WO2024102092A1 - Électrode fournissant une densité d'énergie élevée et un potentiel de fonctionnement élevé, et condensateur comprenant ladite électrode - Google Patents

Électrode fournissant une densité d'énergie élevée et un potentiel de fonctionnement élevé, et condensateur comprenant ladite électrode Download PDF

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Publication number
WO2024102092A1
WO2024102092A1 PCT/TR2022/051577 TR2022051577W WO2024102092A1 WO 2024102092 A1 WO2024102092 A1 WO 2024102092A1 TR 2022051577 W TR2022051577 W TR 2022051577W WO 2024102092 A1 WO2024102092 A1 WO 2024102092A1
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WO
WIPO (PCT)
Prior art keywords
electrode
supercapacitor
thiosemicarbazone
carbon
present
Prior art date
Application number
PCT/TR2022/051577
Other languages
English (en)
Inventor
Tulay BAL DEMIRCI
Sibel YAZAR AYDOGAN
Elif AVCU ALTIPARMAK
Original Assignee
Istanbul Universitesi-Cerrahpasa Rektorlugu
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
Priority claimed from TR2022/016990 external-priority patent/TR2022016990A2/tr
Application filed by Istanbul Universitesi-Cerrahpasa Rektorlugu filed Critical Istanbul Universitesi-Cerrahpasa Rektorlugu
Publication of WO2024102092A1 publication Critical patent/WO2024102092A1/fr

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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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01G11/46—Metal oxides
    • 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
    • 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 present invention relates to an electrode with a high energy density suitable for use with supercapacitors, a supercapacitor with high energy storage values, comprising said electrodes, and the usage areas of said supercapacitors.
  • a supercapacitor also known in the art as a double-layer capacitor or ultracapacitor, consists of electrodes, each coated with activated carbon.
  • a special separator is used in the supercapacitor instead of the dielectric material used in conventional capacitors.
  • the separator is an ion-permeable membrane, such as graphene, that insulates and exchanges electrolyte ions between electrodes.
  • Supercapacitors have a high capacity and can charge very quickly. This allows supercapacitors to be used as a battery. Supercapacitors can store more charge than normal capacitors and provide energy much faster than a battery. Supercapacitors have high energy storage capacity and long life cycles. Supercapacitors have a very high charging and discharging speed and can provide high load currents.
  • Supercapacitor electrodes usually consist of electrically conductive metallic current collectors with thin coatings applied. It is expected that the electrodes will have high corrosion resistance, long-term stability, high conductivity, environmental friendliness and low cost.
  • the amount stored per unit voltage of a supercapacitor is predominantly a function of electrode surface area.
  • supercapacitor electrodes are generally preferred to be porous, spongy materials with high specific surface area.
  • the most commonly used materials in the art as electrodes are activated carbon, carbon fiber cloth, carbide sourced carbon, foamed carbon, graphite, graphene or carbon nanotubes.
  • Lithium-ion batteries which play an important role in energy storage, are widely used today. Lithium-ion batteries are used in many areas such as laptop computers, mobile phones, portable electronic devices, wearable technologies. However, due to the insufficient and expensive lithium sources, the creation of an energy storage unit obtained at a cheaper cost without using a lithium-ion battery is one of the biggest advantages of this study.
  • the present invention relates to an electrode suitable for use in supercapacitors.
  • the present invention also relates to a supercapacitor comprising said electrode as an element.
  • the object of the present invention is to provide an electrode with high operating potentials and a super capacitor comprising said electrode as an element, with the arrangement it contains.
  • An object of the present invention is to provide an electrode with high energy density values and a supercapacitor comprising said electrode as an element, with the arrangement it contains.
  • An object of the present invention is to provide an electrode with high energy density values and a supercapacitor comprising said electrode as an element, with the arrangement it contains.
  • An object of the present invention is to provide an electrode that provides high performance with low production costs and a supercapacitor that comprises said electrode as an element.
  • An object of the present invention is to provide an electrode with bioactive and flexible properties, suitable for use in high technology industries such as wearable technology, and a supercapacitor comprising said electrode as an element.
  • the subject of the invention relates to an electrode providing high energy density suitable for use in super capacitors, and it is only explained with examples that will not constitute any limiting effect on a better understanding of the subject.
  • supercapacitor in the invention, it is meant a device used to store energy.
  • Supercapacitors are capable of storing energy at a value of 10 to 100 times per unit mass or volume than capacitors known in the art.
  • Supercapacitors mainly contain electrodes, electrolyte and separator elements. Combinations and arrangements among these elements contribute to the energy storage properties of the final product supercapacitors. For this reason, experts in the art are working on innovations, researches, and developments on these elements in order to obtain super capacitors with the highest energy storage values.
  • electrode in the present invention, it is meant the conductor to which electric currents can lead.
  • electrodes are one of the essential elements of batteries, capacitors, and supercapacitors.
  • electroactive polymer in the present invention, it is meant a medium that is electrically conductive and does not transmit electrons by means of the movement of the ions within it.
  • separatator in the present invention, it is meant a permeable membrane that provides insulation and exchange of electrolyte ions between electrodes.
  • high operating potential values in the present invention, it is meant capacitors with an operating potential of at least 1 .5 V.
  • high energy density values in the present invention, it is meant capacitors with energy density values of at least 315.5 Wh/kg.
  • the present invention mainly concerns the construction of a supercapacitor assembly. If preferred in the present invention, more than one supercapacitor can be combined to obtain a high energy storage device.
  • unit cell, unit electrode, and unit supercapacitors are mentioned in the present invention, those skilled in the art know that these units can be combined to achieve higher performance.
  • the supercapacitor referred to in the present invention is shown representatively in Figure 1 . According to Figure 1 , the unit comprises the supercapacitor, at least one electrode, a separator, and at least one electrolyte.
  • the supercapacitor of the present invention preferably comprises more than one electrode. Accordingly, the supercapacitor of the present invention comprisesat least one working electrode.
  • the working electrode should be obtained from materials suitable for use as an element in supercapacitors. Accordingly, the working electrode comprises at least one of the material group of activated carbon, carbon felt, graphene, graphene oxide, carbon fiber cloth, carbide sourced carbon, foam carbon material, graphite, graphene, or carbon nanotubes as raw material. If preferred the working electrode may be a composite material comprising at least two selected from the group of activated carbon, carbon fiber cloth, carbide-derived carbon, foamed carbon material, graphite, graphene, graphene oxide, carbon nanotubes material group.
  • the innovative aspect of the present invention is the realization of research and development activities on the working electrode; and said working electrodes are modified with at least one conductive polymer and/or thiosemicarbazone.
  • Polypyrrole compound is preferably used as a conductive polymer in the present invention.
  • pyrrole in the present invention is meant a compound with the formula C4H4NH. Pyrrole has a ring structure containing conjugated IT bonds. Each atom contains an unhybridized p orbital. Non-bonding electrons in nitrogen are delocalized. The formula is shown as 1 .
  • polypyrrole an organic polymer obtained by oxidative polymerization of pyrrole. It is a solid with the formula H(C4H2NH)nH. It is a conductive polymer. The formula is shown as 2.
  • Thiosemicarbazones are generally produced by the condensation reaction of a thiosemicarbazide with an aldehyde or ketone (Formula 3).
  • SH and NH2 groups in the structure are functionalized with aromatic or aliphatic hydrocarbons or aromatic or aliphatic hydrocarbons containing heteroatoms.
  • thiosemicarbazone in the present invention, the it is meant the structures in Formula 4.
  • the metal complex formed by 5-bromo salicylaldehyde-S-methyl thiosemicarbazone iron(lll) chloride salt was used.
  • R, R 1 , R 2 , R 3 , R 4 H, aromatic, aliphatic, cyclic, alicyclic, hydrocarbons, aromatic, aliphatic, cyclic, alicyclic hydrocarbons containing heteroatoms.
  • the present invention relates to a working electrode modified with polypyrrole and/or thiosemicarbazone compounds suitable for use in supercapacitors.
  • modified herein refers to the coating of said compounds on the electrodes to improve the working performance of the working electrodes.
  • the working electrode of the invention preferably comprises both polypyrrole and thiosemicarbazone compounds.
  • the presence of the polypyrrole compound in the working electrode in the present invention increases the electron transfer when it comes into contact with the electrolyte, and the supercapacitor provides high voltage and current density in the electrode structure.
  • the inclusion of the thiosemicarbazone complex at the working electrode in the present invention provided its high energy storage capacity and long cycle function. This function is realized through the proton and electron donating groups in the molecule. There are intermolecular physical and chemical interactions between this complex and the electrode.
  • the working electrode of the present invention also comprises ferric chloride (expressed as FeCta) compound to provide performance.
  • FeCta ferric chloride
  • the presence of FeCta compound on the working electrode accelerates the polymerization, acts as a catalyst, and ensures the polymerization to be performed.
  • a possible embodiment of the present invention comprises at least one working electrode within the supercapacitor; and said working electrode comprises at least one of the active carbon, carbon fiber cloth, carbide sourced carbon, foam carbon, graphite, carbon felt, graphene oxide, graphene or carbon nanotubes material group as raw material.
  • the innovative aspect of the present invention is that the working electrode obtained from these raw materials is modified with polypyrrole polymer material.
  • a possible embodiment of the present invention comprises at least one working electrode within the supercapacitor; and said working electrode comprises at least one of the active carbon, carbon fiber cloth, carbide sourced carbon, foam carbon, graphite, graphene, carbon felt, graphene oxide, graphene or carbon nanotubes material group as raw material.
  • the innovative aspect of the present invention is that the working electrode obtained from these raw materials is modified with a thiosemicarbazone compound.
  • a possible embodiment of the present invention comprises at least one working electrode within the supercapacitor; and said working electrode comprises at least one of the active carbon, carbon fiber cloth, carbide sourced carbon, foam carbon, graphite, graphene, carbon felt, graphene oxide, graphene or carbon nanotubes material group as raw material.
  • the innovative aspect of the present invention is that the working electrode obtained from these raw materials is modified with FeCta compound.
  • a possible embodiment of the present invention comprises at least one working electrode within the supercapacitor; and said working electrode comprises at least one of the active carbon, carbon fiber cloth, carbide sourced carbon, foam carbon, graphite, graphene, carbon felt, graphene oxide, graphene or carbon nanotubes material group as raw material.
  • the innovative aspect of the present invention is that the working electrode obtained from these raw materials is modified with polypyrrole and thiosemicarbazone compound.
  • a possible embodiment of the present invention comprises at least one working electrode within the supercapacitor; and said working electrode comprises at least one of the active carbon, carbon fiber cloth, carbide sourced carbon, foam carbon, graphite, graphene, carbon felt, graphene oxide, graphene or carbon nanotubes material group as raw material.
  • the innovative aspect of the present invention is that the working electrode obtained from these raw materials is modified with polypyrrole, thiosemicarbazone and FeCta compound.
  • the most possible embodiment of the present invention comprises at least one working electrode within the supercapacitor; and said working electrode comprises at least one of the active carbon, carbon fiber cloth, carbide sourced carbon, foam carbon, graphite, graphene, carbon felt, graphene oxide, graphene or carbon nanotubes material group as raw material.
  • the innovative aspect of the present invention is that the working electrode obtained from these raw materials is modified with polypyrrole, FeCta and thiosemicarbazone complex compound.
  • the working electrode of the present invention is modified with a mixture obtained with polypyrrole, FeCta compound and thiosemicarbazone molecule.
  • the inventors carry out the modification processes by high temperature solvothermal method in ethanol/distilled water environment by using working electrode Pyrrole monomer, FeCta metal salt and thiosemicarbazone molecule.
  • a person skilled in the art can perform modification processes by applying different methods, therefore, the scope of protection of the present invention is not narrowed by the modification methods.
  • the innovative aspect of the invention is to modify the working electrode with the compounds, materials or salts shared here, and improve the electrochemical properties.
  • the present invention also relates to a supercapacitor comprising the characterized working electrode.
  • the supercapacitor of the present invention comprises at least one separator.
  • Said separator glass, paper, ceramic, and polymeric membranes may comprise at least one of the material group.
  • filter paper is used as separator.
  • the supercapacitor of the present invention comprises at least one electrolyte.
  • Phosphoric acid, sodium chloride, potassium chloride, sulfuric acid, and deionized water solution may be used as said electrolyte.
  • At least one acid compound is preferably used as the electrolyte in the present invention.
  • sulfuric acid is used as the electrolyte.
  • the supercapacitor of the present invention comprises at least one counter electrode.
  • Counter electrodes known in the art can also be used in the present invention.
  • the scope of protection of the present invention is not limited to the characteristics of the counter electrode.
  • Counter electrodes, preferably obtained from compounds such as platinum and/or graphite, can be used as elements.
  • the inventors have determined that supercapacitors with a working potential of 1.8 V and above can be obtained with the arrangements made on the working electrode.
  • the inventors have determined that a supercapacitor can be obtained with operating performance even after 10000 cycles with the arrangements made in the working electrode.
  • the inventors have determined that a supercapacitor with a power density of around 1800 W/kg at a current density of 2.0 A/g and 9000 W/kg at a current density of 10.0 A/g can be obtained with the arrangements made in the working electrode.
  • the inventors have determined that a super capacitor with an energy density of around 315.5 Wh/kg and above can be obtained with the arrangements made in the working electrode.
  • the expressions around and about mean 50 values down or lower or higher or higher from the given power density, cycle, and energy density values.
  • the working electrode which is the subject of the present invention, comprises compounds that are easy to synthesize and have high yields, suitable for use in modification processes. For this reason, it is possible to obtain a working electrode with low costs but high working performance.
  • Thiosemicarbazone compounds used as modifying compounds in the invention are bioactive compounds as known in the art; and has antiviral, antibacterial, antifungal, antioxidant, antitumor and antidiabetic properties. With this feature, it is predicted that supercapacitors comprising working electrodes modified with thiosemicarbazone compound can be used in high technology branches such as wearable technology.
  • Super capacitor with this arrangement comprises a carbon felt electrode modified with polypyrrole, thiosemicarbazone and FeCI3 compound as the working electrode; graphite sheet as second electrode; 1 M sulfuric acid solution as electrolyte, and ordinary filter paper as separator.
  • the energy-power density Ragone graph of the super capacitor is shared.
  • the highest energy density value that the supercapacitor can offer is 315.5 Wh/kg at 2.0 A/g current density
  • the highest power density value is 9000.0 W/kg at 10.0 A/g current density.
  • Table 2 Working potential, capacitance percentage-cycle life, energy density, power density values of the super capacitor of the present invention.
  • Table 1 provides the working potential, capacitance percentage-cycle life, energy density, and power density values of the super capacitors known in the art, and Table 2 provides same values of the super capacitor of the present invention.
  • Table 1 the biggest problem of supercapacitors in the technical field is that they cannot be used in applications requiring high energy density due to their low energy density. It is observed that supercapacitors with a single unit cell have a working potential below the 1 .8 V working potential.

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

Abstract

La présente invention concerne une électrode, qui a un potentiel de fonctionnement élevé, une durée de vie de cycle élevée, des valeurs élevées de densité d'énergie appropriés pour une utilisation dans des supercondensateurs, et qui a été modifiée avec l'un de ses composés à base de thiosemicarbazone et au moins un polymère conducteur.
PCT/TR2022/051577 2022-11-10 2022-12-23 Électrode fournissant une densité d'énergie élevée et un potentiel de fonctionnement élevé, et condensateur comprenant ladite électrode WO2024102092A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022/016990 TR2022016990A2 (tr) 2022-11-10 YÜKSEK ENERJİ YOĞUNLUĞU ve ÇALIŞMA POTANSİYELİ SAĞLAYAN BİR ELEKTROT, SÖZ KONUSU ELEKTROTU İÇEREN BİR SÜPER KAPASİTÖR
TR2022016990 2022-11-10

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WO2024102092A1 true WO2024102092A1 (fr) 2024-05-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108529619A (zh) * 2018-05-21 2018-09-14 桂林电子科技大学 一种氮硫共掺杂多孔碳材料及其制备方法和应用
CN109192534A (zh) * 2018-11-01 2019-01-11 广东粤迪厚创科技发展有限公司 一种超级电容器新型电极材料及超级电容器
CN109326453A (zh) * 2018-09-10 2019-02-12 中原工学院 一种基于静电纺纳米纤维成纱技术的聚吡咯超级电容器复合电极材料及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108529619A (zh) * 2018-05-21 2018-09-14 桂林电子科技大学 一种氮硫共掺杂多孔碳材料及其制备方法和应用
CN109326453A (zh) * 2018-09-10 2019-02-12 中原工学院 一种基于静电纺纳米纤维成纱技术的聚吡咯超级电容器复合电极材料及其制备方法
CN109192534A (zh) * 2018-11-01 2019-01-11 广东粤迪厚创科技发展有限公司 一种超级电容器新型电极材料及超级电容器

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