CN112908728B - Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor - Google Patents

Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor Download PDF

Info

Publication number
CN112908728B
CN112908728B CN202110053960.4A CN202110053960A CN112908728B CN 112908728 B CN112908728 B CN 112908728B CN 202110053960 A CN202110053960 A CN 202110053960A CN 112908728 B CN112908728 B CN 112908728B
Authority
CN
China
Prior art keywords
electrochemical
polypyrrole
electrode
monovalent anion
doped polypyrrole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110053960.4A
Other languages
Chinese (zh)
Other versions
CN112908728A (en
Inventor
杜祖亮
方岩
王书杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University
Original Assignee
Henan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University filed Critical Henan University
Priority to CN202110053960.4A priority Critical patent/CN112908728B/en
Publication of CN112908728A publication Critical patent/CN112908728A/en
Application granted granted Critical
Publication of CN112908728B publication Critical patent/CN112908728B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention provides a double-anion doped polypyrrole electrode slice, a preparation method thereof and a super capacitor, and belongs to the technical field of electrochemistry. The method adopts specific types of univalent anions for doping, introduces large-volume anions into the polypyrrole, constructs a smooth ion transmission channel, and can widen the electrochemical active voltage window of the polypyrrole; after the electrode plate is prepared, the electrode plate is immersed into a solution containing a high-valence anion dopant for electrochemical circulation, and in the electrochemical circulation process, large-volume rigid high-valence anions partially replace monovalent anions, so that a channel introduced by doping of the monovalent anions is fixed, the volume change of an active material in the electrochemical process can be reduced, and the energy density, the power density and the cycle life of the polypyrrole-based symmetric supercapacitor are improved.

Description

Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor
Technical Field
The invention relates to the technical field of electrochemistry, and particularly relates to a double-anion doped polypyrrole electrode slice, a preparation method thereof and a super capacitor.
Background
Electrochemical Capacitor (EC), also called super Capacitor (Supercapacitor), as a new chemical power source with long service life (10)5The secondary cycle), specific power is big (1500W/kg), can quick charge (can be several seconds), low temperature performance is good (minimum operating temperature-50 ℃), heavy current discharge performance is good, the stored energy is big, has a power density higher than the battery, energy density higher than traditional condenser, not only can use with the battery supporting for electric motor car etc. provides peak power, can even provide power for electric tool or electric motor car alone to reduce the negative effects that the energy brought to the ecology based on petrochemical industry resource burning provides. And the energy-saving device has the advantages of light weight, no maintenance, low pollution, low price and excellent performance, and is praised as a novel green energy source. Therefore, the electrochemical capacitor is likely to be developed into an efficient and practical energy storage device in the future, and has very wide application prospects in the fields of traffic, energy, communication, power electronics, military and national defense, industrial production and the like.
The superiority and inferiority of electrode materials are decisive factors for the performance of electrochemical capacitors, and electrode materials having higher energy density and higher power density have been developed. In the prior art, electrode materials for electrochemical capacitors can be classified into the following three types: noble metal oxides, conductive polymers, and carbon-based electrode materials. Wherein, the resource of the noble metal is limited and the price is high; conductive polymers have poor cycling stability, limiting their applications; the carbon electrode material mainly comprises: the carbon nano tube has the advantages that the carbon nano tube has high contact resistance, low specific capacity and high cost, and the application of the carbon nano tube is limited although the carbon nano tube has excellent conductivity. The polypyrrole has good conductivity, high theoretical specific capacitance, wider theoretical electrochemical active voltage window and simple preparation process, and is a super capacitor electrode material with a very good application prospect. The selected neutral aqueous electrolyte can be used as an electrode active material to construct a symmetrical super capacitor with high capacity, simple assembly process and extremely high safety.
However, in practical application, the polypyrrole-based symmetrical supercapacitor has a narrow operating voltage window, generally within 1.0V, and has an insufficient energy density and power density and a short service life.
Disclosure of Invention
The invention aims to provide a double-anion doped polypyrrole electrode slice, a preparation method thereof and a super capacitor.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a dianion doped polypyrrole electrode slice, which comprises the following steps:
(1) dissolving pyrrole and a monovalent anion dopant in a polar solvent to obtain a mixed solution; the monovalent anion in the monovalent anion dopant comprises one or more of benzene sulfonate ion, naphthalene sulfonate ion, alkyl sulfate ion, alkyl benzene sulfonate ion, and alkyl naphthalene sulfonate ion;
(2) mixing the mixed solution with an oxidant to carry out polymerization reaction, drying a precipitate obtained by the polymerization reaction to obtain monovalent anion doped polypyrrole, and preparing the monovalent anion doped polypyrrole into an electrode slice;
or replacing said step (2) with step (2'): dipping a current collector into the mixed solution for electrochemical oxidation polymerization to obtain an electrode plate;
(3) immersing the electrode slice into a solution containing a high-valence anion dopant for electrochemical circulation to obtain a dianion doped polypyrrole electrode slice; the high-valence anion in the high-valence anion dopant is one or more of m-benzene disulfonate, naphthalene disulfonate and naphthalene trisulfonate.
Preferably, the polar solvent is water, ethanol, methanol, acetonitrile, N-dimethylformamide or dimethyl sulfoxide.
Preferably, the mole ratio of the monovalent anion dopant to the pyrrole is (0.01-10): 1.
preferably, in the step (2), the oxidant is ferric chloride, sodium persulfate, sodium superphosphate, sodium hypochlorite or peroxyacetic acid; the molar ratio of the oxidant to the pyrrole is (0.1-5): 1.
preferably, in the step (2'), the electrochemical oxidative polymerization is performed by a constant voltage pulse method, a constant current method, a constant voltage method, cyclic voltammetry or potentiodynamic scanning method.
Preferably, the concentration of the solution containing the high-valence anion dopant is 0.005-1.0M.
Preferably, the electrochemical cycle adopts a cross-flow charge-discharge method, a constant-voltage charge-discharge method or a cyclic voltammetry method.
Preferably, in the step (2), the process of preparing the monovalent anion doped polypyrrole into the electrode sheet comprises: mixing the monovalent anion doped polypyrrole, the binder, the conductive agent and the solvent to obtain electrode slurry, drying the electrode slurry, pressing the electrode slurry into a sheet, and pressing the sheet onto a current collector to obtain the electrode plate.
The invention provides a dianion doped polypyrrole electrode slice prepared by the preparation method in the scheme.
The invention provides a super capacitor which comprises electrolyte and the double-anion doped polypyrrole electrode slice in the scheme.
The invention provides a preparation method of a dianion doped polypyrrole electrode slice, which comprises the following steps: (1) dissolving pyrrole and a monovalent anion dopant in a polar solvent to obtain a mixed solution; the monovalent anion in the monovalent anion dopant comprises one or more of benzene sulfonate ion, naphthalene sulfonate ion, alkyl sulfate ion, alkyl benzene sulfonate ion, and alkyl naphthalene sulfonate ion; (2) mixing the mixed solution with an oxidant to carry out polymerization reaction, drying a precipitate obtained by the polymerization reaction to obtain monovalent anion doped polypyrrole, and preparing the monovalent anion doped polypyrrole into an electrode slice; or replacing said step (2) with step (2'): dipping a current collector into the mixed solution for electrochemical oxidation polymerization to obtain an electrode plate; (3) immersing the electrode slice into a solution containing a high-valence anion dopant for electrochemical circulation to obtain a dianion doped polypyrrole electrode slice; the high-valence anion in the high-valence anion dopant is one or more of m-benzene disulfonate, naphthalene disulfonate and naphthalene trisulfonate.
The method adopts specific types of univalent anions for doping, introduces large-volume anions into the polypyrrole, constructs a smooth ion transmission channel, and can widen the electrochemical active voltage window of the polypyrrole; after the electrode plate is prepared, the electrode plate is immersed into a solution containing a high-valence anion dopant for electrochemical circulation, and in the electrochemical circulation process, large-volume rigid high-valence anions partially replace monovalent anions, so that a channel introduced by doping of the monovalent anions is fixed, the volume change of an active material in the electrochemical process can be reduced, and the energy density, the power density and the cycle life of the polypyrrole-based symmetric supercapacitor are improved.
Drawings
FIG. 1 is a cyclic voltammogram of an electrochemical capacitor according to application example 1;
fig. 2 is a cyclic voltammogram using the electrochemical capacitor of comparative example 1.
Detailed Description
The invention provides a preparation method of a dianion doped polypyrrole electrode slice, which comprises the following steps:
(1) dissolving pyrrole and a monovalent anion dopant in a polar solvent to obtain a mixed solution; the monovalent anion in the monovalent anion dopant comprises one or more of benzene sulfonate ion, naphthalene sulfonate ion, alkyl sulfate ion, alkyl benzene sulfonate ion, and alkyl naphthalene sulfonate ion;
(2) mixing the mixed solution with an oxidant to carry out polymerization reaction, drying a precipitate obtained by the polymerization reaction to obtain monovalent anion doped polypyrrole, and preparing the monovalent anion doped polypyrrole into an electrode slice;
or replacing said step (2) with step (2'): dipping a current collector into the mixed solution for electrochemical oxidation polymerization to obtain an electrode plate;
(3) immersing the electrode slice into a solution containing a high-valence anion dopant for electrochemical circulation to obtain a dianion doped polypyrrole electrode slice; the high-valence anion in the high-valence anion dopant is one or more of m-benzene disulfonate, naphthalene disulfonate and naphthalene trisulfonate.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
Pyrrole and a monovalent anion dopant are dissolved in a polar solvent to obtain a mixed solution.
In the invention, the monovalent anion in the monovalent anion dopant comprises one or more of benzene sulfonate ion, naphthalene sulfonate ion, alkyl sulfate ion, alkyl benzene sulfonate ion and alkyl naphthalene sulfonate ion, and when the monovalent anion comprises a plurality of monovalent anions, the proportion of each monovalent anion in the monovalent anion dopant has no special requirement, and any proportion can be realized.
In the present invention, when the monovalent anion is benzenesulfonate ion, the monovalent anion dopant may be, but is not limited to, sodium benzenesulfonate. When the monovalent anion is a naphthalenesulfonate ion, the monovalent anion dopant may be specifically, but is not limited to, sodium naphthalenesulfonate. When the monovalent anion is an alkylbenzene sulfonate ion, the alkyl chain length of the alkylbenzene sulfonate ion is preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms; the alkylbenzene sulfonate ion may be, but is not limited to, p-toluenesulfonate ion, 4-octylbenzenesulfonate ion, dodecylbenzenesulfonate ion, hexadecane sulfonate ion, and the monovalent anion dopant may be, but is not limited to, sodium p-toluenesulfonate, 4-octylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium hexadecylbenzenesulfonate. When the monovalent anion is an alkyl naphthalene sulfonate ion, the alkyl chain length of the alkyl naphthalene sulfonate ion is preferably 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms; when the monovalent anion is an alkyl naphthalene sulfonate ion, the alkyl naphthalene sulfonate ion may be, but is not limited to, a methyl naphthalene sulfonate ion, an isopropyl naphthalene sulfonate ion, an isobutyl naphthalene sulfonate ion, specifically; the monovalent anion dopant may be, but is not limited to, methyl naphthalene sulfonic acid, sodium isopropyl naphthalene sulfonate, isobutyl naphthalene sulfonic acid, specifically. When the monovalent anion is an alkylsulfate ion, the alkyl chain length of the alkylsulfate ion is preferably 1 to 20 carbon atoms, more preferably 4 to 12 carbon atoms; when the monovalent anion is an alkylsulfate ion, the alkylsulfate ion may be specifically, but not limited to, methylsulfate ion, butylsulfate ion, octylsulfate ion, dodecylsulfate ion; the monovalent anion dopant may be, but is not limited to, sodium methyl sulfate, butyl sulfate, sodium octyl sulfate, sodium dodecyl sulfate.
In the present invention, the polar solvent is preferably water, ethanol, methanol, acetonitrile, N-dimethylformamide or dimethylsulfoxide, and more preferably water. The water is preferably deionized water.
In the present invention, the mole ratio of the monovalent anion dopant to pyrrole is preferably (0.01 to 10): 1, more preferably (1 to 8): 1, more preferably (2-5): 1.
the method has no special requirement on the dosage of the polar solvent, and can completely dissolve pyrrole and the monovalent anion dopant.
After the mixed solution is obtained, the mixed solution and an oxidant are mixed to carry out polymerization reaction, a precipitate obtained by the polymerization reaction is dried to obtain the monovalent anion doped polypyrrole, and the monovalent anion doped polypyrrole is prepared into the electrode slice.
In the present invention, the oxidizing agent is preferably ferric chloride, sodium persulfate, sodium perphosphate, sodium hypochlorite or peracetic acid; the molar ratio of the oxidant to the pyrrole is preferably (0.1-5): 1, more preferably (1-2): 1. in the present invention, the oxidizing agent is preferably used in the form of an aqueous oxidizing agent solution, and the concentration of the aqueous oxidizing agent solution is preferably 0.1 to 1M.
The present invention preferably performs polymerization by adding an aqueous solution of an oxidizing agent dropwise to the mixed solution. Under the action of the oxidant, pyrrole in the mixed solution is polymerized and precipitated, and monovalent anion is doped into polypyrrole.
In the invention, the temperature of the polymerization reaction is preferably room temperature, the invention has no special requirement on the time of the polymerization reaction, and the polymerization reaction is considered to be finished after the addition of the oxidant aqueous solution is completed and the precipitate is not increased any more.
After the polymerization reaction is finished, the method dries the precipitate obtained by the polymerization reaction to obtain the univalent anion doped polypyrrole. The precipitate is preferably obtained by suction filtration in the present invention. In the present invention, the drying is preferably performed under vacuum, the temperature of the drying is preferably 80 ℃, and the time of the drying is preferably 10 hours. After the drying is completed, the invention preferably further comprises grinding the dried material to obtain the monovalent anion doped polypyrrole. In the present invention, the monovalent doped anionic polypyrrole is in a powder form.
After the monovalent anion doped polypyrrole is obtained, the monovalent anion doped polypyrrole is prepared into the electrode slice.
The preparation process of the electrode plate has no special requirements, and the preparation process known in the field is adopted. In the invention, the preparation process of the electrode slice is preferably as follows: mixing the monovalent anion doped polypyrrole, the binder, the conductive agent and the solvent to obtain electrode slurry, drying the electrode slurry, pressing the electrode slurry into a sheet, and pressing the sheet onto a current collector to obtain the electrode plate.
The invention has no special requirement on the specific type of the binder, and the binder well known in the art can be any, and the specific can be, but is not limited to polytetrafluoroethylene, polyvinylidene fluoride, butyl rubber and polyacrylate. In the present invention, the binder is preferably used in an amount of not more than 10% by mass based on the total mass of the binder, the conductive agent and the monovalent anion-doped polypyrrole.
The invention has no special requirement on the specific type of the conductive agent, and the conductive agent well known in the art can be used, and the specific conductive agent can be, but is not limited to acetylene black, carbon black, graphite powder and carbon fiber. The amount of the conductive agent used in the present invention is not particularly limited, and may be any amount known in the art.
In an embodiment of the invention, the mass ratio of the monovalent anion doped polypyrrole, the binder and the conductive agent is specifically 90:5: 5.
The present invention does not require any particular kind of solvent, and any solvent known in the art for preparing an electrode slurry may be used, and specific examples thereof include, but are not limited to, water, N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethylsulfoxide, tetrahydrofuran, and alcohols. In the invention, the mass ratio of the total mass of the monovalent anion doped polypyrrole, the binder and the conductive agent to the solvent is preferably 1 (0.1-100), and more preferably 1 (1-50).
In the present invention, the monovalent anion doped polypyrrole, the binder, the conductive agent and water are preferably mixed by the following process: and mixing the univalent anion doped polypyrrole, the binder and the conductive agent, dropwise adding a solvent into the obtained mixture, and stirring the mixture into a slurry state to obtain the electrode slurry.
After obtaining the electrode slurry, the invention dries the electrode slurry and then presses it into a sheet.
In the invention, the drying temperature is preferably 80-150 ℃, and the drying time is preferably 2-10 h. The present invention does not require any particular thickness for the sheet, and it can be pressed to a thickness well known in the art.
After the thin sheet is obtained, the thin sheet is pressed on a current collector to obtain the electrode plate.
The current collector is not limited in any way, and current collectors well known in the art can be used. In the present invention, the current collector may be, but not limited to, a metal sheet, a metal mesh, a metal foil, and a foamed metal, and may also support polypyrrole, aligned carbon nanotubes, two-dimensional layered sulfides, and metal carbon/nitrides with two-dimensional layered structures on the basis of the foregoing.
The pressing process of the present invention is not particularly limited, and may be a pressing process well known in the art.
In the invention, the process for preparing the electrode slice can also be as follows: and dipping a current collector into the mixed solution for electrochemical oxidation polymerization to obtain the electrode plate.
The current collector is not limited in any way in the present invention, and the above discussion is omitted here for brevity.
In the present invention, the method used for carrying out the electrochemical oxidative polymerization is preferably a constant voltage pulse method, a constant current pulse method, a galvanostatic method, a constant voltage method, cyclic voltammetry or potentiodynamic scanning method.
In the present invention, when the constant voltage pulse method is used, the voltage is preferably 1.0V (vs Hg/HgCl), and the present invention is preferably turned on for 100ms and turned off for 100ms for a total of 200 cycles;
when the constant current pulse method is employed, the current density is preferably 2mA/cm2The invention is preferably opened for 100ms and closed for 100ms, and 200 cycles are carried out;
when the galvanostatic method is used, the current density is preferably 1.0mA/cm2The time of the electrochemical oxidative polymerization is preferably 30 s;
when a constant voltage method is adopted, the voltage is preferably 0.7-1.4V (vs Hg/HgCl), and the time of the electrochemical oxidative polymerization is preferably 60 s;
when cyclic voltammetry is adopted, the voltage scanning range is preferably 0 to (0.7 to 1.4) V (vs Hg/HgCl), the scanning speed is preferably 50mV/s, and the cyclic voltammetry is preferably cycled for 10 times;
when the potentiodynamic scanning method is adopted, the voltage range is preferably 0 to (0.7 to 1.4) V (vs Hg/HgCl), the scanning speed is preferably 50mV/s, and the method is preferably circulated for 10 times.
The implementation process of the electrochemical oxidative polymerization is not particularly required in the invention, and the electrochemical oxidative polymerization process well known in the art can be adopted.
The pyrrole is polymerized into the polypyrrole through electrochemical oxidation, and the monovalent anion is doped into the polypyrrole.
After the electrode slice is obtained, the electrode slice is immersed into a solution containing a high-valence anion dopant for electrochemical circulation to obtain the dianion doped polypyrrole electrode slice.
In the present invention, the high-valent anion in the high-valent anion dopant is one or more of isophthalate, napadisylate and naphthalenetrisulfonate. When the high-valence anions comprise a plurality of the substances, the proportion of each high-valence anion is not particularly required and can be any.
In the present invention, the concentration of the solution containing a high-valent anionic dopant is preferably 0.005M to 1.0M, more preferably 0.01 to 0.1M; the invention has no special requirement on the dosage of the solution containing the high-valence anion dopant, and the electrode plate can be completely immersed.
In the present invention, the electrochemical cycling preferably employs a constant current charge-discharge method, a constant voltage charge-discharge method, or cyclic voltammetry. When the constant current charge and discharge method is employed, the voltage (vs Hg/HgCl) is preferably: 0 to (1.2 to 2.2) V, more preferably 0 to (1.5 to 2.0) V; the current density is preferably 0.01 to 10A/g, and more preferably 0.05 to 1A/g; the number of cycles is preferably 1 to 100 times, more preferably 3 to 20 times. In the embodiment of the invention, when a constant current charge and discharge method is adopted, the voltage is specifically 0-1.6V (vs Hg/HgCl), the current density is 0.1A/g, and the cycle number is 5 times.
When cyclic voltammetry is adopted, the scanning voltage is preferably 0 to (1.2-2.2) V, more preferably 0 to (1.5-2.0) V; the sweep rate is preferably 1-200 mV/s, more preferably 5-100 mV/s; the number of cycles is preferably 1 to 100, more preferably 3 to 20. In the embodiment of the invention, when cyclic voltammetry is adopted, the scanning voltage is specifically 0-1.6V, the scanning speed is 5mV/s, and the cycle number is 3 times.
When the constant voltage charge-discharge method is employed, the voltage (vs Hg/HgCl) is preferably: 0 to (1.2 to 2.2) V, more preferably 0 to (1.5 to 2.0) V; the number of cycles is preferably 1 to 100, more preferably 3 to 20.
In the electrochemical circulation process, monovalent anions are partially replaced by large-volume rigid high-valence anions, so that a channel introduced by doping of the monovalent anions is fixed, the volume change of an active material in the electrochemical process can be reduced, and the energy density, the power density and the cycle life of the polypyrrole-based symmetric supercapacitor are improved.
The invention provides a dianion doped polypyrrole electrode slice prepared by the preparation method in the scheme. The method adopts specific types of univalent anions for doping, introduces large-volume anions into the polypyrrole, constructs a smooth ion transmission channel, and can widen the electrochemical active voltage window of the polypyrrole; after the electrode plate is prepared, the electrode plate is immersed into a solution containing a high-valence anion dopant for electrochemical circulation, and in the electrochemical circulation process, large-volume rigid high-valence anions partially replace monovalent anions, so that a channel introduced by doping of the monovalent anions is fixed, the volume change of an active material in the electrochemical process can be reduced, and the energy density, the power density and the cycle life of the polypyrrole-based symmetric supercapacitor are improved.
The invention provides a super capacitor which comprises electrolyte and the double-anion doped polypyrrole electrode slice in the scheme.
The super capacitor provided by the invention comprises an electrolyte. In the present invention, the electrolyte solution is preferably an aqueous electrolyte solution, an organic electrolyte solution, a room-temperature ionic liquid electrolyte solution, or a solid electrolyte, and more preferably an aqueous electrolyte solution.
In the present invention, the aqueous electrolyte preferably includes deionized water and an electrolyte salt. The electrolyte salt is preferably one or more of lithium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, sodium chloride, lithium chloride and potassium chloride. In the present invention, the concentration of the aqueous electrolyte is preferably 0.1 to 5M.
In the present invention, the organic electrolyte preferably includes an electrolyte solvent and an electrolyte salt. The electrolyte solvent is preferably one or more of ethylene carbonate, propylene carbonate and acetonitrile; the electrolyte salt is preferably one or more of tetraethyl quaternary ammonium tetrafluoroborate, tetraethyl quaternary phosphonium tetrafluoroborate, tetra-n-propyl quaternary phosphonium tetrafluoroborate, tetraethyl quaternary ammonium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate. In the invention, the concentration of the organic electrolyte is preferably 0.1-5M.
In the present invention, the room temperature ionic liquid electrolyte preferably includes cations and anions; the cation is preferably one or more of quaternary ammonium cation, quaternary phosphonium cation, pyridinium cation, imidazolium cation and sulfonium cation; the anion is preferably BF4 -、PF6 -、NO3 -、SbF6 -、CIO4 -、CF3SO3 -、C3F7COO-、C4F9SO3 -And F3COO-One or more of (a).
In the present invention, the solid electrolyte preferably includes a matrix and an electrolytic salt; the matrix is preferably one or more of polyvinyl benzene sulfonic acid, polyvinylpyrrolidone and polyvinyl alcohol; the electrolytic salt is preferably one or more of quaternary ammonium tetraethyltetrafluoroborate, quaternary phosphonium tetra-n-propyltetrafluoroborate, quaternary phosphonium tetraethylhexafluorophosphate, lithium hexafluorophosphate, lithium tetrafluoroborate, and perchlorate containing 10% by mass of tetramethylammonium. In the invention, the concentration of the solid electrolyte is preferably 0.1-2 mol/L.
In the present invention, when the electrolyte is an aqueous electrolyte, an organic electrolyte, or a room-temperature ionic liquid electrolyte, the supercapacitor preferably further includes a case and a separator. The housing of the present invention is not limited in any way, and may be a housing known in the art, and may be made of metal or plastic. The separator is not particularly limited in the present invention, and a separator known in the art may be used. The separator may be, but is not limited to, a polyethylene film, a polypropylene film, a cellulose film, or a modified polymer thereof.
The preparation method of the super capacitor has no special requirements, and the super capacitor can be prepared by adopting a method well known in the field. In the present invention, the supercapacitor is preferably a symmetric supercapacitor.
The dianion doped polypyrrole electrode plate is used as an electrode plate for preparing a super capacitor, and the obtained capacitor has a wider working voltage window, higher energy density and power density and longer service life.
The dianion-doped polypyrrole electrode sheet, the preparation method thereof and the supercapacitor provided by the invention are described in detail below with reference to examples, but the invention is not limited to these examples.
Example 1
(1) Weighing 0.01mol of pyrrole and 0.02mol of sodium dodecyl sulfate at room temperature, adding into 0.1L of deionized water, and dissolving to obtain a mixed solution;
(2) and (2) taking the aluminum foil with the oriented carbon nanotubes as a current collector, immersing the current collector into the mixed solution, and performing electrochemical oxidative polymerization by using an electrochemical cyclic voltammetry method (0-1.0V (vs Hg/HgCl), 50m V/s, 10 times of circulation), wherein the mass ratio of the polypyrrole to the oriented carbon nanotubes is 9: and 1, obtaining the electrode plate of the polypyrrole/oriented carbon nanotube/aluminum foil doped with the dodecyl sulfate ions.
(3) And (3) immersing the electrode slice into 0.05M aqueous solution of 1, 5-naphthalene disulfonic acid sodium, performing electrochemical oxidative polymerization by adopting an electrochemical cyclic voltammetry method (0-1.6V, 5mV/s, circulation for 3 times), and performing substitution doping on 1, 5-naphthalene disulfonic acid radicals to obtain the double-anion doped electrode slice.
And testing the electrochemical activity voltage window of the electrode plate by adopting a cyclic voltammetry at a sweep rate of 10mV/s, wherein the result shows that the electrochemical activity voltage window of the electrode plate is 0-1.8V (vs Hg/HgCl).
Application example 1
And (3) selecting 0.1M sodium sulfate solution as electrolyte, a polypropylene microporous membrane as a diaphragm and a CR2032 battery case as a shell, and assembling the electrolyte and the double-anion doped electrode slice prepared in the embodiment 1 to obtain the symmetrical supercapacitor.
Measuring the specific capacitance, the energy density and the power density of the symmetrical super capacitor under the conditions that the working voltage window is 0-1.8V (the cyclic voltammetry curve is shown in figure 1) and the constant current density is 0.1-10A/g; after charging and discharging 2000 times at a constant current density of 0.5A/g, the capacity retention rate of the symmetrical supercapacitor was determined. The highest energy density is 36.7Wh/kg, the highest power density is 8650W/kg, and the capacity retention rate after 2000 cycles is 92%.
Comparative example 1
(1) Weighing 0.01mol of pyrrole at room temperature, adding into 0.1L of deionized water, and dissolving to obtain a mixed solution;
(2) and (2) taking the aluminum foil with the oriented carbon nanotubes as a current collector, immersing the current collector into the mixed solution, and performing electrochemical oxidative polymerization by adopting an electrochemical cyclic voltammetry method (0-1.0V, 50mV/s, 10 times of circulation), wherein the mass ratio of the polypyrrole to the oriented carbon nanotubes is 9: 1, obtaining the polypyrrole/oriented carbon nanotube/aluminum foil electrode slice.
The electrochemical activity voltage window of the electrode plate is tested to be 0-0.8V by the method of the embodiment 1.
Application comparative example 1
Selecting 0.1M sodium sulfate solution as electrolyte, a polypropylene microporous membrane as a diaphragm and a CR2032 battery case as a shell, and assembling the electrolyte and the electrode slice prepared in the comparative example 1 to obtain a symmetrical supercapacitor;
measuring the specific capacitance, the energy density and the power density of the symmetrical super capacitor under the conditions that the working voltage window is 0-0.8V (the cyclic voltammetry curve is shown in figure 2) and the constant current density is 0.1-10A/g; after charging and discharging 2000 times at a constant current density of 0.5A/g, the capacity retention rate of the symmetrical supercapacitor was determined. The highest energy density is 10.3Wh/kg, the highest power density is 2658W/kg, and the capacity retention rate after 2000 cycles is 45%.
Comparative example 2
(1) Weighing 0.01mol of pyrrole and 0.02mol of sodium dodecyl sulfate at room temperature, adding into 0.1L of deionized water, and dissolving to obtain a mixed solution;
(2) and (2) taking the aluminum foil with the oriented carbon nanotubes as a current collector, immersing the current collector into the solution, and performing electrochemical oxidative polymerization by adopting an electrochemical cyclic voltammetry method (0-1.0V (vs Hg/HgCl), 50mV/s and 10 times of circulation), wherein the mass ratio of the polypyrrole to the oriented carbon nanotubes is 9: and 1, obtaining the electrode plate of the polypyrrole/oriented carbon nanotube/aluminum foil doped with the dodecyl sulfate ions.
The electrode sheet was tested to have an electrochemically active voltage window of 0 to 1.6V (vs Hg/HgCl) with reference to the method of example 1.
Comparative application example 2
And 0.1M sodium sulfate solution is selected as electrolyte, a polypropylene microporous membrane is taken as a diaphragm, a CR2032 battery case is taken as a shell, and the electrolyte and the electrode slice prepared in the comparative example 2 form a symmetrical supercapacitor.
Measuring the specific capacitance, the energy density and the power density of the symmetrical super capacitor under the constant current density with the working voltage window of 0-1.6V and 0.1-10A/g; after charging and discharging 2000 times at a constant current density of 0.5A/g, the capacity retention rate of the symmetrical supercapacitor was determined. The highest energy density is 28.8Wh/kg, the highest power density is 4160W/kg, and the capacity retention rate after 2000 cycles is 73%.
Example 2
(1) Weighing 0.01mol of pyrrole and 0.02mol of sodium dodecyl sulfate at room temperature, adding into 0.1L of deionized water, and dissolving to obtain a mixed solution;
(2) dropwise adding 50mL of 0.1M sodium persulfate aqueous solution into the mixed solution to oxidize and polymerize the pyrrole monomer, performing suction filtration to obtain a precipitate, performing vacuum drying on the precipitate at 80 ℃ for 10 hours, and manually grinding to obtain polypyrrole doped with dodecyl sulfate ions;
mixing the polypyrrole doped with dodecyl sulfate ions, conductive agent carbon black and binder polyvinylidene fluoride (the number average molecular weight is about 71000) according to the mass ratio of 90:5:5 to obtain an electrode material, stirring the mixture to be slurry under the state of dropwise adding distilled water, drying for 10 hours at 80 ℃, pressing into a sheet, and pressing on a foamed nickel collector plate to obtain the electrode plate.
(3) And (2) immersing the electrode slice into 0.05M aqueous solution of 1,3, 6-naphthalene trisulfonic acid sodium, performing electrochemical oxidative polymerization by adopting an electrochemical constant-current charging and discharging method (0-1.6V (vs Hg/HgCl), 0.1A/g, circulating for 5 times), and performing substitution doping on 1,3, 6-naphthalene trisulfonic acid radicals to obtain the 'double-anion doped polypyrrole/oriented carbon nanotube/aluminum foil' electrode slice.
The electrode sheet was tested to have an electrochemically active voltage window of 0 to 1.7V (vs Hg/HgCl) with reference to the method of example 1.
Application example 2
And (3) selecting 0.2M sodium nitrate solution as electrolyte, a polypropylene microporous membrane as a diaphragm and a CR2032 battery case as a shell, and assembling the electrolyte and the electrode slice obtained in the embodiment 2 to obtain the symmetrical supercapacitor.
Measuring the specific capacitance, the energy density and the power density of the symmetrical super capacitor under the constant current density with the working voltage window of 0-1.7V and 0.1-10A/g; after charging and discharging 2000 times at a constant current density of 0.5A/g, the capacity retention rate of the symmetrical supercapacitor was determined. The maximum energy density is 31.5Wh/kg, the maximum power density is 7630W/kg, and the capacity retention rate after 2000 cycles is 91%.
The embodiment and the comparative example show that the double-anion doped polypyrrole electrode slice prepared by the invention is used for the supercapacitor, and can solve the problems of narrow working voltage window, low energy density and power density and short service life of the polypyrrole-based symmetrical supercapacitor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the dianion doped polypyrrole electrode slice is characterized by comprising the following steps of:
(1) dissolving pyrrole and a monovalent anion dopant in a polar solvent to obtain a mixed solution; the monovalent anion in the monovalent anion dopant comprises one or more of benzene sulfonate ion, naphthalene sulfonate ion, alkyl sulfate ion, alkyl benzene sulfonate ion, and alkyl naphthalene sulfonate ion;
(2) mixing the mixed solution with an oxidant to carry out polymerization reaction, drying a precipitate obtained by the polymerization reaction to obtain monovalent anion doped polypyrrole, and preparing the monovalent anion doped polypyrrole into an electrode slice;
or replacing said step (2) with step (2'): dipping a current collector into the mixed solution for electrochemical oxidation polymerization to obtain an electrode plate;
(3) immersing the electrode slice into a solution containing a high-valence anion dopant for electrochemical circulation to obtain a dianion doped polypyrrole electrode slice; the high-valence anion in the high-valence anion dopant is one or more of m-benzene disulfonate, naphthalene disulfonate and naphthalene trisulfonate.
2. The method according to claim 1, wherein the polar solvent is water, ethanol, methanol, acetonitrile, N-dimethylformamide, or dimethyl sulfoxide.
3. The method according to claim 1, wherein the mole ratio of the monovalent anion dopant to the pyrrole is (0.01 to 10): 1.
4. the process according to claim 1, wherein in the step (2), the oxidizing agent is ferric chloride, sodium persulfate, sodium perphosphate, sodium hypochlorite or peracetic acid; the molar ratio of the oxidant to the pyrrole is (0.1-5): 1.
5. the method according to claim 1, wherein in the step (2'), the electrochemical oxidative polymerization is carried out by a constant voltage pulse method, a constant current pulse method, a galvanostatic method, a constant voltage method, cyclic voltammetry or a potentiodynamic scanning method.
6. The method according to claim 1, wherein the solution containing the high valent anionic dopant has a concentration of 0.005 to 1.0M.
7. The method of claim 1, wherein the electrochemical cycling is performed by a lateral flow charge-discharge method, a constant voltage charge-discharge method, or cyclic voltammetry.
8. The preparation method according to claim 1, wherein in the step (2), the step of preparing the monovalent anion doped polypyrrole into the electrode sheet comprises the following steps: mixing the monovalent anion doped polypyrrole, the binder, the conductive agent and the solvent to obtain electrode slurry, drying the electrode slurry, pressing the electrode slurry into a sheet, and pressing the sheet onto a current collector to obtain the electrode plate.
9. The dianion doped polypyrrole electrode slice prepared by the preparation method of any one of claims 1 to 8.
10. A supercapacitor comprising an electrolyte and the dianionic doped polypyrrole electrode sheet of claim 9.
CN202110053960.4A 2021-01-15 2021-01-15 Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor Active CN112908728B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110053960.4A CN112908728B (en) 2021-01-15 2021-01-15 Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110053960.4A CN112908728B (en) 2021-01-15 2021-01-15 Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor

Publications (2)

Publication Number Publication Date
CN112908728A CN112908728A (en) 2021-06-04
CN112908728B true CN112908728B (en) 2021-10-26

Family

ID=76113514

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110053960.4A Active CN112908728B (en) 2021-01-15 2021-01-15 Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor

Country Status (1)

Country Link
CN (1) CN112908728B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101037786A (en) * 2007-01-25 2007-09-19 西安交通大学 Preparation technique of large-scale anion doped polypyrrole film anticorrosive coating
CN101880460A (en) * 2003-06-18 2010-11-10 信越聚合物株式会社 Electrically conductive composition and preparation method thereof
CN103390511A (en) * 2013-07-30 2013-11-13 河海大学 Preparation method for graphene oxide/polypyrrole composite material of lamellar microstructure
CN107108884A (en) * 2014-10-29 2017-08-29 意大利学院科技基金会 For the method for the graphene oxide composite material for preparing polyaniline/reduction

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200388885A1 (en) * 2019-06-05 2020-12-10 Enevate Corporation Silicon-based energy storage devices with lipo2f2 salt-containing electrolyte formulations

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880460A (en) * 2003-06-18 2010-11-10 信越聚合物株式会社 Electrically conductive composition and preparation method thereof
CN101037786A (en) * 2007-01-25 2007-09-19 西安交通大学 Preparation technique of large-scale anion doped polypyrrole film anticorrosive coating
CN103390511A (en) * 2013-07-30 2013-11-13 河海大学 Preparation method for graphene oxide/polypyrrole composite material of lamellar microstructure
CN107108884A (en) * 2014-10-29 2017-08-29 意大利学院科技基金会 For the method for the graphene oxide composite material for preparing polyaniline/reduction

Also Published As

Publication number Publication date
CN112908728A (en) 2021-06-04

Similar Documents

Publication Publication Date Title
Vizintin et al. Linear and cross-linked ionic liquid polymers as binders in lithium–sulfur batteries
Senthilkumar et al. Redox additive aqueous polymer gel electrolyte for an electric double layer capacitor
TWI556489B (en) Non-aqueous electrolyte secondary battery and positive electrode sheet for use in the battery
TW558850B (en) Redox-active reversible electrode and battery using the same
US20070139862A1 (en) Electrode composite body, electrolyte, and redox capacitor
US8377546B2 (en) Plastics electrode material and secondary cell using the material
CN101443857B (en) Highly electron conductive polymer and electrochemical energy storage device with high capacity and high power using the same
CN113809325B (en) Alkaline aqueous secondary battery based on electroactive covalent organic framework polymer and application thereof
Jinisha et al. Solid-state supercapacitor with impressive performance characteristics, assembled using redox-mediated gel polymer electrolyte
JP5211623B2 (en) Electricity storage device
CN108292568A (en) Electrochemical apparatus and its manufacturing method
EP2309572A1 (en) Plastics electrode material and secondary cell using the material
CN109103031B (en) Solid polymer capacitor and preparation method thereof
CN102010594B (en) Method for preparing conductive polymer/silsesquioxane composite electrode material
CN112927949A (en) Water system mixed electrolyte and application thereof in zinc ion mixed super capacitor
CN114122394B (en) Polyoxazine material and preparation method and application thereof
JP2007250994A (en) Conductive polymer redox type electrochemical element used as polar device
CN112908728B (en) Double-anion doped polypyrrole electrode slice, preparation method thereof and super capacitor
KR100361478B1 (en) Battery and capacitor using quinoxaline resin
Ebina et al. Use of tetraethylammonium bis (oxalato) borate as electrolyte for electrical double-layer capacitors
Yoo Ionic liquid for high voltage supercapacitor
CN110462887A (en) Anode used for electrochemical equipment and the electrochemical appliance for having it
CN114121499B (en) Electrolyte for high-voltage supercapacitor and high-voltage supercapacitor
CN104681281B (en) With excellent high rate performance combination electrode material and preparation method thereof
CN106653386B (en) Charcoal-carbon/polyaniline super capacitor and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant