showing the pore size distribution of micropores of the porous carbon prepared in example 9.
FIG. 5 is a scanning electron microscope photograph of the porous carbon prepared in example 10.
FIG. 6 is a Raman spectrum of the porous carbon prepared in example 10.
FIG. 7 shows the cyclic voltammogram of the supercapacitor prepared in example 11 at a scan rate of 5 mV/s.
FIG. 8 shows the long cycle performance curve of the supercapacitor made in example 12.
FIG. 9 shows the rate performance curve of the porous carbon prepared in example 13.
FIG. 10 is a graph showing constant current charge and discharge curves at 1A/g of the porous carbon prepared in example 13.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the invention provides a preparation method of porous carbon prepared from nitrogen source modified enteromorpha, which comprises the following steps:
washing, drying, crushing and sieving the enteromorpha to obtain enteromorpha powder;
mixing enteromorpha powder with a nitrogen source to obtain a nitrogen source modified enteromorpha precursor;
carbonizing a nitrogen source modified enteromorpha precursor in an inert atmosphere;
washing the carbonized product, and soaking in a chemical activating agent solution;
and heating and activating under a protective atmosphere after dipping to obtain the product.
In some embodiments, the mesh size of the screened enteromorpha powder is 20-300 mesh, preferably 80 mesh.
In some embodiments, the ratio of the mass of the enteromorpha mixed with the nitrogen source is 1: 1-20: 1; further preferably, 3: 1 or 5: 1.
further, the nitrogen source is one or a mixture of more of urea, melamine, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate, and more preferably, the nitrogen source is diammonium hydrogen phosphate.
In some embodiments, the temperature rise rate of the carbonization is 1-20 ℃/min, and the preferred temperature rise rate is 5 ℃/min.
Further, the carbonization temperature is 500-900 ℃, preferably 600 ℃.
Further, the flow rate of the protective gas during carbonization is 0.1-2L/min, preferably 0.6L/min.
In some embodiments, the carbonized product is washed, including the steps of acid washing and deionized water washing.
Further, the acid used in the acid washing is an aqueous solution of hydrochloric acid, nitric acid, or hydrofluoric acid, and preferably an aqueous solution of hydrochloric acid.
Further, the concentration of the acid is 1 to 60 wt%, preferably 1 to 20 wt%.
In some embodiments, chemical activators include, without limitation, KOH solutions, NaOH solutions, K2CO3Solution, H3PO4Solutions or ZnCl2And (3) solution.
Further, the chemical activator is a KOH solution.
Further, the KOH solution is a saturated KOH solution.
Furthermore, the mass ratio of the carbonized product to KOH is 1: 1-1: 5, preferably 1: 4.
In some embodiments, the step of heat activating comprises low temperature activation and high temperature activation; the low-temperature activation temperature is 300-400 ℃, and the time is 30-50 min; the high-temperature activation temperature is 700-900 ℃, and the time is 60-140 min.
Further, the low-temperature activation temperature is 350 ℃, and the time is 30 min; the high temperature activation temperature is 800 deg.C, and the time is 120 min.
In some embodiments, the method further comprises the step of acid washing and water washing the carbonized product after the heating activation.
Further, the acid used for pickling is one or a mixture of hydrochloric acid, nitric acid and hydrofluoric acid.
Further, the pickling temperature is 30-100 ℃, and the pickling time is 120-300 min.
Further, the concentration of the acid is 1 to 60 wt%, preferably 1 to 20 wt%.
In a second aspect, the invention provides porous carbon prepared by the preparation method.
In a third aspect, the present invention provides the use of the above porous carbon in the preparation of a supercapacitor.
The electrode material is prepared by mixing the porous carbon, acetylene black serving as a conductive agent and a binder, the electrode material is pressed to obtain an electrode sheet, and the electrode sheet and electrolyte are assembled to obtain the supercapacitor.
The adhesive is PTFE, the mass ratio of the porous carbon to the conductive agent acetylene black to the adhesive PTFE is 7-9: 1: 1.
example 1:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and urea according to the proportion of 1:1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 2:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and urea according to the proportion of 5: 1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 3:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and urea according to the proportion of 10: 1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 4:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and melamine according to the ratio of 1:1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 5:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and melamine according to the ratio of 5: 1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 6:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and melamine according to the ratio of 10: 1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 7:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha precursor, which comprises the following steps:
the embodiment relates to a preparation method of a nitrogen source modified enteromorpha derived porous carbon precursor, which comprises the following steps:
step one, fully washing the enteromorpha prolifera raw material with tap water, removing impurities, and drying in a forced air drying oven at 120 ℃ for 48 hours to obtain dry enteromorpha prolifera.
And step two, crushing the dried enteromorpha with a crusher, and screening with a 80-mesh screen to obtain enteromorpha powder.
Step three, mixing the enteromorpha powder and diammonium hydrogen phosphate according to the ratio of 3: 1, and obtaining a nitrogen source modified enteromorpha precursor.
Example 8:
the embodiment relates to a preparation method of nitrogen source modified enteromorpha derived porous carbon, which comprises the following steps:
step one, 25g of the precursor prepared in example 2 was weighed, placed in a tube furnace, heated to 600 ℃ at a heating rate of 5 ℃/min, and held at this temperature for 2 h. Nitrogen was used as a shielding gas and the rate of introduction was 1L/min.
And step two, firstly, washing the product obtained in the step one with 20 wt% hydrochloric acid at 80 ℃, then washing the product with deionized water at 80 ℃ to be neutral, and drying the product for 12 hours at 105 ℃.
Step three, weighing 3g of the product obtained in the step two, mixing the product with KOH according to the mass ratio of 1:4, and soaking the product for 5 hours at the temperature of 80 ℃.
And step four, putting the product obtained in the step three into a muffle furnace, raising the temperature to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 800 ℃ and keeping the temperature for 120 min. The nitrogen gas was introduced at a rate of 0.6L/min.
And step five, washing the product obtained in the step four by using 20 wt% hydrochloric acid at 80 ℃ until the product is neutral, and then washing the product by using deionized water until the product is neutral. And drying the obtained product at 105 ℃ for 12h to obtain the nitrogen source modified enteromorpha derived porous carbon.
FIG. 1 is a scanning electron microscope photograph showing the porous carbon, from which it can be seen that the surface of the porous carbon particles shows the characteristic of accumulation of fine carbon particles, FIG. 2 is a nitrogen adsorption/desorption curve of the porous carbon, and the BET method shows that the specific surface area is 3427.1m2Per g, total pore volume 2.69cm3(ii)/g, the average pore diameter of mesopores was 3.26nm, the average pore diameter of micropores was 0.66nm, and the ratio of the specific surface area of mesopores to the specific surface area of micropores was 0.53.
Example 9:
the embodiment relates to a preparation method of nitrogen source modified enteromorpha derived porous carbon, which comprises the following steps:
step one, 25g of the precursor prepared in example 5 was weighed, placed in a tube furnace, heated to 600 ℃ at a heating rate of 5 ℃/min, and held at this temperature for 2 h. Nitrogen was used as a shielding gas and the rate of introduction was 1L/min.
And step two, firstly, washing the product obtained in the step one with 20 wt% hydrochloric acid at 80 ℃, then washing the product with deionized water at 80 ℃ to be neutral, and drying the product for 12 hours at 105 ℃.
Step three, weighing 3g of the product obtained in the step two, mixing the product with KOH according to the mass ratio of 1:4, and soaking the product for 5 hours at the temperature of 80 ℃.
And step four, putting the product obtained in the step three into a muffle furnace, raising the temperature to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 800 ℃ and keeping the temperature for 120 min. The nitrogen gas was introduced at a rate of 0.6L/min.
And step five, washing the product obtained in the step four by using 20 wt% hydrochloric acid at 80 ℃ until the product is neutral, and then washing the product by using deionized water until the product is neutral. And drying the obtained product at 105 ℃ for 12h to obtain the nitrogen source modified enteromorpha derived porous carbon.
FIG. 3 is a scanning electron microscope photograph of the porous carbon, and the surface of the porous carbon particle prepared according to the present invention obtained from FIG. 3 shows a flat surface with fine slits distributed therein as a whole. The pore size distribution curve of the micropores of the porous carbon shown in FIG. 4 shows that the pore size distribution of the micropores of the porous carbon prepared by the present invention is mainly in the range of less than 0.8nm as can be seen from FIG. 4. The implementation effect is as follows: the specific surface area of the porous carbon calculated by the BET method was 3556.6m2In terms of a total pore volume of 2.62cm3(ii)/g, the average pore diameter of mesopores was 3.14nm, the average pore diameter of micropores was 0.66nm, and the ratio of the specific surface area of mesopores to the specific surface area of micropores was 0.48.
Example 10:
the embodiment relates to a preparation method of nitrogen source modified enteromorpha derived porous carbon, which comprises the following steps:
step one, 25g of the precursor prepared in example 7 was weighed, placed in a tube furnace, heated to 600 ℃ at a heating rate of 5 ℃/min and held at this temperature for 2 h. Nitrogen was used as a shielding gas and the rate of introduction was 1L/min.
And step two, firstly, washing the product obtained in the step one with 20 wt% hydrochloric acid at 80 ℃, then washing the product with deionized water at 80 ℃ to be neutral, and drying the product for 12 hours at 105 ℃.
Step three, weighing 3g of the product obtained in the step two, mixing the product with KOH according to the mass ratio of 1:4, and soaking the product for 5 hours at the temperature of 80 ℃.
And step four, putting the product obtained in the step three into a muffle furnace, raising the temperature to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 800 ℃ and keeping the temperature for 120 min. The nitrogen gas was introduced at a rate of 0.6L/min.
And step five, washing the product obtained in the step four by using 20 wt% hydrochloric acid at 80 ℃ until the product is neutral, and then washing the product by using deionized water until the product is neutral. And drying the obtained product at 105 ℃ for 12h to obtain the calcium modified soluble alginate-based porous carbon.
FIG. 5 is a scanning electron microscope photograph of the porous carbon, and it can be seen from FIG. 5 that the surface of the porous carbon particles of the present invention is characterized in that the fine carbon particles are deposited in a multi-layer sheet structure. FIG. 6 shows a Raman spectrum of the porous carbon, and FIG. 6 shows I of the porous carbon prepared by the present inventionG/IDThe larger value of (A) indicates a higher degree of graphitization, and the presence of a 2D band indicates that it has better order and that the interatomic interaction is becoming stronger. The implementation effect is as follows: the porous carbon has a specific surface area of 3642.8m calculated by BET method2Per g, total pore volume of 2.58cm3(ii)/g, the average pore diameter of mesopores was 3.11nm, the average pore diameter of micropores was 0.66nm, and the ratio of the specific surface area of mesopores to the specific surface area of micropores was 0.33.
Example 11:
the embodiment relates to application of porous carbon in an electrode material of an aqueous electrochemical capacitor, which comprises the following steps:
the electrode material for a supercapacitor was prepared by mixing the porous carbon obtained in example 8 with acetylene black as a conductive agent and PTFE as a binder in a mass ratio of 8:1: 1. And (3) coating the electrode material on foamed nickel, drying for 12h at 80 ℃ in vacuum, and pressing for 1min at the pressure of 12MPa by using a tablet press to obtain the electrode sheet. Then 2 electrode sheets and 6mol/L KOH electrolyte are assembled into the super capacitor. Electrochemical performance tests were then performed on the electrochemical workstation. FIG. 7 shows the cyclic voltammogram of this supercapacitor at a scan rate of 5 mV/s. The rectangular shape presented in fig. 7 indicates that the electrochemical capacitor prepared from the porous carbon of the present invention has good charge transport properties.
Example 12:
the embodiment relates to application of porous carbon in an electrode material of an aqueous electrochemical capacitor, which comprises the following steps:
the electrode material for a supercapacitor was prepared by mixing the porous carbon obtained in example 9 with acetylene black as a conductive agent and PTFE as a binder in a mass ratio of 8:1: 1. And (3) coating the electrode material on foamed nickel, drying for 12h at 80 ℃ in vacuum, and pressing for 1min at the pressure of 12MPa by using a tablet press to obtain the electrode sheet. Then 2 electrode sheets and 6mol/L KOH electrolyte are assembled into the super capacitor. Electrochemical performance tests were then performed on the electrochemical workstation. The long cycle performance curve of the supercapacitor is shown in fig. 8. From FIG. 8, it can be seen that the super capacitor of the present invention has a high capacity retention rate, and has a high capacitance value even when the super capacitor is cycled to 3000-10000 circles.
Example 13:
an electrode material for a supercapacitor prepared by mixing the porous carbon prepared in the example 10 with a conductive agent and a binder in a mass ratio of 8:1:1, and performing a constant current charge-discharge test by using 6mol/L KOH as an electrolyte, wherein a rate performance curve of the supercapacitor shown in fig. 9 can be obtained from fig. 9, wherein a specific capacitance value reaches 364.6F/g when a current density is 0.1A/g, can still reach 277.0F/g when the current density is 10A/g, and reaches 230.8F/g when the current density is 50A/g, which indicates that the supercapacitor has good rate performance. Fig. 10 shows the constant current charging and discharging curve of the supercapacitor at a current density of 1A/g, and it can be seen from fig. 10 that the curve exhibits the characteristic of a symmetrical triangle, indicating good electric double layer behavior in the supercapacitor cell.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of porous carbon prepared from nitrogen source modified enteromorpha is characterized by comprising the following steps: the method comprises the following steps:
washing, drying, crushing and sieving the enteromorpha to obtain enteromorpha powder;
mixing enteromorpha powder with a nitrogen source to obtain a nitrogen source modified enteromorpha precursor;
carbonizing a nitrogen source modified enteromorpha precursor in an inert atmosphere;
washing the carbonized product, and soaking in a chemical activating agent solution;
and heating and activating under a protective atmosphere after dipping to obtain the product.
2. The method of claim 1, wherein: the mesh number of the screened enteromorpha powder is 20-300 meshes, and preferably 80 meshes.
3. The method of claim 1, wherein: the mixing mass ratio of the enteromorpha prolifera to the nitrogen source is 1: 1-20: 1; further preferably, 3: 1 or 5: 1;
further, the nitrogen source is one or a mixture of more of urea, melamine, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate, and more preferably, the nitrogen source is diammonium hydrogen phosphate.
4. The method of claim 1, wherein: the temperature rising speed of carbonization is 1-20 ℃/min, and the preferred temperature rising speed is 5 ℃/min;
further, the carbonization temperature is 500-900 ℃, preferably 600 ℃;
further, the flow rate of the protective gas during carbonization is 0.1-2L/min, preferably 0.6L/min.
5. The method of claim 1, wherein: washing the carbonized product, including the steps of acid washing and deionized water washing;
further, the acid used in the acid cleaning is an aqueous solution of hydrochloric acid, nitric acid or hydrofluoric acid, preferably an aqueous solution of hydrochloric acid;
further, the concentration of the acid is 1 to 60 wt%, preferably 1 to 20 wt%.
6. The method of claim 1, wherein: chemical activators include, but are not limited to, KOH solution, NaOH solution, K2CO3Solution, H3PO4Solutions or ZnCl2A solution;
further, the chemical activating agent is KOH solution;
further, the KOH solution is a saturated KOH solution;
furthermore, the mass ratio of the carbonized product to KOH is 1: 1-1: 5, preferably 1: 4.
7. The method of claim 1, wherein: the step of heating activation comprises low-temperature activation and high-temperature activation; the low-temperature activation temperature is 300-400 ℃, and the time is 30-50 min; the high-temperature activation temperature is 700-900 ℃, and the time is 60-140 min;
further, the low-temperature activation temperature is 350 ℃, and the time is 30 min; the high temperature activation temperature is 800 deg.C, and the time is 120 min.
8. The method of claim 1, wherein: also comprises the steps of acid washing and water washing of the carbonized product after heating and activation;
further, the acid used for pickling is one or a mixture of hydrochloric acid, nitric acid or hydrofluoric acid;
further, the pickling temperature is 30-100 ℃, and the pickling time is 120-;
further, the concentration of the acid is 1 to 60 wt%, preferably 1 to 20 wt%.
9. The porous carbon produced by the production method according to any one of claims 1 to 8.
10. Use of the porous carbon of claim 9 in the manufacture of a supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010519113.8A CN111591988A (en) | 2020-06-09 | 2020-06-09 | Porous carbon prepared from nitrogen source modified enteromorpha and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010519113.8A CN111591988A (en) | 2020-06-09 | 2020-06-09 | Porous carbon prepared from nitrogen source modified enteromorpha and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111591988A true CN111591988A (en) | 2020-08-28 |
Family
ID=72181947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010519113.8A Pending CN111591988A (en) | 2020-06-09 | 2020-06-09 | Porous carbon prepared from nitrogen source modified enteromorpha and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111591988A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896268A (en) * | 2014-04-08 | 2014-07-02 | 山东大学 | Method for preparing multistage-aperture activated carbon with high specific surface area |
| CN106517133A (en) * | 2016-10-09 | 2017-03-22 | 华中科技大学 | Nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and preparation method and application thereof |
| CN106744784A (en) * | 2015-11-18 | 2017-05-31 | 中国海洋大学 | A kind of dipping-activation method prepares method of nitrogen oxygen codope Enteromorpha basic unit secondary aperture carbon material and application thereof |
| CN107651687A (en) * | 2017-11-16 | 2018-02-02 | 湘潭大学 | A kind of preparation method and applications of the Carbon Materials rich in pyridine nitrogen |
| CN109534341A (en) * | 2019-01-30 | 2019-03-29 | 中国矿业大学 | A kind of preparation method and applications of N doping pericarp base porous carbon material |
-
2020
- 2020-06-09 CN CN202010519113.8A patent/CN111591988A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896268A (en) * | 2014-04-08 | 2014-07-02 | 山东大学 | Method for preparing multistage-aperture activated carbon with high specific surface area |
| CN106744784A (en) * | 2015-11-18 | 2017-05-31 | 中国海洋大学 | A kind of dipping-activation method prepares method of nitrogen oxygen codope Enteromorpha basic unit secondary aperture carbon material and application thereof |
| CN106517133A (en) * | 2016-10-09 | 2017-03-22 | 华中科技大学 | Nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and preparation method and application thereof |
| CN107651687A (en) * | 2017-11-16 | 2018-02-02 | 湘潭大学 | A kind of preparation method and applications of the Carbon Materials rich in pyridine nitrogen |
| CN109534341A (en) * | 2019-01-30 | 2019-03-29 | 中国矿业大学 | A kind of preparation method and applications of N doping pericarp base porous carbon material |
Non-Patent Citations (1)
| Title |
|---|
| HUANMING WEI ET AL.: "Biomass-derived nitrogen-doped porous carbon with superior capacitive performance and high CO2 capture capacity", 《ELECTROCHIMICA ACTA》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Biomass-derived porous graphitic carbon materials for energy and environmental applications | |
| Huang et al. | High-performance hierarchical N-doped porous carbons from hydrothermally carbonized bamboo shoot shells for symmetric supercapacitors | |
| Li et al. | Green conversion of bamboo chips into high-performance phenol adsorbent and supercapacitor electrodes by simultaneous activation and nitrogen doping | |
| Pourhosseini et al. | Study of micro/macro ordered porous carbon with olive-shaped structure derived from Cladophora glomerata macroalgae as efficient working electrodes of supercapacitors | |
| CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
| Tian et al. | Nitrogen and oxygen-doped hierarchical porous carbons from algae biomass: direct carbonization and excellent electrochemical properties | |
| CN105869912B (en) | A kind of preparation method and applications of starch base Monodispersed activated carbon microballon material | |
| CN108117073B (en) | Method for preparing porous carbon material by using water hyacinth and application | |
| Lu et al. | Preparation and application of capacitive carbon from bamboo shells by one step molten carbonates carbonization | |
| CN109516458A (en) | A kind of biomass-based graded porous carbon and preparation method thereof | |
| CN108128773B (en) | Method for preparing electrode carbon material for electrochemical capacitor by using peanut shells | |
| CN111017927A (en) | Preparation and application method of nitrogen-doped porous carbon based on straw hydrothermal carbonization | |
| WO2021027100A1 (en) | Nitrogen-doped porous carbon material, preparation method therefor and use thereof | |
| CN107311172A (en) | A kind of passion fruit shell base porous carbon materials and its preparation method and application | |
| CN108529587A (en) | A kind of preparation method and applications of the biomass graded hole Carbon Materials of phosphorus doping | |
| KR20150100636A (en) | Electrode material for secondary batteries, method for producing same, and secondary battery | |
| CN107958797A (en) | A kind of preparation method of the biomass-based active carbon electrode material of highly basic ammonia co-activating | |
| CN106629723A (en) | Biomass-based N, S and P-containing co-doped porous carbon and application thereof | |
| CN110817838B (en) | Nitrogen-sulfur co-doped porous carbon material and preparation method and application thereof | |
| CN113603078A (en) | Porous carbon, preparation method and application thereof | |
| Hu et al. | Preparation and property of N-doped porous carbon material by one-step pyrolysis of protein-rich algal biomass | |
| CN112265990A (en) | Preparation method and application of furfural residue porous activated carbon material | |
| Fu et al. | One-step solid-state pyrolysis of bio-wastes to synthesize multi-hierarchical porous carbon for ultra-long life supercapacitors | |
| CN109110756A (en) | Derivative carbon electrode material of a kind of homogeneous corncob and preparation method thereof | |
| CN111137890A (en) | Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |