CN115020122B - 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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- 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
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- 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
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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
- H01G11/30—Electrodes characterised by their material
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- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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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- 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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- Y02E60/13—Energy storage using capacitors
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; performing primary carbonization treatment to obtain paper fiber foam materials after primary carbonization treatment; adding an activated pore-forming agent and a nitrogen source, crushing and mixing to obtain mixed powder; performing secondary carbonization treatment to obtain a carbonized sample; and (3) adjusting to be neutral, and drying to obtain the nitrogen-doped paper fiber porous carbon foam electrode material. The invention obtains the foam skeleton through foaming treatment, obtains the nitrogen doped porous foam carbon with a hierarchical porous structure through one-step carbonization/nitrogen doping/activation, and the preparation process has the advantages of low cost, simplicity, environmental protection and the like, and is suitable for mass production.
Description
Technical Field
The invention belongs to the technical field of soft porous structure electrode materials, and particularly relates to a nitrogen-doped paper fiber porous carbon foam electrode material, and a preparation method and application thereof.
Background
In recent years, with the gradual exhaustion of non-renewable energy sources such as petroleum, coal and the like, development and utilization of green and sustainable energy sources are increasingly emphasized, and electrochemical energy storage technologies are greatly researched and developed; wherein the super capacitor has high power density (10 4 W kg -1 ) Fast charge and discharge rate (10) -3 ～10 -6 s) and long cycle life (10) 5 Secondary) and the like, and the advantages of the method are widely researched and applied.
The carbon-based electrode material has the characteristics of wide sources, light weight, high temperature resistance, good stability and good conductivity,the cycling stability and the multiplying power performance are excellent, the capacity can still be kept 80-90% after tens of thousands of times of charge and discharge, and the material is suitable for being used as an electrode material of a super capacitor. The specific capacitance of the general active carbon material is maintained at about 100F/g, and MnO is used 2 The metal oxide pseudocapacitance materials represented are quite different, resulting in lower energy densities of the supercapacitor produced (1-10 Wh kg -1 ) Limiting its practical application in many fields, the specific capacitance of carbon-based electrode materials can be greatly improved by changing the electrode structure.
The foam material macroscopically shows a three-dimensional net-shaped porous framework, has the special structural characteristics of large specific surface area, high porosity, interconnected transmission channels and the like, and the structure remarkably 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 prior traditional method generally decomposes a carbon source to the surface of a hard template by chemical vapor deposition to prepare a foam carbon-based electrode material; however, such a template-assisted method has disadvantages in that complicated synthesis processes, special synthesis conditions, expensive metal templates (nickel foam metal, etc.), and a large amount of harmful chemicals are required for the subsequent step of removing the templates, and thus it is difficult to satisfy the requirement of mass production.
Disclosure of Invention
The invention aims to provide a nitrogen-doped paper fiber porous carbon foam electrode material, a preparation method and application thereof, so as to solve one or more of the technical problems. The preparation method of the invention takes paper products as raw materials, obtains a foam skeleton through foaming treatment, obtains the nitrogen-doped porous foam carbon with a hierarchical porous structure through one-step carbonization/nitrogen doping/activation, has the advantages of low cost, simplicity, environmental protection and the like, and is suitable for mass production; in addition, the electrochemical test showed that: compared with the traditional active carbon material, the electrode material prepared by the invention has improved specific capacity and rate capability, and has good electrochemical performance.
In order to achieve the above 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 slurry is prepared by taking paper products as raw materials;
performing 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 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 regulating 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 hexadecyl benzene sulfonate, methyl isobutyl carbinol, sodium dodecyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate.
The preparation method is further improved in that the environmental atmosphere during primary carbonization treatment is one of nitrogen atmosphere, argon atmosphere and argon-hydrogen mixed gas atmosphere; 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 heating rate is below 10 ℃/min 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.
A further improvement of the preparation method of the invention is 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 is prepared.
The invention provides an application of a nitrogen-doped paper fiber porous carbon foam electrode material, which is used for preparing an electrode of a super capacitor energy storage device.
The invention further improves that the realization steps of the nitrogen-doped paper fiber porous carbon foam electrode material for preparing the supercapacitor energy storage device electrode comprise:
mixing and grinding the nitrogen-doped paper fiber porous carbon foam electrode material with conductive carbon black and a binder to obtain slurry;
the obtained slurry is coated on a foam nickel current collector, dried and pressed to obtain the electrode.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention is specifically a preparation method of a paper fiber porous carbon foam electrode material based on a biomass derived carbon material, wherein paper products (exemplified by waste paper, filter paper and the like) are used as raw materials, and a foaming agent is added for foaming treatment to obtain a foam skeleton; the nitrogen-doped porous carbon foam having a hierarchical porous structure (explanatory, micropores, mesopores and macropores) is then obtained by one-step carbonization/nitrogen doping/activation. In conclusion, the preparation process provided by the invention has the advantages of low cost, mass production, simplicity, convenience, environmental protection and the like, and realizes the value-added utilization of resources. Further illustratively, the above-described environmentally friendly, low cost method of the present invention avoids the use of complex process flows aided by templates and the subsequent removal of a substantial amount of harmful substances used by templates; the carbonized paper fiber has good conductivity, and can greatly improve the electrochemical performance of the supercapacitor; the paper fiber foam material generates more crosslinking micropores and mesopore 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 super capacitor. 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 compared with the traditional active carbon material, the nitrogen-doped paper fiber porous carbon foam electrode material prepared by the invention has improved specific capacity and rate capability, 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 preparing a carbon material with good conductivity by taking a paper fiber material as a carbon source of a supercapacitor or a battery, the nitrogen source finishes heteroatom doping and occupying space for pore-forming in the activation/carbonization process, the formed porous foam structure reduces the transmission resistance of ions/electrons, increases the specific capacitance and the multiplying power performance of the electrode material, and the electrode material of the high-performance advanced supercapacitor is prepared by a more economic, simple, convenient and environment-friendly synthesis process.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description of the embodiments or the drawings used in the description of the prior art will make a brief description; it will be apparent to those of ordinary skill in the art that the drawings in the following description are of some embodiments of the invention and that other drawings may be derived from them without undue effort.
FIG. 1 is a schematic flow chart of a method for preparing 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 a nitrogen-doped paper fiber carbon foam electrode material prepared in example 2 of the present invention;
FIG. 6 is a schematic diagram of a three-electrode cyclic voltammetry test of a nitrogen-doped paper fiber carbon foam electrode material prepared in example 2 of the present invention at different scan rates;
FIG. 7 is a schematic diagram of 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 schematic view showing the rate performance of the nitrogen-doped paper fiber carbon foam electrode material prepared in example 2 according to the present invention in terms of the change of specific capacitance with current density.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are to be understood as being illustrative of the invention and not limiting the scope of the invention.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the process equipment or devices not specifically identified in the examples below are all conventional in the art.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present invention does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
Referring to fig. 1, a method for preparing a nitrogen-doped paper fiber porous carbon foam electrode material according to an embodiment of the invention includes the following steps:
(1) Preparing fiber slurry by taking paper products as raw materials; illustratively, the paper product may be waste paper or filter paper, etc.;
(2) Adding a preselected surfactant solution into the fiber slurry prepared in the step (1) for 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 hexadecyl benzene sulfonate, methyl isobutyl carbinol (MIBC), sodium dodecyl sulfate (K12) and sodium fatty alcohol polyoxyethylene ether sulfate (AES);
(3) Performing 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 activated pore-forming agent and nitrogen source into the paper fiber foam material subjected to primary carbonization treatment, crushing and mixing to obtain mixed powder; more specifically, the primary carbonization treatment atmosphere is nitrogen atmosphere, 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 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 temperature rising rate is below 10 ℃/min;
(5) And (3) 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 (exemplified, waste paper, filter paper and the like) are taken as raw materials, and a foaming agent is added for foaming treatment to obtain a foam skeleton; the nitrogen-doped porous carbon foam with a hierarchical porous structure (explanatory, micropores, mesopores and macropores) is then obtained by one-step carbonization/nitrogen doping/activation, and is suitable for large-scale preparation.
The preparation method of the nitrogen-doped paper fiber porous carbon foam electrode material provided by the embodiment of the invention can select common filter paper in a laboratory as a raw material because the filter paper has longer fibers and is rich in wood fibers, and specifically comprises the following steps:
step one: cutting filter paper into strips, cleaning, soaking in deionized water for 24 hours, mixing with a dispersing agent solution, and carrying out fluffing and dispersing treatment for 6 hours by using a stirrer to obtain fiber slurry; wherein the dispersing agent is one or more of cellulose sodium sulfate, sodium alkyl diphenyl ether sulfonate, sodium pyrophosphate, polyethylene oxide (PEO) and Polyacrylamide (PAM);
step two: adding the fiber slurry prepared in the first step into a surfactant solution for foaming treatment, and drying in a constant temperature oven for 12 hours;
step three: firstly, pre-carbonizing the paper fiber foam material obtained in the second step for 2 hours in a nitrogen atmosphere with the temperature of 350 ℃ -550 ℃ (preferably, 500 ℃); melamine is used as nitrogen source, K 2 CO 3 For activating the pore-forming agent, fully grinding the three materials in a mortar to form powder;
step four: placing the powder prepared in the third step into a tube furnace again to be treated for 2 hours in a nitrogen atmosphere with the temperature of 600 ℃ -800 ℃ (preferably 700 ℃), and carrying out secondary carbonization; the highest temperature set by the tube furnace for activation/carbonization treatment is 700 ℃ and the heating rate is 5 ℃/min;
step five: and (3) flushing the carbonized sample in the step four with HCl solution and deionized water to be neutral, and drying in an incubator for 12 hours to obtain the nitrogen-doped paper fiber porous carbon foam electrode material (PFCFs).
In the embodiment of the invention, the drying process of the oven is needed in each step, the drying temperature range is 60-80 ℃ and the drying time is 12 hours.
The nitrogen-doped paper fiber porous carbon foam electrode material prepared by the method can be applied to the preparation of high-performance supercapacitor energy storage equipment. In the application of the electrode material of the embodiment of the invention, the PFCFs, the conductive carbon black and the binder are mixed and fully ground by using a mortar to obtain slurry; and uniformly coating the obtained slurry on a foam nickel current collector by using a scraper, drying and pressing to obtain the electrode. Exemplary, in mass ratio, paper fiber carbon foam electrode material: conductive carbon black: binder = 8:1:1, a step of; wherein the binder solution is prepared by dissolving polyvinylidene fluoride Powder (PVDF) in N-methylpyrrolidone (NMP) solution; the drying temperature range is 60-80 ℃ and the treatment time is more than 6 hours; the loading of the slurry on the current collector is about 5 to 10mg.
In summary, the embodiment of the invention adopts the method of foaming the pulp made of paper fiber to form a 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 in cost, and avoids complex process flow assisted by the template and a large amount of harmful substances used for removing the template subsequently. The carbonized paper fiber has good conductivity, and can greatly improve the electrochemical performance of the supercapacitor. The paper fiber foam material generates more crosslinking micropores and mesopore 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 super capacitor. 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 a three-dimensional porous interconnection network structure, high specific surface area and the like, and has simple synthesis steps and low cost. The method can be applied to the preparation of the super capacitor, can remarkably improve the energy density and the power density, can still keep good electrochemical performance after repeated charge and discharge processes, and remarkably enhances 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:
(1) cutting the filter paper sample into strips, immersing the strips in water, and carrying out fluffing treatment for 6 hours by a mechanical stirrer 600r/min to obtain dispersed filter paper fiber slurry;
(2) mixing the filter paper fiber slurry obtained in the step (1) with an SDBS foaming agent solution with the mass fraction of 0.2%, performing foaming treatment for 10min by a mechanical stirrer 2000r/min to form a dense paper fiber foam, and performing drying treatment for 12h at the temperature of a baking oven at the temperature of 60 ℃; a scanning electron microscope image of the paper fiber foam is shown in fig. 2;
(3) the paper fiber foam material obtained in the step (2) is processed at 500 ℃ and N 2 The pre-carbonization treatment is carried out for 2 hours in the atmosphere, and the heating rate is 3 ℃/min. Then with melamine, K 2 CO 3 The ground powders were mixed together. The mass ratio of the three components is as follows: pre-carbonized samples: melamine: k (K) 2 CO 3 ＝1：1/4：4；
(4) And (3) placing the powder obtained in the step (3) in a nitrogen atmosphere in a tube furnace, carbonizing at 600 ℃ for 2 hours, and heating at a rate of 3 ℃/min to obtain the paper fiber porous carbon foam electrode material.
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:
(1) cutting the filter paper sample into strips, immersing the strips in water, and carrying out fluffing treatment for 6 hours by a mechanical stirrer 600r/min to obtain dispersed filter paper fiber slurry;
(2) mixing the filter paper fiber slurry obtained in the step (1) with an SDBS foaming agent solution with the mass fraction of 0.35%, performing foaming treatment for 10min by a mechanical stirrer 2000r/min to form a dense paper fiber foam, and performing drying treatment for 12h at the temperature of a baking oven at the temperature of 60 ℃; a scanning electron microscope image of the paper fiber foam is shown in fig. 2;
(3) the paper fiber foam material obtained in the step (2) is processed at 500 ℃ and N 2 The pre-carbonization treatment is carried out for 2 hours in the atmosphere, and the heating rate is 5 ℃/min. Then with melamine, K 2 CO 3 Mixing and grinding the powder; the mass ratio of the three components is as follows: pre-carbonized samples: melamine: k (K) 2 CO 3 ＝1：1/3：4；
(4) And (3) carbonizing the paper fiber porous carbon foam electrode material obtained in the step (3) in a nitrogen atmosphere in a tube furnace at 700 ℃ for 2 hours at a 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:
(1) cutting the filter paper sample into strips, immersing the strips in water, and carrying out fluffing treatment for 6 hours by a mechanical stirrer 600r/min to obtain dispersed filter paper fiber slurry;
(2) mixing the filter paper fiber slurry obtained in the step (1) with an SDBS foaming agent solution with the mass fraction of 0.5%, performing foaming treatment for 10min by a mechanical stirrer 2000r/min to form a dense paper fiber foam, and performing drying treatment for 12h at the temperature of a baking oven at the temperature of 60 ℃; a scanning electron microscope image of the paper fiber foam is shown in fig. 4;
(3) the paper fiber foam material obtained in the step (2) is processed at 500 ℃ and N 2 The pre-carbonization treatment is carried out for 2 hours in the atmosphere, and the heating rate is 10 ℃/min. Then with melamine, K 2 CO 3 The ground powders were mixed together. The mass ratio of the three components is as follows: pre-carbonized samples: melamine: k (K) 2 CO 3 ＝1：1/2：4；
(4) And (3) carbonizing the paper fiber porous carbon foam electrode material obtained in the step (3) in a nitrogen atmosphere in a tube furnace at 800 ℃ for 2 hours at a heating rate of 10 ℃/min.
Referring to fig. 2 to 4, fig. 2 to 4 show scanning electron microscope images of the paper fiber foam materials prepared in the above examples 1 to 3, which show that the foam structures formed by foaming the paper fiber materials are greatly different by using different mass fractions of the foaming agent solutions; wherein, the paper fiber foam material prepared in the embodiment 2 (the mass fraction of the SDBS foaming agent solution is 0.35%) has uniform cells, more dense fiber connection and large holes divided into more smaller holes, and all levels of holes are mutually staggered to form an obvious foam structure, so that the mass fraction of the optimal foaming agent solution is determined.
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 clear porous interconnection foam structures, and the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2 is taken as an example for the study of electrochemical properties, and specific study methods and results are as follows, as shown in fig. 5 to 8.
Preparation of a positive electrode material: the nitrogen-doped paper fiber porous carbon foam electrode material prepared in example 2, conductive carbon black as a conductive agent and polyvinylidene fluoride as a binder are mixed according to the mass ratio of = 8:1:1, mixing and grinding to obtain homogeneous black slurry, coating the black slurry on the surface of foam nickel subjected to ethanol and deionized water cleaning treatment, drying and pressing to obtain a positive electrode material; the three-electrode system performs electrochemical performance test: the Pt sheet is used as a counter electrode, hg/HgO is used as a reference electrode, and the positive electrode material is used as a working electrode to form a three-electrode system. The materials are placed together in a KOH concentrated solution with electrolyte of 6mol/L, and an electrochemical workstation for testing is CHI660E.
Referring to FIG. 5, FIG. 5 shows a scanning electron microscope image of a porous carbon foam electrode material of nitrogen-doped paper fiber prepared in example 2 of the present invention, and it can be seen that K 2 CO 3 Has obvious activation 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, and the CV curve still 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 shows constant current charge-discharge curves of the porous carbon foam electrode material of the nitrogen-doped paper fiber prepared in example 2 of the present invention under different current densities, the voltage window tested is-1 to 0V, and the test results are shown by the formula(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 reaches 199 at a current density of 0.1A/g.36F/g。
Referring to fig. 8, fig. 8 is a graph showing the 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 was increased by 40 times (20A/g), the specific capacitance remained at 140F/g, and the capacity retention was 70.2%. In conclusion, after carbonization, activation and nitrogen doping modification treatment, the microstructure of the electrode material presents a porous interconnected foam skeleton, and the electrode material has excellent electrochemical performance.
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 slurry is prepared by taking paper products as raw materials;
performing 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 primary carbonization treatment, and crushing and mixing to obtain mixed powder;
performing secondary carbonization treatment on the mixed powder to obtain a carbonized sample;
regulating the carbonized sample to be neutral, and drying to obtain a nitrogen-doped paper fiber porous carbon foam electrode material;
wherein the surfactant is sodium dodecyl benzene sulfonate and sodium hexadecyl benzene sulfonate; the environmental atmosphere during the primary carbonization treatment is argon atmosphere; the environment atmosphere in 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 heating rate is 10 ℃/min during the primary carbonization treatment and the secondary carbonization treatment; the activated 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 provided by the embodiment of the invention is different from that of the embodiment 4 only in that the surfactant is sodium dodecyl sulfate; the environmental atmosphere during the primary carbonization treatment is an argon-hydrogen mixed gas atmosphere; the environment atmosphere during the secondary carbonization treatment is an 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 heating 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 different from that of the embodiment 4 only in that the surfactant is methyl isobutyl carbinol, sodium dodecyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate; the environmental atmosphere during the primary carbonization treatment is nitrogen atmosphere; the environmental atmosphere during the secondary carbonization treatment is 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 heating 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 interconnection networks. The traditional porous foam structure is manufactured by a template auxiliary method, the process flow is complex, and a large amount of harmful chemical reagents are needed to be used when the template is removed later, so that the related processes of electrode manufacturing and foaming are combined, and a method for combining the mechanical foaming of a surfactant and the activation treatment is provided, so that the paper fiber porous carbon foam electrode material is prepared more simply and environmentally-friendly; the long fiber has good conductivity, and the porous foam structure is obtained after activation, carbonization and foaming treatment. The biomass-derived carbon-based material is applied to the field of super capacitors, and has larger specific surface area and good conductivity. The large specific surface area provides higher specific capacitance of the electrode material and high active material loading; the hierarchical porous carbon foam structure reduces resistance for ion/electron transmission and improves the cycle stability and rate capability of the energy storage device. The invention provides a new thought for preparing the high-performance electrode material, and the prepared electrode material has 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 aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (4)
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 slurry is prepared by taking paper products as raw materials;
performing 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 primary carbonization treatment, and crushing and mixing to obtain mixed powder;
performing secondary carbonization treatment on the mixed powder to obtain a carbonized sample;
regulating the carbonized sample to be neutral, and drying to obtain a nitrogen-doped paper fiber porous carbon foam electrode material;
wherein the environmental atmosphere during the primary carbonization treatment is one of nitrogen atmosphere, argon atmosphere and argon-hydrogen mixed gas atmosphere; the environment atmosphere during the secondary carbonization treatment is one of nitrogen atmosphere, argon atmosphere and argon-hydrogen mixed gas atmosphere; 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 heating rate is below 10 ℃/min during the primary carbonization treatment and the secondary carbonization treatment;
the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, methyl isobutyl carbinol, sodium dodecyl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate; the activated pore-forming agent is one or more of potassium carbonate, potassium hydroxide and zinc chloride; the nitrogen source is one or more of melamine, urea, polypyrrole and thiourea.
2. A nitrogen-doped paper fiber porous carbon foam electrode material prepared by the preparation method of claim 1.
3. Use of the nitrogen-doped paper fiber porous carbon foam electrode material according to claim 2 for preparing an electrode of a supercapacitor energy storage device.
4. The use of a nitrogen-doped paper fiber porous carbon foam electrode material according to claim 3, wherein the implementation step of the nitrogen-doped paper fiber porous carbon foam electrode material for preparing an electrode of a supercapacitor energy storage device comprises:
mixing and grinding the nitrogen-doped paper fiber porous carbon foam electrode material with conductive carbon black and a binder to obtain slurry;
the obtained slurry is coated on a foam nickel current collector, dried and pressed to obtain the electrode.
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