CN113184848A - Method for preparing biomass porous carbon for supercapacitor based on shaddock peel - Google Patents
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- 239000002028 Biomass Substances 0.000 title claims abstract description 30
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Power Engineering (AREA)
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Abstract
The invention discloses a method for preparing biomass porous carbon for a supercapacitor based on shaddock peel, which comprises the following steps: (1) cleaning pericarpium Citri Grandis, drying, and pulverizing into granule; (2) placing the granular shaddock peel into a polyethylene reaction kettle filled with deionized water, placing the polyethylene reaction kettle in an oven with the temperature of 180-200 ℃ for hydrothermal heating for 12-24h, and performing solid-liquid separation to obtain a black intermediate product; (3) drying the black intermediate product obtained in the step (2), mixing the dried black intermediate product with ammonia water and zinc chloride according to a certain proportion, and drying to obtain a mixture; (4) under the protection of inert gas, carbonizing the mixture in the step (2) at high temperature, and cooling to room temperature to obtain a black product; (5) the black product was repeatedly washed and subsequently distilledAnd (3) washing with water to neutrality, and drying in vacuum to obtain the biomass porous carbon for the supercapacitor. The invention takes the waste shaddock peel as the raw material, and the waste shaddock peel is carbonized by hydrothermal method and subjected to ZnCl2Activation, and NH4And (3) carrying out N doping on OH to successfully synthesize nitrogen-doped porous carbon, wherein the prepared porous carbon has high porosity.
Description
Technical Field
The invention belongs to the technical field of electrode materials of supercapacitors, and particularly relates to a method for preparing biomass porous carbon for a supercapacitor based on shaddock peel.
Background
A supercapacitor is a high-power energy storage device that rapidly accumulates/releases charges on an electrode/electrolyte interface by electrostatically or electrochemically adsorbing ions, and the development of sustainable, clean and green energy storage technologies has been a great demand in the last decade, and the supercapacitor plays an important role in an electrochemical energy storage system with its ultra-high service life and excellent power density, and basically works with an electrostatic charge storage mechanism without any oxidation-reduction reaction (non-faradaic reaction) at the electrode/electrolyte interface, and has major disadvantages of poor energy density and low specific capacitance, which in turn affects the overall rate performance of the battery.
Various carbon materials have been researched to become materials with great development prospects of the super capacitor, the biomass porous carbon material is widely applied to the super capacitor, biomass mainly comprises lignin, hemicellulose and cellulose, a large amount of shaddock peel is discarded every year, carbon is extracted from the waste shaddock peel, the method is efficient and environment-friendly, and the shaddock peel is a green renewable material with wide sources and is an ideal source for preparing the biological carbon material. The grapefruit is one of the most abundant fruits in the world. The plant is planted in many places in south China, the shaddock peel accounts for about 45% of the total weight, and a white flocculation layer in the shaddock peel contains a large amount of cellulose and hemicellulose and is porous.
In the past decades, Supercapacitors (SCs) have experienced significant growth in research activities and commercialization, and porous carbon, which is the main and most important electrode active material of commercial SCs, is produced on an industrial scale through a conventional carbonization activation strategy, but commercial porous carbon materials have disadvantages of high production costs, corrosion of equipment, emission of toxic gases and by-product pollutants during production, and the like, and in recent years, efforts have been made to develop a novel synthesis strategy for porous carbon materials.
Disclosure of Invention
The invention aims to provide a method for preparing biomass porous carbon for a supercapacitor based on shaddock peel, so as to overcome the technical problems.
The technical purpose of the invention is realized by the following technical scheme:
a method for preparing biomass porous carbon for a supercapacitor based on shaddock peel comprises the following steps:
(1) cleaning pericarpium Citri Grandis, drying, and pulverizing into granule;
(2) placing the granular shaddock peel into a polyethylene reaction kettle filled with deionized water, placing the polyethylene reaction kettle in an oven with the temperature of 180-200 ℃ for hydrothermal heating for 12-24h, and performing solid-liquid separation to obtain a black intermediate product;
(3) drying the black intermediate product obtained in the step (2), mixing the dried black intermediate product with ammonia water and zinc chloride according to a certain proportion, and drying to obtain a mixture;
(4) under the protection of inert gas, carbonizing the mixture in the step (2) at high temperature, and cooling to room temperature to obtain a black product;
(5) and repeatedly washing the black product by using a hydrochloric acid solution, washing the black product to be neutral by using distilled water, and drying the black product in vacuum to obtain the biomass porous carbon for the supercapacitor.
Further, in the step (1), the mesh number of the particles is 100 meshes.
Further, in the step (1), the drying temperature is 80 ℃, and the drying time is 24 h.
Further, in the step (3), the mass ratio of the shaddock peel to the ammonia water and the zinc chloride is 1:1-3: 1-3.
Further, in the step (3), the drying temperature is 105 ℃ and the time is 1 h.
Further, in the step (4), the inert gas is nitrogen.
Further, in the step (4), the high temperature carbonization is performed at 950 ℃ for 1.5-2.5 h.
Further, in the step (4), the temperature rise rate of the high-temperature carbonization is 5 ℃/min.
In conclusion, the preparation method and the obtained product have the following advantages and beneficial effects:
(1) the method adopts the waste shaddock peel as the raw material, the peel of the fruit has high yield per year, is easy to obtain and has low cost, the shaddock peel contains rich protein, organic acid and vitamin, and can be doped with heteroatoms by a high-temperature pyrolysis and chemical activation method, so that the shaddock peel can be used as an ideal carbon material;
(2) the invention takes the waste shaddock peel as the raw material, and the waste shaddock peel is carbonized by hydrothermal method and subjected to ZnCl2Activation, and NH4OH is doped with N to successfully synthesize nitrogen-doped porous carbon, and the prepared porous carbon has high porosity and specific surface area of about 1100m2The N doping increases nitrogen-containing functional groups on the surface of the carbon material, and the doping amount has a remarkable influence on the electrochemical performance of the carbon material; the active carbon contains a large number of micropores and mesopores, the aperture of most mesopores is in the range of 2nm and 5nm, the migration of electrolyte ions is facilitated, and ion adsorption sites are provided;
(3) in a three-electrode system, when the current density is 1A/g, the electrode material prepared by using the synthetic porous carbon has the mass of 1:1:3, and the specific capacitance of a porous carbon sample with the activation temperature of 900 ℃ is the highest and reaches 221F/g.
(4) The invention discloses a green, feasible and low-cost method, a large amount of low-cost shaddock peels are utilized to synthesize a high-performance supercapacitor electrode material, and the prepared electrode material can also ensure the stability of specific capacitance under high current density.
Drawings
Table 1 is the specific capacitance at different current densities;
FIG. 1 is SEM images of porous carbon prepared in example 1 of the present invention under a 5-fold mirror and a 50-fold mirror, respectively;
FIG. 2 is a nitrogen adsorption/desorption curve and a pore diameter distribution diagram of the porous carbon obtained in example 1 of the present invention;
FIG. 3 is a cyclic voltammogram of porous carbon prepared in example 1 of the present invention at different sweep rates;
FIG. 4 is a constant current charge and discharge diagram of porous carbon prepared in example 1 of the present invention at different current densities.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into an oven at 180 ℃ for hydrothermal method heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:1:3, and drying at 105 ℃;
(4) performing 900 ℃ heat treatment on the mixture dried in the step (2) for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
The biomass porous carbon obtained in example 1 was tested.
Fig. 1 is an SEM image of the porous carbon material prepared in example 1 at different magnifications, from which it can be seen that the biomass carbon obtained by this method has a large number of pores, which help to promote ion migration and provide more accessible active sites in the carbon matrix; by observing the SEM image, the biomass carbon is seen to be rough in surface and small in particle, so that higher specific capacitance can be obtained.
Fig. 2 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the porous carbon material prepared in example 1, and according to IUPAC classification, it can be seen that the n2 adsorption-desorption isotherms of these samples belong to the type vi curve. The micropore filling effect occurs in a lower relative pressure range (P/P0 is 0-0.05), the adsorption quantity of N2 is increased sharply along with the increase of the relative pressure, the micropore structure exists in the material, and a large number of micropores and mesopores exist according to the pore size distribution.
FIG. 3 is a cyclic voltammogram of the porous carbon material prepared in example 1 at different scan rates, and it can be seen that the curve is gradually deformed as the scan rate increases, and at high scan rates of 100mV/s, the curve still approximates a symmetric rectangle, indicating that the electrode exhibits ideal electrochemical capacitance behavior.
Fig. 4 is a constant current charge-discharge diagram of the porous carbon material prepared in example 1 at different current densities.
Through calculation, the active material has a specific capacitance of 228F/g at 1A/g, and when the current density is increased to 10A/g, the specific capacitance value can be still kept to 176F/g, and the capacitance retention rate is as high as 78%, which indicates that the material still has higher specific capacitance at large current density due to the excellent pore structure.
Example 2
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into an oven at 180 ℃ for hydrothermal method heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:1:2, and drying at 105 ℃;
(4) performing 900 ℃ heat treatment on the mixture dried in the step (2) for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
Example 3
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into an oven at 180 ℃ for hydrothermal method heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:1:1, and drying at 105 ℃;
(4) performing 900 ℃ heat treatment on the mixture dried in the step (2) for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
Example 4
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into a drying oven at 200 ℃ for hydrothermal heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:1:3, and drying at 105 ℃;
(4) performing heat treatment on the mixture dried in the step (2) at 800 ℃ for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
Example 5
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into an oven at 180 ℃ for hydrothermal method heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:1:3, and drying at 105 ℃;
(4) performing heat treatment on the mixture dried in the step (2) at 700 ℃ for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
Comparative example 1
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into an oven at 180 ℃ for hydrothermal method heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:1:4, and drying at 105 ℃;
(4) performing 900 ℃ heat treatment on the mixture dried in the step (2) for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
Comparative example 2
(1) Crushing the shaddock peel into fine particles, filtering the fine particles by a 100-mesh filter screen, and drying the fine particles in an oven at 80 ℃ for 24 hours;
(2) putting the crushed and dried shaddock peel into a polyethylene reaction kettle filled with deionized water, putting the polyethylene reaction kettle into an oven at 180 ℃ for hydrothermal method heating for 24 hours, and performing solid-liquid separation to obtain a black intermediate product and drying the black intermediate product;
(3) mixing the intermediate product dried in the step (2) with ammonia water and zinc chloride according to the mass ratio of 1:4:1, and drying at 105 ℃;
(4) performing 900 ℃ heat treatment on the mixture dried in the step (2) for 2h by using a tube furnace under the protection of nitrogen, wherein the heating rate is 5 ℃/min, and naturally cooling to room temperature to obtain a black product;
(5) the product was washed several times with 10% hydrochloric acid solution to remove impurities, and then washed with distilled water to neutral pH 7. And (3) drying the cleaned sample at 100 ℃ in vacuum to obtain the target product biomass porous carbon for the supercapacitor.
The biomass porous carbon obtained in examples 2 to 5 and comparative examples 1 to 2 was subjected to the test, and the results are shown in table 1.
TABLE 1
The above-mentioned embodiments are only for describing the preferred mode of the present invention, and do not limit the scope of the present invention, and those skilled in the art should make various changes and modifications to the technical solution of the present invention without departing from the spirit of the present invention, and all such changes and modifications should fall within the protection scope defined by the claims of the present invention.
Claims (8)
1. A method for preparing biomass porous carbon for a supercapacitor based on shaddock peel is characterized by comprising the following steps:
(1) cleaning pericarpium Citri Grandis, drying, and pulverizing into granule;
(2) placing the granular shaddock peel into a polyethylene reaction kettle filled with deionized water, placing the polyethylene reaction kettle in an oven with the temperature of 180-200 ℃ for hydrothermal heating for 12-24h, and performing solid-liquid separation to obtain a black intermediate product;
(3) drying the black intermediate product obtained in the step (2), mixing the dried black intermediate product with ammonia water and zinc chloride according to a certain proportion, and drying to obtain a mixture;
(4) under the protection of inert gas, carbonizing the mixture in the step (2) at high temperature, and cooling to room temperature to obtain a black product;
(5) and repeatedly washing the black product by using a hydrochloric acid solution, washing the black product to be neutral by using distilled water, and drying the black product in vacuum to obtain the biomass porous carbon for the supercapacitor.
2. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (1), the mesh number of the particles is 100 meshes.
3. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (1), the drying temperature is 80 ℃ and the drying time is 24 h.
4. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (3), the mass ratio of the shaddock peel to ammonia water and zinc chloride is 1:1-3: 1-3.
5. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (3), the drying temperature is 105 ℃ and the time is 1 h.
6. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (4), the inert gas is nitrogen.
7. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (4), the high temperature carbonization is performed at 750 ℃ and 950 ℃ for 1.5-2.5 h.
8. The method for preparing the biomass porous carbon for the supercapacitor based on the shaddock peel as claimed in claim 1, wherein in the step (4), the temperature rise rate of the high-temperature carbonization is 5 ℃/min.
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