EP3607571A1 - Verfahren zur herstellung von elektrochemischen kondensatoren - Google Patents

Verfahren zur herstellung von elektrochemischen kondensatoren

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Publication number
EP3607571A1
EP3607571A1 EP18718602.8A EP18718602A EP3607571A1 EP 3607571 A1 EP3607571 A1 EP 3607571A1 EP 18718602 A EP18718602 A EP 18718602A EP 3607571 A1 EP3607571 A1 EP 3607571A1
Authority
EP
European Patent Office
Prior art keywords
methyl
electrodes
electropolymerization
butyl
group
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.)
Withdrawn
Application number
EP18718602.8A
Other languages
English (en)
French (fr)
Inventor
Jesus Salvador Jaime Ferrer
Thomas Goislard De Monsabert
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.)
Nawatechnologies SA
Original Assignee
Nawatechnologies SA
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Filing date
Publication date
Application filed by Nawatechnologies SA filed Critical Nawatechnologies SA
Publication of EP3607571A1 publication Critical patent/EP3607571A1/de
Withdrawn legal-status Critical Current

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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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • 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
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/80—Gaskets; Sealings
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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

Definitions

  • the invention relates to the field of electrical capacitors, and more particularly that of electrochemical capacitors with double layers. State of the art
  • (Super) double layer electrochemical capacitors have been known for a long time. They are based on a capacitive mechanism: the charges adsorb on an electrode by creating a double electrochemical layer. More specifically, they comprise a negative electrode and a positive electrode, separated by a separator and immersed in an electrolyte. If the electrodes and the separator are all flexible sheets, they can be wound; other geometric shapes exist. The presence of a liquid electrolyte requires a sealed container.
  • a basic presentation of ultracapacitors is given, for example, in Maxwell Technologies® Product Guide BOOSTCAP® Ultracapacitors, published by Maxwell in 2009.
  • WO 03/038846 (Maxwell Technologies) describes a double-layer electrochemical capacitor comprising electrodes manufactured from carbon powder, namely a first layer of conductive carbon powder, in contact with the metal collector, and a second layer of activated carbon in contact with the liquid electrolyte contained in a porous separator. These powders generally contain organic binders.
  • WO 2007/062126 and US 2009/0290288 describe electrodes comprising a mixture of conductive carbon, activated carbon and organic binder.
  • Nanostructured carbon-based materials are being considered, and a detailed discussion is given in the article "Review of nanostructured carbon mateiral for electrochemical capacitor applications: advantages and limitations of activated carbon, carbide-derived carbon, zeolite-templated carbon” , carbon aerogels, carbon nanotubes, carbon monoxide, and graphene by W. Gu and G. Yushin, WIRE Energy Circa 2013, doi: 10.1002 / wene.102.
  • VACNTs vertically aligned carbon nanotubes
  • the preparation of which is described for example in WO 2015/071408 (Commission for Atomic Energy and Alternative Energys) represent a favorable substrate for such coatings; this is described in document EP 2 591 151 (Commission for Atomic Energy and Alternative Energys) and in the thesis "Polythiophene nanocomposites / aligned carbon nanotubes: Elaboration, characterizations and applications to supercapacitors in ionic liquid medium” by Sébastien Lade (University of Cergy-Pontoise, 2010) and the publication "Poly (3-methylthiophene) / Vertically Aligned Multi-walled Carbon Nanotubes: Electrochemical Synthesis, Characterizations and Electrochemical Storage Properties in Lonic Liquids" by S.
  • the problem solved by the present invention is to simplify the process for manufacturing supercapacitors comprising a conductive polymer deposited on a substrate, in particular on a substrate made of carbon-based material, in order to reduce the direct and indirect costs of this process.
  • Figure 1 shows a block diagram of the invention.
  • Figures 2 to 14 illustrate an exemplary embodiment of the invention which is described in detail below.
  • FIG. 3 illustrates the steps of the method using the components of the experimental device shown in FIG. 2.
  • FIGS. 4 to 6 relate to an electrochemical cycling test with a progressive rise in voltage: FIG. 4 shows the capacitance as a function of the applied voltage, FIG. 5 shows the evolution of the capacitance of the last ten cycles between 0 V and 2.5 V, Figure 6 shows a voltammogram of the cell with 10% 3MT monomer in EMITFSI electrolyte diluted in acetonitrile. The scanning speed was 5 mV / s.
  • Figures 7 and 8 relate to an electrochemical cycling test with a direct rise to 2.5 V:
  • Figure 7 shows a voltammogram of the cell with 10% 3MT monomer in EMITFSI electrolyte diluted in acetonitrile. The scanning speed was 5 mV / s.
  • Figure 8 shows the evolution of the capacitance of the last ten cycles between 0 V and 2.5 V.
  • Figure 9 shows a voltammogram of the cell with 10% 3MT monomer in EMITFSI electrolyte diluted in acetonitrile.
  • the scanning speed was 5 mV / s.
  • Curve A was recorded with a progressive rise, curve B with a direct rise.
  • Figure 10 shows a voltammogram of the cell with 10% 3MT monomer in electrolyte EMITFSI diluted in acetonitrile, after polymerization in situ (curve C) and without polymer (curve D).
  • Figures 1 to 14 allow to appreciate the visual appearance of the inside of the bag after the cycling tests:
  • Figure 1 1 shows the inside of the bag after electropolymerization.
  • Figure 12 shows the separator after electropolymerization: on the left the part of the separator that touched the rear face of the positive electrode, at the center the part of the separator taken between the two electrodes, on the right the part of the separator which touched the rear face of the negative electrode.
  • Figure 13 shows the electrodes after electropolymerization, on the right the negative activated carbon, on the left the positive formed VACNT with polymer deposition by electropolymerization.
  • Figure 14 shows a scanning electron micrograph of the positive after cycling.
  • the problem is solved by performing the electroplating of the polymer from the same liquid electrolyte that will be used in the capacitor during its operation.
  • the electrodeposition of the polymer is carried out in the same envelope or enclosure as that in which the capacitor will be encapsulated for its operation.
  • the electrodeposition of the polymer is carried out using the same electrodes as those which will be used for the charging and discharging cycles of the capacitor during its operation.
  • the electrodeposition of the polymer is carried out in the same liquid electrolyte that will be used in the capacitor during its operation.
  • the electrodeposition of the polymer is carried out in the same envelope or enclosure as that in which the final capacitor will be encapsulated, and using the same electrodes as those which will be used for the charging and charging cycles. discharge of the capacitor during its operation.
  • the electroplating of the polymer is carried out after encapsulation of the capacitor.
  • Electropolymerization is performed by applying a current or voltage to said electrodes.
  • the electrodeposition is carried out by means of cycling in voltage and current, and / or in pulsed mode, and / or in galvanostatic mode.
  • a first object of the invention is a method of manufacturing an electrochemical capacitor comprising in a sealed envelope: two electrodes, namely a positive electrode and a negative electrode, a separator separating said positive electrode and said negative electrode, and a liquid electrolyte, in which process a polymer is deposited by electropolymerization on at least one of said electrodes, said electropolymerization being carried out after the introduction of said positive electrode, said negative electrode; and said separator in said envelope.
  • Said sealed envelope may be a flexible or rigid envelope, and is advantageously selected from the group formed by: plastic bags, rigid shells made of polymer, shells made of sheet metal internally coated with an electrically insulating film, ceramic shells , glass hulls.
  • the term "shell” here includes housings and all types of sealed containers.
  • Said liquid electrolyte comprises at least one monomer capable of forming a polymer film by electropolymerization.
  • hermetic sealing of said sealed envelope is carried out before proceeding with the electropolymerization.
  • said positive and / or negative electrodes comprise nanoobjects, preferably selected from the group formed by: nanopowders, elongated nanoobjects, nanofibers, nanotubes, carbon nanotubes (possibly doped with heteroatoms), vertically aligned carbon nanotube mats, graphene, graphene derivatives.
  • the said positive and negative electrodes may comprise a porous material with a high specific surface area, such as activated carbon. More particularly, said positive and negative electrodes may comprise carbon nanotubes or nanofibers, preferably vertically aligned.
  • the polymer film is an electrically conductive polymer. A list of polymers which are particularly suitable for carrying out the invention is given in the description below. Similarly, a list of monomers which are particularly suitable for carrying out the invention is given in the description below.
  • said electrolyte comprises at least one ionic liquid.
  • ionic liquids which are particularly suitable for carrying out the invention is given in the description below.
  • said electrolyte also comprises a solvent.
  • solvents that are particularly suitable for carrying out the invention is given in the description below.
  • said separator is a polypropylene sheet. At least the positive electrode or the negative electrode can be wrapped in said separator sheet.
  • Another subject of the invention is an electrochemical capacitor capable of being obtained by the process according to the invention.
  • polymer embraces copolymers.
  • envelope encompasses enclosures.
  • the method according to the invention comprises the following steps:
  • a positive electrode, a negative electrode, a separator separating the two electrodes, and a liquid electrolyte are supplied.
  • the latter comprises at least one monomer capable of forming, by electropolymerization, a polymer film on one of the two electrodes, as well as an envelope.
  • Said liquid electrolyte comprises an ionic liquid, in which said at least one monomer and / or oligomer is dissolved; the liquid electrolyte may comprise a suitable solvent.
  • the positive electrode may be a VACNT mat
  • the negative electrode may be activated carbon
  • the separator may be a polypropylene membrane
  • the liquid electrolyte may comprise an ionic liquid (such as 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide (abbreviated EMITFSI) or N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide (abbreviated PYRTFSI)), the monomer (such as 3-methylthiophene (abbreviated 3MT)), and as the solvent acetonitrile.
  • EMITFSI 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide
  • PYRTFSI N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide
  • 3MT 3-methylthiophen
  • a second step the electrodes and the separator are positioned in said envelope, the collectors which make the connection between each electrode and its terminal situated outside said envelope are placed in place, said liquid electrolyte is poured into said envelope.
  • a third step is deposited by electropolymerization a polymer film on at least one of the electrodes, for example on the positive electrode. This will be done by applying a sufficient voltage across the device.
  • the electropolymerization can be done in any appropriate manner, especially in galvanostatic mode, pulsed mode or cyclic mode.
  • the device is able to function as an electrochemical capacitor.
  • the envelope must be sealed.
  • said envelope is sealed after the second step and before the third step to obtain a device. It is also possible to seal the envelope after the third step; this possibly makes it possible to modify the composition of the liquid electrolyte, or even to replace it.
  • the method according to the invention can be used for many capacitor systems, defined by the nature of the materials forming the substrates of each of the electrodes, by the nature of the polymer deposited on one and / or the other of these electrodes, and by the ionic liquid.
  • said electrodepositable electrically deposited polymer consists of one or more polymers or copolymers selected from the group consisting of polyfluorenes, polypyrenes, polyazulenes, polynaphthalenes, polypyrroles, polycarbazoles and polyindoles.
  • the substrate advantageously comprises nanoobjects, which can be selected from the group formed by: nanopowders, elongate nanoobjects, nanofibers, nanotubes, carbon nanotubes (possibly doped with heteroatoms), carbon nanotubes vertically aligned, or on a substrate comprising a porous material with a high specific surface area, such as activated carbon.
  • nanoobjects can be selected from the group formed by: nanopowders, elongate nanoobjects, nanofibers, nanotubes, carbon nanotubes (possibly doped with heteroatoms), carbon nanotubes vertically aligned, or on a substrate comprising a porous material with a high specific surface area, such as activated carbon.
  • said at least one monomer is selected from the monomer (s) bearing a double bond and / or an aromatic ring and optionally one or more heteroatoms such as an oxygen atom, a nitrogen atom, a sulfur atom or a fluorine atom, and is preferably selected from the group consisting of: pyrrole and its derivatives, and preferably 3-methylpyrrole, 3-ethylpyrrole, 3-butylpyrrole, 3-bromo pyrrole, 3-methoxypyrrole, 3,4-dichloro pyrrole and 3-methylpyrrole; 4-dipropoxypyrrole;
  • thiophene and its derivatives and preferably 3-thiophene acetic acid, 3,4-ethylene dioxythiophene, 3-methyl thiophene, 3-ethyl thiophene, 3-butyl thiophene, 3-bromo thiophene, 3-methoxy thiophene, 3,4-dichloro thiophene and 3,4-dipropoxy thiophene.
  • said at least one ionic liquid advantageously comprises a cation selected from the group consisting of: 1-ethyl-3-methyl imidazolium, 1-methyl-3-propyl imidazolium, 1-methyl-3-isopropyl imidazolium, 1 butyl-3-methyl imidazolium, 1-ethyl-2,3-dimethyl imidazolium, 1-ethyl-3,4-dimethyl imidazolium, N-propyl pyridinium, N-butyl pyridinium, N-tert-butyl pyridinium, N -tert-butanol-pentyl pyridinium, N-methyl-N-propylpyrrolidinium, N-butyl-N-methylpyrrolidinium, N-methyl-N-pentylpyrrolidinium, N-propoxyethyl-N-methylpyrrolidinium, N-methyl-N-propylpiperidinium
  • said at least one ionic liquid advantageously comprises an anion selected from the group consisting of: fluoride (F “ ), chloride (CI “ ), bromide (Br “ ), iodide (), perchlorate (ClO 4 " ) nitrate (N0 3 “ ), tetrafluoroborate (BF 4 " ), hexafluorophosphate (PF 6 " ), N (CN) 2 “ ; RS0 3 “ , RCOO " (where R is an alkyl or phenyl group, possibly substituted); (CF 3) 2 PF 4 -, (CF 3) 3 PF 3, (CF 3) 4 PF 2 -, (CF 3) 5 PF, (CF 3) 6 P ", (CF 2 S0 3") 2, (CF 2 CF 2 SO 3 -) 2 , (CF 3 S0 2 -) 2 N-, CF 3 CF 2 (CF 3 ) 2 CO-, (CF 3 S0 2 -) 2 CH
  • said at least one ionic liquid comprises at least one cation selected from the group consisting of pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, thiazole, oxazole, triazole, ammonium, pyrrolidine and pyrroline derivatives.
  • said at least one solvent is selected from the group consisting of acetic acid, methanol, ethanol, liquid glycols (especially ethylene glycol and propylene glycol), halogenated alkanes (especially dichloromethane), dimethylformamide (abbreviated DMF), ketones (especially acetone and 2-butanone), acetonitrile, tetrahydrofuran (abbreviated THF), N-methylpyrrolidone (abbreviated NMP), dimethyl sulfoxide (abbreviated as DMSO), propylene carbonate.
  • acetic acid especially ethylene glycol and propylene glycol
  • halogenated alkanes especially dichloromethane
  • DMF dimethylformamide
  • ketones especially acetone and 2-butanone
  • THF tetrahydrofuran
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • FIG. 1 One embodiment of the invention is shown schematically in FIG.
  • the sealed envelope which may be for example a flexible bag or a solid shell
  • an assembly of the positive and negative electrodes separated by a separator is placed.
  • the positive electrode is represented by broken lines in order to distinguish it from the negative electrode represented by a solid line: the choice of a broken line does not mean an electrical discontinuity of the electrode.
  • the liquid electrolyte comprises EMITFSI ionic liquid, acetonitrile solvent and 3MT monomer.
  • the sealed envelope is hermetically encapsulated, electroplating is carried out (for example, 1-V cycling) and a ready-to-use capacitor product is obtained.
  • the process according to the invention has many advantages. It simplifies the assembly of the capacitor: the assembly of the device (including the establishment and the connection of the electrical contacts) is made before the deposition of the polymer, the polymer deposit can take place in the sealed device. Thus, the number of steps is reduced, and in particular the manipulation of the electrodes after the electrodeposition of the polymer is avoided.
  • the method according to the invention also avoids the loss of electrolyte: the electrolyte in which the electroplating process of the polymer takes place can be used directly for the operation of the electrochemical capacitor, it is in fact the same liquid (except that it becomes depleted in monomer during electroplating). No drying of the electrodes is necessary before the assembly of the device, since the electrodes are only wet once put in place in their envelope.
  • the invention has been implemented with an experimental device. To do this, the following components were supplied: a plastic bag as an envelope, two metal strips as collectors, two metal strips as a solder ring, a ternary liquid mixture (comprising a monomer (3MT, at a rate of 10% by volume).
  • the positive electrode has been positioned on the separator, the separator, the negative electrode was placed on the separator, the electrodes were wrapped with the separator, the collectors were welded to the metal strips of the electrodes (the solder rings made it possible to improve the welding between the collector and the electrode and also to stiffen the collector), the collectors were sealed to the bag, the bag was filled with the liquid mixture described above, and the bag was sealed; only the collectors protruded outside the pocket.
  • Two identical bags were prepared in this way.
  • a third bag was prepared in the same manner as the two previous ones, but without monomer in the liquid mixture.
  • FIG. 6 shows the capacitance as a function of the applied voltage
  • Figure 5 shows the evolution of the capacitance of the last ten cycles between 0 V and 2.5 V.
  • FIG. 7 shows the voltammogram. A very strong current is noted at a voltage close to 2.3 V; this peak of tension decreases with the number of cycles.
  • Figure 8 changes the capacitance of the last ten cycles between 0 V and 2.5 V.
  • FIG. 9 compares the two systems after in situ polymerization: curve A represents the electropolymerized sample with a progressive rise in voltage (pocket 1), curve B represents the sample electropolymerized with a direct rise (pocket 2).
  • the capacitances obtained with these two variants are fairly close, but it is observed that the peak of electroactivity is for the conditions of gradual rise to about 0.95 V, while it is at about 1, 1 V in direct rise .
  • FIG. 10 compares the curve B of FIG. 9 with the curve obtained in a control bag, prepared identically to that of the bag 2, but without monomer in the liquid mixture (curve C): it can be seen that without monomer l Electropolymerization does not take place, and the device is not able to function as a capacitor.
  • FIG. 1 1 to 14 allow to appreciate the visual appearance of the inside of the pocket after the cycling tests.
  • Figure 11 shows the inside of the pocket; no degradation is observed.
  • FIG. 12 assembles the separator sheet after electropolymerization: on the left, the part of the separator which has been in contact with the rear face of the positive electrode, in the center the part of the separator taken between the two electrodes, on the right the part of the separator which has been in contact with the back side of the negative electrode.
  • Figure 13 shows the electrodes after electropolymerization, on the right the activated carbon negative electrode, on the left the VACNT positive electrode with polymerization by electropolymerization.
  • Figure 14 shows a scanning electron micrograph of the positive electrode after cycling. The electrolyte after the test, the color disappears which confirms the consumption of the monomer. The absence of coloration after polymerization demonstrates the absence of oligomers.
  • Capacitors have also been made with other solvents (eg propylene carbonate), other monomers and other ionic liquids.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
EP18718602.8A 2017-04-03 2018-04-03 Verfahren zur herstellung von elektrochemischen kondensatoren Withdrawn EP3607571A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1752839A FR3064812B1 (fr) 2017-04-03 2017-04-03 Procede de fabrication de condensateurs electrochimiques
PCT/FR2018/050820 WO2018185419A1 (fr) 2017-04-03 2018-04-03 Procédé de fabrication de condensateurs électrochimiques

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EP3607571A1 true EP3607571A1 (de) 2020-02-12

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US (1) US20210110981A1 (de)
EP (1) EP3607571A1 (de)
JP (1) JP2020513166A (de)
CN (1) CN110998770A (de)
FR (1) FR3064812B1 (de)
WO (1) WO2018185419A1 (de)

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FR3094555B1 (fr) 2019-03-25 2023-08-25 Nawatechnologies Procédé de fabrication de condensateurs électrochimiques
CN110349756A (zh) * 2019-05-21 2019-10-18 浙江工业大学 一种自支撑薄膜及其制备方法
CN114555673B (zh) * 2019-11-14 2024-08-20 松下知识产权经营株式会社 介电组合物、介电膜和电容器
CN112795144A (zh) * 2021-01-29 2021-05-14 森曼泰冷链科技(绍兴)有限公司 含导电聚合物的水分散液及其制备方法
CN117467226B (zh) * 2023-12-28 2024-03-19 上海拜安传感技术有限公司 组合物、传感薄膜、传感器、制备方法及应用

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CN110998770A (zh) 2020-04-10
FR3064812B1 (fr) 2022-06-24

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