CN113443626A - Preparation method of mixed biomass activated carbon and application of mixed biomass activated carbon in super capacitor - Google Patents
Preparation method of mixed biomass activated carbon and application of mixed biomass activated carbon in super capacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000002028 Biomass Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003990 capacitor Substances 0.000 title abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 240000007124 Brassica oleracea Species 0.000 claims description 7
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 claims description 7
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 claims description 7
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 claims description 7
- 241001412225 Firmiana simplex Species 0.000 claims description 7
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- 238000001816 cooling Methods 0.000 claims description 6
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- 238000000227 grinding Methods 0.000 claims description 6
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- 238000002791 soaking Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 claims description 3
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- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 240000003826 Eichhornia crassipes Species 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010008 shearing Methods 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 28
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- 238000012360 testing method Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 3
- 238000001994 activation Methods 0.000 abstract description 3
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- 239000002253 acid Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 240000001058 Sterculia urens Species 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 239000006258 conductive agent Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 235000021282 Sterculia Nutrition 0.000 description 2
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- 230000001351 cycling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229940059107 sterculia Drugs 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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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
- H01G11/24—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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- 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
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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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- 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
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Abstract
The invention discloses a preparation method of mixed biomass activated carbon and application of the mixed biomass activated carbon in a super capacitor. The method selects various biomass materials as raw materials, mixes the raw materials according to a certain proportion, and prepares the mixed biomass activated carbon through the treatment processes of pretreatment, carbonization, impregnation, activation, acid washing and the like. The obtained activated carbon is further prepared into an electrode slice, potassium hydroxide solution is used as electrolyte, and the test is carried out in a three-electrode system, and the result shows that the activated carbon has better electrochemical performance. Different from the method for respectively preparing the activated carbon by using single raw material, the method selects a plurality of biomass materials for mixing and firing at one time, so that the firing cost is saved, and the electrode performance of the activated carbon super capacitor can be integrally improved by reasonably selecting the raw materials and the proportion; in addition, the raw materials adopted by the invention are waste biomass in nature, the source is wide, the environment is protected, the preparation process is simple, and the large-scale production is facilitated.
Description
Technical Field
The invention belongs to the field of materials and electrochemistry, and particularly relates to a preparation method of mixed biomass activated carbon and application of the mixed biomass activated carbon in a super capacitor.
Background
The biomass activated carbon is always the focus of research, the biomass activated carbon is rich in source, and a plurality of biomass materials such as corn straws, palm leaves, elm flowers, coconut shells and the like are prepared into the activated carbon to be applied to the electrode of the double electric layer capacitor, so that the activated carbon shows good electrochemical performance. However, in these studies, researchers often only process a single biomass raw material, and a single activated carbon is produced.
In other application research fields of activated carbon, some researchers have studied two mixed biomasses to prepare activated carbon, for example, in order to improve the iodine adsorption value of a single activated carbon, cinnabar and the like [ cinnabar, converly, tao, et al.
In consideration of the fact that various leaves, vegetable leaves and aquatic plant leaves can be used for preparing activated carbon, the characterization analysis is conducted on the microcosmic components and structures of different leaves, the application of the leaves is oriented to the supercapacitor electrode, different leaf materials are designed and screened, the materials are mixed according to a certain proportion, and the mixture is used for preparing mixed leaf-based activated carbon. In the current research, the research of preparing mixed biomass activated carbon, particularly mixed blade-based activated carbon to be applied to a super capacitor is not available, so that in the patent, the mixed blade-based biomass activated carbon is prepared by using various mixed biomasses as raw materials, and the application of the mixed blade-based biomass activated carbon in the super capacitor is provided.
Disclosure of Invention
The invention aims to provide a preparation method of mixed blade-based biomass activated carbon.
The invention also aims to provide the application of the mixed biomass activated carbon prepared by the method in the super capacitor.
The specific embodiment of the invention is as follows:
the invention provides a preparation method of a mixed biomass material, which comprises the following steps:
(1) selecting multiple biomass raw materials (two or more) from different species, mixing according to a certain mass ratio, respectively ultrasonically washing with deionized water and absolute ethyl alcohol for 10-30 min, drying, cutting, and storing;
(2) placing the obtained sample in a tube furnace, carrying out heat treatment at a certain temperature for a period of time under the protection of inert gas, cooling, taking out a product, grinding, carrying out ultrasonic treatment for 10-30 min, uniformly mixing to obtain a carbonized sample, uniformly mixing the carbonized sample with a KOH aqueous solution with a certain mass, soaking at room temperature for a period of time, and drying to obtain a soaked sample;
(3) and (3) placing the obtained impregnated sample in a tube furnace, further carrying out heat treatment for a period of time at a certain temperature under the protection of inert gas, washing the cooled product to be neutral by using hydrochloric acid with a certain concentration, washing by using deionized water and ethanol respectively, and drying to obtain the mixed biomass activated carbon.
According to the scheme, the biomass raw material in the step (1) is two or more of Chinese parasol tree, pistia stratiotes, water hyacinth, Chinese cabbage and purple cabbage; the mass ratio ensures that the mass ratio content of each selected raw material is not less than 5 percent.
In the above scheme, the inert gas in the step (2) refers to one of nitrogen or argon.
In the scheme, the heat treatment process in the step (2) refers to the temperature of 500-.
In the scheme, the mixing mass ratio of the carbonized sample and the KOH in the step (2) is 1:2-5, and the dipping time is 12-24 h.
In the above scheme, the inert gas in the step (3) refers to one of nitrogen or argon.
In the scheme, the heat treatment process in the step (3) refers to the temperature of 700-.
In the scheme, the concentration of the hydrochloric acid in the step (3) is 0.1-2M.
In the above scheme, the washing in step (3) refers to: the product obtained after the hydrochloric acid washing is respectively centrifuged for 1-60 min by deionized water and ethanol at the rotating speed of 500-12000 rpm, and washed for 1-4 times.
The mixed biomass activated carbon provided by the invention is prepared by taking various biomass materials as raw materials, mixing the raw materials according to a certain proportion and carrying out the processes of pretreatment, carbonization, impregnation, activation, acid washing and the like, and through reasonable design of material selection and proportion, not only is the electrochemical performance of the mixed activated carbon prevented from being reduced due to improper materials, but also the performance of the whole supercapacitor of the material is favorably improved. In addition, if the collected terrestrial or aquatic biomass material is a mixture and the composition and mass ratio of the raw materials meet the design requirements, the mixed biomass material meeting the requirements can be directly used for preparing the activated carbon without sorting and weighing mixing processes, and the mixed biomass material is used as the raw material without sorting and separating the raw material, so that the preparation cost can be greatly saved. In addition, the raw materials adopted by the invention are waste biomass in nature, the source is wide, the environment is protected, the preparation process is simple, and the large-scale production is facilitated.
The invention provides an application of mixed biomass activated carbon in a super capacitor, which is characterized in that the prepared mixed biomass activated carbon is used as an active material, acetylene black is used as a conductive agent, polytetrafluoroethylene is used as a binder, the active material and the acetylene black are mixed according to a mass ratio of 8:1:1, N-methyl pyrrolidone is used as a solvent, the mixture is fully ground, coated on foamed nickel (the coating area is 1cm multiplied by 1 cm), dried and tableted to form the electrode slice, and the electrode slice is prepared. Then, the test was performed in a three-electrode system using KOH solution as an electrolyte.
Drawings
FIG. 1 is an optical image of three blade materials selected for mixing in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a Platanus orientalis activated carbon of comparative example 1 according to the present invention;
FIG. 3 is a scanning electron micrograph of phoenix tree activated carbon in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of Pistia stratiotes active carbon in example 3 of the present invention;
FIG. 5 is a cyclic voltammogram at the same scan rate for example 1 of the present invention and the activated carbon samples obtained in comparative example 1, comparative example 2 and comparative example 3 thereof;
FIG. 6 is a constant current charge and discharge curve at the same current density for the activated carbon samples obtained in example 1 of the present invention and comparative examples 1, 2 and 3 thereof;
FIG. 7 is a graph showing the cycle stability at the same current density for the activated carbon samples obtained in example 1 of the present invention and comparative examples 1, 2 and 3 thereof;
FIG. 8 is a cyclic voltammogram at the same scan rate for the activated carbon samples obtained in example 2 of the present invention and comparative examples 1 and 2 thereof;
FIG. 9 is a constant current charge and discharge curve at the same current density for the activated carbon samples obtained in example 2 of the present invention and comparative examples 1 and 2 thereof;
FIG. 10 is a graph showing the cycle stability at the same current density for the activated carbon samples obtained in example 2 of the present invention and comparative examples 1 and 2 thereof.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
The specific synthetic steps of the mixed biomass activated carbon are as follows:
(1) mixing Sterculia brachycarpa, Sterculia brachycarpa and Pistia stratiotes according to the mass ratio of 3:1:2, ultrasonic washing with deionized water and absolute ethyl alcohol respectively for 15 min, drying, cutting into pieces, and storing;
(2) placing the obtained mixture in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, carbonizing for 2 h at constant temperature, naturally cooling, taking out the product, grinding, performing ultrasonic treatment for 15 min to uniformly mix the product, weighing KOH according to a mass ratio of the carbonized sample to the KOH of 1:4 to prepare a 1M aqueous solution, uniformly mixing the aqueous solution with the carbonized sample, soaking for a period of time at room temperature, and drying in an oven to obtain a soaked sample;
(3) placing the obtained impregnated sample in a tube furnace, heating to 800 deg.C at a heating rate of 5 deg.C/min under the protection of nitrogen gas, activating at constant temperature for 1 h, naturally cooling, taking out the product, washing with 1M hydrochloric acid to neutrality, washing with deionized water and ethanol for 3 times, and oven drying to obtain mixed biomass activated carbon (PA)3FP1PS2AC）。
The preparation and application of the mixed biomass activated carbon prepared in the embodiment as a supercapacitor electrode material are as follows:
preparing an electrode slice: with the resultant PA3FP1PS2Mixing AC serving as an active material, acetylene black serving as a conductive agent and polytetrafluoroethylene serving as a binder according to a mass ratio of 8:1:1, fully grinding N-methylpyrrolidone serving as a solvent, coating the mixture on foamed nickel, drying, and tabletting to obtain the mixed biomass active carbon electrode slice.
And (3) electrochemical performance testing: in a three-electrode system, the prepared electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and electrochemical performance test is carried out in 3M potassium hydroxide electrolyte.
Comparative example 1
For comparison with example 1, we carried out comparative experiment 1 and carried out the preparation of the sample of comparative example 1. Comparative example 1 was prepared in substantially the same manner as in example 1, except that the starting material was selected from a single leaf of karaya, and the resulting activated carbon was a karaya activated carbon (PAAC).
Comparative example 2
For comparison with example 1, we also carried out comparative experiment 2, and the preparation of the sample of comparative example 2 was carried out. Comparative example 1 the same procedure as in example 1 was followed except that the starting material was selected from a single phoenix tree leaf and the resulting activated carbon was a phoenix tree activated carbon (FPAC).
Comparative example 3
For comparison with example 1, we also carried out comparative experiment 3, the preparation of the sample of comparative example 3. Comparative example 1 is prepared substantially in the same manner as in example 1, except that the selected raw material is pistia stratiotes and the obtained active carbon is Pistia Stratiotes Active Carbon (PSAC).
Fig. 2, fig. 3 and fig. 4 are scanning electron micrographs of PAAC, FPAC and PSAC, respectively, and it can be seen that the microstructures of PAAC and FPAC are relatively similar, both being distinct hole structures of similar size, while the microstructure of PSAC is distinct from the former two.
Based on the difference of microstructures, the analysis finds that the holes of the French phoenix tree activated carbon and the French phoenix tree activated carbon are large in structure, electrolyte ions can easily pass through the holes, the structure is stable, and the matching performance of different components is expected to be good when the materials with similar microstructures are used for preparing the mixed activated carbon, so that the quality of the activated carbon is favorably ensured; and the pistia stratiotes active carbon can provide larger specific surface area, is favorable for the adsorption of ions in electrolyte and improves the specific capacitance of the material. Therefore, the raw materials with the micro-functional complementary structures are mixed according to a certain proportion, and the mixed biomass activated carbon is prepared by a carbonization activation method, so that the advantages of various structures can be exerted at the same time, and the overall performance of the material is improved.
FIG. 5 shows cyclic voltammograms of four activated carbon samples at a scan rate of 20 mV/s, and all of the plots are seen to resemble rectangles, illustrating that the majority of the double layer energy is due to pseudocapacitance. Compared with other materials, PA3FP1PS2The area enclosed by the cyclic voltammogram of AC is the largest, while the redox peak of PSAC is the most pronounced.
FIG. 6 shows that four activated carbon samples are tested at a current of 1A/gAll curves of constant current charge and discharge curves under the density have certain curvature, and the existence of a pseudocapacitance energy storage mechanism is also illustrated. Of all electrode materials, PA3FP1PS2The maximum specific capacitances of AC and PSAC, 246F/g and 254F/g, respectively, demonstrate the performance advantages of activated carbon prepared according to the selected mixing scheme.
FIG. 7 shows the cycling stability curves of four activated carbons at 5A/g current density, and it can be seen that PA3FP1PS2The specific capacitance of AC is the largest and is 201F/g, and the specific capacitance of other materials does not reach 200F/g when the specific capacitance of other materials is 5A/g, which shows that PA3FP1PS2The rate capability of AC is highest.
In addition, after 1000 cycles of circulation, the stability of all the activated carbon is better than 97%, and the specific capacitance performance analysis of the materials can find that PA3FP1PS2The overall electrochemical performance of AC is optimal, and further illustrates that the activated carbon prepared by mixing the biomass raw materials is beneficial to combining the advantages of various materials and improving the comprehensive performance.
Example 2
The specific synthetic steps of the mixed biomass activated carbon are as follows:
(1) mixing Chinese cabbage and purple cabbage at a mass ratio of 3:1, ultrasonic washing with deionized water and anhydrous ethanol for 15 min, drying, cutting, and storing;
(2) placing the obtained mixture in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, carbonizing for 2 h at constant temperature, naturally cooling, taking out the product, grinding, performing ultrasonic treatment for 15 min to uniformly mix the product, weighing KOH according to a mass ratio of the carbonized sample to the KOH of 1:4 to prepare a 1M aqueous solution, uniformly mixing the aqueous solution with the carbonized sample, soaking for a period of time at room temperature, and drying in an oven to obtain a soaked sample;
(3) and (3) placing the obtained impregnated sample in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen gas, activating for 1 h at a constant temperature, naturally cooling, taking out a product, washing to be neutral by using 1M hydrochloric acid, washing for 3 times by using deionized water and ethanol respectively, and drying to obtain the mixed biomass activated carbon (MBAC 31).
The preparation and application of the mixed biomass activated carbon prepared in the embodiment as a supercapacitor electrode material are as follows:
preparing an electrode slice: mixing the obtained mixed biological activated carbon serving as an active material, acetylene black serving as a conductive agent and polytetrafluoroethylene serving as a binder according to a mass ratio of 8:1:1, fully grinding the mixture by using N-methylpyrrolidone as a solvent, coating the mixture on foamed nickel, drying the foamed nickel, and tabletting and forming the dried foamed nickel to obtain the mixed biological activated carbon electrode slice.
And (3) electrochemical performance testing: in a three-electrode system, the prepared electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and electrochemical performance test is carried out in 6M potassium hydroxide electrolyte.
Comparative example 1
For comparison with example 1, we carried out comparative experiment 1 and carried out the preparation of the sample of comparative example 1. Comparative example 1 the preparation method was substantially the same as that of example 1, except that the selected raw material was a single cabbage and the resulting activated carbon was a cabbage activated carbon (CCAC).
Comparative example 2
For comparison with example 1, we also carried out comparative experiment 2, and the preparation of the sample of comparative example 2 was carried out. Comparative example 1 was prepared substantially the same as example 1 except that the starting material selected was purple cabbage alone and the resulting activated carbon was Purple Cabbage Activated Carbon (PCAC).
FIG. 8 tests the cyclic voltammograms of CCAC, PCAC and MBAC31 at a scan rate of 20 mV/s and again shows that the area enclosed by the cyclic voltammograms of the MBAC31 sample prepared in combination is the largest compared to the single CCAC and PCAC samples.
FIG. 9 Each sample was tested at 0.5A g-1Constant current charge and discharge curves at current density also show that the specific capacitance of the mixed sample MBAC31 is higher than that of the single sample, 366F g-1And the specific capacitances of CCAC and PCAC were 357F/g and 229F/g.
Fig. 10 shows stability curves of 10000 cycles of cycling of three activated carbon samples at 20A/g current density, and it can be seen that the MBAC31 sample prepared by mixing is slightly less stable than the two single materials, but also maintains a high capacity retention rate and the specific capacitance is highest.
Claims (10)
1. A preparation method of mixed biomass activated carbon is characterized by comprising the following steps:
(1) selecting multiple biomass raw materials (two or more) to mix according to a certain mass ratio, respectively ultrasonically washing for 10-30 min by using deionized water and absolute ethyl alcohol, drying, shearing, and storing;
(2) placing the obtained sample in a tube furnace, carrying out heat treatment at a certain temperature for a period of time under the protection of inert gas, cooling, taking out a product, grinding, carrying out ultrasonic treatment for 10-30 min, uniformly mixing to obtain a carbonized sample, uniformly mixing the carbonized sample with a KOH aqueous solution with a certain mass, soaking at room temperature for a period of time, and drying to obtain a soaked sample;
(3) and (3) placing the obtained impregnated sample in a tube furnace, further carrying out heat treatment for a period of time at a certain temperature under the protection of inert gas, washing the cooled product to be neutral by using hydrochloric acid with a certain concentration, washing by using deionized water and ethanol respectively, and drying to obtain the mixed biomass activated carbon.
2. The preparation method of a mixed biomass activated carbon as claimed in claim 1, wherein the biomass raw material selected in the step (1) is two or more of phoenix tree, pistia stratiotes, water hyacinth, Chinese cabbage and purple cabbage; the mass ratio ensures that the mass ratio content of each selected raw material is not less than 5 percent.
3. The method of claim 1, wherein the terrestrial or aquatic biomass material in step (2) is a mixture when collected, and the raw material composition and mass ratio thereof are in accordance with claim 2, and the activated carbon can be directly prepared from the satisfactory mixed biomass material without sorting and weighing mixing.
4. A method for preparing a mixed biomass activated carbon as claimed in claim 1, wherein said inert gas in step (2) is one of nitrogen or argon; the heat treatment process is that the temperature is 500-600 ℃, the constant temperature treatment is carried out for 2-4 h, and the heating rate is 1-5 ℃/min.
5. A preparation method of mixed biomass activated carbon as claimed in claim 1, wherein the mixing mass ratio of the carbonized sample and KOH in the step (2) is 1:2-5, and the impregnation time is 12-24 h.
6. A method for preparing mixed biomass activated carbon as claimed in claim 1 wherein said inert gas in step (3) is one of nitrogen or argon.
7. The preparation method of mixed biomass activated carbon as claimed in claim 1, wherein the heat treatment process in the step (3) is performed at a temperature of 700 ℃ and 900 ℃ for 1-2 h at a constant temperature rate of 1-5 ℃/min.
8. A process as claimed in claim 1, wherein the hydrochloric acid concentration in step (3) is 0.1-2M.
9. A method for the production of mixed biomass activated carbon as claimed in claim 1, wherein said washing in step (3) is: the product obtained after the hydrochloric acid washing is respectively centrifuged for 1-60 min by deionized water and ethanol at the rotating speed of 500-12000 rpm, and washed for 1-4 times.
10. Use of a mixed biomass activated carbon prepared according to the process of any of claims 1 to 9 in a supercapacitor.
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