CN102683033B - Controllable nanoribbon structure of redox polymer electrode and preparation method thereof - Google Patents

Controllable nanoribbon structure of redox polymer electrode and preparation method thereof Download PDF

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CN102683033B
CN102683033B CN201210112495.8A CN201210112495A CN102683033B CN 102683033 B CN102683033 B CN 102683033B CN 201210112495 A CN201210112495 A CN 201210112495A CN 102683033 B CN102683033 B CN 102683033B
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electrode
solution
salen
poly
electrochemical
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CN102683033A (en
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李建玲
张雅琨
高飞
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • 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

Abstract

The invention discloses a controllable nanoribbon structure of redox polymer Poly [Ni(Salen)] electrode, and a preparation method of the controllable nano-ribbon structure, belonging to the technical field of preparation of conductive polymer materials of super-capacitor electrodes. The preparation method comprises the following steps of: firstly preparing blank solution and electrochemical polymerization solution, dissolving tetra-butyl ammonium perchlorate into acetonitrile solution by using the electrochemical deposition method, Ag/AgCl as reference electrode, active carbon as counter electrode, and Ti/MCWNT or conductive glass as working electrode, using the mixed solution as blank solution, and directly performing electro-polymerization on Ti/MCWNT or ITO working electrode to obtain Poly[Ni(Salen)] by using the monomer Ni(Salen) based solution as the formed solution, so as to obtain the nano-ribbon shaped Poly[Ni(Salen)] modified electrochemical active electrode. The preparation method is simple and the preparation speed is high; and the prepared Poly [Ni(Salen)] has good capacitance.

Description

Controllable nano band structure of a kind of redox polymers electrode and preparation method thereof
Technical field
The present invention relates to a kind of ultracapacitor redox polymers---Poly[Ni (Salen)] the controllable nano band structure and preparation method thereof of electrode, belong to electrode of super capacitor conducting polymer materials preparing technical field.
Background technology
Ultracapacitor, as the advanced energy accumulating device of one, has outstanding feature and advantage, can replace traditional storage battery in some field, and the today that day by day becomes to be the theme in energy-conserving and environment-protective, its application more and more causes the attention of countries in the world.The power density of ultracapacitor is far above lithium battery, and charge and discharge cycles number of times can reach more than 500,000 times, and the life-span reaches more than 10 years, and the charging interval is short, can high current charge-discharge.In view of its feature, it can be widely used in consumer electronics product field, can also be used for grid-connected power generation system, distributed energy storage system, intelligent distributed network system field, the field of traffic such as new-energy automobile, military equipment field and the motion control field etc. such as ELECTROMAGNETIC BOMB, relate to the industry-by-industries such as generation of electricity by new energy, intelligent grid, new-energy automobile, energy saving building, industrial energy saving reduction of discharging, especially there is important using value at electric automobile, solar energy storage and space industry.
Electrode material is as determining one of two large key factors (electrode material and electrolyte) of ultracapacitor performance, and its research has become the focus of ultracapacitor research.Conducting polymer is a kind of novel electrode material, has both had the electrical and optical properties of metal and inorganic semiconductor, has again the pliable and tough mechanical performance of organic polymer and machinability, also has electrochemical redox activity.Its energy storage is mainly to rely on pseudo capacitance principle to realize: along with the raising of electrode potential, occur the continuous variation of oxidation state and the invertibity corresponding to charge injection/exit.Conducting polymer is that operating potential window is wide as capacitor material great advantage, can under high voltage, work, make up the not high shortcoming of transition metal oxide series operating voltage, conducting polymer has plasticity, be easy to make thin layer electrode, internal resistance is little, is representing a developing direction of electrochemical capacitance electrode material.
Electrochemical polymerization can better be controlled the beginning of polymerization reaction and stop step, reacts conventionally more clean, and the product obtaining is also relatively purer, and the adhesion of material is stronger.But it is relatively weak to the control of pattern that electrochemistry is prepared polymer, prepare and mostly be bar-shaped or become membrane structure, be unfavorable for the diffusion of electric charge, ion etc., thereby affect the capacitive property of electrode.At present also do not have electrochemical polymerization to prepare the report of nanobelt conducting polymer.
Summary of the invention
The object of the invention is to overcome existing electrochemistry preparation conduction Poly[Ni (Salen)] material pattern is single, be unfavorable for the limitation of mass transfer, a kind of redox polymers Poly[Ni (Salen) for preparing easily the controlled nanobelt structure of pattern be provided] electrode of super capacitor of Electrochemical Modification.
Controllable nano band structure of a kind of redox polymers electrode and preparation method thereof, this redox polymers is Poly[Ni (Salen)], obtain by monomer salicylide ethylenediamine nickel Ni (Salen) electropolymerization, preparation process is as follows:
1. solution allocation
Tetrabutylammonium perchlorate is dissolved in acetonitrile solution as supporting salt, and being mixed with tetrabutylammonium perchlorate's concentration is 0.1 mol L -1blank solution;
Monomer Ni (salen), tetrabutylammonium perchlorate are dissolved in acetonitrile solution, and ultrasonic 5-10 s is with abundant dissolved monomer, and being mixed with monomer Ni (salen) molar concentration is 1 mmol L -1, tetrabutylammonium perchlorate's concentration is 0.1 mol L -1electrochemical polymerization solution;
2. electrochemical polymerization
The blank solution configuring is inserted to airtight three-electrode system, connect electrochemical workstation, work electrode is to drip the titanium sheet (Ti/MWCNT) that has been coated with carbon nano-tube, or electro-conductive glass (ITO), be active carbon to electrode, reference electrode is Ag/AgCl, adopts cyclic voltammetry, sweeps fast 100-200 mV s -1scanning 10-50 circle, makes electrode reach stable.
Work electrode, electrode, reference are remained unchanged, solution in airtight three-electrode system is changed to electrochemical polymerization solution, connect electrochemical workstation, adopt constant potential method to carry out electropolymerization, applying current potential starts after polymerization, Poly[Ni (Salen)] deposit gradually at working electrode surface, form yellow film, to deposit Poly[Ni (Salen)] work electrode of film takes out from electrochemical solution, with acetonitrile drip washing gently, to remove electrolyte solution, monomer and the oligomer on film.A work electrode 60-65 ℃ vacuum drying oven is dried to 24 h, obtains nanobelt structure Poly[Ni (Salen)] modify electrochemical activity electrode.
Voltage range prepared by described constant potential is at 0.70-0.91V, and time range is at 5-60 min.
The invention has the advantages that can be by regulating polymerization current potential and polymerization time simply, effectively control Poly[Ni (Salen)] appearance structure, prepare Poly[Ni (Salen)] Poly[Ni (Salen) of nanobelt structure], obtain the Poly[Ni (Salen) with better diffusivity and capacitive property] and polymer modified electrode.
Accompanying drawing explanation
Fig. 1 is the prepared nano strip Poly[Ni (Salen) that obtains of example 1] scanning electron microscope diagram of modified electrode, multiplication factor is 50 k.
Fig. 2 is the prepared nano strip Poly[Ni (Salen) that obtains of example 2] scanning electron microscope diagram of modified electrode, multiplication factor is 500 k.
Fig. 3 is the prepared nano strip Poly[Ni (Salen) that obtains of example 2] the constant current charge-discharge curve of modified electrode and carbon nanotube electrode, current density is 1mA cm -2.
Fig. 4 is the prepared nano strip Poly[Ni (Salen) that obtains of example 3] scanning electron microscope diagram of modified electrode, multiplication factor is 50 k.
Fig. 5 is the prepared nano strip Poly[Ni (Salen) that obtains of example 3] cyclic voltammogram of modified electrode, sweeping speed is 80 mV s -1.
Embodiment
embodiment 1
1. solution preparation
Tetrabutylammonium perchlorate is dissolved in acetonitrile solution, and being mixed with tetrabutylammonium perchlorate's concentration is 0.1 mol L -1blank solution;
Monomer Ni (salen), tetrabutylammonium perchlorate are dissolved in acetonitrile solution, and ultrasonic 5-10 s is with abundant dissolved monomer, and being mixed with monomer Ni (salen) molar concentration is 1 mmol L -1, tetrabutylammonium perchlorate's concentration is 0.1 mol L -1electrochemical polymerization solution.
2. electrochemical polymerization
The blank solution configuring is inserted to airtight three-electrode system, connect electrochemical workstation, work electrode is ITO electrode, is active carbon to electrode, and reference electrode is Ag/AgCl, adopts cyclic voltammetry, sweeps fast 100-200 mV s -1scanning 10-50 circle, makes electrode reach stable.
Work electrode, electrode, reference are remained unchanged, solution in airtight three-electrode system is changed to electrochemical polymerization solution, connect electrochemical workstation, adopt 0.90 V constant potential electropolymerization, start to apply after current potential, Poly[Ni (Salen)] deposit gradually at working electrode surface, form yellow film, the electropolymerization time is 10 min, to deposit Poly[Ni (Salen)] work electrode of film takes out from electrochemical solution, with acetonitrile drip washing gently, to remove electrolyte solution, monomer and the oligomer on film.A work electrode 60-65 ℃ vacuum drying oven is dried to 24 h, obtains nanobelt structure Poly[Ni (Salen)] modify electrochemical activity electrode.
embodiment 2
1. solution preparation
Tetrabutylammonium perchlorate is dissolved in acetonitrile solution, and being mixed with tetrabutylammonium perchlorate's concentration is 0.1 mol L -1blank solution;
Monomer Ni (salen), tetrabutylammonium perchlorate are dissolved in acetonitrile solution, and ultrasonic 5-10 s is with abundant dissolved monomer, and being mixed with monomer Ni (salen) molar concentration is 1 mmol L -1, tetrabutylammonium perchlorate's concentration is 0.1 mol L -1electrochemical polymerization solution.
2. electrochemical polymerization
The blank solution configuring is inserted to airtight three-electrode system, connect electrochemical workstation, work electrode is Ti/MWCNT electrode, is active carbon to electrode, and reference electrode is Ag/AgCl, adopts cyclic voltammetry, sweeps fast 100-200 mV s -1scanning 10-50 circle, makes electrode reach stable.
Work electrode, electrode, reference are remained unchanged, solution in airtight three-electrode system is changed to electrochemical polymerization solution, connect electrochemical workstation, adopt 0.75 V constant potential to carry out electropolymerization, start to apply after voltage, Poly[Ni (Salen)] deposit gradually at working electrode surface, form yellow film, the electropolymerization time is 20 min, to deposit Poly[Ni (Salen)] work electrode of film takes out from electrochemical solution, with acetonitrile drip washing gently, to remove electrolyte solution, monomer and the oligomer on film.A work electrode 60-65 ℃ vacuum drying oven is dried to 24 h, obtains nanobelt structure Poly[Ni (Salen)] modify electrochemical activity electrode.
embodiment 3
1. solution preparation
Tetrabutylammonium perchlorate is dissolved in acetonitrile solution, and being mixed with tetrabutylammonium perchlorate's concentration is 0.1 mol L -1blank solution;
Monomer Ni (salen), tetrabutylammonium perchlorate are dissolved in acetonitrile solution, and ultrasonic 5-10 s is with abundant dissolved monomer, and being mixed with monomer Ni (salen) molar concentration is 1 mmol L -1, tetrabutylammonium perchlorate's concentration is 0.1 mol L -1electrochemical polymerization solution.
2. electrochemical polymerization
The blank solution configuring is inserted to airtight three-electrode system, connect electrochemical workstation, work electrode is ITO electrode, is active carbon to electrode, and reference electrode is Ag/AgCl, adopts cyclic voltammetry, sweeps fast 100-200 mV s -1scanning 10-50 circle, makes electrode reach stable.
Work electrode, electrode, reference are remained unchanged, solution in airtight three-electrode system is changed to electrochemical polymerization solution, connect electrochemical workstation, adopt 0.85 V constant potential to carry out electropolymerization, start to apply after voltage, Poly[Ni (Salen)] deposit gradually at working electrode surface, form yellow film, the electropolymerization time is 30 min, to deposit Poly[Ni (Salen)] work electrode of film takes out from electrochemical solution, with acetonitrile drip washing gently, to remove electrolyte solution, monomer and the oligomer on film.A work electrode 60-65 ℃ vacuum drying oven is dried to 24 h, obtains nanobelt structure Poly[Ni (Salen)] modify electrochemical activity electrode.

Claims (1)

1. the preparation method of the controllable nano band structure of a redox polymers electrode, it is characterized in that this redox polymers is Poly[Ni (Salen)], obtain by monomer salicylide ethylenediamine nickel Ni (Salen) electropolymerization, preparation process is as follows:
Solution allocation
Tetrabutylammonium perchlorate is dissolved in acetonitrile solution as supporting salt, and being mixed with tetrabutylammonium perchlorate's concentration is 0.1mol L -1blank solution;
Monomer Ni (salen), tetrabutylammonium perchlorate are dissolved in acetonitrile solution, and ultrasonic 5-10s is with abundant dissolved monomer, and being mixed with monomer Ni (salen) molar concentration is 1mmol L -1, tetrabutylammonium perchlorate's concentration is 0.1mol L -1electrochemical polymerization solution;
Electrochemical polymerization
The blank solution configuring is inserted to airtight three-electrode system, connect electrochemical workstation, work electrode is to drip the titanium sheet or the electro-conductive glass that have been coated with carbon nano-tube, be active carbon to electrode, reference electrode is Ag/AgCl, adopts cyclic voltammetry, sweeps fast 100-200mV s -1scanning 10-50 circle, makes electrode reach stable;
Work electrode, electrode, reference electrode are remained unchanged, solution in airtight three-electrode system is changed to electrochemical polymerization solution, connect electrochemical workstation, adopt constant potential method to carry out electropolymerization, applying current potential starts after polymerization, Poly[Ni (salen)] deposit gradually at working electrode surface, form yellow film, to deposit Poly[Ni (salen)] work electrode of film takes out from electrochemical solution, with acetonitrile drip washing gently, to remove electrolyte solution, monomer and the oligomer on film; Work electrode 60-65 ℃ of vacuum drying oven dried to 24h, obtains nanobelt structure Poly[Ni (salen)] electrochemical activity electrode modified;
Voltage range prepared by described constant potential is at 0.70-0.91V; Time range prepared by described constant potential is at 5-60min.
CN201210112495.8A 2012-04-17 2012-04-17 Controllable nanoribbon structure of redox polymer electrode and preparation method thereof Expired - Fee Related CN102683033B (en)

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CN106046063A (en) * 2016-06-21 2016-10-26 中国科学院合肥物质科学研究院 Ni-MOFs (nickel-metal organic frameworks) material and preparation method and application thereof
CN107658149B (en) * 2017-08-31 2019-03-29 北京科技大学 A kind of composite electrode material for super capacitor and preparation method thereof

Citations (2)

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US7292431B2 (en) * 2002-10-03 2007-11-06 Gen 3 Partners, Inc. Electrochemical capacitor and method of use
CN102306552A (en) * 2011-06-21 2012-01-04 中国铝业股份有限公司 Electrode of capacitor and preparation method thereof

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US7292431B2 (en) * 2002-10-03 2007-11-06 Gen 3 Partners, Inc. Electrochemical capacitor and method of use
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