WO2021193631A1 - 電極 - Google Patents

電極 Download PDF

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Publication number
WO2021193631A1
WO2021193631A1 PCT/JP2021/011992 JP2021011992W WO2021193631A1 WO 2021193631 A1 WO2021193631 A1 WO 2021193631A1 JP 2021011992 W JP2021011992 W JP 2021011992W WO 2021193631 A1 WO2021193631 A1 WO 2021193631A1
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WIPO (PCT)
Prior art keywords
electrode
metal base
base layer
thickness
conductive carbon
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Ceased
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PCT/JP2021/011992
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English (en)
French (fr)
Japanese (ja)
Inventor
恭太郎 山田
基希 拝師
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to US17/914,441 priority Critical patent/US20230128978A1/en
Priority to EP21777179.9A priority patent/EP4130728A4/en
Priority to CN202180023256.2A priority patent/CN115398217A/zh
Priority to JP2022510547A priority patent/JP7678794B2/ja
Publication of WO2021193631A1 publication Critical patent/WO2021193631A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025040686A priority patent/JP2025090778A/ja
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

Definitions

  • the present invention relates to electrodes.
  • Patent Document 1 an electrode in which a base thin film and a carbon thin film are laminated in order on one side of a plastic base material is known (see, for example, Patent Document 1 below).
  • the present invention provides an electrode in which the amount of warpage is suppressed while the potential window can be widened.
  • a resin film, a metal base layer, and a conductive carbon layer having sp 2 bond and sp 3 bond are provided in order toward one side in the thickness direction, and the number of atoms having sp 3 bonds and the number of atoms having sp 3 bonds are provided.
  • the metal base layer includes an electrode having a ratio of the number of atoms having sp 3 bonds to the sum of the numbers of atoms having sp 2 bonds of 0.25 or more and a thickness of the metal base layer of less than 50 nm.
  • the present invention (2) includes the electrode according to (1), wherein the material of the metal base layer is at least one metal element selected from the group consisting of titanium, tantalum, chromium, molybdenum, and tungsten. ..
  • the present invention (3) includes the electrode according to (1) or (2), wherein the thickness of the conductive carbon layer is 0.2 nm or more and 50 nm or less.
  • the present invention (4) includes the electrode according to any one of (1) to (3), wherein the material of the resin film is polyethylene terephthalate.
  • the electrode of the present invention can widen the potential window while suppressing the amount of warpage.
  • FIG. 1 shows a cross-sectional view of an embodiment of the electrode of the present invention.
  • FIG. 2 is a perspective view illustrating the curl amount measurement of the embodiment.
  • the electrode 1 has a predetermined thickness and has a film shape (including a sheet shape) extending in a plane direction orthogonal to the thickness direction.
  • the electrode 1 has one surface in the thickness direction that is flat along the surface direction, and the other surface that is spaced apart from the one surface in the thickness direction.
  • the electrode 1 is a resin film 2, a metal base layer 3 arranged on one side in the thickness direction of the resin film 2, and a conductive carbon layer 4 arranged on one side in the thickness direction of the metal base layer 3. And. That is, the electrode 1 includes a resin film 2, a metal base layer 3, and a conductive carbon layer 4 in this order on one side in the thickness direction.
  • the electrode 1 is composed of a resin film 2, a metal base layer 3, and a conductive carbon layer 4. Each layer will be described in detail below.
  • the resin film 2 forms the other surface of the electrode 1 in the thickness direction.
  • the resin film 2 has a film shape extending in the plane direction.
  • the resin film 2 is a base film on the electrode 1.
  • the resin film 2 has flexibility, for example. Specifically, the folding resistance test of the resin film 2 (JIS C 5016 (1994)) is performed, for example, 250 times or more, preferably 500 times or more. If the folding resistance test of the resin film 2 is equal to or higher than the above-mentioned lower limit, the resin film 2 is excellent in flexibility.
  • JIS C 5016 (1994) JIS C 5016 (1994)
  • polyester resin for example, polyethylene terephthalate and polyethylene naphthalate
  • acetate resin for example, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, and polyolefin resin (for example, polycycloolefin polymer).
  • Polyester resin is preferable, and polyethylene terephthalate is more preferable.
  • the thickness of the resin film 2 is not particularly limited, and is, for example, 2 ⁇ m or more, preferably 20 ⁇ m or more, and for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less.
  • the metal base layer 3 is arranged on one side of the resin film 2 in the thickness direction. Specifically, the metal base layer 3 is in contact with all of one surface of the resin film 2 in the thickness direction. The metal base layer 3 extends in the plane direction. The metal base layer 3 is an intermediate layer located between the resin film 2 and the conductive carbon layer 4.
  • Examples of the material of the metal base layer 3 include Group 4 metal elements such as titanium and zirconium, Group 5 metal elements such as vanadium, niobium and tantalum, Group 6 metal elements such as chromium, molybdenum and tungsten, manganese and the like. Group 7 metal elements, Group 8 metal elements such as iron, Group 9 metal elements such as cobalt, Group 10 metal elements such as nickel and platinum, Group 11 metal elements such as gold, and Group 12 metal elements such as zinc. Examples include Group 13 metal elements, Group 13 metal elements such as aluminum and gallium, and Group 14 metal elements such as germanium and tin. These materials can be used alone or in combination.
  • the material of the metal base layer 3 is preferably titanium, tantalum, chromium, molybdenum, or tungsten, more preferably titanium, tungsten, or the like, and further preferably tungsten, from the viewpoint of chemical stability. Can be mentioned.
  • the thickness of the metal base layer 3 is less than 50 nm, preferably 45 nm or less, more preferably 40 nm or less, and further preferably 35 nm or less. When the thickness of the metal base layer 3 exceeds the above-mentioned upper limit, the electrode 1 warps.
  • the thickness of the metal base layer 3 is, for example, 0.1 nm or more, preferably 1 nm or more, and more preferably 5 nm or more. When the thickness of the metal base layer 3 is equal to or greater than the above lower limit, the sensing stability is excellent.
  • the thickness of the metal base layer 3 is determined by the X-ray diffraction method.
  • the X-ray diffraction method will be described in detail in Examples.
  • the conductive carbon layer 4 has conductivity.
  • the conductive carbon layer 4 forms one surface in the thickness direction of the electrode 1.
  • the conductive carbon layer 4 is arranged on one surface of the metal base layer 3 in the thickness direction. Specifically, the conductive carbon layer 4 is in contact with all of one surface of the metal base layer 3 in the thickness direction.
  • the conductive carbon layer 4 extends in the plane direction.
  • the conductive carbon layer 4 has carbon having an sp 2 bond and carbon having an sp 3 bond as main components. That is, the conductive carbon layer 4 is a layer having a graphite-type structure and a diamond structure. As a result, the conductive carbon layer 4 has good conductivity, and the sensitivity to the measurement target is sufficiently improved.
  • the conductive carbon layer 4 can contain oxygen in addition to carbon, for example. Specifically, for example, oxygen is contained in one surface of the conductive carbon layer 4 in the thickness direction.
  • the concentration ratio (O / C) of oxygen to carbon on one side of the conductive carbon layer 4 in the thickness direction is not particularly limited, and is, for example, 0.001 or more, and for example, 0.2 or less.
  • the conductive carbon layer 4 is allowed to be mixed with a small amount of unavoidable impurities other than oxygen.
  • sp 3 bonded atoms count and sp 2 bonded to sp 3 to the sum of the number of atoms are bonded atoms number ratio (sp 3 / sp 3 + sp 2) is 0. It is 25 or more, preferably 0.30 or more, and more preferably 0.35 or more. If the ratio of the number of atoms bonded to sp 3 (sp 3 / sp 3 + sp 2 ) is lower than the above lower limit, the potential window of the electrode 1 cannot be widened.
  • sp 3 bonded atoms count and sp 2 bonded to sp 3 to the sum of the number of atoms are bonded atoms number ratio (sp 3 / sp 3 + sp 2), for example, 0.9 or less, Preferably, it is 0.6 or less. If the ratio of the number of atoms bonded to sp 3 (sp 3 / sp 3 + sp 2 ) is equal to or less than the above upper limit, the conductivity of the conductive carbon layer 4 is ensured and the decrease in the detection sensitivity of the electrode 1 is suppressed. can.
  • the ratio of the number of atoms having sp 3 bonds is the ratio of sp 2 bonds in the spectrum obtained by measuring one side of the conductive carbon layer 4 in the thickness direction by X-ray photoelectron spectroscopy. calculated based on the peak intensity of the peak intensity and sp 3 bonds.
  • the surface resistance of the conductive carbon layer 4 on one surface in the thickness direction is, for example, 1.0 ⁇ 10 4 ⁇ / ⁇ or less, preferably 1.0 ⁇ 10 3 ⁇ / ⁇ or less.
  • the thickness of the conductive carbon layer 4 is, for example, 0.1 nm or more, preferably 0.2 nm or more, and 100 nm or less, preferably 50 nm or less.
  • the thickness of the conductive carbon layer 4 is determined by an X-ray diffraction method. The X-ray diffraction method will be described in detail in Examples.
  • the curl amount of the electrode 1 is small, specifically, the curl amount of the electrode 1 cut into a rectangular shape of 100 mm ⁇ 100 mm is, for example, 40 mm or less, preferably 30 mm or less, more preferably 20 mm or less, and further. It is preferably 15 mm or less, and most preferably 0 mm.
  • the amount of curl as shown in FIG. 2, the electrode 1 cut to the above size is placed on the upper surface of the flat plate 5. The temperature at this time is 23 ° C. After that, when the four corners 6 warp, the amount of each warp (height from the flat plate) is measured, and the curl amount is obtained as the average of them. The smaller the curl amount of the electrode 1, the more the warp amount of the electrode 1 is suppressed.
  • the thickness of the electrode 1 is the total thickness of the resin film 2, the metal base layer 3, and the conductive carbon layer 4, and specifically, for example, 2 ⁇ m or more, preferably 20 ⁇ m or more, and for example, 1000 ⁇ m. Hereinafter, it is preferably 500 ⁇ m or less.
  • the resin film 2 is prepared.
  • the method for forming the metal base layer 3 is not particularly limited, and examples thereof include a dry method, for example, a metal film forming method such as a wet method such as plating.
  • a dry method is preferable.
  • the dry method include a PVD method (physical vapor deposition method) and a CVD method (chemical vapor deposition method), and a PVD method is preferable.
  • the PVD method include a sputtering method, a vacuum vapor deposition method, a laser vapor deposition method, and an ion plating method (arc vapor deposition method, etc.).
  • a sputtering method is used.
  • the target in the sputtering method is, for example, the material of the metal base layer 3.
  • the sputter gas include an inert gas such as Ar and Xe.
  • the pressure in the sputtering is, for example, 1 Pa or less.
  • the film formation temperature is, for example, 50 ° C. or higher, for example, 200 ° C. or lower.
  • the conductive carbon layer 4 is formed on one surface of the metal base layer 3 in the thickness direction.
  • the method for forming the conductive carbon layer 4 include a dry method.
  • the dry method include a PVD method (physical vapor deposition method) and a CVD method (chemical vapor deposition method), and a PVD method is preferable.
  • the PVD method include a sputtering method, a vacuum vapor deposition method, a laser vapor deposition method, and an ion plating method (arc vapor deposition method, etc.).
  • a sputtering method is used.
  • Examples of the sputtering method include an unbalanced magnetron sputtering method (UBM sputtering method), a high-power pulse sputtering method, an electronic cyclotron resonance sputtering method, an RF sputtering method, a DC sputtering method (DC magnetron sputtering method, etc.), and a DC pulse sputtering method. , Ion beam sputtering method and the like. From the viewpoint that the ratio of the number of atoms bonded to sp 3 can be easily set within the above-mentioned desired range, and from the viewpoint of improving the film formation rate and the adhesion to the metal base layer 3, UBM is more preferable. Sputter method can be mentioned.
  • Examples of the target in the sputtering method include sintered carbon.
  • Examples of the sputter gas include an inert gas.
  • the pressure in the sputtering is, for example, 1 Pa or less.
  • the film formation temperature is, for example, 0 ° C. or higher, for example, 100 ° C. or lower.
  • the conductive carbon layer 4 is subjected to known surface treatments such as ion milling, ion impact treatment (ion bombard), electrolytic polishing, and voltage application cycles (number of cycles of 2 or more and 20 or less), if necessary. Can be applied.
  • known surface treatments such as ion milling, ion impact treatment (ion bombard), electrolytic polishing, and voltage application cycles (number of cycles of 2 or more and 20 or less), if necessary. Can be applied.
  • the sp 3 bonded to have a ratio of the number of atoms in order to set a desired range described above, sputtering conditions and surface treatment described above can be appropriately selected.
  • an electrode 1 is obtained in which the resin film 2, the metal base layer 3, and the conductive carbon layer 4 are sequentially provided on one side in the thickness direction.
  • the electrode 1 can be used as various electrodes, preferably an electrode for electrochemical measurement for performing an electrochemical measurement method, specifically, a working electrode (working electrode) for performing cyclic voltammetry (CV) or the like.
  • a working electrode working electrode
  • CV cyclic voltammetry
  • the ratio of the number of atoms are sp 3 bonded to the sum of the number of atoms that are sp 3 bonds and sp 2 bonded to the number of atoms is, since it is 0.25 or more, potential
  • the window can be widened.
  • this electrode 1 since the thickness of the metal base layer 3 is less than 50 nm, the internal stress that imparts (applies) a distorting force to the resin film 2 in the metal base layer 3 is reduced. As a result, the amount of warpage is suppressed.
  • the material of the metal base layer 3 is at least one metal element selected from the group consisting of titanium, tantalum, chromium, molybdenum, and tungsten, the resin film 2 and the conductive carbon layer Sufficient adhesion of 4 can be guaranteed.
  • the thickness of the conductive carbon layer 4 is 0.2 nm or more, stable electrode characteristics can be exhibited. On the other hand, when the thickness of the conductive carbon layer 4 is 50 nm or less, the flexibility is excellent, and the handleability of the electrode 1 is good.
  • the electrode 1 includes one resin film 2, one metal base layer 3, and one conductive carbon layer 4.
  • one resin film 2, two metal base layers 3, and two conductive carbon layers 4 can also be provided. That is, the electrode 1 can include two metal base layers 3 and two conductive carbon layers 4 for one resin film 2.
  • the conductive carbon layer 4, the metal base layer 3, the resin film 2, the metal base layer 3, and the conductive carbon layer 4 are arranged in order in the thickness direction.
  • the above-mentioned metal film forming method can be carried out a plurality of times.
  • Method for measuring the thickness of the metal base layer 3 and the thickness of the conductive carbon layer 4 First, a method for measuring the thickness of the metal base layer 3 and the thickness of the conductive carbon layer 4 is shown below. Specifically, the X-ray reflectivity method is used as the measurement principle, and the X-ray reflectivity is measured under the following ⁇ measurement conditions> using a powder X-ray diffractometer (“RINT-2200” manufactured by Rigaku Corporation). By analyzing the acquired measurement data with analysis software (“GXRR3” manufactured by Rigaku Co., Ltd.), the thickness of the metal base layer 3 and the thickness of the conductive carbon layer 4 of each example and each comparative example were calculated. ..
  • a three-layer model of the resin film 2, the metal base layer 3, and the conductive carbon layer 4 was adopted under the following ⁇ analysis conditions>, and the target thickness and density of the metal base layer 3 was 19.30 g / cm. 3 was input as an initial value, and the target thickness and density of the conductive carbon layer 4 was 19.5 g / cm 3 as an initial value. After that, the thickness of the metal base layer 3 and the thickness of the conductive carbon layer 4 were calculated by performing the minimum square fitting with the measured value.
  • Measuring device Powder X-ray diffractometer (manufactured by Rigaku, "RINT-2000")
  • Light source Cu-K ⁇ ray (wavelength: 1,5418 ⁇ ), 40 kV, 40 mA
  • Optical system Parallel beam optical system Divergence slit: 0.05 mm
  • Light receiving slit 0.05 mm
  • Monochromatic / parallelization Multi-layer Gobel mirror used
  • Measurement mode ⁇ / 2 ⁇ Scan mode Measurement range (2 ⁇ ): 0.3 to 2.0 °
  • Example 1 (Preparation of resin film 2) A resin film 2 made of polyethylene terephthalate having a thickness of 50 ⁇ m was prepared.
  • a metal base layer 3 made of tungsten was formed on one surface of the resin film 2 in the thickness direction by a sputtering method.
  • the thickness of the metal base layer 3 was 40 nm. The conditions of the sputtering method are described below.
  • Target material Tungsten Argon gas pressure: 0.6Pa Target power: 400W Film formation roll temperature: 120 ° C
  • the conductive carbon layer 4 was formed on one surface of the metal base layer 3 in the thickness direction by the UBM sputtering method.
  • the thickness of the conductive carbon layer 4 was 30 nm. The conditions of the UBM sputtering method are described below.
  • Target material Sintered carbon Argon gas pressure: 0.8 Pa
  • Target power 400W
  • the conductive carbon layer 4 was subjected to a voltage application cycle of reciprocating the applied voltage between 0 V and 2.3 V 10 times.
  • Example 2 The same treatment as in Example 1 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 40 nm to 30 nm.
  • Example 3 The same treatment as in Example 1 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 40 nm to 10 nm.
  • Example 4 The same treatment as in Example 1 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 40 nm to 30 nm. Also, the DC bias was changed from 75V to 30V.
  • Example 1 The same treatment as in Example 1 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 40 nm to 50 nm.
  • Example 2 The same treatment as in Example 1 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 40 nm to 50 nm. On the other hand, no DC bias was applied and no voltage application cycle was performed.
  • Example 5 The same treatment as in Example 2 was carried out to obtain an electrode 1. However, in forming the metal base layer 3, chromium was used as the target material. That is, the material of the metal base layer 3 was changed from tungsten to chromium.
  • Example 3 The same treatment as in Example 5 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 30 nm to 50 nm.
  • Example 6 The same treatment as in Example 2 was carried out to obtain an electrode 1. However, in forming the metal base layer 3, molybdenum was used as the target material. That is, the material of the metal base layer 3 was changed from tungsten to molybdenum.
  • Example 4 The same treatment as in Example 6 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 30 nm to 50 nm.
  • Example 7 The same treatment as in Example 2 was carried out to obtain an electrode 1. However, in forming the metal base layer 3, tantalum was used as the target material. That is, the material of the metal base layer 3 was changed from tungsten to tantalum.
  • Example 5 The same treatment as in Example 7 was carried out to obtain an electrode 1. However, the thickness of the metal base layer 3 was changed from 30 nm to 50 nm.
  • Example 8 The same treatment as in Example 2 was carried out to obtain an electrode 1. However, in forming the metal base layer 3, titanium was used as the target material. That is, the material of the metal base layer 3 was changed from tungsten to titanium.
  • Tables 1 and 2 show the materials of the metal base layer 3, the thickness of the metal base layer 3, and the thickness of the conductive carbon layer 4 in Examples 1 to 8 and Comparative Examples 1 to 5. show.
  • Measuring device X-ray photoelectron spectroscopy (XPS) device (manufactured by Shimadzu Corporation, trade name "AXIS Nova")
  • X-ray source Rowland circle diameter 500 mm with monochromator AlK ⁇ (1486.6 eV), 15 kV, 10 mA
  • Photoelectron spectrometer Orbital radius 165 mm, electrostatic double hemispherical analyzer / spherical mirror analyzer combined detector: Delay line detector (DLD) system
  • Energy resolution Ag3d5 / 2 Photoelectron peak is half width 0.48 eV or less
  • Charge neutralization Uniform low energy electron irradiation
  • the electrode 1 was cut into a size of 100 mm in length and 100 mm in width. Next, as shown in FIG. 2, the electrode 1 was placed on the upper surface of the flat plate 5 so that the resin film 2 was on the lower side. The temperature at this time was 23 ° C. After 1 minute, the four corners 6 were warped, and the amount of each warp (height from the flat plate 5) was measured, and the curl amount was obtained as the average of them. From the curl amount, the suppression of the warp amount was evaluated according to the following criteria.
  • ⁇ The curl amount was 40 mm or less.
  • X The curl amount exceeded 40 mm.
  • the electrode is used as an electrode for electrochemical measurement that carries out an electrochemical measurement method.
  • Electrode 2 Resin film 3 Metal base layer 4 Conductive carbon layer

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PCT/JP2021/011992 2020-03-26 2021-03-23 電極 Ceased WO2021193631A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US17/914,441 US20230128978A1 (en) 2020-03-26 2021-03-23 Electrode
EP21777179.9A EP4130728A4 (en) 2020-03-26 2021-03-23 ELECTRODE
CN202180023256.2A CN115398217A (zh) 2020-03-26 2021-03-23 电极
JP2022510547A JP7678794B2 (ja) 2020-03-26 2021-03-23 電極
JP2025040686A JP2025090778A (ja) 2020-03-26 2025-03-13 電極

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JP2020-055726 2020-03-26
JP2020055726 2020-03-26
JP2021-039731 2021-03-11
JP2021039731 2021-03-11

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US (1) US20230128978A1 (https=)
EP (1) EP4130728A4 (https=)
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CN (1) CN115398217A (https=)
TW (1) TWI885107B (https=)
WO (1) WO2021193631A1 (https=)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022202715A1 (ja) * 2021-03-23 2022-09-29 日東電工株式会社 電極
WO2023053905A1 (ja) * 2021-09-30 2023-04-06 日東電工株式会社 電極
WO2023127545A1 (ja) * 2021-12-28 2023-07-06 日東電工株式会社 電極および電気化学測定システム
WO2024111455A1 (ja) 2022-11-21 2024-05-30 日東電工株式会社 電極および電気化学測定システム
WO2024180988A1 (ja) 2023-02-28 2024-09-06 日東電工株式会社 電極および電気化学測定システム

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WO2022202715A1 (ja) * 2021-03-23 2022-09-29 日東電工株式会社 電極
JPWO2022202715A1 (https=) * 2021-03-23 2022-09-29
JP7798863B2 (ja) 2021-03-23 2026-01-14 日東電工株式会社 電極
WO2023053905A1 (ja) * 2021-09-30 2023-04-06 日東電工株式会社 電極
WO2023127545A1 (ja) * 2021-12-28 2023-07-06 日東電工株式会社 電極および電気化学測定システム
WO2024111455A1 (ja) 2022-11-21 2024-05-30 日東電工株式会社 電極および電気化学測定システム
EP4624914A1 (en) 2022-11-21 2025-10-01 Nitto Denko Corporation Electrode and electrochemical measurement system
WO2024180988A1 (ja) 2023-02-28 2024-09-06 日東電工株式会社 電極および電気化学測定システム
EP4675269A1 (en) 2023-02-28 2026-01-07 Nitto Denko Corporation Electrode, and electrochemical measuring system

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EP4130728A4 (en) 2024-03-13
JP7678794B2 (ja) 2025-05-16
TWI885107B (zh) 2025-06-01
JPWO2021193631A1 (https=) 2021-09-30
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