CN113314349A - Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof - Google Patents
Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 68
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
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- 238000002791 soaking Methods 0.000 claims description 19
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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
- H01G11/24—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
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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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Abstract
The invention discloses a polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof. Belongs to the technical field of wood energy storage. The invention fills polyacrylonitrile polymer material in the carbonized wood pore channel, and then fills the polyacrylonitrile polymer material in CO2The physical activation of carbonized wood is completed while the polyacrylonitrile is carbonized at high temperature under the atmosphere, the specific surface area of the carbonized wood is effectively increased while the pore structure of the carbonized wood is efficiently utilized, the polyacrylonitrile/wood-based derived carbon porous material is prepared, and the excellent performance of the supercapacitor is shown.
Description
Technical Field
The invention relates to the technical field of wood energy storage, in particular to a polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof.
Background
With the widespread use of new energy technologies and mobile devices, the demands and requirements of people for advanced energy storage technologies and energy storage devices are constantly increasing. Among a plurality of energy storage devices, the super capacitor has the advantages of high power density, rapid charge and discharge capacity, ultra-long cycle stability and the like, and becomes a research hotspot in the field of energy storage. The performance of the supercapacitor is closely related to the performance of the electrode material, such as the conductivity, specific surface area, chemical stability and the like of the electrode material. Carbon-based materials are currently the most widely used supercapacitor electrode materials.
The artificially synthesized carbon-based materials are generally expensive, the synthesis process is not only complicated, but also the medicines used in the synthesis process are often toxic and harmful, have great pollution to the environment and are severely restricted in the aspect of practical application. Therefore, the method for searching the carbon precursor material which is low in price, does not need a complex synthesis process and is widely distributed in the nature has very important significance for the development and the practical application of the super capacitor.
As an important renewable resource, wood has the advantages of low cost, wide source, abundant reserves, environmental protection, sustainability and the like, and becomes a potential important source of carbon electrode materials. The wood has an anisotropic porous structure, the porous structures can be well reserved after the wood is carbonized, and the porous structure not only has a large specific surface area, but also is very favorable for the rapid penetration of electrolyte, so that the rapid storage and release of charges are facilitated. In addition, the pore channels are also good frameworks, and materials such as high molecular polymers, metal oxides and the like can be filled in the pore channels by utilizing a physical or chemical method, so that a wide development space is provided for the improvement and the functionalization of the performance of the carbonized wood. The effective improvement of the specific surface area of the carbonized wood is also greatly helpful for improving the performance of the supercapacitor of the wood-based derived carbon electrode, and the generally adopted method is to activate the carbonized wood by physical and chemical methods to form more micropores and mesopores on the inner wall of a pore channel so as to improve the specific surface area of the carbonized wood, which obviously does not fully utilize the skeleton structure of the pore channel of the carbonized wood.
Based on the above, in order to fully utilize the pore skeleton structure of the carbonized wood and improve the carbonized woodThe invention has specific surface area and conductive performance, the inside of the carbonized wood pore channel is firstly filled with polyacrylonitrile polymer material, and then CO is filled2The physical activation of carbonized wood is completed while the polyacrylonitrile is carbonized at high temperature under the atmosphere, the specific surface area and the conductivity of the carbonized wood are effectively improved while the pore structure of the carbonized wood is efficiently utilized, the polyacrylonitrile/wood-based derived carbon porous material is prepared, and the excellent performance of the supercapacitor is shown. At present, no report is found on the improvement of the performance of the supercapacitor of the wood-based derived carbon electrode material in such a way.
Disclosure of Invention
In view of the above, the invention provides a polyacrylonitrile/wood-based derived carbon porous material, and a preparation method and an application thereof. The method has the advantages of low cost, simple preparation process, wide sources, environmental protection, sustainability and the like, realizes the efficient utilization of the pore structure of the carbonized wood, obviously improves the specific surface area and the conductivity of the carbonized wood, and improves the energy storage performance of the wood-based derived carbon electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a porous polyacrylonitrile/wood-based derived carbon material is composed of carbonized wood chips and carbonized polyacrylonitrile, wherein the carbonized polyacrylonitrile is in a porous sheet structure and is filled in the pore channels of the carbonized wood chips.
Furthermore, the specific surface area of the polyacrylonitrile/wood-based derived carbon porous material can reach 668.9m2 g-1At a current density of 2mA cm-2When the specific area capacity is up to 4612.2mF cm-2Even when the current density is increased to 100mA cm-2The specific area capacity can still reach 3431.5mF cm-2。
A preparation method of polyacrylonitrile/wood-based derived carbon porous material comprises the following steps:
(1) the wood chips are sequentially washed by deionized water and absolute ethyl alcohol, and the pretreated wood chips are obtained after drying;
the wood sheet material can be poplar, basswood, pine, fir and other wood species;
the drying method comprises freeze drying, vacuum drying, dryer drying, forced air drying, infrared irradiation drying, etc.;
(2) sequentially carrying out low-temperature preoxidation and high-temperature carbonization on the pretreated wood chips to obtain original carbonized wood chips;
polishing and grinding the original carbonized wood chips by using 2000-mesh fine abrasive paper to obtain thin slices with the thickness of 0.5-1 mm;
the low-temperature pre-oxidation in the step has two functions, namely removing impurities in the wood chips on one hand, and keeping the original pore structure of the wood chips on the other hand, so that the functions of fixing oxygen and carbon are achieved, and the pore structure of the wood chips is prevented from being broken due to high-temperature pyrolysis.
(3) Weighing certain mass of polyacrylonitrile powder and polyvinylpyrrolidone powder, dissolving in N, N-dimethylformamide, and stirring for dissolving to obtain a mixed solution A;
n, N-dimethylformamide is used only as a solvent, and its function is to dissolve polyacrylonitrile. N, N-dimethylformamide will run out of solution with water in step (4), and the remaining portion will be volatilized in the subsequent drying.
(4) Soaking the original carbonized wood chips in the mixed solution A, filling polyacrylonitrile into pore channels of the original carbonized wood chips by using a vacuum filling technology, and then soaking in deionized water, washing with the deionized water and drying to obtain the carbonized wood chips filled with the polyacrylonitrile;
(5) sequentially carrying out pre-oxidation and one-step CO treatment on the carbonized wood chips filled with the polyacrylonitrile2Carbonizing and activating to obtain the polyacrylonitrile/wood-based derived carbon porous material.
The purpose of the pre-oxidation in the step is to make polyacrylonitrile filled inside and on the surface of the pore channels of the wood chips stably solidified so as to form stable three-dimensional ion diffusion channels in the carbonization process. In addition, during the pre-oxidation process, the-CN triple bond can be opened into a double bond to form a ring with adjacent carbon atoms, and the ring can be further dehydrogenated during the high-temperature carbonization process to form a standard graphite ring structure, which is beneficial to the improvement of electrochemical performance.
Further, the wood chips in the step (1) are poplar wood chips, and the moisture content is less than 30%.
Further, the drying in the step (1) is freeze drying, and the specific parameters are as follows: the vacuum degree is 10-30 Pa, the condensation temperature is less than-50 ℃, and the time is 12-48 h.
Further, the drying in the step (1) is freeze drying, and the specific parameters are as follows: the vacuum degree is 10-30 Pa, the condensation temperature is less than-50 ℃, and the time is 24 h.
The freeze drying can furthest ensure that the porous channel structure of the wood is prevented from being damaged, the dehydration is thorough, and the freeze drying method can remove more than 95-99% of water.
Further, in the step (2), the low-temperature pre-oxidation temperature is 200-300 ℃, and the time is 1-6 hours;
and the high-temperature carbonization is carried out in an inert atmosphere (argon, nitrogen and the like), the carbonization temperature is 800-1200 ℃, and the carbonization time is 6-10 h.
Further, the molecular weight of the polyacrylonitrile powder in the step (3) is 30000-500000, and the mass ratio of the polyacrylonitrile powder to the polyvinylpyrrolidone powder is 1: 0.5-2.
Further, the molecular weight of the polyacrylonitrile powder in the step (3) is 100000-200000, and the mass ratio of the polyacrylonitrile powder to the polyvinylpyrrolidone powder is 1: 1.
The molecular weight of polyacrylonitrile has a great influence on the filling amount of the mixed solution A in the original carbonized wood chip pore canal, and if the molecular weight is too large, the viscosity of the mixed solution A can be obviously increased, which is not favorable for the filling of the mixed solution A in the original carbonized wood chip pore canal, and can cause the reduction of the loading amount of polyacrylonitrile-derived carbon in the original carbonized wood chip pore canal.
Further, the specific operation of the step (4) is as follows: soaking the original carbonized wood chips in the mixed solution A, placing the soaked original carbonized wood chips in a closed container, pumping the polyacrylonitrile mixed solution into the pore channels of the original carbonized wood chips by adopting a method of repeatedly vacuumizing and filling nitrogen, soaking the soaked original carbonized wood chips in a nitrogen-filled environment for 0.5-24 h, then soaking the original carbonized wood chips in deionized water, soaking the original carbonized wood chips in the deionized water to cure the polyacrylonitrile by utilizing the characteristics that the polyacrylonitrile is incompatible with water and is solidified when meeting the water, dissolving out polyvinylpyrrolidone with functions of a soft membrane plate and pore forming, washing the original carbonized wood chips with the deionized water after soaking for a period of time, and freeze-drying.
In the process, the polyvinylpyrrolidone not only plays a role of a soft template, but also plays a role of forming initial mesopores and micropores on the surface and around the polyacrylonitrile. The polyvinylpyrrolidone is very soluble in water, and can be dissolved in the deionized water again to form micropores and mesopores in some initial forms while the polyacrylonitrile is solidified in the deionized water, so that a carbon structure with more micropores and mesopores can be formed after the polyacrylonitrile is carbonized.
Further, in the step (5), the pre-oxidation temperature is 200-300 ℃, and the time is 1-6 hours;
the CO is2The carbonization and activation temperature is 800-1000 ℃, the time is 6-10 h, and the air flow is 80-100 cm3/min。
The polyacrylonitrile/wood-based derived carbon porous material is applied to preparing electrode materials of super capacitors.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects: the invention discloses a polyacrylonitrile/wood-based derived carbon porous material, a preparation method and application thereof, which skillfully utilizes the characteristic that the original wood structure can be greatly kept after wood carbonization. Wood is used as a carbon precursor, polyacrylonitrile is used as a filled high molecular polymer, a vacuum filling technology is utilized to fill polyacrylonitrile materials into pore channels of carbonized wood, and then CO is added2The polyacrylonitrile is carbonized at high temperature in the atmosphere, and meanwhile, the activation of carbonized wood is completed, so that the carbonized wood has higher porosity, the porous carbon electrode material with larger specific surface area and better conductivity is prepared, and the excellent performance of the super capacitor is shown. The method provided by the invention has the characteristics of simple and flexible process, and can complete carbonization and activation of different materials by one-step high-temperature treatment. The pore structure of the carbonized wood is efficiently utilized, the specific surface area and the conductivity of the carbonized wood are improved, and the problem that only one of the pore structures is used is solvedA preparation method for increasing the specific surface area of carbonized wood by utilizing the pore structure of the carbonized wood or only by activating through physical and chemical methods provides a new idea for the development of materials. In addition, the carbonized wood is used as a carrier, the carbonized wood can be used as a current collector, the current collectors such as expensive foam nickel and the like are not needed, and the cost is obviously reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a transmission electron microscope (200nm) of raw poplar carbide chips obtained in step (2) of example 1 of the present invention;
FIG. 2 is a transmission electron microscopy (200nm) picture of a polyacrylonitrile/wood-based derived carbon porous material prepared according to example 1 of the present invention;
FIG. 3 is a graph showing the nitrogen adsorption and desorption curves of the raw carbonized poplar wood chips obtained in step (2) of example 1 and the polyacrylonitrile/wood-based derived carbon porous material prepared in example 1 according to the present invention;
FIG. 4 is a graph showing that the polyacrylonitrile/wood-based derived carbon porous material prepared according to example 1 of the present invention has a concentration of 5-100 mV s-1Cyclic voltammograms at scan rate;
FIG. 5 is a graph showing that the polyacrylonitrile/wood-based derived carbon porous material prepared according to embodiment 1 of the invention is 10-100 mA cm-2Constant current charge and discharge curve diagram under current density;
FIG. 6 is a graph showing the area specific capacity as a function of current density for raw poplar carbide chips from step (2) of example 1 and polyacrylonitrile/wood-based-derived carbon porous materials prepared in examples 1, 2 and 3 in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the 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.
The medicament required by the embodiment of the invention is a conventional experimental medicament purchased from a commercially available channel; the experimental methods not mentioned in the examples are conventional experimental methods, and are not described in detail herein.
Example 1
The embodiment provides a method for preparing a polyacrylonitrile/wood-based derived carbon porous material, which specifically comprises the following steps:
(1) the natural poplar was air-dried until the water content was less than 30%, and cut into 30mm × 30mm × 2mm thin pieces. The poplar chips are ultrasonically cleaned for a plurality of times by deionized water and absolute ethyl alcohol, then the poplar chips are frozen for 12 hours at the temperature of minus 20 ℃ in a refrigerator, and then the poplar chips are freeze-dried for 24 hours at the temperature of minus 50 ℃ by a freeze dryer to obtain the pretreated poplar chips.
(2) And placing the pretreated poplar chips in a blast drying furnace at 250 ℃ for low-temperature preoxidation for 6 hours, transferring the poplar chips to a tubular furnace at 1000 ℃, and carbonizing for 6 hours under the protection of nitrogen to obtain original carbonized poplar chips. The transmission electron microscope image is shown in FIG. 1. And (3) grinding the original carbonized poplar wood chips by using 2000-mesh fine sand paper, and polishing the ground carbonized poplar wood chips into thin original carbonized poplar wood chips with the thickness of 0.5-1 mm.
(3) 5mL of N, N-dimethylformamide organic solvent is weighed in a beaker, and polyacrylonitrile with the molecular weight of 150000 and the mass of 0.25g and polyvinylpyrrolidone with the mass of 0.25g are respectively added, and magnetic stirring is carried out, so as to obtain a mixed solution A after full dissolution and mixing.
(4) And (2) placing the thin original carbonized poplar wood chips into the mixed solution A, placing the thin original carbonized poplar wood chips into a closed container, pumping the polyacrylonitrile mixed solution into the pore channels of the thin original carbonized poplar wood chips by adopting a method of repeatedly vacuumizing and filling nitrogen, then soaking the thin original carbonized poplar wood chips into deionized water, soaking the thin original carbonized poplar wood chips into the deionized water to solidify the polyacrylonitrile by utilizing the characteristic that the polyacrylonitrile is incompatible with water and is solidified when meeting water, dissolving polyvinylpyrrolidone serving as a soft membrane plate and a pore-forming function, washing the thin original carbonized poplar wood chips with the deionized water, and freeze-drying to obtain the carbonized poplar wood chips filled with the polyacrylonitrile.
(5) Putting the dried carbonized poplar chips filled with polyacrylonitrile into a muffle furnace, and pre-oxidizing for 1h at 260 ℃ to pre-oxidize the polyacrylonitrile; then transferring the carbonized poplar wood chips filled with polyacrylonitrile after preoxidation into a tube furnace at the flow rate of 100cm3CO/min2Under the protection of gas, performing one-step carbonization and activation on polyacrylonitrile and carbonized wood at 800 ℃ for 10 hours to finally obtain the polyacrylonitrile/wood-based derived carbon porous material. The transmission electron microscope image is shown in fig. 2, and it can be seen from the figure that the carbonized polyacrylonitrile is filled in the carbonized wood pore canal in a porous sheet layered structure.
Examples 1 the nitrogen sorption and desorption curves of the raw carbonized poplar wood chips obtained in step (2) and the polyacrylonitrile/wood-based derived carbon porous material prepared in example 1 are shown in fig. 3. As can be seen from fig. 3, compared with the original carbonized poplar wood chips obtained in the step (2) of the example 1, the polyacrylonitrile/wood-based derived carbon porous material prepared in the example 1 has an obvious delayed loop when the relative pressure is 0.4-1.0, which indicates that the material has a rich mesoporous structure and a large specific surface area.
The polyacrylonitrile/wood-based derived carbon porous material is in the range of 5-100 mV s-1The cyclic voltammogram at the scan rate is shown in FIG. 4, and it can be seen from FIG. 4 that even at 100mV s-1The cyclic voltammetry curve still presents a good rectangular shape at a high scanning rate, which indicates that the material has good electrochemical reversibility and capacitance characteristics.
The polyacrylonitrile/wood-based derived carbon porous material is 10-100 mA cm-2The constant current charge and discharge curve under the current density is shown in fig. 5, and as can be seen from fig. 5, the curves all present symmetrical triangular shapes, which shows that the material has good charge and discharge capacitance behavior.
Example 2
The embodiment provides a method for preparing a polyacrylonitrile/wood-based derived carbon porous material, which specifically comprises the following steps:
(1) the natural poplar was air-dried until the water content was less than 30%, and cut into 30mm × 30mm × 2mm thin pieces. The poplar chips are ultrasonically cleaned for a plurality of times by deionized water and absolute ethyl alcohol, then the poplar chips are frozen for 12 hours at the temperature of minus 20 ℃ in a refrigerator, and then the poplar chips are freeze-dried for 24 hours at the temperature of minus 50 ℃ by a freeze dryer to obtain the pretreated poplar chips.
(2) And placing the pretreated poplar chips in a blast drying furnace at 250 ℃ for low-temperature preoxidation for 6 hours, then transferring the poplar chips into a tubular furnace at 1000 ℃, and carbonizing for 6 hours under the protection of nitrogen to obtain the original carbonized poplar chips. And (3) grinding the original carbonized poplar wood chips by using 2000-mesh fine sand paper, and polishing the ground carbonized poplar wood chips into thin original carbonized poplar wood chips with the thickness of 0.5-1 mm.
(3) 5mL of N, N-dimethylformamide organic solvent is weighed in a beaker, and polyacrylonitrile with the molecular weight of 150000 and the mass of 0.25g and polyvinylpyrrolidone with the mass of 0.125g are respectively added, and magnetic stirring is carried out, so as to obtain a mixed solution A after full dissolution and mixing.
(4) Placing the thin original carbonized poplar wood chips into the mixed solution A, placing the thin original carbonized poplar wood chips into a closed container, pumping the polyacrylonitrile mixed solution into the pore channels of the thin original carbonized poplar wood chips by adopting a method of repeatedly vacuumizing and filling nitrogen, then placing the carbonized poplar wood chips filled with the polyacrylonitrile mixed solution into deionized water for soaking, soaking and curing the polyacrylonitrile in the deionized water by utilizing the characteristic that the polyacrylonitrile is incompatible with water and is solidified when meeting water, dissolving polyvinylpyrrolidone with functions of a soft membrane plate and pore forming, and then washing with the deionized water and carrying out freeze drying to obtain the carbonized poplar wood chips filled with the polyacrylonitrile.
(5) The carbonized poplar wood chips filled with polyacrylonitrile were put into a muffle furnace and pre-oxidized at 260 ℃ for 1 hour to pre-oxidize polyacrylonitrile. Then transferring the carbonized poplar wood chips filled with polyacrylonitrile after preoxidation into a tube furnace at the flow rate of 100cm3CO/min2Under the protection of gas, polyacrylonitrile is filled in the polyacrylonitrileCarbonizing poplar wood chips for 10h in one step to obtain the polyacrylonitrile/wood-based derived carbon porous material.
Example 3
The embodiment provides a method for preparing a polyacrylonitrile/wood-based derived carbon porous material, which specifically comprises the following steps:
(1) the natural poplar was air-dried until the water content was less than 30%, and cut into 30mm × 30mm × 2mm thin pieces. The poplar chips are ultrasonically cleaned for a plurality of times by deionized water and absolute ethyl alcohol, then the poplar chips are frozen for 12 hours at the temperature of minus 20 ℃ in a refrigerator, and then the poplar chips are freeze-dried for 24 hours at the temperature of minus 50 ℃ by a freeze dryer to obtain the pretreated poplar chips.
(2) And placing the pretreated poplar chips in a blast drying furnace at 250 ℃ for low-temperature preoxidation for 6 hours, then transferring the poplar chips into a tubular furnace at 1000 ℃, and carbonizing for 6 hours under the protection of nitrogen to obtain the original carbonized poplar chips. And (3) grinding the original carbonized poplar wood chips by using 2000-mesh fine sand paper, and polishing the ground carbonized poplar wood chips into thin original carbonized poplar wood chips with the thickness of 0.5-1 mm.
(3) 5mL of N, N-dimethylformamide organic solvent is weighed in a beaker, and polyacrylonitrile with the molecular weight of 150000 and the mass of 0.25g and polyvinylpyrrolidone with the mass of 0.5g are respectively added, and magnetic stirring is carried out, so as to obtain a mixed solution A after full dissolution and mixing.
(4) Placing the thin original carbonized poplar wood chips into the mixed solution A, placing the thin original carbonized poplar wood chips into a closed container, pumping the polyacrylonitrile mixed solution into the pore channels of the thin original carbonized poplar wood chips by adopting a method of repeatedly vacuumizing and filling nitrogen, then placing the carbonized poplar wood chips filled with the polyacrylonitrile mixed solution into deionized water for soaking, soaking and curing the polyacrylonitrile in the deionized water by utilizing the characteristic that the polyacrylonitrile is incompatible with water and is solidified when meeting water, dissolving polyvinylpyrrolidone with functions of a soft membrane plate and pore forming, and then washing with the deionized water and carrying out freeze drying to obtain the carbonized poplar wood chips filled with the polyacrylonitrile.
(5) The carbonized poplar wood chips filled with polyacrylonitrile were put into a muffle furnace and pre-oxidized at 260 ℃ for 1 hour to pre-oxidize polyacrylonitrile. Then filling the mixture with poly through pre-oxidationTransferring the carbonized poplar wood pieces of acrylonitrile into a tube furnace at the flow rate of 100cm3CO/min2Under the protection of gas, carbonizing and activating the carbonized poplar wood chips filled with polyacrylonitrile at 800 ℃ for 10 hours in one step to finally obtain the polyacrylonitrile/wood-based derived carbon porous material.
The curves of the area specific capacity of the raw carbonized poplar wood chips obtained in the step (2) of the example 1 and the polyacrylonitrile/wood-based derived carbon porous materials prepared in the examples 1, 2 and 3 along with the current density are shown in fig. 6.
As can be seen from FIG. 6, the current density was 2mA cm-2The area specific capacity of the original carbonized poplar chips obtained in the steps (2) of the examples 1, 2 and 3 and the example 1 is 4612.2, 3859.8, 3250.8 and 2737.4mF cm respectively-2When the current density was increased to 100mA cm-2The specific area capacities of examples 1, 2, 3 and carbonized wood were 3431.5, 2884.5, 2284.2, 1868.0mF cm-2The initial capacity retention rates are 74.4%, 74.7%, 70.3% and 68%, respectively, which indicates that the polyacrylonitrile/wood-based derived carbon porous material has excellent rate characteristics.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The polyacrylonitrile/wood-based derived carbon porous material is characterized by consisting of carbonized wood chips and carbonized polyacrylonitrile, wherein the carbonized polyacrylonitrile is in a porous sheet structure and is filled in pore channels of the carbonized wood chips.
2. The polyacrylonitrile/wood-based derived carbon porous material according to claim 1, wherein the specific surface area of the polyacrylonitrile/wood-based derived carbon porous material is 668.9m2 g-1At a current density of 2mA cm-2When the specific area capacity is up to 4612.2mF cm-2Even when the current density is increased to 100mA cm-2The specific area capacity can still reach 3431.5mF cm-2。
3. The method for preparing a polyacrylonitrile/wood-based derived carbon porous material as claimed in any one of claims 1 or 2, comprising the steps of:
(1) the wood chips are sequentially washed by deionized water and absolute ethyl alcohol, and the pretreated wood chips are obtained after drying;
(2) sequentially carrying out low-temperature preoxidation and high-temperature carbonization on the pretreated wood chips to obtain original carbonized wood chips;
(3) weighing certain mass of polyacrylonitrile powder and polyvinylpyrrolidone powder, dissolving in N, N-dimethylformamide, and stirring for dissolving to obtain a mixed solution A;
(4) soaking the original carbonized wood chips in the mixed solution A, filling polyacrylonitrile into pore channels of the original carbonized wood chips by using a vacuum filling technology, and then soaking in deionized water, washing with the deionized water and drying to obtain the carbonized wood chips filled with the polyacrylonitrile;
(5) sequentially carrying out pre-oxidation and one-step CO treatment on the carbonized wood chips filled with the polyacrylonitrile2Carbonizing and activating to obtain the polyacrylonitrile/wood-based derived carbon porous material.
4. The method according to claim 3, wherein the wood chips in the step (1) are poplar wood chips and the moisture content is less than 30%.
5. The method according to claim 3, wherein the drying in step (1) is freeze-drying, and the specific parameters are as follows: the vacuum degree is 10-30 Pa, the condensation temperature is less than-50 ℃, and the time is 12-48 h.
6. The preparation method according to claim 3, wherein the low-temperature pre-oxidation temperature in the step (2) is 200-300 ℃ and the time is 1-6 h;
and the high-temperature carbonization is carried out in an inert atmosphere, the carbonization temperature is 800-1200 ℃, and the carbonization time is 6-10 h.
7. The preparation method according to claim 3, wherein the molecular weight of the polyacrylonitrile powder in the step (3) is 30000-500000, and the mass ratio of the polyacrylonitrile powder to the polyvinylpyrrolidone powder is 1: 0.5-2.
8. The preparation method according to claim 3, wherein the specific operation of the step (4) is as follows: and soaking the original carbonized wood chips in the mixed solution A, placing the soaked original carbonized wood chips in a closed container, pumping the polyacrylonitrile mixed solution into pore channels of the original carbonized wood chips by adopting a method of repeatedly vacuumizing and filling nitrogen, soaking the original carbonized wood chips in a nitrogen-filled environment for 0.5-24 h, then placing the original carbonized wood chips in deionized water for soaking, washing the original carbonized wood chips with the deionized water after soaking for a period of time, and freeze-drying the soaked original carbonized wood chips.
9. The preparation method according to claim 3, wherein the pre-oxidation temperature in the step (5) is 200-300 ℃ and the time is 1-6 h;
said CO2The carbonization and activation temperature is 800-1000 ℃, the time is 6-10 h, and the air flow is 80-100 cm3/min。
10. Use of the polyacrylonitrile/wood-based derived carbon porous material as claimed in any one of claims 1 or 2 in the preparation of supercapacitor electrode materials.
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