CN104425136A - Carbon-based electrode material, preparing method of carbon-based electrode material and super capacitor - Google Patents
Carbon-based electrode material, preparing method of carbon-based electrode material and super capacitor Download PDFInfo
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- CN104425136A CN104425136A CN201310400894.9A CN201310400894A CN104425136A CN 104425136 A CN104425136 A CN 104425136A CN 201310400894 A CN201310400894 A CN 201310400894A CN 104425136 A CN104425136 A CN 104425136A
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- electrode material
- base electrode
- charcoal base
- carbon
- based electrode
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Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003990 capacitor Substances 0.000 title abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000003610 charcoal Substances 0.000 claims description 102
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- 230000004888 barrier function Effects 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- 239000002931 mesocarbon microbead Substances 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003595 mist Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 25
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- 239000011806 microball Substances 0.000 abstract 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005056 compaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 46
- 239000003365 glass fiber Substances 0.000 description 23
- 239000004411 aluminium Substances 0.000 description 22
- 229910052782 aluminium Inorganic materials 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 22
- 239000011230 binding agent Substances 0.000 description 22
- 229920006395 saturated elastomer Polymers 0.000 description 22
- 238000002336 sorption--desorption measurement Methods 0.000 description 12
- -1 tetraethylammonium tetrafluoroborate Chemical compound 0.000 description 8
- 238000003556 assay Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- TUZJVNCNOCMHLW-UHFFFAOYSA-N C(C)[N+](C)(C)CC.Cl(=O)(=O)(=O)O Chemical compound C(C)[N+](C)(C)CC.Cl(=O)(=O)(=O)O TUZJVNCNOCMHLW-UHFFFAOYSA-N 0.000 description 1
- VZWJXOTXHAXZRF-UHFFFAOYSA-N C[N+](CC)(C)C.Cl(=O)(=O)(=O)O Chemical compound C[N+](CC)(C)C.Cl(=O)(=O)(=O)O VZWJXOTXHAXZRF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QGKPFZYVJCURLK-UHFFFAOYSA-N boric acid;tetramethylazanium Chemical compound OB(O)O.C[N+](C)(C)C QGKPFZYVJCURLK-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-N perchloric acid;tetramethylazanium Chemical compound C[N+](C)(C)C.OCl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-N 0.000 description 1
- BLRMUYHDGZLDLY-UHFFFAOYSA-N perchloric acid;triethyl(methyl)azanium Chemical compound OCl(=O)(=O)=O.CC[N+](C)(CC)CC BLRMUYHDGZLDLY-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- MANNXDXMUHZSRP-UHFFFAOYSA-M tetramethylazanium;trifluoromethanesulfonate Chemical compound C[N+](C)(C)C.[O-]S(=O)(=O)C(F)(F)F MANNXDXMUHZSRP-UHFFFAOYSA-M 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- 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
- H01G11/44—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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a carbon-based electrode material, a preparing method of the carbon-based electrode material and a super capacitor. Middle phase carbon micro balls are treated in inert atmosphere or reducing atmosphere at 0 DEG C to 600 DEG C, and the carbon-based electrode material can be obtained. Compared with the prior art, the carbon-based electrode material uses the middle phase carbon micro balls subjected to heating treatment as the electrode material, firstly, through the heating treatment, organic substances in the middle phase carbon micro balls can be removed, so that the structure of the obtained carbon-based electrode material is compact, and the vibration compaction density is increased; then, the specific surface area of the carbon-based electrode material is smaller, and correspondingly, the quantity of active functional groups on the surface of the carbon-based electrode material is small, so that the catalysis effect of the functional groups on the irreversible decomposition of electrolyte can be effectively inhabited, further, an interface of the electrode material and the electrolyte is stabilized, the invertible degree of charge (ion) storage is improved, and the work voltage and the specific capacitance of the super capacitor are effectively improved; next, the carbon-based electrode materials can be obtained through the heating treatment, the preparing method is simple, and the operation is easy.
Description
Technical field
The invention belongs to capacitor technology field, particularly relate to charcoal base electrode material and preparation method thereof, ultracapacitor.
Background technology
In order to alleviate day by day serious energy crisis and environmental problem, countries in the world government all in the development carrying forward vigorously new-energy automobile industry, as electric automobile.But current the faced ultimate challenge of electric automobile is exactly apparatus for storing electrical energy, no matter be lead-acid battery, lithium battery, or fuel cell, the problem such as all have that cost is high, the life-span is short, continual mileage is short and the charging interval is long, therefore, the electrical storage device of people to electric automobile proposes the requirements such as low cost, high power capacity, long-life and high safety.
In recent years, a kind of novel, efficient, practical energy accumulating device-ultracapacitor receives much concern, and is expected to the main apparatus for storing electrical energy becoming New Generation of Electric Vehicle.Ultracapacitor is made up of positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity, become again capacitor with super capacity, electrochemical capacitor, double electric layer capacitor, gold electric capacity, storage capacitor or farad capacitor, be a kind of new energy energy storage device having traditional capacitor and these two kinds of energy storage device advantages of secondary cell concurrently grown up the seventies and eighties in 20th century, its capacity can reach hundreds of to thousands of farad.Compare with secondary cell with traditional capacitor, the energy force rate ordinary capacitor that ultracapacitor stores electric charge is high, and have that charge/discharge rates is fast, efficiency is high, environmentally safe, have extended cycle life, the scope of application is wide, fail safe high, the blank between traditional capacitor and secondary cell has been filled up in its appearance.In fact, ultracapacitor not only has huge potential using value on electric automobile, rushes current feedback circuit also will play a significant role in communication, space flight, national defence etc. as height, and therefore ultracapacitor has become the focus of people's research.
Electrode is the core component of ultracapacitor, is made up of active material and conducting matrix grain, and both positive and negative polarity active material is the source producing electric energy, is the important component part determining battery fundamental characteristics.Material with carbon element because it is cheap and easy to get, operating temperature range is wide, specific area is controlled, pore structure is flourishing, chemical stability is high, mature production technology, the advantage such as environmentally friendly be widely used in preparing electrode material.
The maximum charcoal base electrode material of present use comprises active carbon, activated carbon fiber, charcoal-aero gel, carbon nano-tube and template carbon, mainly through chemical vapour deposition technique, template and high temperature pyrolysis etc.But these methods or complex steps, process are complicated, or condition is harsh, limits its further application in ultracapacitor and large-scale promotion.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of charcoal base electrode material and preparation method thereof, ultracapacitor, and this charcoal base electrode material preparation method is simple.
The invention provides a kind of charcoal base electrode material, by MCMB in inert atmosphere or reducing atmosphere, process under 0 DEG C ~ 600 DEG C conditions and obtain.
Preferably, the specific area of described charcoal base electrode material is 0.01 ~ 10m
2/ g.
Present invention also offers a kind of preparation method of charcoal base electrode material, comprise the following steps:
By MCMB in inert atmosphere or reducing atmosphere, 0 DEG C ~ 600 DEG C process, obtain charcoal base electrode material.
Preferably, the temperature of described process is 60 DEG C ~ 600 DEG C.
Preferably, the temperature of described process is 300 DEG C ~ 500 DEG C.
Preferably, the time of described process is 2 ~ 12h.
Preferably, described inert atmosphere is selected from one or more in helium, argon gas and nitrogen.
Preferably, described reducing atmosphere is the mist of hydrogen and inert gas.
Preferably, the content of described hydrogen is 5% ~ 20% of mist volume.
Present invention also offers a kind of ultracapacitor, comprise positive pole, negative pole, electrolyte and barrier film, described positive pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described negative pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described electrolyte is the organic solution of quaternary ammonium salt; Described positive pole and negative pole have one at least for the charcoal base electrode material described in claim 1 ~ 2 or the charcoal base electrode material prepared by claim 3 ~ 9 any one.
The invention provides a kind of charcoal base electrode material and preparation method thereof, ultracapacitor, by MCMB in inert atmosphere or reducing atmosphere, 0 DEG C ~ 600 DEG C process, charcoal base electrode material can be obtained.Compared with prior art, the present invention is using the MCMB through heat treated as electrode material, and first, heat treated can remove the organic species in MCMB, and the charcoal base electrode material structure obtained is compacted, and tap density increases; Secondly, the specific area of this charcoal base electrode material is less, accordingly, the amount of the active function groups on its surface is little, thus the catalytic action of these functional groups to the irreversible decomposition of electrolyte can be effectively suppressed, and then stabilize this electrode material and electrolyte interface, improve the degree of reversibility that electric charge (ion) stores, therefore this charcoal base electrode material effectively can improve operating voltage and the ratio capacitance of ultracapacitor; Again, this charcoal base electrode material can obtain through heat treated, and preparation method is simple to operation.
Experimental result shows, the ratio capacitance of the ultracapacitor adopting charcoal base electrode material of the present invention to prepare can reach 60mAh/g.
Accompanying drawing explanation
The stereoscan photograph of the charcoal base electrode material that Fig. 1 is MCMB, the embodiment of the present invention 1 ~ 5 prepares;
Fig. 2 is the N of MCMB
2adsorption-desorption isothermal linearity curve figure;
Fig. 3 is the N of the charcoal base electrode material that the embodiment of the present invention 1 prepares
2adsorption-desorption isothermal linearity curve figure;
Fig. 4 is the N of the charcoal base electrode material that the embodiment of the present invention 2 prepares
2adsorption-desorption isothermal linearity curve figure;
Fig. 5 is the N of the charcoal base electrode material that the embodiment of the present invention 3 prepares
2adsorption-desorption isothermal linearity curve figure;
Fig. 6 is the N of the charcoal base electrode material that the embodiment of the present invention 4 prepares
2adsorption-desorption isothermal linearity curve figure;
Fig. 7 is the N of the charcoal base electrode material that the embodiment of the present invention 5 prepares
2adsorption-desorption isothermal linearity curve figure;
Fig. 8 is the specific capacity curve chart of the button cell that the embodiment of the present invention 6 ~ 9 prepares;
Fig. 9 is the specific capacity curve chart of the button cell that the embodiment of the present invention 10 ~ 16 prepares;
Figure 10 is the specific capacity curve chart of the button cell that the embodiment of the present invention 17 ~ 18 prepares;
Figure 11 is the cycle life curve chart of the button cell that the embodiment of the present invention 18 prepares;
Figure 12 is the specific capacity curve chart of the button cell that the embodiment of the present invention 19 ~ 22 prepares;
Figure 13 is the specific capacity curve chart of the button cell that the embodiment of the present invention 23 ~ 24 prepares;
Figure 14 is the cycle life curve chart of the button cell prepared in the embodiment of the present invention 25;
Figure 15 is the specific capacity curve chart of the button cell prepared in the embodiment of the present invention 26;
Figure 16 is the cycle life curve chart of the button cell prepared in the embodiment of the present invention 27.
Embodiment
The invention provides a kind of preparation method of charcoal base electrode material, MCMB is processed in inert atmosphere or reducing atmosphere, under 0 DEG C ~ 600 DEG C conditions, obtains charcoal base electrode material.
Wherein, described MCMB is MCMB well known to those skilled in the art, there is no special restriction, and its source is for commercially available; Described inert atmosphere is inert gas well known to those skilled in the art, there is no special restriction, and the present invention is preferably selected from one or more in helium, argon gas and nitrogen, is more preferably helium, argon gas or nitrogen; Described reducing atmosphere is preferably the mist of hydrogen and inert gas, and wherein the content of hydrogen is preferably 5% ~ 20% of mist volume, is more preferably 8% ~ 15%.
MCMB processed in inert atmosphere or reducing atmosphere, the temperature of described process is preferably 60 DEG C ~ 600 DEG C, is more preferably 300 DEG C ~ 500 DEG C; The time of described process is preferably 0 ~ 12h, is more preferably 2 ~ 10h, is more preferably 4 ~ 10h.
According to the present invention, MCMB preferably naturally cools to normal temperature after heat treated in inert atmosphere or reducing atmosphere, obtains charcoal base electrode material.
MCMB is heat treated in inert gas, can remove low boiling organic species wherein, and the charcoal base electrode material structure obtained comparatively is compacted, and tap density increases; And this charcoal base electrode material can obtain through heat treated, and preparation method is simple to operation.
Present invention also offers a kind of charcoal base electrode material prepared by said method, by MCMB in inert atmosphere or reducing atmosphere, process under 0 DEG C ~ 600 DEG C conditions and obtain.
The condition of described inert atmosphere, reducing atmosphere and process is all same as above, does not repeat them here.
According to the present invention, the specific area of described charcoal base electrode material is less than or equal to 10m
2/ g, is preferably 0.01 ~ 10m
2/ g, is more preferably 0.1 ~ 10m
2/ g, then be preferably 0.1 ~ 5m
2/ g.
Present invention also offers a kind of ultracapacitor, comprise positive pole, negative pole, electrolyte and barrier film, described positive pole is selected from the one in charcoal base electrode material, graphite and active carbon; Described negative pole is selected from the one in charcoal base electrode material, graphite and active carbon; Described electrolyte is the organic solution of quaternary ammonium salt; Described positive pole and negative pole have one at least for charcoal base electrode material, are the charcoal base electrode material of above-mentioned preparation when preferably positive pole is different from negative pole, can only have one for charcoal base electrode material.
The present invention is with the organic solution of quaternary ammonium salt for electrolyte, and it is containing metal or metal ion not, under high voltages, can not form metal deposition, and then can not block the hole of electrode material inside, thus extend the cycle life of ultracapacitor on electrolysis material surface.Described quaternary ammonium salt is preferably selected from tetrafluoro boric acid tetramethyl-ammonium (TMABF
4), trifluoromethanesulfonic acid tetramethyl-ammonium (TMACF
3sO
3), perchloric acid tetramethyl-ammonium (TMAClO
4), tetraethylammonium tetrafluoroborate (TEABF
4), tetraethylammonium hexafluorophosphate (TEAPF
6), tetraethylammonium perchlorate (TEAClO
4), tetrapropyl ammonium tetrafluoroborate (TPABF
4), tetrapropyl ammonium perchlorate (TPAClO
4), tetrafluoro boric acid 4-butyl amine (TBABF
4), tetrabutylammonium perchlorate (TBAClO
4), triethyl methyl ammonium tetrafluoroborate (TEMABF
4), perchloric acid triethyl methyl ammonium (TEMAClO
4), tetrafluoro boric acid dimethyl diethyl ammonium (DEDMABF
4), perchloric acid dimethyl diethyl ammonium (DEDMAClO
4), tetrafluoro boric acid trimethylethyl ammonium (ETMABF
4), perchloric acid trimethylethyl ammonium (ETMAClO
4), tetrafluoro boric acid spiro quaternary ammonium salt (SBP (BF
4)
2) and perchloric acid spiro quaternary ammonium salt (SBP (ClO
4)
2) in one or more.
The organic solvent of the organic solution of described quaternary ammonium salt is preferably one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate and GBL, is more preferably wherein one or both.
According to the present invention, the concentration of the organic solution of quaternary ammonium salt is preferably 1 ~ 1.5mol/L; Described barrier film is barrier film well known to those skilled in the art, there is no special restriction, is preferably glass fibre, is more preferably double glazing fiber in the present invention.
The electrode material that the present invention is ultracapacitor with charcoal base electrode material, the specific area of this charcoal base electrode material is less, accordingly, the amount of the active function groups on its surface is little, thus the catalytic action of these functional groups to the irreversible decomposition of electrolyte can be effectively suppressed, and then stabilize this electrode material and electrolyte interface, improve the degree of reversibility that electric charge (ion) stores, therefore this charcoal base electrode material effectively can improve operating voltage and the ratio capacitance of ultracapacitor.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of charcoal base electrode material provided by the invention and preparation method thereof, ultracapacitor are described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen protection, 400 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze MCMB, obtain its stereoscan photograph, as shown in a in Fig. 1.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 1, obtain its stereoscan photograph, as shown in b in Fig. 1.Can find out by Fig. 1, the charcoal base electrode material that the present invention obtains has spherical structure, close structure, surface irregularity.
Utilize full-automatic specific area and multi-well assay instrument to analyze MCMB, obtain its N
2adsorption-desorption isothermal linearity curve, as shown in Figure 2, in figure ● curve is N
2adsorption isotherm linearity curve, in figure ▲ curve is N
2desorption isothermal curve.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 1, obtain its N
2adsorption-desorption isothermal linearity curve, as shown in Figure 3, in figure ● curve is N
2adsorption isotherm linearity curve, in figure ▲ curve is N
2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 1 according to the curve calculation of Fig. 3 is 0.095m
2/ g.
Embodiment 2
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen protection, 500 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 2, obtain its stereoscan photograph, as shown in c in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 2, obtain its N
2adsorption-desorption isothermal linearity curve, as shown in Figure 4, in figure ● curve is N
2adsorption isotherm linearity curve, in figure ▲ curve is N
2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 2 according to the curve calculation of Fig. 4 is 0.9486m
2/ g.
Embodiment 3
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen protection, 600 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 3, obtain its stereoscan photograph, as shown in d in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 3, obtain its N
2adsorption-desorption isothermal linearity curve, as shown in Figure 5, in figure ● curve is N
2adsorption isotherm linearity curve, in figure ▲ curve is N
2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 3 according to the curve calculation of Fig. 5 is 0.0926m
2/ g.
Embodiment 4
MCMB is loaded porcelain boat, puts into tube furnace, under argon shield, 500 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 4, obtain its stereoscan photograph, as shown in e in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 4, obtain its N
2adsorption-desorption isothermal linearity curve, as shown in Figure 6, in figure ● curve is N
2adsorption isotherm linearity curve, in figure ▲ curve is N
2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 4 according to the curve calculation of Fig. 6 is 0.0233m
2/ g.
Embodiment 5
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen and hydrogen gas mixture (content of hydrogen is 10% of mist volume) are protected, 500 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 5, obtain its stereoscan photograph, as shown in f in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 5, obtain its N
2adsorption-desorption isothermal linearity curve, as shown in Figure 7, in figure ● curve is N
2adsorption isotherm linearity curve, in figure ▲ curve is N
2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 2 according to the curve calculation of Fig. 7 is 0.7212m
2/ g.
Embodiment 6
10mg MCMB and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 6 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 8 ● shown in curve.
Embodiment 7
The charcoal base electrode material obtained in 10mg embodiment 1 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 7 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in △ curve in Fig. 8.
Embodiment 8
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 8 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 8
shown in curve, in Fig. 9
shown in curve.
Embodiment 9
The charcoal base electrode material obtained in 10mg embodiment 3 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 9 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in zero curve in Fig. 8.
As shown in Figure 8, with the charcoal base electrode material obtained in the charcoal base electrode material obtained in MCMB, embodiment 1 and embodiment 2 for negative pole, graphite is positive pole, and quaternary ammonium salt organic solution is that the specific capacity of the ultracapacitor of electrolyte can reach nearly 50mAh/g; The specific capacity of the ultracapacitor being negative pole with the charcoal base electrode material obtained in embodiment 3 is about 30mAh/g.
Embodiment 10
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 0.1mol/L TMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 10 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9
shown in curve.
Embodiment 11
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LTEABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 11 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9 ● shown in curve.
Embodiment 12
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 0.8mol/L TPABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 12 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9 ▲ curve shown in.
Embodiment 13
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LTBABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 13 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in zero curve in Fig. 9.
Embodiment 14
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LTEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 14 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in curve in Fig. 9.
Embodiment 15
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LDEDMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 15 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9
shown in curve.
Embodiment 16
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LETMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 16 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in △ curve in Fig. 9.
Embodiment 17
The charcoal base electrode material obtained in 10mg embodiment 4 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 17 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 10 ▲ curve shown in.
Embodiment 18
The charcoal base electrode material obtained in 10mg embodiment 5 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 18 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in zero curve in Figure 10.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 18 to test, discharge and recharge 600 times under 0 ~ 4V operating voltage and 1mA current density, obtains its cycle life curve, as shown in figure 11, wherein a is discharge capacity, and b is coulombic efficiency.As shown in Figure 11, the capability retention of the button cell that embodiment 18 obtains in 600 charge and discharge process is higher, illustrates that its cycle life is better.
Embodiment 19
10mg MCMB and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 19 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 12 ▲ curve shown in.
Embodiment 20
The charcoal base electrode material obtained in 10mg embodiment 1 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 20 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 12
shown in curve.
Embodiment 21
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 21 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtain its specific capacity curve chart, with shown in zero curve in Figure 13 as shown in zero curve in Figure 12.
Embodiment 22
The charcoal base electrode material obtained in 10mg embodiment 3 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 22 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 12 ● shown in curve.
Embodiment 23
The charcoal base electrode material obtained in 10mg embodiment 4 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 23 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 13 ▲ curve shown in.
Embodiment 24
The charcoal base electrode material obtained in 10mg embodiment 5 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 24 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 13
shown in curve.
As shown in Figure 13, to obtain charcoal base electrode material for negative pole in embodiment 2, embodiment 4 and embodiment 5, active carbon is positive pole, and quaternary ammonium salt organic solution is that the specific capacity of the ultracapacitor of electrolyte can reach 60mAh/g.
Embodiment 25
The charcoal base electrode material obtained in 10mg embodiment 5 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1mol/L TEABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 25 to test, discharge and recharge 600 times under 0 ~ 4V operating voltage and 1mA current density, obtains its cycle life curve chart, as shown in figure 14, wherein a is discharge capacity, and b is coulombic efficiency.From in Figure 14, the capability retention of the button cell obtained in embodiment 25 in 600 charge and discharge process is very high, illustrates that its cycle life is good.
Embodiment 26
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains positive pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as negative pole, layer glass fiber is barrier film, 1mol/L TEABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 26 to test, discharge and recharge under 0 ~ 3.5V operating voltage and 1mA current density, obtain its specific capacity curve chart, as shown in figure 15, as shown in Figure 15, the specific capacity of the ultracapacitor that the charcoal base electrode material prepared in embodiment 2 obtains as positive pole can reach 30mAh/g.
Embodiment 27
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains positive pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as negative pole, layer glass fiber is barrier film, 1mol/L TEABF
4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 27 to test, discharge and recharge 1000 times under 0 ~ 3.5V operating voltage and 1mA current density, obtains its cycle life curve chart, as shown in figure 16, wherein a is discharge capacity, and b is coulombic efficiency.As shown in Figure 16, the capability retention of ultracapacitor in 1000 charge and discharge process that the charcoal base electrode material prepared in embodiment 2 obtains as positive pole is very high, illustrates that its cycle life is better.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a charcoal base electrode material, is characterized in that, by MCMB in inert atmosphere or reducing atmosphere, process under 0 DEG C ~ 600 DEG C conditions and obtain.
2. charcoal base electrode material according to claim 1, is characterized in that, the specific area of described charcoal base electrode material is 0.01 ~ 10m
2/ g.
3. a preparation method for charcoal base electrode material, is characterized in that, comprises the following steps:
By MCMB in inert atmosphere or reducing atmosphere, 0 DEG C ~ 600 DEG C process, obtain charcoal base electrode material.
4. preparation method according to claim 3, is characterized in that, the temperature of described process is 60 DEG C ~ 600 DEG C.
5. preparation method according to claim 3, is characterized in that, the temperature of described process is 300 DEG C ~ 500 DEG C.
6. preparation method according to claim 3, is characterized in that, the time of described process is 2 ~ 12h.
7. preparation method according to claim 3, is characterized in that, described inert atmosphere is selected from one or more in helium, argon gas and nitrogen.
8. preparation method according to claim 3, is characterized in that, described reducing atmosphere is the mist of hydrogen and inert gas.
9. preparation method according to claim 8, is characterized in that, the content of described hydrogen is 5% ~ 20% of mist volume.
10. a ultracapacitor, comprise positive pole, negative pole, electrolyte and barrier film, it is characterized in that, described positive pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described negative pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described electrolyte is the organic solution of quaternary ammonium salt; Described positive pole and negative pole have one at least for the charcoal base electrode material described in claim 1 ~ 2 or the charcoal base electrode material prepared by claim 3 ~ 9 any one.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1985340A (en) * | 2004-07-09 | 2007-06-20 | 大阪瓦斯株式会社 | Active carbon for electric double layer capacitor, active carbon electrode for electric double layer capacitor, and electric double layer capacitor therewith |
CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
CN101916856A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Cathode material for lithium-ion power and energy storage battery and preparation method thereof |
-
2013
- 2013-09-05 CN CN201310400894.9A patent/CN104425136B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1985340A (en) * | 2004-07-09 | 2007-06-20 | 大阪瓦斯株式会社 | Active carbon for electric double layer capacitor, active carbon electrode for electric double layer capacitor, and electric double layer capacitor therewith |
CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
CN101916856A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Cathode material for lithium-ion power and energy storage battery and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
CHENG ZHENG ET AL.: "Non-porous activated mesophase carbon microbeads as a negative electrode material for asymmetric electrochemical capacitors", 《JOURNAL OF POWER SOURCES》 * |
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