CN115020122A - Nitrogen-doped paper fiber porous carbon foam electrode material and preparation method and application thereof - Google Patents
Nitrogen-doped paper fiber porous carbon foam electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 79
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000003763 carbonization Methods 0.000 claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006261 foam material Substances 0.000 claims abstract description 27
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- 239000003990 capacitor Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 5
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- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
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- 239000006260 foam Substances 0.000 abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
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- 239000002033 PVDF binder Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
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- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
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- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Paper (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a nitrogen-doped paper fiber porous carbon foam electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding a surfactant solution into the fiber slurry for foaming treatment, and drying to obtain a paper fiber foam material; carrying out primary carbonization treatment to obtain a paper fiber foam material subjected to primary carbonization treatment; adding an activated pore-forming agent and a nitrogen source, and crushing and mixing to obtain mixed powder; carrying out secondary carbonization treatment to obtain a carbonized sample; adjusting to be neutral, and drying to obtain the nitrogen-doped paper fiber porous carbon foam electrode material. According to the invention, the foam framework is obtained through foaming treatment, the nitrogen-doped porous foamy carbon with a hierarchical porous structure is obtained through one-step carbonization/nitrogen doping/activation, and the preparation process has the advantages of low price, simplicity, convenience, environmental friendliness and the like, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of electrode materials with flexible porous structures, and particularly relates to a nitrogen-doped paper fiber porous carbon foam electrode material as well as a preparation method and application thereof.
Background
In recent years, with the gradual depletion of non-renewable energy sources such as petroleum, coal and the like, the development and utilization of green and sustainable energy sources are more and more emphasized, and the electrochemical energy storage technology is greatly researched and developed; among them, the super capacitor has high power density (10) 4 W kg -1 ) And the charge and discharge rate is high (10) -3 ～10 -6 s) and long cycle life (10) 5 Sub) and the like are widely researched and applied.
The carbon-based electrode material has the characteristics of wide source, light weight, high temperature resistance, good stability and conductivity, excellent cycling stability and rate capability, capacity of 80-90% after ten thousand times of charging and discharging, and suitability for being used as a supercapacitor electrode material. The specific capacitance of the common active carbon material is maintained to be about 100F/g and MnO is used 2 The typical metal oxide pseudocapacitance materials have larger difference, so that the energy density of the prepared super capacitor is lower (1-10 Wh kg) -1 ) The practical application of the carbon-based electrode material in many fields is limited, and the specific capacitance of the carbon-based electrode material can be greatly improved by changing the electrode structure.
The foam material macroscopically shows a three-dimensional reticular porous skeleton, has the special structural characteristics of large specific surface area, high porosity, interconnected transmission channels and the like, and the structure obviously increases the specific capacitance of the electrode material and enables electrolyte ions/electrons to be transmitted at high speed, so that the foam-based electrode has wide development prospect. The existing traditional method generally prepares the foam carbon-based electrode material by decomposing a carbon source on the surface of a hard template through chemical vapor deposition; the template-assisted method has the disadvantages of complicated synthesis process, special synthesis conditions, expensive metal templates (such as nickel foam metal) and the need of using a large amount of harmful chemical substances in the subsequent template removal step, and is difficult to meet the requirement of mass production.
Disclosure of Invention
The invention aims to provide a nitrogen-doped paper fiber porous carbon foam electrode material, and a preparation method and application thereof, so as to solve one or more technical problems. The preparation method of the invention takes paper products as raw materials, obtains the foam framework through foaming treatment, obtains the nitrogen-doped porous foam carbon with the hierarchical porous structure through one-step carbonization/nitrogen doping/activation, has the advantages of low price, simplicity, convenience, environmental protection and the like, and is suitable for large-scale production; in addition, electrochemical tests showed that: compared with the traditional activated carbon material, the electrode material prepared by the invention has improved specific capacity and rate performance and has good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nitrogen-doped paper fiber porous carbon foam electrode material, which comprises the following steps:
adding a surfactant solution into the fiber slurry for foaming treatment, and drying to obtain a paper fiber foam material; wherein the fiber pulp is prepared by taking a paper product as a raw material;
carrying out primary carbonization treatment on the paper fiber foam material to obtain a paper fiber foam material subjected to primary carbonization treatment;
adding an activated pore-forming agent and a nitrogen source into the paper fiber foam material subjected to the primary carbonization treatment, and crushing and mixing to obtain mixed powder;
performing secondary carbonization treatment on the mixed powder to obtain a carbonized sample;
and adjusting the carbonized sample to be neutral, and drying to obtain the nitrogen-doped paper fiber porous carbon foam electrode material.
The preparation method is further improved in that the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate, methyl isobutyl carbinol, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether sodium sulfate.
The preparation method is further improved in that the environment atmosphere during the primary carbonization treatment is one of nitrogen atmosphere, argon atmosphere and argon-hydrogen mixed gas atmosphere; and the environment atmosphere during the secondary carbonization treatment is one of nitrogen atmosphere, argon atmosphere and argon-hydrogen mixed gas atmosphere.
The preparation method is further improved in that the value range of the temperature during the primary carbonization treatment is 350-550 ℃; the value range of the temperature during the secondary carbonization treatment is 600-800 ℃.
The preparation method is further improved in that the temperature rise rate is 10 ℃/min or less during the primary carbonization treatment and the secondary carbonization treatment.
The preparation method is further improved in that the activated pore-forming agent is one or more of potassium carbonate, potassium hydroxide and zinc chloride.
The preparation method is further improved in that the nitrogen source is one or more of melamine, urea, polypyrrole and thiourea.
The nitrogen-doped paper fiber porous carbon foam electrode material prepared by any one of the preparation methods provided by the invention.
The invention provides application of a nitrogen-doped paper fiber porous carbon foam electrode material, and the nitrogen-doped paper fiber porous carbon foam electrode material is used for preparing an electrode of a super capacitor energy storage device.
The invention has the further improvement that the implementation steps of the nitrogen-doped paper fiber porous carbon foam electrode material for preparing the electrode of the supercapacitor energy storage device comprise:
mixing and grinding the nitrogen-doped paper fiber porous carbon foam electrode material, conductive carbon black and a binder to obtain slurry;
and coating the obtained slurry on a foamed nickel current collector, drying and pressing to obtain the electrode.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention is particularly a preparation method of a paper fiber porous carbon foam electrode material based on a biomass derived carbon material, wherein a paper product is taken as a raw material (exemplarily, waste paper, filter paper and the like), and a foaming agent is added for foaming treatment to obtain a foam framework; followed by one-step carbonization/nitrogen doping/activation to obtain nitrogen-doped porous carbon foam having a hierarchical porous structure (illustratively, micropores, mesopores, and macropores). In conclusion, the preparation process has the advantages of low cost, large-scale production, simplicity, convenience, environmental friendliness and the like, and realizes value-added utilization of resources. Further illustratively, the environmentally friendly, low cost method of the present invention avoids the use of template-assisted complex process flows and the subsequent removal of large amounts of harmful substances used by the template; the paper fiber subjected to carbonization treatment has good conductivity, and the electrochemical performance of the supercapacitor can be greatly improved; the paper fiber foam material generates more cross-linked micropores and mesoporous structures through the pore-forming effect of the activating agent, and the prepared paper fiber porous foam electrode material has better electrolyte ion transmission rate, reduces the transmission resistance of electrolyte ions/electrons, and obviously improves the power density of the supercapacitor. Meanwhile, the specific surface area of the material is increased, and the specific capacitance of the electrode material is obviously increased. In addition, electrochemical tests show that the nitrogen-doped paper fiber porous carbon foam electrode material prepared by the method is improved in specific capacity and rate performance compared with the traditional activated carbon material, and has good electrochemical performance.
The preparation method of the nitrogen-doped paper fiber porous carbon electrode disclosed by the embodiment of the invention is suitable for a super capacitor or a battery, the paper fiber material is used as a carbon source to prepare a carbon material with good conductivity, the nitrogen source is used for completing heteroatom doping and occupying pore forming in the activation/carbonization process, the formed porous foam structure reduces the transmission resistance of ions/electrons, the specific capacitance and rate capability of the electrode material are increased, and the electrode material of the high-performance advanced super capacitor is prepared by a more economical, simple, convenient and environment-friendly synthesis process.
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 are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow chart of a preparation method of a nitrogen-doped paper fiber porous carbon foam electrode material according to an embodiment of the invention;
FIG. 2 is a scanning electron microscope image of a paper fiber foam prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a paper fiber foam prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of a paper fiber foam prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of nitrogen-doped paper fiber carbon foam electrode material prepared in example 2 of the present invention;
FIG. 6 is a schematic diagram of three-electrode cyclic voltammetry tests of nitrogen-doped paper fiber carbon foam electrode materials prepared in example 2 of the present invention at different scan rates;
FIG. 7 is a schematic diagram of a constant current charge and discharge test of the nitrogen-doped paper fiber carbon foam electrode material prepared in example 2 of the present invention at different current densities;
FIG. 8 is a graph showing the rate capability of the specific capacitance of the nitrogen-doped paper fiber carbon foam electrode material prepared in example 2 of the present invention as a function of current density.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the process equipment or devices not specifically mentioned in the following examples are conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Referring to fig. 1, a method for preparing a nitrogen-doped paper fiber porous carbon foam electrode material according to an embodiment of the present invention includes the following steps:
(1) preparing fiber pulp by taking a paper product as a raw material; illustratively, the paper product may be waste paper or filter paper or the like;
(2) adding a pre-selected surfactant solution into the fiber slurry obtained in the step (1) to perform foaming treatment and drying treatment to obtain a paper fiber foam material; wherein the surfactant is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), sodium hexadecylbenzene sulfonate, methyl isobutyl carbinol (MIBC), sodium dodecyl sulfate (K12) and fatty alcohol polyoxyethylene ether sodium sulfate (AES);
(3) carrying out primary carbonization treatment on the paper fiber foam material obtained in the step (2) to obtain a paper fiber foam material subjected to primary carbonization treatment; adding an activating pore-forming agent and a nitrogen source into the paper fiber foam material subjected to the primary carbonization treatment, and crushing and mixing to obtain mixed powder; more specifically, the atmosphere of the primary carbonization treatment is nitrogen atmosphere and the like, the temperature is 350-550 ℃, and the heating rate is below 10 ℃/min; preferably, the temperature is selected to be 500 ℃;
(4) placing the mixed powder obtained in the step (3) at the temperature of 600-800 ℃ for secondary carbonization treatment to obtain a carbonized sample; the atmosphere during the secondary carbonization treatment is nitrogen atmosphere, argon atmosphere or argon-hydrogen mixed gas atmosphere; preferably, the temperature is selected to be 700 ℃; the heating rate is below 10 ℃/min;
(5) and (4) regulating the carbonized sample obtained in the step (4) to be neutral, and drying to obtain the nitrogen-doped paper fiber porous carbon foam electrode material (PFCFs).
According to the method provided by the embodiment of the invention, paper products (exemplarily, waste paper, filter paper and the like) are used as raw materials, and foaming agent is added for foaming treatment to obtain a foam framework; and then obtaining the nitrogen-doped porous foam carbon with a hierarchical porous structure (illustratively, micropores, mesopores and macropores) through one-step carbonization/nitrogen doping/activation, and the method is suitable for large-scale preparation.
According to the preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material provided by the embodiment of the invention, as the filter paper has longer fibers and is rich in wood fibers, the filter paper commonly used in laboratories can be selected as a raw material, and the preparation method specifically comprises the following steps:
the method comprises the following steps: cutting filter paper into strips, cleaning, soaking in deionized water for 24h, mixing with a dispersant solution, and performing defibering and dispersion treatment for 6h by using a stirrer to obtain fiber slurry; wherein the dispersant is one or more of sodium cellulose sulfate, sodium alkyl diphenyl ether sulfonate, sodium pyrophosphate, polyethylene oxide (PEO) and Polyacrylamide (PAM);
step two: adding a surfactant solution into the fiber slurry prepared in the step one for foaming treatment, and drying in a thermostat for 12 hours;
step three: pre-carbonizing the paper fiber foam material obtained in the step two in a nitrogen atmosphere at 350-550 ℃ (preferably 500 ℃) for 2 hours; using melamine as nitrogen source, K 2 CO 3 Fully grinding the three materials in a mortar to form powder for activating the pore-forming agent;
step four: placing the powder prepared in the third step into a tubular furnace again to be treated for 2 hours in a nitrogen atmosphere at 600-800 ℃ (preferably 700 ℃), and carrying out secondary carbonization; illustratively, the maximum temperature set for the activation/carbonization treatment of the tube furnace is 700 ℃, and the heating rate is 5 ℃/min;
step five: and (4) washing the sample carbonized in the fourth step to be neutral by using an HCl solution and deionized water, and drying in a thermostat for 12 hours to obtain the nitrogen-doped paper fiber porous carbon foam electrode material (PFCFs).
In the embodiment of the invention, the drying temperature range of the drying process in each step is 60-80 ℃, and the drying time is 12 h.
The nitrogen-doped paper fiber porous carbon foam electrode material prepared by the method disclosed by the embodiment of the invention can be applied to preparation of high-performance super capacitor energy storage equipment. In the application of the electrode material provided by the embodiment of the invention, PFCFs, conductive carbon black and a binder are mixed and fully ground by using a mortar to obtain slurry; and uniformly coating the obtained slurry on a foamed nickel current collector by using a scraper, drying and pressing to obtain the electrode. Exemplary, paper fiber carbon foam electrode materials, by mass ratio: conductive carbon black: binder 8: 1: 1; wherein the binder solution is prepared by dissolving polyvinylidene fluoride Powder (PVDF) in N-methyl pyrrolidone (NMP) solution; the drying temperature range is 60-80 ℃, and the treatment time is more than 6 h; the loading capacity of the slurry on the current collector is about 5-10 mg.
In conclusion, the embodiment of the invention adopts the method of preparing the paper fiber into the slurry for foaming to form the porous foam structure, the nitrogen doping/activating pore-forming process is completed in one step, and the process flow is greatly reduced; the method of the invention is environment-friendly and low-cost, and avoids the complex process flow assisted by the template and the subsequent removal of a large amount of harmful substances used by the template. The paper fiber treated by carbonization has good conductivity, and can greatly improve the electrochemical performance of the super capacitor. The paper fiber foam material generates more cross-linked micropores and mesoporous structures through the pore-forming effect of the activating agent, and the prepared paper fiber porous foam electrode material has better electrolyte ion transmission rate, reduces the transmission resistance of electrolyte ions/electrons, and obviously improves the power density of the supercapacitor. Meanwhile, the specific surface area of the material is increased, and the specific capacitance of the electrode material is obviously increased.
The nitrogen-doped paper fiber porous carbon foam electrode material prepared by the embodiment of the invention has the structural characteristics of three-dimensional porous interconnected network structure, high specific surface area and the like, and is simple in synthesis step and low in cost. The application of the method in preparing the super capacitor can obviously improve the energy density and the power density, can still keep good electrochemical performance after a plurality of charging and discharging processes, and obviously enhance the cycle stability and the specific capacitance.
Example 1
The preparation method of the nitrogen-doped paper fiber porous carbon electrode provided by the embodiment of the invention comprises the following steps:
firstly, cutting a filter paper sample into thin strips, immersing the thin strips into water, and fluffing for 6 hours by a mechanical stirrer at 600r/min to obtain dispersed filter paper fiber slurry;
mixing the filter paper fiber slurry obtained in the step I with 0.2 mass percent of SDBS foaming agent solution, carrying out 2000r/min foaming treatment on the mixture for 10min by using a mechanical stirrer to form compact paper fiber foam, and drying the foam for 12h in an oven at the temperature of 60 ℃; a scanning electron microscope image of the paper fiber foam is shown in fig. 2;
thirdly, the paper fiber foam material obtained in the second step is processed at the temperature of 500 ℃ and N 2 The pre-carbonization treatment is carried out for 2h in the atmosphere, and the heating rate is 3 ℃/min. Subsequently with melamine K 2 CO 3 The ground powders were mixed together. The mixed mass ratio of the three components is as follows: pre-carbonized sample: melamine: k is 2 CO 3 ＝1：1/4：4；
And fourthly, putting the powder obtained in the third step into a tubular furnace to be carbonized for 2 hours at the temperature of 600 ℃ in the nitrogen atmosphere, and obtaining the paper fiber porous carbon foam electrode material with the heating rate of 3 ℃/min.
Example 2
The preparation method of the nitrogen-doped paper fiber porous carbon electrode provided by the embodiment of the invention comprises the following steps:
firstly, cutting a filter paper sample into thin strips, immersing the thin strips into water, and fluffing for 6 hours by a mechanical stirrer at 600r/min to obtain dispersed filter paper fiber slurry;
secondly, mixing the filter paper fiber slurry obtained in the first step with 0.35 mass percent of SDBS foaming agent solution, carrying out 2000r/min foaming treatment on the mixture for 10min by using a mechanical stirrer to form compact paper fiber foam, and drying the foam for 12h at the temperature of 60 ℃ in an oven; a scanning electron microscope image of the paper fiber foam is shown in fig. 2;
thirdly, the paper fiber foam material obtained in the step two is processed at 500 ℃, N 2 The pre-carbonization treatment is carried out for 2h in the atmosphere, and the heating rate is 5 ℃/min. Subsequently with melamine K 2 CO 3 Mixing the ground powder together; the mixed mass ratio of the three components is as follows: pre-carbonized sample: melamine: k is 2 CO 3 ＝1：1/3：4；
Fourthly, the porous carbon foam electrode material of the paper fiber is obtained by putting the porous carbon foam electrode material of the paper fiber in a tubular furnace for carbonization treatment for 2h at 700 ℃ in nitrogen atmosphere and at the heating rate of 5 ℃/min.
Example 3
The preparation method of the nitrogen-doped paper fiber porous carbon electrode provided by the embodiment of the invention comprises the following steps:
firstly, cutting a filter paper sample into thin strips, immersing the thin strips into water, and fluffing for 6 hours by a mechanical stirrer at 600r/min to obtain dispersed filter paper fiber slurry;
secondly, mixing the filter paper fiber slurry obtained in the first step with 0.5 mass percent of SDBS foaming agent solution, carrying out 2000r/min foaming treatment on the mixture for 10min by using a mechanical stirrer to form compact paper fiber foam, and drying the foam for 12h at the temperature of 60 ℃ in an oven; a scanning electron microscope image of the paper fiber foam is shown in fig. 4;
thirdly, the paper fiber foam material obtained in the second step is processed at the temperature of 500 ℃ and N 2 The pre-carbonization treatment is carried out for 2h in the atmosphere, and the heating rate is 10 ℃/min. Subsequently with melamine K 2 CO 3 The ground powders were mixed together. The mixed mass ratio of the three components is as follows: pre-carbonized sample: melamine: k 2 CO 3 ＝1：1/2：4；
Fourthly, placing the porous carbon foam electrode material obtained in the third step in a tubular furnace for carbonization treatment for 2 hours at 800 ℃ in nitrogen atmosphere, wherein the heating rate is 10 ℃/min, and obtaining the paper fiber porous carbon foam electrode material.
Referring to fig. 2 to 4, fig. 2 to 4 show scanning electron micrographs of the paper fiber foam materials prepared in examples 1 to 3, which show that the mass fractions of different foaming agent solutions are different from each other in the foam structure formed by foaming the paper fiber material; wherein, the paper fiber foam material prepared in example 2 (mass fraction of the SDBS foaming agent solution is 0.35%) has uniform cells, dense fiber connection, large pores divided into more smaller pores, and distinct foam structure composed of staggered pores at each level, thereby determining the optimal mass fraction of the foaming agent solution.
The nitrogen-doped paper fiber porous carbon foam electrode materials prepared in examples 1 to 3 of the present invention all have excellent electrochemical properties and a clear porous interconnected foam structure, and the following takes the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2 as an example to conduct a study on the electrochemical properties, and specific study methods and results are as follows, as shown in fig. 5 to 8.
Preparing a positive electrode material: the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2, conductive agent conductive carbon black and binder polyvinylidene fluoride are mixed according to a mass ratio of 8: 1: 1, mixing and grinding to obtain homogeneous black slurry, coating the black slurry on the surface of the foamed nickel washed by ethanol and deionized water, drying and pressing to obtain a positive electrode material; and (3) carrying out electrochemical performance test on the three-electrode system: a three-electrode system is formed by taking a Pt sheet as a counter electrode, Hg/HgO as a reference electrode and the positive electrode material as a working electrode. The electrochemical stations for carrying out the test were CHI660E, which were placed together in a 6mol/L KOH concentrated solution.
Referring to fig. 5, fig. 5 shows a scanning electron microscope image of the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2 of the present invention, and it can be seen that K is 2 CO 3 Has obvious activating and pore-forming functions, and forms a three-dimensional foam structure with a large number of open pores.
Referring to fig. 6, fig. 6 shows a three-electrode cyclic voltammetry test chart of the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2 of the present invention, wherein the CV curve maintains a good rectangular-like shape after the scan rate is increased, which indicates that the capacitance generated by the electrode material is an electric double layer capacitance and has excellent rate capability.
Referring to fig. 7, fig. 7 is a constant current charging and discharging curve of the nitrogen-doped paper fiber porous carbon foam electrode material prepared in embodiment 2 of the present invention under different current densities, the tested voltage window is-1 to 0V, and the formula is shown
(wherein C is specific capacitance, F/g; I is discharge current, A; DeltaV is voltage window, V; Deltat is discharge time, s; m is mass of electrode material, g.) the specific capacitance of the electrode material reaches 199.36F/g under the current density of 0.1A/g.
Referring to fig. 8, fig. 8 is a graph showing rate performance of the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2 of the present invention. When the current density is increased by 40 times (20A/g), the specific capacitance is still kept at 140F/g, and the capacity retention rate is 70.2%. In conclusion, after the electrode material is subjected to carbonization, activation and modification treatment of nitrogen doping, the microstructure presents a porous interconnected foam skeleton, and excellent electrochemical performance is shown.
Example 4
The preparation method of the nitrogen-doped paper fiber porous carbon electrode provided by the embodiment of the invention comprises the following steps:
adding a surfactant solution into the fiber slurry for foaming treatment, and drying to obtain a paper fiber foam material; wherein the fiber pulp is prepared by taking a paper product as a raw material;
carrying out primary carbonization treatment on the paper fiber foam material to obtain a paper fiber foam material subjected to primary carbonization treatment;
adding an activating pore-forming agent and a nitrogen source into the paper fiber foam material subjected to the primary carbonization treatment, and crushing and mixing to obtain mixed powder;
performing secondary carbonization treatment on the mixed powder to obtain a carbonized sample;
adjusting the carbonized sample to be neutral, and drying to obtain the nitrogen-doped paper fiber porous carbon foam electrode material;
wherein the surfactant is sodium dodecyl benzene sulfonate and sodium hexadecyl benzene sulfonate; the environment atmosphere during the primary carbonization treatment is argon atmosphere; the environment atmosphere during the secondary carbonization treatment is argon atmosphere; the value range of the temperature during the primary carbonization treatment is 350 ℃; the value range of the temperature during the secondary carbonization treatment is 600 ℃; the temperature rise rate is 10 ℃/min during the primary carbonization treatment and the secondary carbonization treatment; the activating pore-forming agent is potassium carbonate, potassium hydroxide and zinc chloride; the nitrogen source is melamine, urea, polypyrrole and thiourea.
Example 5
The preparation method of the nitrogen-doped paper fiber porous carbon electrode in the embodiment of the invention is only different from the embodiment 4 in that the surfactant is sodium dodecyl sulfate; the environment atmosphere during the primary carbonization treatment is argon-hydrogen mixed gas atmosphere; the environment atmosphere during the secondary carbonization treatment is argon-hydrogen mixed gas atmosphere; the value range of the temperature during the primary carbonization treatment is 450 ℃; the value range of the temperature during the secondary carbonization treatment is 700 ℃; the temperature rise rate is 8 ℃/min during the primary carbonization treatment and the secondary carbonization treatment; the activating pore-forming agent is potassium hydroxide; the nitrogen source is urea.
Example 6
The preparation method of the nitrogen-doped paper fiber porous carbon electrode provided by the embodiment of the invention is only different from the preparation method of the embodiment 4 in that the surfactant is methyl isobutyl carbinol, sodium dodecyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate; the environment atmosphere during the primary carbonization treatment is a nitrogen atmosphere; the environment atmosphere during the secondary carbonization treatment is a nitrogen atmosphere; the value range of the temperature during the primary carbonization treatment is 550 ℃; the value range of the temperature during the secondary carbonization treatment is 800 ℃; the temperature rise rate is 3 ℃/min during the primary carbonization treatment and the secondary carbonization treatment; the activating pore-forming agent is potassium hydroxide and zinc chloride; the nitrogen source is polypyrrole and thiourea.
In summary, the embodiment of the invention provides a preparation method of a nitrogen-doped paper fiber porous carbon foam electrode material, and belongs to the technical field of porous structure electrode materials of three-dimensional interconnected networks. A template auxiliary method is usually needed for manufacturing a traditional porous foam structure, the process flow is complex, and a large amount of harmful chemical reagents are needed to be used when the template is removed, so that the relevant processes of electrode manufacturing and foaming are combined, a method combining mechanical foaming and activation treatment by adopting a surfactant is provided, and the paper fiber porous carbon foam electrode material is prepared simply, conveniently and environmentally; the long fiber has good conductivity, and a porous foam structure is obtained after activation, carbonization and foaming treatment. The biomass-derived carbon-based material is applied to the field of supercapacitors, and shows large specific surface area and good conductivity. The large specific surface area provides higher specific capacitance of the electrode material and high loading capacity of the active material; the hierarchical porous carbon foam structure reduces resistance for transmission of ions/electrons, and improves the cycle stability and rate capability of the energy storage device. The invention provides a new idea for preparing high-performance electrode materials, and the prepared electrode materials have excellent electrochemical properties such as high specific capacitance, good cycle stability and the like.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material is characterized by comprising the following steps of:
adding a surfactant solution into the fiber slurry for foaming treatment, and drying to obtain a paper fiber foam material; wherein the fiber pulp is prepared by taking a paper product as a raw material;
carrying out primary carbonization treatment on the paper fiber foam material to obtain a paper fiber foam material subjected to primary carbonization treatment;
adding an activating pore-forming agent and a nitrogen source into the paper fiber foam material subjected to the primary carbonization treatment, and crushing and mixing to obtain mixed powder;
performing secondary carbonization treatment on the mixed powder to obtain a carbonized sample;
and adjusting the carbonized sample to be neutral, and drying to obtain the nitrogen-doped paper fiber porous carbon foam electrode material.
2. The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material according to claim 1, wherein the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate, methyl isobutyl carbinol, sodium dodecyl sulfate and sodium fatty alcohol polyoxyethylene ether sulfate.
3. The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material as claimed in claim 1, wherein the environment atmosphere during the primary carbonization treatment is one of a nitrogen atmosphere, an argon atmosphere and an argon-hydrogen mixed gas atmosphere; and the environment atmosphere during the secondary carbonization treatment is one of nitrogen atmosphere, argon atmosphere and argon-hydrogen mixed gas atmosphere.
4. The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material according to claim 1, wherein the temperature during the primary carbonization treatment ranges from 350 ℃ to 550 ℃; the value range of the temperature during the secondary carbonization treatment is 600-800 ℃.
5. The method for preparing the nitrogen-doped paper fiber porous carbon foam electrode material according to claim 4, wherein the temperature rise rate during the primary carbonization treatment and the secondary carbonization treatment is below 10 ℃/min.
6. The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material according to claim 1, wherein the activating pore-forming agent is one or more of potassium carbonate, potassium hydroxide and zinc chloride.
7. The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material according to claim 1, wherein the nitrogen source is one or more of melamine, urea, polypyrrole and thiourea.
8. A nitrogen-doped paper fiber porous carbon foam electrode material prepared by the preparation method of any one of claims 1 to 7.
9. The application of the nitrogen-doped paper fiber porous carbon foam electrode material as claimed in claim 8, wherein the nitrogen-doped paper fiber porous carbon foam electrode material is used for preparing an electrode of a super capacitor energy storage device.
10. The application of the nitrogen-doped paper fiber porous carbon foam electrode material as claimed in claim 9, wherein the implementation step of the nitrogen-doped paper fiber porous carbon foam electrode material for preparing the electrode of the supercapacitor energy storage device comprises the following steps:
mixing and grinding the nitrogen-doped paper fiber porous carbon foam electrode material, conductive carbon black and a binder to obtain slurry;
and coating the obtained slurry on a foamed nickel current collector, drying and pressing to obtain the electrode.
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