JP2005520002A - 高硬度及び寸法安定性を有するイオン伝導性隔膜 - Google Patents
高硬度及び寸法安定性を有するイオン伝導性隔膜 Download PDFInfo
- Publication number
- JP2005520002A JP2005520002A JP2003526982A JP2003526982A JP2005520002A JP 2005520002 A JP2005520002 A JP 2005520002A JP 2003526982 A JP2003526982 A JP 2003526982A JP 2003526982 A JP2003526982 A JP 2003526982A JP 2005520002 A JP2005520002 A JP 2005520002A
- Authority
- JP
- Japan
- Prior art keywords
- diaphragm
- composite diaphragm
- composite
- ion exchange
- less
- 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
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249962—Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
- Y10T428/249964—Fibers of defined composition
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249981—Plural void-containing components
Abstract
Description
(b)前記の隔膜にその全体を通じて含浸されたイオン交換材料であって、含浸後の延伸膨脹ポリテトラフルオロエチレン隔膜が、10,000秒よりも大きなガーレイ(Gurley)数を有し、その際、前記イオン交換材料が、前記隔膜に実質的に含浸せしめられ、前記隔膜の内部容積を実質的に閉塞している、イオン交換材料
から形成された複合隔膜を提供する。
インストロン試験機、モデル番号5567(Instron Corporation, シリーズIX-自動化材料試験システム1.00)を使用して試験を実施した。サンプルは、幅1インチ×長さ6インチであった。ゲージの長さ(クランプ間の距離)は、2インチであった。20℃及び相対湿度50%で20インチ/分のクロスヘッド速度でサンプルの引張を行った。破断時伸び及び最大荷重を記録した。マトリックス引張強度は、最大荷重をサンプルの初期断面積で除算し、多孔度の測定値でさらに除算することによって測定した。多孔度は、サンプルの重量をその長さ、幅及び厚さで除算することによって最初に密度を計算し、次いでその密度を完全緻密の材料の密度で除算することによって決定した。完全緻密PTFEの密度を2.19g/cm2であるとみなした。
基材の厚さを三豊社製のスナップゲージ、品番2804F−10を使用して測定した。それぞれの試料について最低4個所の領域で測定を実施し、次いで平均値を求めた。乾燥後の複合隔膜の厚さを上記のスナップゲージを使用して、かつ走査型電子顕微鏡写真を使用して測定した。
水和後における横断方向、縦方向及びz方向の膨脹を次のような手法に従って測定した:室温及び40〜60%の相対湿度で最低1日中保存した3インチ×3インチのサンプルを80℃の脱イオン水中に5分間入れ、イオン伝導性隔膜が完全水和の状態にあることを確実にした。次いで、サンプルを取り出し、ラバーマットの上に載置した。サンプルの角部を直角見本を使用して整列し、平らに拡げた。膨潤後の横断方向及び縦方向の長さを精度0.016インチ(1/64インチ)のルーラを使用して測定した。膨潤後の厚さを上述の厚さ測定技法を使用して測定した。寸法安定性をそれぞれの方向における変化率(%)として記録した。面貫通水和膨脹を厚さの増加率(%)として記録した。
ICMサンプルの硬度をCSEM Instruments, Inc.(スイス在)製のマイクロ硬度試験装置を使用して、Micro Photonics Inc., Irvine, CAによって測定した。ICMのサンプルの中に直径1mmの炭化タングステン製のインデンタを10N/分の速度で圧入した。最大侵入深さを15,000nmに設定し、硬度をMPaで算出した。サンプルが載置される基板からの影響を取り除くためにこの深さを選択した。初期のサンプル厚さの60%よりも小さい深さをすべての試験で使用した。
最大の力 使用せず
最大深さ 15,000nm
ローディング速度 10N/分
アンロード速度 10N/分
休止 15秒間
キャリブレーション 20%/0.010
及びプレファランス 30N/100μm
ポアソン係数 0.50
計算法 Oliver及びPharr
インデントのタイプ WC,直径1mm
温度 周囲
相対湿度 周囲
ガーレイ(Gurley)通気試験で、1平方インチのサンプルに4.88インチの水圧で100cm3の空気を通過させるのに必要な時間(秒)を測定する。サンプルをガーレイデンソメータ(ASTM0726−58)で測定する。サンプルをクランプ板の間に挟みこむ。次いで、シリンダを静かに落下させる。自動式のタイマー(又はストップウオッチ)を使用して、シリンダによって100cm3の空気を押しのけるのに必要とされる時間(分)を記録する。この時間がガーレイ数である。
サイズが既知であるサンプルの重量を測定し、その材料をサンプルの長さ及び幅で除算することによって、面積当たりの質量を測定する。
200Ωもしくはそれ以下の電気的ショートが発生するまでガス拡散媒体の繊維がICMサンプルを貫通するのに必要な圧力(psi)を測定することによって、ショートに対する圧力を測定した。本発明のICMを2層のCarbelTMガス拡散媒体CL(GDM)(ジャパン・ゴアテックス社から入手可能)の間に挟み、かつ電極境界層が隔膜に対向するようにした。マニュアル作動式のメカニカルプレス上に載置した1インチ(5.6cm2)の鋼製トッププラテンを下降させ、トッププラテンから電気的に隔離された鋼製ボトムプラテン上に留置されたサンプルと接触させた。次いで、約50psi/分で圧力を上昇させた。トッププラテン及びボトムプラテン間の電気抵抗をデジタルマルチメータを使用して測定した。抵抗が低下して200Ωよりも小さくなった時に圧力を記録した。
Branca’405の8欄30〜36行に記載の試験法に従ってアスペクト比を測定した。
次のような方法で燃料電池の耐久性を測定した:PRIMEATM5510電極(ジャパン・ゴアテックス社製)の間で電解質として本発明の複合ICMを使用してMEAを構成し、かつアノード及びカソードの両方においてPt負荷量を0.4mg/cm2とし、アノード側及びカソード側の両方にCarbelTMガス拡散媒体CL(ジャパン・ゴアテックス社から入手可能)を備えた。電池のサイズは、すべての場合について25cm2であった。電池の組み立て工程は、次の通りであった。
b)25cm2の三又蛇溝型フローフィールド(triple serpentine channel design flowfield; Fuel Cell Technologies, Inc., Albuquerque, NMの提供)を作業台上に載置した。
c)窓型のCHR(Furon)cohrelasticシリコーンコート布帛製ガスケットであって、その内側に25cm2のGDMが嵌合するようなサイズを備えたガスケット(Tate Engineering Systems, Inc., Baltimore, MDの提供)をフローフィールドの頂部に載置した。
d)1枚のCarbel CL(登録商標)GDMをガスケットの内側に配置した。
e)ポリエチレンナフタレート(PEN)フィルム製であって、すべての側面についてGDMとわずかに重なり合うようなサイズを備えたもう1個の窓型のガスケット(Tekra Corp., Charlotte, NCから入手可能)をGDMの頂部に載置した。
f)上記工程(a)で作製したアノード/隔膜/カソードシステムをガスケットの頂部に載置した。
g)上記工程(b)〜(e)を反対の順序で繰り返してカソード室(カソードコンパートメント)を形成した。
h)電池をバイスに取り付け、8個の固定用ボルトを使用して45in-lbに締結した。
当業者によって認められ得るように、本発明は、常用の隔膜の硬度よりも著しく大きな硬度を有し、より大きな縦方向及び横断方向寸法安定性を備えたポリマー樹脂の複合隔膜を提供する。結果として、本発明の隔膜は、改良された孔開き耐性とより長い隔膜寿命を提供する。
公称厚さが1.38ミルであるタイプ1のePTFE隔膜を10インチの木製刺繍枠に取り付けた。100容量%のペルフルオロスルホン酸/テトラフルオロエチレン共重合体樹脂溶液を含むイオン交換材料溶液を調製した(H+の形をしており、自体、10%のペルフルオロスルホン酸/テトラフルオロエチレン共重合体樹脂、10%の水及び80%の、旭硝子(株)から商標名Flemion type F950 (950EW)、以下「F950」という、で商業的に入手可能な低分子量アルコールの混合物からなる)。この溶液を隔膜の両側に4インチの発泡材ブラシを使用して塗布し、隔膜の内部容積に含浸させ、それを実質的に閉塞した。次いで、サンプルをヘアドライヤーを使用して2分間にわたって乾燥し、その後、180℃で3分間にわたってオーブン乾燥した。この手法をさらに2回繰り返して内部容積をより完全に閉塞した。乾燥後の複合隔膜の厚さを測定したところ、基材の約50%であることが判明した。硬度は、第1表に認めることができる。また、このサンプルの寸法安定性は第2表に、強度及びマトリックス引張強度は第5表に、それぞれ記載されている。
公称厚さが0.78ミルであるタイプ2のePTFE隔膜を10インチの木製刺繍枠に取り付けた。100容量%のペルフルオロスルホン酸/テトラフルオロエチレン共重合体樹脂溶液を含むイオン交換材料溶液を調製した(H+の形をしており、自体、10%のペルフルオロスルホン酸/テトラフルオロエチレン共重合体樹脂、10%の水及び80%の、旭硝子(株)から商標名Flemion type F950 (950EW)、以下「F950」という、で商業的に入手可能な低分子量アルコールの混合物からなる)。この溶液を隔膜の両側に4インチの発泡材ブラシを使用して塗布し、隔膜の内部容積に含浸させ、それを実質的に閉塞した。次いで、サンプルをヘアドライヤーを使用して2分間にわたって乾燥し、その後、180℃で3分間にわたってオーブン乾燥した。この手法をさらに3回繰り返して内部容積をより完全に閉塞した。乾燥後の複合隔膜の厚さを測定したところ、基材の約18%(18μm)であることが判明した。このサンプルの寸法安定性は第2表に認めることができる。また、硬度は、第1表に認めることができる。
前記実施例2で使用したものと同一の手法を使用してサンプルを調製した。ショートに対する圧力を測定し、結果を第3表に示す。
前記実施例1で使用したものと同一の手法を使用してサンプルを調製した。このサンプルを、上記した方法に従って燃料電池の耐久性に関して試験した。第4表に示すように、燃料電池の耐久性は、1,000時間であった。
前記実施例2で使用したものと同一の手法を使用してサンプルを調製した。このサンプルを、上記した方法に従って燃料電池の耐久性に関して試験した。上記した隔膜の寿命は、2,000時間であった。
公称厚さが25μmであるePTFEで補強したGORE-SELECT(登録商標)隔膜、ペルフルオロスルホン酸/テトラフルオロエチレン(TFE)/共重合体のカチオン交換隔膜、をBaharらの米国特許第5,547,551号に従って作製した。サンプルを上記したような寸法安定性試験、硬度試験及び燃料電池耐久性試験、そして強度測定に供した。結果は、第1表〜第5表に記載する通りである。
Nafion 101(N101)、ペルフルオロスルホン酸/テトラフルオロエチレン(TFE)/共重合体のカチオン交換隔膜、付与された公称厚さが1ミル(0.025mm)であって強化処理されていない、Ion Power Inc. (Glasgow, DE)から商業的に入手可能な1,000EW重量のフィルム、を入手した。サンプルを上記したような硬度、寸法安定性、そして燃料電池耐久性の試験に供した。結果は、それぞれ、第1表、第2表及び第4表に記載する通りである。
Claims (21)
- (a)フィブリルによって相互に結合されたノードから本質的になるとともに、前記ノードが、実質的に平行に整列されており、高度に伸長されておりかつ25:1もしくはそれ以上のアスペクト比を有している、内部微細構造を有する延伸膨脹ポリテトラフルオロエチレン隔膜、及び
(b)前記隔膜にその全体を通じて含浸されたイオン交換材料であって、含浸後の延伸膨脹ポリテトラフルオロエチレン隔膜が、10,000秒よりも大きなガーレイ(Gurley)数を有し、その際、前記イオン交換材料が、前記隔膜に実質的に含浸せしめられ、前記隔膜の内部容積を実質的に閉塞している、イオン交換材料
を含む複合隔膜。 - 1,000MPaよりも大きな硬度を有する、請求項1に記載の複合隔膜。
- 1,500MPaよりも大きな硬度を有する、請求項1に記載の複合隔膜。
- 2,000MPaよりも大きな硬度を有する、請求項1に記載の複合隔膜。
- 縦方向の寸法安定性が6%未満である、請求項1に記載の複合隔膜。
- 縦方向の寸法安定性が4%未満である、請求項1に記載の複合隔膜。
- 縦方向の寸法安定性が2%未満である、請求項1に記載の複合隔膜。
- 横断方向の寸法安定性が10%未満である、請求項1に記載の複合隔膜。
- 横断方向の寸法安定性が8%未満である、請求項1に記載の複合隔膜。
- 横断方向の寸法安定性が6%未満である、請求項1に記載の複合隔膜。
- 横断方向の寸法安定性が4%未満である、請求項1に記載の複合隔膜。
- ショートに対する圧力が400psiよりも大である、請求項1に記載の複合隔膜。
- ショートに対する圧力が200psiよりも大である、請求項1に記載の複合隔膜。
- 請求項1に記載の複合隔膜とアノード及びカソードを含む隔膜電極アセンブリ。
- 請求項14に記載の隔膜電極アセンブリを含む燃料電池。
- 請求項1に記載の複合隔膜と少なくとも1個のアノード及びカソードを含む電解質セル。
- 縦方向の強度が8,500psiよりも大である、請求項1に記載の複合隔膜。
- 横断方向の強度が8,500psiよりも大である、請求項1に記載の複合隔膜。
- 面貫通水和膨脹が30%よりも大である、請求項1に記載の複合隔膜。
- 面貫通水和膨脹が40%よりも大である、請求項1に記載の複合隔膜。
- 相互に結合された通路及び経路を形成したノード及びフィブリルの微細構造を有しかつ硬度が1,000mPaよりも大である基材と、前記基材にその全体を通じて含浸されたイオン交換材料とを含む複合隔膜であって、前記複合隔膜が、10,000秒よりも大きなガーレイ(Gurley)数を有し、その際、前記イオン交換材料が、前記基材に実質的に含浸せしめられ、前記通路及び経路を実質的に閉塞している、複合隔膜。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/950,839 | 2001-09-10 | ||
US09/950,839 US6613203B1 (en) | 2001-09-10 | 2001-09-10 | Ion conducting membrane having high hardness and dimensional stability |
PCT/US2002/027338 WO2003022912A2 (en) | 2001-09-10 | 2002-08-27 | Ion conducting membrane having high hardness and dimensional stability |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2005520002A true JP2005520002A (ja) | 2005-07-07 |
JP2005520002A5 JP2005520002A5 (ja) | 2006-01-05 |
JP4975951B2 JP4975951B2 (ja) | 2012-07-11 |
Family
ID=25490910
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003526982A Expired - Lifetime JP4975951B2 (ja) | 2001-09-10 | 2002-08-27 | 高硬度及び寸法安定性を有するイオン伝導性隔膜 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6613203B1 (ja) |
EP (1) | EP1490426B1 (ja) |
JP (1) | JP4975951B2 (ja) |
KR (1) | KR20040033038A (ja) |
CN (1) | CN100372883C (ja) |
AU (1) | AU2002323440B2 (ja) |
CA (1) | CA2459984C (ja) |
DE (1) | DE60215554T2 (ja) |
HK (1) | HK1072441A1 (ja) |
WO (1) | WO2003022912A2 (ja) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008018400A1 (fr) * | 2006-08-09 | 2008-02-14 | Sumitomo Electric Fine Polymer, Inc. | Membrane de résine fluorée, composite de résine fluorée, composite poreux de résine fluorée, procédés pour la production de ceux-ci et élément de type membrane pour la séparation |
WO2009107273A1 (ja) * | 2008-02-26 | 2009-09-03 | トヨタ自動車株式会社 | 燃料電池用補強型電解質膜、燃料電池用膜-電極接合体、及びそれを備えた固体高分子形燃料電池 |
JP2009289747A (ja) * | 2008-05-29 | 2009-12-10 | General Electric Co <Ge> | 高分子電解質膜及び製造方法 |
DE112009002507T5 (de) | 2008-10-17 | 2012-01-19 | Japan Gore-Tex, Inc. | Verstärkte Brennstoffzellen-Elektrolytmembran, Membran/Elektriden-Anordnung für eine Brennstoffzelle und Polymerelektrolyd-Brennstofftelle, inder dies enthalten ist |
US8795923B2 (en) | 2007-04-19 | 2014-08-05 | Toyota Jidosha Kabushiki Kaisha | Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly |
WO2015080292A1 (ja) | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | 高分子電解質膜 |
WO2015080294A1 (ja) | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | 高分子電解質膜 |
US9421499B2 (en) | 2012-01-27 | 2016-08-23 | Sumitomo Electric Fine Polymer, Inc. | Microporous modified-polytetrafluoroethylene membrane, porous-modified-polytetrafluoroethylene-membrane composite and production process thereof, and separation membrane element |
JP2018511463A (ja) * | 2015-03-10 | 2018-04-26 | ゼネラル・エレクトリック・カンパニイ | 多層支持基材を有するイオン交換膜 |
JP2019220458A (ja) * | 2018-06-15 | 2019-12-26 | 日本碍子株式会社 | 電気化学セル |
US10688448B2 (en) | 2013-11-29 | 2020-06-23 | Daikin Industries, Ltd. | Porous body, polymer electrolyte membrane, filter material for filter, and filter unit |
US11084895B2 (en) | 2013-11-29 | 2021-08-10 | Daikin Industries, Ltd. | Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body |
US11135551B2 (en) | 2017-03-20 | 2021-10-05 | Bl Technologies, Inc. | Ion-exchange membrane having an imprinted non-woven substrate |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001517876A (ja) * | 1997-09-22 | 2001-10-09 | ダブリュ.エル.ゴア アンド アソシエーツ,ゲゼルシャフト ミット ベシュレンクテル ハフツング | 電気化学的エネルギー貯蔵手段 |
US7473485B2 (en) | 2002-09-04 | 2009-01-06 | Utc Power Corporation | Extended electrodes for PEM fuel cell applications |
US20040081886A1 (en) * | 2002-10-25 | 2004-04-29 | David Zuckerbrod | Separator for electrochemical devices |
US7378176B2 (en) * | 2004-05-04 | 2008-05-27 | Angstrom Power Inc. | Membranes and electrochemical cells incorporating such membranes |
US7632587B2 (en) | 2004-05-04 | 2009-12-15 | Angstrom Power Incorporated | Electrochemical cells having current-carrying structures underlying electrochemical reaction layers |
JP2005332672A (ja) * | 2004-05-19 | 2005-12-02 | Aisin Seiki Co Ltd | 膜電極接合体、高分子電解質型燃料電池 |
US7836888B2 (en) * | 2004-09-21 | 2010-11-23 | Pavad Medical, Incorporated | Airway implant and methods of making and using |
US7882842B2 (en) * | 2004-09-21 | 2011-02-08 | Pavad Medical, Inc. | Airway implant sensors and methods of making and using the same |
EP1842259A4 (en) | 2004-12-28 | 2008-05-28 | Utc Fuel Cells Llc | MEA SEAL STRUCTURE WITH CATALYZED LAYER |
US7419732B2 (en) * | 2005-02-11 | 2008-09-02 | Gore Enterprise Holdings, Inc. | Method for reducing degradation in a fuel cell |
US8652705B2 (en) | 2005-09-26 | 2014-02-18 | W.L. Gore & Associates, Inc. | Solid polymer electrolyte and process for making same |
WO2007109106A1 (en) * | 2006-03-16 | 2007-09-27 | Bdf Ip Holdings Ltd. | Fluorination of a porous hydrocarbon-based polymer for use as composite membrane |
US7709120B2 (en) * | 2007-06-28 | 2010-05-04 | Gm Global Technology Operations, Inc. | Method to maximize fuel cell stack shorting resistance |
WO2009039654A1 (en) * | 2007-09-25 | 2009-04-02 | Angstrom Power Incorporated | Fuel cell cover |
CN101849312B (zh) | 2007-09-25 | 2014-05-07 | 法商Bic公司 | 包括空间节约型流体增压室的燃料电池系统以及相关方法 |
US7989115B2 (en) * | 2007-12-14 | 2011-08-02 | Gore Enterprise Holdings, Inc. | Highly stable fuel cell membranes and methods of making them |
WO2009085327A2 (en) | 2008-01-03 | 2009-07-09 | Utc Power Corporation | Protective and precipitation layers for pem fuel cell |
CA2714991C (en) * | 2008-02-29 | 2015-11-24 | Angstrom Power Incorporated | Electrochemical cell and membranes related thereto |
EP2426762A4 (en) | 2009-05-01 | 2012-10-17 | Nissan Motor | GAS DIFFUSION LAYER FOR A FUEL CELL |
CN103329326A (zh) | 2011-01-28 | 2013-09-25 | Utc电力公司 | 燃料电池密封件 |
US9379398B2 (en) * | 2011-12-20 | 2016-06-28 | Nissan North America, Inc. | Apparatus and method of in situ catalyst degradation detection during fuel cell operation |
CN108713269B (zh) | 2016-03-11 | 2022-02-25 | W.L.戈尔及同仁股份有限公司 | 反射层叠件 |
CN108232261B (zh) * | 2016-12-21 | 2022-03-22 | 东丽先端材料研究开发(中国)有限公司 | 一种聚合物复合电解质膜及其制备方法 |
WO2018231232A1 (en) | 2017-06-15 | 2018-12-20 | W. L. Gore & Associates, Inc. | Highly reinforced ionomer membranes for high selectivity and high strength |
CN108428917A (zh) * | 2018-01-13 | 2018-08-21 | 素水能源科技(上海)有限公司 | 磺化聚酰亚胺-Nafion复合膜及其制备方法 |
CN110120485B (zh) | 2018-02-06 | 2021-06-18 | 比亚迪股份有限公司 | 聚合物隔膜及其制备方法和应用以及锂离子电池及其制备方法 |
JP7342103B2 (ja) * | 2018-07-27 | 2023-09-11 | ダブリュ.エル.ゴア アンド アソシエイツ,インコーポレイティド | 連続アイオノマー相を有する一体型複合膜 |
CN114023978B (zh) * | 2021-10-28 | 2024-02-02 | 中汽创智科技有限公司 | 一种气体扩散层基材的制备方法 |
Family Cites Families (107)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2681319A (en) | 1951-01-10 | 1954-06-15 | Rohm & Haas | Permselective films of anionexchange resins |
US2827426A (en) | 1954-02-12 | 1958-03-18 | Rohm & Haas | Cationic permselective membranes and their use in electrolysis |
US2951818A (en) | 1955-02-10 | 1960-09-06 | Bayer Ag | Ion exchanger membranes from polyvinylidene chloride and phenolic resin reactants |
US2965697A (en) | 1956-11-05 | 1960-12-20 | Electric Storage Battery Co | Battery diaphragm |
US3692569A (en) | 1970-02-12 | 1972-09-19 | Du Pont | Surface-activated fluorocarbon objects |
CA962021A (en) | 1970-05-21 | 1975-02-04 | Robert W. Gore | Porous products and process therefor |
JPS5171888A (en) | 1974-12-19 | 1976-06-22 | Sumitomo Electric Industries | Sekisokozokaranaru fuirumu oyobi sonoseizohoho |
US4012303A (en) | 1974-12-23 | 1977-03-15 | Hooker Chemicals & Plastics Corporation | Trifluorostyrene sulfonic acid membranes |
US4104394A (en) | 1975-12-15 | 1978-08-01 | Sumitomo Electric Industries, Ltd. | Method for diametrically expanding thermally contractive ptfe resin tube |
US4082893A (en) | 1975-12-24 | 1978-04-04 | Sumitomo Electric Industries, Ltd. | Porous polytetrafluoroethylene tubings and process of producing them |
US4065534A (en) | 1976-04-20 | 1977-12-27 | Ppg Industries, Inc. | Method of providing a resin reinforced asbestos diaphragm |
US4110392A (en) | 1976-12-17 | 1978-08-29 | W. L. Gore & Associates, Inc. | Production of porous sintered PTFE products |
JPS53149881A (en) | 1977-06-03 | 1978-12-27 | Asahi Glass Co Ltd | Strengthened cation exchange resin membrane and production thereof |
US4207163A (en) | 1977-09-26 | 1980-06-10 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
US4207164A (en) | 1977-10-03 | 1980-06-10 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
US4224121A (en) | 1978-07-06 | 1980-09-23 | General Electric Company | Production of halogens by electrolysis of alkali metal halides in an electrolysis cell having catalytic electrodes bonded to the surface of a solid polymer electrolyte membrane |
US4262041A (en) | 1978-02-02 | 1981-04-14 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Process for preparing a composite amphoteric ion exchange membrane |
IT1110461B (it) | 1978-03-01 | 1985-12-23 | Oronzio De Nora Impianti | Membrane anioniche costituite da copolimeri di (2) o (4)-vinilpiridina con divinilbenzene o con monomeri vinilici alogenati |
GB2025835B (en) | 1978-05-31 | 1982-10-27 | Nitto Electric Ind Co | Producing a porous polytetrafluorethylene article |
JPS55145540A (en) | 1979-04-28 | 1980-11-13 | Kanegafuchi Chem Ind Co Ltd | Joining method of cation exchange membrane |
US4210510A (en) | 1979-07-25 | 1980-07-01 | Bendix Autolite Corporation | Gas sensor with closely wound termination springs |
ATE24550T1 (de) | 1980-01-29 | 1987-01-15 | Atochem | Diaphragma fuer die elektrolyse und verfahren zu seiner herstellung. |
US4774039A (en) | 1980-03-14 | 1988-09-27 | Brunswick Corporation | Dispersing casting of integral skinned highly asymmetric polymer membranes |
US4629563B1 (en) | 1980-03-14 | 1997-06-03 | Memtec North America | Asymmetric membranes |
US4313832A (en) | 1980-06-12 | 1982-02-02 | Rohm And Haas Company | Method for treatment of aqueous solutions with ion exchange fibers |
US4469744A (en) | 1980-07-11 | 1984-09-04 | E. I. Du Pont De Nemours And Company | Protective clothing of fabric containing a layer of highly fluorinated ion exchange polymer |
US4518650A (en) | 1980-07-11 | 1985-05-21 | E. I. Du Pont De Nemours And Company | Protective clothing of fabric containing a layer of highly fluorinated ion exchange polymer |
US4311567A (en) | 1980-11-17 | 1982-01-19 | Ppg Industries, Inc. | Treatment of permionic membrane |
JPS57137490A (en) | 1981-01-16 | 1982-08-25 | Du Pont | Film, electrochemical tank and electrolytic method |
JPS5847471B2 (ja) | 1981-02-13 | 1983-10-22 | 工業技術院長 | 電解用接合体の製造法 |
GB2097788B (en) | 1981-04-03 | 1985-04-24 | Lilly Co Eli | Benzothiophene compounds and process for preparing them |
US4433082A (en) | 1981-05-01 | 1984-02-21 | E. I. Du Pont De Nemours And Company | Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof |
US4453991A (en) | 1981-05-01 | 1984-06-12 | E. I. Du Pont De Nemours And Company | Process for making articles coated with a liquid composition of perfluorinated ion exchange resin |
US4596837A (en) | 1982-02-22 | 1986-06-24 | Daikin Industries Ltd. | Semisintered polytetrafluoroethylene article and production thereof |
US4598011A (en) | 1982-09-10 | 1986-07-01 | Bowman Jeffery B | High strength porous polytetrafluoroethylene product having a coarse microstructure |
JPS59109506A (ja) | 1982-12-14 | 1984-06-25 | Daikin Ind Ltd | 新規なポリテトラフルオロエチレン・フアインパウダ− |
JPS59109534A (ja) | 1982-12-14 | 1984-06-25 | Nitto Electric Ind Co Ltd | ポリテトラフルオロエチレン多孔質体 |
US4528083A (en) | 1983-04-15 | 1985-07-09 | United Technologies Corporation | Device for evolution of oxygen with ternary electrocatalysts containing valve metals |
JPS6084590A (ja) | 1983-10-17 | 1985-05-13 | キヤノン株式会社 | 画像処理システム |
US4664801A (en) | 1983-10-27 | 1987-05-12 | Brunswick Corporation | Filter cartridge sealing composition and process therefor |
US4671754A (en) | 1984-03-28 | 1987-06-09 | Sumitomo Electric Industries, Ltd. | Apparatus for manufacturing porous polytetrafluoroethylene material |
IL72506A (en) | 1984-07-25 | 1987-08-31 | Univ Ben Gurion | Ion-exchange membranes and processes for the preparation thereof |
JPS61130347A (ja) | 1984-11-30 | 1986-06-18 | Asahi Glass Co Ltd | 新規な電解用複層隔膜 |
JPS61276987A (ja) | 1985-06-03 | 1986-12-06 | Agency Of Ind Science & Technol | ガス及び液透過性電極用材料 |
US4822605A (en) | 1986-02-18 | 1989-04-18 | Exovir, Inc. | Compositions and methods employing the same for the treatment of viral and cancerous skin lesions and the like |
DE3786943T2 (de) | 1986-03-07 | 1994-03-17 | Tanaka Precious Metal Ind | Gasdurchlässige Elektrode. |
US4816431A (en) | 1986-04-03 | 1989-03-28 | Nagakazu Furuya | Process for preparing materials for reaction layer of gas permeable electrode |
US5256503A (en) | 1986-04-07 | 1993-10-26 | Scimat Limited | Process for making a composite membrane |
US4698243A (en) | 1986-06-20 | 1987-10-06 | The Dow Chemical Company | Method for sizing and hydrolyzing polytetrafluoroethylene fabrics, fibers, yarns, or threads |
US4849311A (en) | 1986-09-24 | 1989-07-18 | Toa Nenryo Kogyo Kabushiki Kaisha | Immobilized electrolyte membrane |
US4743480A (en) | 1986-11-13 | 1988-05-10 | W. L. Gore & Associates, Inc. | Apparatus and method for extruding and expanding polytetrafluoroethylene tubing and the products produced thereby |
JPS63191041A (ja) | 1987-02-03 | 1988-08-08 | Komori Printing Mach Co Ltd | 濃度測定位置合わせ方法 |
US4863604A (en) | 1987-02-05 | 1989-09-05 | Parker-Hannifin Corporation | Microporous asymmetric polyfluorocarbon membranes |
US4804592A (en) | 1987-10-16 | 1989-02-14 | The United States Of America As Represented By The United States Department Of Energy | Composite electrode for use in electrochemical cells |
EP0313263B1 (en) | 1987-10-19 | 1993-03-24 | W.L. Gore & Associates, Inc. | Rapid recoverable ptfe and a process for its manufacture |
US4865925A (en) | 1987-12-14 | 1989-09-12 | Hughes Aircraft Company | Gas permeable electrode for electrochemical system |
US4902308A (en) | 1988-06-15 | 1990-02-20 | Mallouk Robert S | Composite membrane |
US4865930A (en) | 1988-10-27 | 1989-09-12 | Hughes Aircraft Company | Method for forming a gas-permeable and ion-permeable membrane |
US5041195A (en) | 1988-11-17 | 1991-08-20 | Physical Sciences Inc. | Gold electrocatalyst, methods for preparing it, electrodes prepared therefrom and methods of using them |
US5133842A (en) | 1988-11-17 | 1992-07-28 | Physical Sciences, Inc. | Electrochemical cell having electrode comprising gold containing electrocatalyst |
US4954388A (en) | 1988-11-30 | 1990-09-04 | Mallouk Robert S | Fabric reinforced composite membrane |
US4902423A (en) | 1989-02-02 | 1990-02-20 | W. L. Gore & Associates, Inc. | Highly air permeable expanded polytetrafluoroethylene membranes and process for making them |
US4990228A (en) | 1989-02-28 | 1991-02-05 | E. I. Du Pont De Nemours And Company | Cation exchange membrane and use |
US5098625A (en) | 1989-03-14 | 1992-03-24 | Yeu Ming Tai Chemical Industrial Co., Ltd. | Process for forming an expanded porous tetrafluoroethylene polymer |
US4985296A (en) | 1989-03-16 | 1991-01-15 | W. L. Gore & Associates, Inc. | Polytetrafluoroethylene film |
AT391473B (de) | 1989-04-06 | 1990-10-10 | Chemiefaser Lenzing Ag | Monoaxial verstreckter formkoerper aus polytetrafluoraethylen und verfahren zu seiner herstellung |
US5183545A (en) | 1989-04-28 | 1993-02-02 | Branca Phillip A | Electrolytic cell with composite, porous diaphragm |
US5094895A (en) | 1989-04-28 | 1992-03-10 | Branca Phillip A | Composite, porous diaphragm |
US5075006A (en) | 1989-08-09 | 1991-12-24 | Exxon Research And Engineering Company | Isocyanurate crosslinked polyurethane membranes and their use for the separation of aromatics from non-aromatics |
US5234751A (en) | 1989-09-12 | 1993-08-10 | Sumitomo Electric Industries, Ltd. | Porous material of polytetrafluoroethylene and process for producing the same |
US5225131A (en) | 1989-12-07 | 1993-07-06 | Daikin Industries, Ltd. | Process for producing multilayer polytetrafluoroethylene porous membrane and semisintered polytetrafluoroethylene multilayer structure |
US5154827A (en) | 1990-01-22 | 1992-10-13 | Parker-Nannifin Corporation | Laminated microporous fluorocarbon membrane and fluorocarbon filter cartridge using same |
US5066403A (en) | 1990-07-12 | 1991-11-19 | The United States Of America As Represented By The Secretary Of Commerce | Process for separating azeotropic or close-boiling mixtures by use of a composite membrane, the membrane, and its process of manufacture |
US5521023A (en) | 1990-08-16 | 1996-05-28 | Kejha; Joseph B. | Composite electrolytes for electrochemical devices |
JPH04162365A (ja) | 1990-10-25 | 1992-06-05 | Tanaka Kikinzoku Kogyo Kk | 燃料電池用電極の作製法 |
US5082472A (en) | 1990-11-05 | 1992-01-21 | Mallouk Robert S | Composite membrane for facilitated transport processes |
US5275725A (en) | 1990-11-30 | 1994-01-04 | Daicel Chemical Industries, Ltd. | Flat separation membrane leaf and rotary separation apparatus containing flat membranes |
US5234777A (en) | 1991-02-19 | 1993-08-10 | The Regents Of The University Of California | Membrane catalyst layer for fuel cells |
JP3077113B2 (ja) | 1991-03-15 | 2000-08-14 | ジャパンゴアテックス株式会社 | 白金族または白金族合金をめっきした微細多孔質フッ素樹脂材およびその製造法 |
US5217666A (en) | 1991-05-29 | 1993-06-08 | Daikin Industries Ltd. | Process for producing porous polytetrafluoroethylene film |
CA2074349C (en) | 1991-07-23 | 2004-04-20 | Shinji Tamaru | Polytetrafluoroethylene porous film and preparation and use thereof |
EP0545068A3 (en) | 1991-11-08 | 1993-12-22 | Du Pont | Wetting of diaphragms |
US5336384A (en) | 1991-11-14 | 1994-08-09 | The Dow Chemical Company | Membrane-electrode structure for electrochemical cells |
CA2131902C (en) | 1992-03-13 | 2004-08-03 | Paul Martakos | Controlled porosity expanded polytetrafluoroethylene products and fabrication |
US5350643A (en) | 1992-06-02 | 1994-09-27 | Hitachi, Ltd. | Solid polymer electrolyte type fuel cell |
US5209850A (en) | 1992-06-19 | 1993-05-11 | W. L. Gore & Associates, Inc. | Hydrophilic membranes |
US5273694A (en) | 1992-08-28 | 1993-12-28 | E. I. Du Pont De Nemours And Company | Process for making ion exchange membranes and films |
US5228994A (en) | 1992-10-13 | 1993-07-20 | Millipore Corporation | Composite microporous membranes |
US5415888A (en) | 1993-04-26 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Method of imprinting catalytically active particles on membrane |
US5447636A (en) | 1993-12-14 | 1995-09-05 | E. I. Du Pont De Nemours And Company | Method for making reinforced ion exchange membranes |
JP3003500B2 (ja) | 1994-04-28 | 2000-01-31 | ダイキン工業株式会社 | ポリテトラフルオロエチレン複合多孔膜 |
US5545475A (en) | 1994-09-20 | 1996-08-13 | W. L. Gore & Associates | Microfiber-reinforced porous polymer film and a method for manufacturing the same and composites made thereof |
US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
USRE37307E1 (en) | 1994-11-14 | 2001-08-07 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
US5599614A (en) * | 1995-03-15 | 1997-02-04 | W. L. Gore & Associates, Inc. | Integral composite membrane |
US6254978B1 (en) * | 1994-11-14 | 2001-07-03 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
JP3221541B2 (ja) | 1995-01-26 | 2001-10-22 | 日本電信電話株式会社 | 光導波路と光ファイバとの接続構造および接続方法 |
US5552100A (en) | 1995-05-02 | 1996-09-03 | Baxter International Inc. | Method for manufacturing porous fluoropolymer films |
US5814405A (en) * | 1995-08-04 | 1998-09-29 | W. L. Gore & Associates, Inc. | Strong, air permeable membranes of polytetrafluoroethylene |
DE19544912A1 (de) * | 1995-12-01 | 1997-06-05 | Gore W L & Ass Gmbh | PTFE-Körper aus mikroporösem Polytetrafluorethylen mit Füllstoff und Verfahren zu dessen Herstellung |
US5672438A (en) | 1995-10-10 | 1997-09-30 | E. I. Du Pont De Nemours And Company | Membrane and electrode assembly employing exclusion membrane for direct methanol fuel cell |
WO1997040924A1 (en) * | 1996-04-30 | 1997-11-06 | W.L. Gore & Associates, Inc. | Integral ion-exchange composite membranes |
DE19625389A1 (de) * | 1996-06-25 | 1998-01-02 | Gore W L & Ass Gmbh | Flexibler Verbundstoff |
JPH1092444A (ja) * | 1996-09-13 | 1998-04-10 | Japan Gore Tex Inc | 電気化学反応装置用固体高分子電解質複合体及びそれを用いた電気化学反応装置 |
US6130175A (en) * | 1997-04-29 | 2000-10-10 | Gore Enterprise Holdings, Inc. | Integral multi-layered ion-exchange composite membranes |
US6059943A (en) * | 1997-07-30 | 2000-05-09 | Lynntech, Inc. | Composite membrane suitable for use in electrochemical devices |
US6042959A (en) * | 1997-10-10 | 2000-03-28 | 3M Innovative Properties Company | Membrane electrode assembly and method of its manufacture |
-
2001
- 2001-09-10 US US09/950,839 patent/US6613203B1/en not_active Expired - Lifetime
-
2002
- 2002-08-27 CN CNB028204441A patent/CN100372883C/zh not_active Expired - Lifetime
- 2002-08-27 AU AU2002323440A patent/AU2002323440B2/en not_active Ceased
- 2002-08-27 EP EP02757421A patent/EP1490426B1/en not_active Expired - Lifetime
- 2002-08-27 KR KR10-2004-7003534A patent/KR20040033038A/ko not_active Application Discontinuation
- 2002-08-27 CA CA 2459984 patent/CA2459984C/en not_active Expired - Lifetime
- 2002-08-27 DE DE60215554T patent/DE60215554T2/de not_active Expired - Lifetime
- 2002-08-27 JP JP2003526982A patent/JP4975951B2/ja not_active Expired - Lifetime
- 2002-08-27 WO PCT/US2002/027338 patent/WO2003022912A2/en active IP Right Grant
-
2005
- 2005-06-21 HK HK05105134A patent/HK1072441A1/xx not_active IP Right Cessation
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008018400A1 (fr) * | 2006-08-09 | 2008-02-14 | Sumitomo Electric Fine Polymer, Inc. | Membrane de résine fluorée, composite de résine fluorée, composite poreux de résine fluorée, procédés pour la production de ceux-ci et élément de type membrane pour la séparation |
US9463420B2 (en) | 2006-08-09 | 2016-10-11 | Sumitomo Electric Fine Polymer, Inc. | Manufacturing methods for a porous fluororesin composite |
US8795923B2 (en) | 2007-04-19 | 2014-08-05 | Toyota Jidosha Kabushiki Kaisha | Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly |
WO2009107273A1 (ja) * | 2008-02-26 | 2009-09-03 | トヨタ自動車株式会社 | 燃料電池用補強型電解質膜、燃料電池用膜-電極接合体、及びそれを備えた固体高分子形燃料電池 |
DE112008003733T5 (de) | 2008-02-26 | 2011-02-03 | Japan Gore-Tex, Inc. | Verstärkte Polyelektrolytmembran für eine Brennstoffzelle, Brennstoffzellenelektrodenmembran und feste Polymerelektrolytbrennstoffzelle umfassend die Brennstoffzellenmembranelektrodenanordnung |
JP2009289747A (ja) * | 2008-05-29 | 2009-12-10 | General Electric Co <Ge> | 高分子電解質膜及び製造方法 |
US8802314B2 (en) | 2008-10-17 | 2014-08-12 | Toyota Jidosha Kabushiki Kaisha | Reinforced electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell, and polymer electrolyte fuel cell comprising the same |
DE112009002507T5 (de) | 2008-10-17 | 2012-01-19 | Japan Gore-Tex, Inc. | Verstärkte Brennstoffzellen-Elektrolytmembran, Membran/Elektriden-Anordnung für eine Brennstoffzelle und Polymerelektrolyd-Brennstofftelle, inder dies enthalten ist |
DE112009002507B8 (de) | 2008-10-17 | 2018-08-30 | Toyota Jidosha Kabushiki Kaisha | Verstärkte brennstoffzellen-elektrolytmembran, membran-elektroden-anordnung und polymerelektrolytbrennstoffzelle, diese enthaltend und herstellungsverfahren dazu |
DE112009002507B4 (de) | 2008-10-17 | 2018-05-24 | Japan Gore-Tex, Inc. | Verstärkte brennstoffzellen-elektrolytmembran, membran-elektroden-anordnung und polymerelektrolytbrennstoffzelle, diese enthaltend und herstellungsverfahren dazu |
US9421499B2 (en) | 2012-01-27 | 2016-08-23 | Sumitomo Electric Fine Polymer, Inc. | Microporous modified-polytetrafluoroethylene membrane, porous-modified-polytetrafluoroethylene-membrane composite and production process thereof, and separation membrane element |
KR20180118258A (ko) | 2013-11-29 | 2018-10-30 | 아사히 가세이 가부시키가이샤 | 고분자 전해질막 |
US10688448B2 (en) | 2013-11-29 | 2020-06-23 | Daikin Industries, Ltd. | Porous body, polymer electrolyte membrane, filter material for filter, and filter unit |
US11084895B2 (en) | 2013-11-29 | 2021-08-10 | Daikin Industries, Ltd. | Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body |
KR20160090381A (ko) | 2013-11-29 | 2016-07-29 | 아사히 가세이 가부시키가이샤 | 고분자 전해질막 |
WO2015080294A1 (ja) | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | 高分子電解質膜 |
KR20180117729A (ko) | 2013-11-29 | 2018-10-29 | 아사히 가세이 가부시키가이샤 | 고분자 전해질막 |
KR20160091386A (ko) | 2013-11-29 | 2016-08-02 | 아사히 가세이 가부시키가이샤 | 고분자 전해질막 |
US10944121B2 (en) | 2013-11-29 | 2021-03-09 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte film |
WO2015080292A1 (ja) | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | 高分子電解質膜 |
US10644339B2 (en) | 2013-11-29 | 2020-05-05 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte membrane |
US10486151B2 (en) | 2015-03-10 | 2019-11-26 | Bl Technologies, Inc. | Ion-exchange membrane with multi-layered support substrate |
JP2018511463A (ja) * | 2015-03-10 | 2018-04-26 | ゼネラル・エレクトリック・カンパニイ | 多層支持基材を有するイオン交換膜 |
US11135551B2 (en) | 2017-03-20 | 2021-10-05 | Bl Technologies, Inc. | Ion-exchange membrane having an imprinted non-woven substrate |
US11766638B2 (en) | 2017-03-20 | 2023-09-26 | Bl Technologies, Inc. | Ion-exchange membrane having an imprinted non-woven substrate |
JP2019220458A (ja) * | 2018-06-15 | 2019-12-26 | 日本碍子株式会社 | 電気化学セル |
Also Published As
Publication number | Publication date |
---|---|
DE60215554D1 (de) | 2006-11-30 |
CN1608099A (zh) | 2005-04-20 |
EP1490426A2 (en) | 2004-12-29 |
EP1490426B1 (en) | 2006-10-18 |
AU2002323440B2 (en) | 2006-05-25 |
JP4975951B2 (ja) | 2012-07-11 |
DE60215554T2 (de) | 2007-07-05 |
HK1072441A1 (en) | 2005-08-26 |
WO2003022912A3 (en) | 2004-09-30 |
WO2003022912A2 (en) | 2003-03-20 |
CN100372883C (zh) | 2008-03-05 |
KR20040033038A (ko) | 2004-04-17 |
US6613203B1 (en) | 2003-09-02 |
CA2459984A1 (en) | 2003-03-20 |
CA2459984C (en) | 2008-08-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4975951B2 (ja) | 高硬度及び寸法安定性を有するイオン伝導性隔膜 | |
AU2002323440A1 (en) | Ion conducting membrane having high hardness and dimensional stability | |
USRE37307E1 (en) | Ultra-thin integral composite membrane | |
USRE37701E1 (en) | Integral composite membrane | |
US5547551A (en) | Ultra-thin integral composite membrane | |
JP4402625B2 (ja) | 部分要素からなる複合膜 | |
KR102112648B1 (ko) | 고분자 전해질막 | |
US6254978B1 (en) | Ultra-thin integral composite membrane | |
EP1615282A1 (en) | Solid polymer electrolyte membrane, membrane electrode assembly for solid polymer fuel cell, and method for producing solid polymer electrolyte membrane | |
CN101186139B (zh) | 多层电解质强化复合膜的制造方法 | |
JP2007109657A (ja) | 燃料電池のための多層高分子電解質膜 | |
CN101421876B (zh) | 固体高分子型燃料电池用电解质膜、膜-电极接合体(mea)、和燃料电池 | |
US20130280642A1 (en) | Porous nano-fiber mats to reinforce proton conducting membranes for pem applications | |
JP5331122B2 (ja) | 燃料電池用補強型電解質膜、燃料電池用膜−電極接合体、及びそれを備えた固体高分子形燃料電池 | |
EP1223628A1 (en) | Bonded electrode/film for solid polymer fuel cell and method for producing the same | |
JP5189394B2 (ja) | 高分子電解質膜 | |
US20090068528A1 (en) | Heat treatment of perfluorinated ionomeric membranes | |
JP2003297393A (ja) | 固体高分子型燃料電池用電解質膜及び膜電極接合体 | |
JP2013026122A (ja) | 燃料電池用電解質膜 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050826 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050826 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080206 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080226 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20080424 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20080502 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080826 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20080930 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081224 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20090317 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090414 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20090713 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20090721 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091013 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20100305 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20111011 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20111014 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120412 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4975951 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150420 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |