JP6197437B2 - Conductive sheet, fuel cell, and method for producing conductive sheet - Google Patents
Conductive sheet, fuel cell, and method for producing conductive sheet Download PDFInfo
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
本発明は、導電性シート、燃料電池、および導電性シートの製造方法に関する。 The present invention relates to a conductive sheet, a fuel cell, and a method for manufacturing a conductive sheet.
固体高分子形燃料電池は、高分子電解質膜の両面に触媒層が形成された膜電極接合体を、ガスの流路が形成されたセパレータによって挟んだ構成を有する。膜電極接合体とセパレータとの間に、ガスを拡散させるガス拡散層が配置される。 The polymer electrolyte fuel cell has a configuration in which a membrane electrode assembly in which catalyst layers are formed on both surfaces of a polymer electrolyte membrane is sandwiched between separators in which gas flow paths are formed. A gas diffusion layer for diffusing a gas is disposed between the membrane electrode assembly and the separator.
例えば特許文献１に記載のガス拡散層は、金属製の発泡体からなる基材に、撥水性樹脂層、および金メッキ等からなる導電性被覆層が形成された構成を有する。撥水樹脂層および導電性被覆層によって、耐食性および導電性が向上する。 For example, the gas diffusion layer described in Patent Document 1 has a configuration in which a water-repellent resin layer and a conductive coating layer made of gold plating or the like are formed on a base material made of a metal foam. Corrosion resistance and conductivity are improved by the water-repellent resin layer and the conductive coating layer.
また、これとは別に、シート状の金網からなる基材にＤＬＣ（Ｄｉａｍｏｎｄ−Ｌｉｋｅ−Ｃａｒｂｏｎ；ダイヤモンドライクカーボン）を被覆した構成を有するガス拡散層について検討が進められている。ＤＬＣによる被覆によって、金メッキ等に比べてコストを抑えつつ耐食性および導電性を向上できる。ＤＬＣはスパッタリング法等のＰＶＤ法（Ｐｈｙｓｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ；物理気相成長法または物理的蒸着法）によって形成される。 Separately from this, a gas diffusion layer having a structure in which a base made of a sheet-like wire mesh is coated with DLC (Diamond-Like-Carbon) has been studied. By covering with DLC, corrosion resistance and conductivity can be improved while suppressing costs compared to gold plating or the like. DLC is formed by PVD methods (Physical Vapor Deposition; physical vapor deposition or physical vapor deposition) such as sputtering.
しかしながら、被覆対象である金網を構成している線材と線材との交差部では線材同士が接する接触箇所の近傍が影になり易いため、金網に対しＰＶＤ法を行うと、その部分では被膜が形成され難く耐食性が相対的に低くなる。 However, since the vicinity of the contact point where the wires are in contact with each other is likely to become a shadow at the intersection of the wire and the wire constituting the wire mesh to be coated, a coating is formed at that portion when the PVD method is performed on the wire mesh. The corrosion resistance is relatively low.
本発明は、このような課題に鑑みてなされたものであり、耐食性向上を図り得る導電性シート、燃料電池、および導電性シートの製造方法を提供することを目的とする。 This invention is made | formed in view of such a subject, and it aims at providing the manufacturing method of the electroconductive sheet which can aim at corrosion resistance improvement, a fuel cell, and an electroconductive sheet.
上記目的を達成するための本発明の導電性シートは、線材と線材とが交差する交差部を有する金網からなる。耐食性を有する腐食防止部が、交差部における線材同士が接する接触箇所の近傍だけに形成されている。 In order to achieve the above object, the conductive sheet of the present invention comprises a wire mesh having an intersection where the wire and the wire intersect. The corrosion prevention part which has corrosion resistance is formed only in the vicinity of the contact location where the wire materials in the crossing part contact.
上記目的を達成するための本発明の燃料電池は、電解質膜の両面に触媒成分を含む層が形成された膜電極接合体、膜電極接合体を挟む一対のセパレータ、および、膜電極接合体とセパレータとの間に配置されたガス拡散層を有する。ガス拡散層は、線材と線材とが交差する交差部を有する金網からなり、交差部における線材同士が接する接触箇所の近傍だけに耐食性を有する腐食防止部が形成されている。 In order to achieve the above object, a fuel cell of the present invention comprises a membrane electrode assembly in which layers containing a catalyst component are formed on both surfaces of an electrolyte membrane, a pair of separators sandwiching the membrane electrode assembly, and a membrane electrode assembly, It has a gas diffusion layer arranged between the separators. The gas diffusion layer is made of a wire mesh having an intersection where the wire and the wire intersect, and a corrosion preventing portion having corrosion resistance is formed only in the vicinity of a contact portion where the wires are in contact with each other at the intersection.
上記目的を達成するための本発明の導電性シートの製造方法は、金網を準備する金網準備工程と、金網準備工程後、耐食性を有する腐食防止部を金網に形成する腐食防止部形成工程と、を有する。腐食防止部形成工程において、腐食防止部は、金網を構成する線材と線材との交差部における線材同士が接する接触箇所の近傍だけに形成される。 The method for producing a conductive sheet of the present invention for achieving the above object includes a wire mesh preparation step of preparing a wire mesh, a corrosion prevention portion forming step of forming a corrosion prevention portion having corrosion resistance on the wire mesh after the wire mesh preparation step, Have In the corrosion prevention portion forming step, the corrosion prevention portion is formed only in the vicinity of the contact portion where the wire rods contact each other at the intersection of the wire rod and the wire rod constituting the wire mesh.
本発明によれば、金網を構成している線材の交差部において、腐食防止部が線材同士の接触箇所の近傍からガスや水等の腐食の要因となるものを遮断するため、線材同士の接触箇所の近傍ひいては接触箇所の腐食が防止され、耐食性が向上する。 According to the present invention, at the crossing portion of the wire constituting the wire mesh, the corrosion prevention portion blocks the cause of corrosion such as gas or water from the vicinity of the contact point between the wire, The corrosion of the vicinity of the part and the contact part is prevented, and the corrosion resistance is improved.
以下、添付した図面を参照しながら、本発明の実施形態を説明する。なお、図面の寸法比率は、説明の都合上誇張されており、実際の比率と異なる。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, the dimension ratio of drawing is exaggerated on account of description, and differs from an actual ratio.
図１〜図３を参照して、実施形態の燃料電池１０は、電池の最小単位である燃料電池セル１２０を複数積層するとともに電気的に接続した燃料電池スタック１２６を有する。燃料電池１０は、燃料電池セル１２０の積層方向における燃料電池スタック１２６の両端に、積層された複数の燃料電池セル１２０から電気を集める集電板１３０を有する。燃料電池１０は、燃料電池スタック１２６および集電板１３０を燃料電池セル１２０の積層方向から加圧して挟持するエンドプレート１３１を有する。燃料電池１０は、エンドプレート１３１同士を連結する連結板１３４を有する。 1 to 3, the fuel cell 10 of the embodiment includes a fuel cell stack 126 in which a plurality of fuel cells 120 that are the minimum unit of the battery are stacked and electrically connected. The fuel cell 10 has current collecting plates 130 that collect electricity from the plurality of stacked fuel cells 120 at both ends of the fuel cell stack 126 in the stacking direction of the fuel cells 120. The fuel cell 10 includes an end plate 131 that pressurizes and sandwiches the fuel cell stack 126 and the current collector plate 130 from the stacking direction of the fuel cells 120. The fuel cell 10 includes a connecting plate 134 that connects the end plates 131 to each other.
集電板１３０は燃料電池スタック１２６と電気的に接続している。集電板１３０は、エンドプレート１３１を貫通して突出する突起部１３３と電気的に接続している。突起部１３３を介して電気が取り出される。集電板１３０およびエンドプレート１３１は、例えば金属によって形成される。集電板１３０とエンドプレート１３１とは絶縁されている。 The current collector plate 130 is electrically connected to the fuel cell stack 126. The current collector plate 130 is electrically connected to a protrusion 133 that protrudes through the end plate 131. Electricity is taken out through the protrusion 133. The current collector plate 130 and the end plate 131 are made of, for example, metal. The current collector plate 130 and the end plate 131 are insulated.
燃料電池スタック１２６の一端に配置された集電板１３０およびエンドプレート１３１に、燃料電池セル１２０に連通するマニホールド１３２が複数形成されている。水素等の燃料ガスおよび空気等の酸化剤ガス、ならびに冷却水等の冷却流体は、複数のマニホールド１３２のうちの半数を通じ各燃料電池セル１２０に供給され、また、各燃料電池セル１２０を通った後、マニホールド１３２の残りの半数を通じて排出される。 A plurality of manifolds 132 communicating with the fuel cell 120 are formed on the current collecting plate 130 and the end plate 131 arranged at one end of the fuel cell stack 126. A fuel gas such as hydrogen and an oxidant gas such as air and a cooling fluid such as cooling water are supplied to each fuel cell 120 through half of the plurality of manifolds 132, and also passed through each fuel cell 120. Thereafter, it is discharged through the remaining half of the manifold 132.
連結板１３４はエンドプレート１３１に締結される。連結板１３４は、燃料電池スタック１２６のまわりを覆う。連結板１３４は、例えば金属によって形成される。 The connecting plate 134 is fastened to the end plate 131. The connecting plate 134 covers the periphery of the fuel cell stack 126. The connecting plate 134 is made of, for example, metal.
図３および図４を参照して、燃料電池セル１２０は、電気化学反応が進行する膜電極接合体１２１、ならびに膜電極接合体１２１を挟むカソードセパレータ１２３およびアノードセパレータ１２４を有する。燃料電池セル１２０は、膜電極接合体１２１とカソードセパレータ１２３との間、および膜電極接合体１２１とアノードセパレータ１２４との間に、導電性およびガス拡散性を有するガス拡散層１２５を有する。 3 and 4, the fuel cell 120 includes a membrane electrode assembly 121 in which an electrochemical reaction proceeds, and a cathode separator 123 and an anode separator 124 that sandwich the membrane electrode assembly 121. The fuel cell 120 includes a gas diffusion layer 125 having electrical conductivity and gas diffusibility between the membrane electrode assembly 121 and the cathode separator 123 and between the membrane electrode assembly 121 and the anode separator 124.
図４に示すように、膜電極接合体１２１は、高分子電解質膜１２１ａと、高分子電解質膜１２１ａの一方の面に形成されるカソード触媒層１２１ｂと、高分子電解質膜１２１ａの他方の面に形成されるアノード触媒層１２１ｃと、を有する。カソード触媒層１２１ｂおよびアノード触媒層１２１ｃの各々を囲むフレーム１２２が高分子電解質膜１２１ａの両面に設けられている。 As shown in FIG. 4, the membrane electrode assembly 121 includes a polymer electrolyte membrane 121a, a cathode catalyst layer 121b formed on one surface of the polymer electrolyte membrane 121a, and the other surface of the polymer electrolyte membrane 121a. And an anode catalyst layer 121c to be formed. Frames 122 surrounding each of the cathode catalyst layer 121b and the anode catalyst layer 121c are provided on both surfaces of the polymer electrolyte membrane 121a.
高分子電解質膜１２１ａは、例えばフッ素樹脂等から形成され、水素イオンを伝導するイオン交換膜である。カソード触媒層１２１ｂおよびアノード触媒層１２１ｃは、それぞれ、導電性の担体に担持された触媒成分と、高分子電解質と、を含む。カソード触媒層１２１ｂに用いられる触媒成分は、酸素の還元反応に触媒作用を有するものであれば特に制限はなく、公知の触媒を使用できる。アノード触媒層１２１ｃに用いられる触媒成分は、水素の酸化反応に触媒作用を有するものであれば特に制限はなく、公知の触媒を使用できる。触媒成分は、例えば、白金、ルテニウム、イリジウム、ロジウム、パラジウム、オスミウム、タングステン、鉛、鉄、クロム、コバルト、ニッケル、マンガン、バナジウム、モリブデン、ガリウム、アルミニウム等の金属、及びそれらの合金等から選択される。 The polymer electrolyte membrane 121a is an ion exchange membrane formed of, for example, a fluororesin or the like and conducting hydrogen ions. Each of the cathode catalyst layer 121b and the anode catalyst layer 121c includes a catalyst component supported on a conductive carrier and a polymer electrolyte. The catalyst component used for the cathode catalyst layer 121b is not particularly limited as long as it has a catalytic action for the oxygen reduction reaction, and a known catalyst can be used. The catalyst component used for the anode catalyst layer 121c is not particularly limited as long as it has a catalytic action in the oxidation reaction of hydrogen, and a known catalyst can be used. The catalyst component is selected from, for example, metals such as platinum, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, aluminum, and alloys thereof. Is done.
図３に示すように、カソードセパレータ１２３に、マニホールド１３２に連通するマニホールド１２３ｃが形成されている。フレーム１２２に、マニホールド１３２に連通するマニホールド１２２ａが形成されている。アノードセパレータ１２４に、マニホールド１３２に連通するマニホールド１２４ｃが形成されている。マニホールド１２３ｃ、１２２ａ、１２４ｃは、互いに連通する。 As shown in FIG. 3, the cathode separator 123 is formed with a manifold 123 c that communicates with the manifold 132. A manifold 122 a that communicates with the manifold 132 is formed in the frame 122. A manifold 124 c communicating with the manifold 132 is formed in the anode separator 124. The manifolds 123c, 122a, and 124c communicate with each other.
図４を参照して、カソードセパレータ１２３における膜電極接合体１２１側の面に形成された流路１２３ａは、図３に示す複数のマニホールド１２３ｃのうち酸化剤ガスが流れるものと連通している。 Referring to FIG. 4, the flow path 123 a formed on the surface of the cathode separator 123 on the membrane electrode assembly 121 side communicates with the one through which the oxidizing gas flows among the plurality of manifolds 123 c shown in FIG. 3.
酸化剤ガスは、流路１２３ａからガス拡散層１２５を通過してカソード触媒層１２１ｂに達する。ガス拡散層１２５は、流路１２３ａとカソード触媒層１２１ｂとの間で酸化剤ガスを均一に拡散させる。 The oxidant gas passes through the gas diffusion layer 125 from the flow path 123a and reaches the cathode catalyst layer 121b. The gas diffusion layer 125 diffuses the oxidant gas uniformly between the flow path 123a and the cathode catalyst layer 121b.
フレーム１２２とカソードセパレータ１２３との間に酸化剤ガスの漏出を防止するシール部材を設けてもよいが、図示を省略している。流路１２３ａとは反対側の面に形成された流路１２３ｂを冷却流体が流れる。カソードセパレータ１２３は、例えば金属によって形成される。 Although a seal member for preventing leakage of the oxidant gas may be provided between the frame 122 and the cathode separator 123, the illustration is omitted. The cooling fluid flows through the channel 123b formed on the surface opposite to the channel 123a. The cathode separator 123 is made of, for example, metal.
アノードセパレータ１２４における膜電極接合体１２１側の面に形成された流路１２４ａは、図３に示す複数のマニホールド１２４ｃのうち燃料ガスが流れるものと連通している。燃料ガスは、流路１２４ａからガス拡散層１２５を通過してアノード触媒層１２１ｃに達する。ガス拡散層１２５は、流路１２４ａとアノード触媒層１２１ｃとの間で燃料ガスを均一に拡散させる。 A flow path 124a formed on the surface of the anode separator 124 on the membrane electrode assembly 121 side communicates with a flow of fuel gas among the plurality of manifolds 124c shown in FIG. The fuel gas passes through the gas diffusion layer 125 from the flow path 124a and reaches the anode catalyst layer 121c. The gas diffusion layer 125 uniformly diffuses the fuel gas between the flow path 124a and the anode catalyst layer 121c.
フレーム１２２とアノードセパレータ１２４との間に燃料ガスの漏出を防止するシール部材を設けてもよいが、図示を省略している。流路１２４ａとは反対側の面に形成された流路１２４ｂを冷却流体が流れる。アノードセパレータ１２４は、例えば金属によって形成される。 Although a sealing member for preventing leakage of fuel gas may be provided between the frame 122 and the anode separator 124, the illustration is omitted. The cooling fluid flows through the flow path 124b formed on the surface opposite to the flow path 124a. The anode separator 124 is made of, for example, metal.
ガス拡散層１２５として、図５に示すように金網１００から形成される導電性シート１が用いられる。 As the gas diffusion layer 125, the conductive sheet 1 formed from the wire mesh 100 as shown in FIG. 5 is used.
図６および図７に示すように、金網１００は、縦横に織り込まれた線材１０１によって形成される。金網１００は、織物の構造に限定されず、線材１０１を編んだ編み物の構造を有してもよい。金網１００の表面は、Ｃｒからなる中間層とともにＤＬＣ（Ｄｉａｍｏｎｄ−Ｌｉｋｅ−Ｃａｒｂｏｎ；ダイヤモンドライクカーボン）によって被覆されている。 As shown in FIGS. 6 and 7, the wire mesh 100 is formed by a wire 101 woven vertically and horizontally. The wire mesh 100 is not limited to a woven structure, and may have a knitted structure in which the wire 101 is knitted. The surface of the wire net 100 is covered with DLC (Diamond-Like-Carbon) together with an intermediate layer made of Cr.
本実施形態では線材１０１は単線であるが、これに限定されない。線材１０１は細い単線を複数束ねて形成したものであってもよい。線材１０１を形成する材料は、例えば、ステンレス、アルミニウム、銅である。 In the present embodiment, the wire 101 is a single wire, but is not limited thereto. The wire 101 may be formed by bundling a plurality of thin single wires. The material for forming the wire 101 is, for example, stainless steel, aluminum, or copper.
耐食性を有する腐食防止部１１０が、線材１０１と線材１０１とが交差する交差部１０２における、線材１０１同士が接する接触箇所１０３の近傍１０４だけに形成されている。接触箇所１０３および接触箇所１０３の近傍１０４は、交差部１０２を形成する二つの線材１０１のうちの一方が他方に押圧されて凹んだ凹形状を有する。 The corrosion prevention part 110 having corrosion resistance is formed only in the vicinity 104 of the contact portion 103 where the wires 101 are in contact with each other at the intersection 102 where the wires 101 and 101 intersect. The contact portion 103 and the vicinity 104 of the contact portion 103 have a concave shape in which one of the two wire members 101 forming the intersecting portion 102 is depressed by being pressed against the other.
図８に示すように、導電性シート１の製造方法は、金網１００を準備する金網準備工程Ｓ１と、金網準備工程Ｓ１後、腐食防止部１１０を形成する腐食防止部形成工程Ｓ２と、を有する。 As shown in FIG. 8, the method for manufacturing the conductive sheet 1 includes a wire mesh preparation step S1 for preparing the wire mesh 100, and a corrosion prevention portion forming step S2 for forming the corrosion prevention portion 110 after the wire mesh preparation step S1. .
金網準備工程Ｓ１では、金網１００がローラによって圧延され、その後、Ｃｒの中間層およびＤＬＣが金網１００に被覆される。スパッタリング装置によって、Ｃｒの中間層やＤＬＣが金網１００に被覆される。ＤＬＣが被覆されることによって、金網１００の導電性および耐食性が向上する。 In the wire mesh preparation step S1, the wire mesh 100 is rolled by a roller, and thereafter, the intermediate layer of Cr and DLC are coated on the wire mesh 100. The metal mesh 100 is covered with a Cr intermediate layer or DLC by a sputtering apparatus. By coating DLC, the conductivity and corrosion resistance of the wire mesh 100 are improved.
腐食防止部形成工程Ｓ２では、撥水剤を含む液に浸漬された金網１００がその液から引き上げられる。撥水剤を含む液から金網１００が引き上げられると、線材１０１同士の接触箇所１０３の近傍１０４では液が残り、その他の部分では液が流れ落ちる。この状態で金網１００を乾燥させることによって接触箇所１０３の近傍１０４に残った液の中の溶媒が蒸発すると、固形分である撥水剤が残り、その結果、撥水性を有する腐食防止部１１０が形成される。 In the corrosion prevention portion forming step S2, the wire net 100 immersed in a liquid containing a water repellent is pulled up from the liquid. When the wire mesh 100 is pulled up from the liquid containing the water repellent, the liquid remains in the vicinity 104 of the contact portion 103 between the wires 101, and the liquid flows down in other portions. When the metal net 100 is dried in this state and the solvent in the liquid remaining in the vicinity 104 of the contact point 103 evaporates, a water repellent agent that is a solid content remains, and as a result, the corrosion preventing unit 110 having water repellency is formed. It is formed.
図９に示すように、腐食防止部形成工程Ｓ２では、長尺形状を有する金網１００が搬送され、撥水剤を含む液１４０への金網１００の浸漬および液１４０からの金網１００の引き上げが連続的に行われる。 As shown in FIG. 9, in the corrosion prevention portion forming step S <b> 2, the metal mesh 100 having a long shape is conveyed, and the metal mesh 100 is immersed in the liquid 140 containing the water repellent and the metal mesh 100 is pulled up from the liquid 140 continuously. Done.
長尺形状を有する金網１００は、ロールトゥロール方式によって、金網１００が巻回された巻出しロール１４１および巻取りロール１４２の間で搬送される。巻出しロール１４１および巻取りロール１４２は、それぞれモータＭ１、Ｍ２によって回転する。 The wire mesh 100 having a long shape is conveyed between an unwinding roll 141 and a winding roll 142 around which the wire mesh 100 is wound by a roll-to-roll method. The unwinding roll 141 and the winding roll 142 are rotated by motors M1 and M2, respectively.
液１４０は、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）またはテトラフルオロエチレン‐ヘキサフルオロプロピレン共重合体（ＦＥＰ）等の撥水剤を、界面活性剤の存在下で溶媒である水中に分散させることによって調製される。 The liquid 140 is obtained by, for example, dispersing a water repellent such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) in water as a solvent in the presence of a surfactant. Prepared.
液１４０から引き上げられた金網１００は、一対のローラ１４３の間を通る。これによって、金網１００に過剰に付着した液１４０が除去される。その後、金網１００は、付着した液１４０の溶媒を蒸発させる乾燥炉１４４を通過する。 The wire mesh 100 pulled up from the liquid 140 passes between the pair of rollers 143. As a result, the liquid 140 excessively attached to the wire mesh 100 is removed. Thereafter, the wire mesh 100 passes through a drying furnace 144 that evaporates the solvent of the attached liquid 140.
金網１００が乾燥炉１４４を通過する間に、付着した液１４０の溶媒が蒸発し、金網１００に腐食防止部１１０が形成される。乾燥炉１４４は、例えば温風乾燥炉である。乾燥炉１４４内の温度は、例えば８０℃〜１５０℃である。 While the wire mesh 100 passes through the drying furnace 144, the solvent of the attached liquid 140 evaporates, and the corrosion prevention unit 110 is formed in the wire mesh 100. The drying furnace 144 is, for example, a hot air drying furnace. The temperature in the drying furnace 144 is, for example, 80 ° C to 150 ° C.
上で述べた形態では、液１４０に浸漬させた金網１００を引き上げて腐食防止部１１０を形成したが、これに限定されない。図１０に示すように、交差部１０２およびその近傍だけに耐食性を有するシール材１１１を塗布して腐食防止部１１０を形成してもよい。 In the embodiment described above, the wire mesh 100 immersed in the liquid 140 is pulled up to form the corrosion preventing part 110, but the present invention is not limited to this. As shown in FIG. 10, the corrosion preventing portion 110 may be formed by applying a sealant 111 having corrosion resistance only to the intersection 102 and the vicinity thereof.
この場合、シール材１１１は、例えば、交差部１０２に対応した位置に孔が形成されたマスクを介して交差部１０２およびその近傍だけに塗布される。その後、例えば金網１００の面方向に移動するブレードＢが金網１００の上の余分なシール材１１１を除去することによって、線材１０１同士の接触箇所１０３の近傍１０４だけにシール材１１１が配置される。このシール材１１１が硬化して腐食防止部１１０となる。シール材１１１の材料は、例えば、ゴム、ビニル系樹脂、シリコン樹脂、ウレタン樹脂、エポキシ樹脂を含む。 In this case, for example, the sealing material 111 is applied only to the intersection 102 and the vicinity thereof through a mask in which holes are formed at positions corresponding to the intersection 102. Thereafter, for example, the blade B moving in the surface direction of the wire mesh 100 removes the excess seal material 111 on the wire mesh 100, whereby the seal material 111 is disposed only in the vicinity 104 of the contact portion 103 between the wire materials 101. The sealing material 111 is hardened to become the corrosion preventing portion 110. The material of the sealing material 111 includes, for example, rubber, vinyl resin, silicon resin, urethane resin, and epoxy resin.
本発明者らは、実際に作製した導電性シート１の試験片を用い、ＪＩＳ Ｇ ０５７９に準じて分極曲線を取得した。比較例として腐食防止部１１０のない金網１００についても同様の試験を行った。 The present inventors obtained a polarization curve according to JIS G 0579 using the test piece of the conductive sheet 1 actually produced. As a comparative example, the same test was performed on the wire mesh 100 without the corrosion prevention unit 110.
試験によって得られた図１１の分極曲線に示すように、腐食防止部１１０を有する導電性シート１では、腐食防止部１１０がない場合に比べ腐食電流が減少した。この結果より、腐食防止部１１０を形成することによって、導電性シート１の耐食性が向上することを確認できた。 As shown in the polarization curve of FIG. 11 obtained by the test, in the conductive sheet 1 having the corrosion prevention part 110, the corrosion current decreased compared to the case without the corrosion prevention part 110. From this result, it was confirmed that the corrosion resistance of the conductive sheet 1 was improved by forming the corrosion preventing portion 110.
実施形態の作用効果を述べる。 The effect of embodiment is described.
金網１００では、交差部１０２の線材１０１同士の接触箇所１０３の近傍１０４は影になり易い。このため、金網準備工程Ｓ１において金網１００に対してスパッタリングが行われると、接触箇所１０３の近傍１０４は、ＤＬＣによって被覆され難く耐食性が相対的に低い。しかし、実施形態の導電性シート１においては、腐食防止部１１０が形成され、これが接触箇所１０３の近傍１０４からガスや水等の腐食の要因となるものを遮断するため、接触箇所１０３の近傍１０４ひいては接触箇所１０３の腐食が防止され、耐食性が向上する。 In the wire mesh 100, the vicinity 104 of the contact portion 103 between the wire members 101 of the intersecting portion 102 is likely to be a shadow. For this reason, when sputtering is performed on the wire mesh 100 in the wire mesh preparation step S1, the vicinity 104 of the contact portion 103 is difficult to be covered with DLC and has relatively low corrosion resistance. However, in the conductive sheet 1 according to the embodiment, the corrosion preventing portion 110 is formed, and this blocks the thing that causes corrosion such as gas and water from the vicinity 104 of the contact portion 103, and therefore, the vicinity 104 of the contact portion 103. As a result, corrosion of the contact portion 103 is prevented, and corrosion resistance is improved.
燃料電池１０では、燃料ガス、酸化剤ガス、および電気化学反応によって生成した水が、ガス拡散層１２５である導電性シート１を通り、さらに膜電極接合体１２１における電気化学反応にともなって生成するＨ+や過酸化水素が存在する。Ｈ+や過酸化水素は腐食を生じさせ易い。しかし、燃料電池１０では、腐食防止部１１０が線材１０１同士の接触箇所１０３の近傍１０４からこれらを遮断して腐食を防止するため、燃料電池１０の性能が低下し難い。 In the fuel cell 10, fuel gas, oxidant gas, and water generated by an electrochemical reaction pass through the conductive sheet 1 that is the gas diffusion layer 125, and are further generated along with the electrochemical reaction in the membrane electrode assembly 121. H + and hydrogen peroxide are present. H + and hydrogen peroxide are likely to cause corrosion. However, in the fuel cell 10, the corrosion prevention unit 110 blocks these from the vicinity 104 of the contact portion 103 between the wires 101 to prevent corrosion, so that the performance of the fuel cell 10 is unlikely to deteriorate.
腐食防止部１１０は接触箇所１０３の近傍１０４だけに形成されており、金網１００の他の部分では線材１０１が露出する。このため、絶縁性を有する腐食防止部１１０が金網１００に形成されても、露出した線材１０１によって導電性が確保され、導電性シート１は耐食性と導電性とを両立できる。 The corrosion prevention part 110 is formed only in the vicinity 104 of the contact point 103, and the wire 101 is exposed in the other part of the wire mesh 100. For this reason, even if the corrosion prevention part 110 which has insulation is formed in the wire mesh 100, electroconductivity is ensured by the exposed wire 101, and the electroconductive sheet 1 can satisfy | fill both corrosion resistance and electroconductivity.
線材１０１同士の接触箇所１０３の近傍１０４は、二つの線材１０１のうちの一方が他方に押圧されて凹んだ凹形状を有する。このため、液１４０やシール材１１１が接触箇所１０３の近傍１０４に偏在し易く、腐食防止部１１０を形成し易い。 The vicinity 104 of the contact point 103 between the wire rods 101 has a concave shape in which one of the two wire rods 101 is depressed by the other. For this reason, the liquid 140 and the sealing material 111 are likely to be unevenly distributed in the vicinity 104 of the contact location 103, and the corrosion preventing portion 110 can be easily formed.
腐食防止部１１０は、撥水剤を含む液１４０に浸漬した金網１００を引き上げて形成されるため、接触箇所１０３の近傍１０４以外の部分では液１４０が線材１０１から自然に流れ落ちる。従って腐食防止部１１０を接触箇所１０３の近傍１０４だけに容易に形成できる。 Since the corrosion preventing part 110 is formed by pulling up the wire mesh 100 immersed in the liquid 140 containing a water repellent, the liquid 140 naturally flows down from the wire 101 at portions other than the vicinity 104 of the contact point 103. Therefore, the corrosion preventing portion 110 can be easily formed only in the vicinity 104 of the contact location 103.
腐食防止部１１０が撥水性を有することによって、腐食の要因となる水等が接触箇所１０３の近傍１０４から効果的に排除されるため、より効果的に腐食を防止できる。 Since the corrosion prevention unit 110 has water repellency, water or the like that causes corrosion is effectively excluded from the vicinity 104 of the contact portion 103, so that corrosion can be more effectively prevented.
腐食防止部１１０は、交差部１０２およびその近傍だけにシール材１１１を塗布して形成されるようにすれば、シール材１１１は必要な個所だけに塗布され、それ以外の箇所に塗布されないため、原材料の使用を抑えられる。 If the corrosion prevention unit 110 is formed by applying the sealing material 111 only to the intersection 102 and the vicinity thereof, the sealing material 111 is applied only to a necessary portion and is not applied to other portions. Reduce the use of raw materials.
＜変形例＞
図１２に示すように、変形例の線材１５１は、第１実施形態と異なる断面形状を有する。その他の構成および製造方法については、変形例の導電性シート１Ａは、第１実施形態と略同様であるため、同様の構成については第１実施形態と同様の符号を付し、ここでの重複する説明を省略する。導電性シート１Ａは、燃料電池１０において第１実施形態の導電性シート１に代えてこれと同様にガス拡散層１２５として用いることができる。
<Modification>
As shown in FIG. 12, the wire 151 of a modification has a cross-sectional shape different from that of the first embodiment. About another structure and manufacturing method, since electroconductive sheet 1A of a modification is substantially the same as 1st Embodiment, about the same structure, the code | symbol similar to 1st Embodiment is attached | subjected, and duplication here Description to be omitted is omitted. The conductive sheet 1A can be used as the gas diffusion layer 125 in the same manner as the conductive sheet 1 in the fuel cell 10 instead of the conductive sheet 1 of the first embodiment.
線材１５１の断面は、多角形形状を有する。線材１５１は、その外面１５２と、他の線材１５１との間に隙間を形成する。この隙間は、液１４０またはシール材１１１が溜る溜り部を構成する。 The cross section of the wire 151 has a polygonal shape. The wire 151 forms a gap between the outer surface 152 and another wire 151. This gap constitutes a reservoir where the liquid 140 or the sealing material 111 accumulates.
変形例では、線材１５１同士の接触箇所１０３の近傍１０４に、線材１５１同士の押圧によって凹部が形成されるとともに、一の線材１５１の外面１５２が、液１４０またはシール材１１１が溜る溜り部を構成する。このため、液１４０やシール材１１１が線材１５１同士の接触箇所１０３の近傍１０４により偏在し易くなり、変形例は、第１実施形態の効果に加え、接触箇所１０３の近傍１０４に腐食防止部１１０がより形成され易いという効果を奏する。 In the modification, a recess is formed in the vicinity 104 of the contact point 103 between the wires 151 by pressing between the wires 151, and the outer surface 152 of one wire 151 constitutes a reservoir where the liquid 140 or the seal material 111 is accumulated. To do. For this reason, the liquid 140 and the sealing material 111 are likely to be unevenly distributed in the vicinity 104 of the contact portion 103 between the wires 151, and in the modified example, in addition to the effect of the first embodiment, the corrosion prevention unit 110 is provided near the contact portion 103. Produces the effect that is more easily formed.
本発明は、上述した実施形態に限定されるものではなく、特許請求の範囲の範囲内で種々改変できる。 The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims.
例えば、上述の実施形態において金網準備工程Ｓ１で金網１００の表面に被覆する材料はＤＬＣに限定されず、耐食性および導電性が良好な他の材料であってもよい。 For example, in the above-described embodiment, the material coated on the surface of the wire mesh 100 in the wire mesh preparation step S1 is not limited to DLC, and may be another material having good corrosion resistance and conductivity.
また、金網１００の被覆方法は、スパッタリング法に限定されず、イオンプレーティング法等の他のＰＶＤ法（Ｐｈｙｓｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ；物理気相成長法または物理的蒸着法）であってもよい。 Moreover, the coating method of the metal mesh 100 is not limited to the sputtering method, but may be other PVD methods (Physical Vapor Deposition; physical vapor deposition method or physical vapor deposition method) such as an ion plating method.
上記実施形態において、液１４０から金網１００が引き上げられたとき、液１４０は、線材１０１同士の接触箇所１０３の近傍１０４以外の部分では流れ落ちるが、完全には落ちず、接触箇所１０３の近傍１０４以外の部分に僅かに残る場合がある。また、ブレードＢによって余分なシール材１１１を完全には除去できず、接触箇所１０３の近傍１０４以外の部分にシール材１１１が僅かに残る場合がある。本発明は、このように、接触箇所１０３の近傍１０４以外の部分に液１４０に含まれる撥水剤やシール材１１１が完全に除去されず僅かに残るが、これらが線材１０１の導電性を著しく妨げない形態を含む。 In the above embodiment, when the wire mesh 100 is pulled up from the liquid 140, the liquid 140 flows down at a portion other than the vicinity 104 of the contact point 103 between the wire rods 101, but does not completely drop, and other than the vicinity 104 of the contact point 103. It may remain slightly in the part. Further, the excess sealing material 111 cannot be completely removed by the blade B, and the sealing material 111 may remain slightly in a portion other than the vicinity 104 of the contact point 103. In the present invention, the water repellent and the sealing material 111 contained in the liquid 140 are not completely removed and remain slightly in portions other than the vicinity 104 of the contact point 103 as described above, but these significantly increase the conductivity of the wire 101. Includes forms that do not interfere.
１、１Ａ 導電性シート、
１０ 燃料電池、
１００ 金網、
１０１、１５１ 線材、
１０２ 線材と線材との交差部、
１０３ 線材同士の接触箇所、
１０４ 線材同士の接触箇所の近傍、
１１０ 腐食防止部、
１１１ シール材、
１２０ 燃料電池セル、
１２１ 膜電極接合体、
１２１ａ 高分子電解質膜、
１２１ｂ カソード触媒層（触媒成分を含む層）、
１２１ｃ アノード触媒層（触媒成分を含む層）、
１２２ フレーム、
１２２ａ マニホールド、
１２３ カソードセパレータ、
１２３ａ 酸化剤ガスの流路、
１２３ｂ 冷却流体の流路、
１２３ｃ マニホールド、
１２４ アノードセパレータ、
１２４ａ 燃料ガスの流路、
１２４ｂ 冷却流体の流路、
１２４ｃ マニホールド、
１２５ ガス拡散層、
１２６ 燃料電池スタック、
１３０ 集電板、
１３１ エンドプレート、
１３２ マニホールド、
１３３ 突起部、
１４０ 撥水剤を含む液、
１４４ 乾燥炉、
Ｂ ブレード。
1, 1A conductive sheet,
10 Fuel cell,
100 wire mesh,
101, 151 wire,
102 Intersection of wire and wire,
103 Contact points between wires,
104 In the vicinity of the contact point between the wires,
110 Corrosion prevention part,
111 sealing material,
120 fuel cells,
121 membrane electrode assembly,
121a polymer electrolyte membrane,
121b cathode catalyst layer (a layer containing a catalyst component),
121c Anode catalyst layer (a layer containing a catalyst component),
122 frames,
122a manifold,
123 cathode separator,
123a oxidant gas flow path,
123b cooling fluid flow path,
123c manifold,
124 anode separator,
124a Fuel gas flow path,
124b cooling fluid flow path;
124c manifold,
125 gas diffusion layer,
126 fuel cell stack,
130 current collector,
131 end plate,
132 manifold,
133 protrusions,
140 liquid containing water repellent,
144 drying oven,
B Blade.
Claims (6)
前記交差部における前記線材同士の接触箇所の近傍は、当該交差部を形成する二つの前記線材のうちの一方が他方に押圧されて凹んだ凹形状を有する、導電性シート。 It consists of a wire mesh having an intersecting portion where the wire and the wire intersect, and a corrosion prevention portion having corrosion resistance is formed only in the vicinity of the contact point where the wires in the intersecting portion contact each other ,
The vicinity of the contact location of the said wire rods in the said cross | intersection part is an electroconductive sheet which has the concave shape which one of the two said wire materials which form the said cross | intersection part pressed into the other, and was dented .
当該膜電極接合体を挟む一対のセパレータ、および、
前記膜電極接合体と前記セパレータとの間に配置されたガス拡散層を有し、
当該ガス拡散層は、線材と線材とが交差する交差部を有する金網からなり、前記交差部における前記線材同士が接する接触箇所の近傍だけに耐食性を有する腐食防止部が形成されている、燃料電池。 A membrane electrode assembly in which layers containing a catalyst component are formed on both surfaces of the electrolyte membrane,
A pair of separators sandwiching the membrane electrode assembly, and
A gas diffusion layer disposed between the membrane electrode assembly and the separator;
The gas diffusion layer is made of a wire mesh having a crossing portion where a wire and a wire cross each other, and a corrosion prevention portion having corrosion resistance is formed only in the vicinity of a contact portion where the wires are in contact with each other at the crossing portion. .
当該金網準備工程後、前記金網を構成する線材と線材との交差部における前記線材同士が接する接触箇所の近傍で前記線材同士の一方が他方に押圧されて凹んだ凹形状を有する部分だけに、耐食性を有する腐食防止部を形成する腐食防止部形成工程と、を有する、導電性シートの製造方法。 Wire mesh preparation process for preparing the wire mesh,
After the wire mesh preparation step, only in a portion having a concave shape in which one of the wire rods is pressed against the other in the vicinity of the contact portion where the wire rods contact each other at the intersection of the wire rod and the wire rod constituting the wire mesh, A corrosion prevention part forming step of forming a corrosion prevention part having corrosion resistance .
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