JPH10308228A - Polymer electrolyte fuel cell and method of manufacturing the same - Google Patents
Polymer electrolyte fuel cell and method of manufacturing the sameInfo
- Publication number
- JPH10308228A JPH10308228A JP9115681A JP11568197A JPH10308228A JP H10308228 A JPH10308228 A JP H10308228A JP 9115681 A JP9115681 A JP 9115681A JP 11568197 A JP11568197 A JP 11568197A JP H10308228 A JPH10308228 A JP H10308228A
- Authority
- JP
- Japan
- Prior art keywords
- polymer electrolyte
- fuel cell
- electrode catalyst
- cathode
- fluorocarbon resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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)
Abstract
(57)【要約】
【課題】高分子電解質のイオン伝導度を維持したまま、
高分子電解質膜の機械的強度を強くした高分子電解質型
燃料電池を提供すること。
【解決手段】高分子電解質１の少なくとも一方の面の周
縁部に炭化フッソ系の樹脂２が被覆されており、炭化フ
ッソ系樹脂２で被覆した高分子電解質の中心部に炭化フ
ッソ系樹脂２と接する大きさの電極触媒層４が被覆され
ており、電極触媒層４より大きいガス拡散相３３が電極
触媒層４と接するよう接合されている構成。
(57) [Abstract] [Problem] To maintain the ionic conductivity of a polymer electrolyte,
To provide a polymer electrolyte fuel cell in which the mechanical strength of a polymer electrolyte membrane is increased. A peripheral portion of at least one surface of a polymer electrolyte is coated with a fluorocarbon resin, and a center portion of the polymer electrolyte coated with the fluorocarbon resin is coated with the fluorocarbon resin. A configuration in which the electrode catalyst layer 4 having a size in contact with the electrode catalyst layer 4 is covered, and a gas diffusion phase 33 larger than the electrode catalyst layer 4 is joined so as to be in contact with the electrode catalyst layer 4.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高分子電解質型燃料電
池及びその製造方法に関する。The present invention relates to a polymer electrolyte fuel cell and a method for producing the same.
【０００２】[0002]
【従来の技術】従来の高分子電解質型燃料電池は、電解
質である炭化フッソ系の高分子電解質薄膜と、アノ−ド
およびカソ−ドの電極、さらにカ−ボンあるいは金属製
のセパレ−タ−や冷却板から構成されてきた。2. Description of the Related Art A conventional polymer electrolyte fuel cell is composed of a fluorocarbon polymer electrolyte thin film as an electrolyte, anode and cathode electrodes, and a carbon or metal separator. And cooling plates.
【０００３】電池反応に寄与する電極と電解質は、貴金
属触媒を担持したカ−ボン粉末と電解質と同等の材料の
混合物を構成材料とし、これに場合によってはフルオロ
カ−ボン化合物系の撥水材などを添加した混合物を、カ
−ボン繊維から構成されるカ−ボンペ−パ−などに保持
し、電解質である高分子膜と接合して構成してきた。通
常、アノ−ドおよびカソ−ドの構成材料は同一であり、
炭化水素系燃料を改質した水素リッチなガスを燃料とす
る場合、改質ガス中に含まれる一酸化炭素による触媒の
被毒を抑制するため、アノ−ド側のみにルテニウムなど
の耐ＣＯ被毒材料を添加して構成することも考えられて
きた。The electrode and the electrolyte that contribute to the battery reaction are composed of a mixture of a carbon powder carrying a noble metal catalyst and a material equivalent to the electrolyte, and in some cases, a fluorocarbon compound-based water repellent material. Is added to a carbon paper made of carbon fibers and the like, and the mixture is joined to a polymer membrane as an electrolyte. Usually, the constituent materials of the anode and the cathode are the same,
When a hydrogen-rich gas obtained by reforming a hydrocarbon-based fuel is used as a fuel, CO poisoning such as ruthenium is applied only to the anode side to suppress poisoning of the catalyst by carbon monoxide contained in the reformed gas. It has also been considered to add poison materials to the composition.
【０００４】電解質は、スルホン基を含む炭化フッソ系
の高分子であり、プロトン伝導性の電解質である。燃料
電池の性能を向上させるためには、電解質のイオン伝導
度を向上させることが重要な因子の一つであるため、通
常は高分子電解質の膜厚を薄くすることによって内部抵
抗を小さくすることが試みられている。The electrolyte is a fluorocarbon polymer containing a sulfone group, and is a proton conductive electrolyte. Improving the ionic conductivity of the electrolyte is one of the important factors in improving the performance of the fuel cell, so it is usually necessary to reduce the internal resistance by reducing the thickness of the polymer electrolyte. Have been tried.
【０００５】[0005]
【発明が解決しょうとする課題】しかしながら、従来の
高分子電解質型燃料電池では、高分子電解質を薄くすれ
ばするほど電解質の抵抗は小さくなるが、それに反して
電解質膜の機械的強度が小さくなると言う課題が有っ
た。However, in a conventional polymer electrolyte fuel cell, the thinner the polymer electrolyte is, the lower the resistance of the electrolyte is. However, if the mechanical strength of the electrolyte membrane is reduced. There was a problem to say.
【０００６】本発明は、従来の高分子電解質型燃料電池
のこの様な課題を考慮し、高分子電解質のイオン伝導度
を実質上維持したまま、高分子電解質の機械的強度を従
来に比べてより一層強くすることが出来る高分子電解質
型燃料電池及びその製造方法を提供することを目的とす
る。The present invention has been made in consideration of such a problem of a conventional polymer electrolyte fuel cell, and has a mechanical strength of a polymer electrolyte as compared with a conventional one while substantially maintaining the ionic conductivity of the polymer electrolyte. It is an object of the present invention to provide a polymer electrolyte fuel cell that can be further strengthened and a method for manufacturing the same.
【０００７】[0007]
【課題を解決するための手段】請求項１記載の本発明
は、高分子電解質と、その高分子電解質を挟持するガス
拡散電極としてのアノ−ドとカソ−ドとを有する高分子
電解質型燃料電池において、前記高分子電解質は前記ア
ノード及び／又は前記カソードより面積が大きく、前記
高分子電解質の少なくとも一方の面における、前記高分
子電解質と前記アノード又は前記カソードとの接合面以
外の部位が炭化フッ素系樹脂で被覆されている高分子電
解質型燃料電池である。According to the present invention, there is provided a polymer electrolyte fuel comprising a polymer electrolyte, and an anode and a cathode as gas diffusion electrodes sandwiching the polymer electrolyte. In the battery, the polymer electrolyte has a larger area than the anode and / or the cathode, and a portion of at least one surface of the polymer electrolyte other than a bonding surface between the polymer electrolyte and the anode or the cathode is carbonized. This is a polymer electrolyte fuel cell covered with a fluororesin.
【０００８】請求項２記載の本発明は、高分子電解質
と、その高分子電解質を挟持するガス拡散電極としての
アノ−ドとカソ−ドとを有する高分子電解質型燃料電池
において、前記高分子電解質は前記アノード及び／又は
前記カソードより面積が大きく、前記高分子電解質の少
なくとも一方の面における、前記高分子電解質と前記ア
ノード又は前記カソードとの接合面以外の部位が炭化フ
ッ素系樹脂で被覆されており、前記少なくとも一方の面
における前記アノード又は前記カソードは、前記少なく
とも一方の面における前記炭化フッソ系樹脂で被覆され
ていない面積より大きい高分子電解質型燃料電池であ
る。According to a second aspect of the present invention, there is provided a polymer electrolyte fuel cell comprising a polymer electrolyte, and an anode and a cathode as gas diffusion electrodes sandwiching the polymer electrolyte. The electrolyte has a larger area than the anode and / or the cathode, and at least one surface of the polymer electrolyte other than a bonding surface between the polymer electrolyte and the anode or the cathode is coated with a fluorocarbon resin. The anode or the cathode on the at least one surface is a polymer electrolyte fuel cell having a larger area than the area of the at least one surface not covered with the fluorocarbon resin.
【０００９】請求項３記載の本発明は、高分子電解質
と、その高分子電解質を挟持するガス拡散電極としての
アノ−ドとカソ−ドとを有し、前記アノ−ドおよびカソ
−ドが、電極触媒を担持したカ−ボン粉末を主体とする
電極触媒層と、前記電極触媒を担持していないカ−ボン
粉末又はカ−ボン繊維を主体とするガス拡散相とから構
成されている高分子電解質型燃料電池において、前記高
分子電解質の少なくとも一方の面の外周部付近に炭化フ
ッソ系の樹脂が被覆されており、前記少なくとも一方の
面における前記炭化フッソ系樹脂で被覆されていない前
記高分子電解質の実質上中心部に前記炭化フッソ系樹脂
と接する大きさの電極触媒層が被覆されており、前記電
極触媒層より大きいガス拡散相が前記電極触媒層と接す
るよう接合されている高分子電解質型燃料電池である。According to a third aspect of the present invention, there is provided a polymer electrolyte, and an anode and a cathode serving as gas diffusion electrodes sandwiching the polymer electrolyte, wherein the anode and the cathode are provided. An electrode catalyst layer mainly composed of carbon powder carrying an electrode catalyst, and a gas diffusion phase mainly composed of carbon powder or carbon fiber not carrying said electrode catalyst. In the molecular electrolyte fuel cell, at least one surface of the polymer electrolyte is coated with a fluorocarbon-based resin in the vicinity of an outer peripheral portion thereof, and the at least one surface is not coated with the fluorocarbon-based resin. A substantially central portion of the molecular electrolyte is coated with an electrode catalyst layer having a size in contact with the fluorocarbon resin, and a gas diffusion phase larger than the electrode catalyst layer is joined so as to be in contact with the electrode catalyst layer. It is a polymer electrolyte fuel cell.
【００１０】請求項６記載の本発明は、高分子電解質
と、その高分子電解質を挟持するガス拡散電極としての
アノ−ドとカソ−ドとを有し、前記アノ−ドおよびカソ
−ドが、電極触媒を担持したカ−ボン粉末を主体とする
電極触媒層と、前記電極触媒を担持していないカ−ボン
粉末又はカ−ボン繊維を主体とするガス拡散相とから構
成されている高分子電解質型燃料電池の製造方法であっ
て、前記高分子電解質の少なくとも一方の面の外周部付
近に炭化フッソ系の樹脂を被覆する樹脂被覆工程と、前
記樹脂被覆工程の後、前記少なくとも一方の面における
前記炭化フッソ系樹脂で被覆されていない前記高分子電
解質の実質上中心部に、前記炭化フッソ系樹脂の内周端
部と接する大きさの電極触媒層を形成する電極触媒層形
成工程と、前記電極触媒層形成工程の後、前記電極触媒
層より大きいガス拡散相を前記電極触媒層と接するよう
接合する接合工程とを備えている高分子電解質型燃料電
池の製造方法である。According to a sixth aspect of the present invention, there is provided a polymer electrolyte, and an anode and a cathode serving as gas diffusion electrodes sandwiching the polymer electrolyte, wherein the anode and the cathode are provided. An electrode catalyst layer mainly composed of carbon powder carrying an electrode catalyst, and a gas diffusion phase mainly composed of carbon powder or carbon fiber not carrying said electrode catalyst. A method for producing a molecular electrolyte fuel cell, comprising: a resin coating step of coating a fluorocarbon-based resin near an outer peripheral portion of at least one surface of the polymer electrolyte; and after the resin coating step, An electrode catalyst layer forming step of forming an electrode catalyst layer having a size in contact with an inner peripheral end of the fluorocarbon resin at a substantially central portion of the polymer electrolyte that is not coated with the fluorocarbon resin on the surface. , The electrode After medium layer forming step, a method for producing a polymer electrolyte fuel cell and a bonding step of bonding so as to be in contact with the electrode catalyst layer larger gas diffusion phases from the electrode catalyst layer.
【００１１】このような構成により、例えば、高分子電
解質のイオン伝導度を維持したまま、高分子電解質膜の
機械的強度を強くすることが可能である。With such a configuration, for example, it is possible to increase the mechanical strength of the polymer electrolyte membrane while maintaining the ionic conductivity of the polymer electrolyte.
【００１２】[0012]
【発明の実施の形態】以下、本発明にかかる高分子電解
質型燃料電池の実施の形態を図面を参照しながら説明す
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the polymer electrolyte fuel cell according to the present invention will be described below with reference to the drawings.
【００１３】図１は、本発明の一実施の形態の高分子電
解質型燃料電池の概略の構成を説明するためのイメ−ジ
図であり、同図を用いて本実施の形態の構成及び作用を
述べる。FIG. 1 is an image diagram for explaining a schematic configuration of a polymer electrolyte fuel cell according to an embodiment of the present invention. The configuration and operation of the embodiment will be described with reference to FIG. State.
【００１４】図１中において、１が高分子電解質膜、２
が炭化フッソ系樹脂の相である。高分子電解質は、通常
１０μｍ〜１００μｍ程度の膜厚を有するプロトン伝導
体であり、発明が解決しょうとする課題の欄で述べた様
に、抵抗を小さくするため膜厚を薄くすると機械的強度
が弱くなり、電極１３のアノ−ド側とカソ−ド側に導入
するガスの差圧などが生じると電解質膜が破れて、アノ
−ドガスとカソ−ドガスのクロスリ−クが発生しやすく
なる。ここで、電極１３は、図１に示した高分子電解質
膜１上で、炭化フッソ系樹脂の相２に囲まれた中央部の
四角形の穴の位置に設けられている。尚、図１は、高分
子電解質膜１上において、アノードとカソードの双方の
電極の内、その片側の電極の記載を省略している。In FIG. 1, reference numeral 1 denotes a polymer electrolyte membrane;
Is a phase of a fluorocarbon resin. The polymer electrolyte is a proton conductor having a film thickness of usually about 10 μm to 100 μm. As described in the section of the problem to be solved by the invention, when the film thickness is reduced to reduce the resistance, the mechanical strength is increased. If the pressure is weakened and a pressure difference between the gas introduced to the anode side and the cathode side of the electrode 13 is generated, the electrolyte membrane is broken and cross-leak between the anode gas and the cathode gas is liable to occur. Here, the electrode 13 is provided on the polymer electrolyte membrane 1 shown in FIG. 1 at the position of a square hole at the center surrounded by the phase 2 of the fluorocarbon resin. FIG. 1 omits the illustration of one of the anode and cathode electrodes on the polymer electrolyte membrane 1.
【００１５】このとき、アノ−ドとカソ−ドに挟持され
た部分の電解質膜の機械的強度は比較的強く、電極と接
合されていない部分の電解質膜が破れることがほとんど
である。At this time, the mechanical strength of the portion of the electrolyte membrane sandwiched between the anode and the cathode is relatively strong, and the portion of the electrolyte membrane not joined to the electrode is often broken.
【００１６】そこで、本実施の形態の様に、高分子電解
質と電極との接合面以外の電極周辺部の高分子電解質の
少なくとも一方の面を炭化フッ素系樹脂で被覆すること
によって、高分子電解質のイオン伝導度を維持したま
ま、高分子電解質膜の機械的強度を強くすることが可能
である。Therefore, as in the present embodiment, at least one surface of the polymer electrolyte around the electrode other than the bonding surface between the polymer electrolyte and the electrode is coated with a fluorocarbon-based resin to thereby provide the polymer electrolyte. It is possible to increase the mechanical strength of the polymer electrolyte membrane while maintaining the ionic conductivity of the polymer electrolyte membrane.
【００１７】尚、高分子電解質１は、一般的にスルホン
基を含む炭化フッソ系の高分子が利用される。そのため
補強用に用いる炭化フッソ系樹脂の相２もこれと同じス
ルホン基を含む炭化フッソ系樹脂を用いても良いが、ス
ルホン基を含む炭化フッソ系樹脂は高価であるので、テ
フロン等を用いる方が、価格的に安くなり更に良い。The polymer electrolyte 1 is generally a fluorocarbon polymer containing a sulfone group. For this reason, the same fluorocarbon resin containing a sulfone group may be used for the phase 2 of the fluorocarbon resin used for reinforcement. However, since the fluorocarbon resin containing a sulfone group is expensive, it is preferable to use Teflon or the like. However, it is cheaper in price and better.
【００１８】次に、図２は、本発明の他の実施の形態の
高分子電解質型燃料電池の概略の構成を説明するための
イメ−ジ図であり、同図を用いて本実施の形態の構成及
び作用を述べる。Next, FIG. 2 is an image diagram for explaining a schematic configuration of a polymer electrolyte fuel cell according to another embodiment of the present invention. Will be described.
【００１９】図２において、１が高分子電解質膜、２が
炭化フッソ系樹脂の相、３が電極である。高分子電解質
は、通常１０μｍ〜１００μｍ程度の膜厚を有するプロ
トン伝導体であり、抵抗を小さくするため膜厚を薄くす
ると機械的強度が弱くなり、アノ−ド側とカソ−ド側に
導入するガスの差圧などが生じると電解質膜が破れて、
アノ−ドガスとカソ−ドガスのクロスリ−クが発生しや
すくなる。このとき、アノ−ドとカソ−ドに挟持された
部分の電解質膜の機械的強度は比較的強く、電極と接合
されていない部分の電解質膜が破れることがほとんどで
ある。特に、電極周辺のエッジ部で電解質膜が破れる場
合が多い。そこで、高分子電解質１と電極３との接合面
以外の電極周辺部の高分子電解質の少なくとも一方の面
を炭化フッ素系樹脂２で被覆し、炭化フッソ系樹脂で被
覆されていない高分子電解質の中心部の面積より大きい
電極３を有して構成することによって、高分子電解質の
イオン伝導度を維持したまま、高分子電解質膜の機械的
強度、特に電極周辺のエッジ部の機械的強度を強くする
ことが可能である。In FIG. 2, 1 is a polymer electrolyte membrane, 2 is a phase of a fluorocarbon resin, and 3 is an electrode. The polymer electrolyte is a proton conductor having a film thickness of usually about 10 μm to 100 μm. When the film thickness is reduced to reduce the resistance, the mechanical strength becomes weak, and the polymer electrolyte is introduced to the anode side and the cathode side. If a gas differential pressure occurs, the electrolyte membrane will break,
Cross-leak between the anode gas and the cathode gas is likely to occur. At this time, the mechanical strength of the portion of the electrolyte membrane sandwiched between the anode and the cathode is relatively strong, and the portion of the electrolyte membrane not joined to the electrode is often broken. In particular, the electrolyte membrane often breaks at the edge around the electrode. Therefore, at least one surface of the polymer electrolyte around the electrode other than the bonding surface between the polymer electrolyte 1 and the electrode 3 is coated with the fluorocarbon resin 2 and the polymer electrolyte not coated with the fluorocarbon resin is used. By having the electrode 3 larger than the area of the central portion, the mechanical strength of the polymer electrolyte membrane, particularly the mechanical strength at the edge around the electrode is increased while maintaining the ionic conductivity of the polymer electrolyte. It is possible to
【００２０】次に、図３は、本発明の他の実施の形態の
高分子電解質型燃料電池の概略の構成を説明するための
イメ−ジ図であり、同図を用いて本実施の形態の構成及
び作用を述べる。Next, FIG. 3 is an image diagram for explaining a schematic configuration of a polymer electrolyte fuel cell according to another embodiment of the present invention, and FIG. Will be described.
【００２１】図３において、１が高分子電解質膜、２が
炭化フッソ系樹脂の相、３３が電極の一部を構成するガ
ス拡散相、４が電極の一部を構成する電極触媒層であ
る。高分子電解質は、通常１０μｍ〜１００μｍ程度の
膜厚を有するプロトン伝導体であり、抵抗を小さくする
ため膜厚を薄くすると機械的強度が弱くなり、アノ−ド
側とカソ−ド側に導入するガスの差圧などが生じると電
解質膜が破れて、アノ−ドガスとカソ−ドガスのクロス
リ−クが発生しやすくなる。このとき、アノ−ドとカソ
−ドに挟持された部分の電解質膜の機械的強度は比較的
強く、電極と接合されていない部分の電解質膜が破れる
ことがほとんどである。特に、電極周辺のエッジ部で電
解質膜が破れる場合が多い。そこで、高分子電解質１の
少なくとも一方の面の周縁部（外周部付近）に炭化フッ
ソ系の樹脂２を被覆し、炭化フッソ系樹脂で被覆した高
分子電解質の中心部に炭化フッソ系樹脂と接する大きさ
の電極触媒層４を被覆し、電極触媒層より大きいガス拡
散相３３を電極触媒層４と接するよう接合することによ
って、高分子電解質のイオン伝導度を維持したまま、高
分子電解質膜の機械的強度、特に電極周辺のエッジ部の
機械的強度を強くすることが可能である。In FIG. 3, 1 is a polymer electrolyte membrane, 2 is a phase of a fluorocarbon resin, 33 is a gas diffusion phase forming a part of the electrode, and 4 is an electrode catalyst layer forming a part of the electrode. . The polymer electrolyte is a proton conductor having a film thickness of usually about 10 μm to 100 μm. When the film thickness is reduced to reduce the resistance, the mechanical strength becomes weak, and the polymer electrolyte is introduced to the anode side and the cathode side. When a gas pressure difference or the like is generated, the electrolyte membrane is broken, and cross-linking between the anode gas and the cathode gas is likely to occur. At this time, the mechanical strength of the portion of the electrolyte membrane sandwiched between the anode and the cathode is relatively strong, and the portion of the electrolyte membrane not joined to the electrode is often broken. In particular, the electrolyte membrane often breaks at the edge around the electrode. Therefore, at least one peripheral portion (near the outer peripheral portion) of the polymer electrolyte 1 is coated with the fluorocarbon resin 2, and the center portion of the polymer electrolyte coated with the fluorocarbon resin is in contact with the fluorocarbon resin. By covering the electrode catalyst layer 4 having a size and bonding a gas diffusion phase 33 larger than the electrode catalyst layer so as to be in contact with the electrode catalyst layer 4, the ionic conductivity of the polymer electrolyte is maintained while maintaining the ionic conductivity of the polymer electrolyte. It is possible to increase the mechanical strength, particularly the mechanical strength at the edge around the electrode.
【００２２】次に、図４は、本発明の他の実施の形態の
高分子電解質型燃料電池の概略の構成を説明するための
イメ−ジ図であり、同図を用いて本実施の形態の構成及
び作用を述べる。FIG. 4 is an image diagram for explaining a schematic configuration of a polymer electrolyte fuel cell according to another embodiment of the present invention. Referring to FIG. Will be described.
【００２３】図４において、１が高分子電解質膜、２が
炭化フッソ系樹脂の相、３３が電極の一部を構成するガ
ス拡散相、４が電極の一部を構成する電極触媒層であ
る。高分子電解質は、通常１０μｍ〜１００μｍ程度の
膜厚を有するプロトン伝導体であり、抵抗を小さくする
ため膜厚を薄くすると機械的強度が弱くなり、アノ−ド
側とカソ−ド側に導入するガスの差圧などが生じると電
解質膜が破れて、アノ−ドガスとカソ−ドガスのクロス
リ−クが発生しやすくなる。このとき、アノ−ドとカソ
−ドに挟持された部分の電解質膜の機械的強度は比較的
強く、電極と接合されていない部分の電解質膜が破れる
ことがほとんどである。特に、電極周辺のエッジ部で電
解質膜が破れる場合が多い。そこで、高分子電解質１の
両方の面の周縁部に炭化フッソ系の樹脂２を被覆し、炭
化フッソ系樹脂で被覆した高分子電解質の中心部に炭化
フッソ系樹脂と接する大きさの電極触媒層４を被覆し、
電極触媒層より大きいガス拡散相３３を電極触媒層と接
するよう接合することによって、高分子電解質のイオン
伝導度を維持したまま、高分子電解質膜の機械的強度、
特に電極周辺のエッジ部の機械的強度を強くすることが
可能である。In FIG. 4, 1 is a polymer electrolyte membrane, 2 is a phase of a fluorocarbon resin, 33 is a gas diffusion phase constituting a part of the electrode, and 4 is an electrode catalyst layer constituting a part of the electrode. . The polymer electrolyte is a proton conductor having a film thickness of usually about 10 μm to 100 μm. When the film thickness is reduced to reduce the resistance, the mechanical strength becomes weak, and the polymer electrolyte is introduced to the anode side and the cathode side. When a gas pressure difference or the like is generated, the electrolyte membrane is broken, and cross-linking between the anode gas and the cathode gas is likely to occur. At this time, the mechanical strength of the portion of the electrolyte membrane sandwiched between the anode and the cathode is relatively strong, and the portion of the electrolyte membrane not joined to the electrode is often broken. In particular, the electrolyte membrane often breaks at the edge around the electrode. Accordingly, an electrode catalyst layer having a size in which the periphery of both surfaces of the polymer electrolyte 1 is coated with the fluorocarbon resin 2 and the center of the polymer electrolyte coated with the fluorocarbon resin is in contact with the fluorocarbon resin. 4 and
By joining the gas diffusion phase 33 larger than the electrode catalyst layer so as to be in contact with the electrode catalyst layer, the mechanical strength of the polymer electrolyte membrane can be maintained while maintaining the ionic conductivity of the polymer electrolyte.
In particular, it is possible to increase the mechanical strength of the edge around the electrode.
【００２４】次に、図５は、本発明の他の実施の形態の
高分子電解質型燃料電池の概略の構成を説明するための
イメ−ジ図であり、同図を用いて本実施の形態の構成及
び作用を述べる。FIG. 5 is an image diagram for explaining a schematic structure of a polymer electrolyte fuel cell according to another embodiment of the present invention. Referring to FIG. Will be described.
【００２５】図５において、１が高分子電解質膜、２が
炭化フッソ系樹脂の相、３３が電極の一部を構成するガ
ス拡散相、４が電極の一部を構成する電極触媒層、５が
燃料である水素や酸化材である空気などを電極に供給す
るためのガスマニホ−ルドである。高分子電解質は、通
常１０μｍ〜１００μｍ程度の膜厚を有するプロトン伝
導体であり、抵抗を小さくするため膜厚を薄くすると機
械的強度が弱くなり、アノ−ド側とカソ−ド側に導入す
るガスの差圧などが生じると電解質膜が破れて、アノ−
ドガスとカソ−ドガスのクロスリ−クが発生しやすくな
る。このとき、アノ−ドとカソ−ドに挟持された部分の
電解質膜の機械的強度は比較的強く、電極と接合されて
いない部分の電解質膜が破れることがほとんどである。
特に、電極周辺のエッジ部で電解質膜が破れる場合が多
い。そこで、高分子電解質１の両方の面の周縁部に炭化
フッソ系の樹脂２を被覆し、炭化フッソ系樹脂２で被覆
した高分子電解質の中心部に炭化フッソ系樹脂と接する
大きさの電極触媒層４を被覆し、電極触媒層より大きい
ガス拡散相３３を電極触媒層と接するよう接合すること
によって、高分子電解質のイオン伝導度を維持したま
ま、高分子電解質膜の機械的強度、特に電極周辺のエッ
ジ部の機械的強度を強くすることが可能である。また、
このとき炭化フッ素系の樹脂の相２はガスマニホ−ルド
の周縁部をガスシ−ルするガスケットの役目を同時に果
たしている。In FIG. 5, 1 is a polymer electrolyte membrane, 2 is a phase of a fluorocarbon resin, 33 is a gas diffusion phase constituting a part of an electrode, 4 is an electrode catalyst layer constituting a part of an electrode, and 5 Is a gas manifold for supplying hydrogen as fuel or air as oxidizing material to the electrodes. The polymer electrolyte is a proton conductor having a film thickness of usually about 10 μm to 100 μm. When the film thickness is reduced to reduce the resistance, the mechanical strength becomes weak, and the polymer electrolyte is introduced to the anode side and the cathode side. When a gas pressure difference occurs, the electrolyte membrane is broken,
Cross-leak between gas and cathode gas is likely to occur. At this time, the mechanical strength of the portion of the electrolyte membrane sandwiched between the anode and the cathode is relatively strong, and the portion of the electrolyte membrane not joined to the electrode is often broken.
In particular, the electrolyte membrane often breaks at the edge around the electrode. Therefore, an electrode catalyst having a size in which the periphery of both surfaces of the polymer electrolyte 1 is coated with the fluorocarbon resin 2 and the center of the polymer electrolyte coated with the fluorocarbon resin 2 is in contact with the fluorocarbon resin. By coating the layer 4 and joining the gas diffusion phase 33 larger than the electrode catalyst layer so as to be in contact with the electrode catalyst layer, the mechanical strength of the polymer electrolyte membrane, particularly the electrode strength, is maintained while maintaining the ionic conductivity of the polymer electrolyte. It is possible to increase the mechanical strength of the peripheral edge portion. Also,
At this time, the phase 2 of the fluorocarbon resin simultaneously serves as a gasket for gas-sealing the periphery of the gas manifold.
【００２６】次に、上記実施の形態で述べた構成による
具体的な実験例を図面を用いて述べ、同時に本発明の高
分子電解質型燃料電池の製造方法にかかる一実施の形態
についても説明する。 （実験例１）本実験例は、図１で述べた構成とほぼ対応
した高分子電解質型燃料電池の単セルによる例である。Next, specific experimental examples using the configuration described in the above embodiment will be described with reference to the drawings, and at the same time, one embodiment of a method for manufacturing a polymer electrolyte fuel cell according to the present invention will be described. . (Experimental Example 1) This experimental example is an example using a single cell of a polymer electrolyte fuel cell which almost corresponds to the configuration described in FIG.
【００２７】即ち、本実験例では、高分子電解質として
１６ｃｍ角に切断したデュポン社製のナフィオン１１２
（図１の高分子電解質膜１に対応）を用いた。アセチレ
ンブラック系カ−ボン粉末に平均粒径約３０オングスト
ロームの白金触媒を３０ｗｔ％担持した触媒担持カ−ボ
ン粉末と、デュポン社製のナフィオン溶液を酢酸ブチル
溶媒に分散し、ペ−スト状の電極触媒スラリ−を得た。
この電極触媒スラリ−を、１０ｃｍ角に切断した東レ製
のカ−ボン不織布の一方の面に、白金触媒量がカ−ボン
不織布の面積に対して０．３ｍｇ／ｃｍ2となるようス
クリ−ン印刷法により塗布し、電極（図１の電極１３に
対応）とした。カ−ボン不織布に塗布した電極触媒スラ
リ−を粗乾燥後、塗布面が高分子電解質膜と接するよう
にそれら２枚の電極で高分子電解質膜の中央部を挟持
し、１５０℃、５０ｋｇ／ｃｍ2でホットプレスして高
分子電解質膜と電極を接合した。接合した電極／高分子
電解質膜接合体の電極周辺部の高分子電解質膜の一方の
面に、炭化フッ素系樹脂製の粘着剤付きテ−プを（幅：
１ｃｍ、厚さ：５０μｍ）、電極との隙間ができないよ
うに張り付け高分子電解質膜を補強した。即ち、この場
合、粘着剤付きテ−プを４枚用意して、それらを電極の
周辺に張り付けるものである（図１の炭化フッソ系樹脂
の相２に対応）。That is, in this experimental example, Nafion 112 manufactured by DuPont was cut into a 16 cm square as a polymer electrolyte.
(Corresponding to the polymer electrolyte membrane 1 in FIG. 1). A catalyst-supporting carbon powder in which 30 wt% of a platinum catalyst having an average particle size of about 30 angstroms is supported on acetylene black-based carbon powder and a Nafion solution manufactured by DuPont are dispersed in a butyl acetate solvent, and a paste-like electrode is prepared. A catalyst slurry was obtained.
The, manufactured by Toray Industries, cut into 10cm square of mosquitoes - - The electrode catalyst slurry on one surface of the carbon nonwoven fabric, a platinum catalyst amount of Ca - subscription so that the area of carbon nonwoven and 0.3 mg / cm 2 - down It was applied by a printing method to form an electrode (corresponding to the electrode 13 in FIG. 1). After roughly drying the electrode catalyst slurry applied to the carbon nonwoven fabric, the center portion of the polymer electrolyte membrane is sandwiched between the two electrodes so that the coated surface is in contact with the polymer electrolyte membrane, and the temperature is 150 ° C., 50 kg / cm. By hot pressing in step 2 , the polymer electrolyte membrane and the electrode were joined. On one surface of the polymer electrolyte membrane around the electrode of the bonded electrode / polymer electrolyte membrane assembly, tape with an adhesive made of a fluorocarbon resin (width:
1 cm, thickness: 50 μm), and the polymer electrolyte membrane was reinforced so as not to form a gap with the electrode. That is, in this case, four tapes with an adhesive are prepared and attached to the periphery of the electrode (corresponding to the phase 2 of the fluorocarbon resin shown in FIG. 1).
【００２８】この電極／高分子電解質膜接合体を、グラ
ッシ−カ−ボン製のセパレ−タ−に組み込んで高分子電
解質型燃料電池の単セルを構成した.高分子電解質型燃
料電池は５０℃の電池温度で作動させ、アノ−ド側には
６０℃で加湿した純水素を、カソ−ド側には４０℃で加
湿した空気をそれぞれ大気圧で供給し、アノ−ド側の燃
料利用率は、電流密度１０００ｍＡ／ｃｍ2のとき９５
％となるよう水素流量を調整した。This electrode / polymer electrolyte membrane assembly was assembled into a glass carbon separator to form a single cell of a polymer electrolyte fuel cell. The battery is operated at the battery temperature of 60 ° C., and pure hydrogen humidified at 60 ° C. is supplied to the anode side and air humidified at 40 ° C. is supplied to the cathode side at atmospheric pressure. Is 95 at a current density of 1000 mA / cm 2
% Was adjusted.
【００２９】本実験例に基づく高分子電解質型燃料電池
の性能曲線６（図６では、白丸で表した）と、比較のた
めに従来法によって構成した炭化フッ素系樹脂による補
強なしの高分子電解質型燃料電池の性能曲線７（図６で
は、黒丸で表した）を図６に示す。図６より、本実験例
の高分子電解質型燃料電池は従来と同等の性能が得られ
ることを確認した。図６の横軸、縦軸は、それぞれ電流
密度と電池電圧を示している。The performance curve 6 of the polymer electrolyte fuel cell based on the present experimental example (indicated by white circles in FIG. 6) and the polymer electrolyte without reinforcement by the fluorocarbon resin formed by the conventional method for comparison. FIG. 6 shows a performance curve 7 (represented by a black circle in FIG. 6) of the fuel cell. From FIG. 6, it was confirmed that the polymer electrolyte fuel cell of this experimental example can obtain the same performance as the conventional one. The horizontal axis and the vertical axis in FIG. 6 indicate the current density and the battery voltage, respectively.
【００３０】次に、本実験例に基づく高分子電解質型燃
料電池のクロスリ−ク特性曲線８（図７では、白丸で表
した）と、比較のために従来法によって構成した炭化フ
ッ素系樹脂による補強なしの高分子電解質型燃料電池の
クロスリ−ク特性曲線９（図７では、黒丸で表した）を
図７に示す。このとき、高分子電解質型燃料電池は５０
℃の電池温度で作動させ、カソ−ド側には５０℃で加湿
した空気を大気圧で供給した。アノ−ド側は、出口を絞
り、無加湿の純水素を所定の圧力で供給し、アノ−ド側
とカソ−ド側に所定の差圧が発生するよう調整して、ア
ノ−ド側にクロスリ−クした空気中の窒素量をガスクロ
マトグラフィ−で定量して、クロスリ−ク量を求めた。
図７より、明らかに本実験例の高分子電解質型燃料電池
の性能を維持したまま、高分子電解質膜の機械的強度、
特に電極周辺のエッジ部の機械的強度を強くし、耐差圧
特性も向上することを確認した。試験後、比較のために
従来法によって構成した炭化フッ素系樹脂による補強な
しの高分子電解質型燃料電池を解体し調べたところ、電
極周辺部、つまり電極と高分子電解質膜との界面近傍の
高分子電解質膜が破れていることが判明した。 （実験例２）本実験例は、図２で述べた構成とほぼ対応
した高分子電解質型燃料電池の単セルによる例である。Next, a cross leak characteristic curve 8 (indicated by a white circle in FIG. 7) of the polymer electrolyte fuel cell based on the present experimental example and a comparison with the fluorocarbon resin formed by the conventional method for comparison. FIG. 7 shows a cross leak characteristic curve 9 (represented by a black circle in FIG. 7) of the polymer electrolyte fuel cell without reinforcement. At this time, the polymer electrolyte fuel cell is 50
The battery was operated at a battery temperature of 50 ° C., and air humidified at 50 ° C. was supplied to the cathode side at atmospheric pressure. On the anode side, the outlet is throttled, pure non-humidified hydrogen is supplied at a predetermined pressure, and a predetermined pressure difference is generated between the anode side and the cathode side. The amount of nitrogen in the cross leaked air was quantified by gas chromatography to determine the amount of cross leak.
From FIG. 7, it is apparent that the mechanical strength of the polymer electrolyte membrane is maintained while maintaining the performance of the polymer electrolyte fuel cell of this experimental example.
In particular, it was confirmed that the mechanical strength of the edge portion around the electrode was increased and the differential pressure resistance was also improved. After the test, for comparison, a polymer electrolyte fuel cell without reinforcement with a fluorocarbon resin formed by the conventional method was disassembled and examined. The results showed that the height of the periphery of the electrode, that is, the vicinity of the interface between the electrode and the polymer electrolyte membrane, was high. It was found that the molecular electrolyte membrane was broken. (Experimental Example 2) This experimental example is an example using a single cell of a polymer electrolyte fuel cell which almost corresponds to the configuration described in FIG.
【００３１】即ち、高分子電解質として１６ｃｍ角に切
断したデュポン社製のナフィオン１１２（図２の高分子
電解質膜１に対応）を用いた。中心部１０ｃｍ角を切断
して穴をあけた、１５ｃｍ角の炭化フッソ系樹脂製の粘
着剤付きシ−ト（厚さ：５０μｍ、図１の炭化フッソ系
樹脂の相２に対応）を、上記高分子電解質膜の一方の面
に張り付けた。アセチレンブラック系カ−ボン粉末に平
均粒径約３０オングストロームの白金触媒を３０ｗｔ％
担持した触媒担持カ−ボン粉末と、デュポン社製のナフ
ィオン溶液を酢酸ブチル溶媒に分散し、ペ−スト状の電
極触媒スラリ−を得た。この電極触媒スラリ−を、１
０．２ｃｍ角に切断した東レ製のカ−ボン不織布の一方
の面に、白金触媒量がカ−ボン不織布の面積に対して
０．３ｍｇ／ｃｍ2となるようスクリ−ン印刷法により
塗布し、電極（図２の電極３に対応）とした。カ−ボン
不織布に塗布した電極触媒スラリ−を粗乾燥後、塗布面
が高分子電解質膜と接するように２枚の電極で炭化フッ
素系樹脂シ−ト付きの高分子電解質膜を挟持し、１５０
℃、５０ｋｇ／ｃｍ2でホットプレスして高分子電解質
膜と電極を接合した。このとき炭化フッ素系樹脂シ−ト
の中心部の１０ｃｍ角の穴の部分に電極がきて、高分子
電解質膜と電極が直接接合し、かつ炭化フッ素系樹脂の
穴より電極は４辺が１ｍｍづつ大きいため、電極周辺部
は炭化フッ素系樹脂と重なりを持つように接合した。That is, Nafion 112 manufactured by DuPont (corresponding to the polymer electrolyte membrane 1 in FIG. 2) cut into 16 cm square was used as the polymer electrolyte. A 15 cm square sheet of fluorocarbon resin with an adhesive (thickness: 50 μm, corresponding to phase 2 of the carbonized fluorocarbon resin in FIG. 1) having a hole cut by cutting a 10 cm square in the center was prepared. It was attached to one surface of a polymer electrolyte membrane. 30 wt% of a platinum catalyst having an average particle size of about 30 angstroms to acetylene black carbon powder
The supported catalyst-supporting carbon powder and a Nafion solution manufactured by DuPont were dispersed in a butyl acetate solvent to obtain a paste-like electrode catalyst slurry. This electrode catalyst slurry is
0.2cm angle cut Toray Industries mosquito - on one side of the carbon nonwoven fabric, a platinum catalyst amount of Ca - subscriptions so as to be 0.3 mg / cm 2 of the area of the carbon nonwoven fabric - was applied by screen printing method , Electrode (corresponding to electrode 3 in FIG. 2). After roughly drying the electrode catalyst slurry applied to the carbon nonwoven fabric, the polymer electrolyte membrane with a fluorocarbon resin sheet is sandwiched between two electrodes so that the coated surface is in contact with the polymer electrolyte membrane, and
The polymer electrolyte membrane and the electrode were joined by hot pressing at 50 ° C. and 50 kg / cm 2 . At this time, an electrode comes to a hole of 10 cm square at the center of the fluorocarbon resin sheet, the polymer electrolyte membrane and the electrode are directly bonded, and the electrode has four sides of 1 mm each from the hole of the fluorocarbon resin. Because of its large size, the electrode periphery was joined so as to overlap with the fluorocarbon resin.
【００３２】この電極／高分子電解質膜接合体を、グラ
ッシ−カ−ボン製のセパレ−タ−に組み込んで高分子電
解質型燃料電池の単セルを構成した。高分子電解質型燃
料電池は５０℃の電池温度で作動させ、アノ−ド側には
６０℃で加湿した純水素を、カソ−ド側には４０℃で加
湿した空気をそれぞれ大気圧で供給し、アノ−ド側の燃
料利用率は、電流密度１０００ｍＡ／ｃｍ2のとき９５
％となるよう水素流量を調整した。This electrode / polymer electrolyte membrane assembly was assembled in a glass carbon separator to form a single cell of a polymer electrolyte fuel cell. The polymer electrolyte fuel cell is operated at a cell temperature of 50 ° C., and pure hydrogen humidified at 60 ° C. is supplied to the anode side and air humidified at 40 ° C. is supplied to the cathode side at atmospheric pressure. The fuel utilization on the anode side is 95 at a current density of 1000 mA / cm 2 .
% Was adjusted.
【００３３】本実験例に基づく高分子電解質型燃料電池
の性能曲線６（図８では、白丸で表した）と、比較のた
めに従来法によって構成した炭化フッ素系樹脂による補
強なしの高分子電解質型燃料電池の性能曲線７（図８で
は、黒丸で表した）を図８に示す。図８より、本実験例
の高分子電解質型燃料電池は従来と同等の性能が得られ
ることを確認した。The performance curve 6 of the polymer electrolyte fuel cell based on this experimental example (indicated by white circles in FIG. 8) and the polymer electrolyte without reinforcement by a fluorocarbon resin formed by a conventional method for comparison. FIG. 8 shows a performance curve 7 (represented by a black circle in FIG. 8) of the fuel cell. From FIG. 8, it was confirmed that the performance of the polymer electrolyte fuel cell of this experimental example was equivalent to that of the conventional one.
【００３４】次に、本実験例に基づく高分子電解質型燃
料電池のクロスリ−ク特性曲線８（図９では、白丸で表
した）と、比較のために従来法によって構成した炭化フ
ッ素系樹脂による補強なしの高分子電解質型燃料電池の
クロスリ−ク特性曲線９（図９では、黒丸で表した）を
図９に示す。このとき、高分子電解質型燃料電池は５０
℃の電池温度で作動させ、カソ−ド側には４０℃で加湿
した空気を大気圧で供給した。アノ−ド側は、出口を絞
り、無加湿の純水素を所定の圧力で供給し、アノ−ド側
とカソ−ド側に所定の差圧が発生するよう調整して、ア
ノ−ド側にクロスリ−クした空気中の窒素量をガスクロ
マトグラフィ−で定量して、クロスリ−ク量を求めた。
図９より、明らかに本実験例の高分子電解質型燃料電池
の性能を維持したまま、高分子電解質膜の機械的強度、
特に電極周辺のエッジ部の機械的強度を強くし、耐差圧
特性も向上することを確認した。試験後、比較のために
従来法によって構成した炭化フッ素系樹脂による補強な
しの高分子電解質型燃料電池を解体し調べたところ、電
極周辺部、つまり電極と高分子電解質膜との界面近傍の
高分子電解質膜が破れていることが判明した。 （実験例３）本実験例は、図４で述べた構成とほぼ対応
した高分子電解質型燃料電池の単セルによる例である。Next, a cross leak characteristic curve 8 (shown by a white circle in FIG. 9) of the polymer electrolyte fuel cell based on the present experimental example and, for the sake of comparison, a cross-linking characteristic curve of the fluorocarbon resin formed by the conventional method. FIG. 9 shows a cross leak characteristic curve 9 (represented by a black circle in FIG. 9) of the polymer electrolyte fuel cell without reinforcement. At this time, the polymer electrolyte fuel cell is 50
The battery was operated at a battery temperature of 40 ° C., and air humidified at 40 ° C. was supplied to the cathode side at atmospheric pressure. On the anode side, the outlet is throttled, pure non-humidified hydrogen is supplied at a predetermined pressure, and a predetermined pressure difference is generated between the anode side and the cathode side. The amount of nitrogen in the cross leaked air was quantified by gas chromatography to determine the amount of cross leak.
From FIG. 9, it is apparent that the mechanical strength of the polymer electrolyte membrane is maintained while maintaining the performance of the polymer electrolyte fuel cell of this experimental example.
In particular, it was confirmed that the mechanical strength of the edge portion around the electrode was increased and the differential pressure resistance was also improved. After the test, for comparison, a polymer electrolyte fuel cell without reinforcement with a fluorocarbon resin formed by the conventional method was disassembled and examined. The results showed that the height of the periphery of the electrode, that is, the vicinity of the interface between the electrode and the polymer electrolyte membrane, was high. It was found that the molecular electrolyte membrane was broken. (Experimental Example 3) This experimental example is an example using a single cell of a polymer electrolyte fuel cell which almost corresponds to the configuration described in FIG.
【００３５】高分子電解質として１６ｃｍ角に切断した
デュポン社製のナフィオン１１２を用いた。この高分子
電解質膜（図４の高分子電解質膜１に対応）の両方の面
に、中心部１０ｃｍ角を切断して穴をあけた、１５ｃｍ
角の炭化フッソ系樹脂製の粘着剤付きシ−ト（厚さ：３
０μｍ、図４の炭化フッソ系樹脂の相２に対応）を張り
付けた。アセチレンブラック系カ−ボン粉末に平均粒径
約３０オングストロームの白金触媒を３０ｗｔ％担持し
た触媒担持カ−ボン粉末と、デュポン社製のナフィオン
溶液を酢酸ブチル溶媒に分散し、ペ−スト状の電極触媒
スラリ−を得た。この電極触媒スラリ−を、炭化フッ素
系樹脂シ−ト付きの高分子電解質膜の両面にドクタ−ブ
レ−ド法により白金触媒量が０．３ｍｇ／ｃｍ2となる
よう塗布した。このとき炭化フッ素系樹脂の中心部の１
０ｃｍ角の穴の内側に高分子電解質膜と接するよう約４
０μｍの厚みで塗布した。塗布した電極触媒スラリ−
（図４の電極触媒層に対応）を粗乾燥後、１０．２ｃｍ
角に切断した２枚の東レ製のカ−ボン不織布（図４のガ
ス拡散相に対応）で炭化フッ素系樹脂シ−ト付きの高分
子電解質膜を挟持し、１５０℃、５０ｋｇ／ｃｍ2でホ
ットプレスして高分子電解質膜と電極を接合した。この
とき炭化フッ素系樹脂シ−トの中心部の１０ｃｍ角の穴
の部分にカ−ボン不織布がきて、高分子電解質膜と電極
触媒スラリ−（電極触媒層）とカ−ボン不織布（ガス拡
散層）とが接合し、かつ炭化フッ素系樹脂の穴よりカ−
ボン不織布は４辺が１ｍｍづつ大きいため、カ−ボン不
織布周辺部は炭化フッ素系樹脂と重なりを持つように接
合した。また、電極触媒層は炭化フッ素系樹脂シ−トの
厚みより若干厚めに塗布され、カ−ボン不織布とをホッ
トプレスする際、電極触媒層の一部がカ−ボン不織布に
めり込みながら、かつ均一に薄く高分子電解質膜と接合
されているため、無駄な電極触媒層がカ−ボン不織布に
存在することなく、効率的に電極反応に寄与するため、
実質的に白金などの貴金属触媒の電極面積当たりの担持
量を低減することができる。As the polymer electrolyte, Nafion 112 manufactured by DuPont was cut into a 16 cm square. On both sides of this polymer electrolyte membrane (corresponding to the polymer electrolyte membrane 1 in FIG. 4), a center 10 cm square was cut to make a hole,
Corner sheet made of fluorocarbon resin with adhesive (thickness: 3
0 μm, corresponding to the phase 2 of the fluorocarbon resin shown in FIG. 4). A catalyst-supporting carbon powder in which 30 wt% of a platinum catalyst having an average particle size of about 30 angstroms is supported on acetylene black-based carbon powder and a Nafion solution manufactured by DuPont are dispersed in a butyl acetate solvent, and a paste-like electrode is prepared. A catalyst slurry was obtained. This electrode catalyst slurry was applied to both surfaces of a polymer electrolyte membrane provided with a fluorocarbon resin sheet by a doctor blade method so that the platinum catalyst amount was 0.3 mg / cm 2 . At this time, 1 of the central part of the fluorocarbon resin
Approximately 4 mm inside the 0 cm square hole so that it contacts the polymer electrolyte membrane.
It was applied at a thickness of 0 μm. Coated electrode catalyst slurry
After roughly drying (corresponding to the electrode catalyst layer of FIG. 4) 10.2 cm
A polymer electrolyte membrane with a fluorocarbon resin sheet is sandwiched between two pieces of Toray carbon nonwoven fabric (corresponding to the gas diffusion phase in FIG. 4) cut into corners, and heated at 150 ° C. and 50 kg / cm 2 . Hot pressing was performed to join the polymer electrolyte membrane and the electrode. At this time, a carbon non-woven fabric is formed in a 10 cm square hole at the center of the fluorocarbon resin sheet, and a polymer electrolyte membrane, an electrode catalyst slurry (electrode catalyst layer) and a carbon non-woven fabric (gas diffusion layer) are formed. ) Are joined together, and the hole is formed through the fluorocarbon resin.
Since the four sides of the carbon non-woven fabric were larger by 1 mm, the periphery of the carbon non-woven fabric was joined so as to overlap with the fluorocarbon resin. Also, the electrode catalyst layer is applied slightly thicker than the thickness of the fluorocarbon resin sheet, and when hot pressing with a carbon nonwoven fabric, a part of the electrode catalyst layer is uniformly immersed in the carbon nonwoven fabric. Since it is thinly bonded to the polymer electrolyte membrane, there is no useless electrode catalyst layer in the carbon nonwoven fabric, and it efficiently contributes to the electrode reaction.
Substantially, the amount of the noble metal catalyst such as platinum carried per electrode area can be reduced.
【００３６】この電極／高分子電解質膜接合体を、グラ
ッシ−カ−ボン製のセパレ−タ−に組み込んで高分子電
解質型燃料電池の単セルを構成した。高分子電解質型燃
料電池は５０℃の電池温度で作動させ、アノ−ド側には
６０℃で加湿した純水素を、カソ−ド側には４０℃で加
湿した空気をそれぞれ大気圧で供給し、アノ−ド側の燃
料利用率は、電流密度１０００ｍＡ／ｃｍ2のとき９５
％となるよう水素流量を調整した。The electrode / polymer electrolyte membrane assembly was assembled into a glass carbon separator to form a single cell of a polymer electrolyte fuel cell. The polymer electrolyte fuel cell is operated at a cell temperature of 50 ° C., and pure hydrogen humidified at 60 ° C. is supplied to the anode side and air humidified at 40 ° C. is supplied to the cathode side at atmospheric pressure. The fuel utilization on the anode side is 95 at a current density of 1000 mA / cm 2 .
% Was adjusted.
【００３７】本実験例に基づく高分子電解質型燃料電池
の性能曲線６（図１０では、白丸で表した）と、比較の
ために従来法によって構成した炭化フッ素系樹脂による
補強なしの高分子電解質型燃料電池の性能曲線７（図１
０では、黒丸で表した）を図１０に示す。図１０より、
本実験例の高分子電解質型燃料電池は従来と同等の性能
が得られることを確認した。The performance curve 6 of the polymer electrolyte fuel cell based on the present experimental example (indicated by white circles in FIG. 10) and the polymer electrolyte without reinforcement by the fluorocarbon resin formed by the conventional method for comparison. Curve 7 of the fuel cell shown in FIG.
0 is represented by a black circle) is shown in FIG. From FIG.
It was confirmed that the polymer electrolyte fuel cell of the present experimental example can obtain the same performance as the conventional one.
【００３８】次に、本実験例に基づく高分子電解質型燃
料電池のクロスリ−ク特性曲線８（図１１では、白丸で
表した）と、比較のために従来法によって構成した炭化
フッ素系樹脂による補強なしの高分子電解質型燃料電池
のクロスリ−ク特性曲線９（図１１では、黒丸で表し
た）を図１１に示す。このとき、高分子電解質型燃料電
池は５０℃の電池温度で作動させ、カソ−ド側には４０
℃で加湿した空気を大気圧で供給した。アノ−ド側は、
出口を絞り、無加湿の純水素を所定の圧力で供給し、ア
ノ−ド側とカソ−ド側に所定の差圧が発生するよう調整
して、アノ−ド側にクロスリ−クした空気中の窒素量を
ガスクロマトグラフィ−で定量して、クロスリ−ク量を
求めた。図１１より、明らかに本実験例の高分子電解質
型燃料電池の性能を維持したまま、高分子電解質膜の機
械的強度、特に電極周辺のエッジ部の機械的強度を強く
し、耐差圧特性も向上することを確認した。試験後、比
較のために従来法によって構成した炭化フッ素系樹脂に
よる補強なしの高分子電解質型燃料電池を解体し調べた
ところ、電極周辺部、つまり電極と高分子電解質膜との
界面近傍の高分子電解質膜が破れていることが判明し
た。Next, a cross leak characteristic curve 8 (shown by white circles in FIG. 11) of the polymer electrolyte fuel cell based on the present experimental example, and a comparison using a fluorocarbon resin formed by a conventional method for comparison. FIG. 11 shows a cross leak characteristic curve 9 (represented by a black circle in FIG. 11) of the polymer electrolyte fuel cell without reinforcement. At this time, the polymer electrolyte fuel cell is operated at a cell temperature of 50 ° C.
Air humidified at ° C was supplied at atmospheric pressure. On the anode side,
The outlet is throttled, pure humidified hydrogen is supplied at a predetermined pressure, and a predetermined pressure difference is generated between the anode side and the cathode side. The amount of nitrogen was determined by gas chromatography to determine the amount of cross leak. From FIG. 11, it is apparent that while maintaining the performance of the polymer electrolyte fuel cell of this experimental example, the mechanical strength of the polymer electrolyte membrane, particularly the mechanical strength at the edge portion around the electrode, was increased, and the differential pressure resistance was improved. Confirmed that it also improved. After the test, for comparison, a polymer electrolyte fuel cell without reinforcement with a fluorocarbon resin constructed by the conventional method was disassembled and examined, and the result was that the height around the electrode, that is, near the interface between the electrode and the polymer electrolyte membrane, was high. It was found that the molecular electrolyte membrane was broken.
【００３９】以上のように本発明は、高分子電解質と電
極との接合面以外の電極周辺部の高分子電解質の少なく
とも一方の面を炭化フッ素系樹脂で被覆することによっ
て、または、高分子電解質と電極との接合面以外の電極
周辺部の高分子電解質の少なくとも一方の面を炭化フッ
素系樹脂で被覆し、炭化フッソ系樹脂で被覆されていな
い高分子電解質の中心部の面積より大きい電極を有して
構成することによって、または、高分子電解質の少なく
とも一方の面の周縁部に炭化フッソ系の樹脂を被覆し、
炭化フッソ系樹脂で被覆した高分子電解質の中心部に炭
化フッソ系樹脂と接する大きさの電極触媒層を被覆し、
電極触媒層より大きいガス拡散相を電極触媒層と接する
よう接合することによって、高分子電解質のイオン伝導
度を維持したまま、高分子電解質膜の機械的強度を強く
することが可能である。As described above, the present invention provides a method in which at least one surface of the polymer electrolyte around the electrode other than the bonding surface between the polymer electrolyte and the electrode is coated with a fluorocarbon resin, or At least one surface of the polymer electrolyte around the electrode other than the bonding surface between the electrode and the electrode is coated with a fluorocarbon resin, and an electrode larger than the area of the center of the polymer electrolyte not coated with the fluorocarbon resin is used. By having and configuring, or covering the periphery of at least one surface of the polymer electrolyte with a fluorocarbon resin,
An electrode catalyst layer of a size in contact with the fluorocarbon resin is coated on the center of the polymer electrolyte coated with the fluorocarbon resin,
By joining a gas diffusion phase larger than the electrode catalyst layer so as to be in contact with the electrode catalyst layer, it is possible to increase the mechanical strength of the polymer electrolyte membrane while maintaining the ionic conductivity of the polymer electrolyte.
【００４０】[0040]
【発明の効果】以上述べたところから明らかなように本
発明は、高分子電解質のイオン伝導度を維持したまま、
高分子電解質膜の機械的強度をより強く出来ると言う長
所を有する。As is apparent from the above description, the present invention provides a method for maintaining the ionic conductivity of a polymer electrolyte.
It has the advantage that the mechanical strength of the polymer electrolyte membrane can be increased.
【図１】本発明の一実施の形態の概略構成図である。FIG. 1 is a schematic configuration diagram of an embodiment of the present invention.
【図２】本発明の他の実施の形態の概略構成図である。FIG. 2 is a schematic configuration diagram of another embodiment of the present invention.
【図３】本発明の他の実施の形態の概略構成図である。FIG. 3 is a schematic configuration diagram of another embodiment of the present invention.
【図４】本発明の他の実施の形態の概略構成図である。FIG. 4 is a schematic configuration diagram of another embodiment of the present invention.
【図５】本発明の他の実施の形態の概略構成図である。FIG. 5 is a schematic configuration diagram of another embodiment of the present invention.
【図６】本発明に基づいた実験例１の高分子電解質型燃
料電池の特性図である。FIG. 6 is a characteristic diagram of a polymer electrolyte fuel cell of Experimental Example 1 based on the present invention.
【図７】本発明に基づいた実験例１の高分子電解質型燃
料電池のクロスリ−ク特性図である。FIG. 7 is a cross leak characteristic diagram of the polymer electrolyte fuel cell of Experimental Example 1 based on the present invention.
【図８】本発明に基づいた実験例２の高分子電解質型燃
料電池の特性図である。FIG. 8 is a characteristic diagram of a polymer electrolyte fuel cell of Experimental Example 2 based on the present invention.
【図９】本発明に基づいた実験例２の高分子電解質型燃
料電池のクロスリ−ク特性図である。FIG. 9 is a cross leak characteristic diagram of a polymer electrolyte fuel cell of Experimental Example 2 based on the present invention.
【図１０】本発明に基づいた実験例３の高分子電解質型
燃料電池の特性図である。FIG. 10 is a characteristic diagram of a polymer electrolyte fuel cell of Experimental Example 3 based on the present invention.
【図１１】本発明に基づいた実験例３の高分子電解質型
燃料電池のクロスリ−ク特性図である。FIG. 11 is a cross leak characteristic diagram of a polymer electrolyte fuel cell of Experimental Example 3 based on the present invention.
１ 高分子電解質膜 ２ 炭化フッソ系樹脂の相 ３ 電極 ４ 電極触媒層 ５ ガスマニホ−ルド ６ 実験例の高分子電解質型燃料電池の性能曲線 ７ 従来法による高分子電解質型燃料電池の性能曲線 ８ 実験例の高分子電解質型燃料電池のクロスリ−ク
特性曲線 ９ 従来法による高分子電解質型燃料電池のクロスリ
−ク特性曲線 ３３ ガス拡散相Reference Signs List 1 polymer electrolyte membrane 2 phase of fluorocarbon resin 3 electrode 4 electrode catalyst layer 5 gas manifold 6 performance curve of polymer electrolyte fuel cell of experimental example 7 performance curve of polymer electrolyte fuel cell by conventional method 8 experiment Example 9 cross-leak characteristic curve of polymer electrolyte fuel cell 9 Cross-leak characteristic curve of conventional polymer electrolyte fuel cell 33 Gas diffusion phase
───────────────────────────────────────────────────── フロントページの続き (72)発明者 蒲生 孝治 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koji Gamo 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (6)
持するガス拡散電極としてのアノ−ドとカソ−ドとを有
する高分子電解質型燃料電池において、 前記高分子電解質は前記アノード及び／又は前記カソー
ドより面積が大きく、前記高分子電解質の少なくとも一
方の面における、前記高分子電解質と前記アノード又は
前記カソードとの接合面以外の部位が炭化フッ素系樹脂
で被覆されていることを特徴とする高分子電解質型燃料
電池。1. A polymer electrolyte fuel cell comprising a polymer electrolyte, and an anode and a cathode as gas diffusion electrodes sandwiching the polymer electrolyte, wherein the polymer electrolyte is the anode and / or the cathode. The area is larger than the cathode, and at least one surface of the polymer electrolyte other than a bonding surface between the polymer electrolyte and the anode or the cathode is coated with a fluorocarbon resin. Polymer electrolyte fuel cell.
持するガス拡散電極としてのアノ−ドとカソ−ドとを有
する高分子電解質型燃料電池において、 前記高分子電解質は前記アノード及び／又は前記カソー
ドより面積が大きく、前記高分子電解質の少なくとも一
方の面における、前記高分子電解質と前記アノード又は
前記カソードとの接合面以外の部位が炭化フッ素系樹脂
で被覆されており、 前記少なくとも一方の面における前記アノード又は前記
カソードは、前記少なくとも一方の面における前記炭化
フッソ系樹脂で被覆されていない面積より大きいことを
特徴とする高分子電解質型燃料電池。2. A polymer electrolyte fuel cell comprising a polymer electrolyte, and an anode and a cathode as gas diffusion electrodes sandwiching the polymer electrolyte, wherein the polymer electrolyte is the anode and / or the cathode. Area larger than the cathode, at least one surface of the polymer electrolyte, a portion other than the bonding surface between the polymer electrolyte and the anode or the cathode is coated with a fluorocarbon resin, the at least one of the The polymer electrolyte fuel cell according to claim 1, wherein the anode or the cathode on a surface is larger than the area of the at least one surface not covered with the fluorocarbon resin.
持するガス拡散電極としてのアノ−ドとカソ−ドとを有
し、前記アノ−ドおよびカソ−ドが、電極触媒を担持し
たカ−ボン粉末を主体とする電極触媒層と、前記電極触
媒を担持していないカ−ボン粉末又はカ−ボン繊維を主
体とするガス拡散相とから構成されている高分子電解質
型燃料電池において、 前記高分子電解質の少なくとも一方の面の外周部付近に
炭化フッソ系の樹脂が被覆されており、前記少なくとも
一方の面における前記炭化フッソ系樹脂で被覆されてい
ない前記高分子電解質の実質上中心部に前記炭化フッソ
系樹脂と接する大きさの電極触媒層が被覆されており、
前記電極触媒層より大きいガス拡散相が前記電極触媒層
と接するよう接合されていることを特徴とする高分子電
解質型燃料電池。3. A polymer electrolyte, comprising an anode and a cathode as gas diffusion electrodes sandwiching the polymer electrolyte, wherein the anode and the cathode carry an electrode catalyst. A polymer electrolyte fuel cell comprising an electrode catalyst layer mainly composed of carbon powder, and a gas diffusion phase mainly composed of carbon powder or carbon fiber not supporting the electrode catalyst, Near the outer peripheral portion of at least one surface of the polymer electrolyte is coated with a fluorocarbon resin, and the substantially central portion of the polymer electrolyte that is not coated with the fluorocarbon resin on the at least one surface. An electrode catalyst layer having a size in contact with the fluorinated carbon-based resin is coated,
A polymer electrolyte fuel cell, wherein a gas diffusion phase larger than the electrode catalyst layer is joined so as to be in contact with the electrode catalyst layer.
ケットを兼ねることを特徴とする請求項１から３のいず
れか一つに記載の高分子電解質型燃料電池。4. The polymer electrolyte fuel cell according to claim 1, wherein the coated fluorocarbon resin also functions as a gasket.
着剤付きの又は粘着剤付きでない薄膜シ−ト状であるこ
とを特徴とする請求項１から４のいずれか一つに記載の
高分子電解質型燃料電池。5. The high-pressure resin according to claim 1, wherein the coated fluorocarbon resin is in the form of a thin film sheet with or without an adhesive. Molecular electrolyte fuel cell.
持するガス拡散電極としてのアノ−ドとカソ−ドとを有
し、前記アノ−ドおよびカソ−ドが、電極触媒を担持し
たカ−ボン粉末を主体とする電極触媒層と、前記電極触
媒を担持していないカ−ボン粉末又はカ−ボン繊維を主
体とするガス拡散相とから構成されている高分子電解質
型燃料電池の製造方法であって、 前記高分子電解質の少なくとも一方の面の外周部付近に
炭化フッソ系の樹脂を被覆する樹脂被覆工程と、 前記樹脂被覆工程の後、前記少なくとも一方の面におけ
る前記炭化フッソ系樹脂で被覆されていない前記高分子
電解質の実質上中心部に、前記炭化フッソ系樹脂の内周
端部と接する大きさの電極触媒層を形成する電極触媒層
形成工程と、 前記電極触媒層形成工程の後、前記電極触媒層より大き
いガス拡散相を前記電極触媒層と接するよう接合する接
合工程と、を備えていることを特徴とする高分子電解質
型燃料電池の製造方法。6. A polymer electrolyte, comprising an anode and a cathode as gas diffusion electrodes sandwiching the polymer electrolyte, wherein the anode and the cathode carry an electrode catalyst. -Manufacture of a polymer electrolyte fuel cell comprising an electrode catalyst layer mainly composed of carbon powder and a gas diffusion phase mainly composed of carbon powder or carbon fiber not carrying the electrode catalyst. A method, comprising: a resin coating step of coating a fluorocarbon resin near an outer peripheral portion of at least one surface of the polymer electrolyte; and after the resin coating step, the fluorocarbon resin on the at least one surface. An electrode catalyst layer forming step of forming an electrode catalyst layer having a size in contact with an inner peripheral end of the fluorocarbon resin at a substantially central portion of the polymer electrolyte that is not coated with, the electrode catalyst layer forming step After, before A joining step of joining a gas diffusion phase larger than the electrode catalyst layer so as to be in contact with the electrode catalyst layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11568197A JP3810178B2 (en) | 1997-05-06 | 1997-05-06 | Method for producing polymer electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11568197A JP3810178B2 (en) | 1997-05-06 | 1997-05-06 | Method for producing polymer electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10308228A true JPH10308228A (en) | 1998-11-17 |
| JP3810178B2 JP3810178B2 (en) | 2006-08-16 |
Family
ID=14668646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11568197A Expired - Fee Related JP3810178B2 (en) | 1997-05-06 | 1997-05-06 | Method for producing polymer electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3810178B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002208413A (en) * | 2001-01-09 | 2002-07-26 | Toshiba Corp | Solid polymer electrolyte fuel cell |
| JP2002329504A (en) * | 2001-04-27 | 2002-11-15 | Matsushita Electric Ind Co Ltd | Polymer electrolyte fuel cell |
| JP2005285677A (en) * | 2004-03-30 | 2005-10-13 | Toyota Motor Corp | Polymer electrolyte fuel cell |
| JP2006100267A (en) * | 2004-08-30 | 2006-04-13 | Asahi Glass Co Ltd | Solid polymer electrolyte membrane electrode assembly and solid polymer fuel cell |
| JP2006331718A (en) * | 2005-05-24 | 2006-12-07 | Hitachi Ltd | Fuel cell |
| JP2006338936A (en) * | 2005-05-31 | 2006-12-14 | Nissan Motor Co Ltd | Method for producing electrolyte membrane-electrode assembly |
| US7521144B2 (en) | 2004-08-30 | 2009-04-21 | Asahi Glass Company, Limited | Membrane-electrode assembly for polymer electrolyte fuel cells, and polymer electrolyte fuel cell |
| US8097112B2 (en) | 2005-06-20 | 2012-01-17 | Panasonic Corporation | Method for manufacturing membrane-electrode assembly |
| JP2012099492A (en) * | 2005-06-20 | 2012-05-24 | Panasonic Corp | Membrane-electrode assembly |
| JP2015050058A (en) * | 2013-09-02 | 2015-03-16 | 凸版印刷株式会社 | Membrane electrode assembly and method for manufacturing the same |
| JP2015130365A (en) * | 2006-01-25 | 2015-07-16 | ソシエテ ビックＳｏｃｉｅｔｅ Ｂｉｃ | Method of operating a fuel cell with passive reactant supply |
-
1997
- 1997-05-06 JP JP11568197A patent/JP3810178B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002208413A (en) * | 2001-01-09 | 2002-07-26 | Toshiba Corp | Solid polymer electrolyte fuel cell |
| JP2002329504A (en) * | 2001-04-27 | 2002-11-15 | Matsushita Electric Ind Co Ltd | Polymer electrolyte fuel cell |
| JP2005285677A (en) * | 2004-03-30 | 2005-10-13 | Toyota Motor Corp | Polymer electrolyte fuel cell |
| JP2006100267A (en) * | 2004-08-30 | 2006-04-13 | Asahi Glass Co Ltd | Solid polymer electrolyte membrane electrode assembly and solid polymer fuel cell |
| US7521144B2 (en) | 2004-08-30 | 2009-04-21 | Asahi Glass Company, Limited | Membrane-electrode assembly for polymer electrolyte fuel cells, and polymer electrolyte fuel cell |
| JP2006331718A (en) * | 2005-05-24 | 2006-12-07 | Hitachi Ltd | Fuel cell |
| JP2006338936A (en) * | 2005-05-31 | 2006-12-14 | Nissan Motor Co Ltd | Method for producing electrolyte membrane-electrode assembly |
| US8097112B2 (en) | 2005-06-20 | 2012-01-17 | Panasonic Corporation | Method for manufacturing membrane-electrode assembly |
| JP2012099492A (en) * | 2005-06-20 | 2012-05-24 | Panasonic Corp | Membrane-electrode assembly |
| JP2012099491A (en) * | 2005-06-20 | 2012-05-24 | Panasonic Corp | Membrane-electrode assembly and method for manufacturing the same |
| JP2015130365A (en) * | 2006-01-25 | 2015-07-16 | ソシエテ ビックＳｏｃｉｅｔｅ Ｂｉｃ | Method of operating a fuel cell with passive reactant supply |
| JP2015050058A (en) * | 2013-09-02 | 2015-03-16 | 凸版印刷株式会社 | Membrane electrode assembly and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3810178B2 (en) | 2006-08-16 |
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