Electrochemical element, electrochemical element roll, and manufacturing method for electrochemical element

Abstract

To provide an electrochemical element that achieves both weight reduction and impact resistance, while also improving productivity.SOLUTION: An electrochemical element includes, in order, a gas-permeable glass film, an electrode layer, and an electrolyte layer. The bending radius is greater than 20 mm and not more than 200 mm, and the thickness of the glass film is 20 μm or more and 200 μm or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an electrochemical element, an electrochemical element roll, and a method for manufacturing an electrochemical element. [Background technology]

[0002] Solid oxide fuel cells (SOFCs) and proton-conducting ceramic fuel cells (PCFCs) have attracted attention as fuel cells due to their high power generation efficiency and the fact that they do not require precious metals. While electrolyte-supported and electrode-supported fuel cells are known for SOFCs and PCFCs, these have the drawback of being vulnerable to impacts and prone to cracking, particularly when installed in mobility devices such as automobiles and drones. To address these drawbacks, efforts are being made to improve impact resistance, and metal-supported fuel cells have been proposed.

[0003] For example, Patent Document 1 discloses a metal-supported electrochemical element having at least a metal substrate as a support, an electrode layer formed on the metal substrate, a buffer layer formed on the electrode layer, and an electrolyte layer formed on the buffer layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 047656 Summary of the Invention [Problem to be solved by the invention]

[0005] However, while conventional metal-supported electrochemical elements offer improved impact resistance, they are relatively heavy due to the metal support, which can make them difficult to handle during installation. Furthermore, when they are installed in mobility vehicles, this can be detrimental to improving fuel efficiency. Furthermore, metal-supported electrochemical elements are produced in batches, which reduces productivity.

[0006] An object of one aspect of the present invention is to provide an electrochemical element that can achieve both weight reduction and impact resistance, and can also improve productivity. [Means for solving the problem]

[0007] An electrochemical element according to one embodiment of the present invention comprises a gas-permeable glass film, an electrode layer, and an electrolyte layer in this order, the bending radius being greater than 20 mm and not greater than 200 mm, and the thickness of the glass film being not less than 20 μm and not greater than 200 μm. [Effects of the Invention]

[0008] According to an electrochemical element according to one aspect of the present invention, it is possible to achieve both weight reduction and impact resistance, and to improve productivity. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram illustrating the configuration of an electrochemical element according to an embodiment of the present invention. [Figure 2] 1 is a flowchart showing a method for manufacturing an electrochemical device according to an embodiment of the present invention. [Figure 3] 3A to 3C are diagrams illustrating a method for manufacturing an electrochemical element according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an embodiment of the present invention will be described in detail. To facilitate understanding of the description, the same components in the drawings will be denoted by the same reference numerals, and duplicated descriptions will be omitted. Also, the scale of each component in the drawings may differ from the actual scale.

[0011] FIG. 1 is a schematic diagram showing the configuration of an electrochemical element according to this embodiment. As shown in FIG. 1 , the electrochemical element 1 according to this embodiment includes, in this order, a gas-permeable glass film 2, an electrode layer 3, an electrolyte layer 4, and a counter electrode layer 5. The bending radius of the electrochemical element 1 is greater than 20 mm and less than 200 mm, and the thickness of the glass film 2 is greater than or equal to 20 μm and less than or equal to 200 μm. This configuration allows the electrochemical element 1 to achieve reduced weight and improved impact resistance. Furthermore, because the glass film 2 has sufficient flexibility, the electrochemical element 1 can be manufactured using a roll-to-roll process, improving productivity. That is, the electrochemical element 1 achieves both reduced weight and improved impact resistance, while also improving productivity. The bending radius of the electrochemical element 1 can be measured by the following method.

[0012] Several vinyl chloride poles with radii varying in 10 mm increments were prepared, ranging from 20 mm to 100 mm. In an environment of 23°C, electrochemical element 1 was placed along the pole with the glass film 2 facing outward, and cellophane tape (Nichiban Co., Ltd., "CT405AP-24," adhesive strength 3.93 N / 10 cm) was used to confirm whether both sides could be fixed, or whether the glass film would break. The smallest radius of the pole at which both sides could be fixed without the glass film breaking was defined as the bending radius. The size of the electrochemical element 1 used for measurement was 20 mm on the short side and the same length as the outer radius of the pole.

[0013] The bending radius of the electrochemical device 1 is preferably 30 mm or more and 180 mm or less, and more preferably 50 mm or more and 150 mm or less. If the bending radius of the electrochemical device 1 is within the above preferred range, the impact resistance of the electrochemical device 1 can be further improved.

[0014] The glass film 2 may have a sheet-like shape. The glass film 2 is formed using a long glass ribbon. The glass film 2 is obtained by cutting the long glass ribbon, for example. In this specification, the term "long" refers to an elongated shape having a length that is sufficiently longer than its width, and includes, for example, an elongated rectangular shape having a length that is 10 times or more, preferably 20 times or more, as compared to its width.

[0015] The glass film 2 can be formed using any suitable glass material. The glass material constituting the glass film 2 is preferably inorganic glass. Examples of inorganic glass classified by composition include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass, and examples of inorganic glass classified by alkali component include alkali-free glass and low-alkali glass. The content of alkali metal components (e.g., Na2O, K2, and Li2O) in the above glass is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0016] The thickness of the glass film 2 is preferably 25 mm or more and 190 mm or less, and more preferably 30 mm or more and 180 mm or less. When the thickness of the glass film 2 is within the above preferred range, the electrochemical device 1 can be made lighter and have improved impact resistance. Furthermore, because the glass film 2 is easily bendable, the electrochemical device 1 can be easily manufactured using a roll-to-roll process, thereby further improving productivity.

[0017] The glass film 2 may have a plurality of through holes 21. Specifically, the through holes 21 penetrate from the upper surface (the surface facing the electrode layer 3) to the lower surface (the surface opposite the electrode layer 3) of the glass film 2. This allows gas to pass from the lower surface to the upper surface of the glass film 2, making it possible to provide a PCFC that can achieve reduced weight and improved impact resistance.

[0018] The shape of the through-hole 21 in a plan view may be circular, and the diameter of the through-hole 21 may be 5 mm or more and 20 mm or less. The through-hole 21 may be formed by, for example, laser processing.

[0019] The length and width of the glass film 2 are not particularly limited and can be designed appropriately depending on the size of the electrochemical device 1. The length of the glass film 2 is, for example, preferably 50 mm or more and 5000 mm or less, and more preferably 100 mm or more and 1500 mm or less. The width of the glass film 2 is, for example, preferably 50 mm or more and 5000 mm or less, and more preferably 100 mm or more and 1500 mm or less. The length and width of the glass films 2 may be the same or different.

[0020] The density of the glass film 2 is not particularly limited and may be, for example, 2.3 g / cm 3 More than 3.0g / cm 3 The following may be used.

[0021] The manufacturing method of the glass film 2 is not particularly limited, and a general manufacturing method may be used. The glass film 2 is manufactured, for example, by melting a mixture containing a main raw material such as silica or alumina, an antifoaming agent such as mirabilite or antimony oxide, and a reducing agent such as carbon at a temperature of 1400°C to 1600°C, forming the mixture into a thin plate, and then cooling it. The glass film 2 may be chemically polished with a solvent such as hydrofluoric acid, as necessary, to make the glass film thinner or to improve its smoothness.

[0022] A common method may be used as the method for forming the glass film 2. Examples of methods that can be used for forming the glass film 2 include a slot downdraw method, a fusion method, and a float method. Among these, when the fusion method is used, the surface of the glass film 2 is not contaminated with tin or the like as in the case of the float method, so polishing is not necessary and it is easy to ensure surface smoothness and thinness. Therefore, from these viewpoints, it is preferable to use the fusion method.

[0023] A commercially available glass film may be used as is for the glass film 2, or a commercially available glass sheet may be polished to a desired thickness and used. Examples of commercially available glass sheets include "7059," "1737," or "EAGLE2000" manufactured by Corning Incorporated, "AN100" manufactured by Asahi Glass Co., Ltd., "NA-35" manufactured by NH Technoglass Co., Ltd., "OA-10G" manufactured by Nippon Electric Glass Co., Ltd., and "D263" or "AF45" manufactured by Schott.

[0024] The electrode layer 3 is an anode. When the electrochemical device 1 is a PCFC, the electrode layer 3 has hydrogen permeability. That is, the electrode layer 3 is permeable to protons (H + ion) conductivity and oxygen ion (O 2- ) It has no conductivity. The thickness of the electrode layer 3 can be, for example, 1 μm or more and 1000 μm or less.

[0025] Examples of materials constituting the electrode layer 3 include hydrogen-permeable membranes such as Pd (palladium) membranes and Pd alloy membranes. Specific examples of palladium alloys include Pd-Au (palladium-gold), Pd-Ag (palladium-silver), Pd-Pt (palladium-platinum), and Pd-Cu (palladium-copper). Furthermore, trace amounts of Group 3 elements, Group 4 elements, Group 5 elements, iron group elements, and platinum group elements may be added to the palladium or palladium alloys. Specific examples of additive elements include Y (yttrium), Ho (holmium), Ti (titanium), Zr (zirconium), Ni (nickel), Nb (niobium), V (vanadium), and Ru (ruthenium).

[0026] The electrolyte layer 4 may contain an oxide. This makes it possible to provide a PCFC or SOFC that can achieve lighter weight and improved impact resistance. When the electrochemical device 1 is a PCFC, the material constituting the electrolyte layer 4 may be BaZr x Ce 1-x-z Y zExamples include O3 (BZCY), yttrium-doped barium zirconate (BZY), yttrium-doped barium cerate (BCY), etc. The thickness of the electrolyte layer 4 is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 1 μm or less.

[0027] The counter electrode layer 5 is a cathode. The counter electrode layer 5 has a function of adsorbing oxygen molecules and dissociating and ionizing them. In the counter electrode layer 5, protons conducted via the electrolyte layer 4 react with oxygen ions. The thickness of the counter electrode layer 5 can be, for example, 1 μm or more and 1000 μm or less.

[0028] The counter electrode layer 5 may be made of a known material that is used as a cathode for a fuel cell. 0.6 Sr 0.4 Co 0.2 Fe 0.8 Lanthanum strontium cobalt ferrite (LSCF) such as O3, Sm 0.5 Sr 0.5 Samarium strontium cobaltite (SSC) such as CoO3, Ba 0.5 Sr 0.5 Co 0.6 Fe 0.4 Examples include barium strontium cobalt ferrite (BSCF) such as O3.

[0029] The glass film 2, the electrode layer 3, the electrolyte layer 4, and the counter electrode layer 5 may be in contact with each other, or other layers may be provided between the layers. The electrochemical device 1 may be a glass-supported SOFC or a glass-supported PCFC.

[0030] FIG. 2 is a flowchart illustrating a method for manufacturing an electrochemical device according to this embodiment, and FIG. 3 is a diagram illustrating a method for manufacturing an electrochemical device according to this embodiment. As shown in FIG. 2 , the method for manufacturing an electrochemical device 1 according to this embodiment includes the following steps: Step S1: forming an electrode layer 3 on a glass film 2 having a thickness of 20 μm to 200 μm and being gas-permeable while transporting the glass film 2 by a roll-to-roll process; Step S2: forming an electrolyte layer 4 on the electrode layer 3; and Step S3: forming a counter electrode layer 5 on the electrolyte layer 4. Thus, the method for manufacturing an electrochemical device 1 according to this embodiment can provide an electrochemical device 1 that is lightweight and has improved impact resistance. Furthermore, because the electrochemical device 1 is manufactured using a roll-to-roll process, the productivity of the electrochemical device 1 can be improved.

[0031] 3 , a roll-to-roll transport device 100 is used to transport a rolled glass film 2 from a payout roller 110, while a processing device 120 forms an electrode layer 3 on the glass film 2. Subsequently, the processing device 120 can form an electrolyte layer 4 on the electrode layer 3, and a counter electrode layer 5 on the electrolyte layer 4.

[0032] The processing device 120 includes, for example, a sputtering device, a screen printing machine, etc. The laminate 9, which is transported from the processing device 120 and is made of the glass film 2, the electrode layer 3, the electrolyte layer 4, and the counter electrode layer 5, is wound into a roll by a winding roller 130, thereby obtaining an electrochemical element roll 10. The glass film 2, the electrode layer 3, the electrolyte layer 4, and the counter electrode layer 5 are the same as the respective components of the electrochemical element 1 described above, and therefore description thereof will be omitted here.

[0033] In the method for producing the electrochemical device 1, after step S3 of forming the counter electrode layer 5, the obtained electrochemical device roll 10 is cut to a predetermined size to obtain the electrochemical device 1. The method for cutting the electrochemical device roll 10 is, for example, a method of dividing the electrochemical device roll 10 by irradiating it with laser light.

[0034] When using a method of dividing the electrochemical element roll 10 by irradiating it with laser light, the electrochemical element roll 10 may be divided using a laser light irradiator that irradiates any suitable laser light. A stage is disposed movably relative to the laser light irradiator, and a laser light source is disposed fixedly. The laser light irradiator moves the stage to change the position of the laser light irradiated onto the electrochemical element roll 10.

[0035] Examples of laser light include gas lasers such as CO2 lasers and excimer lasers; solid-state lasers such as YAG lasers; semiconductor lasers; and ultrashort pulse lasers.

[0036] As shown in FIG. 3 , the electrochemical element roll 10 of this embodiment is an electrochemical element 1 wound into a roll. That is, the electrochemical element roll 10 has a long shape and includes a gas-permeable glass film 2, an electrode layer 3, and an electrolyte layer 4, in this order. The bending radius of the electrochemical element 1 is greater than 20 mm and not greater than 200 mm, and the thickness of the glass film 2 is 20 μm or greater and 200 μm or less. This configuration enables the electrochemical element roll 10 to be lightweight and have improved impact resistance. The bending radius of the electrochemical element roll 10 can be measured by the method for measuring the bending radius of the electrochemical element 1 described above. [Example]

[0037] Hereinafter, the embodiment will be described in more detail with reference to examples and comparative examples, but the embodiment is not limited to these examples and comparative examples.

[0038] <Fabrication of electrochemical devices> Glass substrates were prepared by forming multiple through holes of approximately 10 μm to 15 μm in size using laser processing in an area 2.5 mm from the center of each 100 mm square glass film ("OA-10G" manufactured by Nippon Electric Glass Co., Ltd.) having the thickness shown in Table 1.

[0039] A 200 nm thick Pd film was deposited on a glass substrate as an electrode layer by DC sputtering. A 1 μm thick BaZr 0.1 Ce 0.7 Y 0.2 O3(BZCY) electrolyte thin film, BaCe 0.8 Y 0.2 O3(BCYO) and Zr 0.9 Y 0.1 The film was formed by radio frequency sputtering using an O2 (ZYO) target. The radio frequency sputtering conditions were as follows: under vacuum, O2 was introduced at a flow rate of 0.1 sccm and Ar at a flow rate of 49.9 sccm, the substrate temperature was 400°C, the sputtering pressure was 2 Pa, and the sputtering time was 7 hours. For the BCYO target, the distance from the glass substrate was 70 mm and the sputtering power was 70 W, and for the ZYO target, the distance from the glass substrate was 120 mm and the sputtering power was 30 W. A La was placed on the front of the electrolyte thin film as a counter electrode layer. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 (LSCF) powder paste (Fuel cell materials) was screen printed.

[0040] As a result, electrochemical devices of Examples 1 and 2 and Comparative Examples 1 and 2 were obtained, in which a glass film, an electrode layer made of Pd, an electrolyte layer made of BZCY, and a counter electrode layer made of LSCF were laminated in this order.

[0041] <Evaluation> The electrochemical elements of each of the examples and comparative examples were evaluated for bending radius and impact resistance as follows. The evaluation results are shown in Table 1.

[0042] (bending radius) Several vinyl chloride poles with radii varying in 10 mm increments were prepared, ranging from 20 mm to 100 mm. In an environment of 23 °C, an electrochemical element was placed along the pole with the glass film facing outward. Cellophane tape (Nichiban Co., Ltd., "CT405AP-24," adhesive strength 3.93 N / 10 cm) was used to confirm whether both sides could be fixed, or whether the glass film would crack. The smallest radius of the pole that could fix both sides without cracking the glass film was defined as the bending radius. The size of the electrochemical element used for measurement was 20 mm for the short side and the same length as the outer radius of the pole. A bending radius of more than 20 mm and up to 200 mm was evaluated as practically usable, while a bending radius of less than 20 mm or more than 200 mm was evaluated as unusable.

[0043] (shock resistance) The electrochemical element was cut into a 5 cm x 5 cm piece and attached to a glass plate to prepare an evaluation sample. A piercing rod (0.5 mm in diameter) was dropped onto the sample from a height of 10 cm at a rate of 20 mm / min, and the glass film was visually inspected for cracks and evaluated according to the following criteria. Good: No cracks Defective: Cracked

[0044] An overall evaluation was made with an A rating if the bending radius was practically usable and the impact resistance was good, and a B rating if the bending radius was unusable for practical use or the impact resistance was poor, or if the bending radius was unusable for practical use and the impact resistance was poor. An evaluation result of A was considered a pass, and a B was considered a fail.

[0045] [Table 1]

[0046] As shown in Table 1, the electrochemical elements of Examples 1 and 2 had a bend radius that was practically usable, good impact resistance, and an overall rating of A. The electrochemical element of Comparative Example 1 had good impact resistance, but the bend radius was not practically usable, and an overall rating of B. The electrochemical element of Comparative Example 2 had a bend radius that was practically usable, but poor impact resistance, and an overall rating of B.

[0047] Although the embodiments have been described above, they are presented as examples and the present invention is not limited to the above embodiments. The above embodiments can be implemented in various other forms, and various combinations, omissions, substitutions, modifications, etc. can be made without departing from the spirit of the invention. These embodiments and their modifications are included within the scope and spirit of the invention, and are also included in the inventions and their equivalents as set forth in the claims. [Explanation of symbols]

[0048] 1. Electrochemical element 2. Glass film 21 Through hole 3 electrode layer 4 Electrolyte layer 5. Counter electrode layer 10 Electrochemical element roll

Claims

1. A glass sheet including a gas-permeable glass film, an electrode layer, and an electrolyte layer in this order, and a bending radius of more than 20 mm and 200 mm or less, The electrochemical element, wherein the glass film has a thickness of 20 μm or more and 200 μm or less.

2. 2. The electrochemical device according to claim 1, wherein the electrolyte layer comprises an oxide.

3. The electrochemical element according to claim 1 , wherein the glass film has a plurality of through holes.

4. A long, gas-permeable glass film, an electrode layer, and an electrolyte layer are provided in this order, and the bending radius is more than 20 mm and 200 mm or less. The electrochemical element roll, wherein the glass film has a thickness of 20 μm or more and 200 μm or less.

5. forming an electrode layer on a glass film having a thickness of 20 μm or more and 200 μm or less and being gas permeable, while transporting the glass film by a roll-to-roll method; forming an electrolyte layer on the electrode layer; and forming a counter electrode layer on the electrolyte layer.

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