CN111302339A - Porous carbon material prepared from xanthoceras sorbifolia bunge shell residue waste as well as preparation method and application of porous carbon material - Google Patents

Porous carbon material prepared from xanthoceras sorbifolia bunge shell residue waste as well as preparation method and application of porous carbon material Download PDF

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CN111302339A
CN111302339A CN202010112755.6A CN202010112755A CN111302339A CN 111302339 A CN111302339 A CN 111302339A CN 202010112755 A CN202010112755 A CN 202010112755A CN 111302339 A CN111302339 A CN 111302339A
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porous carbon
xanthoceras sorbifolia
carbon material
waste
residue waste
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韩奎华
李金晓
牛胜利
齐建荟
滕召才
王梅梅
张继刚
张晓峰
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Shandong University
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    • 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
    • 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
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    • 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, 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
    • 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
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract

The invention relates to a porous carbon material prepared from xanthoceras sorbifolia bunge shell residue waste, and a preparation method and application thereof. The preparation method comprises the following steps: s1, placing the xanthoceras sorbifolia shell residue waste in an inert atmosphere for heating and carbonizing, wherein the carbonizing temperature is 400-800 ℃, and the carbonizing time is 80-150 min; s2, carrying out acid washing on the product obtained in the step S1, and then washing the product to be neutral; s3, soaking the product prepared in the step S2 in a chemical activating agent; s4, heating and activating the product obtained in the step S3 at 700-900 ℃ for 60-140 min; acid washing, water washing and drying to obtain the porous carbon material of the xanthoceras sorbifolia bunge husk residue waste. The porous carbon material obtained by the invention is used for the electrode of the super capacitor and has excellent performance; provides a method for treating solid waste left after the extraction of effective components from the xanthoceras sorbifolia shells, and realizes the high-efficiency clean utilization of resources by changing waste into valuable.

Description

Porous carbon material prepared from xanthoceras sorbifolia bunge shell residue waste as well as preparation method and application of porous carbon material
Technical Field
The invention belongs to the technical field of solid waste disposal and utilization and biochar material preparation, and particularly relates to a porous carbon material prepared from xanthoceras sorbifolia bunge shell residue waste and application of the porous carbon material.
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 xanthoceras sorbifolia belongs to xanthoceras of sapindaceae, is a single species, namely deciduous shrub or small tree, is a unique rare woody oil plant in China, and is also an agricultural and forestry crop supported by gravity development of the ministry of forestry and science and technology in China. The tree species is suitable for urban and garden greening, can grow in hills, gravel lands and clay land-level yellow lands, is resistant to light salt and alkali and cold, is free from freezing damage at the temperature of-40 ℃, and has good edible value, ecological value, medicinal value and the like.
The whole shinyleaf yellowhorn plant has high development value, and the flowers, the leaves and the branches can be extracted with medicines for diminishing inflammation, sterilizing, clearing damp and the like. The kernel contains 55-67% of oil, the oil is rich in linoleic acid, linolenic acid, eicosenoic acid and other edible fatty acids, and is also suitable for squeezing to prepare biodiesel; the xanthoceras sorbifolia Bunge husk contains triterpenes, flavonoids, alkaloids, monoterpenes, fatty acids and other compounds, wherein the separated saponin compound, xanthoceras sorbifolia Bunge husk glycoside, has pharmacological effects of resisting inflammation, treating infantile enuresis, enhancing memory, resisting tumor and the like. The weight of the shell in the shinyleaf yellowhorn fruit accounts for more than 50% of the total weight, the content of effective components extracted from dry fruit shells is less, and the residue after extraction accounts for more than 95% of the total weight. The relevant patents do not relate to the problem of disposal and efficient utilization of solid residues after extraction of active ingredients.
The existing research discloses a preparation method of xanthoceraside, relates to a new preparation method of xanthoceraside in xanthoceras sorbifolia bunge, and can realize the preparation of high-efficiency and high-purity xanthoceraside. The preparation method is simple, convenient and reliable, and reduces excessive intermediate operation links, thereby reducing the product loss and obviously improving the yield compared with the prior method.
The existing research discloses an application of a xanthoceras sorbifolia bunge flavone extract in the field of blood sugar and blood fat reduction and an extraction method thereof, aiming at providing a method for extracting flavone from xanthoceras sorbifolia bunge shells and an extract with health care function, wherein the method has the advantages of high efficiency, high yield, short time consumption, simple operation, low production cost and low corrosion to equipment, and the flavone can be used in the field of blood sugar and blood fat reduction; the technical scheme is as follows: drying shinyleaf yellowhorn shells in an oven to constant weight, crushing to obtain powder, adding petroleum ether to degrease for 3 times, adding ethanol solution with a certain volume into filter residues, taking ionic liquid as a phase transfer catalyst, reacting at 40-80 ℃ for 3-25 min to extract flavone compounds, concentrating an extracting solution to obtain a concentrated solution, adding AB-8 macroporous resin with equal mass into the concentrated solution, mixing and stirring uniformly, drying, adding AB-8 resin, washing with water to be colorless, leaching with the ethanol solution, collecting eluent, concentrating the eluent under reduced pressure, and drying to obtain a product.
The prior art discloses a method for extracting flavone from xanthoceras sorbifolia shells, which has the advantages of high efficiency, high yield, short time consumption, simple operation, low production cost and low equipment corrosivity. The technical scheme is as follows: soaking the degreased crushed xanthoceras sorbifolia shells in a certain amount of solution, performing ultrasonic extraction in an ultrasonic device for a period of time, performing suction filtration on an extracting solution, concentrating filtrate, and performing freeze-drying to obtain the xanthoceras sorbifolia flavone concentrate.
The prior art discloses a method for extracting xanthoceraside from xanthoceras sorbifolia shells, carpopodium and/or flowers, which comprises the steps of firstly selecting dry and mildew-free xanthoceras sorbifolia shells, carpopodium and/or flowers; pulverizing into 20-40 mesh; extracting with 50-95 vol% alcohol or water to obtain extractive solution; extracting with alcohol or water, concentrating, and separating with macroporous resin, removing sugar and pectin, and enriching effective components.
The patent about the preparation of porous carbon material by using xanthoceras sorbifolia shells is as follows:
the prior art discloses a method for preparing nano porous carbon from xanthoceras sorbifolia seed coats, the nano porous carbon, a super capacitor electrode plate and a preparation method of the super capacitor electrode plate, through regulation and control of activation temperature and the dosage of an activator, the specific surface area of the xanthoceras sorbifolia seed coat porous carbon can reach 2148m/g, a porous structure is formed by a large number of micropores which are regularly and closely arranged, the pore diameter is distributed below 2nm, the specific capacitance of the electrode prepared from the porous carbon can reach 420F/g under the current density of 0.5A/g, the electrode still has excellent specific capacitance (128F/g) when the current density is increased to 20A/g, and the capacitance retention rate of the electrode is still up to 98.7% after the electrode is charged and discharged for 1000 times under the condition that the current density is 10A/g. The porous carbon material prepared by taking the shinyleaf yellowhorn seed coat as the raw material has good electrochemical performance, can be used as an electrode material of a super capacitor, and provides a new thought and way for comprehensive development and utilization of shinyleaf yellowhorn resources.
The prior art discloses preparation and application of a biomass carbon/sulfur composite material, comprising the steps of dehydrating and drying xanthoceras sorbifolia shells, crushing the xanthoceras sorbifolia shells, adding a pore-forming agent, and carbonizing the xanthoceras sorbifolia shells at high temperature under an inert gas atmosphere to obtain a porous biomass carbon material; grinding and uniformly mixing the porous biomass carbon material and the sublimed sulfur according to a certain proportion, heating and melting through heat treatment to enable the sulfur to be diffused into pores of carbon, and removing the residual sulfur on the surface by adopting a solvent dissolving method to prepare the biomass carbon/sulfur composite material. The sulfur is filled in the porous carbon material, so that the electrical contact capacity of the sulfur and the carbon material is improved, and the volume energy density of the composite material is improved; the porous structure of the carbon material can achieve the effect of anchoring soluble polysulfide and can accommodate the volume change of sulfur during charge/discharge. When the composite material is used as a positive electrode material of a lithium-sulfur battery or a negative electrode material of a sodium-ion battery, the composite material has good electrochemical performance.
The prior art discloses xanthoceras sorbifolia shell particle activated carbon and a preparation method thereof. The method comprises the following steps: (1) drying xanthoceras sorbifolia shells and then crushing; (2) dipping in zinc chloride solution; (3) high-temperature carbonization and activation; (4) rinsing, drying and sieving to obtain the finished product of the active carbon. Has the advantages that: the raw material for preparing the activated carbon by using the xanthoceras sorbifolia shells is sufficient, and the raw material is from the processing residues of the xanthoceras sorbifolia biodiesel, so that the activated carbon is changed into valuable; the activated carbon prepared by the method of activating the xanthoceras sorbifolia shell by the zinc chloride solution is simple in preparation process, low in production cost, low in pollution, low in corrosion to equipment, high in mechanical strength and durable; the activated carbon prepared from xanthoceras sorbifolia shells by a zinc chloride activation method has the advantages of large specific surface area, developed pore structure and good adsorption performance.
The above research is directed to the direct use of xanthoceras sorbifolia shells in the preparation of porous carbon, activated carbon materials, but the inventors found that: the fruit shell has good medicine extraction value, the price of the fruit shell is 4-16 yuan per kilogram, and the cost is high when the fruit shell is directly used for preparing the active carbon. In addition, with the development and comprehensive utilization of natural xanthoceras sorbifolia bunge medicines, residues after various active ingredients are extracted from xanthoceras sorbifolia bunge shells or harmful organic solvents are contained, and the residues are usually returned to the field by composting, so that the residues are difficult to reasonably and efficiently utilize.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing porous carbon from residue waste after extracting effective components from xanthoceras sorbifolia shells, and also provides a method for efficiently treating and utilizing the residue. Compared with the traditional biomass material, the method adopts the waste of the xanthoceras sorbifolia after natural active ingredients are extracted as the raw material, and due to various extraction processes, the pore connectivity can be increased through cell wall breaking and component extraction, so that the method is favorable for removing impurity metal ions, is favorable for activating agent high-temperature pore forming, and increases the specific surface area and pore volume of the porous carbon. The porous carbon prepared by the method has the advantages of low impurity, less ash content and good wettability, and the assembled two-electrode system double electric layer super capacitor has excellent specific capacitance, smaller equivalent series resistance and higher charge-discharge efficiency, and particularly has excellent large-current charge-discharge capacity and energy density when charged and discharged under high multiplying power.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a method for preparing a porous carbon material from xanthoceras sorbifolia husk residue waste is provided, which comprises the following steps:
extracting natural components of the xanthoceras sorbifolia bunge shell to obtain xanthoceras sorbifolia bunge shell residue waste;
carbonizing, acid washing and activating the xanthoceras sorbifolia shell residue waste, then carrying out acid washing, water washing and drying again to obtain the xanthoceras sorbifolia waste-based porous carbon electrode material.
The research of the application finds that: compared with the method for directly preparing the carbon material by using the xanthoceras sorbifolia bunge husks, the porous carbon electrode material prepared by using the xanthoceras sorbifolia bunge husks waste with natural effective components extracted as the raw material has more excellent electrical properties, effectively reduces the manufacturing cost of the porous carbon electrode material, and realizes the comprehensive utilization of the xanthoceras sorbifolia bunge husks.
In a second aspect of the invention, the porous carbon material prepared from the xanthoceras sorbifolia shell residue waste prepared by any one of the above methods is provided.
According to the invention, through cell wall breaking and component extraction, the pore connectivity can be increased, the removal of impurity metal ions is facilitated, the high-temperature pore forming by an activating agent is facilitated, and the specific surface area and the pore volume of the porous carbon are increased.
In a third aspect of the invention, the application of the porous carbon material in preparing a porous carbon electrode for a supercapacitor and the supercapacitor is provided.
The porous carbon prepared by the method has the advantages of low impurity, less ash content and good wettability, and the assembled two-electrode system double electric layer super capacitor has excellent specific capacitance, smaller equivalent series resistance and higher charge-discharge efficiency, and particularly has excellent large-current charge-discharge capacity and energy density when charged and discharged under high multiplying power.
The invention has the beneficial effects that:
(1) compared with the existing method for preparing porous carbon and active carbon from xanthoceras sorbifolia shells, the xanthoceras sorbifolia shell residue waste is solid waste left after active ingredients are extracted by processes such as organic solvents, the porous carbon is prepared from the residue waste, waste is changed into valuable, the raw material cost of the porous carbon and the active carbon is greatly reduced, and the overall benefit of the xanthoceras sorbifolia shells is greatly improved.
(2) Compared with other existing biomass raw materials such as walnut shells, coconut shells, peanut shells, rice husks and the like, the xanthoceras sorbifolia shells belong to thin-walled tissues, contain rich vascular bundle structures, have large vacuoles for cells, and are rich in various natural products, after the extraction process, the cell walls of residue waste are damaged, the pores have better connectivity, the carbonization process is more favorable for generating rich pores, the carbonized products are uniformly mixed with an activating agent, and the porous carbon prepared by activation has higher specific surface area and pore volume.
(3) The porous carbon electrode material provided by the invention has higher specific capacity and good rate capability, and the super capacitor under the condition of large current can be prepared by adopting the porous carbon provided by the invention, and the specific capacitance can respectively reach 422F/g, 370F/g, 330F/g and 272F/g when the current density is 0.1A/g, 1.0A/g, 10A/g and 100A/g under the condition of aqueous electrolyte (6M KOH).
(4) After the xanthoceras sorbifolia bunge shell is subjected to active ingredient extraction and processing, the content of residue impurities is low, the porous carbon structure is more uniform, the content of impurities is low, the porous carbon impurities can be conveniently controlled, the cost is reduced, and the quality of the porous carbon is greatly improved.
(5) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a pore size distribution diagram of a carbon material obtained in example 1 of the present invention.
FIG. 2 shows N in the carbon material obtained in example 1 of the present invention2Adsorption-desorption curve.
FIG. 3 shows the carbon material obtained in example 1 of the present invention at 50mVs-1Cyclic voltammetry at sweep rate.
FIG. 4 shows a carbon material obtained in example 1 of the present invention at 5Ag-1Constant current charge and discharge curve at current density.
FIG. 5 is a graph of rate performance for example 1 of the present invention.
FIG. 6 is a cycle performance curve of example 1 of the present invention.
FIG. 7 is a microscopic morphology image of the carbon material obtained in example 1 of the present invention, taken by scanning electron microscopy.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application 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 example embodiments according to the present application. 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 specific embodiment of the invention, the application of the xanthoceras sorbifolia shell residue waste in the porous carbon electrode material of the supercapacitor is provided.
In another embodiment of the present invention, the waste xanthoceras sorbifolia shell residue has a special structure, which is beneficial to carbonization and activation for pore-forming and hole-expanding, and can form a good pore structure. Meanwhile, the structure of the porous ceramic is rich in vascular bundles and thin-walled tissues, which is beneficial to carbonization and pore-forming, and is beneficial to uniform mixing of an activating agent and high-temperature pore-forming. The porous carbon material for the super capacitor is prepared by using the xanthoceras sorbifolia shell waste, so that the structural advantages of plant tissues of the porous carbon material can be fully utilized, and the waste is converted into a high-performance electrode material.
In another embodiment of the present invention, there is provided a method for preparing a porous carbon material from xanthoceras sorbifolia husk residue waste, the method comprising:
s1, placing the xanthoceras sorbifolia shell residue waste in an inert atmosphere for heating and carbonizing, wherein the carbonizing temperature is 400-800 ℃, and the carbonizing time is 80-150 min;
s2, carrying out acid washing on the product obtained in the step S1, and then washing the product to be neutral;
s3, soaking the product prepared in the step S2 in a chemical activating agent;
s4, heating and activating the product obtained in the step S3 at 700-900 ℃ for 60-140 min; and (3) pickling, washing with water and drying to obtain the xanthoceras sorbifolia waste-based porous carbon electrode material.
In the embodiment of the present invention, in the step S1, the waste xanthoceras sorbifolia husk residue comprises organic solvent extraction, CO2The residual wastes after the effective components in the xanthoceras sorbifolia shells are extracted by one or a combination of processes of supercritical extraction and ultrasonic wave and microwave assistance.
In a specific embodiment of the present invention, in step S2, the acid used for the acid cleaning includes one or more of an aqueous solution of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid. The concentration of the acid used for acid washing is 1-60 wt%, and the temperature ranges of the acid washing and the water washing are 20-99 ℃.
According to the invention, calcium ions and part of impurities in the carbonized product are washed away by acid washing, and meanwhile, the removal effect can be increased by heating, and meanwhile, a certain pore structure can be further provided before activation, which is beneficial to further pore forming in the activation process;
in another embodiment of the present invention, in step S3,
the chemical activator includes but is not limited to KOH, NaOH, K2CO3，H3PO4，ZnCl2One or more of (a);
the impregnation ratio of the product prepared in the step S2 to KOH is 1: 1-1: 5;
in another embodiment of the present invention, in step S4,
the acid used for pickling comprises one or a combination of more of aqueous solutions of sulfuric acid, hydrochloric acid, nitric acid and hydrofluoric acid;
pickling for 10-30 min; the concentration of acid used for acid washing is 1-60 wt%, and the temperature of acid washing and water washing is 20-99 ℃.
In another embodiment of the present invention, the porous carbon material prepared by the method is provided. The specific surface area of the porous carbon material prepared by the method is 2000-4000 m calculated by a BET method2The active sites capable of adsorbing charges can be provided, so that the energy density of the super capacitor is improved; the pore volume is up to 1.69cm3The/g, the mesopores are distributed in a concentrated way around 2nm, the micropores are distributed in a concentrated way around 0.6nm, and the diameter distribution and the porosity are adjustable within a certain range.
In still another embodiment of the present invention, there is provided a porous carbon electrode for a supercapacitor, the porous carbon electrode being made of the xanthoceras sorbifolia waste-based porous carbon material, a conductive additive (conductive agent), and a binder;
in another embodiment of the invention, the weight ratio of the xanthoceras sorbifolia waste-based porous carbon to the conductive additive (conductive agent) to the binder is 7-9:1-2: 1-2.
Among them, the binder used in the present invention includes, but is not limited to, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), polyvinyl alcohol, sodium carboxymethylcellulose, polyolefins, rubbers, polyurethanes, etc., which have been widely used at present;
the conductive additive used in the present invention includes, but is not limited to, conductive carbon black, acetylene black, graphite-based additives, carbon nanotube additives, etc., which have been widely used at present.
In another embodiment of the present invention, a method for preparing the above porous carbon electrode for a supercapacitor is provided, wherein a mixing manner of the porous carbon based on xanthoceras sorbifolia residue waste, the binder and the conductive additive is a currently common method: the preparation method comprises the steps of preparing mixed slurry of the shinyleaf yellowhorn waste-based porous carbon, the binder and the conductive additive through slurry mixing, uniformly coating the slurry on a current collector, and heating, pressing and molding the uniformly mixed shinyleaf yellowhorn shell residue waste-based porous carbon, the binder and the conductive additive mixed with active substances.
The current collector used in the present invention includes, but is not limited to, copper foil, aluminum foil, nickel mesh, stainless steel foil, etc., which have been widely used at present.
In yet another embodiment of the present invention, there is provided a use of the porous carbon material and/or the porous carbon electrode in a supercapacitor.
The present invention is further illustrated by the following specific examples, which are provided for the purpose of illustration only and are not intended to be limiting. If the experimental conditions not specified in the examples are specified, they are generally according to the conventional conditions, or according to the conditions recommended by the sales companies; the present invention is not particularly limited, and may be commercially available.
Example 1:
the embodiment relates to a method for preparing porous carbon for a supercapacitor by adopting xanthoceras sorbifolia husk residue waste, which comprises the following steps:
step one, performing ethanol extraction (80 ℃ hot extraction method, 80 percent (volume fraction) ethanol solution reflux extraction for 3 times, each time for 2 hours, wherein the volume ratio (g: ml) of the xanthoceras sorbifolia shell powder to the 80 percent ethanol solution is 1:10) on xanthoceras sorbifolia shells, drying and crushing the residue waste at 105 ℃ for 24 hours, and sieving the residue waste with a 80-mesh sieve.
And step two, putting the powder obtained in the step one into a tubular furnace for carbonization at 600 ℃ for 2 hours, wherein the protective gas is selected from nitrogen and the flow rate is 1L/min. The heating rate was 5 ℃/min.
And step three, placing the product obtained in the step two and 10 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product in a forced air drying oven at 105 ℃.
And step four, mixing the product obtained in the step three with KOH according to the mass ratio of 1:4, and placing the mixture in an atmosphere muffle furnace for activation for 2 hours at 800 ℃. The heating rate was 5 ℃/min. Nitrogen was used as a shielding gas at a flow rate of 0.1L/min.
And step five, placing the product obtained in the step four and 10 wt% hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product to obtain the porous carbon material.
The implementation effect is as follows: the product is prepared byThe specific surface area is 2456m calculated by a BET method2G, pore volume of 1.36cm3The average pore diameter of macropores and mesopores calculated by a BJH method is 2.21nm, and the material is a material with higher specific surface area. The electrode material for the supercapacitor is prepared by mixing the carbon material, the conductive agent and the binder according to the mass ratio of 8:1:1, 6mol/L KOH is used as electrolyte to carry out constant current charge-discharge test, the specific capacitance value reaches 422F/g when the current density is 0.1A/g, 370F/g when the current density is 10A/g, and 272F/g when the current density is 100A/g. Under the current density of 5A/g, the capacity retention rate is up to 97 percent after 5000 times of cyclic charge and discharge.
Example 2:
the embodiment relates to a method for preparing porous carbon for a supercapacitor by adopting xanthoceras sorbifolia husk residue waste, which comprises the following steps
Step one, performing ethanol extraction (80 ℃ hot extraction method, 80% (volume fraction) ethanol solution reflux extraction for 3 times, each time for 2 hours, drying the residue waste of xanthoceras sorbifolia Bunge shell powder at a volume ratio (g: ml) of 80% ethanol solution of 1:10) at 105 ℃ for 24 hours, crushing, and sieving with a 120-mesh sieve.
And step two, putting the powder obtained in the step one into a tubular furnace for carbonization at 600 ℃ for 2 hours, wherein the protective gas is selected from nitrogen and the flow rate is 1.5L/min. The heating rate was 10 ℃/min.
And step three, placing the product obtained in the step two and 20 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product in a forced air drying oven at 105 ℃.
And step four, mixing the product obtained in the step three with KOH according to the mass ratio of 1:5, and placing the mixture in an atmosphere muffle furnace for activation for 2 hours at the temperature of 750 ℃. The heating rate was 10 ℃/min. Nitrogen was used as a shielding gas at a flow rate of 0.5L/min.
And step five, placing the product obtained in the step four and 20 wt% hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product to obtain the porous carbon material.
The implementation effect is as follows: the specific surface area of the product is 3215m by calculation through a BET method2Per g, pore volume of 1.79cm3The average pore diameter of macropores and mesopores calculated by a BJH method is 2.31nm, and the material is a material with higher specific surface area. The electrode material for the supercapacitor is prepared by mixing the carbon material, a conductive agent and a binder according to the mass ratio of 8:1:1, 6mol/L KOH is used as electrolyte to carry out constant current charge-discharge test, the specific capacitance value reaches 340F/g when the current density is 0.1A/g, the specific capacitance value reaches 293F/g when the current density is 10A/g, and the specific capacitance value still reaches 222F/g when the current density is 100A/g.
Example 3:
the embodiment relates to a method for preparing porous carbon for a supercapacitor by using xanthoceras sorbifolia residue waste after ethanol extraction, which comprises the following steps:
step one, performing ethanol extraction (80 ℃ hot extraction method, 80% (volume fraction) ethanol solution reflux extraction for 3 times, each time for 2 hours, wherein the volume ratio (g: ml) of the xanthoceras sorbifolia shell powder to the 80% ethanol solution is 1:10) on xanthoceras sorbifolia shells, drying the residue waste at 105 ℃ for 24 hours, crushing the residue waste, and sieving the crushed residue with an 80-mesh sieve.
And step two, putting the powder obtained in the step one into a tubular furnace, carbonizing for 1.8 hours at the temperature of 600 ℃, and selecting nitrogen as protective gas with the flow of 0.5L/min. The heating rate was 10 ℃/min.
And step three, placing the product obtained in the step two and 5 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product in a forced air drying oven at 105 ℃.
And step four, mixing the product obtained in the step three with KOH according to the mass ratio of 1:5, and placing the mixture in an atmosphere muffle furnace for activation for 2 hours at 800 ℃. The heating rate was 5 ℃/min. Nitrogen was used as a shielding gas at a flow rate of 0.1L/min.
And step five, placing the product obtained in the step four and 5 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the mixture to be neutral by using deionized water, and drying the mixture to obtain the porous carbon material.
The implementation effect is as follows: the specific surface area of the product is 3376m calculated by a BET method2Per g, pore volume of 2.21cm3The average pore diameter of macropores and mesopores calculated by a BJH method is 2.62nm, and the material is a material with higher specific surface area. The carbon material is electrically conductiveThe electrode material for the super capacitor is prepared by mixing the agent and the binder in a mass ratio of 8:1:1, and a constant current charge and discharge test is carried out by taking 6mol/L KOH as electrolyte, wherein the specific capacitance value reaches 438F/g when the current density is 0.1A/g, and the specific capacitance value reaches 266F/g when the current density is 10A/g.
Example 4:
the embodiment relates to a method for preparing porous carbon for a supercapacitor from xanthoceras sorbifolia shells, which comprises the following steps:
step one, performing ethanol extraction (80 ℃ hot extraction method, 80% (volume fraction) ethanol solution reflux extraction for 3 times, each time for 2 hours, wherein the volume ratio (g: ml) of the xanthoceras sorbifolia shell powder to the 80% ethanol solution is 1:10) on xanthoceras sorbifolia shells, drying the residue waste at 105 ℃ for 24 hours, crushing the residue waste, and sieving the crushed residue with an 80-mesh sieve.
And step two, putting the powder obtained in the step one into a tubular furnace, carbonizing for 1.5h at 600 ℃, and selecting nitrogen as protective gas with the flow of 0.5L/min. The heating rate was 10 ℃/min.
And step three, placing the product obtained in the step two and 5 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product in a forced air drying oven at 105 ℃.
And step four, mixing the product obtained in the step three with KOH according to the mass ratio of 1:3, and placing the mixture in an atmosphere muffle furnace for activation for 2 hours at 800 ℃. The heating rate was 5 ℃/min. Nitrogen was used as a shielding gas at a flow rate of 0.5L/min.
And step five, placing the product obtained in the step four and 5 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the mixture to be neutral by using deionized water, and drying the mixture to obtain the porous carbon material.
The implementation effect is as follows: the specific surface area of the product is 2780m by calculation through a BET method2G, pore volume of 1.64cm3The average pore diameter of macropores and mesopores calculated by a BJH method is 2.37nm, and the material is a material with higher specific surface area. The electrode material for the super capacitor is prepared by mixing the carbon material, a conductive agent and a binder according to the mass ratio of 8:1:1, a constant current charge-discharge test is carried out by taking 6mol/L KOH as electrolyte, the specific capacitance value reaches 321F/g when the current density is 0.1A/g, and the current density is 10A-When g is used, 255F/g can be achieved.
Example 5:
the embodiment relates to a method for preparing porous carbon for a supercapacitor by using xanthoceras sorbifolia shells, which comprises the following steps:
step one, drying the xanthoceras sorbifolia shells at 105 ℃ for 24 hours, crushing, and sieving with a 80-mesh sieve.
And step two, putting the powder obtained in the step one into a tubular furnace for carbonization at 600 ℃ for 2 hours, wherein the protective gas is selected from nitrogen and the flow rate is 1L/min. The heating rate was 5 ℃/min.
And step three, placing the product obtained in the step two and 10 wt% of hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product in a forced air drying oven at 105 ℃.
And step four, mixing the product obtained in the step three with KOH according to the mass ratio of 1:4, and placing the mixture in an atmosphere muffle furnace for activation for 2 hours at 800 ℃. The heating rate was 5 ℃/min. Nitrogen was used as a shielding gas at a flow rate of 0.1L/min.
And step five, placing the product obtained in the step four and 10 wt% hydrochloric acid in a water bath kettle at 80 ℃ for magnetic stirring for 30min, then washing the product to be neutral by using deionized water, and drying the product to obtain the porous carbon material.
The implementation effect is as follows: the specific surface area of the product is 2385m calculated by a BET method2G, pore volume of 1.45cm3The average pore diameter of macropores and mesopores calculated by a BJH method is 2.15nm, and the material is a material with higher specific surface area. The electrode material for the supercapacitor is prepared by mixing the carbon material, a conductive agent and a binder according to the mass ratio of 8:1:1, 6mol/L KOH is used as electrolyte to carry out constant current charge-discharge test, the specific capacitance value reaches 335F/g when the current density is 0.1A/g, the specific capacitance value reaches 270F/g when the current density is 10A/g, and the specific capacitance value still reaches 185F/g when the current density is 100A/g.
The comparison of the above embodiments shows that the specific surface area and the pore volume of the porous carbon are increased by using the waste obtained by extracting the natural effective components from the xanthoceras sorbifolia as the raw material, the prepared porous carbon has the advantages of low impurity content, low ash content and good wettability, and the assembled two-electrode system electric double layer supercapacitor has the advantages of excellent specific capacitance, small equivalent series resistance and high charge and discharge efficiency.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. 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. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. A method for preparing a porous carbon material from xanthoceras sorbifolia bunge husk residue waste is characterized by comprising the following steps:
extracting natural components of the xanthoceras sorbifolia bunge shell to obtain xanthoceras sorbifolia bunge shell residue waste;
carbonizing, acid washing and activating the xanthoceras sorbifolia shell residue waste, then carrying out acid washing, water washing and drying again to obtain the xanthoceras sorbifolia waste-based porous carbon electrode material.
2. The method for preparing porous carbon material from xanthoceras sorbifolia husk residue waste as claimed in claim 1, wherein the extraction method comprises organic solvent extraction, CO extraction2Supercritical extraction and one or more of ultrasonic wave and microwave assistance.
3. The method for preparing a porous carbon material from the xanthoceras sorbifolia shell residue waste as claimed in claim 1, wherein the carbonization is performed under the protection of inert gas, the temperature is 400-800 ℃, and the carbonization time is 80-150 min.
4. The method for preparing a porous carbon material from the waste of xanthoceras sorbifolia husk residue according to claim 1, wherein the acid washing is performed with at least one aqueous solution of sulfuric acid, hydrochloric acid, nitric acid or hydrofluoric acid.
5. The method for preparing a porous carbon material from the waste of xanthoceras sorbifolia husk residue as claimed in claim 1, wherein the activating comprises: and (3) soaking the carbonized and acid-washed product I in an activating agent, and then heating and activating the obtained product II.
6. The method for preparing a porous carbon material from the xanthoceras sorbifolia husk residue waste as claimed in claim 5, wherein the heating temperature for heating and activating is 700-900 ℃ and the time is 60-140 min.
7. The method for preparing porous carbon material from xanthoceras sorbifolia husk residue waste as claimed in claim 5, wherein the activating agent comprises KOH, NaOH, K2CO3，H3PO4，ZnCl2One or more of (a).
8. The method for preparing the porous carbon material by using the xanthoceras sorbifolia shell residue waste prepared by the method of any one of claims 1 to 7.
9. The use of the porous carbon material of claim 8 in the preparation of a porous carbon electrode for a supercapacitor, wherein the porous carbon electrode is prepared from the porous carbon material prepared from the xanthoceras sorbifolia residue waste of claim 6, a conductive additive and a binder.
10. Use of the porous carbon material of claim 8 in the preparation of a supercapacitor.
CN202010112755.6A 2020-02-24 2020-02-24 Porous carbon material prepared from xanthoceras sorbifolia bunge shell residue waste as well as preparation method and application of porous carbon material Pending CN111302339A (en)

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