CN114477170A - Method for improving intrinsic performance and recycling of biomass derived carbon material - Google Patents
Method for improving intrinsic performance and recycling of biomass derived carbon material Download PDFInfo
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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
- C01B32/318—Preparation characterised by the starting materials
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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
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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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention discloses a method for improving intrinsic performance and recycling of a biomass-derived carbon material, and belongs to the technical field of energy materials. Washing and drying biomass materials, grinding the biomass materials into powder, mixing the powder, zinc salt and water, drying the mixture to be colloidal, carrying out pyrolysis treatment in an inert atmosphere, soaking the obtained carbon powder in an acid solution, washing the carbon powder to be neutral by deionized water, mixing the obtained carbon powder with the deionized water, carrying out ultrasonic treatment, and carrying out centrifugal drying; and (3) preparing the obtained carbon material into an electrode, evaluating the electrochemical performance, taking the carbon material off the supporting electrode, putting the electrode into an ultrasonic reactor for ultrasonic treatment, and centrifugally drying to complete regeneration. The method provided by the invention has the advantages of simple operation, low cost, short experimental period, strong controllability, excellent electrochemical performance and good reproducibility, and shows wide application prospect.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a method for improving intrinsic performance and recycling of a biomass-derived carbon material.
Background
With the rapid development of global economy, the demand for energy is increasing day by day, and the use of a large amount of traditional fossil energy such as coal, oil, natural gas and the like causes irreversible change of the environment on one hand, and leads to serious energy crisis easily caused by overuse on the other hand. In view of the above problems, on one hand, energy is saved and the utilization efficiency thereof needs to be improved, and on the other hand, scientific and technical workers are prompted to actively research and develop green and environment-friendly renewable energy technologies, such as fuel cells, electrolytic water, metal-air batteries, supercapacitors, solar energy, wind energy and the like.
Oxygen Reduction Reaction (ORR) is an extremely important electrode Reaction in the field of energy conversion and energy storage technologies such as fuel cells, metal-air batteries, and electrolysis of water. However, the kinetics of the oxygen reduction reaction are generally slow, and a large amount of noble metal catalyst such as Pt or Ir is required to improve the reaction activity, which not only increases the cost of the catalyst and severely limits the large-scale use of the catalyst, but also is easy to poison and deactivate the noble metal catalyst. Therefore, it is an urgent problem to develop a novel catalyst material with low cost, high activity and high stability to reduce the dependence on noble metals such as platinum.
Compared with the catalyst of low noble metal and non-noble metal, the metal-free porous carbon material has the advantages of good conductivity, high stability, adjustable porosity, morphology and functionality and the like, and shows stronger competitive advantages, but the original ecological carbon has poorer adsorption/activation performance on oxygen and ORR intermediates, and the original ecological carbon needs to be modified in order to improve the ORR activity of the original ecological carbon. In 2009, Dai et al prepared nitrogen-doped carbon nanotube arrays by chemical vapor deposition, and the catalysts, no matter the ORR electron transfer number, limiting current, initial potential, etc., were comparable to commercial Pt/C in alkaline medium. Many research results show that the regulation of sp2 carbon can obviously improve the ORR activity, and at present, three modes of doping of non-metal heterogeneous elements, charge transfer between physical molecules such as polymer functionalized graphene and manufacturing of structural defects are commonly adopted. Due to the difference of electronegativity, atomic size and combination state, the heterogeneous element doping can refine spin and charge distribution, improve hydrophilicity/hydrophobicity and adjust the absorption capacity of the ORR intermediate, and is combined with pore channels with different lengths to greatly promote mass transfer in the reaction process, and the synergistic effects can obviously improve the ORR catalytic performance of sp2 carbon, so that the non-metal heterogeneous element doping is concerned more widely in three regulation and control modes. Among many heteroatom-doped carbon materials, although carbon nanotubes, carbon nanocages, graphene, etc., which have an attractive nanostructure and are functionalized, exhibit good ORR catalytic performance, the production of the above carbon nanomaterials is heavily dependent on fossil fuel precursors (such as CH4, phenol, and pitch) and harsh or energy-intensive synthesis conditions (such as arc discharge, chemical vapor deposition, and laser ablation, etc., and thus environmental damage is still unavoidable. Mainly contains protein and mineral substances. Depending on the source of the biomass carbon material, it can be broadly summarized as nano biomass carbon (including glucose and cellulose derivatives, starch, chitin/chitosan, lignin), lignocellulose biomass carbon (including soybean, coconut shell, fruit peel, eggplant, etc.), animal-based biomass carbon material (such as feather, silk, hair, bone, blood, egg, sludge, leather, etc.) and other biomass carbon materials derived from carbohydrates and polysaccharides. The ORR activity of the porous carbon is closely related to the number of active centers, and the number of the active centers is related to the type and content of heteroatoms, so that the main strategy for improving the ORR activity of the carbon material is to (1) prepare a nano carbon material with large specific surface area and rich porous structure; (2) doping the heteroatom to generate more active sites; (3) increasing the degree of graphitization increases its electrical conductivity. N is the most common heteroatom, and most biomasses are rich in this element. It is noted that during carbonization, heteroatoms in the biomass are easily lost. From the reported diffraction patterns of biomass-derived carbon materials, the heteroatoms appear to be uniformly distributed, however, they are all at a relatively low heteroatom content, reducing their ORR performance. One common approach to this problem is to introduce additional heteroatoms into the carbon materials, and research in this area has focused primarily on introducing additional heteroatoms into the carbon materials to improve their ORR performance. Compared with the mode of additionally introducing the heteroatoms, the method has more important significance on how to improve the inherent surface heteroatom content, fully exert the inherent ORR advantages and increase the recycling performance.
Disclosure of Invention
In view of the above, the present invention provides a method for simply and conveniently improving intrinsic properties and recycling of biomass-derived carbon materials without introducing foreign heteroatoms in order to further improve activity and recycling of biomass-derived carbon materials.
In order to realize the purpose, the invention adopts the following technical scheme:
a method of increasing the intrinsic properties of a biomass-derived carbon material, the method comprising the steps of:
(1) washing the biomass material with deionized water, drying and grinding into powder;
(2) mixing the powder obtained in the step (1), zinc salt and water, drying the mixture to be colloidal at 50-90 ℃, pyrolyzing the mixture for 1-6 hours at 700-1000 ℃ in an inert atmosphere, cooling the mixture, soaking the obtained carbon powder in an acid solution for 2-24 hours, and washing the carbon powder to be neutral by using deionized water;
(3) mixing the carbon powder obtained in the step (2) with deionized water, and putting the mixture into an ultrasonic reactor for ultrasonic treatment;
(4) and (4) placing the sample obtained in the step (3) into a centrifuge for centrifugal treatment, and drying.
Further, the biomass material in the step (1) comprises dried beancurd sticks, spinach, pollen and bamboo fungi; the drying temperature is 40-60 ℃, and the particle size of the powder is 20-200 meshes.
Further, the zinc salt in the step (2) comprises zinc chloride, zinc sulfate and zinc nitrate, and the weight ratio of the powder, the zinc salt and the water is 0.2: 1: 10-3: 1: between 50; the inert atmosphere comprises argon, helium and nitrogen.
Further, the acidic solution in the step (2) comprises a sulfuric acid solution, a hydrochloric acid solution and a nitric acid solution, and the concentration of the acidic solution is 0.1-2M.
Further, the weight ratio of the carbon powder to the deionized water in the step (3) is 1: 50-1: 200, the parameters of the sonication were as follows: the power is 100-500 w; the magnetic stirring speed is 100-1000 rpm; the reaction time is 1-8 h, wherein the total time of ultrasonic energy collection is 100-1200 seconds.
Further, the conditions of the centrifugation treatment of the step (4) are as follows: the centrifugal speed is 4000rpm, and the centrifugal time is 5-30 min.
In one aspect, the invention provides a carbon material prepared by the above method.
In another aspect, the invention provides the use of the carbon material in fuel cells, supercapacitors and metal-air batteries.
Further, the carbon material is used as an electrode material.
The invention also provides a method for recycling the carbon material, wherein the carbon material is prepared into an electrode for electrochemical performance evaluation, the carbon material is taken off from the support electrode after testing, and then the carbon material is placed into an ultrasonic reactor for ultrasonic treatment, and the regeneration is completed after centrifugal drying.
Further, the parameters of the sonication were as follows: the power is 100-500 w; the magnetic stirring speed is 100-1000 rpm; the reaction time is 1-8 h, wherein the total time of ultrasonic energy collection is 100-1200 seconds.
Further, the electrolyte used in the evaluation of electrochemical properties was O2Saturated 0.1MKOH solution, evaluated in a potentiodynamic polarization curve (potential range)0.8V-0.4V vs. SCE, a scanning speed of 10mV/s, a rotating speed of 400-2500 rpm), and cyclic voltammetry (a potential range of-0.8V-0.4V vs. SCE, a scanning speed of 20 mV/s).
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the biomass in the presence of the pore-forming agent is subjected to high-temperature pyrolysis, then is subjected to ultrasonic reaction kettle and treatment centrifugation, and the content of high-content heteroatoms is increased by stripping the low-content heteroatom part on the surface, so that the intrinsic activity of the biomass derived carbon material is improved, and the sample subjected to cyclic test can basically recover the performance after being subjected to ultrasonic reaction kettle and centrifugation treatment, thereby realizing regeneration;
(2) the method provided by the invention has the advantages of simple operation, low cost, short experimental period, strong controllability, excellent electrochemical performance and good reproducibility. The biomass derived carbon material prepared by the method can be used as an excellent ORR catalyst material for a fuel cell, an electrode material for a super capacitor and a metal air battery, and a catalyst carrier material, and shows wide application prospects.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
Fig. 1 is SEM images before and after sonication of porous carbon prepared using dried beancurd stick in example 1, wherein (a) to (c) are SEM images of 50K times, 10K times, and 1K times, respectively, of the porous carbon before sonication, and (d) to (f) are SEM images of 50K times, 10K times, and 1K times, respectively, of the porous carbon after sonication.
Fig. 2 is SEM images of porous carbon prepared by using lettuce pollen in example 2 before and after ultrasonication, wherein (a) to (c) are SEM images of the porous carbon before ultrasonication at 50K times, 10K times, and 1K times, respectively, and (d) to (f) are SEM images of the porous carbon after ultrasonication at 50K times, 10K times, and 1K times, respectively.
Fig. 3 is SEM images of the porous carbon prepared using spinach of example 3 before and after ultrasonication, wherein (a) to (c) are SEM images of the porous carbon before ultrasonication at 50K times, 10K times, and 1K times, respectively, and (d) to (f) are SEM images of the porous carbon after ultrasonication at 50K times, 10K times, and 1K times, respectively.
Fig. 4 is a test chart of electrochemical properties of the porous carbon prepared in example 1, in which (a) is a cyclic voltammetry test chart and (b) is a linear voltammetry electrochemical test chart.
FIG. 5 is a test chart of electrochemical properties of porous carbon prepared in example 2, wherein (a) is a cyclic voltammetry test chart, and (b) is a linear voltammetry electrochemical test chart.
Fig. 6 is a test chart of electrochemical properties of the porous carbon prepared in example 3, in which (a) is a cyclic voltammetry test chart and (b) is a linear voltammetry electrochemical test chart.
Fig. 7 is a potentiodynamic polarization curve before and after cycle testing of the porous carbon derived from dried beancurd stick prepared in example 1 and after ultrasonic centrifugation treatment, wherein Y-850 represents the polarization curve of the porous carbon prepared in example 1, ADT represents the polarization curve of the porous carbon after 5000 cycles of cyclic voltammetry scanning accelerated aging testing, and ADT-U represents the polarization curve of the porous carbon immediately after ultrasonic and centrifugation double process treatment after accelerated aging testing.
FIG. 8 is a zeta potential polarization curve before and after the cycle test and after the ultrasonic centrifugation treatment of the spinach-derived carbon material prepared in example 3, wherein S-850 represents the polarization curve of the porous carbon prepared in example 3, ADT represents the polarization curve of the porous carbon after 5000 cycles of cyclic voltammetry scan accelerated aging test, and ADT-U represents the polarization curve of the porous carbon after the accelerated aging test and then subjected to the ultrasonic and centrifugation double process treatment.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
the drugs used in this example: zinc chloride, sulfuric acid, dried beancurd sticks, absolute ethyl alcohol and deionized water.
A method for improving intrinsic activity of biomass-derived carbon material mainly comprises the following steps:
(1) cleaning the purchased biomass material dried bean curd sticks with deionized water, removing dust on the surface, drying and dehydrating the cleaned material in a drying oven at 60 ℃, and grinding the dried material into powder for later use;
(2) mixing and stirring 2g of dried bean milk cream, 4g of zinc chloride and 100ml of deionized water at normal temperature for 12 hours, and then putting the mixed liquid into a drying oven at 60 ℃ for drying for 12 hours until the mixed liquid is brown black colloid;
(3) putting the brown black colloid in the step (2) into a tube furnace, introducing nitrogen, heating to 850 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 2 hours to obtain black solid powder;
(4) grinding the black solid powder obtained in the step (3), wherein the ground powder is at 0.5mol/L H2SO4Pickling for 12 h;
(5) washing the solution in the step (4) by using deionized water, centrifuging until the pH value of the supernatant solution is 7, washing by using absolute ethyl alcohol, and centrifuging once to obtain a precipitate; the centrifugation speed is 4000rpm, and the centrifugation time is 10 min;
(6) putting the precipitate obtained in the step (5) into a drying oven at 60 ℃ for drying for 12h to obtain a dried bean curd stick carbon powder sample;
(7) mixing 0.5g of carbon powder obtained in the step (6) with 60ml of deionized water, and putting the mixture into an ultrasonic reactor for ultrasonic treatment, wherein the ultrasonic power is 300W, the ultrasonic time is 10h, the ultrasonic energy gathering time is 4h, and the rotating speed is 400 rpm;
(8) putting the sample obtained in the step (7) into a centrifuge for centrifugal treatment, and drying solid powder to obtain an ultrasonic dried bean curd stick carbon powder sample; the centrifugation rate was 4000rpm and the centrifugation time was 10 min.
Compared with a sample which is not subjected to ultrasonic and centrifugal treatment, the small protruding materials attached to the surface part of the carbon particles on the sample subjected to ultrasonic and centrifugal treatment are obviously reduced, higher-content heteroatoms are improved, and the improvement of ORR activity is facilitated.
Example 2:
the drugs used in this example: zinc chloride, sulfuric acid, pollen, absolute ethyl alcohol and deionized water.
A method for improving intrinsic activity of biomass-derived carbon material mainly comprises the following steps:
(1) cleaning the purchased biological material lettuce pollen with deionized water to remove dust on the surface, drying and dehydrating the washed material in a drying oven, and grinding the dried material into powder for later use;
(2) mixing and stirring 2g of lettuce pollen powder, 4g of zinc chloride and 100ml of deionized water for 12 hours, and then putting the mixed liquid into a drying oven at 70 ℃ for drying for 12 hours until the mixed liquid is brown black colloid;
(3) putting the brown black colloid in the step (2) into a tube furnace, introducing nitrogen, heating to 850 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h to obtain black solid powder;
(4) grinding the black solid powder obtained in the step (3), wherein the ground powder is 0.5mol/L H2SO4Pickling for 12 h;
(5) washing the solution in the step (4) by using deionized water, centrifuging until the pH value of the supernatant solution is 7, washing by using absolute ethyl alcohol, and centrifuging once to obtain a precipitate; the centrifugation speed is 4000rpm, and the centrifugation time is 10 min;
(6) putting the precipitate obtained in the step (5) into a drying box at 70 ℃ for drying for 12h to obtain an ultrasonic pre-rape pollen carbon powder sample;
(7) mixing the carbon powder sample obtained in the step (6) with deionized water, and putting the mixture into an ultrasonic reactor for ultrasonic treatment;
(8) putting the sample obtained in the step (7) into a centrifuge for centrifugal treatment, and drying solid powder to obtain an ultrasonic rape pollen carbon powder sample; the centrifugation rate was 4000rpm and the centrifugation time was 10 min.
Example 3:
the drugs used in this example: zinc chloride, sulfuric acid, spinach, absolute ethyl alcohol and deionized water.
A method for improving intrinsic activity of biomass-derived carbon material mainly comprises the following steps:
(1) and washing the purchased biomass material spinach with deionized water to remove dust on the surface. Drying and dehydrating the washed material in a drying oven, and grinding into powder for later use;
(2) 2g of spinach powder, 8g of zinc chloride and 100ml of deionized water are mixed and stirred for 12 hours, and then the mixed liquid is put into a drying oven at 70 ℃ to be dried for 12 hours until brown black colloid;
(3) putting the brown black colloid in the step (2) into a tube furnace, introducing nitrogen, heating to 850 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h to obtain black solid powder;
(4) grinding the black solid powder obtained in the step (3), wherein the ground powder is 0.5mol/L H2SO4Pickling for 12 h;
(5) washing the solution in the step (4) by using deionized water, centrifuging until the pH value of the solution is 7, washing by using absolute ethyl alcohol, and centrifuging once to obtain a precipitate; the centrifugation speed is 4000rpm, and the centrifugation time is 10 min;
(6) putting the precipitate obtained in the step (5) into a drying box at 70 ℃ for drying for 12h to obtain an ultrasonic front spinach carbon powder sample;
(7) mixing a carbon powder sample before ultrasonic treatment with deionized water, and putting the mixture into an ultrasonic reactor for ultrasonic treatment;
(8) putting the sample obtained in the step (7) into a centrifuge for centrifugal treatment, and drying solid powder to obtain an ultrasonic spinach carbon powder sample; the centrifugation speed was 4000rpm and the centrifugation time was 10 min.
Application example:
the carbon powder materials before and after the ultrasound prepared in the embodiment 1, the embodiment 2 and the embodiment 3 are directly used as working electrodes, platinum meshes are used as counter electrodes, mercury oxide is used as reference electrodes, a three-electrode measuring system is assembled, and the electrolyte is 0.1M KOH for electrochemical performance test.
The electrolyte used in electrochemical performance test of the carbon powder materials before and after the ultrasound prepared in the embodiments 1, 2 and 3 of the invention as the oxygen reduction catalyst material is N2、O2Saturated 0.1MKOH solution, evaluated by cyclic voltammetric tests (potential range-0)8V-0.4V vs. SCE, scanning speed 20mV/s), potentiodynamic polarization curve (potential range-0.8V-0.4V vs. SCE, scanning speed 10mV/s, rotation speed 400-2500 rpm), the specific results are shown in FIGS. 4-6.
Fig. 7 shows potentiodynamic polarization curves of the porous carbon prepared in example 1 before and after cycle testing and after ultrasonic centrifugation treatment, wherein Y-850 represents the polarization curve of the porous carbon prepared in example 1, ADT represents the polarization curve of the porous carbon after 5000-cycle cyclic voltammetry scanning accelerated aging testing, and ADT-U represents the polarization curve of the porous carbon after accelerated aging testing and then subjected to ultrasonic and centrifugation double process treatment.
FIG. 8 shows zeta potential polarization curves before and after cycling tests and after ultrasonic centrifugation treatment of the spinach-derived carbon material prepared in example 3, wherein S-850 represents the polarization curve of the porous carbon prepared in example 1, ADT represents the polarization curve of the porous carbon after 5000 cycles of cyclic voltammetry scanning accelerated aging tests, and ADT-U represents the polarization curve of the porous carbon after the accelerated aging tests and immediately after the ultrasonic and centrifugation double process treatment.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method of enhancing the intrinsic properties of a biomass-derived carbon material, the method comprising the steps of:
(1) washing the biomass material with deionized water, drying and grinding into powder;
(2) mixing the powder obtained in the step (1), zinc salt and water, drying the mixture to be colloidal at 50-90 ℃, pyrolyzing the mixture for 1-6 hours at 700-1000 ℃ in an inert atmosphere, cooling the mixture, soaking the obtained carbon powder in an acid solution for 2-24 hours, and washing the carbon powder to be neutral by using deionized water;
(3) mixing the carbon powder obtained in the step (2) with deionized water, and putting the mixture into an ultrasonic reactor for ultrasonic treatment;
(4) and (4) placing the sample obtained in the step (3) into a centrifuge for centrifugal treatment, and drying.
2. The method according to claim 1, wherein the biomass material in step (1) comprises dried beancurd stick, spinach, pollen, bamboo fungus; the drying temperature is 40-60 ℃, and the particle size of the powder is 20-200 meshes.
3. The method of claim 1, wherein the zinc salts in step (2) comprise zinc chloride, zinc sulfate, and zinc nitrate, and the weight ratio of the powder, zinc salt, and water is in the range of 0.2: 1: 10-3: 1: between 50; the inert atmosphere comprises argon, helium and nitrogen; the acid solution comprises a sulfuric acid solution, a hydrochloric acid solution and a nitric acid solution, and the concentration of the acid solution is 0.1-2M.
4. The method according to claim 1, wherein the weight ratio of the carbon powder to the deionized water in step (3) is 1: 50-1: 200, the parameters of the sonication were as follows: the power is 100-500 w; the magnetic stirring speed is 100-1000 rpm; the reaction time is 1-8 h, wherein the total time of ultrasonic energy collection is 100-1200 seconds.
5. The method according to claim 1, wherein the conditions of the centrifugation in the step (4) are: the centrifugal speed is 4000rpm, and the centrifugal time is 5-30 min.
6. A carbon material produced by the method according to any one of claims 1 to 5.
7. Use of the carbon material of claim 6 in fuel cells, supercapacitors and metal air batteries.
8. Use according to claim 7, wherein the carbon material is used as an electrode material.
9. The method for recycling the carbon material as claimed in claim 6, wherein the carbon material is prepared into an electrode, the electrochemical performance of the electrode is evaluated, the electrode is taken off from the carbon material, the electrode is placed in an ultrasonic reactor for ultrasonic treatment, and the regeneration is completed after centrifugal drying.
10. The method according to claim 9, wherein the electrolyte used in the evaluation of electrochemical properties is O2Saturated 0.1m koh solution; the evaluation of the electrochemical performance comprises a potentiodynamic polarization curve and a cyclic voltammetry test; the parameters of the sonication were as follows: the power is 100-500 w; the magnetic stirring speed is 100-1000 rpm; the reaction time is 1-8 h, wherein the total time of ultrasonic energy collection is 100-1200 seconds.
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