AU2020101283A4 - Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage - Google Patents
Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage Download PDFInfo
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- AU2020101283A4 AU2020101283A4 AU2020101283A AU2020101283A AU2020101283A4 AU 2020101283 A4 AU2020101283 A4 AU 2020101283A4 AU 2020101283 A AU2020101283 A AU 2020101283A AU 2020101283 A AU2020101283 A AU 2020101283A AU 2020101283 A4 AU2020101283 A4 AU 2020101283A4
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- activated carbon
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- super capacitor
- electrode material
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003990 capacitor Substances 0.000 title claims abstract description 41
- 238000003914 acid mine drainage Methods 0.000 title claims abstract description 27
- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000004146 energy storage Methods 0.000 title claims abstract description 8
- 239000010902 straw Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 26
- 239000008188 pellet Substances 0.000 claims description 25
- 239000011261 inert gas Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 19
- 239000005539 carbonized material Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention discloses a method for manufacturing a straw-based activated carbon
electrode material for super capacitor with energy storage efficiency enhanced through acid mine
drainage (AMD). In the method, straws are soaked in the AMD, carbonized and activated at high
5 temperature, and the resulting activated products are soaked in acid, washed with water, and dried
to obtain an activated carbon as an electrode material for super capacitor. With a
microporous/mesoporous phase-combining pore structure, a higher specific surface area, and cycle
stability, the activated carbon manufactured by the present invention is a relatively ideal electrode
material for super capacitor; moreover, not only can the method of the present invention realize the
10 higher value application of straws, but also reduces the environmental pollution caused by the AMD.
DRAWINGS
FIG.1I
600 2C a [email protected].
- P 400
E
Q~ 300- E 1.0
0V
0
100
-AC.500-2.6
0. -AC-500-O 0 L 0.0
0.0 01 0.4 0'6 0.8 1.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4,5 5.0
Relative pressure (P/PO) Pore size (nm)
FIG. 2
Description
FIG.1I
600 a 2C [email protected].
- P 400 E Q~ 300- E 1.0 V
0 100 -AC.500-2.6 0. -AC-500-O 0 L 0.0
0.0 01 0.4 0'6 0.8 1.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4,5 5.0 Relative pressure (P/PO) Pore size (nm)
FIG. 2
The present invention relates to the field of electrochemistry, and in particular to a method for manufacturing a straw-based activated carbon electrode material for super capacitor.
With the rapid development of economy, a large number of non-renewable energy sources, such as fossil fuel, are drying up, environment which human being lives on is being polluted, and environmental problems, such as greenhouse effect, acid rain, and ozone hole, have severe effects on people's quality of life. Therefore, sustainable development strategy has been put forward; a variety of clean energy and renewable energy, such as wind energy, tidal energy, solar energy, and geothermal energy, are investigated, developed and utilized, and these energy sources can be converted into electric energy for storage and used in daily life. However, efficient storage and energy release is a challenge to be overcome, and developing a green, eco-friendly, and efficient energy storage device has been a research hotspot.
So far, energy accumulators principally include a variety of batteries (e.g., lead storage battery, lithium-sulfur battery, lithium ion battery, and fuel cell), conventional capacitors, and super capacitors. A super capacitor refers to a novel power energy storage electronic part enabling rapid charge and discharge, featuring high power and long service life, and filling in gaps in specific energy and specific power between conventional capacitors and batteries. Further, with advantages of high safety and broad range of application, super capacitors can be used in a plurality of fields and has received widespread attention today. Therefore, it is of practical significance in research on super capacitors.
Electrode material is a key factor influencing the properties of super capacitors. Specifically, featuring high specific surface area, porosity, and excellent electrical conductivity, carbon materials become electrode materials most widely used in electric double-layer capacitors; however, carbon materials are mostly from non-renewable energy sources, such as coal and petroleum, and the environment is polluted in the manufacturing process thereof Therefore, seeking for a renewable raw material is a research focus in the prior art. China is an agricultural country, and more than 4 billion tons of agricultural solid waste is produced every year, of which the total amount of crop straw is 0.7 billion tons. Use of agricultural solid waste straws as raw materials not only reduces environmental pollution, but also maximizes resource utilization and save costs. In recent years, considerable research has been undertaken to manufacture activated carbon using corn straw, rice straw, and wheat straw, but performance optimization for straw-based activated carbon is less desirable. Therefore, how to optimize electrochemical properties of the straw-based activated carbon has become a focus of attention so far.
The present invention provides a method for manufacturing a straw-based activated carbon electrode material for super capacitor with energy storage efficiency enhanced through acid mine drainage, and aims to effectively manufacture a high-performance electrode material with structural stability, high electrical conductivity, and high porosity.
To solve the above technical problems, the present invention adopts the following technical solution:
A method for manufacturing a straw-based activated carbon electrode material for super capacitor with energy storage efficiency enhanced through acid mine drainage (AMD) is provided, where: straws are soaked in the AMD, carbonized and activated at high temperature, and the resulting activated products are soaked in acid, washed with water, and dried to obtain an activated carbon as an electrode material for super capacitor. The method is specifically conducted according to the following steps:
(1) drying straws for 4-5 h at 80-100°C, pulverizing, and sieving through a 40-100 mesh sieve, to obtain straw pellets for use;
(2) soaking the straw pellets in the AMD at a pH of 1.0-6.0, sonicating for 1-2 h, soaking for 8 9 h at room temperature again, and then drying in an oven at 80-100°C to obtain treated straw pellets;
(3) placing the treated straw pellets in a high-temperature pipe boiler, heating to 400-600°C under an inert gas atmosphere at a heating rate of 2-15°C/min, carbonizing for 0.5-2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, taking out and grinding the straw pellets into powders to obtain carbonized material powders;
(4) mixing the carbonized material powders with an activator in a mass ratio of 1:(1-4), then adding deionized water (mass-to-volume ratio of carbonized material powders to water = 1 g:(30 150) mL)), ultrasonically dispersing uniformly, and heating in a water bath at 80°C for 10-12 h; drying the resulting products in a drying oven for 2-3 h at 80-100°C, then placing in the high temperature pipe boiler, heating to 650-900°C under the inert gas atmosphere at a heating rate of 2 15°C/min, activating for 0.5-2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, to obtain activated products; and
(5) placing the activated products in concentrated acid, ultrasonically soaking for 10-30 min, washing with water at 80°C until neutral, then drying the products in the oven for 10-12 h at 80 100°C, and finally sieving through a 200-400 mesh sieve to obtain an activated carbon as an electrode material for super capacitor.
Further, the activated carbon is mixed with a conductive agent and a binder in a mass ratio of (7-9):(1-2):(1-2), and an adequate amount of organic solvent is added dropwise and stirred well to obtain a coating liquid; the coating liquid is applied uniformly to a current collector using a screen printing plate, and vacuum dried for 12-14 h at 90-100°C; finally, the current collector is pressed on a sheeter at 10-15 MPa for 10-30 s to manufacture a super capacitor electrode slice. Further, the conductive agent is acetylene black, carbon black, or graphite, and preferably acetylene black; the binder is polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), and preferably PTFE; the organic solvent is absolute ethanol or N-methylpyrrolidone, and preferably N-methylpyrrolidone; the current collector is copper foil, aluminum foil, nickel foam, or carbon paper, and preferably nickel foam.
Further, the straw is rice straw, wheat straw, rape stalk, or corn stalk.
Further, the inert gas in steps (3) and (4) is high purity nitrogen, high purity argon, or carbon dioxide, and preferably high purity nitrogen.
Further, the activator in step (4) is solid powders of at least one of potassium hydroxide, sodium hydroxide, phosphoric acid, or zinc chloride, and preferably analytically pure solid potassium hydroxide powder.
Further, the concentrated acid in step (5) is concentrated nitric acid or concentrated hydrochloric acid, and preferably concentrated hydrochloric acid; the concentrated acid has a mass concentration of 20-37.5%.
The AMD of the present invention can either obtained from AMD-contaminated reservoirs, e.g., AMD-contaminated reservoirs in a pyrite mine, or artificially synthesized. There are heteroatoms (nitrogen, oxygen, and sulfur) and metal ions (magnesium, manganese, etc.). In manufacturing the activated carbon, these heteroatoms can be doped in situ to form different functional groups; these functional groups can participate in Faradaic reactions to provide a pseudocapacitor and enhance the wettability of the carbon material, leading to an increase in specific capacitance of the super capacitor.
Compared with the prior art, the invention has the following beneficial effects:
1. A super capacitor manufactured with blank straw has a specific capacitance of 168.0 Fg 1
, whereas the super capacitor manufactured by soaking straws in the AMD in the present invention has a specific capacitance of as high as 261.8 Fg1 , increasing by 55.8% compared with the specific capacitance of the super capacitor manufactured with blank straw. The activated carbon obtained by the method of the present invention is a relatively ideal electrode material for super capacitor, featuring structural stability, excellent porosity (with a microporous/mesoporous phase-combining pore structure and a higher specific surface area), high specific capacitance, and cycle stability.
2. The present invention realizes the higher value application of straws; moreover, doping by soaking straws in the AMD not only reduces the environmental pollution caused by the AMD, but also turns waste into wealth, saves costs, realizes waste resourcization, and possesses both environmental and economic benefits.
3. The method provided by the present invention is easy to operate and feasible, featuring relatively mild reaction conditions, energy conservation, environmental protection, simple post treatment process, and high reproducibility.
FIG. 1 depicts field emission scanning electron microscopy (FESEM) images of an activated carbon sample AC-500-2.6 obtained in Example 1 of the present invention, where a and b correspond to different magnifications;
FIG. 2 depicts low-temperature nitrogen (N2) adsorption-desorption isotherms (a) and pore volume distribution (b) of activated carbon samples AC-500-2.6 and AC-500-0 obtained in Example 1 of the present invention.
The method of the present invention will be described below in conjunction with examples. The section merely describes exemplarily and explanatorily; the embodiments described below are only a part of, not all of, the embodiments of the invention, and the invention is not so limited.
Example 1
In the example, an activated carbon was manufactured according to the following steps:
(1) drying collected straws for 5 h at 80°C, pulverizing, and sieving through a 40-mesh sieve, to obtain straw pellets for use;
(2) soaking the straw pellets in AMD (pH 2.6), sonicating for 2 h, soaking for 8 h at room temperature again, and then drying in an oven at 90°C to obtain treated straw pellets;
(3) placing 6 g of the treated straw pellets in a high-temperature pipe boiler, heating to 500°C under an inert gas atmosphere at a heating rate of 5°C/min, carbonizing for 1 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, taking out and grinding the straw pellets into powders to obtain carbonized material powders;
(4) mixing 3 g of the carbonized material powders with 6 g of solid potassium hydroxide (KOH) powders, then adding 200 mL of deionized water, ultrasonically dispersing uniformly, and heating in a water bath at 80°C for 10 h;
drying the resulting products in a drying oven for 3 h at 90°C, then placing in the high temperature pipe boiler, heating to 650°C under the inert gas atmosphere at a heating rate of 5°C/min, activating for 2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, to obtain activated products; and
(5) placing the activated products in 36.5 g/L concentrated hydrochloric acid, ultrasonically soaking for 15 min with an ultrasound machine (rated power: 100 W), washing with deionized water at 80°C until neutral, then drying the products in the oven for 10 h at 100°C, and finally sieving through a 200-mesh sieve to obtain an activated carbon as an electrode material for super capacitor, labeled as AC-500-2.6.
For the purpose of comparison, a blank control sample without soaking in the AMD was prepared, labeled as AC-500-0, in the same way as AC-500-2.6. The only difference was that step (2) was omitted.
FIG. 1 depicts FESEM images of the activated carbon sample AC-500-2.6 at different magnifications. As can clearly be seen from the figure, the material has a rough surface, which is attributable to a large number of micropores.
FIG. 2 depicts low-temperature N 2 adsorption-desorption isotherms (a) and pore volume distribution (b) of activated carbon samples AC-500-2.6 and AC-500-0. From FIG. 2(a), low temperature N 2 adsorption-desorption isotherms of activated carbon samples AC-500-2.6 and AC
500-0 have Type-IV isotherm behaviors according to International Union of Pure and Applied Chemistry (IUPCA). A steep adsorption curve at a relative pressure of <0.01 indicates maximum contribution of micropores to surface area. N 2 adsorption above partial pressure (P/PO=0.4) barely increases, indicating that N 2 molecules have almost completely filled in micropores and the activated carbon is dominated by micropores, with a small amount of mesopores. From FIG. 2(b), sample AC-500-2.6 has more significant mesopores than AC-500-0, suggesting that the activated carbon manufactured after soaking straws in the AMD has a more ordered porous structure, where there are not only a large number of micropores, but also some mesopores. Ample porous structure and high specific surface area of the activated carbon can serve as a channel of ion exchange. Therefore, the activated carbon is expected to be used as an electrode material for super capacitor.
After testing, the activated carbon AC-500-2.6 obtained in the example had a specific surface area of 1623 m2 g-1 and a total pore volume of 0.84cm 3 g- 1; with narrow pore size distribution, AC 500-2.6 was dominated by micropores and had a small amount of mesopores. Blank control AC 500-0 obtained had a specific surface area of 1380 m 2 g 1 and a total pore volume of 0.80 cm 3 g, and the pore size thereof was dominated by micropores.
The activated carbon obtained in step (5) was mixed with conductive agent acetylene black and binder polytetrafluoroethylene (PTFE) in a mass ratio of 8:1:1 and stirred well to obtain a coating liquid; the resulting coating liquid was applied uniformly to a 1 cm2 current collector nickel foam using a screen printing plate, and vacuum dried for 12 h at 100°C; finally, the current collector was pressed on a sheeter at 12 MPa for 30 s to manufacture a super capacitor electrode slice.
Using a three-electrode system and 6 M KOH solution as electrolyte, the super capacitor electrode slice obtained in the example was tested on CH1660 Electrochemical Workstation. After testing, a cyclic voltammetry curve corresponding to the electrode slice obtained in the example at different sweep rates appeared a quasi-rectangular shape, suggesting that the electrode slice was a typical carbon material-based electric double-layer capacitor; charge-discharge tests found a symmetrical triangular curve, suggesting that charge transfer reaction occurred in the electrical double layer; when a current density was 1 Ag, the corresponding specific capacitance of the activated carbon material was 198.1 Fg-1 , increasing by approximately 17.9% compared with the specific capacitance of the activated carbon manufactured with blank straw.
Example 2
In the example, an activated carbon was manufactured according to the following steps:
(1) drying collected straws for 5 h at 80°C, pulverizing, and sieving through a 40-mesh sieve, to obtain straw pellets for use;
(2) placing 200 mL of AMD at an initial pH of 2.6 in a beaker and adjusting the AMD to pH 4.0; soaking the straw pellets in AMD (pH 4.0), sonicating for 2 h, soaking for 8 h at room temperature again, and then drying in an oven at 90°C to obtain treated straw pellets;
(3) placing 6 g of the treated straw pellets in a high-temperature pipe boiler, heating to 550°C under an inert gas atmosphere at a heating rate of 5°C/min, carbonizing for 1 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, taking out and grinding the straw pellets into powders to obtain carbonized material powders;
(4) mixing 3 g of the carbonized material powders with 9 g of solid KOH powders, then adding 200 mL of deionized water, ultrasonically dispersing uniformly, and heating in a water bath at 80°C for 10 h;
drying the resulting products in a drying oven for 3 h at 90°C, then placing in the high temperature pipe boiler, heating to 750°C under the inert gas atmosphere at a heating rate of 5°C/min, activating for 2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, to obtain activated products; and
(5) placing the activated products in 36.5 g/L concentrated hydrochloric acid, ultrasonically soaking for 15 min with an ultrasound machine (rated power: 100 W), washing with deionized water at 80°C until neutral, then drying the products in the oven for 10 h at 100°C, and finally sieving through a 200-mesh sieve to obtain an activated carbon as an electrode material for super capacitor.
After testing, the activated carbon obtained in the example had a specific surface area of 1703 m2 g 1 and a total pore volume of 0.91 cm3 g- 1 ; with narrow pore size distribution, the activated carbon was dominated by micropores and mesopores.
The activated carbon obtained in step (5) was mixed with conductive agent acetylene black and binder PTFE in a mass ratio of 8:1:1 and stirred well to obtain a coating liquid; the resulting coating liquid was applied uniformly to a 1 cm 2 current collector nickel foam using a screen printing plate, and vacuum dried for 12 h at 100°C; finally, the current collector was pressed on a sheeter at 12 MPa for 30 s to manufacture a super capacitor electrode slice.
Using a three-electrode system and 6 M KOH solution as electrolyte, the super capacitor electrode slice obtained in the example was tested on CH1660 Electrochemical Workstation. After testing, a cyclic voltammetry curve corresponding to the electrode slice obtained in the example at different sweep rates appeared a quasi-rectangular shape, suggesting that the electrode slice was a typical carbon material-based electric double-layer capacitor; charge-discharge tests found a symmetrical triangular curve, suggesting that charge transfer reaction occurred in the electrical double layer; when a current density was 1 Ag-1 , the corresponding specific capacitance of the activated carbon material was 261.8 Fg-1 , increasing by approximately 55.8% compared with the specific capacitance of the activated carbon manufactured with blank straw.
Example 3
In the example, an activated carbon was manufactured according to the following steps:
(1) drying collected straws for 5 h at 80°C, pulverizing, and sieving through a 40-mesh sieve, to obtain straw pellets for use;
(2) placing 200 mL of AMD (pH 6.0) in a beaker, soaking the straw pellets in the AMD, sonicating for 2 h, soaking for 8 h at room temperature again, and then drying in an oven at 90°C to obtain treated straw pellets;
(3) placing 6 g of the treated straw pellets in a high-temperature pipe boiler, heating to 600°C under an inert gas atmosphere at a heating rate of 5°C/min, carbonizing for 1 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, taking out and grinding the straw pellets into powders to obtain carbonized material powders;
(4) mixing 3 g of the carbonized material powders with 12 g of solid KOH powders, then adding 200 mL of deionized water, ultrasonically dispersing uniformly, and heating in a water bath at 80°C for 10 h;
drying the resulting products in a drying oven for 3 h at 90°C, then placing in the high temperature pipe boiler, heating to 850°C under the inert gas atmosphere at a heating rate of 5°C/min, activating for 2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, to obtain activated products; and
(5) placing the activated products in 36.5 g/L concentrated hydrochloric acid, ultrasonically soaking for 15 min with an ultrasound machine (rated power: 100 W), washing with deionized water at 80°C until neutral, then drying the products in the oven for 10 h at 100°C, and finally sieving through a 200-mesh sieve to obtain an activated carbon as an electrode material for super capacitor.
After testing, the activated carbon obtained in the example had a specific surface area of 891 m 2 g 1 and a total pore volume of 0.75 cm3g- 1; with narrow pore size distribution, the activated carbon was dominated by micropores and had a thimbleful mesopores.
The activated carbon obtained in step (5) was mixed with conductive agent acetylene black and binder PTFE in a mass ratio of 8:1:1 and stirred well to obtain a coating liquid; the resulting coating liquid was applied uniformly to a 1 cm2 current collector nickel foam using a screen printing plate, and vacuum dried for 12 h at 100°C; finally, the current collector was pressed on a sheeter at 12 MPa for 30 s to manufacture a super capacitor electrode slice.
Using a three-electrode system and 6 M KOH solution as electrolyte, the super capacitor electrode slice obtained in the example was tested on CH1660 Electrochemical Workstation. After testing, a cyclic voltammetry curve corresponding to the electrode slice obtained in the example at different sweep rates appeared a quasi-rectangular shape, suggesting that the electrode slice was a typical carbon material-based electric double-layer capacitor; charge-discharge tests found a symmetrical triangular curve, suggesting that charge transfer reaction occurred in the electrical double layer; when a current density was 1 Ag1 , the corresponding specific capacitance of the activated carbon material was 139.1 Fg 1 , increasing by approximately 17.7% compared with the specific capacitance of the activated carbon manufactured with blank straw.
The above descriptions are merely preferred examples of the present invention, and are not intended to limit the present invention. Any modification, equivalent substitute and improvement without departing from the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims (5)
1. A method for manufacturing a straw-based activated carbon electrode material for super capacitor with energy storage efficiency enhanced through acid mine drainage (AMD), wherein: straws are soaked in the AMD, carbonized and activated at high temperature, and the resulting activated products are soaked in acid, washed with water, and dried to obtain an activated carbon as an electrode material for super capacitor.
2. The manufacturing method according to claim 1, comprising the following steps:
(1) drying straws for 4-5 h at 80-100°C, pulverizing, and sieving through a 40-100 mesh sieve, to obtain straw pellets for use;
(2) soaking the straw pellets in the AMD at a pH of 1.0-6.0, sonicating for 1-2 h, soaking for 8 9 h at room temperature again, and then drying in an oven at 80-100°C to obtain treated straw pellets;
(3) placing the treated straw pellets in a high-temperature pipe boiler, heating to 400-600°C under an inert gas atmosphere at a heating rate of 2-15°C/min, carbonizing for 0.5-2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, taking out and grinding the straw pellets into powders to obtain carbonized material powders;
(4) mixing the carbonized material powders with an activator in a mass ratio of 1:(1-4), then adding deionized water (mass-to-volume ratio of carbonized material powders to water = 1 g:(30 150) mL)), ultrasonically dispersing uniformly, and heating in a water bath at 80°C for 10-12 h;
drying the resulting products in a drying oven for 2-3 h at 80-100°C, then placing in the high temperature pipe boiler, heating to 650-900°C under the inert gas atmosphere at a heating rate of 2 15°C/min, activating for 0.5-2 h at a constant temperature, then stopping heating, holding under the inert gas atmosphere to cool to room temperature, to obtain activated products; and
(5) placing the activated products in concentrated acid, ultrasonically soaking for 10-30 min, washing with water at 80°C until neutral, then drying the products in the oven for 10-12 h at 80 100°C, and finally sieving through a 200-400 mesh sieve to obtain an activated carbon as an electrode material for super capacitor.
3. The manufacturing method according to claim 1 or 2, wherein: the activated carbon is mixed with a conductive agent and a binder in a mass ratio of (7-9):(1-2):(1-2), and an adequate amount of organic solvent is added dropwise and stirred well to obtain a coating liquid; the coating liquid is applied uniformly to a current collector using a screen printing plate, and vacuum dried for 12-14 h at 90-100°C; finally, the current collector is pressed on a sheeter at 10-15 MPa for 10-30 s to manufacture a super capacitor electrode slice.
4. The manufacturing method according to claim 1 or 2, wherein: the straw is rice straw, wheat straw, rape stalk, or corn stalk.
5. The manufacturing method according to claim 2, wherein: the inert gas in steps (3) and (4) is high purity nitrogen, high purity argon, or carbon dioxide.
Adsorption (cm3/g STP) DRAWINGS
Relative pressure (P/P0)
13 1/1
FIG. 2 Pore volume (cm3/ nm-1 g-1) FIG. 1
Pore size (nm)
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| CN114906847A (en) * | 2022-05-16 | 2022-08-16 | 内蒙古科技大学 | A kind of wet activation method of gasification residue carbon residue and its application |
| CN115231568A (en) * | 2022-05-27 | 2022-10-25 | 塔里木大学 | Graphene-like carbon nanosheets macroporous cross-linked cotton stalk biomass carbon electrode material and preparation method thereof |
| CN115959659A (en) * | 2022-12-12 | 2023-04-14 | 上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) | A kind of preparation method of activated carbon particle and activated carbon particle |
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| CN113511654B (en) * | 2021-04-16 | 2022-11-15 | 中国科学院山西煤炭化学研究所 | A kind of capacitor carbon and preparation method thereof |
| CN119480465A (en) * | 2024-11-11 | 2025-02-18 | 中南大学 | A two-stage activation preparation method for high specific capacitance supercapacitor carbon-based material |
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| AT407871B (en) * | 1995-11-13 | 2001-07-25 | Burgenlaendische Elek Zitaetsw | Process for producing activated carbon from plant material |
| KR100744984B1 (en) * | 1999-11-16 | 2007-08-02 | 혼다 기켄 고교 가부시키가이샤 | Electrode for electric double layer capacitor and manufacturing method thereof |
| CN100572270C (en) * | 2007-03-19 | 2009-12-23 | 合肥工业大学 | A kind of method of making organic system activated carbon for super capacitors material with stalk |
| CN101708845B (en) * | 2009-11-20 | 2011-08-24 | 中南林业科技大学 | Method for preparing activated carbon from rice husk and straw as raw materials |
| JP6131450B2 (en) * | 2013-04-23 | 2017-05-24 | 株式会社化研 | Method for purifying radioactive polluted water or factory effluent and method for forming cerium oxide-supported activated carbon used in radioactive polluted water or factory effluent purifying method |
| US9975778B2 (en) * | 2014-07-25 | 2018-05-22 | Farad Power, Inc | Method of making chemically activated carbon |
| CN105000558B (en) * | 2015-08-14 | 2017-11-28 | 赵常然 | A kind of method that activated carbon is directly produced in spent acid |
| CN106829956A (en) * | 2017-03-19 | 2017-06-13 | 西南石油大学 | A kind of method that utilization titanium white waste acid prepares active sludge carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114906847A (en) * | 2022-05-16 | 2022-08-16 | 内蒙古科技大学 | A kind of wet activation method of gasification residue carbon residue and its application |
| CN115231568A (en) * | 2022-05-27 | 2022-10-25 | 塔里木大学 | Graphene-like carbon nanosheets macroporous cross-linked cotton stalk biomass carbon electrode material and preparation method thereof |
| CN115231568B (en) * | 2022-05-27 | 2024-04-02 | 塔里木大学 | Graphene-like carbon nanosheet macroporous cross-linked cotton stalk biomass carbon electrode material and preparation method thereof |
| CN115959659A (en) * | 2022-12-12 | 2023-04-14 | 上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) | A kind of preparation method of activated carbon particle and activated carbon particle |
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