CN105513826A - Preparation method of pyrrole-o-toluidine copolymer with porous structure - Google Patents
Preparation method of pyrrole-o-toluidine copolymer with porous structure Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000012074 organic phase Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 17
- 238000001291 vacuum drying Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000008346 aqueous phase Substances 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 150000003233 pyrroles Chemical class 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 239000007772 electrode material Substances 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 239000012071 phase Substances 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 229920000128 polypyrrole Polymers 0.000 description 26
- 230000008569 process Effects 0.000 description 17
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 230000004087 circulation Effects 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
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- 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
- H01G11/48—Conductive polymers
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a preparation method of a pyrrole-o-toluidine copolymer with a porous structure. The preparation method of the pyrrole-o-toluidine copolymer with the porous structure comprises the following steps: 1, dissolving pyrrole and o-toluidine in an organic solvent to form an organic phase; 2, dissolving ammonium persulfate and low-carbon alcohol in water to form a water phase; 3, mixing the organic phase with the water phase, then standing and reacting; 4, filtering, then vacuum drying to obtain the pyrrole-o-toluidine copolymer. The method is simple and practicable, is mild in reaction conditions, simple in composition of a reaction system and free of additional templates, can be used for preparing the polymer of a loose and porous structure by only relying on the easily-removed low-carbon alcohol, and is pure in product, simple and convenient in post-treatment, low in cost and low in requirement on equipment performance; the obtained product presents the loose and porous structure, has high specific capacity, energy density, power density and high cycling stability, is especially suitable for being applied to supercapacitor electrode materials, and can also be applied to the field of sensing, catalysis and heavy metal ion adsorption materials.
Description
Technical field
The invention belongs to the preparing technical field of conductive polymers based ultra-capacitor electrode material, be specifically related to the preparation method of a kind of loose structure pyrroles-o-toluidine copolymer.
Background technology
Conducting polymer materials has that cost is low, environmental pollution is little, charge density is high, potential window is wide and the plurality of advantages such as redox active is adjustable, and it has huge potential using value in electrochemical super-capacitor field, thus obtain the extensive concern of people.Polypyrrole, owing to having better flexibility in electrochemical process, makes it in conducting polymer, become a kind of super capacitor of most attraction or the electrode material of battery.But the doping of conducting polymer in electrochemical process/go doping (redox) characteristic to make its volume repeatedly expand and shrink, often causes the mechanical degradation of material, thus the chemical property of deteriorated material, reduce electrode cycle life.There is bibliographical information (SharmaR.K., RastogiA.C., DesuS.B.Electrochim.Acta2008,53,7690.) at 2mAcm
-2constant current density condition under, electrochemical super-capacitor part its ratio capacitance value after circulation 1000 times based on Platinum reduces 50%, and (initial ratio capacitance is 120Fg
-1).In addition, the dense growth of polypyrrole strand hinders the infiltration of electrolyte at material internal, and this significantly can reduce the ratio capacitance of material (particularly thicker film or coating).At present, overcome above-mentioned defect mainly through two kinds of technological approaches, one is prepare polypyrrole based combined electrode material, by polypyrrole and material with carbon element (as active carbon, carbon nano-tube, Graphene etc.), inorganic oxide/peroxide is (as ruthenium-oxide, nickel oxide, cobaltosic oxide etc.) and other metallic compounds be mixed and made into composite material to improve mechanical performance and the chemical property of polypyrrole, thus improve electrochemical capacitance and cycle life, but the composite parts that this approach uses is usually expensive, and often need preliminary treatment in early stage and special preparation technology to mix with polypyrrole, process is complicated, cost is higher, two is the structure and the pattern that change electrode material, the polypyrrole of preparation nanostructure or porous pattern, the polypyrrole of this class formation effectively can reduce the mechanical degradation problem of charge and discharge process and improve the utilance of electrode material, thus improves electrochemical capacitance and cycle life and lower relative to front a kind of approach cost.The conventional method realizing this approach adopts template (hard template or soft template) to control polymerization to obtain the polypyrrole with nanometer/loose structure, but final template need be removed totally from material, cause last handling process complexity and remaining template can make material property deteriorated.
At present, the surfactant (1.LeiW., HeP., WangY., etal.Electrochim.Acta2014,132,112 that still need dependence more with polypyrrole energy storage (electrode) material that special construction is prepared in interfacial polymerization of bibliographical information; 2.YangQ.H., HouZ.Z., HuangT.Z.J.Appl.Polym.Sci.2015,132,41615.), ionic liquid (1.HouL., YuanC., LiD., etal.Electrochim.Acta2011,56,6049; 2. Chinese patent, or electrochemical means (Chinese patent CN201110418753), assisting CN201010560901), cause that complicated process of preparation, last handling process are loaded down with trivial details, cost is relatively high, and simple polypyrrole material is limit by performance own and is difficult to improve specific capacity and cyclical stability further.
Summary of the invention
Technical problem to be solved by this invention is, for above-mentioned deficiency of the prior art, to provide the preparation method of a kind of loose structure pyrroles-o-toluidine copolymer.The method is simple, reaction condition is gentle, reaction system composition is simple, without the need to any additional template, only rely on the low-carbon alcohols effect of easily removing can obtain loose and porous structure polymer, products pure, reprocessing is easy, cost is lower, require low to equipment performance.Products therefrom presents loose and porous structure, has higher specific capacity, energy density, power density and good cyclical stability, is particularly suitable for ultra-capacitor electrode material, also can be used for the fields such as sensing, catalysis and heavy metal ion adsorbing material.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of loose structure pyrroles-o-toluidine copolymer, is characterized in that, comprise the following steps:
Step one, pyrroles and o-toluidine be dissolved in organic solvent form organic phase; The mole of described pyrroles is 40% ~ 70% of pyrroles and o-toluidine integral molar quantity; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.1mol/L ~ 0.5mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.1mol/L ~ 0.5mol/L, and the concentration of low-carbon alcohols is 0.4mol/L ~ 0.7mol/L;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to (1 ~ 3): under 5 DEG C ~ 30 DEG C conditions, leave standstill reaction 4h ~ 24h after the volume ratio of (1 ~ 3) mixing;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, by described filter cake ethanol cyclic washing, then use deionized water cyclic washing until cleaning solution is colourless, again by the filter cake vacuumize after washing, obtain pyrroles-o-toluidine copolymer.
The preparation method of above-mentioned a kind of loose structure pyrroles-o-toluidine copolymer, it is characterized in that, organic solvent described in step one is toluene or carrene.
The preparation method of above-mentioned a kind of loose structure pyrroles-o-toluidine copolymer, is characterized in that, low-carbon alcohols described in step 2 is one or both in methyl alcohol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol and glycerol.
The preparation method of above-mentioned a kind of loose structure pyrroles-o-toluidine copolymer, is characterized in that, vacuum drying temperature described in step 4 is 50 DEG C ~ 60 DEG C, and the vacuum drying time is 24h ~ 48h.
The present invention compared with prior art has the following advantages:
1, the inventive method is simple, reaction condition is gentle, reaction system composition is simple, without the need to any additional template, only rely on the low-carbon alcohols effect of easily removing can obtain loose and porous structure polymer, products pure, reprocessing is easy, cost is lower, require low to equipment performance.Products therefrom presents loose and porous structure, has higher specific capacity, energy density, power density and good cyclical stability, is particularly suitable for ultra-capacitor electrode material, also can be used for the fields such as sensing, catalysis and heavy metal ion adsorbing material.
2, the present invention adopts o-toluidine as raw material, and first, o-toluidine price is lower, can reduce polymer cost further, and reaction condition is gentle, low for equipment requirements, is conducive to large-scale production; The second, polyortho methylaniline itself has stronger electro-chemical activity, and it is introduced the electro-chemical activity that can improve polymer in polypyrrole strand in the mode of copolymerization, significantly improves the ratio capacitance of polymer; Three, there is a series of methyl in polyortho methylaniline segment strand, these side bases can expand the distance between polymer molecular chain, avoid closely piling up in molecular chain growth process, overcome the shortcoming of polypyrrole strand dense growth; Four, copolymer can be made to form the microstructure of porous by the amphiphilic of poly-omethylaniline segment and hydrogen bond action in polymerization process, and loose structure is conducive to the expansion repeatedly and the compression that adapt to polymer volume in charge and discharge process on the one hand, reduce mechanical degradation, improve cycle life, be conducive to transmission and the infiltration of electric charge and electrolyte on the other hand, these can significantly improve the electrochemical capacitance characteristic of material.
3, the present invention adopts structure to induce interfacial polymerization, and utilize in organic phase that o-toluidine is as common monomer, in aqueous phase, low-carbon alcohols is as structure inducer, and in their actings in conjunction, next step has synthesized the pyrroles-o-toluidine copolymer of loose and porous structure.Fabrication of High Specific Capacitance and the good polymeric material of cyclical stability can be obtained by control pyrroles/o-toluidine mol ratio, low-carbon alcohols kind and concentration and reaction temperature, its ratio capacitance value reaches 381F/g, apparently higher than polypyrrole (114F/g) prepared by traditional chemical oxidizing process, even higher than polypyrrole nano material or the polypyrrole combination electrode material of many bibliographical informations, be particularly suitable for ultra-capacitor electrode material, also have broad application prospects in sensing, catalysis and the field such as heavy metal ion adsorbed.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of pyrroles-o-toluidine copolymer prepared by the embodiment of the present invention 1.
Fig. 2 is the cyclic voltammetry curve of pyrroles-o-toluidine copolymer prepared by the polypyrrole material prepared of traditional chemical oxidizing process and the embodiment of the present invention 1.
Fig. 3 is the constant current charge-discharge curve of pyrroles-o-toluidine copolymer prepared by the embodiment of the present invention 1.
Fig. 4 is the cyclical stability of pyrroles-o-toluidine copolymer scan round 1000 times prepared by the polypyrrole material prepared of traditional chemical oxidizing process and the embodiment of the present invention 1.
Embodiment
Embodiment 1
The preparation method of the loose structure pyrroles-o-toluidine copolymer of the present embodiment comprises the following steps:
Step one, pyrroles and o-toluidine be dissolved in toluene according to the mol ratio of 6:4 form organic phase; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.4mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.4mol/L, and the concentration of low-carbon alcohols is 0.6mol/L; Described low-carbon alcohols is ethanol and normal propyl alcohol, and the mol ratio of ethanol and normal propyl alcohol is 1:1;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to 1:1 volume ratio mixing after under 20 DEG C of water bath condition leave standstill reaction 10h;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, described filter cake ethanol cyclic washing is removed unreacted monomer and oligomer, then deionized water cyclic washing is used until cleaning solution is colourless, again by the filter cake vacuumize after washing, vacuum drying temperature is 50 DEG C, and the vacuum drying time is 48h, obtains pyrroles-o-toluidine copolymer.
Fig. 1 is the scanning electron microscope (SEM) photograph of pyrroles-o-toluidine copolymer prepared by the present embodiment, as can be seen from the figure pyrroles-o-toluidine copolymer presents loose and porous structure, this structure can increase the electro-chemical activity surface of material, is conducive to obtaining higher ratio capacitance and cyclical stability.
Fig. 2 is the cyclic voltammetry curve of pyrroles-o-toluidine copolymer prepared by the polypyrrole material prepared of traditional chemical oxidizing process and the present embodiment, as can be seen from the figure pyrroles-o-toluidine copolymer cyclic voltammetry curve area is obviously comparatively large, this means that the ratio capacitance of this copolymer prepares the ratio capacitance of polypyrrole far above traditional chemical oxidizing process.Be 381F/g by calculating the ratio capacitance value of loose structure pyrroles-o-toluidine copolymer, the polypyrrole nano material even reported higher than some pertinent literatures or the ratio capacitance of Pt/Polypyrrole composite material.
Fig. 3 is the constant current charge-discharge curve of pyrroles-o-toluidine copolymer prepared by the present embodiment, energy density under 2A/g condition of loose structure pyrroles-o-toluidine copolymer prepared by the present embodiment can be calculated easily and power density is respectively 49.7Wh/kg and 1200W/kg, the polypyrrole nano material common far above some from Fig. 3.
Fig. 4 is the cyclical stability of pyrroles-o-toluidine copolymer scan round 1000 times prepared by the polypyrrole material prepared of traditional chemical oxidizing process and the present embodiment, as can be seen from the figure polypyrrole prepared by traditional chemical oxidizing process is compared, loose structure pyrroles-o-toluidine copolymer prepared by the present invention has better cyclical stability, ratio capacitance declines relatively slow, still 88% of initial ratio capacitance can be kept, far above polypyrrole (only keeping 44% of initial ratio capacitance after 1000 circulations) prepared by traditional chemical oxidizing process after 1000 circulations.
Embodiment 2
The preparation method of the loose structure pyrroles-o-toluidine copolymer of the present embodiment comprises the following steps:
Step one, pyrroles and o-toluidine be dissolved in toluene according to the mol ratio of 4:6 form organic phase; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.5mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.5mol/L, and the concentration of low-carbon alcohols is 0.7mol/L; Described low-carbon alcohols is ethanol;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to 3:1 volume ratio mixing after under 30 DEG C of water bath condition leave standstill reaction 4h;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, described filter cake ethanol cyclic washing is removed unreacted monomer and oligomer, then deionized water cyclic washing is used until cleaning solution is colourless, again by the filter cake vacuumize after washing, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 24h, obtains pyrroles-o-toluidine copolymer.
Pyrroles-o-toluidine copolymer prepared by the present embodiment presents loose and porous structure, ratio capacitance value is 327F/g, energy density under 2A/g condition and power density are respectively 44.5Wh/kg and 1068W/kg, there is better cyclical stability, ratio capacitance declines relatively slow, still can keep 84% of initial ratio capacitance after 1000 circulations.
Embodiment 3
The preparation method of the loose structure pyrroles-o-toluidine copolymer of the present embodiment comprises the following steps:
Step one, pyrroles and o-toluidine be dissolved in toluene according to the mol ratio of 7:3 form organic phase; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.1mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.1mol/L, and the concentration of low-carbon alcohols is 0.4mol/L; Described low-carbon alcohols is methyl alcohol;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to 1:3 volume ratio mixing after under 5 DEG C of water bath condition leave standstill reaction 24h;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, described filter cake ethanol cyclic washing is removed unreacted monomer and oligomer, then deionized water cyclic washing is used until cleaning solution is colourless, again by the filter cake vacuumize after washing, vacuum drying temperature is 55 DEG C, and the vacuum drying time is 36h, obtains pyrroles-o-toluidine copolymer.
Pyrroles-o-toluidine copolymer prepared by the present embodiment presents loose and porous structure, ratio capacitance value is 362F/g, energy density under 2A/g condition and power density are respectively 47.3Wh/kg and 1000W/kg, there is better cyclical stability, ratio capacitance declines relatively slow, still can keep 80% of initial ratio capacitance after 1000 circulations.
Embodiment 4
The preparation method of the loose structure pyrroles-o-toluidine copolymer of the present embodiment comprises the following steps:
Step one, pyrroles and o-toluidine be dissolved in carrene according to the mol ratio of 7:3 form organic phase; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.1mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.1mol/L, and the concentration of low-carbon alcohols is 0.4mol/L; Described low-carbon alcohols is ethylene glycol;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to 1:2 volume ratio mixing after under 10 DEG C of water bath condition leave standstill reaction 15h;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, described filter cake ethanol cyclic washing is removed unreacted monomer and oligomer, then deionized water cyclic washing is used until cleaning solution is colourless, again by the filter cake vacuumize after washing, vacuum drying temperature is 55 DEG C, and the vacuum drying time is 40h, obtains pyrroles-o-toluidine copolymer.
Pyrroles-o-toluidine copolymer prepared by the present embodiment presents loose and porous structure, ratio capacitance value is 371F/g, energy density under 2A/g condition and power density are respectively 48.3Wh/kg and 1120W/kg, there is better cyclical stability, ratio capacitance declines relatively slow, still can keep 90% of initial ratio capacitance after 1000 circulations.
Embodiment 5
The preparation method of the loose structure pyrroles-o-toluidine copolymer of the present embodiment comprises the following steps:
Step one, pyrroles and o-toluidine be dissolved in carrene according to the mol ratio of 4:6 form organic phase; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.5mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.5mol/L, and the concentration of low-carbon alcohols is 0.7mol/L; Described low-carbon alcohols is isopropyl alcohol;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to 2:1 volume ratio mixing after under 5 DEG C of water bath condition leave standstill reaction 24h;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, described filter cake ethanol cyclic washing is removed unreacted monomer and oligomer, then deionized water cyclic washing is used until cleaning solution is colourless, again by the filter cake vacuumize after washing, vacuum drying temperature is 50 DEG C, and the vacuum drying time is 48h, obtains pyrroles-o-toluidine copolymer.
Pyrroles-o-toluidine copolymer prepared by the present embodiment presents loose and porous structure, ratio capacitance value is 330F/g, energy density under 2A/g condition and power density are respectively 43.3Wh/kg and 1039W/kg, there is better cyclical stability, ratio capacitance declines relatively slow, still can keep 86% of initial ratio capacitance after 1000 circulations.
Embodiment 6
The preparation method of the loose structure pyrroles-o-toluidine copolymer of the present embodiment comprises the following steps:
Step one, pyrroles and o-toluidine be dissolved in carrene according to the mol ratio of 5:5 form organic phase; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.3mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.3mol/L, and the concentration of low-carbon alcohols is 0.5mol/L; Described low-carbon alcohols is ethanol and glycerol, and the mol ratio of ethanol and glycerol is 2:1;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to 1:1 volume ratio mixing after under 30 DEG C of water bath condition leave standstill reaction 6h;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, described filter cake ethanol cyclic washing is removed unreacted monomer and oligomer, then deionized water cyclic washing is used until cleaning solution is colourless, again by the filter cake vacuumize after washing, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 24h, obtains pyrroles-o-toluidine copolymer.
Pyrroles-o-toluidine copolymer prepared by the present embodiment presents loose and porous structure, ratio capacitance value is 320F/g, energy density under 2A/g condition and power density are respectively 44.3Wh/kg and 1063W/kg, there is better cyclical stability, ratio capacitance declines relatively slow, still can keep 83% of initial ratio capacitance after 1000 circulations.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalence change, all still belong in the protection range of technical solution of the present invention.
Claims (4)
1. a preparation method for loose structure pyrroles-o-toluidine copolymer, is characterized in that, comprise the following steps:
Step one, pyrroles and o-toluidine be dissolved in organic solvent form organic phase; The mole of described pyrroles is 40% ~ 70% of pyrroles and o-toluidine integral molar quantity; In described organic phase, the total concentration of pyrroles and o-toluidine is 0.1mol/L ~ 0.5mol/L;
Step 2, be dissolved in the water ammonium persulfate and low-carbon alcohols formation aqueous phase; In described aqueous phase, the concentration of ammonium persulfate is 0.1mol/L ~ 0.5mol/L, and the concentration of low-carbon alcohols is 0.4mol/L ~ 0.7mol/L;
Step 3, by aqueous phase described in organic phase described in step one and step 2 according to (1 ~ 3): under 5 DEG C ~ 30 DEG C conditions, leave standstill reaction 4h ~ 24h after the volume ratio of (1 ~ 3) mixing;
Step 4, by step 3 leave standstill reacted material filtering, obtain filter cake, by described filter cake ethanol cyclic washing, then use deionized water cyclic washing until cleaning solution is colourless, again by the filter cake vacuumize after washing, obtain pyrroles-o-toluidine copolymer.
2. the preparation method of a kind of loose structure pyrroles-o-toluidine copolymer according to claim 1, it is characterized in that, organic solvent described in step one is toluene or carrene.
3. the preparation method of a kind of loose structure pyrroles-o-toluidine copolymer according to claim 1, is characterized in that, low-carbon alcohols described in step 2 is one or both in methyl alcohol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol and glycerol.
4. the preparation method of a kind of loose structure pyrroles-o-toluidine copolymer according to claim 1, is characterized in that, vacuum drying temperature described in step 4 is 50 DEG C ~ 60 DEG C, and the vacuum drying time is 24h ~ 48h.
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