CN115249589A - Method for preparing activated carbon for supercapacitor by using coal gasification fine ash - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000003245 coal Substances 0.000 title claims abstract description 59
- 238000002309 gasification Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000003213 activating effect Effects 0.000 claims abstract description 31
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims description 64
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 21
- 230000004913 activation Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 36
- 238000001994 activation Methods 0.000 description 17
- 239000011148 porous material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 235000001759 Citrus maxima Nutrition 0.000 description 2
- 244000276331 Citrus maxima Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- 244000097592 Ptelea trifoliata Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
A method for preparing activated carbon for a supercapacitor by using coal gasification fine ash belongs to the field of activated carbon preparation. The invention aims to solve the problems that high-value utilization of coal gasification fine ash is difficult to realize in the prior art, and the synthesis process of activated carbon for a supercapacitor is complex. The preparation method comprises the following steps: 1. pickling with HCl at constant temperature; 2. pickling with HF at constant temperature; 3. and (4) activating. The method is used for preparing the activated carbon for the supercapacitor by using the coal gasification fine ash.
Description
Technical Field
The invention belongs to the field of activated carbon preparation.
Background
Coal gasification technology has been rapidly developed in China in recent years as an important way for clean and efficient utilization of coal. However, the production of coal gasification fine ash is rapidly increasing along with the large-scale operation of coal gasification plants. And because an effective treatment method is lacked, the coal gasification fine ash is still treated by adopting a stockpiling and landfill method at present, which not only causes waste of coal resources, but also causes serious influence on the ecological environment, and is becoming a key technical problem restricting the sustainable development of the modern coal chemical industry.
The existing coal gasification fine ash resource utilization mostly adopts a combustion mode. In the patent of 'a device and a method for directly burning high-water content coal gasification fine ash' (the patent number is 202111496300.X, the application published: 12 and 9 in 2021, and the application published: CN 114046505A), air is heated to 300 ℃ by an air preheating device, so that coal gasification fine ash containing 31-55% of water is directly burned in an incinerator, but the treatment method is not favorable for realizing high-value utilization of the coal gasification fine ash. In order to solve the problem, a high-value treatment technology of the coal gasification fine ash is needed to promote large-scale resource treatment of the coal gasification fine ash.
The coal gasification fine ash has the characteristics of fine granularity and high porosity, and has the potential of being used as a raw material of the active carbon of the super capacitor. Meanwhile, the existing activated carbon for the super capacitor has the problems of complex synthesis process, high cost, low yield, large influence of equipment conditions on the electrochemical performance of materials and the like. In order to solve the problems, domestic and foreign researchers use waste or cheap raw materials to prepare the activated carbon for the super capacitor. According to the patent of a method for preparing biomass porous carbon for a supercapacitor based on shaddock peel (patent number 202110437801.4, published, 7-month-30-2021 and application published, CN 113184848A), the shaddock peel is subjected to crushing, high-temperature hydrothermal carbonization, zinc chloride activation and other steps to prepare the supercapacitor active carbon with the specific capacitance of 132F/g. In the patent of a method for preparing a supercapacitor based on biogas residue activated carbon after biomass anaerobic dry fermentation (the patent number is 201711045392.3, the published date is 2018, 1 and 30 months, and the application publication number is CN 107644742A), biogas residue after biomass fermentation is used as a raw material, and the activated carbon with the specific capacitance of 208F/g is prepared by washing, drying, carbonizing at 500 ℃ and activating potassium hydroxide. Although the biomass is abundant in yield and cheap in price, the carbonization process is required. In a patent of a method for preparing activated carbon of a super capacitor (the patent number is 201810251425.8, the published date is 2018, 6 and 15, and the application publication number is CN 108163855A), the activated carbon with the specific capacitance of 152F/g is prepared by high-temperature melting of potassium hydroxide, mixing and activating of potassium hydroxide and petroleum coke, acid washing and water washing, but the step is complicated because the potassium hydroxide is required to be in a molten state before activation.
Disclosure of Invention
The invention aims to solve the problems that high-value utilization of coal gasification fine ash is difficult to realize in the prior art and the synthesis process of activated carbon for a super capacitor is complex, and further provides a method for preparing activated carbon for the super capacitor by using the coal gasification fine ash.
A method for preparing activated carbon for a supercapacitor by using coal gasification fine ash comprises the following steps:
1. adding the coal gasification fine ash into HCl solution for constant temperature acid washing, then carrying out suction filtration, washing and drying to obtain a product after constant temperature acid washing;
2. adding the product after constant-temperature acid washing into 5-40% by mass of HF solution, keeping the temperature constant for 1-4 h at 30-80 ℃, and then performing suction filtration, washing and drying to obtain a residual carbon sample;
the mass ratio of the product after constant-temperature acid washing to the HF solution with the mass percent of 5-40% is 1 (2-5);
3. and activating the residual carbon sample, and then sequentially cooling, pickling, filtering, washing and drying to obtain the activated carbon for the supercapacitor.
The invention has the beneficial effects that:
the method takes the coal gasification fine ash as a raw material, and utilizes the characteristics of high yield of the coal gasification fine ash and developed residual carbon pores, so that the activated carbon for the supercapacitor obtained by the method has rich pores, large specific surface area and high specific capacitance. Firstly, the minerals such as metal oxide, silicon dioxide and silicate in the coal gasification fine ash are removed by HCl-HF combined acid washing, and the recovery of residual carbon is realized. And then activating the residual carbon sample to obtain an activated carbon product with ultrahigh specific surface area. The invention utilizes the porous structure of the residual carbon in the coal gasification fine ash to activate the residual carbonThe etching reaction of the particle surface creates a large amount of pore structure. Compared with the traditional activated carbon preparation process, the activation method does not need a carbonization process. The specific surface area of the finally obtained activated carbon product is up to 1200m 2 /g～2290m 2 (ii) in terms of/g. Taking the sample with the highest specific surface area as an example, the sample shows better capacitance characteristics, rate capability and cycle characteristics. After the material is cycled for 10000 times under the current density of 10A/g, the capacitance retention rate of the material reaches 128.7 percent, and the capacitance value is 135.56F/g. The invention realizes the high-value utilization of the coal gasification fine ash, and simultaneously has the advantages of simpler activation process and lower cost.
Compared with the traditional process, the preparation process of the invention does not need carbonization and preheating processes (the preparation process can be directly activated at 500-1000 ℃), reduces the cost of raw materials and greatly simplifies the preparation process. The method not only can bring more economic benefits and social benefits for enterprises, but also has great significance for promoting the development of renewable energy sources, assisting the realization of the aims of 'carbon peak reaching and carbon neutralization' and improving the utilization rate of coal resources.
Drawings
FIG. 1 is a constant current charge/discharge test chart of a three-electrode battery prepared by using a D-8-5 activated carbon sample, wherein 1 is 0.5A/g,2 is 1A/g,3 is 5A/g,4 is 10A/g, and 5 is 20A/g;
FIG. 2 is a graph of the cycling stability test of a three-electrode battery prepared by using a D-8-5 activated carbon sample under a current density of 10A/g for 10000 cycles, wherein 1 is a capacitance retention rate, and 2 is a specific value.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a method for preparing activated carbon for a supercapacitor by using coal gasification fine ash, which comprises the following steps:
1. adding the coal gasification fine ash into HCl solution for constant-temperature acid washing, then carrying out suction filtration, washing and drying to obtain a product after constant-temperature acid washing;
2. adding the product after constant-temperature acid washing into 5-40% of HF solution by mass percent, keeping the temperature for 1-4 h at the temperature of 30-80 ℃, and then performing suction filtration, washing and drying to obtain a residual carbon sample;
the mass ratio of the product after constant-temperature acid washing to the HF solution with the mass percent of 5-40% is 1 (2-5);
3. and activating the residual carbon sample, and then sequentially cooling, pickling, filtering, washing and drying to obtain the activated carbon for the supercapacitor.
In the first step of the specific embodiment, the coal gasification fine ash is added into HCl solution for constant-temperature acid washing to remove minerals such as metal oxides; and adding the product after constant-temperature acid washing into an HF solution to remove minerals such as silicon dioxide, silicate and the like.
The gasified ash is different from the common raw materials in the prior patent, and the residual carbon has a rich pore structure in the gasification process, so that in order to realize high-value utilization of the gasified fine ash and promote large-scale resource treatment, the embodiment discloses a method for preparing activated carbon for a supercapacitor by using the gasified fine ash.
The beneficial effects of this embodiment are:
in the present embodiment, the gasified fine ash is used as a raw material, and the characteristics of large yield of the gasified fine ash and developed pores of residual carbon are utilized, so that the activated carbon for the supercapacitor obtained by the present embodiment has rich pores, a large specific surface area and a high specific capacitance. Firstly, the minerals such as metal oxide, silicon dioxide and silicate in the coal gasification fine ash are removed by HCl-HF combined acid washing, and the recovery of residual carbon is realized. And then activating the residual carbon sample to obtain an activated carbon product with ultrahigh specific surface area. In the embodiment, the porous structure of the residual carbon in the coal gasification fine ash is utilized, and a large amount of porous structures are generated through the etching reaction of the activating agent on the surfaces of the residual carbon particles. Compared with the traditional activated carbon preparation process, the activation method used in the embodiment does not need a carbonization process. The specific surface area of the finally obtained activated carbon product is up to 1200m 2 /g～2290m 2 (ii) in terms of/g. Taking the sample with the highest specific surface area as an example, the sample shows better capacitance characteristics, rate capability and cycle characteristics. The capacity retention of the material after 10000 times of circulation under the current density of 10A/g128.7% is reached, and the capacitance value is 135.56F/g. The embodiment realizes high-value utilization of the coal gasification fine ash, simplifies the activation process and has lower cost.
Compared with the traditional process, the preparation process of the embodiment does not need carbonization and preheating processes (the carbonization and preheating processes can be directly activated at 500-1000 ℃), reduces the cost of raw materials and greatly simplifies the preparation process. The method not only can bring more economic benefits and social benefits for enterprises, but also has great significance for promoting the development of renewable energy sources, assisting the realization of the aims of carbon peak reaching and carbon neutralization and improving the utilization rate of coal resources.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the constant-temperature acid washing in the step one is specifically to add the coal gasification fine ash into 5-20% of HCl solution by mass percent, and then carry out acid washing for 1-4 h at a constant temperature under the condition that the temperature is 30-80 ℃; the mass ratio of the coal gasification fine ash to the HCl solution with the mass percent of 5-20% is 1 (2-5). The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the washing in the first step, the second step and the third step is to take distilled water as a washing liquid and wash the washing liquid until the washing liquid is neutral. The rest is the same as the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the acid washing in the third step is specifically washing for 1-6 h by using dilute hydrochloric acid with the mass percent of 10-15%. The others are the same as in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the activation in the third step is to uniformly mix the carbon residue sample with the activating agent and then activate the mixture for 0.5 to 3 hours under the conditions of specific atmosphere and temperature of 500 to 1000 ℃; the mass ratio of the carbon residue sample to the activating agent is 1 (1-5). The rest is the same as the first to fourth embodiments.
Concrete exampleThe sixth implementation mode comprises the following steps: the difference between this embodiment and one of the first to fifth embodiments is: the specific atmosphere is water vapor and CO 2 、N 2 And Ar, wherein the flow rate of the specific atmosphere is 100 mL/min-1000 mL/min; the activating agent is KOH, naOH or ZnCl 2 、ZnSO 4 And H 3 PO 4 One or more of them are mixed. The rest is the same as the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: the activation in the third step is specifically to activate the carbon residue sample for 0.5 to 3 hours under the condition of the atmosphere containing active gas and the temperature of 500 to 1000 ℃. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the atmosphere containing the active gas is the active gas or the combination of inert gas and the active gas; the active gas is water vapor and CO 2 One or a combination of two of them; the inert gas is N 2 And Ar in one or a combination of two; the flow rate of the atmosphere containing the active gas is 100 mL/min-1000 mL/min. The others are the same as in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and step two, adding the product after constant-temperature acid washing into an HF solution with the mass percent of 20-40%, keeping the temperature for 3-4 h at the temperature of 30-60 ℃, and then performing suction filtration, washing and drying to obtain a residual carbon sample. The other points are the same as those in the first to eighth embodiments.
The specific implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the mass ratio of the product after the constant-temperature acid washing in the step two to the HF solution with the mass percent of 5-40% is 1 (4-5). The others are the same as in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a method for preparing activated carbon for a supercapacitor by using coal gasification fine ash comprises the following steps:
1. adding the coal gasification fine ash into HCl solution for constant-temperature acid washing, then carrying out suction filtration, washing and drying to obtain a product after constant-temperature acid washing;
the coal gasification fine ash is dry ash;
2. adding the product after constant-temperature acid washing into an HF solution with the mass percent of 20%, keeping the temperature constant for 3 hours at the temperature of 60 ℃, and then performing suction filtration, washing and drying to obtain a residual carbon sample;
the mass ratio of the product after constant-temperature acid washing to the HF solution with the mass percent of 20% is 1:5;
3. and activating the residual carbon sample, and then sequentially cooling, pickling, filtering, washing and drying to obtain the activated carbon for the supercapacitor, which is marked as G-8-5.
The coal gasification fine ash comprises dry ash, water ash and cake ash, and in the step one, the dry ash is one of coal gasification fine ash.
The constant-temperature acid washing in the step one is specifically to add the coal gasification fine ash into a 15% HCl solution by mass percent, and then carry out constant-temperature acid washing for 3 hours at the temperature of 60 ℃; the mass ratio of the coal gasification fine ash to the HCl solution with the mass percent of 15% is 1:5.
The washing in the first step, the second step and the third step is specifically to use distilled water as a washing liquid and wash the washing liquid until the washing liquid is neutral; the acid washing in the third step is specifically washing for 1 hour by using dilute hydrochloric acid with the mass percentage of 10%;
the activation in the third step is specifically that the carbon residue sample and the activating agent are uniformly mixed, then the mixture is placed in a horizontal tube furnace at 800 ℃ and activated for 1h under the conditions of specific atmosphere and 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:5; the specific atmosphere is N 2 The specific atmosphere flow is 200mL/min; the activating agent is KOH;
example two: the difference between the present embodiment and the first embodiment is: the activation in the third step is specifically to uniformly mix the carbon residue sample with an activating agent, then place the mixture in a horizontal tube furnace at 800 ℃, and activate the mixture for 1 hour under the conditions of specific atmosphere and 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:4; and marking the activated carbon for the supercapacitor obtained in the step three as G-8-4. The rest is the same as in the first embodiment.
Example three: the difference between the present embodiment and the first embodiment is: the activation in the third step is specifically that the carbon residue sample and the activating agent are uniformly mixed, then the mixture is placed in a horizontal tube furnace at 800 ℃ and activated for 1h under the conditions of specific atmosphere and 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:3; and marking the activated carbon for the supercapacitor obtained in the step three as G-8-3. The rest is the same as the first embodiment.
Example four: the difference between the present embodiment and the first embodiment is: the activation in the third step is specifically that the carbon residue sample and the activating agent are uniformly mixed, then the mixture is placed in a horizontal tube furnace at 800 ℃ and activated for 1h under the conditions of specific atmosphere and 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:2; and marking the activated carbon for the supercapacitor obtained in the step three as G-8-2. The rest is the same as the first embodiment.
Example five: the difference between the present embodiment and the first embodiment is: the activation in the third step is specifically to uniformly mix the carbon residue sample with an activating agent, then place the mixture in a horizontal tube furnace at 800 ℃, and activate the mixture for 1 hour under the conditions of specific atmosphere and 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:1; and marking the activated carbon for the supercapacitor obtained in the step three as G-8-1. The rest is the same as the first embodiment.
Comparison test one: the difference between the present embodiment and the first embodiment is: the activation in the third step is specifically that a carbon residue sample and an activating agent are uniformly mixed, then distilled water is added, the mixture is soaked for 4 hours at room temperature, the soaked mixture is dried for 24 hours at the temperature of 90 ℃ to remove moisture, then the obtained solid is ground and placed in a horizontal tube furnace, the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min, and the activation is carried out for 1 hour at the specific atmosphere and the temperature of 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:4; the volume ratio of the mass of the carbon residue sample to the distilled water is 1g; and marking the activated carbon for the supercapacitor obtained in the step three as G-J-10-8-4. The rest is the same as in the first embodiment.
Comparative experiment two: the difference between the present embodiment and the first embodiment is: the activation in the third step is specifically that the carbon residue sample and the activating agent are uniformly mixed, then the mixture is placed in a horizontal tube furnace, the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min, and the mixture is activated for 1 hour under the conditions of specific atmosphere and 800 ℃; the mass ratio of the residual carbon sample to the activating agent is 1:4; and marking the activated carbon for the supercapacitor obtained in the step three as G-10-8-4. The rest is the same as the first embodiment.
(1) N was performed by using the activated carbon for a supercapacitor obtained in the examples and comparative experiments 2 Adsorption test experiments, the specific surface area of each sample was evaluated.
TABLE 1 specific surface area and Total pore volume of samples under different activation conditions
As can be seen from the results in table 1, the specific surface area of comparative test two is higher than that of comparative test one, which proves that when the activated carbon for a supercapacitor is prepared by using the coal gasification fine ash as the raw material, the specific surface area of the activated carbon product is not greatly affected by the residual carbon and KOH soaking and non-soaking. And the sample without soaking carbon residue and KOH obtains higher specific surface area instead, which reaches 2,071.42m 2 G (comparative run two). The specific surface area and the total pore volume of the comparative experiment two and the example two are similar. This shows that whether preheating is carried out or not does not influence the preparation of the activated carbon for the supercapacitor from the coal gasification fine ash.
(2) Variation of the amount of activator KOH
TABLE 2 specific surface area and total pore volume for each sample at different KOH activators
From the results in table 2, it can be seen that as the amount of KOH as an activator is increased, the specific surface area of the obtained activated carbon product is also increased. Example one the sample obtained has the highest specific surface area reaching 2224.62m 2 (ii) in terms of/g. According to the national active carbon standard for super capacitors (GB/T37386-2019), the first and second embodiments meet the product requirements of the active carbon for the I-grade super capacitor, the third and fourth embodiments meet the product requirements of the active carbon for the II-grade super capacitor, and the fifth embodiment meets the product of the active carbon for the III-grade super capacitor.
(3) Evaluation of electrochemical Properties of D-8-5 sample
Uniformly mixing 24mg of D-8-5 sample, 3mg of acetylene black and 3mg of polytetrafluoroethylene according to the mass ratio of 80% to 10%, adding 0.5mL of N-methyl-2-pyrrolidone (NMP) solvent to obtain slurry, and uniformly coating the slurry on a foamed nickel collector (with the area of 1 cm) 2 ) The coating mass was about 5mg. The coated electrode was dried in a vacuum oven at 120 ℃ for 12h, cooled to room temperature and then taken out and pressed into a sheet under a pressure of 10MPa to give a sample coated current collector in a three-electrode cell: a platinum sheet was used as the counter electrode, a saturated calomel electrode was used as the reference electrode, the sample coated current collector was used as the working electrode, and a 6M KOH solution was used as the electrolyte.
FIG. 1 is a constant current charge/discharge test chart of a three-electrode battery prepared by using a D-8-5 activated carbon sample, wherein 1 is 0.5A/g,2 is 1A/g,3 is 5A/g,4 is 10A/g, and 5 is 20A/g; FIG. 2 is a graph of a three-electrode battery prepared from a D-8-5 activated carbon sample and used for testing the cycling stability of the battery after 10000 cycles at a current density of 10A/g, wherein 1 is a capacitance retention rate, and 2 is a specific ratio; the data in figure 1 are detailed in a table 3, and the activated carbon product has better capacitance characteristic and cycle characteristic after electrochemical performance test. The mass specific capacitance of the material reaches 113.34F/g (Table 3) at a current density of 10A/g. Meanwhile, in a constant current charge and discharge test, after circulation for 10000 times, the capacitance retention rate of the material reaches 128.7 percent, and the specific capacitance value is 135.56F/g (figure 2).
TABLE 3 Mass specific capacitance of D-8-5 at different current densities
Claims (10)
1. A method for preparing activated carbon for a supercapacitor by using coal gasification fine ash is characterized by comprising the following steps:
1. adding the coal gasification fine ash into HCl solution for constant temperature acid washing, then carrying out suction filtration, washing and drying to obtain a product after constant temperature acid washing;
2. adding the product after constant-temperature acid washing into 5-40% by mass of HF solution, keeping the temperature constant for 1-4 h at 30-80 ℃, and then performing suction filtration, washing and drying to obtain a residual carbon sample;
the mass ratio of the product after constant-temperature acid washing to the HF solution with the mass percent of 5-40% is 1 (2-5);
3. and activating the residual carbon sample, and then sequentially cooling, pickling, filtering, washing and drying to obtain the activated carbon for the supercapacitor.
2. The method for preparing activated carbon for a supercapacitor by using coal gasification fine ash according to claim 1, wherein the constant temperature acid washing in the step one is to add the coal gasification fine ash into a 5-20% HCl solution by mass percent, and then perform constant temperature acid washing for 1-4 h at a temperature of 30-80 ℃; the mass ratio of the coal gasification fine ash to the HCl solution with the mass percent of 5-20% is 1 (2-5).
3. The method for preparing activated carbon for a supercapacitor by using coal gasification fine ash according to claim 1, wherein the washing in the first step, the second step and the third step is performed by using distilled water as a washing liquid and washing until the washing liquid is neutral.
4. The method for preparing activated carbon for a supercapacitor by using coal gasification fine ash according to claim 1, wherein the acid washing in the step three is specifically washing for 1-6 h by using dilute hydrochloric acid with the mass percent of 10-15%.
5. The method for preparing activated carbon for a supercapacitor by using coal gasification fine ash according to claim 1, wherein the activation in the third step is to mix the residual carbon sample with the activating agent uniformly, and then activate the mixture for 0.5 to 3 hours under the specific atmosphere and at the temperature of 500 to 1000 ℃; the mass ratio of the carbon residue sample to the activating agent is 1 (1-5).
6. The method for preparing activated carbon for super capacitor from coal gasification fine ash according to claim 5, wherein the specific atmosphere is steam and CO 2 、N 2 And Ar, wherein the specific atmosphere flow is 100 mL/min-1000 mL/min; the activating agent is KOH, naOH or ZnCl 2 、ZnSO 4 And H 3 PO 4 One or more of them are mixed.
7. The method for preparing activated carbon for a supercapacitor by using coal gasification fine ash according to claim 1, wherein the activation in the third step is specifically to activate the carbon residue sample for 0.5h to 3h under the condition of an atmosphere containing active gas and a temperature of 500 ℃ to 1000 ℃.
8. The method of claim 7, wherein the atmosphere containing active gas is active gas or a combination of inert gas and active gas; the active gas is water vapor and CO 2 One or a combination of two of them; the inert gas is N 2 And Ar in one or a combination of two; the atmosphere flow containing active gasIs 100mL/min to 1000mL/min.
9. The method for preparing activated carbon for a supercapacitor by using coal gasification fine ash according to claim 1, wherein in the second step, the product after constant temperature pickling is added into an HF solution with the mass percent of 20-40%, the temperature is kept constant for 3-4 h at the temperature of 30-60 ℃, and then the sample is subjected to suction filtration, washing and drying to obtain a residual carbon sample.
10. The method for preparing activated carbon for a supercapacitor from coal gasification fine ash according to claim 1, wherein the mass ratio of the product after constant-temperature acid washing in the step two to the HF solution with the mass percent of 5-40% is 1 (4-5).
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