Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/14—Metallic material, boron or silicon
  • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
  • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering

Definitions

• the present invention relates to an electrode and an electrochemical measurement system.
• Patent Document 1 An electrode comprising a substrate, a metal underlayer, and a conductive carbon layer is known (see, for example, Patent Document 1 below).
• Patent Document 1 describes an example in which the material of the metal underlayer is titanium.
• the electrode is used for electrochemical measurements, and a balance is required between excellent activity toward ferricyanide compounds and a wide potential window.
• the present invention provides an electrode and electrochemical measurement system that has a good balance between activity toward ferricyanide compounds and a wide potential window.
• the present invention [1] is an electrode having a substrate, a metal underlayer, and a conductive carbon layer in this order toward one side in the thickness direction, the material of the metal underlayer is an alloy containing a first metal and a second metal, the first metal has a first potential window determined using a first electrochemical measurement system having a first sample electrode having the substrate, a metal underlayer made of the first metal, and the conductive carbon layer, and a first activity with respect to a ferricyanide compound determined using the first electrochemical measurement system, the second metal has a second potential window determined using a second electrochemical measurement system having a second sample electrode having the substrate, a metal underlayer made of the second metal, and the conductive carbon layer, and a second activity with respect to the ferricyanide compound determined using the second electrochemical measurement system, the first metal and the second metal are different from each other, the second activity is equal to or greater than the first activity, and the first potential window is equal to or greater than the second potential window.
• the present invention [2] includes the electrode described in [1], in which the first metal or the second metal is at least one selected from the group consisting of tantalum, titanium, aluminum, zirconium, niobium, and tungsten.
• the present invention [3] includes the electrode described in [1] or [2], in which the first metal is at least one selected from the group consisting of tantalum, titanium, aluminum, zirconium, and niobium.
• the present invention [4] includes an electrode according to any one of [1] to [3], in which the second metal is at least one selected from the group consisting of zirconium, niobium, and tungsten.
• the present invention [5] includes an electrode according to any one of [1] to [4], in which the first metal or the second metal includes two selected from the group consisting of tantalum, titanium, aluminum, zirconium, niobium, and tungsten.
• the present invention [6] includes the electrode described in any one of [1] to [5], in which the substrate is a resin film.
• the present invention [7] includes an electrode described in any one of [1] to [6], which is an electrode for electrochemical measurements.
• the present invention [8] includes an electrochemical measurement system having the electrode described in [7].
• the material of the metal underlayer is an alloy containing a first metal and a second metal, the second activity is equal to or greater than the first activity, and the first potential window is equal to or greater than the second potential window. Therefore, the electrode has a good balance between activity toward ferricyanide compounds and a wide potential window.
• the electrochemical measurement system has a good balance between activity toward ferricyanide compounds and a wide potential window.
• FIG. 1 shows a cross-sectional view of one embodiment of an electrode of the present invention. A cross-sectional view of a sample electrode is shown.
• FIG. 1 is a schematic diagram of an embodiment of an electrochemical measurement system of the present invention. 1 shows the relationship between the width of the potential window and the ferricyanide activity for the first and second metals, in an example where the first metal is titanium. 1 shows the relationship between the width of the potential window and the ferricyanide activity for the first and second metals, in an example where the first metal is tantalum. 1 shows the relationship between the width of the potential window and the ferricyanide activity for the first and second metals, in an example where the first metal is aluminum.
• the relationship between the width of the potential window and the ferricyanide activity for the first and second metals is shown in the example where the first metal is zirconium.
• the relationship between the width of the potential window and the ferricyanide activity for the first and second metals is shown in the example where the first metal is niobium.
• Electrode 1 As shown in Fig. 1, the electrode 1 has a thickness. The electrode 1 extends in a planar direction. The planar direction is perpendicular to the thickness direction. The electrode 1 has a film shape or a sheet shape. There is no distinction between a film and a sheet. The thickness of the electrode 1 is, for example, 2 ⁇ m or more, preferably 10 ⁇ m or more, and, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less. In this embodiment, the electrode 1 includes a substrate 2, a metal underlayer 3, and a conductive carbon layer 4 in this order toward one side in the thickness direction.
• the substrate 2 is disposed at the other end of the electrode 1 in the thickness direction.
• the substrate 2 extends in the surface direction.
• the substrate 2 has a film shape or a sheet shape.
• Examples of the material of the substrate 2 include resin, ceramics, and metal.
• the substrate 2 is preferably flexible.
• Examples of the material of the substrate 2 include resin from the viewpoint of ensuring the flexibility of the substrate 2. In other words, the substrate 2 is preferably a resin film.
• the resin examples include polyester resin, acetate resin, polyethersulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, and polyphenylene sulfide resin.
• the resins can be used alone or in combination.
• a polyester resin can be used, and preferably, polyethylene terephthalate can be used.
• the substrate 2 is a ceramic foil.
• the material is metal
• the thickness of the substrate 2 is, for example, 1.9 ⁇ m or more, preferably 9 ⁇ m or more, and, for example, 999 ⁇ m or less, preferably 499 ⁇ m or less.
• the metal underlayer 3 is disposed on one surface of the substrate 2 in the thickness direction.
• the metal underlayer 3 contacts one surface of the substrate 2 in the thickness direction.
• the metal underlayer 3 extends in the planar direction.
• the metal underlayer 3 is an underlayer. The underlayer assists the conductivity of the conductive carbon layer 4.
• the material of the metal underlayer 3 is an alloy.
• the alloy contains a first metal and a second metal.
• the first metal has a first potential window and a first activity.
• the first potential window is determined using a first electrochemical measurement system 10A shown in FIG. 3.
• a wide potential window is required for the electrode 1.
• the first electrochemical measurement system 10A includes a first sample electrode 1A.
• the first sample electrode 1A includes a substrate 2, a metal underlayer 3 made of a first metal, and a conductive carbon layer 4.
• the first sample electrode 1A further includes an insulating tape 5.
• the first activity is evaluated by ⁇ Ep for the ferricyanide compound, which is determined by CV using the first electrochemical measurement system 10A.
• a lower ⁇ Ep indicates a higher first activity.
• the first sample electrode 1A the measurement of the first potential window using the first sample electrode 1A, and the measurement of the first activity using the first sample electrode 1A will be described later.
• the first metal is, for example, a typical element and/or a transition element.
• the first metal is at least one selected from the group consisting of tantalum, titanium, aluminum, zirconium, and niobium. More preferably, the first metal is at least one selected from the group consisting of tantalum, titanium, aluminum, zirconium, and niobium.
• the electrode 1 When the electrode 1 is used as an electrode for electrochemical measurement of a ferricyanide compound, the first metal improves activity against the ferricyanide compound.
• the volume ratio of the first metal to the total amount of 100 parts by volume of the first metal and the second metal is, for example, 10 parts by volume or more, preferably 25 parts by volume or more, more preferably 60 parts by volume or more, even more preferably 75 parts by volume or more, and for example, 95 parts by volume or less, preferably 90 parts by volume or less.
• the volume ratio of the first metal to the alloy is, for example, 10% by volume or more, preferably 25% by volume or more, more preferably 60% by volume or more, even more preferably 75% by volume or more, and for example, 95% by volume or less, preferably 90% by volume or less.
• the volume fraction of the first metal is equal to or greater than the lower limit described above, the potential window can be widened when the electrode is used as an electrode for electrochemical measurements. If the volume fraction of the first metal is equal to or less than the upper limit described above, activity toward ferricyanide compounds can be improved.
• the second metal has a second potential window and a second activity.
• the electrode 1 is required to have high activity with respect to ferricyanide compounds.
• the second potential window is determined using a second electrochemical measurement system 10B shown in FIG. 3.
• a wide potential window is required for the electrode 1.
• the second electrochemical measurement system 10B includes a second sample electrode 1B.
• the second sample electrode 1B includes a substrate 2, a metal underlayer 3 made of a second metal, and a conductive carbon layer 4B.
• the second sample electrode 1B further includes an insulating tape 5.
• the second activity is evaluated by ⁇ Ep against the ferricyanide compound, which is determined by CV using the second electrochemical measurement system 10B.
• the second sample electrode 1B, the measurement of the second potential window using the second sample electrode 1B, and the measurement of the second activity using the second sample electrode 1B will be described later.
• the first metal and the second metal are different from each other.
• the second activity is equal to or greater than the first activity
• the first potential window is equal to or greater than the second potential window
• the second activity is higher than the first activity, and the first potential window is equal to or larger than the second potential window. Also, preferably, the second activity is equal to or larger than the first activity, and the first potential window is wider than the second potential window.
• the second activity is higher than the first activity, and the first potential window is wider than the second potential window.
• the second metal is, for example, a typical element and/or a transition element.
• the second metal is at least one selected from the group consisting of tantalum, titanium, aluminum, zirconium, niobium, and tungsten.
• each of the first metal and the second metal is at least one selected from the group consisting of tantalum, titanium, aluminum, zirconium, niobium, and tungsten.
• the second metal is at least one selected from the group consisting of zirconium, niobium, and tungsten.
• the first metal or the second metal preferably includes two selected from the group consisting of tantalum, titanium, aluminum, zirconium, niobium, and tungsten. Examples of combinations of the first metal and the second metal are shown below.
• Figures 4 to 8 show the relationship between the width of the potential window and the ferricyanide activity for the first and second metals. In Figures 4 to 8, combinations of the first and second metals are connected by lines.
• examples of combinations of the first metal and the second metal include an example where the first metal is titanium and the second metal is zirconium, an example where the first metal is titanium and the second metal is niobium, an example where the first metal is titanium and the second metal is tungsten, and an example where the first metal is titanium and the second metal is zirconium and niobium.
• the first metal is titanium
• at least one metal is selected as the second metal from the group consisting of zirconium, niobium, and tungsten, whose second potential window and second activity are plotted in the hatched area.
• examples of combinations of the first metal and the second metal include an example where the first metal is tantalum and the second metal is titanium, an example where the first metal is tantalum and the second metal is zirconium, an example where the first metal is tantalum and the second metal is niobium, and an example where the first metal is tantalum and the second metal is tungsten.
• the second metal is tantalum
• at least one metal is selected as the second metal from the group consisting of titanium, zirconium, niobium, and tungsten, whose second potential window and second activity are plotted in the hatched area.
• examples of combinations of the first metal and the second metal include an example where the first metal is aluminum and the second metal is niobium, and an example where the first metal is aluminum and the second metal is tungsten.
• the second metal is aluminum
• at least one metal is selected as the second metal from the group consisting of niobium and tungsten, whose second potential window and second activity are plotted in the hatched area.
• examples of combinations of the first metal and the second metal include an example in which the first metal is zirconium and the second metal is niobium, and an example in which the first metal is zirconium and the second metal is tungsten.
• the second metal when the second metal is zirconium, at least one metal is selected as the second metal from the group consisting of niobium and tungsten, whose second potential window and second activity are plotted in the hatched area.
• an example of a combination of a first metal and a second metal is where the first metal is niobium and the second metal is tungsten.
• the second metal is niobium
• tungsten is selected as the second metal, as the second potential window and second activity are plotted in the hatched area.
• the volume ratio of the second metal to a total of 100 parts by volume of the first metal and the second metal is, for example, 5 parts by volume or more, preferably 10 parts by volume or more, and, for example, 90 parts by volume or less, preferably 75 parts by volume or less, more preferably 40 parts by volume or less, and even more preferably 25 parts by volume or less.
• the volume ratio of the second metal to the alloy is, for example, 5% by volume or more, preferably 10% by volume or more, and, for example, 90% by volume or less, preferably 75% by volume or less, more preferably 40% by volume or less, and even more preferably 25% by volume or less.
• the volume fraction of the second metal is equal to or less than the upper limit, the potential window can be widened when the electrode is used as an electrode for electrochemical measurements. If the volume fraction of the second metal is equal to or more than the lower limit, the activity toward ferricyanide compounds can be improved.
• the first metal and the second metal are each identified by ESCA, SEM-EDX, TEM-EDX, and/or XRF.
• the identification method is not limited to the above.
• the thickness of the metal underlayer 3 is, for example, 5 nm or more, preferably 10 nm or more, preferably 15 nm or more, more preferably 20 nm or more, and, for example, 400 nm or less, preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less.
• Conductive carbon layer 4 The conductive carbon layer 4 is disposed at one end of the electrode 1 in the thickness direction. The conductive carbon layer 4 is disposed on one surface of the metal underlayer 3 in the thickness direction. The conductive carbon layer 4 is in contact with one surface of the metal underlayer 3 in the thickness direction. The conductive carbon layer 4 is disposed on the opposite side of the substrate 2 with respect to the metal underlayer 3 in the thickness direction.
• the conductive carbon layer 4 may have, for example, sp2 bonds and sp3 bonds. When the conductive carbon layer 4 has sp2 bonds and sp3 bonds, the conductive carbon layer 4 has a graphite structure and a diamond structure.
• the conductive carbon layer 4 may contain, for example, oxygen in addition to carbon. Furthermore, the conductive carbon layer 4 is allowed to contain a small amount of inevitable impurities other than oxygen.
• 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 metal underlayer 3 is then formed on one surface in the thickness direction of the substrate 2.
• Methods for forming the metal underlayer 3 include, for example, a dry method and a wet method.
• a dry method is preferably used.
• a PVD method physical vapor deposition method
• a CVD method chemical vapor deposition method
• a PVD method is preferably used.
• the PVD method for example, sputtering, vacuum deposition, laser deposition, and ion plating are exemplified.
• sputtering is exemplified.
• a sputtering device In the sputtering, a sputtering device is used.
• the sputtering device includes a first target containing a first metal and a second target containing a second metal. If there are multiple first metals, a part of the first metal may be included in the first target, and the remainder of the first metal may be included in the second target. If there are multiple second metals, a part of the second metal may be included in the second target, and the remainder of the second metal may be included in the first target.
• the first target and the second target are spaced apart from each other. Electric power can be applied to each of the first target and the second target.
• the electric power applied to each of the first target and the second target is set appropriately according to the volume ratio of the first metal and the second metal, respectively.
• the sputtering gas can be, for example, an inert gas.
• the inert gas can be, for example, Ar.
• the pressure during sputtering is, for example, 0.01 Pa or more and 5 Pa or less.
• the film formation temperature is, for example, -10°C or more, preferably 20°C or more, and, for example, 200°C or less, preferably 150°C or less.
• the conductive carbon layer 4 is then formed on one side of the metal base layer 3 in the thickness direction.
• the method for forming the conductive carbon layer 4 is not particularly limited.
• the conductive carbon layer 4 can be formed by the same method as the method for forming the metal base layer 3, preferably by sputtering.
• the target for sputtering is, for example, sintered carbon.
• the electrode 1 can be preferably used as an electrode for electrochemical measurement for performing an electrochemical measurement method, specifically, as a working electrode for performing cyclic voltammetry (CV).
• CV cyclic voltammetry
• Examples of the subject of electrochemical measurement include ferricyanide compounds.
• Examples of ferricyanide compounds include potassium ferricyanide and sodium ferricyanide.
• the electrochemical measurement system 10 includes a working electrode 11, a reference electrode 12, a counter electrode 13, a potentiostat 14, and an ammeter (not shown).
• the working electrode 11 includes the electrode 1 described above.
• the electrochemical measurement system 10 includes the electrode 1 described above.
• the electrode 1 is used for electrochemical measurement.
• Examples of the reference electrode 12 include a silver/silver chloride electrode, a saturated calomel electrode, and a standard hydrogen electrode.
• Examples of the counter electrode 13 include a platinum electrode, a gold electrode, and a nickel electrode.
• the working electrode 11, reference electrode 12, and counter electrode 13 described above can be immersed in the target liquid 15.
• the target liquid 15 contains the above-mentioned measurement target. For example, when performing CV, a potential is applied to the working electrode 11 (electrode 1) and this is scanned.
• the material of the metal underlayer 3 is an alloy containing a first metal and a second metal, the second activity is equal to or greater than the first activity, and the first potential window is equal to or greater than the second potential window. Therefore, the electrode 1 has a good balance between activity toward ferricyanide compounds and a wide potential window.
• the electrochemical measurement system 10 includes the above-described electrode 1. It has a good balance between activity toward ferricyanide compounds and a wide potential window.
• the electrode 1 may further include a hard coat layer.
• the hard coat layer is disposed, for example, on the other surface of the substrate 2 in the thickness direction.
• the sputtering may include only one target.
• the target is made of an alloy including a first metal and a second metal.
• Example 1 First, a substrate 2 made of polyethylene terephthalate having a thickness of 100 ⁇ m was prepared.
• a metal underlayer 3 was formed on one side of the substrate 2 in the thickness direction by sputtering.
• the thickness of the metal underlayer 3 was 30 nm. The sputtering conditions are described below.
• First target titanium Second target: niobium Sputtering gas: Ar Sputtering pressure: 0.3 Pa Power of first target: 3.3 W/ cm2 Power of second target: 4.3 W/ cm2
• a conductive carbon layer 4 was formed on one side of the metal base layer 3 in the thickness direction by sputtering.
• the thickness of the conductive carbon layer 4 was 10 nm. The sputtering conditions are described below.
• Target sintered carbon Sputtering gas: Ar Sputtering pressure: 0.3 Pa
• Target power 3.9 W/ cm2
• Examples 2 to 14, Comparative Examples 1 to 6 An electrode 1 was obtained by the same treatment as in Example 1. However, the composition of the metal underlayer 3 was changed according to the descriptions in Tables 1 to 4.
• [evaluation] 1. Volume ratio of the first metal and the second metal Based on the deposition rates V1 and V2, the volume ratios of the first metal and the second metal in the metal underlayer 3 were calculated.
• the deposition rate V1 of the first metal is obtained by dividing the thickness when only the first metal is deposited by the product of power and time.
• the deposition rate V2 of the second metal is obtained by dividing the thickness when only the second metal is deposited by the product of power and time.
• the volume ratio of the first metal and the second metal is obtained by the ratio of the deposition rate V1 to the deposition rate V2.
• an insulating tape 5 having a hole of 2 mm in diameter was attached to one side of the conductive carbon layer 4 in the thickness direction to prepare a sample electrode 1S having an electrode area of 3.14 mm2 .
• Cyclic voltammetry (CV) was performed using this sample electrode 1S as the working electrode 11.
• the sample electrode 1S was immersed in a 1M KCl aqueous solution.
• 1 mM of [Fe(CN) 6 ] 4- (ferricyanide ion) was added to the aqueous solution as an electrode active material.
• the potential sweep was started from 0 V, and the potential was swept from positive to negative in the range of -0.1 to 0.5 V.
• the potential sweep speed was 0.1 V/s.
• the CV measurement was performed at 23°C.
• the number of CV measurements was 3.
• the average value of the ⁇ Ep values of three CV measurements was obtained as the initial ⁇ Ep.
• the ⁇ Ep at this time was taken as the activity of the electrode 1 with respect to potassium ferricyanide.
• the sample electrode of each comparative example was the first sample electrode 1A or the second sample electrode 1B.
• the ⁇ Ep of the first sample electrode 1A measured in the same manner as above was taken as the first activity.
• the ⁇ Ep of the second sample electrode 1B was taken as the second activity.
• the width of the potential window was evaluated for each electrode 1 of each example. The results are shown in Tables 1 to 4.
• an insulating tape 5 having a hole with a diameter of 2 mm was attached to one side of the conductive carbon layer 4 in the thickness direction to prepare a sample electrode 1S having an electrode area of 3.14 mm2 .
• the sample electrode 1S was used as the working electrode 11
• a silver/silver chloride electrode was used as the reference electrode
• a platinum electrode was used as the counter electrode
• the sample was connected to a potentiostat (described above) to prepare an electrochemical measurement system 10 for each of the examples and comparative examples.
• a 50 mmol/L aqueous sulfuric acid solution was used as the electrolyte.
• a potential was applied to the reference electrode of the electrochemical measurement system 10 at a sweep rate of 0.1 V/s.
• the potential range in which the current value obtained at this time was ⁇ 509 ⁇ A/cm 2 to +509 ⁇ A/cm 2 was defined as the range of the potential window.
• the range of the potential window was calculated by taking the difference (distance) between the maximum potential on the oxidation side and the potential on the reduction side as ⁇ V (V).
• the sample electrode of each comparative example was the first sample electrode 1A or the second sample electrode 1B.
• the ⁇ V of the first sample electrode 1A measured in the same manner as above was taken as the first potential window.
• the ⁇ V of the second sample electrode 1B was taken as the second potential window.
• Electrode 1A First sample electrode 1B Second sample electrode 2 Substrate 3 Metal underlayer 4 Conductive carbon layer 5 Insulating tape 10 Electrochemical measurement system 10A First electrochemical measurement system 10B Second electrochemical measurement system
• the electrode and electrochemical measurement system of the present invention are suitably used in the field of electrochemical measurements.

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