CN111573667A - Energy storage carbon material, supercapacitor and preparation method thereof - Google Patents
Energy storage carbon material, supercapacitor and preparation method thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 69
- 238000004146 energy storage Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000002006 petroleum coke Substances 0.000 claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000005977 Ethylene Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000011232 storage material Substances 0.000 abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 7
- 150000001340 alkali metals Chemical class 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 238000004227 thermal cracking Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an energy storage carbon material, a supercapacitor and a preparation method of the supercapacitor, and relates to the technical field of carbon material preparation. The petroleum coke and the alkali reagent mixture are subjected to thermal cracking treatment in the mixed atmosphere of low-carbon alkane and high-temperature steam, the petroleum coke and the alkali reagent generate an etching reaction to produce hydrogen, carbon monoxide and carbon dioxide, and different gases escape to form a plurality of complicated pore channel structures of micropores, mesopores and macropores in the petroleum coke, and meanwhile, alkali metal steam K or Na generated at high temperature can be inserted into the carbon layer to increase the lattice spacing of the carbon layer. The low-carbon alkane can be added to prepare an olefin product through cracking at a high temperature required by the preparation of a carbon material through petroleum coke alkali etching reaction. The preparation method well couples the energy storage material production process and the ethylene production process, not only fully optimizes and utilizes heat, but also effectively improves the energy density of the energy storage material and further reduces the production cost.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, and particularly relates to an energy storage carbon material, a supercapacitor and a preparation method thereof.
Background
The super capacitor has the characteristics of high power density, quick charge and discharge, long cycle life, safety, reliability and the like, is widely applied to the military and civil fields, and the energy storage performance of the super capacitor depends on the used electrode material to a great extent. The prior commercial active carbon electrode material has the defects of poor conductivity, uneven pore diameter distribution and unsuitability for large-current charge and discharge and high working voltage.
The heavy oil has the advantage of wide raw material source as one of excellent natural raw materials for producing the energy storage carbon material. The heavy oil is a complex mixture consisting of a plurality of aliphatic hydrocarbons, naphthenic hydrocarbons and polycyclic aromatic hydrocarbons, has complex and multi-level composition and structure, not only contains a large number of hydrocarbon and non-hydrocarbon compounds, but also contains supermolecular aggregates such as colloid, asphaltene and the like, and in addition, the heavy oil also contains a large number of aromatic hydrocarbon structures and abundant heteroatoms such as S, N, P, O and the like. There are scholars both at home and abroad who propose a method for preparing energy storage carbon materials by heavy oil or other carbon sources.
Chinese patent CN103265008A discloses a nitrogen-doped porous carbon and a preparation method thereof. According to the invention, a nitrogen source reacts with formaldehyde to generate a prepolymer which is used as an N atom doping raw material, the prepolymer is mixed with a template agent and a carbon source and carbonized at high temperature to prepare the nitrogen-doped porous carbon, and nitrogen-doped porous carbon with different pore structures and nitrogen contents is obtained by controlling the type and temperature of the nitrogen source, the mass ratio of the carbon source to the nitrogen source, the dosage of the template agent and the like, so that the loss of nitrogen in the heat treatment process is effectively prevented.
Pin-Yi Zhao et al, Tianjin university, heated pitch to 290 ℃ in air for pre-oxidation and carbonized at 1000 ℃ for 1h in nitrogen atmosphere, found that not only the doping of carbon material oxygen atoms is achieved, but also the melting point of pitch after pretreatment is improved, so that a carbon material with a more uniform structure can be obtained after carbonization.
The patent CN103121680A discloses a preparation method of a super-high energy storage electro-carbon material, which takes high-softening-point asphalt as a carbon source, phenolic resin as a template agent, and a plasticizer to be mixed and granulated, and is carbonized and activated in an activation furnace in a sectional manner, and the micro-powder super-high energy storage electro-carbon material is prepared by acid washing, water washing, drying and crushing.
Chinese patent CN110817835A discloses a porous carbon material and a preparation method thereof, the process adopts an organic matter polymerization phase separation carbonization method, a boron source is added into a mixed solution containing thermosetting resin, an organic solvent and a curing agent, and the porous carbon material with the average aperture of 25 nm-5 mu m is obtained by heating and curing and high-temperature treatment at 700-1200 ℃.
In summary, the existing method for preparing the energy storage carbon material with high conductivity and stable structure mainly improves the specific surface area and the pore structure with balanced distribution structure of the carbon material by doping atoms such as a template agent or S, N, P, O and the like to improve the specific capacitance and rate performance, and the required energy is usually high-temperature carbonization and microwave carbonization.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an energy storage carbon material, a super capacitor and a preparation method thereof so as to solve the technical problems.
The invention is realized by the following steps:
the inventor creatively discovers that: the method does not improve the specific surface area of a carbon material and construct a pore structure with balanced distribution to improve the specific capacitance and rate capability by doping atoms such as a template agent or S, N, P, O and the like, but carries out thermal cracking treatment on a petroleum coke and alkali reagent mixture at the high temperature of 700-1000 ℃ under the mixed atmosphere of low-carbon alkane and high-temperature steam, on one hand, the petroleum coke generates an etching reaction with the alkali reagent to produce hydrogen, carbon monoxide and carbon dioxide gas, and a plurality of intricate and complex micropores, mesopores and macropores can be formed in the petroleum coke by different gas escapeThe pore channel structure can ensure that the alkali metal steam K or Na generated at high temperature can be inserted into the carbon layer to increase the lattice spacing of the carbon layer. On the other hand, the petroleum coke is oxidized with high-temperature steam to form oxygen-containing functional groups and H on the petroleum coke2And by the escape of different gases, a plurality of complicated pore channel structures of micropores, mesopores and macropores can be formed in the petroleum coke. The oxygen-containing functional groups can improve the surface wettability of the carbon material, while at the same time can create additional pseudocapacitance.
The generated alkali metal steam is inserted into the carbon layer, so that the lattice spacing of the carbon layer is increased, the specific surface area and the pore volume of the energy storage carbon material are improved, the electrochemical performance of the carbon material is improved, and simultaneously, the oxygen atoms in the carbon material are doped, and the energy storage density of the carbon material is further improved by utilizing the high-valence oxidation-reduction change of the oxygen atoms.
The low-carbon alkane can be added to prepare an olefin product through cracking at a high temperature required by the preparation of a carbon material through petroleum coke alkali etching reaction. The olefin product can be used for further separation to obtain single olefin such as ethylene. The preparation method well couples the energy storage material production process and the ethylene production process, not only fully optimizes and utilizes heat, but also effectively improves the energy density of the energy storage material and further reduces the production cost.
A method for preparing an energy storage carbon material by taking petroleum coke as a raw material comprises the following steps: the petroleum coke reacts with an alkali reagent in the atmosphere of low-carbon alkane and steam to obtain an energy storage carbon material and an olefin product.
In the process, the gas produced by petroleum coke carbonization and activation can achieve the purpose of further reducing the alkene partial pressure, and the high-temperature steam can also carry out oxygen atom doping on the produced energy storage carbon material, so that the energy storage density of the carbon material is further improved.
In the preferred embodiment of the present invention, the temperature of the reaction is 600-900 ℃, and the reaction time is 1-3 h.
In a preferred embodiment of the present invention, the reaction temperature is 750-; preferably, the reaction is carried out in a pyrolysis furnace.
The inventor practice proves that the specific capacity of the prepared energy storage carbon material is higher in the reaction temperature and time, and in addition, in other embodiments, the reaction temperature and time can be adaptively adjusted according to actual needs.
Furthermore, the high temperature of the reaction not only provides the required temperature for the alkali etching reaction of petroleum coke, but also provides reaction conditions for the subsequent cracking of low-carbon alkane, so that the alkane in the carpet generates olefin products, the utilization rate of energy is greatly improved, the energy density of the energy storage material is effectively improved, and the production cost is further reduced.
In a preferred embodiment of the present invention, the lower alkane is at least one of ethane, propane, butane and liquefied gas.
The light alkanes can be cracked at high temperature to produce olefin products, and it should be noted that the invention only lists a few light alkanes, and in other embodiments, other alkanes or cycloalkanes with 1-6 carbon atoms can be selected.
In the preferred embodiment of the present invention, the mass ratio of the water vapor to the light alkane and the gas reaction residence time are the conventional industrial ethane steam cracking process parameters.
In a preferred embodiment of the present invention, the alkali agent is at least one of potassium hydroxide and sodium hydroxide.
The alkali reagent can react with petroleum coke to generate alkali metal steam and H2CO and CO2Through the escape of different gases, a plurality of complicated pore channel structures of micropores, mesopores and macropores can be formed in petroleum coke, and the insertion of the generated alkali metal steam in the carbon layer also increases the lattice spacing of the carbon layer, improves the specific surface area and the pore volume of the energy storage carbon material and is beneficial to improving the electrochemical performance of the carbon material.
In a preferred embodiment of the present invention, the mass ratio of the petroleum coke to the alkali reagent is 1-5; preferably, the mass ratio of petroleum coke to alkaline agent is 1-3.
Within the above range, the specific capacity of the obtained carbon material is optimum, and in other embodiments, it may be adaptively adjusted as necessary.
In a preferred embodiment of the present invention, the petroleum coke contains more than 80 wt% of C, more than 3 wt% of H, more than 3 wt% of S, more than 1.5 wt% of N, and more than 1 wt% of O.
The quality of petroleum coke has certain influence on the electrochemical performance and energy storage density of the energy storage carbon material.
In a preferred embodiment of the present invention, before the petroleum coke is reacted in the atmosphere of light alkane and steam, the petroleum coke and the alkali agent are subjected to milling and screening. The petroleum coke is milled with a certain amount of alkali reagent to achieve the purpose of full mixing, and the petroleum coke is fully etched at high temperature to generate a large number of pore channels.
In a preferred embodiment of the present invention, the petroleum coke after grinding and sieving has a particle size of 50-200 mesh; preferably, the particle size of the petroleum coke after grinding and screening is 100-200 meshes.
Carbon materials with higher specific capacity can be prepared in the particle size range.
In a preferred embodiment of the present invention, the olefin product after the collection reaction is subjected to deep separation to obtain a single olefin; preferably, byproduct coke particles generated by condensation reaction in the cracking of the low-carbon alkane are collected, and the byproduct coke particles are used as a carbon source for preparing the energy storage carbon material.
Preferably, the gas after the reaction is collected and passes through a cryogenic separation system of a subsequent ethylene device to obtain a single olefin product. In addition, the carbon material obtained after the treatment by the process is acidic, washed to be neutral by water and dried to obtain the required target product, namely the petroleum-based energy storage carbon material.
The coke particles can also directly participate in the etching reaction of the alkali reagent to prepare the energy storage carbon material.
An energy storage carbon material produced by the above method.
In a preferred embodiment of the present invention, the energy storage carbon material isThe specific capacity of the material is 160-300F/g. Specific surface area of 1200-3000m2(ii)/g, the average pore diameter is 1.5-8.5 nm.
The energy storage carbon material prepared by the preparation method provided by the invention has the advantages of large specific surface area, low production cost, large specific capacity and high porosity.
A capacitor comprises a conductive agent, an electrolyte and an energy storage carbon material, wherein the conductive agent is graphite.
In other embodiments, the electrolyte is a KOH solution.
The invention has the following beneficial effects:
the invention provides an energy storage carbon material, a super capacitor and a preparation method thereof. The preparation method of the energy storage carbon material provided by the invention does not improve the specific surface area and the structure of the carbon material by doping atoms such as a template agent or S, N, P, O and the like to improve the specific capacitance and rate capability, but carries out thermal cracking treatment on petroleum coke and an alkali reagent mixture in the mixed atmosphere of low-carbon alkane and high-temperature steam, wherein the petroleum coke reacts with the alkali reagent to generate gases such as K, Na alkali metal steam and the like on one hand, and carries out oxidation action with the high-temperature steam on the other hand to form oxygen-containing functional groups and H on the petroleum coke2And by the escape of different gases, a plurality of complicated pore channel structures of micropores, mesopores and macropores can be formed in the petroleum coke.
The insertion of the generated alkali metal steam in the carbon layer also increases the lattice spacing of the carbon layer, improves the specific surface area and pore volume of the energy storage carbon material, and is beneficial to improving the electrochemical performance of the carbon material, and simultaneously, the doping of oxygen atoms in the carbon material further improves the energy storage density of the carbon material by utilizing the high-valence oxidation-reduction change of the oxygen atoms.
The low-carbon alkane can be added to prepare an olefin product through cracking at a high temperature required by the preparation of a carbon material through petroleum coke alkali etching reaction. The olefin product can be used for further separation to obtain single olefin such as ethylene. The preparation method well couples the energy storage material production process and the ethylene production process, not only fully optimizes and utilizes heat, but also effectively improves the energy density of the energy storage material and further reduces the production cost.
The energy storage carbon material and the capacitor prepared by the method have the advantages of large specific surface area, low production cost, large specific capacity and high porosity.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of an energy storage carbon material. The feedstock was selected from petroleum coke having the composition shown in table 1. The preparation method of the energy storage carbon material comprises the following steps: carbonizing and activating petroleum coke under the atmosphere of steam and ethane, wherein the grain diameter of the petroleum coke is 100 meshes, the alkali reagent is potassium hydroxide, and the mass ratio of the alkali reagent to the petroleum coke is 1:1, the reaction temperature is 750 ℃, and the reaction is carried out in a pyrolysis furnace for 1 h. The mass ratio of the mixed steam of the water vapor and the ethane and the gas retention time in the carbonization process are the conventional industrial ethane steam cracking process parameters which are respectively 0.3 s and 0.5s, and finally, the ethylene content of the gas generated by the reaction is analyzed.
Table 1 main properties of petroleum coke.
Item | Petroleum coke |
ω(C),% | 89.21 |
ω(H),% | 3.62 |
ω(S),% | 3.74 |
ω(N),% | 2.02 |
ω(O),% | 1.41 |
Example 2
The embodiment provides a preparation method of an energy storage carbon material. The feedstock was selected from petroleum coke having the composition shown in table 1. The preparation method of the energy storage carbon material comprises the following steps: carbonizing and activating petroleum coke under the atmosphere of steam and ethane, wherein the grain diameter of the petroleum coke is 100 meshes, the alkali reagent is potassium hydroxide, and the mass ratio of the alkali reagent to the petroleum coke is 2: 1, the reaction temperature is 800 ℃, and the reaction is carried out in a pyrolysis furnace for 2 hours. The mass ratio of the water vapor to the ethane mixed steam in the carbonization process is 0.3, the residence time of the reaction gas is 0.5s, and finally, the ethylene content of the gas generated by the reaction is analyzed.
Example 3
The embodiment provides a preparation method of an energy storage carbon material. The starting material was the same as in example 1, except that: the grain size of the petroleum coke is 200 meshes, the mass ratio of the alkali reagent to the petroleum coke is 2, the reaction temperature is 800 ℃, and the treatment time is 2 hours. The rest of the preparation method is the same as that of example 1.
Example 4
The embodiment provides a preparation method of an energy storage carbon material. The starting material was the same as in example 1, except that: the grain size of the petroleum coke is only 200 meshes, the mass ratio of the alkali reagent to the petroleum coke is 3, the reaction temperature is 850 ℃, and the treatment time is 2 hours. The rest of the preparation method is the same as that of example 1.
Example 5
The embodiment provides a preparation method of an energy storage carbon material. The starting material was the same as in example 1, except that: carbonizing and activating under the mixed steam of water vapor and propane, wherein the grain size of petroleum coke is 200 meshes, the mass ratio of an alkali reagent to the petroleum coke is 3, the reaction temperature is 850 ℃, and the treatment time is 2 hours. The rest of the preparation method is the same as that of example 1.
Example 6
The embodiment provides a preparation method of an energy storage carbon material. The starting material was the same as in example 1, except that: carbonizing and activating under the mixed gas of steam, ethane and propane (the mass ratio is 1:1) mixed steam, wherein the grain diameter of petroleum coke is 200 meshes, the mass ratio of an alkali reagent to the petroleum coke is 3, the reaction temperature is 850 ℃, and the treatment time is 2 hours. The rest of the preparation method is the same as that of example 1.
Comparative example 1
And (2) carrying out carbonization and activation on petroleum coke with the same properties as those in the table 1 in a nitrogen atmosphere, wherein the grain diameter of the petroleum coke is 100 meshes, the alkali reagent is potassium hydroxide, the mass ratio of the alkali reagent to the petroleum coke is 1, the reaction temperature is 750 ℃, and the reaction time is 1 h.
Experimental example 1
The energy storage carbon materials prepared in examples 1-6 and comparative example 1 were taken for capacity analysis and ethylene yield statistical analysis, respectively.
When an electrochemical test is carried out, graphite is used as a conductive agent, polytetrafluoroethylene is used as a binder, 6mol/L KOH solution is used as an electrolyte solution, and the following mass ratios are used for preparing an electrode for constant current charge and discharge: carbon energy storage material: graphite: polytetrafluoroethylene 70:15: 15;
the current density was 0.05A/g.
The capacity analysis and ethylene yield data of the prepared energy storage carbon material are shown in table 2, and as can be seen from table 2, the specific capacity of the energy storage carbon material prepared by the method provided by the embodiment of the invention is obviously superior to that of the comparative example 1, and the ethylene yield of the embodiment 4 is optimal.
Table 2 analytical data for reaction products.
Item | Specific capacity, F/g | Ethylene yield% |
Comparative example 1 | 105 | |
Example 1 | 166 | 48.27 |
Example 2 | 208 | 50.52 |
Example 3 | 241 | 51.36 |
Example 4 | 283 | 54.15 |
Example 5 | 278 | 37.25 |
Example 6 | 281 | 42.13 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing an energy storage carbon material by taking petroleum coke as a raw material is characterized by comprising the following steps: the petroleum coke reacts with an alkali reagent in the atmosphere of low-carbon alkane and steam to obtain an energy storage carbon material and an olefin product.
2. The method as claimed in claim 1, wherein the reaction temperature is 600-900 ℃, and the reaction time is 1-3 h;
preferably, the reaction temperature is 750-850 ℃, and the reaction time is 1-2 h; preferably, the reaction is carried out in a pyrolysis furnace.
3. The method of claim 2, wherein the lower alkane is at least one of ethane, propane, butane, and liquefied gas.
4. The method of claim 1, wherein the alkaline reagent is at least one of potassium hydroxide and sodium hydroxide.
5. The method of claim 4, wherein the mass ratio of the petroleum coke to the alkaline agent is 1-5; preferably, the mass ratio of the petroleum coke to the alkali reagent is 1-3.
6. The method of claim 1, further comprising milling and sieving the petroleum coke with an alkaline agent before reacting the petroleum coke in the atmosphere of the light alkane and the steam.
7. The method of claim 6, wherein the petroleum coke after milling screening has a particle size of 50-200 mesh; preferably, the particle size of the petroleum coke after grinding and screening is 100-200 meshes.
8. The method according to claim 1, characterized in that the olefin product after the reaction is collected and subjected to cryogenic separation to obtain single olefin; preferably, byproduct coke particles generated by condensation reaction in the cracking of the low-carbon alkane are collected and used as a carbon source for preparing the energy storage carbon material.
9. An energy storage carbon material produced by the method of any one of claims 1-8; preferably, the specific capacity of the energy storage carbon material is 160-300F/g.
10. An ultracapacitor comprising a conductive agent, an electrolyte, and the energy storing carbon material of claim 9, preferably, the conductive agent is graphite.
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