CN110589826A - N, P co-doped carbon aerogel and preparation method and application thereof - Google Patents
N, P co-doped carbon aerogel and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention relates to the technical field of carbon aerogel, in particular to N, P co-doped carbon aerogel and a preparation method and application thereof. The invention takes biomass fiber as raw material and adopts acid NaClO2Pretreatment, NH4H2PO4The N, P co-doped carbon aerogel is prepared by doping, freezing and forming, carbonization and activation, the method is simple to operate, renewable natural resources are fully utilized, the raw material source is wide, and the method is green and environment-friendly; wherein NH4H2PO4Not only can be used as a doping agent but also can be used as an activating agent, thereby saving raw materialsThe cost is low, and the N, P one-step doping also enables the preparation process to be simple and convenient, and is suitable for large-scale production; n, P the co-doping overcomes the limitation that the specific capacitance of the carbon material is not high, and the obtained N, P co-doped carbon aerogel has ultrahigh mesoporous rate by combining two-step activation (carbonization is the first-step activation, and activation is the second-step activation), so that the cost is controlled, and the excellent electrochemical performance effect is achieved.
Description
Technical Field
The invention relates to the technical field of carbon aerogel, in particular to N, P co-doped carbon aerogel and a preparation method and application thereof.
Background
The carbon aerogel is a novel porous carbon material, has the characteristics of high porosity and high specific surface area of the aerogel and the advantages of conductivity, high temperature resistance, acid and alkali resistance, degradability and the like of the carbon material, and has potential application value in the fields of catalyst carriers, adsorption materials, electrochemistry and the like.
In recent years, carbon aerogel has attracted extensive attention as an electrode material for researchers in the field of supercapacitors. However, the carbon aerogel reported in the prior art has the problems of low specific capacitance and complex preparation method.
Disclosure of Invention
The invention aims to provide N, P co-doped carbon aerogel and a preparation method and application thereof, the preparation method provided by the invention is simple to operate, and the prepared N, P co-doped carbon aerogel has ultrahigh mesoporous rate and specific capacitance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of N, P co-doped carbon aerogel, which comprises the following steps:
pretreating biomass fibers by using pretreatment liquid containing sodium hypochlorite, glacial acetic acid, water and ethanol, mixing the obtained pretreated fibers with water, and then performing fiber opening treatment to obtain a water-biomass fiber suspension;
mixing the water-biomass fiber suspension with NH4H2PO4Mixing, and freezing and forming to obtain N, P co-doped cellulose aerogel;
and sequentially carrying out carbonization treatment and activation treatment on the N, P co-doped cellulose aerogel to obtain N, P co-doped carbon aerogel.
Preferably, the biomass fiber comprises one or more of kapok fiber, pulp fiber, poplar willow catkin fiber and typha fiber.
Preferably, the usage ratio of the biomass fibers to the sodium hypochlorite, the glacial acetic acid, the water and the ethanol in the pretreatment liquid is (1-7) g: (1-14) g: (0.2-1.0) mL: (100-350) mL: (100-350) mL.
Preferably, the fiber opening treatment time is 8-15 min; the fiber opening treatment is carried out under the ultrasonic condition, and the power of the ultrasonic is 1000-1600W.
Preferably, the mass concentration of the water-biomass fiber suspension is 0.4-1.0%, and the water-biomass fiber suspension and NH are mixed4H2PO4The mass ratio of (1): (1-4).
Preferably, the carbonization treatment is carried out in a protective atmosphere and comprises pre-carbonization and carbonization which are sequentially carried out;
the temperature of the pre-carbonization is 300-500 ℃, and the heat preservation time is 1-3.5 h;
the carbonization temperature is 600-900 ℃, and the heat preservation time is 1-3 h.
Preferably, the activation treatment is carried out in an activation atmosphere, the activation gas providing the activation atmosphere comprising CO2One or more of water vapor, flue gas, oxygen and air;
the temperature of the activation treatment is 600-900 ℃, and the heat preservation time is 0.5-3 h.
The invention provides N, P co-doped carbon aerogel prepared by the preparation method in the technical scheme, which comprises carbon aerogel, and N and P doped in the carbon aerogel.
Preferably, the N, P co-doped carbon aerogel contains 4.27-6.64% of N and 3.07-3.73% of P by mass;
the mesoporous rate of the N, P co-doped carbon aerogel is 34.81-73.92%.
The invention provides application of N, P co-doped carbon aerogel in the technical scheme as an electrode material.
The invention provides a preparation method of N, P co-doped carbon aerogel, which comprises the following steps: pretreating biomass fibers by using pretreatment liquid containing sodium hypochlorite, glacial acetic acid, water and ethanol, mixing the obtained pretreated fibers with water, and then performing fiber opening treatment to obtain a water-biomass fiber suspension; mixing the water-biomass fiber suspension with NH4H2PO4Mixing, and freezing and forming to obtain N, P co-doped cellulose aerogel; and sequentially carrying out carbonization treatment and activation treatment on the N, P co-doped cellulose aerogel to obtain N, P co-doped carbon aerogel. The invention takes biomass fiber as raw material and adopts acid NaClO2Pretreatment, NH4H2PO4The N, P co-doped carbon aerogel is prepared by doping, freezing, forming, carbonizing and activating, the method is simple to operate, renewable natural resources are fully utilized, the raw material source is wide, and the method is green and environment-friendly; wherein NH4H2PO4The organic silicon/inorganic composite material is used as a dopant and an activator, so that the raw material cost is saved, the N, P is doped in one step, the preparation process is simple and convenient, and the organic silicon/inorganic composite material is suitable for large-scale production; n, P the co-doping overcomes the limitation that the specific capacitance of the carbon material is not high, and the obtained N, P co-doped carbon aerogel has ultrahigh mesoporous rate by combining two-step activation (carbonization is the first-step activation, and activation is the second-step activation), so that the cost is controlled, and the excellent electrochemical performance effect is achieved. The data of the examples show that the mesoporous rate of N, P co-doped carbon aerogel prepared from kapok fiber can reach 73.92%, under the test conditions of the examples, the specific capacitance of N, P co-doped carbon aerogel can reach 367F/g, and the desalting amount can reach 28.39 mg/g.
Detailed Description
The invention provides a preparation method of N, P co-doped carbon aerogel, which comprises the following steps:
pretreating biomass fibers by using pretreatment liquid containing sodium hypochlorite, glacial acetic acid, water and ethanol, mixing the obtained pretreated fibers with water, and then performing fiber opening treatment to obtain a water-biomass fiber suspension;
subjecting the water-to-organismsCellulose suspension and NH4H2PO4Mixing, and freezing and forming to obtain N, P co-doped cellulose aerogel;
and sequentially carrying out carbonization treatment and activation treatment on the N, P co-doped cellulose aerogel to obtain N, P co-doped carbon aerogel.
The method comprises the steps of pretreating biomass fibers by using pretreatment liquid containing sodium hypochlorite, glacial acetic acid, water and ethanol, mixing the obtained pretreated fibers with water, and then performing fiber opening treatment to obtain a water-biomass fiber suspension. In the invention, the biomass fiber preferably comprises one or more of kapok fiber, pulp fiber, salix mongolica fiber and cattail fiber, and more preferably is kapok fiber, pulp fiber, salix mongolica fiber or cattail fiber. The diameter and length of the biomass fiber are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the dosage ratio of the biomass fibers to the sodium hypochlorite, the glacial acetic acid, the water and the ethanol in the pretreatment solution is preferably (1-7) g: (1-14) g: (0.2-1.0) mL: (100-350) mL: (100-350) mL, more preferably (1-4) g: (1-8) g: (0.5-1.0) mL: (200-350) mL: (200-350) mL.
According to the invention, the biomass fiber is preferably mixed with sodium hypochlorite, glacial acetic acid, water and ethanol and then subjected to pretreatment, more preferably, the biomass fiber, the water, the ethanol, part of the sodium hypochlorite and part of the glacial acetic acid are mixed and then subjected to first pretreatment, and then the rest of the sodium hypochlorite and the rest of the glacial acetic acid are added into the obtained system to perform second pretreatment. In the invention, the part of sodium hypochlorite is preferably 40-60% of the total mass of sodium hypochlorite, and more preferably 50%; the part of the glacial acetic acid is preferably 40-60% of the total mass of the glacial acetic acid, and more preferably 50%. In the invention, the first pretreatment and the second pretreatment are preferably carried out under stirring conditions, and the rotation speed of stirring is preferably 300-650 rpm independently; the time of the first pretreatment and the second pretreatment is preferably 50-70 min independently, and more preferably 60 min; the first and second pretreatments are preferably carried out at room temperature, i.e. without additional heating or cooling.
In the invention, in the pretreatment process, sodium hypochlorite and glacial acetic acid react to generate hypochlorous acid and sodium acetate, and the bleaching effect of the hypochlorous acid can remove lignin and surface vegetable wax in the biomass fiber, increase oxygen-containing functional groups on the surface and facilitate the doping of N, P; the sodium hypochlorite and the glacial acetic acid are added in two times, so that the full action of each component is ensured.
After the pretreatment is finished, the invention preferably performs vacuum filtration on the obtained mixed system, and washes the obtained solid material with water to be neutral to obtain the pretreated fiber. The operation of the vacuum filtration and washing in the present invention is not particularly limited, and a method known to those skilled in the art may be used.
After the pretreated fiber is obtained, the pretreated fiber is mixed with water and then subjected to fiber opening treatment, so that the water-biomass fiber suspension is obtained. In the invention, the mass concentration of the water-biomass fiber suspension is preferably 0.4-1.0%, and more preferably 0.6-0.8%. In the present invention, the fiber opening treatment is preferably performed at room temperature, i.e., without additional heating or cooling; the time for the fiber opening treatment is preferably 8-15 min; the fiber opening treatment is preferably carried out under the ultrasonic condition, and the power of the ultrasonic is preferably 1000-1600W. The present invention preferably utilizes a cell sonicator to provide sonication conditions. The invention can prepare the nano-cellulose through fiber opening treatment, and is beneficial to further preparing the cellulose aerogel.
After obtaining the water-biomass fiber suspension, the invention mixes the water-biomass fiber suspension with NH4H2PO4And (3) mixing, and performing freeze forming to obtain N, P co-doped cellulose aerogel. In the present invention, the water-biomass fiber suspension is mixed with NH4H2PO4Is preferably 1: (1 to 4), more preferably 1: (1-2). In the invention, the temperature of the freezing forming is preferably-45 to-55 ℃, and the time is preferably 48 to 72 hours. The present invention preferably performs the freeze-forming in a freeze-dryer. The invention removes the water in the water-biomass fiber suspension by freezing and forming, and simultaneously the nano-cellulose forms light under the push of hydrogen bond and ice crystalA porous cellulose aerogel.
After N, P co-doped cellulose aerogel is obtained, the N, P co-doped cellulose aerogel is sequentially subjected to carbonization treatment and activation treatment, and N, P co-doped carbon aerogel is obtained. In the invention, the carbonization treatment is preferably carried out in a protective atmosphere, the protective gas for providing the protective atmosphere preferably comprises one or more of nitrogen, helium, neon, argon and xenon, and more preferably nitrogen, so that the cost is reduced; the flow rate of the protective gas is preferably 800-1200 mL/min, and more preferably 1000 mL/min. In the present invention, the carbonization treatment preferably includes pre-carbonization and carbonization performed in sequence; the pre-carbonization temperature is preferably 300-500 ℃, and more preferably 300-400 ℃; the heat preservation time is preferably 1-3.5 h, and more preferably 1-2 h; the heating rate from room temperature to the temperature required by pre-carbonization is preferably 1-5 ℃/min, and more preferably 2-3 ℃/min. In the invention, the carbonization temperature is preferably 600-900 ℃, and more preferably 700-800 ℃; the heat preservation time is preferably 1-3 h, and more preferably 1-2 h; the heating rate from the pre-carbonization temperature to the temperature required for carbonization is preferably 1-5 ℃/min, and more preferably 2-3 ℃/min. The pre-carbonization is preferably carried out under the above conditions, which is favorable for removing impurities or volatile substances in N, P co-doped cellulose aerogel, and NH is generated in the pre-carbonization process4H2PO4Decomposing the mixture into ammonia gas and phosphoric acid, serving as a nitrogen source and a phosphorus source, and activating N, P co-doped cellulose aerogel; during carbonization, N, P codoped cellulose aerogel is carbonized, and NH is added simultaneously4H2PO4The N, P co-doped cellulose aerogel is continuously activated by the phosphoric acid generated by decomposition, so that the formation of a porous material is facilitated; therefore, in the whole process of carbonization treatment, the invention not only realizes the carbonization of N, P co-doped cellulose aerogel, but also utilizes NH4H2PO4The first-step activation is realized, so that a great number of micropores are generated in the carbon aerogel, and the N, P co-doped carbon aerogel with high mesoporous rate can be obtained through subsequent activation treatment (namely, the second-step activation).
After the carbonization treatment is finished, the hair is treatedAnd (3) carrying out activation treatment on the obtained carbonized product to obtain N, P co-doped carbon aerogel. In the present invention, the activation treatment is preferably performed in an activation atmosphere, and the activation gas for providing the activation atmosphere preferably includes CO2One or more of water vapor, flue gas, oxygen and air, and more preferably CO2(ii) a The flow rate of the activating gas is preferably 400-800 mL/min, and more preferably 450-500 mL/min. In the invention, the temperature of the activation treatment is preferably 600-900 ℃, and more preferably 700-800 ℃; the heat preservation time is preferably 0.5-3 h, and more preferably 1-2 h. In the activation treatment process, activated gas continuously generates a wall etching reaction on the basis of a carbonized product containing a large number of micropores, so that the large number of micropores are enlarged, and the preparation of N, P co-doped carbon aerogel with high mesoporous rate is facilitated; the invention preferably carries out activation treatment under the above conditions, which is beneficial to ensuring that a large amount of mesoporous structures are formed under relatively stable conditions and avoiding excessive etching.
After the activation treatment is completed, the present invention preferably cools the obtained activated product in a protective atmosphere to obtain N, P co-doped carbon aerogel. In the present invention, the protective gas required in the cooling process is preferably the same as the optional range of the protective gas in the carbonization process, and will not be described herein. The cooling method is not particularly limited, and specifically, the cooling method is, for example, natural cooling to room temperature.
The invention provides N, P co-doped carbon aerogel prepared by the preparation method in the technical scheme, which comprises carbon aerogel, and N and P doped in the carbon aerogel. In the invention, the mass content of N in the N, P co-doped carbon aerogel is preferably 4.27-6.64%, and the mass content of P is preferably 3.07-3.73%; the mesoporous rate of the N, P co-doped carbon aerogel is preferably 34.81-73.92%.
The invention provides application of N, P co-doped carbon aerogel in the technical scheme as an electrode material. The invention is not particularly limited to the described applications, as such may be achieved in a manner well known to those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
Mixing 1g of cattail fiber, 1g of sodium hypochlorite, 0.2mL of glacial acetic acid, 100mL of water and 100mL of ethanol, stirring at the rotating speed of 400rpm for 1h, then adding 1g of sodium hypochlorite and 0.2mL of glacial acetic acid, and continuing to stir for 1 h; carrying out vacuum filtration on the obtained mixed system, and washing the obtained solid material to be neutral by using water to obtain pretreated fiber; mixing the pretreated fiber with water, and carrying out ultrasonic treatment for 15min under the condition of 1000W ultrasonic power by using a cell ultrasonic crusher to obtain a water-typha orientalis fiber suspension with the mass concentration of 0.8%;
according to the water-typha fibre suspension and NH4H2PO4The mass ratio of (1): 2, mixing the water-typha fiber suspension with NH4H2PO4Mixing, and freezing and molding (the temperature is-50 ℃ and the time is 80 hours) to obtain N, P codoped cellulose aerogel;
placing the N, P co-doped cellulose aerogel into a tube furnace, and carrying out carbonization treatment under the protection of nitrogen, wherein the nitrogen flow is 1000mL/min, and the carbonization treatment conditions are as follows: heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 2h, then heating to 700 ℃ at the speed of 5 ℃/min, and preserving heat for 2 h; after the carbonization treatment is finished, the nitrogen is removed, and CO is immediately introduced2Keeping the temperature at 800 ℃ for activation treatment for 1.5h with the flow of 400 mL/min; after the activation treatment, CO is added2And (4) after the reaction is removed, replacing nitrogen again, and naturally cooling to room temperature to obtain N, P co-doped carbon aerogel.
Example 2
Mixing 7g of kapok fiber, 7g of sodium hypochlorite, 0.5mL of glacial acetic acid, 350mL of water and 350mL of ethanol, stirring at the rotating speed of 500rpm for 1h, then adding 7g of sodium hypochlorite and 0.5mL of glacial acetic acid, and continuing to stir for 1 h; carrying out vacuum filtration on the obtained mixed system, and washing the obtained solid material to be neutral by using water to obtain pretreated fiber; mixing the pretreated fibers with water, and carrying out ultrasonic treatment for 13min under the condition of 1200W ultrasonic power by using a cell ultrasonic crusher to obtain a water-kapok fiber suspension liquid with the mass concentration of 0.8%;
according to the water-kapok fiber suspension and NH4H2PO4The mass ratio of (1): 1, mixing the water-kapok fiber suspension with NH4H2PO4Mixing, and freezing and molding (at-50 ℃ for 72h) to obtain N, P codoped cellulose aerogel;
placing the N, P co-doped cellulose aerogel into a tube furnace, and carrying out carbonization treatment under the protection of nitrogen, wherein the nitrogen flow is 1000mL/min, and the carbonization treatment conditions are as follows: heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 2h, then heating to 800 ℃ at the speed of 5 ℃/min, and preserving heat for 2 h; after the carbonization treatment is finished, the nitrogen is removed, and CO is immediately introduced2Keeping the temperature at 800 ℃ for activation treatment for 2h with the flow rate of 450 mL/min; after the activation treatment, CO is added2And (4) after the reaction is removed, replacing nitrogen again, and naturally cooling to room temperature to obtain N, P co-doped carbon aerogel.
Example 3
Mixing 4g of kapok fiber, 4g of sodium hypochlorite, 0.25mL of glacial acetic acid, 200mL of water and 200mL of ethanol, stirring at the rotating speed of 500rpm for 1h, then adding 4g of sodium hypochlorite and 0.25mL of glacial acetic acid, and continuing to stir for 1 h; carrying out vacuum filtration on the obtained mixed system, and washing the obtained solid material to be neutral by using water to obtain pretreated fiber; mixing the pretreated fiber with water, and carrying out ultrasonic treatment for 15min under the condition of 1000W ultrasonic power by using a cell ultrasonic crusher to obtain a water-kapok fiber suspension with the mass concentration of 0.6%;
according to the water-kapok fiber suspension and NH4H2PO4The mass ratio of (1): 3, mixing the water-kapok fiber suspension with NH4H2PO4Mixing, and freezing and molding (at-55 ℃ for 72h) to obtain N, P co-doped cellulose aerogel;
putting the N, P codoped cellulose aerogel into a tubular furnace, and carrying out carbonization treatment under the protection of nitrogen, wherein the nitrogen flow is 1000mL/min, and the carbonized partThe physical conditions are as follows: heating to 350 ℃ at the speed of 2 ℃/min, preserving heat for 2h, then heating to 800 ℃ at the speed of 5 ℃/min, and preserving heat for 2 h; after the carbonization treatment is finished, the nitrogen is removed, and CO is immediately introduced2Keeping the temperature at 800 ℃ for activation treatment for 1.5h with the flow rate of 500 mL/min; after the activation treatment, CO is added2And (4) after the reaction is removed, replacing nitrogen again, and naturally cooling to room temperature to obtain N, P co-doped carbon aerogel.
Characterization and Performance testing
The N, P co-doped carbon aerogel prepared in the embodiment 1-3 is characterized and tested in performance, and the characteristics are as follows:
measuring the doping amount of N and P in N, P co-doped carbon aerogel by an XPS method;
measuring the mesoporous rate of the N, P co-doped carbon aerogel by adopting a nitrogen adsorption and desorption test method;
n, P co-doped carbon aerogel, Hg/HgO and Pt electrodes are respectively used as a working electrode, a reference electrode and a counter electrode, 6mol/L KOH aqueous solution is used as electrolyte, and the test is carried out under the current density of 1A/g, so that the specific capacitance of N, P co-doped carbon aerogel is obtained;
introducing a NaCl aqueous solution with the initial concentration of 500mg/L into a desalting device prepared from N, P co-doped carbon aerogel, and testing under the condition that the voltage is 1.4V to obtain the desalting amount of N, P co-doped carbon aerogel;
the test results are shown in Table 1.
TABLE 1 characterization and performance test results of N, P co-doped carbon aerogel prepared in examples 1-3
| Sample (I) | Example 1 | Example 2 | Examples3 |
| Amount of N to be doped (wt%) | 5.87 | 4.27 | 6.04 |
| Amount of P doped (wt%) | 3.55 | 3.07 | 3.73 |
| Mesoporosity (%) | 51.27 | 73.92 | 59.95 |
| Specific capacitance (F/g) | 314 | 367 | 275 |
| Amount of desalination (mg/g) | 26.40 | 28.39 | 24.89 |
To demonstrate the dual activation (i.e., use of NH during the carbonization process) of the present invention4H2PO4The first activation and the subsequent activation treatment as the second activation) were carried out, and carbon aerogel samples were prepared under the conditions of different amounts of ammonium dihydrogen phosphate added and carbon dioxide activation time, and the specific surface area and pore size distribution of each carbon aerogel sample were measured, as shown in table 2.
Table 2 shows the specific surface area and pore size distribution data of the carbon aerogel samples
In Table 2, the sample can be represented as NPxCAyWherein x represents the mass ratio of ammonium dihydrogen phosphate to the water-biomass fiber suspension, and y represents the carbon dioxide activation time (min); NP in Table 22CA90The samples were prepared according to example 1, NP3CA90The samples were prepared according to example 3, NP1CA120The samples were prepared according to the method of example 2, and the conditions were otherwise identical to those of example 2 except that x (mass ratio of ammonium dihydrogen phosphate to water-biomass fiber suspension) and y (carbon dioxide activation time) were selected according to the respective sample expressions.
As can be seen from Table 2, the amount of ammonium dihydrogen phosphate increased, and the specific surface area and the mesoporous rate of the carbon aerogel increased; the activation time of the carbon dioxide is prolonged, and the specific surface area and the mesoporous rate of the carbon aerogel are also increased. Wherein, NP0CA90Has a specific surface area of 435m2·g-1The mesoporous rate is only 25.06 percent, after being doped with ammonium dihydrogen phosphate, NP is1CA90To a specific surface area of 790m2·g-1The mesoporosity is increased to 34.81%; continued increase in carbon dioxide activation time, NP1CA120Increase the specific surface area to 1553m2·g-1The mesoporosity increased to 73.92%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of N, P codoped carbon aerogel is characterized by comprising the following steps:
pretreating biomass fibers by using pretreatment liquid containing sodium hypochlorite, glacial acetic acid, water and ethanol, mixing the obtained pretreated fibers with water, and then performing fiber opening treatment to obtain a water-biomass fiber suspension;
mixing the water-biomass fiber suspension with NH4H2PO4Mixing, and freezing and forming to obtain N, P co-doped cellulose aerogel;
and sequentially carrying out carbonization treatment and activation treatment on the N, P co-doped cellulose aerogel to obtain N, P co-doped carbon aerogel.
2. The preparation method of claim 1, wherein the biomass fiber comprises one or more of kapok fiber, pulp fiber, poplar fiber and cattail fiber.
3. The preparation method according to claim 1 or 2, wherein the use amount ratio of the biomass fibers to the sodium hypochlorite, the glacial acetic acid, the water and the ethanol in the pretreatment solution is (1-7) g: (1-14) g: (0.2-1.0) mL: (100-350) mL: (100-350) mL.
4. The production method according to claim 1, wherein the time for the opening treatment is 8 to 15 min; the fiber opening treatment is carried out under the ultrasonic condition, and the power of the ultrasonic is 1000-1600W.
5. The preparation method according to claim 1, wherein the mass concentration of the water-biomass fiber suspension is 0.4-1.0%, and the water-biomass fiber suspension is mixed with NH4H2PO4The mass ratio of (1): (1-4).
6. The preparation method according to claim 1, wherein the carbonization treatment is performed in a protective atmosphere, and comprises pre-carbonization and carbonization which are performed in sequence;
the temperature of the pre-carbonization is 300-500 ℃, and the heat preservation time is 1-3.5 h;
the carbonization temperature is 600-900 ℃, and the heat preservation time is 1-3 h.
7. The method according to claim 1 or 6, wherein the activation treatment is performed in an activation atmosphere, and an activation gas for providing the activation atmosphere includes CO2One or more of water vapor, flue gas, oxygen and air;
the temperature of the activation treatment is 600-900 ℃, and the heat preservation time is 0.5-3 h.
8. The N, P co-doped carbon aerogel prepared by the preparation method of any one of claims 1 to 7, which comprises carbon aerogel and N and P doped in the carbon aerogel.
9. The N, P codoped carbon aerogel according to claim 8, wherein the N, P codoped carbon aerogel contains N by mass in a range of 4.27-6.64% and P by mass in a range of 3.07-3.73%;
the mesoporous rate of the N, P co-doped carbon aerogel is 34.81-73.92%.
10. Use of N, P codoped carbon aerogel as claimed in claim 8 or 9 as an electrode material.
Priority Applications (1)
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