Conductive fabric

Abstract

To provide a conductive fabric that has excellent acid resistance and oxidation resistance, is lightweight and low-cost, and is useful as an electrode for batteries using an electrolytic solution.SOLUTION: A conductive fabric is obtained by using a fabric consisting of polyester fibers as a base material, and laminating on the surface of the polyester fibers, in this order, a layer A: an electroless nickel plating layer, a layer B: an electrolytic nickel plating layer or an electrolytic silver plating layer, a layer C: an electrolytic tin-nickel alloy plating layer, and a layer D: an electrolytic gold plating layer or an electrolytic platinum plating layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an electrode that is in contact with an electrolyte and is used in a battery, etc. More specifically, the present invention relates to a lightweight, low-cost electrode. [Background technology]

[0002] Electrodes used in batteries and the like that come into contact with acidic electrolytes are required to be acid-resistant and oxidation-resistant, but conventional metal meshes and punched porous metal foils are heavy and expensive. A porous metal body made of an alloy containing nickel and tin has been proposed (Patent Document 1), and is used as a current collector, but it cannot be said to have sufficient oxidation resistance.

[0003] Meanwhile, the present inventors have previously proposed an alkali-resistant conductive material having an inner metal layer selected from copper, silver, nickel, and gold on polyamide fibers and an outer metal layer made of tin or a tin alloy (Patent Document 2). However, this material does not have excellent oxidation resistance and acid resistance, and is not suitable for use as an electrode in a battery that comes into contact with an acidic electrolyte. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2012-132083 [Patent Document 2] Patent Publication No. 2023-176919 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an electrode that comes into contact with an electrolyte in a battery or the like, which has excellent acid resistance and oxidation resistance, and is lightweight and low cost. [Means for solving the problem]

[0006] As a result of extensive research, the inventors discovered that the above-mentioned problems could be solved by laminating specific metal layers in a specific order on the fibers of a woven fabric having openings (void ratio), and thus completed the present invention.

[0007] That is, the present invention relates to the following conductive fabric. (1) A woven fabric made of polyester fiber is used as a base material, and the surface of the polyester fiber is Layer A: Electroless nickel plating layer Layer B: Electrolytic nickel plating layer or electrolytic silver plating layer C layer: Electrolytic tin-nickel alloy plating layer D layer: Electrolytic gold plating layer or electrolytic platinum plating layer A conductive fabric in which the above are layered in this order.

[0008] (2) The conductive fabric according to (1), wherein the tin content in the layer C is 50 to 80 mol % as measured by laser-induced breakdown spectroscopy.

[0009] (3) The conductive fabric according to (1), wherein the opening ratio of the fabric made of polyester fibers is 1 to 50%. (4) The conductive fabric according to (1), further comprising an electroless copper plating layer between the A layer and the B layer. [Effects of the Invention]

[0010] The conductive fabric of the present invention has excellent acid resistance and oxidation resistance, and, unlike conventional metal meshes and punched porous metal foils, is lightweight and can be produced at low cost. Therefore, it is useful as an electrode for batteries, particularly batteries using acidic electrolytes. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing an outline of an oxidation resistance test in an example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] 1. Base material The conductive fabric of the present invention uses a woven fabric made of polyester fibers as a base material. Examples of polyesters that form the polyester fibers include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate, and copolymers containing these as the main repeating units with aromatic dicarboxylic acids such as isophthalic acid and 5-sulfoisophthalic acid metal salt, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, hydroxycarboxylic acid condensates such as ε-caprolactone, and glycol components such as diethylene glycol, trimethylene glycol, tetramethylene glycol, and hexamethylene glycol. Among these, polyethylene terephthalate (PET) is preferred because of its versatility and excellent strength.

[0013] The substrate made of the woven fabric is made of yarn made of polyester fiber. The polyester fiber yarn may be a spun yarn or a filament yarn. The filament yarn may be a monofilament or a multifilament formed by bundling a plurality of monofilaments. In the case of a multifilament, the number of filaments is preferably 2 to 50, and more preferably 2 to 20.

[0014] In the present invention, among the above, filament yarn is preferred. This is because filament yarn has a smaller surface area than spun yarn, resulting in a smaller contact area with the electrolyte. For this reason, among filament yarns, monofilament yarns made of a single filament are more preferred.

[0015] The fiber diameter (thickness) of the yarn is not particularly limited, but is preferably 20 to 100 μm, more preferably 20 to 80 μm, or the single yarn fineness is 5 to 100 dtex (decitex), more preferably 5 to 70 dtex.

[0016] When the yarn is a multifilament yarn, the total fiber diameter of the multiple filament yarns may be within the above range, and if the fiber diameter of the yarn is within this range, a conductive fabric having an excellent balance between flexibility and material strength can be obtained.

[0017] Examples of woven fabrics made of the polyester fiber of the present invention include plain weave fabrics, twill weave fabrics, satin weave fabrics, etc. Among these, plain weave fabrics are preferred from the viewpoint of dimensional stability and ease of handling, and twill weave fabrics are preferred from the viewpoint of being able to increase the thread density of the mesh (i.e., reduce the mesh opening and aperture ratio).

[0018] Furthermore, the woven fabric made of the polyester fiber of the present invention is preferably a mesh woven fabric. The mesh opening size is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 100 μm. The thread density of the mesh is not particularly limited, but the warp thread density and / or weft thread density is preferably about 80 to 500 threads / inch, more preferably about 150 to 450 threads / inch.

[0019] The substrate can have an appropriate opening ratio depending on the application. For example, the substrate can be a mesh fabric having a structure with an opening ratio of preferably 1 to 90%, more preferably about 2 to 50%. When the opening ratio is within the above range, a conductive fabric can be obtained that has an excellent balance of flexibility, material strength, and oxidation resistance. The opening ratio of the substrate can be calculated using the following formula (Equation 1) from the measured mesh wire diameter (the thickness of the polyester fibers that make up the mesh) and the mesh size.

[0020] (Number 1) {opening ÷ (opening + mesh wire diameter)} squared × 100 (%)

[0021] The thickness of the substrate is not particularly limited, but is preferably 30 μm or more, more preferably 50 μm or more, and particularly preferably 80 μm or more. The upper limit of the thickness is not particularly limited, but is preferably 200 μm or less, more preferably 150 μm or less, and particularly preferably 135 μm or less.

[0022] 2. Metal layer In the conductive fabric of the present invention, at least the following metal layers are laminated in this order on the surface of the polyester fiber constituting the substrate. Layer A: Electroless nickel plating layer Layer B: Electrolytic nickel plating layer or electrolytic silver plating layer C layer: Electrolytic tin-nickel alloy plating layer D layer: Electrolytic gold plating layer or electrolytic platinum plating layer

[0023] (1) A layer (base layer) Layer A is a base layer that is laminated directly on the surface of the polyester fiber that constitutes the substrate. The base layer is laminated so as to cover not only the front or back surface of the polyester fiber, but also all of the portions of the polyester fiber that come into contact with the outside air. In other words, it is preferable to cover the surface of the polyester fiber with the base layer so that the polyester fiber itself does not come into contact with the electrolyte, for example, when the conductive fabric of the present invention is immersed in an electrolyte solution.

[0024] Layer A (base layer) is composed of an electroless nickel plating layer. The use of nickel improves the adhesion between the polyester fiber and the plating film. The electroless nickel plating layer is formed by electroless nickel plating.

[0025] Electroless nickel plating is a plating technique in which nickel is deposited on the surface of a material by a chemical reaction using a reducing agent. The specific plating method is not particularly limited, and any plating method known to those skilled in the art can be used. For example, electroless nickel plating can be performed by applying an electroless plating catalyst to a substrate using a colloidal solution containing a tin compound and a palladium compound, rinsing the substrate with water, and then immersing the substrate in a known electroless nickel plating bath such as an aqueous nickel sulfate solution containing a reducing agent.

[0026] The reducing agent is not particularly limited as long as it is a water-soluble compound that has the ability to reduce water-soluble metal compounds in the plating bath to metal, and examples that can be used include hydrazine derivatives, formaldehyde compounds, hydroxylamines, sugars, phosphorous acid, formic acid, boron hydride compounds, hypophosphites, dimethylamine borane, ascorbic acid, etc. These may be used alone or in combination of two or more.

[0027] The metal amount of the electroless nickel plating layer is not particularly limited, but is preferably 3 to 40 g / m 2 and more preferably 5 to 30 g / m 2 The metal amount of the electroless nickel plating layer is 3 g / m 2 By setting the thickness to 40 g / m or more, sufficient adhesion can be obtained. 2 By setting the following, it is possible to suppress an increase in manufacturing costs.

[0028] The electroless nickel plating film may be an alloy film containing other metals. The other metals are not particularly limited, and examples include transition metal elements of Group 5 or 6 of the periodic table, such as tungsten, molybdenum, niobium, tantalum, and vanadium. The other metals may also include phosphorus and boron derived from the reducing agent, and carbon, nitrogen, oxygen, sulfur, and the like derived from the additive. The other metals may be used alone or in combination of two or more. Among these, phosphorus is preferred because it provides better acid resistance.

[0029] (2) B layer (middle layer) Layer B is an intermediate layer formed on the surface of Layer A and between Layer C (described later) and Layer A, and is composed of an electrolytic nickel-plated layer or an electrolytic silver-plated layer. Layer B is formed so as to cover the entire surface of Layer A. In other words, Layer A is not exposed to the outside air, and it is desirable to prevent direct contact between Layer A and the electrolyte, even when the conductive fabric of the present invention is immersed in an electrolyte solution. In the present invention, by providing Layer B on the surface of Layer A, the surface resistivity of the conductive fabric can be reduced without reducing its oxidation resistance.

[0030] Layer B in the present invention may be either an electrolytic nickel plated layer or an electrolytic silver plated layer, but is preferably an electrolytic nickel layer from the viewpoint of reducing the oxygen overvoltage of the conductive fabric.

[0031] <Electrolytic nickel plating layer> The electrolytic nickel plating layer is formed by electrolytic nickel plating. Electrolytic nickel plating is a technique for forming a metallic nickel film on a substrate by using the reducing power of electrons generated by passing an electric current through an electrolytic nickel plating solution containing a water-soluble nickel compound. The specific plating method is not particularly limited, and any electrolytic nickel plating method known to those skilled in the art can be used.

[0032] Examples of electrolytic nickel plating solutions include a Watts bath containing nickel sulfate, nickel chloride, and boric acid, a nickel sulfamate bath containing nickel sulfamate, and a strike bath (Wood's bath) containing nickel chloride. Various nickel baths containing nickel monohydroxide, nickel carbonate, and nickel acetate can also be used. Primary brighteners, secondary brighteners, potential adjusters, pitting inhibitors, and the like may also be added to the electrolytic nickel plating solution.

[0033] The conditions for forming an electrolytic nickel plating layer by electroplating (electroplating method) are as follows: pH of the plating bath is in the range of 2 to 7, the plating bath temperature is in the range of 20 to 60°C, the plating time is in the range of 60 to 1200 seconds, and the current density is 0.5 A / dm 2 ~5.0A / dm 2 It is preferable that the range is within the range of, but is not limited to, these.

[0034] The metal amount of the electrolytic nickel plating layer is not particularly limited, but is preferably 10 to 80 g / m 2 and more preferably 20 to 40 g / m 2 The metal amount of the electrolytic nickel plating layer is 10 g / m 2 By setting the metal content of the electrolytic nickel plating layer at 80 g / m or more, sufficient conductivity and oxidation resistance as a conductive fabric can be obtained.2 By setting the following, it is possible to suppress an increase in manufacturing costs.

[0035] <Electrolytic silver plating layer> The electrolytic silver plating layer is formed by electrolytic silver plating. The electrolytic silver plating method is not particularly limited, and any electrolytic silver plating method known to those skilled in the art can be used.

[0036] The specific plating method for electrolytic silver plating is not particularly limited, and any electrolytic plating method known to those skilled in the art can be used, such as a method of depositing silver in an alkaline electrolytic silver plating bath containing cyanide, or a cyanide-free electrolytic silver plating bath that does not contain cyanide in consideration of the toxicity of cyanide.

[0037] In the electrolytic silver plating of the present invention, an electrolytic plating method using a non-cyanide-containing silver plating solution can be employed.

[0038] The silver concentration of the silver plating solution is not particularly limited, but is preferably 1 to 30 g / L in terms of silver.

[0039] The electrolytic plating conditions for forming an electrolytic silver plating layer are as follows: pH of the plating bath is in the range of 0.5 to 12, the plating bath temperature is in the range of 20 to 50°C, the plating time is in the range of 10 to 1200 seconds, and the current density is 0.5 A / dm 2 ~5A / dm 2 It is preferable that the range is within the range of

[0040] The metal amount of the electrolytic silver plating layer is not particularly limited, but is preferably 5 to 50 g / m 2 and more preferably 10 to 30 g / m 2 The metal amount of the electrolytic silver plating layer is 5 g / m 2 By setting the metal content of the electrolytic silver plating layer at 50 g / m or more, sufficient conductivity and oxidation resistance as a conductive fabric can be obtained. 2 By setting the following, it is possible to suppress an increase in manufacturing costs.

[0041] (3)C layer Layer C is a layer formed on the surface of Layer B and between Layer D and Layer B, which will be described later, and is composed of an electrolytic tin-nickel alloy plating layer. Layer C is formed so as to cover the entire surface of Layer B. In other words, Layer B is not exposed to the outside air, and it is desirable to prevent direct contact between Layer B and the electrolyte, even when the conductive fabric of the present invention is immersed in an electrolyte solution, for example. In the present invention, a conductive fabric having excellent oxidation resistance can be obtained by providing Layer C on the surface of Layer B. In the present invention, electrolytic plating is employed as a method for forming Layer C.

[0042] The electrolytic tin-nickel alloy plating layer is formed by electrolytic plating of a tin-nickel alloy. The specific method of electrolytic plating is not particularly limited, and any electrolytic plating method known to those skilled in the art can be used.

[0043] The tin-nickel alloy in the electrolytic tin-nickel alloy plating layer is an alloy containing at least tin and nickel, and by laminating such alloy layers, a conductive fabric with excellent oxidation resistance can be obtained.

[0044] The tin content is not particularly limited, but is preferably 50 wt% or more, more preferably 55 wt% or more, and particularly preferably 60 wt% or more of the total alloy. The upper limit of the tin content is not particularly limited, but is preferably 80 wt% or less, more preferably 75 wt% or less, and particularly preferably 70 wt% or less.

[0045] The nickel content is not particularly limited, but is preferably 20 wt% or more, more preferably 25 wt% or more, and particularly preferably 30 wt% or more of the total alloy amount. The upper limit of the nickel content is not particularly limited, but is preferably 50 wt% or less, more preferably 45 wt% or less, and particularly preferably 40 wt% or less.

[0046] The alloy ratio in the electrolytic tin-nickel alloy plating layer in the present invention is preferably within a range of 1:1 to 8:2 by weight of tin:nickel, and more preferably within a range of 6:4 to 7:3 by weight of tin:nickel. When the tin-nickel alloy ratio is within a range of 1:1 to 8:2 by weight of tin:nickel, the effect of improving oxidation resistance is sufficiently exhibited.

[0047] The tin-nickel alloy may contain metals other than tin and nickel, such as cobalt, molybdenum, and phosphorus.

[0048] In the present invention, the content of each metal in the electrolytic tin-nickel alloy plating film is measured by laser-induced breakdown spectroscopy.

[0049] The conditions for forming an electrolytic tin-nickel alloy plating layer by electrolytic plating are as follows: pH of the plating bath is in the range of 4 to 12, the plating bath temperature is in the range of 30 to 60°C, the plating time is in the range of 60 to 1200 seconds, and the current density is 0.5 A / dm 2 ~5.0A / dm 2 It is preferable that the range is within the range of

[0050] The metal amount of the electrolytic tin-nickel alloy plating layer is preferably 10 to 80 g / m 2 and more preferably 20 to 60 g / m 2 The metal amount of the electrolytic tin-nickel alloy plating layer is 10 g / m 2 If the thickness is 80 g / m or more, the base B layer can be sufficiently covered, and the oxidation resistance can be improved. 2 If the thickness is less than this, it is possible to suppress a decrease in oxidation resistance and an increase in manufacturing costs due to cracks occurring in the C layer.

[0051] (4)D layer Layer D is formed on the surface of Layer C and is the outermost metal layer that constitutes the conductive fabric. Layer D is a precious metal layer made of electrolytic gold plating or electrolytic platinum plating.

[0052] In the present invention, by providing Layer D on the surface of Layer C, it is possible to suppress the formation of an oxidation layer on the surface of the conductive fabric in an oxidizing environment, and to suppress the decrease in conductivity.

[0053] The D layer in the present invention may be either an electrolytic gold-plated layer or an electrolytic platinum-plated layer, but is preferably an electrolytic platinum-plated layer from the viewpoint of oxidation resistance.

[0054] <Electrolytic gold plating layer> The electrolytic gold plating layer is formed by electrolytic gold plating. The specific method of electrolytic gold plating is not particularly limited, and any method known to those skilled in the art can be used. By laminating such a precious metal layer, a conductive fabric with excellent oxidation resistance can be obtained.

[0055] The conditions for forming an electrolytic gold plating layer by electrolytic plating are as follows: pH of the plating bath is in the range of 1 to 12, the plating bath temperature is in the range of 30 to 80°C, the plating time is in the range of 5 to 60 seconds, and the current density is 0.3 A / dm 2 ~2.0A / dm 2 It is preferable that the range is within the range of

[0056] The metal content of the electrolytic gold plating layer is not particularly limited, but is preferably 0.3 to 3.0 g / m 2 and more preferably 0.5 to 1.5 g / m 2 The metal amount of the electrolytic gold plating layer is 0.3 g / m 2 If the metal content of the electrolytic gold plating layer is 3.0 g / m or more, a conductive fabric can be obtained that can sufficiently maintain conductivity even in a severe oxidizing environment. 2 If it is equal to or less than this, an increase in manufacturing costs can be suppressed.

[0057] <Electroplated platinum layer> The electrolytic platinum plating layer is formed by electrolytic platinum plating. The specific method of electrolytic platinum plating is not particularly limited, and any method known to those skilled in the art can be used. By laminating such a precious metal layer, a conductive fabric with excellent oxidation resistance can be obtained.

[0058] The conditions for forming an electrolytic platinum plating layer by electrolytic plating are as follows: pH of the plating bath is in the range of 0.5 to 12, the plating bath temperature is in the range of 30 to 80°C, the plating time is in the range of 5 to 120 seconds, and the current density is 0.5 A / dm 2 ~2.0A / dm 2 It is preferable that the range is within the range of

[0059] The metal content of the electrolytic platinum plating layer is not particularly limited, but is preferably 0.5 to 5.0 g / m 2 and more preferably 1.0 to 3.0 g / m 2 The metal content of the electrolytic platinum plating layer is 0.5 g / m 2 If the metal content of the electrolytic platinum plating layer is 5.0 g / m or more, a conductive fabric can be obtained that can sufficiently maintain conductivity even in a severe oxidizing environment. 2 If it is equal to or less than this, an increase in manufacturing costs can be suppressed.

[0060] 3.Conductive fabric (1) Layer composition The conductive fabric of the present invention is a fabric made of polyester fibers having the above-mentioned metal layers A to D laminated on the surface. The laminate structure is polyester fiber / Layer A / Layer B / Layer C / Layer D in this order. That is, Layer A is laminated directly on the polyester fiber, and Layer D is provided as the outermost layer.

[0061] Layer A, which can form a plating film with good adhesion to the textile substrate, is laminated directly onto the substrate as a base layer, and then layer B, a conductive layer with good conductivity and excellent oxidation resistance, is formed on top of that, followed by layer C, which has extremely good oxidation resistance (i.e., the metal layer is difficult to dissolve), and then layer D is formed on top of layer C. This prevents a decrease in conductivity (i.e., contact resistance) due to the formation of an oxide film on layer C, and makes it possible to increase oxidation resistance while maintaining conductivity.

[0062] In the present invention, it is necessary to provide the metal layers A to D in this order, but in addition, any other layer can be added between each layer as needed. An example of such an optional layer is a copper-plated layer between layers A and B. By providing a copper-plated layer between layers A and B, the conductivity of the conductive fabric can be further improved.

[0063] The copper plating layer may be formed by either electrolytic copper plating or electroless copper plating, with electroless copper plating being preferred. Existing plating baths can be used for electroless copper plating, including those using Rochelle salt, EDTA, quadrol, or the like as a copper complexing agent, formaldehyde baths using formaldehyde as a reducing agent, and formaldehyde-free baths using glyoxylic acid or the like as a reducing agent.

[0064] The plating temperature and plating time of the electroless copper plating bath can be adjusted appropriately depending on the plating film thickness and metal amount. The metal amount of the electroless copper plating layer is preferably 3 to 50 g / m 2 and more preferably 5 to 30 g / m 2 The metal amount of the electroless copper plating layer is 5 g / m 2 By setting the metal amount of the electroless copper plating layer at 30 g / m or more, excellent conductivity as a conductive fabric can be obtained. 2 By setting the following, it is possible to suppress an increase in manufacturing costs.

[0065] The conductive fabric of the present invention can have an appropriate opening ratio depending on the application. For example, when the conductive fabric is used as an electrode that comes into contact with an electrolyte in a battery or the like, the conductive fabric can be made into a mesh conductive fabric having an opening ratio of preferably 2 to 90%, more preferably about 3 to 50%.

[0066] The thickness of the conductive fabric of the present invention is not particularly limited, but is preferably 30 to 200 μm, more preferably 40 to 175 μm, and particularly preferably 50 to 150 μm.

[0067] The conductive fabric of the present invention has excellent acid resistance and oxidation resistance, and is lighter and less expensive than conventional metal meshes and punched porous metal foils. Although there are no particular limitations on the lightness, the weight of the conductive fabric of the present invention is preferably 300 g / m 2 or less, more preferably 250 g / m 2 Below 200 g / m, particularly preferably 2 The lower limit of the weight is not particularly limited, but is preferably 50 g / m 2 More preferably, 100 g / m 2 More preferably, 150 g / m 2 That's all.

[0068] The conductive fabric of the present invention has excellent acid resistance and oxidation resistance, and is therefore useful as an electrode that comes into contact with an electrolyte used in a battery or the like. [Example]

[0069] The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way.

[0070] <Evaluation method> The oxidation resistance evaluation test was carried out according to the following procedure. (1) Electrical connection As shown in Figure 1, the sample (size: 5 cm × 4 cm) was used as the anode and a SUS mesh (wire diameter 150 μm, 60 mesh) as the cathode. The sample was immersed in 200 mL of electrolyte (10 mM sulfuric acid) at 50 °C, and the current density was 10 A / dm 2 The power was applied for 20 minutes.

[0071] (2) Measurement of surface resistivity The surface resistivity was measured before and after the current treatment, and the rate of change was calculated to evaluate the oxidation resistance. Specifically, a resistivity meter [(trade name "Loresta MCP-T360"; manufactured by Nitto Seiko Analytech Co., Ltd.) and (trade name "LSP Probe"; manufactured by Nitto Seiko Analytech Co., Ltd.)] were used to measure the surface resistivity before the current treatment (before the test) and after the current treatment (after the test), and the rate of change (= "surface resistivity after the test / surface resistivity before the test") was calculated. The smaller this value, the better the conductivity and the higher the oxidation resistance.

[0072] (3) Conductivity measurement in the thickness direction After the electrical current treatment, the sample was sandwiched between two gold-plated brass plates (area 25.4 mm × 25.4 mm, thickness 10 mm), and under a pressure of 1 MPa, the resistance between the two gold-plated brass plates was measured using a Milliohm High Tester 3540 (manufactured by Hioki E.E. Corporation) (unit: mΩ·cm 2 The smaller this value, the better the electrical conductivity and the higher the oxidation resistance.

[0073] Example 1 As the base material, a mesh twill fabric was prepared, consisting of polyethylene terephthalate fibers (monofilaments) with a fiber diameter (mesh wire diameter) of approximately 80 μm for both the warp and weft threads, with a mesh size of 32 μm and a warp and weft density of 225 threads / inch.

[0074] The mesh twill fabric had a thickness of 135 μm and an opening rate of 8.2%. The opening rate was calculated using the following formula (Equation 2).

[0075] (Number 2) {Mesh opening ÷ (Mesh opening + Mesh wire diameter)} 2 ×100(%)

[0076] (Step 1) Formation of Layer A This mesh twill fabric was immersed for 18 seconds in an aqueous solution containing 0.3 g / L of palladium (II) chloride, 30 g / L of tin (II) chloride, and 250 ml / L of 36% hydrochloric acid at 20°C, then rinsed with water. It was then immersed for 45 seconds in an aqueous solution of 0.1 N hydroboric acid at 35°C, rinsed with water, and immersed in an electroless nickel plating bath.

[0077] [Electroless nickel plating bath composition] Nickel sulfate hexahydrate; 13.6g / L Trisodium citrate dihydrate; 21.2 g / L Sodium phosphinate: 13.6 g / L Ammonium chloride: 9.1 g / L Ammonia: 4.5 ml / L Plating bath pH: 8.4

[0078] [Electroless nickel plating conditions] Immersion temperature: 50℃ Soaking time: 30 minutes

[0079] An electroless nickel plating film was formed on the surface of the resulting mesh twill fabric. The electroless nickel plating film covered all of the polyester fibers that make up the mesh twill fabric and that were in contact with the outside air. The amount of metal measured by atomic absorption spectrometry was 25 g / m 2 It was.

[0080] (Step 2) Formation of Layer B The mesh twill fabric on whose surface an electroless nickel plating layer was formed in the above step was immersed in an electrolytic nickel plating bath. [Electrolytic nickel plating bath composition] Nickel sulfate hexahydrate; 160g / L Trisodium citrate dihydrate; 60g / L

[0081] [Electrolytic nickel plating conditions] Plating bath pH: 5.5 Plating bath temperature: 40℃ Plating time: 600 seconds Current density; 2A / dm 2

[0082] An electrolytic nickel plating film was formed on the surface of the obtained mesh twill fabric. The electrolytic nickel plating film covered all of the parts of the electroless nickel plating film formed on the surface of the polyester fibers constituting the mesh twill fabric in the above process that were in contact with the outside air. The metal amount was 32 g / m 2 It was.

[0083] (Step 3) Formation of layer C The mesh twill fabric on whose surface an electrolytic nickel plating layer had been formed in the above step was immersed in an electrolytic tin-nickel alloy plating bath. [Composition of electrolytic tin-nickel alloy plating bath] The electrolytic tin-nickel alloy plating bath used was a plating bath manufactured by Kizai Corporation (trade name "Nice One HI"). Nice One HI bath bath: 500mL / L Nice One HI 1-P; 24 g / L

[0084] [Conditions for electrolytic tin-nickel alloy plating] Plating bath pH: 8.5 Plating bath temperature: 50℃ Plating time: 360 seconds Current density; 3A / dm 2

[0085] An electrolytic tin-nickel alloy plating film was formed on the surface of the obtained mesh twill fabric. The electrolytic tin-nickel alloy plating film covered all of the parts of the electrolytic nickel plating film formed on the surface of the polyester fibers constituting the mesh twill fabric in the above process that were in contact with the outside air. The metal amount was 38 g / m 2 It was.

[0086] The composition of the tin-nickel alloy constituting the electrolytic tin-nickel alloy plating film is as follows: The composition of the alloy in the plating film was measured by laser-induced breakdown spectroscopy. Tin content: 62.2wt% Nickel content: 37.8wt% Tin:Nickel (weight ratio) = 62:38

[0087] (Step 4) Formation of D layer The mesh twill fabric, on the surface of which an electrolytic tin-nickel alloy plating layer was formed in the above step, was immersed in an electrolytic gold plating bath. [Electrolytic gold plating bath composition] The electrolytic gold plating bath used was Eco Gold 24 manufactured by Nisshin Seiki Co., Ltd.

[0088] [Electrolytic gold plating conditions] Plating bath pH: 8.5 Plating bath temperature: 50℃ Plating time: 10 seconds Current density; 1.2A / dm 2

[0089] An electrolytic gold plating film was formed on the surface of the resulting mesh twill fabric. The electrolytic gold plating film covered all of the areas of the electrolytic tin-nickel alloy plating film formed on the surface of the polyester fibers constituting the mesh twill fabric in the above process that were in contact with the outside air. The metal content was 0.9 g / m 2 It was. The conductive fabric made of the mesh twill fabric having the metal coating thus obtained was subjected to an oxidation resistance evaluation test, and the results are shown in Table 1.

[0090] <Example 2> Step 1 was carried out in the same manner as step 1 (formation of layer A) in Example 1, and then in step 2 (formation of layer B), electrolytic silver plating was carried out under the following conditions instead of electrolytic nickel plating.

[0091] [Electrolytic silver plating bath composition] The electrolytic silver plating bath used was "Dyne Silver GPE-ST15" manufactured by Daiwa Kasei Co., Ltd. ("Dyne Silver" is a product name; it is a mixture of the following four chemical solutions). The silver concentration in the plating bath was 15 g / L in silver equivalent. Dyne Silver MEC (silver salt); 100g / L Dyne Silver ACC (acid); 185g / L Dyne Silver LIG (complexing agent); 180g / L Dyne Silver MUB (conductive salt); 100g / L

[0092] [Electrolytic silver plating conditions] Plating bath temperature: 30℃ Plating time: 600 seconds Current density; 1.0A / dm 2

[0093] An electrolytic silver plating film was formed on the surface of the obtained mesh twill fabric. The electrolytic silver plating film was formed by coating the electroless nickel plating film formed on the surface of the polyester fibers constituting the mesh twill fabric in step 1, which was carried out in the same manner as in Example 1, so as to cover all of the portions of the film that come into contact with the outside air. The metal amount was 30 g / m 2 It was. Other than the above, steps 3 and 4 were carried out in the same manner as in Example 1 to obtain a conductive fabric. The oxidation resistance of this fabric was evaluated, and the results are shown in Table 1.

[0094] Example 3 As the base material, a mesh plain weave fabric was prepared, with a mesh size of 35 μm and a warp and weft density of 420 threads / inch, both of which were made of polyethylene terephthalate fibers (monofilaments) with a fiber diameter of approximately 25 μm. The thickness of this mesh plain weave fabric was 37 μm, and the opening ratio was 34%.

[0095] (Step 1) Formation of Layer A This mesh plain weave fabric was immersed for 18 seconds in an aqueous solution containing 0.3 g / L of palladium (II) chloride, 30 g / L of tin (II) chloride, and 250 ml / L of 36% hydrochloric acid at 20°C, then rinsed with water. It was then immersed for 45 seconds in an aqueous solution of 0.1 N hydroboric acid at 35°C, rinsed with water, and immersed in an electroless nickel plating bath.

[0096] [Electroless nickel plating bath composition] Nickel sulfate hexahydrate; 13.6g / L Trisodium citrate dihydrate; 21.2 g / L Sodium phosphinate: 13.6 g / L Ammonium chloride: 9.1 g / L Ammonia: 9.1 ml / L Plating bath pH: 8.4

[0097] [Electroless nickel plating conditions] Immersion temperature: 50℃ Soaking time: 3 minutes

[0098] An electroless nickel plating film was formed on the surface of the obtained mesh plain weave fabric. The electroless nickel plating film covered all of the polyester fibers that make up the mesh plain weave fabric and that were in contact with the outside air. The metal content was 6 g / m 2 It was.

[0099] (Step 2) Formation of copper plating layer The mesh plain weave fabric having the electroless nickel plating layer formed on its surface in the above step was immersed in an electroless copper plating bath.

[0100] [Electroless copper plating bath composition] Copper chloride dihydrate; 8.75 g / L EDP-300 (ADEKA Corporation); 20g / L 32% sodium hydroxide solution; 40 ml / L 37% formaldehyde aqueous solution; 8.75 ml / L

[0101] [Electroless copper plating conditions] Plating bath temperature: 40℃ Plating time: 600 seconds

[0102] An electroless copper plating film was formed on the surface of the obtained mesh plain weave fabric. The electroless copper plating film covered all of the polyester fibers that make up the mesh plain weave fabric and that were in contact with the outside air. The metal content was 21 g / m 2 It was.

[0103] (Step 3) Formation of Layer B The mesh plain weave fabric having the electroless copper plating layer formed on its surface in the above step was immersed in an electrolytic nickel plating bath having the same composition as in Example 1, and plated under the same conditions.

[0104] An electrolytic nickel plating film was formed on the surface of the obtained mesh plain weave fabric. The electrolytic nickel plating film covered all of the parts of the electroless copper plating film formed in the above process that were in contact with the outside air. The metal amount was 32 g / m 2 It was.

[0105] (Step 4) Formation of layer C The mesh plain weave fabric having an electrolytic nickel plating layer formed on its surface in the above step was immersed in an electrolytic tin-nickel alloy plating bath having the following composition. [Composition of electrolytic tin-nickel alloy plating bath] Nice One HI bath bath: 500mL / L Nice One HI 1-P; 38g / L

[0106] [Conditions for electrolytic tin-nickel alloy plating] Plating bath pH: 8.5 Plating bath temperature: 50℃ Plating time: 1080 seconds Current density; 1A / dm 2

[0107] An electrolytic tin-nickel alloy plating film was formed on the surface of the obtained mesh plain weave fabric. The electrolytic tin-nickel alloy plating film covered all of the parts of the electrolytic nickel plating film formed on the surface of the polyester fibers constituting the mesh twill fabric in the above process that were in contact with the outside air. The metal amount was 53 g / m 2 It was.

[0108] The composition of the tin-nickel alloy that constitutes the electrolytic tin-nickel alloy plating film is as follows: Tin content: 69.2wt% Nickel content: 30.8wt% Tin:Nickel (weight ratio) = 69:31

[0109] (Step 5) Formation of D layer The mesh plain weave fabric having an electrolytic tin-nickel alloy plating layer formed on its surface in the above step was immersed in the same electrolytic gold plating bath as in step 4 of Example 1 (formation of layer D), and plated under the same conditions.

[0110] An electrolytic gold plating film was formed on the surface of the obtained mesh plain weave fabric. The electrolytic gold plating film covered all of the areas of the electrolytic tin-nickel alloy plating film formed on the surface of the polyester fibers constituting the mesh plain weave fabric in the above process that were in contact with the outside air. The metal content was 1.0 g / m 2 It was. The conductive fabric made of the mesh plain weave fabric having the metal coating thus obtained was subjected to an oxidation resistance evaluation test. The results are shown in Table 1.

[0111] Example 4 The same procedures as in Example 3 were carried out except that in step 5 (formation of layer D) in Example 3, electrolytic platinum plating was carried out under the following conditions instead of electrolytic gold plating.

[0112] [Composition of electrolytic platinum plating bath] As the electrolytic platinum plating bath, a plating bath (product name "PTP-W") manufactured by Nisshin Seiki Co., Ltd. was used.

[0113] [Conditions for electrolytic platinum plating] Plating bath temperature: 60℃ Plating time: 90 seconds Current density; 3.0A / dm 2

[0114] An electrolytic platinum plating film was formed on the surface of the obtained mesh plain weave fabric. The electrolytic platinum plating film was formed by covering all parts that were in contact with the outside air with an electrolytic tin-nickel alloy plating film formed in the same manner as in step 4 (formation of layer C) of Example 3. The metal amount was 1.9 g / m 2 It was. The conductive fabric made of the mesh plain weave fabric having the metal coating thus obtained was subjected to an oxidation resistance evaluation test. The results are shown in Table 1.

[0115] <Comparative Example 1> A conductive fabric was obtained in the same manner as in Example 2, except that step 3 (formation of layer C: electrolytic tin-nickel alloy plating layer) was not performed. The oxidation resistance of this fabric was evaluated, and the results are shown in Table 1.

[0116] <Comparative Example 2> A conductive fabric was obtained in the same manner as in Example 2, except that an electrolytic nickel plating layer was formed instead of step 3 (layer C: formation of electrolytic tin-nickel alloy plating layer). The oxidation resistance of this fabric was evaluated, and the results are shown in Table 1. The composition of the electrolytic nickel plating bath and the conditions for electrolytic nickel plating were the same as in step 2 (formation of layer B) in Example 1.

[0117] [Table 1]

[0118] (*1) Measurement became impossible two minutes after the start of the electrical current treatment due to a disconnection caused by the disappearance of the metal layer. The disappearance of the metal layer is thought to be due to the dissolution and falling off of the metal layer. (*2) Measurement became impossible 15 minutes after the start of the electrical current treatment because a disconnection occurred due to the disappearance of the metal layer. The disappearance of the metal layer is thought to be due to the dissolution and falling off of the metal layer. [Industrial Applicability]

[0119] The conductive fabric of the present invention has excellent acid resistance and oxidation resistance, and, unlike conventional metal meshes and punched porous metal foils, is lightweight and can be produced at low cost. Therefore, it is useful as an electrode for batteries, particularly batteries using acidic electrolytes. [Explanation of symbols]

[0120] 1: Conductive fabric 2: SUS mesh

Claims

1. The base material is a woven fabric made of polyester fiber, and the surface of the polyester fiber is Layer A: Electroless nickel plating layer Layer B: Electrolytic nickel plating layer or electrolytic silver plating layer C layer: Electrolytic tin-nickel alloy plating layer D layer: Electrolytic gold plating layer or electrolytic platinum plating layer A conductive fabric in which the above are layered in this order.

2. 2. The conductive fabric according to claim 1, wherein the tin content in the C layer is 50 to 80 wt % as measured by laser-induced breakdown spectroscopy.

3. 2. The conductive fabric according to claim 1, wherein the opening ratio of the woven fabric made of polyester fibers is 1 to 50%.

4. The conductive fabric according to claim 1 , further comprising an electroless copper plating layer between the A layer and the B layer.

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