CN104916447A - High-rate porous carbon electrode material for super capacitor and preparation method - Google Patents
High-rate porous carbon electrode material for super capacitor and preparation method Download PDFInfo
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- CN104916447A CN104916447A CN201410091451.0A CN201410091451A CN104916447A CN 104916447 A CN104916447 A CN 104916447A CN 201410091451 A CN201410091451 A CN 201410091451A CN 104916447 A CN104916447 A CN 104916447A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003990 capacitor Substances 0.000 title abstract description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- -1 zeolite imidazole compound Chemical class 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010335 hydrothermal treatment Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 229940015043 glyoxal Drugs 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract 3
- 239000010941 cobalt Substances 0.000 abstract 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 3
- 239000000047 product Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000011148 porous material Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a hierarchical porous carbon for preparing the electrode material of a super capacitor and a preparation method of the hierarchical porous carbon. The preparation method of the hierarchical porous carbon includes the following steps that: a zinc and cobalt-containing zeolite imidazole compound is prepared; and the zinc and cobalt-containing zeolite imidazole compound is subjected to carbonization treatment under high temperature, so that the hierarchical porous carbon can be obtained. A large number of mesopores and micropores exist in the porous carbon, and the bore diameters of the mesopores and micropores are distributed hierarchically. The formation of the above structure is conducive to the formation of the transmission of electrolyte ions in the porous carbon material and the formation of a double-electric layer. With the hierarchical porous carbon adopted as an electrode active material, the rate capability of the super capacitor is excellent; the zeolite imidazole compound is subjected to carbonization under 800 DEG C, the molar ratio of zinc and cobalt of the zeolite imidazole compound being 1:9, so that the hierarchical porous carbon of which the specific capacitance can achieve 176F/g under 100mV/s scanning speed can be obtained.
Description
Technical field
The invention belongs to electrode material for super capacitor technical field, be specially a kind of ultracapacitor porous carbon electrode material and preparation method thereof, this electrode material has the feature of aperture classification fire wall.
Background technology
Ultracapacitor is a kind of novel energy-storing device between traditional physical capacitor and secondary cell.Ultracapacitor have energy density high, have extended cycle life, the advantage such as fast charging and discharging, be thus with a wide range of applications at mobile electronic device and electric automobiles, be subject in recent years studying widely and paying close attention to.
Ultracapacitor is divided into two classes by operation principle, is double electric layer capacitor and fake capacitance capacitor respectively.Active carbon, because cheap price and high specific area, thus becomes a kind of electrode material that current commercialization ultracapacitor extensively adopts.But active carbon has the low shortcoming of mesoporous rate, be unfavorable for electrolyte ion transmission wherein, be thus not suitable for the electrode material as high-multiplying-power super capacitor.
Graded porous carbon contains abundant micropore and mesoporous.The existence of a large amount of micropore makes material have high specific area, and mesoporous a large amount of existence can reduce electrolyte ion migration resistance in the material.The ultracapacitor doing electrode active material with graded porous carbon has higher capability retention when working under high current density.
The method preparing classifying porous material with carbon element has multiple, wherein representative with template most.The people such as Yaqin Huang do carbon source and template with animal skeleton, and being lived by KOH is processed, and obtains high-specific surface area graded porous carbon.This material with carbon element shows high ratio capacitance and high rate performance (Carbon.2011,49,838 – 843).The method that the people such as Huiming Cheng adopt nickel hydroxide to mix with phenolic resins, obtains classifying porous material with carbon element through high temperature cabonization.This carbon electrode material shows good high rate performance (Angew.Chem.Int.Ed.2008,47,373 – 376).
Be a kind of typical poromerics containing zinc zeolite imidazole compound ZIF-8, its carbonization can be obtained the micro-pore carbon material of aperture integrated distribution.In ZIF-8, introduce graphitization catalyst, its carbonizing production part graphitization can be realized.And the formation of graphite farmland band can promote the formation that carbon granule is inner mesoporous.The present invention adopts to be had the method that the cobalt ions of catalyzed graphitization activity, the zinc ion without catalyzed graphitization activity and glyoxal ethyline carry out reacting and prepares bimetallic ion zeolite imidazole compound.Then bimetallic ion zeolite imidazole compound is at high temperature processed, obtain classifying porous material with carbon element.Graded porous carbon prepared by this method is a kind of high-multiplying-power super capacitor electrode material of extensive application prospect.
Summary of the invention
The object of the present invention is to provide a kind of classifying porous material with carbon element and preparation method thereof, concrete preparation method is for obtaining graded porous carbon by charing bimetallic ion zeolite imidazole compound.Mesopore micropore size distribution in this material can be regulated and controled by the mol ratio changing two metal ion species.This graded porous carbon has desirable electrochemical capacitor characteristic, is suitable as the electrode material of high-multiplying-power super capacitor.
Classifying porous carbon electrode material for ultracapacitor provided by the invention, it is characterized in that: in preparation containing in the process of zinc zeolite imidazole compound ZIF-8, add cobalt ions to form bimetallic ion zeolite imidazole compound, then above-mentioned zeolite imidazole compound is carried out high temperature cabonization process, obtain graded porous carbon.A large amount of mesopores and micropore is there is in this graded porous carbon, and aperture classification fire wall.Being formed of this structure is beneficial to the transmission of electrolyte ion in porous carbon materials and the formation of electric double layer.The ultracapacitor doing electrode active material with this graded porous carbon shows excellent high rate performance.
Present invention also offers the preparation method of described classifying porous carbon electrode material, comprise the steps:
(1) respectively by glyoxal ethyline, zinc salt and salt solubility in organic solvent, then three kinds of solution are mixed, and mixed solution are carried out hydrothermal treatment consists;
(2) by the mixture solvent centrifuge washing of above hydrothermal treatment consists removing wherein unreacted glyoxal ethyline and slaine, then the mixture obtained is carried out drying in an oven;
(3) mixture that step (2) obtains is carried out carbonization under an inert atmosphere, obtain graded porous carbon head product;
(4) the graded porous carbon head product acid solution that step (3) obtains is washed, be then washed to neutrality, after drying, obtain classifying porous carbon electrode material.
The preparation method of classifying porous carbon electrode material provided by the invention, in step (1) and (2), described solvent is DMF or methyl alcohol.In step (1), described zinc salt is one or more in zinc nitrate, zinc chloride, zinc acetate, and cobalt salt is one or more in cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate; The mol ratio of zinc salt and glyoxal ethyline is 10:1-1:10, and the mol ratio of zinc salt and cobalt salt is 100:1-1:100.
The preparation method of classifying porous carbon electrode material provided by the invention, the inert atmosphere described in step (3) is one or more in nitrogen, argon gas, helium; Described acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, and carburizing temperature is 500-1200 DEG C, time 0.5-12h.
The preparation method of classifying porous carbon electrode material provided by the invention, in step (4), acid solution used is one or more in hydrochloric acid, sulfuric acid, nitric acid.
The preparation method of classifying porous carbon electrode material provided by the invention, in step (1), the temperature of hydrothermal treatment consists is 50-200 DEG C, and the time of process is 24-72h.
Advantage of the present invention: provided by the present invention is a kind of ultracapacitor classifying porous material with carbon element and preparation method thereof.The classifying porous material with carbon element adopting method provided by the present invention to prepare has higher specific area.In addition, this classifying porous material with carbon element has the controlled feature of micropore size.Owing to there is microporous mesoporous synergy, graded porous carbon shows the more excellent high rate performance of specific activity charcoal.
Accompanying drawing explanation
Fig. 1 is the graph of pore diameter distribution of classifying porous material with carbon element prepared by the embodiment of the present invention 1;
Fig. 2 is the cyclic voltammetry curve of classifying porous carbon electrode prepared by the embodiment of the present invention 1;
Fig. 3 is the graph of pore diameter distribution of classifying porous material with carbon element prepared by the embodiment of the present invention 2;
Fig. 4 is the cyclic voltammetry curve of classifying porous carbon electrode prepared by the embodiment of the present invention 2;
Fig. 5 is the graph of pore diameter distribution of classifying porous material with carbon element prepared by the embodiment of the present invention 3;
Fig. 6 is the cyclic voltammetry curve of classifying porous carbon electrode prepared by the embodiment of the present invention 3.
Embodiment
The following examples will be further described the present invention, but therefore not limit claim of the present invention.
Embodiment 1
By 2.23g Zn (NO
3)
26H
2o, 0.12g Co (NO
3)
26H
2o and 0.6g2-methylimidazole is dissolved in 180ml DMF.Then mixed solution is placed in water heating kettle, hydrothermal treatment consists 24h at 140 DEG C.Hydrothermal product DMF solution washing more than 3 times, is then placed in product in baking oven and carries out drying at 60 DEG C.By desciccate in nitrogen atmosphere at 800 DEG C carbonization 3h.Obtain carbonization afterproduct potassium hydroxide solution to process, then spend the sample after deionized water process to neutral.After processing above-mentioned product hydrochloric acid solution, by washed with de-ionized water to neutral.By the product baking oven dry 24h at 60 DEG C after cleaning, obtain graded porous carbon.
Physical absorption test shows that this material with carbon element presents concentrated pore-size distribution (as shown in Figure 1) in 1.3nm and 5.1nm place, and the material with carbon element obtaining aperture classification fire wall is described.By above-mentioned graded porous carbon in active material: conductive agent: make electrode slice after the ratio of binding agent=85:10:5 mixes, then do electrolyte with the 6M KOH aqueous solution, adopt three electrode cycle voltammetries to characterize pole piece, result as shown in Figure 2.Under 100mV/s sweeps speed, the cyclic voltammetry curve of this electrode is still close to rectangle, illustrates that the porous carbon electrode material adopting method provided by the present invention to prepare has very high high rate performance.The ratio capacitance of this material with carbon element under 100mV/s sweeps speed reaches 170F/g.
Embodiment 2
By 2.11g Zn (NO
3)
26H
2o, 0.23g Co (NO
3)
26H
2o and 0.6g2-methylimidazole is dissolved in 180ml DMF, then mixed solution is placed in water heating kettle, hydrothermal treatment consists 24h at 140 DEG C.Hydrothermal product DMF solution washing more than 3 times, is then placed in baking oven and carries out drying at 60 DEG C by product.By dried product carbonization 3h at 800 DEG C in nitrogen atmosphere.Carbonized product, with after potassium hydroxide solution process, spends deionized water to neutral.Again the sample hydrochloric acid solution obtained is processed, use washed with de-ionized water.By the sample baking oven dry 24h at 60 DEG C after cleaning, obtain graded porous carbon.
Physical absorption result shows this material with carbon element has concentrated pore-size distribution at 1.2nm and 1.8nm place, and result as shown in Figure 3.By above-mentioned material with carbon element in active material: conductive agent: make electrode slice after the ratio of binding agent=85:10:5 mixes, then test its chemical property in the 6M KOH aqueous solution by cyclic voltammetry, result as shown in Figure 4.The ratio capacitance of porous carbon electrode material under 100mV/s sweeps speed adopting method provided by the present invention to prepare reaches 176F/g.
Embodiment 3
By 1.87g Zn (NO
3)
26H
2o, 0.47g Co (NO
3)
26H
2o and 0.6g2-methylimidazole is dissolved in 180ml DMF, then mixed solution is placed in water heating kettle, hydrothermal treatment consists 24h at 140 DEG C.Hydrothermal product DMF solution washing more than 3 times, is then placed in baking oven and carries out drying at 60 DEG C by product.By dried product carbonization 3h at 800 DEG C in nitrogen atmosphere.Carbonized product, with after potassium hydroxide solution process, spends deionized water to neutral.Again the sample hydrochloric acid solution obtained is processed, use washed with de-ionized water.By the sample baking oven dry 24h at 60 DEG C after cleaning, obtain graded porous carbon.
Physical absorption result shows this material with carbon element has concentrated pore-size distribution at 1.2nm and 5.0nm place, and result as shown in Figure 5.By above-mentioned material with carbon element in active material: conductive agent: make electrode slice after the ratio of binding agent=85:10:5 mixes, then by cyclic voltammetry, its chemical property in the 6M KOH aqueous solution is tested, as shown in Figure 6.The ratio capacitance of porous carbon electrode material under 100mV/s sweeps speed adopting method provided by the present invention to prepare reaches 132F/g.
Embodiment 4
By 0.9116g zinc chloride, 0.5g Co (NO
3)
26H
2o and 0.564g2-methylimidazole is dissolved in 191.5ml DMF, then mixed solution is placed in water heating kettle, hydrothermal treatment consists 24h at 140 DEG C.Hydrothermal product DMF solution washing more than 3 times, is then placed in baking oven and carries out drying at 60 DEG C by product.By dried product carbonization 3h at 500 DEG C in nitrogen atmosphere.Carbonized product, with after potassium hydroxide solution process, spends deionized water to neutral.Again the sample hydrochloric acid solution obtained is processed, use washed with de-ionized water.By the sample baking oven dry 24h at 60 DEG C after cleaning, obtain graded porous carbon.
Embodiment 5
By 1.227g zinc acetate, 0.5g Co (NO
3)
26H
2o and 0.64g2-methylimidazole is dissolved in 200ml DMF, then mixed solution is placed in water heating kettle, hydrothermal treatment consists 24h at 140 DEG C.Hydrothermal product DMF solution washing more than 3 times, is then placed in baking oven and carries out drying at 60 DEG C by product.By dried product carbonization 3h at 1000 DEG C in nitrogen atmosphere.Carbonized product, with after potassium hydroxide solution process, spends deionized water to neutral.Again the sample hydrochloric acid solution obtained is processed, use washed with de-ionized water.By the sample baking oven dry 24h at 60 DEG C after cleaning, obtain graded porous carbon.
Embodiment 6
2.5g zinc acetate, 0.5824g cobalt acetate and 1.22g2-methylimidazole are dissolved in 360mlN, dinethylformamide, then mixed solution are placed in water heating kettle, hydrothermal treatment consists 24h at 140 DEG C.Hydrothermal product DMF solution washing more than 3 times, is then placed in baking oven and carries out drying at 60 DEG C by product.By dried product carbonization 3h at 1200 DEG C in nitrogen atmosphere.Carbonized product, with after potassium hydroxide solution process, spends deionized water to neutral.Again the sample hydrochloric acid solution obtained is processed, use washed with de-ionized water.By the sample baking oven dry 24h at 60 DEG C after cleaning, obtain graded porous carbon.
Claims (8)
1. the classifying porous carbon electrode material for ultracapacitor, it is characterized in that: in preparation containing in the process of zinc zeolite imidazole compound ZIF-8, add cobalt ions to form bimetallic ion zeolite imidazole compound, then above-mentioned zeolite imidazole compound is carried out high temperature cabonization process, obtain graded porous carbon.
2. described in claim 1 for the preparation method of the classifying porous carbon electrode material of ultracapacitor, it is characterized in that, comprise the steps:
(1) respectively by glyoxal ethyline, zinc salt and salt solubility in organic solvent, then three kinds of solution are mixed, and mixed solution are carried out hydrothermal treatment consists;
(2) by the mixture solvent centrifuge washing of above hydrothermal treatment consists removing wherein unreacted glyoxal ethyline and slaine, then the mixture obtained is carried out drying in an oven;
(3) mixture that step (2) obtains is carried out carbonization under an inert atmosphere, obtain graded porous carbon head product;
(4) the graded porous carbon head product acid solution that step (3) obtains is washed, be then washed to neutrality, after drying, obtain classifying porous carbon electrode material.
3. according to described in claim 2 for the preparation method of the classifying porous carbon electrode material of ultracapacitor, it is characterized in that: in step (1) and (2), described solvent is DMF or methyl alcohol.
4. according to described in claim 2 for the preparation method of the classifying porous carbon electrode material of ultracapacitor, it is characterized in that: in step (1), described zinc salt is one or more in zinc nitrate, zinc chloride, zinc acetate, and cobalt salt is one or more in cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate.
5. according to described in claim 2 for the preparation method of the classifying porous carbon electrode material of ultracapacitor, it is characterized in that: the mol ratio of zinc salt and glyoxal ethyline is 10:1-1:10 in step (1), the mol ratio of zinc salt and cobalt salt is 100:1-1:100.
6. according to described in claim 2 for the preparation method of the classifying porous carbon electrode material of ultracapacitor, it is characterized in that: in step (3), carburizing temperature is 500-1200 DEG C.
7. according to described in claim 2 for the preparation method of the classifying porous carbon electrode material of ultracapacitor, it is characterized in that: in step (4), acid solution used is one or more in hydrochloric acid, sulfuric acid, nitric acid.
8., according to the preparation method for the classifying porous carbon electrode material of ultracapacitor described in claim 2, it is characterized in that: in step (1), the temperature of hydrothermal treatment consists is 50-200 DEG C.
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