CN103093973B - The preparation method of super capacitor material - Google Patents
The preparation method of super capacitor material Download PDFInfo
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- CN103093973B CN103093973B CN201310049512.2A CN201310049512A CN103093973B CN 103093973 B CN103093973 B CN 103093973B CN 201310049512 A CN201310049512 A CN 201310049512A CN 103093973 B CN103093973 B CN 103093973B
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000003990 capacitor Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 6
- 229910003471 inorganic composite material Inorganic materials 0.000 claims abstract description 5
- 238000001523 electrospinning Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 69
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 31
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 21
- 238000010041 electrostatic spinning Methods 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 12
- 235000011837 pasties Nutrition 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005421 electrostatic potential Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000012644 addition polymerization Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 20
- 238000009413 insulation Methods 0.000 description 20
- 238000010792 warming Methods 0.000 description 20
- 239000003575 carbonaceous material Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 14
- 239000002134 carbon nanofiber Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 229910021607 Silver chloride Inorganic materials 0.000 description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 11
- 238000010998 test method Methods 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000006245 Carbon black Super-P Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of preparation method of super capacitor material, which solve existing electrode material complex manufacturing, production cost is higher, specific capacitance is lower technical problem, comprise the following steps: inorganic acid is added in organic solvent, addition polymerization compound again, obtained uniform organic/inorganic mixed solution, then to be volatilized by organic solvent or electrospinning process obtains organic/inorganic composite material, obtain material with carbon element through pre-oxidation, K cryogenic treatment and high temperature cabonization again, then make electrode material for super capacitor.The present invention can be used for the manufacture of electrode of super capacitor.
Description
Technical field
The present invention relates to Material Field, be specifically related to a kind of preparation method of super capacitor material.
Background technology
Lithium ion battery have specific energy large, have extended cycle life, the good and advantages of environment protection of fail safe, be sent to great expectations and be applied to power vehicle and hybrid vehicle.But lithium ion battery exists the low shortcoming of specific power density, limit its application in power vehicle and field of hybrid electric vehicles.The instantaneous power of ultracapacitor is large, the life-span is long, fast charging and discharging performance is good, volume is little, serviceability temperature wide ranges, is expected to make up the deficiency of lithium ion battery as new-energy automobile single power source, thus promotes the development of new-energy automobile energetically.
Ultracapacitor is divided into double electric layers supercapacitor and pseudocapacitors.Double electric layers supercapacitor electrode material mainly material with carbon element, pseudocapacitors electrode material mainly comprises metal oxide and conducting polymer.At present, pseudocapacitors is due to the reason such as expensive, cycle performance is poor and unrealized complete commercialization.Commercialization ultracapacitor is mainly based on double electric layers supercapacitor.
Porous carbon materials has the advantages such as specific area is large, Stability Analysis of Structures, long service life, cost performance are high, becomes the main electrode material of commercialization ultracapacitor.Preparation method's mainly activation method and template of porous carbon materials, they all exist, and operation is various, energy consumption is high, pollution is large, high in cost of production shortcoming.In theory, the specific capacitance of porous carbon materials is directly proportional to its specific area, but research shows, is not that more bulky capacitor value is higher for specific area, also relevant with the factor such as the pore size of porous carbon materials, pore-size distribution, surface texture and surface charge state.
The patent No. be 200510031195.7 Chinese invention patent disclose a kind of active carbon with high specific surface area preparation method and ultracapacitor manufacture method, it adopts KOH etching method to prepare the active carbon of specific area up to 2000 ~ 3000m2/g, and specific capacitance is only 84F/g.According to [MingjiangZhong, Eun Kyung Kim and John P.McGann et al.J.Am.Chem.Soc.2012,134,14846-14857] report, with the porous carbon materials being rich in nitrogen-doping that polyacrylonitrile-butyl polyacrylate diblock copolymer is precursor power, although specific area only has 500m2/g, at 1mol/L H
2sO
4in electrolyte, specific capacitance is still up to (166 ± 5) F/g, and CO afterwards
2activation and KOH etching all do not have remarkable effect to the raising of specific capacitance.Therefore, element doping to simplification production technology, reduce production cost, to prepare high performance electrode material for super capacitor significant.
Summary of the invention
The present invention is exactly to overcome existing electrode material complex manufacturing, production cost is higher, specific capacitance is lower technical problem, provides the preparation method of the super capacitor material that a kind of technique is simple, production cost is lower, specific capacitance is higher.
For this reason, the invention provides a kind of preparation method of electrode material for super capacitor, it comprises the following steps: the inorganic acid of 0.2 ~ 8wt% adds in organic solvent by (1), then adds the polymer of 9 ~ 12wt%, obtained uniform organic/inorganic mixed solution; (2) organic/inorganic mixed solution step (1) obtained is volatilized by organic solvent or electrospinning process obtains organic/inorganic composite material; (3) organic/inorganic composite material that step (2) obtains is obtained material with carbon element through pre-oxidation, K cryogenic treatment and high temperature cabonization; Low temperature refers to 300 ~ 500 DEG C; High temperature refers to 600 ~ 1000 DEG C; (4) material with carbon element that step (3) obtains is made electrode material for super capacitor.
Preferably, the organic solvent volatilization condition in step (2) is as follows: under the environment of temperature 25 ~ 60 DEG C, relative humidity >=30%, leave standstill 6 ~ 36 hours.
Preferably, electrostatic spinning process parameter in step (2) is: spinning humidity < 30%, and through being 0.6 ~ 1.8mm in syringe needle, spinning solution flow is 0.2 ~ 0.8mL/h, electrostatic potential is 12 ~ 20kV, adopts single needle or Multi needle spinning.
Preferably, the pre-oxidizing conditions in step (3) is as follows: carry out pre-oxidation at 240 ~ 300 DEG C, and programming rate is 1 ~ 10 DEG C/min, and cooling rate is 1 ~ 10 DEG C/min, and preoxidation time is 1 ~ 5 hour; K cryogenic treatment condition is as follows: inert atmosphere, at 300 ~ 500 DEG C, programming rate is 1 ~ 20 DEG C/min, and temperature retention time is 1 ~ 10 hour; High temperature cabonization condition is as follows: inert atmosphere, at 600 ~ 1000 DEG C, programming rate is 1 ~ 20 DEG C/min, and cooling rate is 1 ~ 20 DEG C/min, and carbonization time is 0.5 ~ 10 hour.
Preferably, in step (4), the material with carbon element of 80 ~ 95wt% is mixed with the conductive black of 0 ~ 10wt%, add 5 ~ 10wt% Kynoar and 10 ~ 20 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state; Adopt platinized platinum as collector, the above-mentioned homogenize material mixed is coated in collector platinized platinum surface, obtained electrode material for super capacitor.
Preferably, inorganic acid comprises one or more combinations of phosphoric acid, polyphosphoric acids, phosphorous acid, metaphosphoric acid.
Preferably, organic solvent comprises one or more combinations of DMA, DMF or 1-METHYLPYRROLIDONE.
Preferably, polymer comprises one or more combinations of polyacrylonitrile, polyamide, polyimides.
By the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at H
2sO
4, KOH, NaCl or Na
2sO
4soak 12 ~ 36 hours in electrolyte.With Pt electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
The present invention has the following advantages:
(1) inorganic acid plays element doping and pore double action in whole preparation process, and the rich Nitrogen element of material with carbon element precursor polymer, has prepared the nitrogen of high-specific capacitance super, P elements codope material with carbon element simultaneously;
(2) the present invention preparation is simple, controllability is strong, with low cost, be easy to apply, and the organic solvent that the present invention uses can recycling, is conducive to environmental protection and reduces costs.
Accompanying drawing explanation
Fig. 1 is the SEM figure of porous material prepared by the embodiment of the present invention 2, and wherein (a) is H3PO4/PAN composite porous polymer, and (b) is porous carbon materials.
Fig. 2 is the SEM figure of carbon nano-fiber prepared by the embodiment of the present invention 6 and comparative example 1, and the SEM that wherein (a) is embodiment 6 schemes, and the SEM that (b) is comparative example 1 schemes.
Fig. 3 is the charge and discharge cycles curve of material with carbon element under 3A/g constant current of inventive embodiments 2, embodiment 6 and comparative example 1 preparation.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described further.
Embodiment 1
0.042g polyphosphoric acids is added 19g 1-METHYLPYRROLIDONE, stirs 10 hours, then add wherein by 2g polyamide (PAI), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Pour in surface plate by homogeneous mixed solution, placement 36 hours under the condition of constant temperature 25 DEG C, constant humidity 30%, solvent evaporates is complete, self assembly completes, and obtains H
3pO
4/ PAI composite porous polymer.
By this H
3pO
4/ PAI composite porous polymer carries out pre-oxidation 5 hours at 240 DEG C, and heating rate is 10 DEG C/min, and rate of temperature fall is 1 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 300 DEG C of insulations 10 hours with 20 DEG C/min, is then warming up to 600 DEG C of insulations 10 hours with 20 DEG C/min, is finally cooled to room temperature with 10 DEG C/min, namely obtains porous carbon materials.
90wt% porous carbon materials is fully mixed by mortar grinder mode with 5wt% conductive black Super-P, adds 5wt% Kynoar and 10 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed is coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then dried pole piece is soaked 12 hours in 1M KOH electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 2
By 1.222g mass concentration be 85% phosphoric acid add 19g DMF, stir 10 hours, then 2g polyacrylonitrile (PAN) added wherein, ultrasonic or heating hydrotropy, finally stir 24 hours.
Pour in surface plate by homogeneous mixed solution, placement 24 hours under the condition of constant temperature 35 DEG C, constant humidity 60%, solvent evaporates is complete, self assembly completes, and obtains H
3pO
4/ PAN composite porous polymer.
By this H
3pO
4/ PAN composite porous polymer carries out pre-oxidation 2 hours at 270 DEG C, and heating rate is 3 DEG C/min, and rate of temperature fall is 5 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 400 DEG C of insulations 2 hours with 5 DEG C/min, is then warming up to 800 DEG C of insulations 5 hours with 5 DEG C/min, is finally cooled to room temperature with 10 DEG C/min, namely obtains porous carbon materials.
80wt% porous carbon materials is fully mixed by mortar grinder mode with 10wt% conductive black Super-P, adds 10wt% Kynoar and 20 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed be coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at 1M H
2sO
4soak 24 hours in electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 3
1.826g phosphorous acid is added 19g DMA, stirs 10 hours, then add wherein by 2 polyimides (PII), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Pour in surface plate by homogeneous mixed solution, placement 6 hours under the condition of constant temperature 60 DEG C, constant humidity 40%, solvent evaporates is complete, self assembly completes, and obtains H
3pO
4/ PII composite porous polymer.
By this H
3pO
4/ PII composite porous polymer carries out pre-oxidation 2 hours at 270 DEG C, and heating rate is 1 DEG C/min, and rate of temperature fall is 1 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 500 DEG C of insulations 1 hour with 1 DEG C/min, is then warming up to 1000 DEG C of insulations 0.5 hour with 1 DEG C/min, is finally cooled to room temperature with 20 DEG C/min, namely obtains porous carbon materials.
By 95wt% porous carbon materials in mortar fully grinding evenly, add 5wt% Kynoar and 15 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed be coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at 1M Na
2sO
4soak 24 hours in electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 4
0.8g metaphosphoric acid is added 19g DMF, stirs 10 hours, then add wherein by 2.7g polyacrylonitrile (PAN), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Pour in surface plate by homogeneous mixed solution, placement 24 hours under the condition of constant temperature 40 DEG C, constant humidity 50%, solvent evaporates is complete, self assembly completes, and obtains H
3pO
4/ PAN composite porous polymer.
By this H
3pO
4/ PAN composite porous polymer carries out pre-oxidation 1 hour at 300 DEG C, and heating rate is 5 DEG C/min, and rate of temperature fall is 5 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 400 DEG C of insulations 5 hours with 2 DEG C/min, is then warming up to 900 DEG C of insulations 3 hours with 5 DEG C/min, is finally cooled to room temperature with 5 DEG C/min, namely obtains porous carbon materials.
85wt% porous carbon materials is fully mixed by mortar grinder mode with 5wt% conductive black Super-P, adds 10wt% Kynoar and 15 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed is coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then dried pole piece is soaked 12 hours in 1M NaCl electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 5
0.042g polyphosphoric acids is added 19g 1-METHYLPYRROLIDONE, stirs 10 hours, then add wherein by 2g polyamide (PAI), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Homogeneous mixed solution is carried out electrostatic spinning; The humidity that controls environment in electrostatic spinning process is 15%, and employing internal diameter is the stainless steel syringe needle of 1.8mm, and spinning solution flow is 0.8mL/h, and the electrostatic potential of applying is 12kV.
The H that electrostatic spinning is obtained
3pO
4/ PAI composite nano fiber carries out pre-oxidation 5 hours at 240 DEG C, and heating rate is 1 DEG C/min, and rate of temperature fall is 10 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 300 DEG C of insulations 10 hours with 20 DEG C/min, is then warming up to 600 DEG C of insulations 10 hours with 20 DEG C/min, is finally cooled to room temperature with 1 DEG C/min, namely obtains carbon nano-fiber.
80wt% carbon nano-fiber is fully mixed by mortar grinder mode with 10wt% conductive black Super-P, adds 10wt% Kynoar and 20 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed is coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then dried pole piece is soaked 36 hours in 6M KOH electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 6
By 0.6g mass concentration be 85% phosphoric acid add 19g DMF, stir 10 hours, then 2g polyacrylonitrile (PAN) added wherein, ultrasonic or heating hydrotropy, finally stir 24 hours.
Homogeneous mixed solution is carried out electrostatic spinning.The humidity that controls environment in electrostatic spinning process is 15%, and employing internal diameter is the stainless steel syringe needle of 1.2mm, and spinning solution flow is 0.4mL/h, and the electrostatic potential of applying is 16kV.
The H that electrostatic spinning is obtained
3pO
4/ PAN composite nano fiber carries out pre-oxidation 2 hours at 270 DEG C, and heating rate is 3 DEG C/min, and rate of temperature fall is 5 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 400 DEG C of insulations 2 hours with 5 DEG C/min, is then warming up to 800 DEG C of insulations 5 hours with 5 DEG C/min, is finally cooled to room temperature with 10 DEG C/min, namely obtains carbon nano-fiber.
90wt% carbon nano-fiber is fully mixed by mortar grinder mode with 2wt% conductive black Super-P, adds 8wt% Kynoar and 15 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed be coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at 1M H
2sO
4soak 24 hours in electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 7
By 1.222g mass concentration be 85% phosphoric acid add 19g DMF, stir 10 hours, then 2g polyacrylonitrile (PAN) added wherein, ultrasonic or heating hydrotropy, finally stir 24 hours.
Homogeneous mixed solution is carried out electrostatic spinning.The humidity that controls environment in electrostatic spinning process is 15%, and employing internal diameter is the stainless steel syringe needle of 1.2mm, and spinning solution flow is 0.4mL/h, and the electrostatic potential of applying is 18kV.
The H that electrostatic spinning is obtained
3pO
4/ PAN composite nano fiber carries out pre-oxidation 2 hours at 270 DEG C, and heating rate is 10 DEG C/min, and rate of temperature fall is 1 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 500 DEG C of insulations 1 hour with 1 DEG C/min, is then warming up to 800 DEG C of insulations 5 hours with 1 DEG C/min, is finally cooled to room temperature with 10 DEG C/min, namely obtains carbon nano-fiber.
90wt% carbon nano-fiber is fully mixed by mortar grinder mode with 2wt% conductive black Super-P, adds 8wt% Kynoar and 15 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed be coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at 1M H
2sO
4soak 24 hours in electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 8
1.826g phosphorous acid is added 19g DMA, stirs 10 hours, then add wherein by 2 polyimides (PII), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Homogeneous mixed solution is carried out electrostatic spinning.The humidity that controls environment in electrostatic spinning process is 15%, and employing internal diameter is the stainless steel syringe needle of 1.0mm, and spinning solution flow is 0.4mL/h, and the electrostatic potential of applying is 20kV.
The H that electrostatic spinning is obtained
3pO
4/ PII composite nano fiber carries out pre-oxidation 3 hours at 270 DEG C, and heating rate is 4 DEG C/min, and rate of temperature fall is 10 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 400 DEG C of insulations 2 hours with 2 DEG C/min, is then warming up to 900 DEG C of insulations 3 hours with 5 DEG C/min, is finally cooled to room temperature with 10 DEG C/min, namely obtains carbon nano-fiber.
85wt% carbon nano-fiber is fully mixed by mortar grinder mode with 5wt% conductive black Super-P, adds 10wt% Kynoar and 10 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed is coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then dried pole piece is soaked 12 hours in 1M NaCl electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Embodiment 9
0.8g metaphosphoric acid is added 19g DMF, stirs 10 hours, then add wherein by 2.7g polyimides (PII), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Homogeneous mixed solution is carried out electrostatic spinning.The humidity that controls environment in electrostatic spinning process is 15%, and employing internal diameter is the stainless steel syringe needle of 1.2mm, and spinning solution flow is 0.2mL/h, and the electrostatic potential of applying is 14kV.
The H that electrostatic spinning is obtained
3pO
4/ PII composite nano fiber carries out pre-oxidation 5 hours at 250 DEG C, and heating rate is 3 DEG C/min, and rate of temperature fall is 1 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 300 DEG C of insulations 5 hours with 10 DEG C/min, is then warming up to 1000 DEG C of insulations 0.5 hour with 5 DEG C/min, is finally cooled to room temperature with 20 DEG C/min, namely obtains carbon nano-fiber.
95wt% carbon nano-fiber is ground in mortar evenly, add 5wt% Kynoar and 10 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed be coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at 1MNa
2sO
4soak 12 hours in electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Comparative example 1
Add in 19g DMF by 2g polyacrylonitrile (PAN), ultrasonic or heating hydrotropy, finally stirs 24 hours.
Homogeneous PAN solution is carried out electrostatic spinning.The humidity that controls environment in electrostatic spinning process is 15%, and employing internal diameter is the stainless steel syringe needle of 1.2mm, and spinning solution flow is 0.4mL/h, and the electrostatic potential of applying is 16kV.
The PAN nanofiber obtained by electrostatic spinning carries out pre-oxidation 2 hours at 270 DEG C, and heating rate is 3 DEG C/min, and rate of temperature fall is 5 DEG C/min.
This pre-oxidation product is placed in retort, in a nitrogen atmosphere, is warming up to 400 DEG C of insulations 2 hours with 5 DEG C/min, is then warming up to 800 DEG C of insulations 5 hours with 5 DEG C/min, is finally cooled to room temperature with 10 DEG C/min, namely obtains carbon nano-fiber.
90wt% carbon nano-fiber is fully mixed by mortar grinder mode with 2wt% conductive black Super-P, adds 8wt% Kynoar and 15 times successively to the 1-METHYLPYRROLIDONE of Kynoar quality, stir into pasty state.Adopt platinized platinum as collector, the above-mentioned homogenize material mixed be coated in collector platinized platinum surface, by the pole piece made 100 DEG C of vacuumizes 12 hours, then by dried pole piece at 1M H
2sO
4soak 24 hours in electrolyte.With platinum electrode be to electrode, Ag/AgCl for reference electrode, adopt three electrode test methods to carry out loop test under-0.1 ~ 0.9V voltage range, 3A/g constant current conditions, and calculate unit capacitance values.
Claims (10)
1. a preparation method for electrode material for super capacitor, is characterized in that comprising the following steps:
(1) inorganic acid of 0.2 ~ 8wt% is added in organic solvent, then add the polymer of 9 ~ 12wt%, obtained uniform organic/inorganic mixed solution;
(2) organic/inorganic mixed solution step (1) obtained is volatilized by organic solvent or electrospinning process obtains organic/inorganic composite material;
(3) organic/inorganic composite material that step (2) obtains is obtained material with carbon element through pre-oxidation, K cryogenic treatment and high temperature cabonization;
(4) material with carbon element that step (3) obtains is made electrode material for super capacitor;
Low temperature in described step (3) refers to 300 ~ 500 DEG C; High temperature refers to 600 ~ 1000 DEG C.
2. the preparation method of electrode material for super capacitor according to claim 1, is characterized in that the organic solvent volatilization condition in described step (2) is as follows: under the environment of temperature 25 ~ 60 DEG C, relative humidity >=30%, leave standstill 6 ~ 36 hours.
3. the preparation method of electrode material for super capacitor according to claim 1, it is characterized in that the electrostatic spinning process parameter in described step (2) is: spinning humidity < 30%, through being 0.6 ~ 1.8mm in syringe needle, spinning solution flow is 0.2 ~ 0.8mL/h, electrostatic potential is 12 ~ 20kV, adopts single needle or Multi needle spinning.
4. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, it is characterized in that the pre-oxidizing conditions in described step (3) is as follows: carry out pre-oxidation at 240 ~ 300 DEG C, programming rate is 1 ~ 10 DEG C/min, cooling rate is 1 ~ 10 DEG C/min, and preoxidation time is 1 ~ 5 hour.
5. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, it is characterized in that the K cryogenic treatment condition in described step (3) is as follows: inert atmosphere, programming rate is 1 ~ 20 DEG C/min, and temperature retention time is 1 ~ 10 hour.
6. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, it is characterized in that the high temperature cabonization condition in described step (3) is as follows: inert atmosphere, programming rate is 1 ~ 20 DEG C/min, cooling rate is 1 ~ 20 DEG C/min, and carbonization time is 0.5 ~ 10 hour.
7. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, it is characterized in that in described step (4), the material with carbon element of 80 ~ 95wt% is mixed with the conductive black of 0 ~ 10wt%, add 5 ~ 10wt% Kynoar and 10 ~ 20 times successively to the 1-METHYLPYRROLIDONE of described Kynoar quality, stir into pasty state; Adopt platinized platinum as collector, the above-mentioned homogenize material mixed is coated in collector platinized platinum surface, obtained electrode material for super capacitor.
8. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, is characterized in that described inorganic acid comprises one or more combinations of phosphoric acid, polyphosphoric acids, phosphorous acid, metaphosphoric acid.
9. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, is characterized in that described organic solvent comprises one or more combinations of DMA, DMF or 1-METHYLPYRROLIDONE.
10. the preparation method of the electrode material for super capacitor according to Claims 2 or 3, is characterized in that described polymer comprises one or more combinations of polyacrylonitrile, polyamide, polyimides.
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| CN102074683A (en) * | 2010-12-10 | 2011-05-25 | 江南大学 | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof |
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| CN102074683A (en) * | 2010-12-10 | 2011-05-25 | 江南大学 | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof |
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| 李胜军.尖晶石型LiMn2O4及LiMxMn2-xO4的合成与性能研究.《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅱ辑》.2005,(第01期), * |
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