CN105551823A - Carbon-carbon composite electrode material, preparation method and application - Google Patents
Carbon-carbon composite electrode material, preparation method and application Download PDFInfo
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- CN105551823A CN105551823A CN201610073809.6A CN201610073809A CN105551823A CN 105551823 A CN105551823 A CN 105551823A CN 201610073809 A CN201610073809 A CN 201610073809A CN 105551823 A CN105551823 A CN 105551823A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title abstract description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title abstract 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 89
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000003990 capacitor Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012190 activator Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000013467 fragmentation Methods 0.000 claims description 4
- 238000006062 fragmentation reaction Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940077239 chlorous acid Drugs 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000010891 electric arc Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- 238000010792 warming Methods 0.000 description 10
- -1 carbon nano-tube compound Chemical class 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 5
- 229960001231 choline Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000004804 winding 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a preparation method of a carbon-carbon composite electrode material. The method comprises the following steps: activating carbon nanotubes, and then mixing the carbon nanotubes with activated carbon; carrying out wet ball-milling, washing and drying; and sintering the mixture to obtain the carbon-carbon composite electrode material. According to the compound method provided by the invention, the carbon nanotubes and the activated carbon can be evenly compounded; the prepared carbon-carbon composite electrode material is applied to preparation of an electrode plate after being bonded with a binder and the like, and can provide the conductivity, the power characteristic and the cycling stability; under the equal content of the carbon nanotubes, the method provided by the invention can obtain relatively high energy density and relatively good electrical properties; the carbon-carbon composite electrode material is simple in production technology and relatively low in demands on equipment and experiment condition, and has the advantages of low cost, short preparation period, high yield, good comprehensive economical benefits and the like; and industrial production is easy to achieve.
Description
Technical field
The invention belongs to the preparation field of electrode material for super capacitor, relate to a kind of carbon-to-carbon combination electrode material, Preparation method and use, be specifically related to electrode material of a kind of activated carbon for super capacitors and carbon nano-tube compound and preparation method thereof.
Background technology
Ultracapacitor (Supercapacitors) is also known as electrochemical capacitor (ElectrochemicalCapacitors) or double electric layer capacitor (ElectricDoubleLayerCapacitors), it is a kind of novel energy-storing element between traditional capacitor and battery, there is more high-specific capacitance super and energy density compared with traditional capacitor, compared with battery, then there is higher power density; And ultracapacitor has that charge/discharge rates is fast, environmentally safe and the advantage such as to have extended cycle life, and all has a wide range of applications at numerous areas such as portable instrument equipment, back-up source, electric vehicle mixed power, communication apparatus, computer, fuel cells.In new energy electric motor vehicle, combine ECs and rechargeable battery formation hybrid battery, both can meet vehicle launch, acceleration, climbing and brake recuperated energy time changed power requirement, battery size can be reduced again, increasing storage battery service life, improve energy utilization efficiency, the modernization for urban public transport provides new pattern.
At present, the principal element restricting supercapacitor applications is that its energy density (the electric energy wh/kg namely stored by Unit Weight) is on the low side.The energy density of ultracapacitor contrasts with the energy density of the secondary cell of extensive use in the market: ultracapacitor: 1 ~ 20wh/kg; Excide battery: 20wh/kg; Cadmium nickel, Ni-MH battery: 20 ~ 60wh/kg; Lithium battery: 120 ~ 140wh/kg; Visible, super capacitor energy density is relatively low, and therefore, the energy density how improving ultracapacitor is that ultracapacitor is developed so far the important topic being badly in need of solving to meet its requirement as energy storage device.
Electrode material is the core component of ultracapacitor, is the key factor affecting ultracapacitor capacitive character energy and production cost.The computing formula of super capacitor energy density:
E＝1/2C·V
2
C＝ε·A/3.6πd·10
-6(μF)
Wherein E is energy density, and C is electrode ratio capacitance value, and V is interelectrode voltage drop, and ε is relative dielectric constant, and A is electrode material area, and d is dielectric thickness.Visible, for the ultracapacitor of development high-energy-density, the electrode material with high specific capacitance must be developed.
Therefore, the electrode material of exploitation high-performance, low cost is the important content of ultracapacitor research work.The more ECs electrode material of current research is: material with carbon element series, metal oxide is serial, conducting polymer is serial and composite material etc., and wherein, what obtain commercial Application is material with carbon element series, as; Active carbon, active carbon fiber fabrics, carbon aerogels etc.
Active carbon is current most widely used electrode material for super capacitor, but, time merely using active carbon as electrode material for super capacitor, capacitance loss is very large, the ratio capacitance of normal activated carbon is generally at below 180F/g, and energy density is less than 5wh/kg, and this is mainly because absorbent charcoal material conductivity is poor, be unfavorable for quick storage electric charge, the poor-performing of stored energy, needs to add high conductivity material if graphite, carbon fiber etc. are to improve its conductivity in use, reduces electrode interior impedance.
Carbon nano-tube (CNT) has unique hollow structure, good conductivity, high-specific surface area, chemical stability, the hole being applicable to electrolyte ion migration and mutual winding can form the advantages such as the network configuration of nanoscale, be regarded as desirable electrode material for super capacitor, become study hotspot in recent years.Particularly CNT is used for the preparation of carbon/carbon complex as additive, is doped in internal resistance and the charge-discharge velocity that in active carbon with high specific surface area, effectively can reduce ultracapacitor, and the cycle performance of the activated carbon electrodes significantly improved.
Although CNT shows the performance of various excellence in supercapacitor applications, because its preparation cost is high and device therefor is complicated, the ultracapacitor based on CNT is made also to be confined at present grind examination on a small scale.Therefore, develop that a kind of cost is low, the preparation method of the simple active carbon/carbon combination electrode material of preparation method, the road promoting its industrialization will play vital effect.
CN1934665 discloses a kind of new method preparing the electrode of blend based on active carbon and carbon nano-tube on the current collector, has good ageing properties, improves conductivity and/or electric capacity.But its preparation process be by active carbon and carbon nano-tube blended, add binding agent afterwards, coating on the current collector.Easily reunite in the mixed process of active carbon and carbon nano-tube, in the preparation process of electrode slice, the addition 5% ~ 50% of carbon nano-tube, carbon nano-tube addition is too much, be unfavorable for capacity boost, addition is less, does not have the effect of improvement, and produces deterioration impact to the electric property of electrode slice after the mixing of active carbon and carbon nano-tube.
Therefore, this area needs the electrode material developing a kind of activated carbon for super capacitors and carbon nano-tube compound, and it has higher energy density, and electric property.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of carbon-to-carbon combination electrode material, Preparation method and use, described carbon-to-carbon combination electrode material has the advantages such as the high conductivity of the high-ratio surface sum carbon nano-tube of active carbon concurrently, and preparation method is simple, with low cost, realizes suitability for industrialized production.
Goal of the invention of the present invention realizes especially by following scheme:
First aspect, the preparation method of described carbon-to-carbon combination electrode material, described method comprises the steps:
Carbon nano-tube activated, mix afterwards, carry out wet ball grinding with active carbon, after washing, drying, roasting, obtains carbon-to-carbon combination electrode material.
The present invention activates carbon nano-tube, adds the hydrophilic group on its surface, and fine dispersion is in water, and after mixing with active carbon, ball milling carries out even compound, after sintering, obtain carbon-to-carbon combination electrode material.Complex method provided by the invention makes carbon nano-tube and active carbon can even compound, for the preparation of electrode slice after the carbon-to-carbon combination electrode material prepared and binding agent etc. bond, can provide conductivity, power characteristic and stable circulation; Under the content of carbon nanotubes of equivalent, method provided by the invention can obtain higher energy density, and better electric property.
Preferably, the step of described carbon nano-tube activation is: by carbon nanotube dispersed in water, add oxidizing acid, be uniformly mixed and activate, obtain the carbon nano tube paste be dispersed in water.
Preferably, described carbon nano-tube is the combination of any a kind or at least 2 kinds in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes.
Preferably, the length of described carbon nano-tube is 5 ~ 50 μm, such as 6 μm, 18 μm, 25 μm, 36 μm, 47 μm etc.
Preferably, described carbon nano-tube is by the preparation of catalyse pyrolysis, arc discharge, template and laser evaporation method.
Preferably, described oxidizing acid is selected from the combination of any a kind or at least 2 kinds in nitric acid, sulfuric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid; Preferred described concentration of nitric acid >=10wt%, preferably 30 ~ 40wt%; The addition of described oxidizing acid is preferably 0.1 ~ 100 times of carbon nanotube mass, preferably 20 ~ 30 times further.
For nitric acid, the lower effect not reaching surface oxidation of concentration, concentration is higher, comparatively large to the destruction of material surface, and introduces too much impurity anions on surface.
Preferably, described by the mode of carbon nanotube dispersed in water for stirring, described mixing speed preferably 5000 ~ 6000 turns/min, such as 5300 turns/min, 5500 turns/min, 5700 turns/min etc.
Preferably, described granularity of activated carbon D50 is 10 ~ 100 orders, such as 20 orders, 50 orders, 70 orders, 90 orders etc.
Preferably, described active carbon specific area>=1500m
2/ g, such as 1700m
2/ g, 1900m
2/ g, 2000m
2/ g, 2300m
2/ g etc., preferably>=1700m
2/ g.
Preferably, described active carbon has hole, and more than 10% of hole is mesopore, and preferably more than 20% is mesopore, and in the hole that described active carbon has, what the ratio of mesopore was exemplary can be 15%, 18%, 22%, 25%, 28% etc.; The aperture preferably 2 ~ 50nm of described mesopore, such as 3nm, 10nm, 18nm, 27nm, 33nm, 43nm etc.
Preferably, described active carbon obtains by the following method:
Front burnt particle will be forged heat up in oxidizing atmosphere and carry out pre-oxidation, obtain pre-oxidation Jiao; Pre-oxidation is burnt and activator mix, activates under an inert atmosphere afterwards, and then remaining activated dose of washing removing obtains active carbon.
Preferably, described in forge front burnt grain diameter be 10 ~ 100 orders, such as 20 orders, 50 orders, 70 orders, 90 orders etc.
Preferably, forge front burnt particle front coke powder is broken to be obtained by will forge, the combination of any a kind or at least 2 kinds in described pulverizing preferred mechanical fragmentation, air-flow crushing, ball milling, sand milling, preferred mechanical fragmentation described in.
Preferably, forge described in front Jiao be selected from petroleum forge before burnt or coal measures forge front Jiao.
Preferably, in described oxidizing atmosphere, oxygen content is 5 ~ 30v%, such as 6v%, 10v%, 15v%, 20v%, 26v% etc.
Preferably, the speed of described intensification is 5 ~ 25 DEG C/min, such as 6 DEG C/min, 10 DEG C/min, 12 DEG C/min, 16 DEG C/min, 20 DEG C/min, 24 DEG C/min etc., Pre oxidation preferably 250 ~ 550 DEG C, such as 260 DEG C, 300 DEG C, 320 DEG C, 380 DEG C, 450 DEG C, 500 DEG C, 530 DEG C etc., preoxidation time is 1 ~ 4h preferably, such as 2h, 3h etc.
Preferably, described activator is alkali metal hydroxide, preferred NaOH and/or potassium hydroxide, further preferred NaOH; Described activator is preferably Powdered and/or sheet; Described activator is 50 ~ 200 object sodium hydroxide powder more preferably; Described pre-oxidation is burnt is preferably 1:1 ~ 6 with the mixed proportion of activator;
Preferably, the temperature of described activation is 650 ~ 950 DEG C, such as 660 DEG C, 700 DEG C, 720 DEG C, 780 DEG C, 850 DEG C, 900 DEG C, 930 DEG C etc.
Preferably, described pre-oxidation and activation are all carried out in closed body of heater, preferably carry out in revolution oxidation furnace or middle temperature type resistance furnace, preferably carry out in revolution oxidation furnace.
Preferably, described inertia protection gas is the combination of any a kind or at least 2 kinds in nitrogen, argon gas, helium or neon, is preferably nitrogen;
Preferably, the solid content of described active carbon is 30 ~ 60%, such as 35%, 38%, 42%, 48%, 53%, 58% etc., and granularity D50 is preferably 10 ~ 100 orders, such as 20 orders, 50 orders, 70 orders, 90 orders etc.
Preferably, solid-liquid ratio 1:0.5 ~ 3 of described wet ball grinding, such as 1:0.7,1:0.9,1:1,1:1.3,1:1.5,1:1.6,1:1.9,1:2.2,1:2.5,1:2.7,1:2.9 etc., preferred 1:1; The rotating speed preferably 30 ~ 60rpm/min of wet ball grinding, preferred 40rpm/min;
Preferably, the ball milling pearl of described wet ball grinding is zirconia ball, and preferable particle size is the zirconia ball of 3 ~ 5mm; The ball material mass ratio of described zirconia ball and ball milling material is preferably 8 ~ 12:1, further preferred 10:1;
Preferably, after described wet ball grinding, the granularity D50 of material is 6.5 ~ 7.5 μm, such as 6.7 μm, 7 μm, 7.3 μm etc.
Preferably, described sintering temperature is 200 ~ 800 DEG C, such as 220 DEG C, 260 DEG C, 320 DEG C, 450 DEG C, 560 DEG C, 650 DEG C, 720 DEG C etc., is preferably 400 ~ 600 DEG C; Described sintering time is preferably 1 ~ 5h, such as 2h, 3h, 4h etc., more preferably 3h.
As optimal technical scheme, the preparation method of carbon-to-carbon combination electrode material provided by the invention comprises the steps:
(1) preparation of active carbon: forging front burnt under oxygenous volume is the atmosphere of 5 ~ 30% by being crushed to 10 ~ 100 objects, being warming up to 250 ~ 550 DEG C with the speed of 5 ~ 25 DEG C/min and carrying out pre-oxidation treatment 1 ~ 4h in closed body of heater; Then pre-oxidation Jiao is mixed by 1:1 ~ 6 with activator, under inert gas shielding, be warming up to 650 ~ 950 DEG C activate, after cooling, obtain through the operation such as choline, washing that solid content is 30 ~ 60%, granularity D50 is 10 ~ 100 object active carbons;
(2) preparation of carbon nano-tube homogenate: by the carbon nano-tube ultrasonic disperse of 1 weight portion drying in deionized water, add 0.1 ~ 100 weight portion acid with strong oxidizing property to process its surface, and high-speed stirred mixing 4 ~ 12h, obtain homodisperse carbon nano tube paste; Described ultrasonic power is at below 100kHz;
(3) active carbon/carbon compound: the solid content that the carbon nanotube dispersed slurry obtain step (2) and step (1) obtain is 30 ~ 60%, granularity D50 is 10 ~ 100 object active carbon mixing and ball milling; washing, oven dry; under inert gas shielding; high temperature sintering, obtains the active carbon/carbon combination electrode material that described content of carbon nanotubes is 4 ~ 8%.
Second aspect, present invention also offers a kind of purposes of first aspect carbon-to-carbon combination electrode material, and described carbon-to-carbon combination electrode material is used for electrode material for super capacitor and asymmetric lithium ion super capacitor electrode material field.
The third aspect, the invention provides a kind of ultracapacitor carbon-to-carbon combination electrode material, described carbon-to-carbon combination electrode material is prepared by the method described in first aspect.
Fourth aspect, the invention provides a kind of electrode for super capacitor, described electrode for super capacitor obtains by the following method: be first dissolved in methyl pyrrolidone by PVDF, then conductive agent, active carbon/carbon combination electrode material is added, be uniformly dispersed in high speed dispersor, the slurry of obtained thickness; Slurry is coated in uniformly on current collector corrodes aluminium foil, at 120 DEG C of dry 12h, with powder compressing machine pressurize 30s under 9Mpa, obtains activated carbon for super capacitors/carbon nano-tube combination electrode material electrode slice.
Compared with prior art, the present invention has following beneficial effect:
(1) complex method provided by the invention makes carbon nano-tube and active carbon can even compound, for the preparation of electrode slice after the carbon-to-carbon combination electrode material prepared and binding agent etc. bond, can provide conductivity, power characteristic and stable circulation; Under the content of carbon nanotubes (4 ~ 8%) of equivalent, method provided by the invention can obtain higher energy density, and better electric property;
(2) the present invention activates carbon nano-tube, and add the hydrophilic group on its surface, fine dispersion is in water; After mixing with active carbon, ball milling carries out even compound, after sintering, obtain carbon-to-carbon combination electrode material, production technology is simple, lower to the requirement of equipment and experiment condition, easily realize suitability for industrialized production, there is the advantages such as cost is low, manufacturing cycle is short, yield is high, overall economic efficiency is good.
Accompanying drawing explanation
The active carbon AC that Fig. 1 embodiment 1 obtains, the stereoscan photograph of carbon-to-carbon combination electrode material AC/CNTs;
The active carbon AC of Fig. 2 embodiment example 1, the powder conductivity rate of carbon-to-carbon combination electrode material AC/CNTs;
Fig. 3 is the charging and discharging curve of the electrode slice of application examples 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A kind of carbon-to-carbon combination electrode material, obtains by the following method:
(1) 60 objects will be crushed to and forge front Jiao (air velocity 300L/h) in air atmosphere, and be warming up to 450 DEG C with the speed of 5 DEG C/min and carry out pre-oxidation treatment 2h in revolution oxidation furnace, obtain pre-oxidation Jiao; Then by burnt for pre-oxidation with activator NaOH in mass ratio 1:3 mix, at inert gas N
2be warming up to 800 DEG C under (flow velocity 30L/h) protection to activate in middle temperature type resistance furnace, obtain through operations such as choline, washing, centrifugations the active carbon that solid content is 30 ~ 60% after cooling, conductivity is 8.28S/cm;
(2) by ultrasonic for the carbon nano-tube of 1 weight portion drying (0 ~ 100kHz) dispersion in deionized water, adding 6 weight portion mass fractions is the nitric acid of 35%, in high speed dispersor, mix and blend (rate of dispersion is 5000 ~ 6000 turns) 10h, obtains homodisperse carbon nano tube paste (content of carbon nanotubes 5wt%);
(3) solid content that carbon nanotube dispersed slurry step (2) obtained and step (1) obtain is the active carbon mixing and ball milling of 30 ~ 60%, with more than 70 DEG C deionized water washings to neutral, centrifugation, at 120 DEG C of dry 12h, material after oven dry is calcined 2 ~ 4 hours in the nitrogen atmosphere of 800 ~ 900 DEG C, obtain the carbon-to-carbon combination electrode material that content of carbon nanotubes is 8%, the specific area 1809m of described carbon-to-carbon combination electrode material
2/ g, powder conductivity rate is illustrated in figure 2 18.23S/cm.
Application examples 1
The carbon-to-carbon combination electrode material obtained by embodiment 1 and conductive agent SuperP, binding agent PVDF in mass ratio 90:5:5 mix and prepare electrode slice, in Et4NBF4/PC (propene carbonate of the tetraethyl ammonium tetrafluoroborate containing the 1mol/L) electrolyte of 1.0M, in the scope of 1.2 ~ 2.5V, loop test is carried out with the current density of 50mA/g, as shown in Figure 2, the ratio capacitance of the electrode slice that application examples 1 provides is 190F/g to test result.
Embodiment 2
A kind of carbon-to-carbon combination electrode material, obtains by the following method:
(1) 60 objects will be crushed to and forge front Jiao (air velocity 300L/h) in air atmosphere, and be warming up to 450 DEG C with the speed of 5 DEG C/min and carry out pre-oxidation treatment 2h in revolution oxidation furnace, obtain pre-oxidation Jiao; Then by burnt for pre-oxidation with activator NaOH in mass ratio 1:3 mix, at inert gas N
2be warming up to 800 DEG C under (flow velocity 30L/h) protection to activate in middle temperature type resistance furnace, obtain through operations such as choline, washing, centrifugations the active carbon that solid content is 30 ~ 60% after cooling, conductivity is 8.28S/cm;
(2) by ultrasonic for the carbon nano-tube of 1 weight portion drying (0 ~ 100kHz) dispersion in deionized water, adding 6 weight portion mass fractions is the nitric acid of 35%, in high speed dispersor, mix and blend (rate of dispersion is 5000 ~ 6000 turns) 10h, obtains homodisperse carbon nano tube paste (content of carbon nanotubes 5wt%);
(3) solid content that carbon nanotube dispersed slurry step (2) obtained and step (1) obtain is the active carbon mixing and ball milling of 30 ~ 60%, with more than 70 DEG C deionized water washings to neutral, centrifugation, at 120 DEG C of dry 12h, material after oven dry is calcined 2 ~ 4 hours in the nitrogen atmosphere of 800 ~ 900 DEG C, obtain the specific area 1883m that content of carbon nanotubes is 4% carbon-to-carbon combination electrode material, described carbon-to-carbon combination electrode material
2/ g, powder conductivity rate is 10.34S/cm.
Application examples 2
The carbon-to-carbon combination electrode material obtained by embodiment 2 and conductive agent SuperP, binding agent PVDF in mass ratio 90:5:5 mix and prepare electrode slice, in Et4NBF4/PC (propene carbonate of the tetraethyl ammonium tetrafluoroborate containing the 1mol/L) electrolyte of 1.0M, in the scope of 1.2 ~ 2.5V, carry out loop test with the current density of 50mA/g, ratio capacitance is 170F/g.
Embodiment 3
A kind of carbon-to-carbon combination electrode material, obtains by the following method:
(1) 60 objects will be crushed to and forge front Jiao (air velocity 300L/h) in air atmosphere, and be warming up to 450 DEG C with the speed of 5 DEG C/min and carry out pre-oxidation treatment 2h in revolution oxidation furnace, obtain pre-oxidation Jiao; Then by burnt for pre-oxidation with activator NaOH in mass ratio 1:3 mix, at inert gas N
2be warming up to 800 DEG C under (flow velocity 30L/h) protection to activate in middle temperature type resistance furnace, obtain through operations such as choline, washing, centrifugations the active carbon that solid content is 30 ~ 60% after cooling, conductivity is 8.28S/cm;
(2) by ultrasonic for the carbon nano-tube of 1 weight portion drying (0 ~ 100kHz) dispersion in deionized water, adding 6 weight portion mass fractions is the nitric acid of 35%, in high speed dispersor, mix and blend (rate of dispersion is 5000 ~ 6000 turns) 10h, obtains homodisperse carbon nano tube paste (content of carbon nanotubes 5wt%);
(3) solid content that carbon nanotube dispersed slurry step (2) obtained and step (1) obtain is the active carbon mixing and ball milling of 30 ~ 60%, with more than 70 DEG C deionized water washings to neutral, centrifugation, at 120 DEG C of dry 12h, material after oven dry is calcined 2 ~ 4 hours in the nitrogen atmosphere of 800 ~ 900 DEG C, obtain the specific area 1730m that content of carbon nanotubes is 12% carbon-to-carbon combination electrode material, described carbon-to-carbon combination electrode material
2/ g, powder conductivity rate is 21.52S/cm.
Application examples 3
The active carbon/carbon combination electrode material obtained by embodiment 3 and conductive agent SuperP, binding agent PVDF in mass ratio 90:5:5 mix and prepare electrode slice, in Et4NBF4/PC (propene carbonate of the tetraethyl ammonium tetrafluoroborate containing the 1mol/L) electrolyte of 1.0M, in the scope of 1.2 ~ 2.5V, carry out loop test with the current density of 50mA/g, ratio capacitance is 150F/g.
Comparative example 1
Only be with the difference of embodiment 1, the quality such as the carbon nano-tube of step (2) are replaced with the standby Graphene of reduction-oxidation legal system, carbon-to-carbon combination electrode material, and the specific area of described carbon-to-carbon combination electrode material is 1920m
2/ g, powder conductivity rate is 12.72S/cm.
Contrast application examples 1
Comparative example 1 is obtained with conductive agent SuperP, binding agent PVDF in mass ratio 90:5:5 mix and prepare electrode slice, in Et4NBF4/PC (the tetraethyl ammonium tetrafluoroborate containing 1mol/L the propene carbonate) electrolyte of 1.0M, in the scope of 1.2 ~ 2.5V, carry out loop test with the current density of 50mA/g, ratio capacitance is 165F/g.
Comparative example 2
A kind of electrode material, obtains by the following method:
(1) 60 objects will be crushed to and forge front Jiao (air velocity 300L/h) in air atmosphere, and be warming up to 450 DEG C with the speed of 5 DEG C/min and carry out pre-oxidation treatment 2h in revolution oxidation furnace; Then by burnt for pre-oxidation with activator NaOH in mass ratio 1:3 mix, at inert gas N
2be warming up to 800 DEG C under (flow velocity 30L/h) protection to activate in middle temperature type resistance furnace; choline after cooling; with more than 80 DEG C hot washes to neutral rear ball milling, centrifugation; at 120 DEG C of dry 12h; material after oven dry is calcined 2 ~ 4 hours in the nitrogen atmosphere of 800 ~ 900 DEG C; obtain burnt class active carbon electrode material, specific area 1940m
2/ g, powder conductivity rate is 8.28S/cm.
Contrast application examples 2
Burnt class active carbon electrode material comparative example 2 prepared and carbon nano-tube, conductive agent SuperP, binding agent PVDF in mass ratio 83:7:5:5 mix and prepare electrode slice, in Et4NBF4/PC (the tetraethyl ammonium tetrafluoroborate containing 1mol/L the propene carbonate) electrolyte of 1.0M, in the scope of 1.2 ~ 2.5V, carry out loop test with the current density of 50mA/g, ratio capacitance is 172F/g.
Comparative example 3
Only be with the difference of embodiment 1, in step (2) carbon nanotube dispersed in deionized water after, do not add nitric acid, directly stir in high speed dispersor, the powder conductivity rate preparing electrode material is 9.47S/cm.
Contrast application examples 3
Burnt class active carbon electrode material comparative example 3 prepared and carbon nano-tube, conductive agent SuperP, binding agent PVDF in mass ratio 83:7:5:5 mix and prepare electrode slice, in Et4NBF4/PC (the tetraethyl ammonium tetrafluoroborate containing 1mol/L the propene carbonate) electrolyte of 1.0M, in the scope of 1.2 ~ 2.5V, carry out loop test with the current density of 50mA/g, ratio capacitance is 172F/g.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for carbon-to-carbon combination electrode material, is characterized in that, described method comprises the steps:
Carbon nano-tube activated, mix afterwards, carry out wet ball grinding with active carbon, after washing, drying, roasting, obtains carbon-to-carbon combination electrode material.
2. preparation method as claimed in claim 1, is characterized in that, the step of described carbon nano-tube activation is: by carbon nanotube dispersed in water, add oxidizing acid, be uniformly mixed and activate, obtain the carbon nano tube paste be dispersed in water;
Preferably, described carbon nano-tube is the combination of any a kind or at least 2 kinds in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, the tube wall number of described multi-walled carbon nano-tubes preferably 2 ~ 10;
Preferably, the length of described carbon nano-tube is 5 ~ 50 μm;
Preferably, described carbon nano-tube is by the preparation of catalyse pyrolysis, arc discharge, template and laser evaporation method;
Preferably, described oxidizing acid is selected from the combination of any a kind or at least 2 kinds in nitric acid, sulfuric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid; Preferred described concentration of nitric acid >=10wt%, preferably 30 ~ 40wt%; The addition of described oxidizing acid is preferably 0.1 ~ 100 times of carbon nanotube mass, preferably 20 ~ 30 times further;
Preferably, described is stirring by the mode of carbon nanotube dispersed in water, and described mixing speed is 5000 ~ 6000 turns/min preferably.
3. preparation method as claimed in claim 1 or 2, it is characterized in that, described granularity of activated carbon D50 is 10 ~ 100 orders;
Preferably, described active carbon specific area>=1500m
2/ g, preferably>=1700m
2/ g;
Preferably, described active carbon has hole, and more than 10% of hole is mesopore, and preferably more than 20% is mesopore; The aperture preferably 2 ~ 50nm of described mesopore.
4. the preparation method as described in one of Claims 1 to 5, is characterized in that, described active carbon obtains by the following method:
Front burnt particle will be forged heat up in oxidizing atmosphere and carry out pre-oxidation, obtain pre-oxidation Jiao; Pre-oxidation is burnt and activator mix, activates under an inert atmosphere afterwards, and then remaining activated dose of washing removing obtains active carbon.
5. preparation method as claimed in claim 4, is characterized in that, described in forge front burnt grain diameter be 10 ~ 100 orders;
Preferably, forge front burnt particle front coke powder is broken to be obtained by will forge, the combination of any a kind or at least 2 kinds in described pulverizing preferred mechanical fragmentation, air-flow crushing, ball milling, sand milling, preferred mechanical fragmentation described in;
Preferably, forge described in front Jiao be selected from petroleum forge before burnt or coal measures forge front Jiao;
Preferably, in described oxidizing atmosphere, oxygen content is 5 ~ 30v%;
Preferably, the speed of described intensification is 5 ~ 25 DEG C/min, Pre oxidation preferably 250 ~ 550 DEG C, and preoxidation time is 1 ~ 4h preferably;
Preferably, described activator is alkali metal hydroxide, preferred NaOH and/or potassium hydroxide, further preferred NaOH; Described activator is preferably Powdered and/or sheet; Described activator is 50 ~ 200 object sodium hydroxide powder more preferably; Described pre-oxidation is burnt is preferably 1:1 ~ 6 with the mixed proportion of activator;
Preferably, the temperature of described activation is 650 ~ 950 DEG C;
Preferably, described pre-oxidation and activation are all carried out in closed body of heater, preferably carry out in revolution oxidation furnace or middle temperature type resistance furnace, preferably carry out in revolution oxidation furnace;
Preferably, described inertia protection gas is the combination of any a kind or at least 2 kinds in nitrogen, argon gas, helium or neon, is preferably nitrogen;
Preferably, the solid content of described active carbon is 30 ~ 60%, granularity D50 be preferably 10 ~ 100 orders.
6. the preparation method as described in one of Claims 1 to 5, is characterized in that, solid-liquid ratio 1:0.5 ~ 3 of described wet ball grinding, preferred 1:1; The rotating speed preferably 30 ~ 60rpm/min of wet ball grinding, preferred 40rpm/min;
Preferably, the ball milling pearl of described wet ball grinding is zirconia ball, and preferable particle size is the zirconia ball of 3 ~ 5mm; The ball material mass ratio of described zirconia ball and material is preferably 8 ~ 12:1, further preferred 10:1;
Preferably, after described wet ball grinding, the granularity D50 of material is 6.5 ~ 7.5 μm.
7. the preparation method as described in one of claim 1 ~ 6, is characterized in that, described sintering temperature is 200 ~ 800 DEG C, is preferably 400 ~ 600 DEG C; Described sintering time is preferably 1 ~ 5h, more preferably 3h.
8. as a purposes for one of claim 1 ~ 7 carbon-to-carbon combination electrode material, it is characterized in that, described carbon-to-carbon combination electrode material is used for electrode material for super capacitor and asymmetric lithium ion super capacitor electrode material field.
9. a ultracapacitor carbon-to-carbon combination electrode material, is characterized in that, described carbon-to-carbon combination electrode material is prepared by the method one of claim 1 ~ 7 Suo Shu.
10. an electrode for super capacitor, it is characterized in that, described electrode for super capacitor obtains by the following method: be first dissolved in methyl pyrrolidone by PVDF, then carbon-to-carbon combination electrode material prepared by the described method of one of conductive agent, claim 1 ~ 7 is added, be uniformly dispersed in high speed dispersor, the slurry of obtained thickness; Slurry is coated in uniformly on current collector corrodes aluminium foil, at 120 DEG C of dry 12h, with powder compressing machine pressurize 30s under 9MPa, obtains activated carbon for super capacitors/carbon nano-tube combination electrode material electrode slice.
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