CN113929094A - Preparation method of ultralow-ash coal-based capacitance carbon - Google Patents
Preparation method of ultralow-ash coal-based capacitance carbon Download PDFInfo
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- CN113929094A CN113929094A CN202111162251.6A CN202111162251A CN113929094A CN 113929094 A CN113929094 A CN 113929094A CN 202111162251 A CN202111162251 A CN 202111162251A CN 113929094 A CN113929094 A CN 113929094A
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- 239000003245 coal Substances 0.000 title claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
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- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 3
- 239000003830 anthracite Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- 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
- C01B32/354—After-treatment
-
- 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
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a preparation method of ultra-low ash coal-based capacitance carbon, which comprises the following steps of (1) crushing raw smokeless coal and then screening to obtain undersize coal powder; (2) adding acid and a dispersing agent into the obtained coal powder for reaction treatment, and then carrying out solid-liquid separation, washing and drying on a reaction product to obtain acid-treated coal; (3) activating the obtained acid-treated coal to obtain an activated material; (4) adding water and a complexing agent into the obtained activated material, and then carrying out electrophoresis treatment under the ultrasonic condition; and (5) carrying out solid-liquid separation, washing and drying on the product obtained in the step (4) to obtain the coal-based capacitance carbon. The capacitance carbon obtained by the invention has large specific surface area and ultralow ash content, can be directly used as a product, and can also be made into an electrode material according to production requirements to be applied to the field of energy storage. When the coal-based capacitance carbon is used as an electrode material, high specific capacitance and good rate characteristic are shown.
Description
Technical Field
The invention relates to the field of coal-based carbon materials, in particular to a preparation method of ultra-low ash coal-based capacitance carbon.
Background
The ash content of the coal-based capacitance carbon is almost completely from raw material coal, and the ash component mainly comprises SiO2、Al2O3、CaO、MgO、Fe2O3、K2O、Na2O, and the like. The ash content has great influence on the manufacturing process of the coal-based capacitance carbon and the performance of the product. In the manufacturing process, most inorganic substances in ash have certain influence on pore-forming in the activation process, particularly on the aspect of specific surface area; the coal-based capacitance carbon ash content is too high, so that the application of the coal-based capacitance carbon ash content in electrode materials is limited, and the specific capacitance value of the electrode materials can be influenced. Common deliming methods in the process of preparing the coal-based capacitance carbon include direct acid pickling deliming, acid-alkali mixing deliming and the like. However, when washing is carried out after the acid-base deliming reaction, an oil film is formed, and some unreacted coal and other impurities are still present in the oil film, which can have adverse effects on the final ash content. The common deashing method is adopted for treatment, and some metal ions cannot be removed, so that the performance of the whole electrode material is influenced.
In addition, in the prior art, biomass materials such as wood, rice hulls and the like are mostly used as raw materials for preparing the super capacitor carbon, and the preparation can be found through papers. The existing super-capacitor carbon is prepared by taking bituminous coal and anthracite as raw materials, and the acid-base deliming technology and the conventional carbon activation process are adopted, so that the prepared super-capacitor carbon is high in ash content and poor in capacitance performance.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing ultra-low ash coal-based capacitance carbon, so as to successfully prepare high-performance coal-based capacitance carbon which can be used as an electrode material or directly used as a product.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of ultra-low ash coal-based capacitance carbon comprises the following steps:
(1) crushing raw smokeless coal and then screening to obtain undersize coal powder;
(2) adding acid and a dispersing agent into the obtained coal powder for reaction treatment, and then carrying out solid-liquid separation, washing and drying on a reaction product to obtain acid-treated coal;
(3) activating the obtained acid-treated coal to obtain an activated material;
(4) adding water and a complexing agent into the obtained activated material, and then carrying out electrophoresis treatment under the ultrasonic condition; and
(5) and (4) carrying out solid-liquid separation, washing and drying on the product obtained in the step (4) to obtain the coal-based capacitance carbon.
According to the preparation method of the invention, preferably, the sieving in the step (1) is multi-stage sieving, and the particle size of the undersize coal powder obtained after multi-stage sieving is smaller than 400 meshes (namely, the undersize coal powder can pass through a 400-mesh Taylor standard sieve), such as 200 meshes, 300 meshes and 400 meshes in turn.
According to the preparation method of the present invention, preferably, in the step (2), the reaction treatment by adding the acid and the dispersant to the obtained pulverized coal is performed in two steps, wherein the first step is the reaction treatment by adding the hydrofluoric acid and the dispersant, and the second step is the reaction treatment by further adding the dispersant and one of the hydrochloric acid and the sulfuric acid.
According to the production method of the present invention, preferably, in the first step and the second step, the mass ratio of the acid added to the pulverized coal is 2:1 to 6:1, such as 3: 4:1 or 5: 1; it is understood by those skilled in the art that the acid in the first and second steps is an acid solution, wherein the concentration of the acid may be 20-30 wt%.
According to the production method of the present invention, preferably, the dispersant is added in an amount of 0.2 to 2 wt%, such as 0.5 wt%, 1 wt%, or 1.5 wt%, based on the mass of the pulverized coal in the first and second steps.
According to the preparation method of the present invention, preferably, the dispersant is at least one of ethanol, polyethylene wax, polyethylene glycol, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and sodium dodecylbenzene sulfonate.
According to the preparation method of the invention, in the step (4), when the electrophoresis treatment is carried out under ultrasound, the frequency of the ultrasound treatment is 25 KHz-60 KHz, and the power is 150W-240W. Electrophoretic processing is well known in the art, for example the electrophoretic voltage may be set at 5-25v, such as 10, 15 or 20 v.
According to the preparation method of the present invention, preferably, in the step (4), the complexing agent is added in an amount of 5 to 20 wt%, such as 10 wt% or 15 wt%, based on the mass of the pulverized coal. The complexing agent is at least one selected from EDTA, sodium tripolyphosphate, oxalic acid, sulfosalicylic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and disodium nitrilotriacetate.
In step (3) of the present invention, the activation treatment is well known in the art, and in the activation treatment, KOH can be used as an activating agent, and the activation treatment can be performed at 750-900 ℃ for 60-90min under a nitrogen atmosphere.
Compared with the prior art, the invention has the following advantages:
(1) compared with the conventional method of directly screening coal to a fixed mesh number, the method adopts multiple grading and screening of coal, ensures that the particle size of the anthracite is kept uniform and the subsequent coal fully reacts with acid;
(2) in the invention, the combined treatment of the dispersing agent and the sequential acid is adopted in the acidification treatment process, and a layer of oil film can appear in the direct acidification process, so that the oil film contains a large amount of impurities which influence ash content. The combined treatment of the dispersing agent and the sequential acid has the advantages that impurities affecting ash content in an oil film can be removed through the dispersing agent, so that the acid liquid is fully contacted with coal, and the ash content can be reduced through acidification;
(3) the complexing agent and the dispersing agent adopted by the invention have low price, are easy to separate by a subsequent process, have no secondary pollution and are green and environment-friendly;
(4) the ultralow-ash coal-based capacitance carbon prepared by the method realizes ultralow ash content through multi-step deashing and deep deashing, and has larger specific surface area and pore diameter, thereby promoting the rapid migration of ions and the transmission of charges;
(5) when the ultra-low ash coal-based capacitance carbon prepared by the invention is used as an electrode material, the carbon has high specific capacitance and good rate characteristic. At a current density of 0.5 A.g-1Lower ratioThe capacitance can reach 368F g-1At a current density of 100 A.g-1The lower specific capacitance can reach 127.5 F.g-1. The specific surface area of the ultra-low ash coal-based capacitance carbon is tested and found to be 2419.52m2In conclusion, the ultra-low ash coal-based capacitance carbon prepared by the invention has ultra-low ash and good electrochemical performance and chemical stability, and has good application prospects in the fields of supercapacitors, electrocatalysis, material transmission, photoelectric functions and the like.
Drawings
Fig. 1 is an SEM image of the pulverized coal prepared in example 1 of the present invention, with a magnification of 10000 times.
Fig. 2 is an SEM image of a picture of ultra-low ash coal-based capacitive carbon prepared in example 1 of the present invention, at 3000 times magnification.
Fig. 3 is an XRD pattern of ultra-low ash coal-based capacitance carbon prepared in example 1 of the present invention.
Fig. 4 is a raman plot of ultra-low ash coal-based capacitance carbon prepared in example 1 of the present invention.
Fig. 5 is a nitrogen-sorption and desorption graph of the ultra-low ash coal-based capacitance carbon prepared in example 1 of the present invention.
Fig. 6 is a graph of the pore size distribution of the ultra-low ash coal-based capacitance carbon prepared in example 1 of the present invention.
Fig. 7 is a cyclic voltammogram of the ultra-low ash coal-based capacitive carbon prepared in example 1 of the present invention at different sweep rates.
Fig. 8 is a constant current charge and discharge curve of the ultra-low ash coal-based capacitance carbon prepared in example 1 of the present invention at different current densities.
Fig. 9 is a rate characteristic curve of the ultra-low ash coal-based capacitance carbon prepared in example 1 of the present invention.
Fig. 10 is an electrochemical impedance plot of the ultra-low ash coal-based capacitive carbon prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings, but the present invention is not limited to the examples listed, and shall include equivalent modifications and variations of the technical solutions defined in the claims appended to the present application.
Example 1
The preparation method of the ultralow-ash coal-based capacitance carbon specifically comprises the following steps:
s1, putting anthracite into a crusher to be crushed for 1 hour in total, shutting down and starting up every 3 minutes to prevent the crusher from being overheated to cause shutdown;
s2, screening the coal crushed in the step S1 for three times through 200-mesh, 300-mesh and 400-mesh screens in sequence;
s3, taking out 15g of the crushed and multi-time classified coal sample, adding 0.15g of ethanol and 60g of hydrofluoric acid (the concentration is 20 percent, the same is applied below), and reacting under the stirring state;
s4, adding 60g of hydrochloric acid and 0.15g of ethanol into the product obtained in the step S3; reacting under the stirring state;
s5, after the solution obtained in the step S4 is subjected to solid-liquid separation, adding distilled water for washing, and putting the washed solution into a vacuum drying oven for drying overnight;
s6, taking out the coal sample obtained in the step S5, putting the coal sample into a tubular furnace for activation, and performing activation treatment for 60min at 800 ℃ in a nitrogen atmosphere by using KOH as an activating agent;
s7, pouring the activated product into a beaker, adding distilled water, adding 0.2g of EDTA, and carrying out ultrasonic electrophoresis treatment under the conditions that the ultrasonic frequency is 45KHz and the power is 180W;
s8, carrying out solid-liquid separation on the product obtained in the step S7, adding distilled water for washing to be neutral, and then drying overnight to obtain a product labeled as F1.
The carbon F1 with ultra-low ash content and coal-based capacitance is subjected to the tests of appearance, structure, electrochemical performance, specific surface and pore size distribution, and the test results are as follows:
comparing fig. 1 and fig. 2, it is found that the coal-based capacitance carbon prepared after being activated by deashing treatment has obvious pores, and the size of the activated carbon is larger compared with the SEM of raw coal. This is probably due to the simultaneous carbonization of the carbonaceous material and activation by the activating agent during the heat activation. And the generation of pores may be caused by the good incorporation of KOH into the carbon layer, which is in sufficient contact with the coal fines.
(II) Structure
As can be seen from the XRD chart of fig. 3, the prepared coal-based capacitance carbon showed diffraction peaks near 23.7 ° and 44 °, corresponding to (002) and (100) diffraction peaks, respectively. Wherein (002) diffraction peak can be classified as a typical characteristic peak of low graphitization degree, which proves that the prepared coal-based capacitance carbon has a micro-graphitized structure and is beneficial to charge transfer in the charging and discharging process. In addition, the diffraction peak is strong when the 2 theta is less than 10 degrees, which indicates that the material contains a large number of nanometer micropores.
In the Raman spectrum of FIG. 4, 1339 and 1595cm-1Two obvious graphite carbon characteristic peaks exist at the displacement, which correspond to a D peak and a G peak respectively. Wherein ID/IG1.48, which indicates that the prepared capacitance carbon has a large number of defects and a certain graphitization degree, and the defects of the pore structure are increased probably due to the addition of the complexing agent and the activation of the activating agent in the carbonization process, and are mainly reflected in the increase of micropores and mesopores.
(III) specific surface and pore size distribution test
The prepared coal-based capacitance carbon is subjected to pore structure analysis by adopting a nitrogen adsorption-desorption isothermal curve and a pore size distribution curve, and as can be seen from figure 5, the isothermal curve of the capacitance carbon is of a mixed type, and the adsorption rate is very high in a low-pressure range, which shows that the capacitance carbon is used for N2The adsorption amount of (A) rapidly increases with the increase of the relative pressure, indicating that the capacitance carbon and N2The strong interaction force also indicates that the capacitance carbon mainly has micropores. However, the high-pressure region has a hysteresis loop, which indicates that the sample contains mesopores. The same conclusion can be drawn from the pore size distribution of fig. 6, which is likely to be a more complete ash removal during deliming, in combination with the complexing agent, allowing the coal to react fully with the activator, producing a large number of micropores and a small number of mesopores upon activation.
(IV) electrochemical test
And carrying out electrochemical test on the prepared capacitance carbon material under a three-electrode system. FIG. 7 shows the variation of the CV curve at different sweep rates, and it can be seen that the curve is changed as the sweep rate is increasedThe enclosed area becomes large, is approximately rectangular, and shows good symmetry, which indicates that the prepared capacitance carbon has the characteristic of double-electric-layer capacitance. FIG. 8 is a GCD curve for different current densities, where the specific capacitance varies with current density as shown in FIG. 9. It can be seen that the current density was 0.5A · g-1When the specific capacitance is large, 368 F.g-1. As the current density increases, the specific capacitance becomes smaller. At 100 A.g-1The specific capacitance can be maintained at 127.5 F.g-1. This is probably because abundant micropores and mesopores in the material are utilized to the maximum extent, providing channels for the storage and transmission of ions at high current density, resulting in high specific capacitance and stable electrochemical performance. EIS tests of the capacitance carbon show that the sample has better ion diffusion capability in a high-frequency area. In the low frequency region, the resistance of the material is calculated to be 0.31 omega, which is matched with the high frequency region, and the prepared capacitance carbon has excellent ion diffusion performance. In conclusion, electrochemical tests show that the ultralow-ash coal-based capacitance carbon material with good capacitance performance and rate characteristic can be prepared by adopting a method of jointly using deliming, a dispersing agent and a complexing agent.
(V) ash Change
Comparing the ash content of the raw coal after activation with that before activation, the ash content is reduced from 5.01% to 1.47%, which shows that the coal is classified and screened, and the impurities in the coal can be effectively removed through acid deashing and dispersant treatment. And then the coal-based capacitance carbon material with developed pores, uniform dispersion and good capacitance performance can be obtained by combined treatment of activation and a complexing agent.
Embodiment 2-8 preparation method of ultra-low ash coal-based capacitance carbon
The preparation steps of the preparation method of the coal-based capacitance carbon in the embodiments 2 to 8 are basically the same as those of the embodiment 1, and the differences are only the differences of relevant parameters, and specific different parameters are shown in the following table 1:
table 1 summary of the raw material amounts and process parameters in examples 2 to 8
Comparative example 1
This comparative example is compared with example 1, except that no dispersant is added in steps S3 and S4, and the amount of EDTA added in step S7 is 0.75g, the rest being the same. The resulting product is labeled F1'.
In comparison with example 1, it was found that the lack of dispersant resulted in poor contact of the coal with the acid solution during the acidification process, and some of the coal fines did not react with the acid. The absence of dispersants also leads to the appearance of an oil film during the acidification, in which the impurities that influence the deliming are present. Therefore, the whole deashing effect is not good, and the ash content is 2.19%. Meanwhile, SEM shows that the shape structure of the activated coal-based capacitance carbon has a blocky structure and also has a plurality of pore channel structures. Part of the blocky appearance is that part of the pore channel structure is not formed, so that the specific surface area of the capacitance carbon is 1937m2/g。
Comparative example 2
The comparative example is different from example 1 in that the crushed coal in step S2 was directly sieved through a 300 mesh sieve, and the amount of EDTA added in step S7 was 0.75g, and the rest was the same. The resulting product is labeled F2'.
Compared with the implementation case, the coal with different particle sizes appears due to the fact that multiple grading screening is lacked and the direct screening is carried out, the deashing effect is not good after the acidification and the activation are carried out in the later period, and the ash content is 2.57%. Meanwhile, SEM finds that the pore channels of the activated coal-based capacitance carbon are not uniform, so that the specific surface area is small and is 1652.91m2/g。
Comparative example 3
This comparative example is compared with example 1 except that the amount of EDTA added in step S7 was 0, and the rest was the same. The resulting product is labeled F3'.
Compared with the embodiment, the method has the advantages that some metal ions are generated in the ash due to the lack of the complexing agent, so that the integral ash is generatedThe score is very high. Therefore, the whole deashing effect is not good, and the ash content is 2.85%. Meanwhile, SEM shows that the morphology structure of the activated coal-based capacitance carbon has some pore channel structures, but the pore channel sizes are not uniform. The specific surface area of the obtained capacitance carbon was 1467.7m2/g。
The capacitance carbons prepared in examples 1 to 8 and comparative examples 1 to 3 were used as active materials, respectively, and electrode materials were prepared according to the "preparation method of electrode materials" disclosed in "preparation method of straw-based active carbon supercapacitor electrode materials with enhanced energy storage efficiency by manganese ore" in the granted patent No. ZL 201910618975.3, and the specific preparation method was:
mixing the capacitance carbon obtained in the step with acetylene black serving as a conductive agent and PTFE serving as a binder according to a mass ratio of 8:1:1, and uniformly stirring to obtain a coating solution; uniformly coating the obtained coating solution on a screen printing plate with an area of 1cm2And (3) drying the current collector on the foamed nickel in vacuum at 100 ℃ for 12h, and finally pressing the current collector into a sheet for 30s under 12MPa by using a tablet machine to obtain the electrode sheet of the super capacitor.
And performing electrochemical test according to an electrochemical test method disclosed in 'a preparation method of straw-based activated carbon supercapacitor electrode material with enhanced energy storage efficiency by manganese ore' with the granted patent number of ZL 201910618975.3, wherein the specific test method comprises the following steps: a three-electrode system is adopted, the prepared electrode material is used as a working electrode, Ag/AgCl (saturated KCl solution) is used as a reference electrode, a Pt sheet is used as an auxiliary electrode, 6mol/L KOH aqueous solution is used as electrolyte, and cyclic volt-ampere, electrochemical impedance and constant-current charge and discharge tests are performed on a Shanghai Hua CHI660E electrochemical workstation. The results of the relevant tests are shown in tables 2 and 3.
TABLE 2 capacitance Performance data for capacitance carbons prepared in each of the examples and comparative examples
Table 3 specific capacitance values of the capacitive carbon of example 1 at different current densities
| Current Density (A. g)-1) | 0.5 | 1 | 2 | 5 | 10 | 20 | 50 | 100 |
| Specific capacitance (F.g)-1) | 368 | 297 | 262 | 239 | 226 | 204 | 171 | 127 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the ultralow-ash coal-based capacitance carbon is characterized by comprising the following steps of:
(1) crushing raw smokeless coal and then screening to obtain undersize coal powder;
(2) adding acid and a dispersing agent into the obtained coal powder for reaction treatment, and then carrying out solid-liquid separation, washing and drying on a reaction product to obtain acid-treated coal;
(3) activating the obtained acid-treated coal to obtain an activated material;
(4) adding water and a complexing agent into the obtained activated material, and then carrying out electrophoresis treatment under the ultrasonic condition; and
(5) and (4) carrying out solid-liquid separation, washing and drying on the product obtained in the step (4) to obtain the coal-based capacitance carbon.
2. The method of claim 1, wherein: the screening in the step (1) is multi-stage screening, and the granularity of undersize coal dust obtained after multi-stage screening is smaller than 400 meshes.
3. The method of claim 1, wherein: in the step (2), acid and a dispersing agent are added into the obtained coal powder for reaction treatment, and the reaction treatment is carried out in two steps, wherein in the first step, hydrofluoric acid and the dispersing agent are added for reaction treatment, and in the second step, one of hydrochloric acid and sulfuric acid and the dispersing agent are further added for reaction treatment.
4. The production method according to claim 3, characterized in that: in the first step and the second step, the mass ratio of the addition amount of the acid to the pulverized coal is 2:1-6: 1.
5. The method of claim 4, wherein: in the first step and the second step, the addition amount of the dispersing agent is 0.2-2 wt% of the mass of the coal powder.
6. The production method according to any one of claims 1 to 5, characterized in that: the dispersing agent is at least one of ethanol, polyethylene wax, polyethylene glycol, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and sodium dodecyl benzene sulfonate.
7. The method of claim 1, wherein: in the step (4), when the electrophoresis treatment is carried out under the ultrasonic condition, the frequency of the ultrasonic treatment is 25 KHz-60 KHz, and the power is 150W-240W.
8. The method of claim 1, wherein: in the step (4), the addition amount of the complexing agent is 5-20 wt% of the mass of the coal powder.
9. The production method according to claim 1 or 8, characterized in that: the complexing agent is at least one selected from EDTA, sodium tripolyphosphate, oxalic acid, sulfosalicylic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and disodium nitrilotriacetate.
10. The method of claim 1, wherein: in the step (3), during the activation treatment, KOH is used as an activating agent, and the activation treatment is carried out for 60-90min at the temperature of 750-900 ℃ under the nitrogen atmosphere.
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