WO2009113585A1 - Film pour élément électrochimique, électrode pour élément électrochimique et batterie - Google Patents

Film pour élément électrochimique, électrode pour élément électrochimique et batterie Download PDF

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Publication number
WO2009113585A1
WO2009113585A1 PCT/JP2009/054683 JP2009054683W WO2009113585A1 WO 2009113585 A1 WO2009113585 A1 WO 2009113585A1 JP 2009054683 W JP2009054683 W JP 2009054683W WO 2009113585 A1 WO2009113585 A1 WO 2009113585A1
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Prior art keywords
film
polyimide
electrode
electrochemical element
polyamic acid
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PCT/JP2009/054683
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English (en)
Japanese (ja)
Inventor
西出　宏之
研一 小柳津
源成 崔
彰彦 八手又
Original Assignee
学校法人 早稲田大学
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Priority to JP2010502855A priority Critical patent/JPWO2009113585A1/ja
Publication of WO2009113585A1 publication Critical patent/WO2009113585A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a film for an electrochemical element, an electrode for an electrochemical element, and a battery using a polyimide having redox activity.
  • Polyimide is the highest in terms of heat resistance as an engineering plastic and is widely used in all industrial fields. To date, many types of polyimide have been developed and commercialized.
  • a typical method for synthesizing polyimide is a two-step synthesis method (diamine method via polyamic acid) in which a ring-opening polyaddition-dehydration cyclization reaction of diamine and tetracarboxylic dianhydride is performed.
  • the reaction in the first stage proceeds by stirring the two monomers in an amide solvent such as dimethylacetamide at room temperature, and a high molecular weight polyamic acid is easily generated.
  • polyimides are insoluble and infusible, they are molded into a film or the like in the form of a polyamic acid that is a soluble precursor, and then heated to around 250 ° C. to form a thermal imide by a dehydration cyclization reaction corresponding to the second stage. And converting to polyimide.
  • Polyimide is in demand as an interlayer insulating film and protective film for integrated circuits and mounting substrates as an insulating film for electronic materials due to its high heat resistance and lower dielectric constant than ceramics.
  • Various photosensitive polyimides have been reported for the purpose of drawing polyimide films.
  • the formation of charge transfer complexes based on the strong electron accepting property of the imide skeleton has been investigated, and it has been studied as a material exhibiting photoconductivity.
  • optical materials based on a large third-order nonlinear susceptibility, and separation membrane materials based on heat resistance and solvent resistance are being studied.
  • polyimide is generally accepted as an insulating material, no oxidation-reduction reaction has been investigated, and there are no examples of investigation as a charge storage material.
  • phthalimide exhibits electrochemically reversible oxidation-reduction with an anion radical which is a one-electron reductant. That is, when phthalimide is represented by Im, the redox reaction represented by the following formula (1) occurs at a base potential in the vicinity of ⁇ 1 to ⁇ 1.5 V vs Ag / AgCl, and the chemical stability is high with Im ⁇ . It is clear from the ESR spectrum and the like.
  • an object of the present invention is to provide a film for an electrochemical device using a novel polyimide film exhibiting an electrochemically reversible oxidation-reduction reaction.
  • the film for an electrochemical element of the present invention is characterized in that the surface roughness is made of polyamide having an RMS value of 10 ⁇ m or more.
  • polyimide is characterized by dehydrating and cyclizing polyamic acid.
  • the polyimide is obtained by dehydrating and cyclizing the polyamic acid after dispersing a conductivity-imparting agent in the polyamic acid.
  • the polyimide is formed by dehydrating and cyclizing the polyamic acid after forming a film by dispersing a conductivity-imparting agent in the polyamic acid.
  • the conductivity-imparting agent is any one of carbon black, carbon fiber, acetylene black, carbon nanotube, and fullerene.
  • the polyamic acid is obtained by ring-opening polyaddition of tetracarboxylic dianhydride and diamine.
  • the tetracarboxylic dianhydride is any of 4,4′-oxydiphthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride, To do.
  • the diamine is any one of 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-oxydianiline, 4,4′-methylenedianiline, ethylenediamine, and propylenediamine.
  • the electrode for an electrochemical device of the present invention comprises a current collector having electronic conductivity and a polyimide adhered to at least one surface of the current collector, and the polyimide is a film for an electrochemical device of the present invention.
  • the battery of the present invention is characterized in that the negative electrode is the electrode for an electrochemical element of the present invention.
  • a novel electrochemical element film using a polyimide film exhibiting an electrochemically reversible oxidation-reduction reaction can be provided.
  • Example 1 It is the schematic which shows the whole battery structure in one Example of the battery of this invention.
  • the electrode produced in Example 1 it is a graph showing the measurement result of the electrical potential difference with a reference electrode at the time of changing the amount of charging / discharging.
  • the electrode produced in Example 2 it is a graph showing the measurement result of the electrical potential difference with a reference electrode at the time of changing the amount of charging / discharging.
  • the battery produced in Example 3 it is a graph showing the measurement result of the voltage at the time of changing charge / discharge amount.
  • 6 is a SEM image of a polyimide film surface in Example 4.
  • the film for an electrochemical element of the present invention is made of polyimide having a surface roughness of RMS value of 10 ⁇ m or more.
  • the RMS value is a mean square root of surface roughness (Root Mean Square) and can be measured by an atomic force microscope (AFM), a scanning tunneling microscope (STM), or the like.
  • AFM atomic force microscope
  • STM scanning tunneling microscope
  • the film for electrochemical elements of this invention has a function which can take in / out an electric charge only with a polyimide. That is, the film for an electrochemical element of the present invention has redox activity and exhibits an electrochemically reversible oxidation-reduction reaction without adding an additive such as a conductivity-imparting agent. This is due to the fact that the surface area of the polyimide is increased by setting the surface roughness of the polyimide to an RMS value of 10 ⁇ m or more. By increasing the surface area of the polyimide, the performance of the electrochemical device film can be improved. In order to increase the surface roughness of the polyimide, for example, the surface of the polyimide may be scraped with a sandpaper or the like.
  • the polyimide used for the film for an electrochemical element of the present invention can be easily obtained by a method of converting polyamic acid to polyimide by dehydration cyclization, that is, thermal imidization.
  • the polyamic acid those synthesized by various methods can be used.
  • the polyamic acid can be obtained by ring-opening polyaddition of tetracarboxylic dianhydride and diamine.
  • 4,4'-oxydiphthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and the like are preferably used as the tetracarboxylic dianhydride.
  • 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-oxydianiline, 4,4′-methylenedianiline, ethylenediamine, propylenediamine, and the like are preferably used.
  • the film for an electrochemical element of the present invention uses a polyimide imparted with redox activity by increasing the surface area, and further, in order to increase the surface area of the polyimide, a conductive agent may be dispersed in the polyimide.
  • a polyimide in which the conductivity-imparting agent is dispersed can be obtained by dispersing the conductivity-imparting agent in the polyamic acid and then dehydrating and cyclizing the polyamic acid.
  • a polyimide in which the conductivity-imparting agent is dispersed may be obtained by forming a film by dispersing the conductivity-imparting agent in the polyamic acid and then dehydrating and cyclizing the polyamic acid.
  • the conductivity-imparting agent is not limited to a specific one as long as it has affinity for polyamic acid and can be easily dispersed in polyamic acid, but carbon black, carbon fiber, acetylene black, carbon nanotube, fullerene Etc. are preferably used.
  • the polyimide constituting the electrochemical device film of the present invention is represented by the general formula of Chemical Formula 2 or Chemical Formula 3.
  • R1 to R3 are aromatic groups such as 1,4-phenylene groups and 1,3-phenylene groups, and aliphatic chains such as alkylene groups and alkyl ethers.
  • the polymer skeleton may be cross-linked at R1 to R3.
  • the use of a crosslinked structure is preferable because it prevents elution into a solvent when used as an electrode and has high durability. However, if it does not elute only by swelling in a solvent, it has a crosslinked structure. It does not have to be.
  • the imide group may contain in the bridge
  • the imide group phthalimide, pyromellitic imide, and the like are preferable because they exhibit electrochemically reversible redox characteristics.
  • the electrode for an electrochemical element of the present invention is formed by adhering a polyimide film made of the polyimide of the present invention to at least one surface of a current collector having electrical conductivity.
  • the electrode substrate as a current collector in contact with the polyimide is not limited to a specific one, but is a metal substrate such as platinum, gold, iron, stainless steel, or glassy carbon, pyrolytic graphite, carbon felt.
  • a transparent substrate such as a carbon substrate such as ITO vapor-deposited glass or ITO-coated polyethylene terephthalate can be used.
  • the polyimide electrode may be a composite electrode in which the material of the electrode substrate described above is dispersed in the polyimide film of the present invention.
  • the battery of the present invention uses the negative electrode as the electrode for an electrochemical element of the present invention. That is, the battery of the present invention includes a polyimide film constituting the electrode for an electrochemical element of the present invention as an electrode active material.
  • the film for an electrochemical device of the present invention serves as a charge storage material that is a material having the ability to store charges.
  • a battery is formed by sandwiching an electrolyte between the positive electrode and the negative electrode.
  • the active material constituting the electrode paired with the electrochemical device electrode of the present invention is not limited to a specific material, but the negative electrode is the electrochemical device electrode of the present invention and the positive electrode is 2, 2, 6
  • a battery having particularly excellent characteristics is formed by using an electrode having a radical polymer having a, 6-tetramethylpiperidine-1-oxyl (TEMPO) group in the side chain as an electrode active material.
  • TEMPO 6-tetramethylpiperidine-1-oxyl
  • the battery of the present invention operates as a negative electrode of a chargeable / dischargeable secondary battery. That is, an output voltage corresponding to the difference between the oxidation-reduction potential of the electrode active material used on the positive electrode side and the oxidation-reduction potential of Equation (1) on the negative electrode side is generated.
  • the imide is generally ⁇ 1 to ⁇ 1.5 V vs. Since it is oxidized and reduced at a base potential of Ag / AgCl or lower, an organic secondary battery having a large output voltage can be configured by combining with an appropriate positive electrode active material.
  • a radical polymer electrode having a TEMPO group is +0.5 V vs. Since oxidation / reduction can be performed at a noble potential of Ag / AgCl or higher, if a battery is configured by sandwiching an electrolyte solution or an electrolyte membrane with an electrode for an electrochemical element made of polyimide as a negative electrode and a radical polymer electrode as a positive electrode, the voltage is around 2V.
  • a novel organic secondary battery that can be repeatedly charged and discharged by voltage, and can be charged and discharged at high speed because both the radical polymer and polyimide have large electrode reaction rate constants. Can be configured.
  • reference numeral 1 denotes a pair of aluminum casings constituting the outer shell of the battery.
  • the aluminum casing 1 there are an insulating packing 2, a negative electrode current collector 3, a negative electrode 4, and a separator 5.
  • the positive electrode 6 and the positive electrode current collector 7 are accommodated in this order.
  • the electrode for an electrochemical element of the present invention is used for the negative electrode 4.
  • the obtained polyimide electrode was immersed in an electrolytic solution, and the electrolytic solution was infiltrated into voids in the electrode.
  • As the electrolytic solution a 0.1 mol / l tetrabutylammonium perchlorate acetonitrile solution was used.
  • a half-cell was prepared using a platinum electrode as the counter electrode and an Ag / AgCl electrode as the reference electrode.
  • the half-cell produced as described above was charged at a constant current of 200 ⁇ A until the voltage became ⁇ 1.8 V, and then discharged at 200 ⁇ A.
  • the voltage became substantially constant for about 100 seconds around ⁇ 1.4 V, and then dropped rapidly.
  • the polyimide electrode of this example was operating as a charge storage material.
  • charging was performed again, and charging and discharging were repeated 100 times in the range of -0.8 to -1.8 V.
  • the obtained polyimide electrode was immersed in an electrolytic solution, and the electrolytic solution was infiltrated into voids in the electrode.
  • As the electrolytic solution a 0.1 mol / l tetrabutylammonium perchlorate acetonitrile solution was used.
  • a half-cell was prepared using a platinum electrode as the counter electrode and an Ag / AgCl electrode as the reference electrode.
  • the half-cell produced as described above was charged at a constant current of 200 ⁇ A until the voltage became ⁇ 1.8 V, and then discharged at 200 ⁇ A. As a result, as shown in FIG. 3, the voltage became almost constant for 60 seconds around ⁇ 1.4 V, and then dropped rapidly. Thus, it was confirmed that the polyimide electrode of this example was operating as a charge storage material. When the voltage dropped to -0.8V, charging was performed again, and charging / discharging was repeated 10 times in the range of -0.8 to -1.8V.
  • a substrate on which an ITO layer (150 nm) was previously formed on a glass substrate was placed on a spin coater.
  • a 5 wt% solution of polyamic acid dissolved in N, N-dimethylacetamide was spin-coated for 10 seconds at a rotation speed of 1000 rotations / second, and then for 60 seconds at 6000 rotations / second, and then 150 ° C., 180 ° C., 200 ° C.
  • a polymer thin film was obtained by heating stepwise at 20 ° C. and 220 ° C. for 20 minutes and at 250 ° C. for 30 minutes, respectively. Scraping over 30 seconds by the reciprocating motion at a speed of 1 cm / s while applying a uniform pressure of 100 g / cm 2 by using a sandpaper of # 240 the thin film to obtain a film having an increased surface roughness.
  • An electrochromic cell using a polythiophene layer as a working electrode and a polyimide layer as a counter electrode was produced. Between the electrodes, 0.5 mm silicon rubber was used as a spacer, and an electrolyte solution in which poly (ethylene glycol), KPF 6 , and propylene carbonate were mixed at a weight ratio of 5: 20: 100 was injected.
  • a substrate on which an ITO layer (150 nm) was previously formed on a glass substrate was placed on a spin coater.
  • a 5 wt% solution of polyamic acid dissolved in N, N-dimethylacetamide was spin coated at 1000 rpm for 10 seconds, followed by 6000 rpm for 60 seconds, then 150 ° C., 180 ° C., 200 ° C.
  • a polymer thin film was obtained by heating stepwise at 20 ° C. and 220 ° C. for 20 minutes and at 250 ° C. for 30 minutes, respectively. The thin film was scraped with sandpaper to obtain a film with increased surface roughness.
  • the substrate on which the ITO / polyimide structure was formed as described above was placed on the substrate holder in the chamber of the vacuum evaporator.
  • a filament wound with Al was attached to the electrode in the chamber.
  • reducing the pressure in the chamber at a vacuum degree of 1 ⁇ 3 ⁇ 10? 5 Pa range, deposition rate 5 ⁇ 7 ⁇ / sec, was deposited with aluminum as a cathode.
  • the inside of the chamber was returned to atmospheric pressure, and the substrate was taken out.
  • a memory element having an ITO / polyimide / Al structure was fabricated on a glass substrate.
  • the electrical conductivity changed rapidly at a predetermined threshold voltage. The behavior was observed repeatedly and stably. In the state holding force test, the ON and OFF states were stably held several hundred times or more.
  • FIG. 5 shows an SEM image of the surface of the polyimide film in which the surface roughness is increased by the above method and becomes redox active.
  • the surface roughness parameter worked as an effective redox active layer when the roughness factor was 10 ⁇ m or more in RMS value.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention porte sur un film pour élément électrochimique, un nouveau film polyimide, qui a subi une réaction d'oxydation/ réduction réversible de façon électrochimique, étant utilisé. Le film comporte du polyamide ayant une rugosité de surface d'au moins 10 µm en tant que valeur moyenne quadratique (RMS). Le polyimide est obtenu en soumettant l'acide polyamide à une cyclodéshydratation. Le polyimide peut être obtenu par cyclodéshydratation à partir de l'acide polyamide après qu'un agent pour conférer une conductivité a été dispersé dedans, ou par cyclodéshydratation de l'acide polyamide après qu'un agent pour conférer une conductivité a été dispersé dedans et après fabrication du film.
PCT/JP2009/054683 2008-03-11 2009-03-11 Film pour élément électrochimique, électrode pour élément électrochimique et batterie WO2009113585A1 (fr)

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JP2010502855A JPWO2009113585A1 (ja) 2008-03-11 2009-03-11 電気化学素子用膜、電気化学素子用電極及び電池

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JP2008060911 2008-03-11
JP2008-060911 2008-03-11

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Cited By (9)

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WO2011040308A1 (fr) * 2009-09-30 2011-04-07 宇部興産株式会社 Composition de résine liante pour électrode, pâte de mélange d'électrode, et électrode
JP2011086480A (ja) * 2009-10-15 2011-04-28 Toray Ind Inc リチウムイオン電池電極用バインダー、それを用いたリチウムイオン電池電極用ペーストおよびリチウムイオン電池電極の製造方法
WO2012057302A1 (fr) * 2010-10-28 2012-05-03 株式会社カネカ Procédé de production de film de polyimide électriquement conducteur
JP2014078416A (ja) * 2012-10-11 2014-05-01 Ube Ind Ltd 電極用バインダー樹脂組成物、電極合剤ペースト、及び電極
WO2015003725A1 (fr) 2013-07-09 2015-01-15 Friedrich-Schiller-Universität Jena Polymères électroactifs, procédé de fabrication correspondant, électrode et utilisation correspondantes
WO2017047778A1 (fr) * 2015-09-17 2017-03-23 日本電気株式会社 Composition de résine
CN108976793A (zh) * 2018-08-07 2018-12-11 江苏亚宝绝缘材料股份有限公司 一种预警微裂纹的透明聚酰亚胺薄膜及其制备方法
JP2022525751A (ja) * 2019-03-14 2022-05-19 エボニック オペレーションズ ゲーエムベーハー 成形された有機電荷蓄積装置の製造方法
WO2022153357A1 (fr) * 2021-01-12 2022-07-21 日本電信電話株式会社 Batterie secondaire au lithium et son procédé de production

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JP2006324179A (ja) * 2005-05-20 2006-11-30 Matsushita Electric Ind Co Ltd 電極およびそれを用いた電気化学素子
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JP2006324179A (ja) * 2005-05-20 2006-11-30 Matsushita Electric Ind Co Ltd 電極およびそれを用いた電気化学素子
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040308A1 (fr) * 2009-09-30 2011-04-07 宇部興産株式会社 Composition de résine liante pour électrode, pâte de mélange d'électrode, et électrode
US9418772B2 (en) 2009-09-30 2016-08-16 Ube Industries, Ltd. Binder resin composition for electrode, electrode mixture paste, and electrode
JP2011086480A (ja) * 2009-10-15 2011-04-28 Toray Ind Inc リチウムイオン電池電極用バインダー、それを用いたリチウムイオン電池電極用ペーストおよびリチウムイオン電池電極の製造方法
CN103180390A (zh) * 2010-10-28 2013-06-26 株式会社钟化 导电性聚酰亚胺膜的制造方法
WO2012057302A1 (fr) * 2010-10-28 2012-05-03 株式会社カネカ Procédé de production de film de polyimide électriquement conducteur
JP2014078416A (ja) * 2012-10-11 2014-05-01 Ube Ind Ltd 電極用バインダー樹脂組成物、電極合剤ペースト、及び電極
WO2015003725A1 (fr) 2013-07-09 2015-01-15 Friedrich-Schiller-Universität Jena Polymères électroactifs, procédé de fabrication correspondant, électrode et utilisation correspondantes
US10103384B2 (en) 2013-07-09 2018-10-16 Evonik Degussa Gmbh Electroactive polymers, manufacturing process thereof, electrode and use thereof
WO2017047778A1 (fr) * 2015-09-17 2017-03-23 日本電気株式会社 Composition de résine
US11404694B2 (en) 2015-09-17 2022-08-02 Nec Corporation Resin composition
CN108976793A (zh) * 2018-08-07 2018-12-11 江苏亚宝绝缘材料股份有限公司 一种预警微裂纹的透明聚酰亚胺薄膜及其制备方法
WO2020029392A1 (fr) * 2018-08-07 2020-02-13 江苏亚宝绝缘材料股份有限公司 Film de polyimide transparent ayant une fonction d'avertissement précoce de fissures légères et son procédé de préparation
JP2022525751A (ja) * 2019-03-14 2022-05-19 エボニック オペレーションズ ゲーエムベーハー 成形された有機電荷蓄積装置の製造方法
WO2022153357A1 (fr) * 2021-01-12 2022-07-21 日本電信電話株式会社 Batterie secondaire au lithium et son procédé de production
JP7530015B2 (ja) 2021-01-12 2024-08-07 日本電信電話株式会社 リチウム二次電池の製造方法

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