CN111704133A - Preparation method of self-supporting porous carbon electrode material - Google Patents
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 238000007581 slurry coating method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a self-supporting porous carbon electrode material, and belongs to the technical field of electrode material preparation. The specific method comprises the following steps: dissolving acrylamide, N' -methylene bisacrylamide, sodium carboxymethyl cellulose, potassium tetraborate and a chemical activating agent in water to obtain a mixed solution, adding an initiator, carrying out free radical polymerization at 65-75 ℃ to obtain hydrogel, freeze-drying the hydrogel to obtain dry gel, and carbonizing, washing and drying the dry gel to obtain the self-supporting porous carbon electrode material. The self-supporting porous carbon material is obtained by the steps of free radical polymerization, freeze drying, carbonization and the like from an acrylamide micromolecule raw material, the structure and the performance of the prepared porous carbon can be conveniently regulated and controlled through reaction conditions, the preparation process is simple and convenient and easy to control, and the obtained porous carbon electrode material has large specific surface area and excellent capacitance performance.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a preparation method of a self-supporting porous carbon electrode material.
Background
Energy crisis and environmental pollution are two major challenges facing human beings, and the development and utilization of new energy are gold keys for solving the two major problems. However, new energy sources such as solar energy and wind energy generally have the characteristic of large volatility, and a high-efficiency energy storage and conversion device is the key for utilizing the new energy sources. The super capacitor is one of the most potential new energy storage devices, and has many advantages of high power density, rapid charge and discharge, long cycle life, etc. The research on the electrode material with excellent performance has important significance for the development of the super capacitor.
The carbon material has the advantages of good conductivity, stable chemical property and the like, and is the most widely used electrode material of the super capacitor at present. A wide variety of carbon-rich substances are used in the preparation of carbon electrode materials, including carbon nanotubes, graphene, phenolic resins, biomass, and the like. Although carbon nanotubes have excellent physical and chemical properties, the relatively small specific surface area limits the application of the carbon nanotubes as high-performance supercapacitor electrode materials; graphene is very easy to stack among layers due to strong inter-layer van der waals force, so that the actual specific capacitance is low, and the expensive price is also an important obstacle for limiting the application of graphene; the preparation of the carbon aerogel by the phenolic resin is deeply researched, however, the pore structure of the carbon aerogel is very sensitive to the pH value of a reaction system in the synthetic process of the phenolic resin, the pH value is required to be accurately controlled when the carbon aerogel with a specific structure is synthesized, the preparation difficulty is increased, and the strong toxicity of the phenolic resin synthetic raw material is very unfavorable for environmental protection; the preparation of the porous carbon electrode material by the biomass attracts much attention, but the composition and the structure of the biomass are greatly influenced by source and individual difference, so that the performance stability of the prepared porous carbon material is difficult to ensure. Therefore, research on the preparation of high-performance carbon-based electrode materials by a novel carbon source and a simple and easily-controlled method becomes an important topic of research on supercapacitors.
On the other hand, most of the porous carbon materials with high specific surface area prepared at present are powdery, and compared with powdery carbon materials, the self-supporting carbon materials have remarkable advantages. The self-supporting porous carbon material has certain mechanical strength, can keep a certain shape without depending on any support, is more convenient in electrode manufacturing, does not need to add a binder or a slurry coating mode, and avoids large contact resistance caused by the binder and other additives, reduction of effective contact area of an active material and electrolyte and other adverse factors. In addition, the self-supporting porous carbon material also provides favorable conditions for loading the pseudocapacitance material on the surface of the pseudocapacitance material. There have been some disclosures in the prior art relating to self-supporting porous carbon materials, such as: the Chinese patent with application number 201611192154.0 discloses a preparation method of self-supporting mesoporous carbon, which comprises the steps of taking a self-supporting sheet MFI molecular sieve as a hard template, dissolving furfural and oxalic acid in ethanol, drying, pre-carbonizing and carbonizing to obtain a self-supporting mesoporous carbon material; the Chinese invention patent with the application number of 201710175633.X discloses a preparation method of self-supporting flexible nitrogen-doped carbon sponge, which is prepared by one-step pyrolysis by taking commercial melamine sponge as a raw material; the Chinese invention patent with the application number of 201910383857.9 discloses a preparation method of a self-supporting porous carbon electrode loaded with a two-dimensional material, wherein the self-supporting porous carbon is prepared by directly carbonizing wood with a natural pore structure, such as Phoebe nankinensis. In the preparation process of the self-supporting porous carbon, a template agent is generally required to be used, so the preparation and removal steps of the template agent are involved in the process, and the process is relatively complicated, and the structure and the performance of the porous carbon are difficult to regulate and control because the porous carbon is prepared by directly carbonizing commercial self-supporting high polymer materials or biomass.
Disclosure of Invention
The invention aims to solve the defects in the background technology and provides a preparation method of a self-supporting porous carbon electrode material. The preparation method does not use a template agent, does not need complex steps of preparing and removing the template agent, and overcomes the defect that the structure and the performance of the porous carbon are difficult to regulate and control by directly carbonizing the commercial self-supporting high polymer material or the biomass.
Technical scheme
According to the method, acrylamide is used as a raw material, gel is obtained through acrylamide free radical polymerization, a chemical activating agent and potassium tetraborate are added into a reaction system before polymerization, so that the chemical activating agent and the potassium tetraborate are uniformly embedded in the gel, porous carbon is obtained through high-temperature carbonization, and the prepared porous carbon is self-supporting due to the addition of the potassium tetraborate. The preparation method of the self-supporting porous carbon realizes carbonization and activation in one step, the process is simple, and the prepared porous carbon is self-supporting, has large specific surface area and excellent capacitance performance. The specific scheme is as follows:
a preparation method of a self-supporting porous carbon electrode material comprises the following steps:
(1) preparation of hydrogel: uniformly mixing acrylamide, N' -methylene bisacrylamide, sodium carboxymethyl cellulose, a chemical activating agent, potassium tetraborate tetrahydrate and water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen for half an hour, adding an initiator, and reacting at 65-75 ℃ for 1-4 hours to obtain hydrogel;
(2) carbonization of the gel: and (3) freeze-drying the obtained hydrogel to obtain xerogel, and then carbonizing, washing and drying the xerogel to obtain the self-supporting porous carbon electrode material.
In the step (1), the mass ratio of acrylamide, N' -methylene bisacrylamide, sodium carboxymethylcellulose, a chemical activating agent, potassium tetraborate tetrahydrate and water is 0.02-0.1: 0.002-0.015: 0-0.03: 0-0.1: 0.01-0.15: 1, preferably 0.03-0.06: 0.002-0.008: 0.008-0.012: 0.03-0.06: 1.
Further, in the step (1), the chemical activating agent is selected from KOH, NaOH and K2CO3、Na2CO3Or KHCO3One or a combination of two or more of them at an arbitrary ratio.
Further, in the step (1), the initiator is potassium persulfate or ammonium persulfate.
Further, in the step (1), the dosage of the initiator is 1-6% of the mass of the acrylamide.
Further, in the step (2), the carbonization is performed in N2The reaction is carried out in the atmosphere at the temperature of 700 ℃ and 1000 ℃ for 1-3 h.
The reaction principle of the invention is as follows: the composite gel is prepared through free radical polymerization, acrylamide is used as a monomer, N, N' -methylene bisacrylamide is used as a cross-linking agent, sodium carboxymethyl cellulose is used as a modifier, a chemical activating agent and potassium tetraborate are added into a reaction system before polymerization, hydrogel is gradually formed along with the progress of the polymerization reaction, the chemical activating agent and the potassium tetraborate are embedded in a gel matrix in situ, then dry gel is obtained through cold freeze drying, and the dry gel is subjected to high-temperature carbonization, water washing, drying and other steps to obtain the porous carbon. Because the gel contains the chemical activator, the activation of the porous carbon is realized simultaneously in the high-temperature carbonization process, the potassium tetraborate added into the gel improves the skeleton strength of the porous carbon, and the prepared porous carbon is self-supporting.
The invention has the following beneficial effects:
(1) the invention discloses a novel method for preparing porous carbon by taking acrylamide as a carbon source and through free radical polymerization gelation and high-temperature carbonization.
(2) Free radical polymerization reaction of acrylamide is basically not affected by KOH and K2CO3And the like, so that the chemical activator can be directly added into a polymerization reaction system and embedded in the formed gel, thereby synchronously completing the activation of the porous carbon in the high-temperature carbonization process.
(3) The potassium tetraborate is added into the gel, so that the prepared porous carbon is self-supporting and is beneficial to further modification and application of the porous carbon.
(4) The prepared porous carbon has large specific surface area which can reach 3500m2The specific capacitance per gram is good, and the mass specific capacitance at the current density of 0.5A/g can reach 370F/g.
Drawings
FIG. 1 is a photograph of self-supporting porous carbon electrode materials prepared in example 1 and comparative example 1;
FIG. 2 is a scanning electron micrograph of the porous carbon electrode material obtained in example 4.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the embodiments and the accompanying drawings. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
A preparation method of a self-supporting porous carbon electrode material comprises the following steps:
(1) preparation of hydrogel: 0.36g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.01g of sodium carboxymethylcellulose, 0.30g of potassium tetraborate tetrahydrate and 9.0g of water are stirred and mixed uniformly to form a uniform solution, nitrogen is introduced to remove oxygen for half an hour, then 10mg of ammonium persulfate (dissolved in 1.0g of water) is added in sequence, and the reaction is carried out for 2 hours at 70 ℃ to obtain the hydrogel.
(2) Carbonization of the gel: and (3) freeze-drying the obtained hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ under the condition of nitrogen, and washing and drying to obtain the porous carbon material.
The self-supporting porous carbon material prepared by the method has the specific surface area of 486.2m2And/g, when the charge-discharge current density is 0.5A/g, the specific capacitance is 210.1F/g.
Comparative example 1
The procedure was the same as in example 1 except that the amount of potassium tetraborate tetrahydrate was changed to 0g in this example.
The specific surface area of the prepared porous carbon electrode material is 153.4m2And/g, when the charge-discharge current density is 0.5A/g, the specific capacitance is 104.5F/g.
Example 2
The procedure was the same as in example 1 except that the amount of potassium tetraborate tetrahydrate was changed to 0.10g in this example.
The specific surface area of the prepared porous carbon electrode material is 325.8m2And/g, when the charge-discharge current density is 0.5A/g, the specific capacitance is 180.6F/g.
Example 3
The procedure was the same as in example 1 except that the amount of potassium tetraborate tetrahydrate was changed to 0.50g in this example.
The specific surface area of the prepared porous carbon electrode material is 513.9m2And a specific capacitance of 223.2F/g when the charge-discharge current density is 0.5A/g.
Fig. 1 is a photograph of the porous carbon electrode materials prepared in example 1 and example 1, wherein fig. 1a is the porous carbon electrode material prepared in comparative example 1, and fig. 1b is the porous carbon electrode material prepared in example 1, as can be seen from the test results of fig. 1 and comparative example 1, examples 1 to 3: the porous carbon prepared without adding the potassium tetraborate tetrahydrate is in a collapsed state and cannot keep the original appearance of the polymer gel, while the porous carbon prepared by adding the potassium tetraborate tetrahydrate keeps the original appearance of the polymer gel and is self-supporting, and the addition of the potassium tetraborate tetrahydrate improves the capacitance performance of the prepared porous carbon.
Example 4
A preparation method of a self-supporting porous carbon electrode material comprises the following steps:
(1) preparation of hydrogel: 0.36g of acrylamide, 0.04g N, N' -methylene bisacrylamide, 0.01g of sodium carboxymethylcellulose, 0.30g of potassium tetraborate tetrahydrate and 0.50g of K2CO3And 9.0g of water are stirred and mixed uniformly to obtain a mixed solution, nitrogen is introduced to remove oxygen for half an hour, then 10mg of ammonium persulfate (dissolved in 1.0g of water) is added, and the reaction is carried out for 2 hours at 70 ℃ to obtain the hydrogel.
(2) Carbonization of the gel: and (3) freeze-drying the obtained hydrogel to obtain dry gel, carbonizing the dry gel for 2 hours at 800 ℃ under the condition of nitrogen, and washing and drying to obtain the porous carbon electrode material.
Fig. 2 is a scanning electron microscope image of the porous carbon electrode material prepared in example 4, and it can be seen from fig. 2 that the porous carbon is composed of interconnected carbon walls and has a rich pore structure.
The self-supporting porous carbon material prepared by the method has the specific surface area of 3398.3m2And/g, the specific capacitance is 362.7F/g when the charge-discharge current density is 0.5A/g.
Example 5
The procedure is as in example 4, except that K is changed2CO3Amount of addition of (D), this exampleIn, K2CO3The amount added was 0.1 g.
The specific surface area of the prepared porous carbon electrode material is 1223.9m2And/g, when the charge-discharge current density is 0.5A/g, the specific capacitance is 256.6F/g.
Example 6
The procedure is as in example 4, except that K is changed2CO3In this example, K2CO3The amount added was 0.3 g.
The specific surface area of the prepared porous carbon electrode material is 2652.7m2And/g, when the charge-discharge current density is 0.5A/g, the specific capacitance is 298.4F/g.
Example 7
The procedure is as in example 4, except that K is changed2CO3In this example, K2CO3The amount added was 0.7 g.
The specific surface area of the prepared porous carbon electrode material is 3501.9m2And/g, the specific capacitance is 372.4F/g when the charge-discharge current density is 0.5A/g.
From the test results of example 1 and examples 4-7, it can be seen that: k2CO3Has good activating effect, and is accompanied by K2CO3The addition amount is increased, the specific surface area of the prepared porous carbon is increased, and the capacitance performance is improved.
In conclusion, the invention provides a novel method for preparing self-supporting porous carbon by taking acrylamide as a raw material. Because the free radical polymerization reaction of the acrylamide is basically not influenced by the added alkaline activator, the activator, other modifiers and the monomer can be mixed to form a uniform solution before polymerization, so that the chemical activator and other modifiers can be uniformly embedded in the polyacrylamide gel, the activation of the porous carbon is realized simultaneously during high-temperature carbonization, and the preparation process of the porous carbon is simplified. Meanwhile, the potassium tetraborate added into the polyacrylamide gel enables the three-dimensional skeleton of the gel to be kept stable in the carbonization process, and the prepared porous carbon is self-supporting and provides convenience for application and further modification of the porous carbon.
The present invention is not limited to the above embodiments, and those skilled in the art can make various equivalent changes and substitutions without departing from the principle of the present invention after learning the content of the present invention, and these equivalent changes and substitutions should be considered as belonging to the protection scope of the present invention.
Claims (6)
1. The preparation method of the self-supporting porous carbon electrode material is characterized by comprising the following steps:
(1) preparation of hydrogel: uniformly mixing acrylamide, N' -methylene bisacrylamide, sodium carboxymethyl cellulose, a chemical activating agent, potassium tetraborate tetrahydrate and water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen, adding an initiator, and reacting at 65-75 ℃ for 1-4 hours to obtain hydrogel;
(2) carbonization of the gel: freeze-drying the obtained hydrogel to obtain xerogel, and then carbonizing, washing and drying the xerogel to obtain the self-supporting porous carbon electrode material;
in the step (1), the mass ratio of acrylamide, N' -methylene bisacrylamide, sodium carboxymethyl cellulose, chemical activating agent, potassium tetraborate tetrahydrate and water is 0.02-0.1: 0.002-0.015: 0-0.03: 0-0.1: 0.01-0.15: 1.
2. The preparation method of the self-supporting porous carbon electrode material as claimed in claim 1, wherein in the step (1), the mass ratio of the acrylamide, the N, N' -methylenebisacrylamide, the sodium carboxymethylcellulose, the chemical activator, the potassium tetraborate tetrahydrate and the water is 0.03-0.06: 0.002-0.008: 0.008-0.012: 0.03-0.06: 1.
3. The method for preparing a self-supporting porous carbon electrode material according to claim 1, wherein in step (1), the chemical activator is selected from KOH, NaOH, K2CO3、Na2CO3Or KHCO3One or more than two of them at any ratioExample combinations.
4. The method for preparing a self-supporting porous carbon electrode material according to claim 1, wherein in step (1), the initiator is potassium persulfate or ammonium persulfate.
5. The preparation method of the self-supporting porous carbon electrode material as claimed in claim 1, wherein in the step (1), the amount of the initiator is 1-6% by mass of the acrylamide.
6. The method for preparing a self-supporting porous carbon electrode material according to any one of claims 1 to 5, wherein in step (2), the carbonization is performed in N2The reaction is carried out in the atmosphere at the temperature of 700 ℃ and 1000 ℃ for 1-3 h.
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| CN112919460A (en) * | 2021-01-29 | 2021-06-08 | 北京理工大学 | Self-supporting porous carbon electrode material |
| CN113764680A (en) * | 2021-07-28 | 2021-12-07 | 中山大学 | High-activity carbon-based electrode material for microbial fuel cell and preparation method and application thereof |
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| CN106698415A (en) * | 2016-12-29 | 2017-05-24 | 陈大明 | High-strength carbon foam (CF) material and preparation method thereof |
| CN110562951A (en) * | 2019-09-03 | 2019-12-13 | 聊城大学 | preparation method of polyacrylamide hydrogel-based nitrogen-doped porous carbon |
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| CN106698415A (en) * | 2016-12-29 | 2017-05-24 | 陈大明 | High-strength carbon foam (CF) material and preparation method thereof |
| CN110562951A (en) * | 2019-09-03 | 2019-12-13 | 聊城大学 | preparation method of polyacrylamide hydrogel-based nitrogen-doped porous carbon |
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| CN113764680B (en) * | 2021-07-28 | 2023-08-22 | 中山大学 | High-activity carbon-based electrode material for microbial fuel cell, and preparation method and application thereof |
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