CN101611509B - 由碳和可交联的树脂纤维形成的用于电化学电池的电极基质 - Google Patents

由碳和可交联的树脂纤维形成的用于电化学电池的电极基质 Download PDF

Info

Publication number
CN101611509B
CN101611509B CN2007800393920A CN200780039392A CN101611509B CN 101611509 B CN101611509 B CN 101611509B CN 2007800393920 A CN2007800393920 A CN 2007800393920A CN 200780039392 A CN200780039392 A CN 200780039392A CN 101611509 B CN101611509 B CN 101611509B
Authority
CN
China
Prior art keywords
resin
described step
further characterized
curing agent
adopts
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.)
Active
Application number
CN2007800393920A
Other languages
English (en)
Other versions
CN101611509A (zh
Inventor
R·D·布劳尔特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Audi AG
Original Assignee
UTC Power Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by UTC Power Corp filed Critical UTC Power Corp
Publication of CN101611509A publication Critical patent/CN101611509A/zh
Application granted granted Critical
Publication of CN101611509B publication Critical patent/CN101611509B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/22—Condensation polymers of aldehydes or ketones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Inert Electrodes (AREA)

Abstract

制备电化学电池电极基质的方法，包括形成斩碎碳纤维、斩碎可交联的树脂纤维(将其成型到毡制品如酚醛清漆、暂时粘结剂如聚乙烯醇纤维或粉末中之后仍可熔化)的含水或干混合物，分别通过无纺、湿法布置或干法布置毡制品成型工艺由含水混合物的含水悬浮体或干混合物的空气悬浮体形成无纺毡制品，该含水或干混合物中可以包含树脂固化剂如六亚甲基四胺，或者可以将其涂布到成型毡制品之上，将一层或多层成型毡制品在树脂熔融、交联且随后固化的温度如150～200℃下压制1～5分钟达到控制的厚度和控制的孔隙率，和将压制毡制品在基本上惰性气氛中热处理。

Description

由碳和可交联的树脂纤维形成的用于电化学电池的电极基质
技术领域
本公开内容涉及用于电化学电池如燃料电池的碳复合电极基质，其由斩碎碳纤维和斩碎未固化可交联的树脂纤维的无纺毡制品形成，通过干法布置或湿法布置造纸工艺制得，压制在一起并固化，树脂发生交联以将所有纤维粘合在一起，随后热处理以使该材料碳化和任选地部分石墨化。
背景技术
多孔碳-碳复合材料可以用作各种电化学电池如质子交换膜燃料电池、磷酸燃料电池、直接甲醇燃料电池中的电极基质，其也公知为气体扩散层(GDL)，用作用于电解水的电池中的阴极和用作各种电池中的电导体。该碳-碳复合材料典型地是由碳纤维和热固性树脂的混合物形成的。一些基质可以除了碳纤维和热固性树脂之外还含有碳或石墨粉。US 4 851 304中揭示了燃料电池基质的结构、和用于形成这些基质的方法的良好实例。制备基质的典型方法由如下组成：(1)通过湿法布置造纸工艺在含水悬浮体中由斩碎碳纤维和临时粘合剂形成无纺毡制品，(2)将该毡制品浸渍溶解于溶剂中的酚醛树脂，随后除去溶剂但不使树脂固化，由此形成预浸料坯，(3)将一层或多层预浸料坯毡制品在足以使树脂固化的温度下压制以同时获得期望的厚度和期望的孔隙率，(4)在惰性气氛中热处理到750～1000℃以使酚醛树脂转化为碳，和(5)在惰性气氛中热处理到2000～3000℃，其使碳部分石墨化，由此改进导热率和导电率以及改进耐腐蚀性。
前述专利所述的技术是技术上可接受的，但是难以接受地昂贵的。前述方法成本的大约16％是用于将碳纤维纸浸渍酚醛树脂。将粉末化酚醛树脂加到造纸工艺中的尝试并未获得成功。这点部分是由于高树脂含量导致毡制品粘着到造纸机的辊上。粉末化树脂在造纸过程的干燥部分期间迁移到毡制品表面上。这样导致高的树脂表面浓度，导致粘着。这也部分是由于不能从含水悬浮体中除去全部酚醛粉末，其导致环境问题。
发明概述
公开的方法通过消除了树脂浸渍步骤的要求而以更低成本提供了电极基质。
树脂浸渍的消除是基于实现了与碳纤维混合的未固化的、可交联的树脂纤维在固化时将交联以将所有纤维充分粘合在一起，并随后成功地进行热处理以形成碳和任选地石墨。在干燥过程期间将树脂纤维与固定它们的碳纤维互相混合，由此消除了消除了导致粘着的高表面树脂浓度。
本文中的方法包括，(1)形成斩碎碳纤维和在形成毡制品之后仍可熔化的斩碎可交联的树脂纤维的含水或干混合物，(2)通过无纺毡制品成型工艺由含水或空气悬浮体形成无纺毡制品，(3)将一层或多层毡制品在足以熔融、交联和固化树脂的温度下压制到期望的厚度和期望的孔隙率，和(4)在惰性气氛中进行热处理。
该方法可以通过在含水或干混合物中包含树脂固化剂来进行，或者该方法可以优选地通过在压制毡制品和固化树脂之前采用树脂固化剂的溶液涂布成型毡制品来进行。出于几个原因而优选这种方式。一个原因是需要很少的固化剂。初始混合物中必须包含过量的固化剂以确保足够的固化剂，即使在毡制品制作过程的滤液中损失其一些数量。相反，固化剂溶液非常充分地扩散到毡制品中，使得对于适当固化容易控制固化剂与树脂的比例，且由此不会使过量部分浪费。
该方法可以通过改变碳纤维和可交联的树脂纤维的长度来进行裁剪，由此到达期望的性能。
根据下列示例性实施方式的详细描述，其它改进、特征和优点将变得更明显。
实施方式
本文中公开的电极基质，以及本文中公开的其制备方法，可以具有不同特性且可以由多种组分和可调节的工艺步骤来制备。碳纤维可以是传统的，衍生自聚丙烯腈、粘胶纤维、沥青、中间相沥青、或者基于酚类的碳纤维，其公称直径为4微米～10微米，选择直径以裁剪基质的性能。可以改变碳纤维或未固化的树脂纤维的长度以影响最终基质的性能。通常认为斩碎纤维的长度大于1mm，同时碾碎纤维的长度典型地小于1mm。碾碎纤维将获得具有更大各向同性性能的结构，但是由斩碎纤维制得的那些将具有更大各向异性性能。例如，可以调整纤维尺寸以使它们更容易分布于在湿法布置过程中使用的悬浮体中。
该方法中采用过量酚形成的任意热塑性酚醛树脂适合用于本文中的可交联的树脂纤维。除了未固化的酚醛清漆树脂纤维之外，部分固化的酚醛清漆树脂纤维也是可接受的，只要它们在热压过程期间具有足够流动性以使碳纤维粘合在一起。不可固化为半固态的真正热塑性树脂是不可接受的。未固化的、可交联的纤维可从各种来源获得。例如，未固化的酚醛清漆纤维可从Nippon Kynol获得，其公称直径为10～15微米，但是更小直径的酚醛清漆纤维也是可接受的。未固化酚醛清漆纤维典型地为1.5mm～6mm长，且可以利用不同长度的混合物来支持制造工艺(更容易分布于悬浮体中)或是改变最终产物的特性。
碳纤维与未固化酚醛清漆纤维的重量比为大约50∶50，其中对于一些基质应用35∶65～65∶35的范围是可接受的。
酚醛清漆树脂是通过酚类和甲醛在酸性条件下的反应制得的任意热固性树脂，其中甲醛数量不足以使聚合物发生交联。酚醛清漆树脂是双阶段热固性树脂，其本身无反应性，且需要硬化剂或固化催化剂(本文中称作“固化剂”)，典型地为六亚甲基四胺(下文中称作“hexa”)。酚醛清漆树脂在hexa的存在下在约150～200℃的温度下交联和固化。可熔酚醛树脂是在碱性条件下采用过量甲醛形成的单阶段酚醛树脂。残留甲醛在固化期间反应以在链间形成亚甲基桥。部分固化的可熔酚醛树脂和其它单阶段酚醛树脂纤维可以用于本文中的方法，只要该纤维未完全固化且在热压过程期间具有足够流动性以使碳纤维粘合在一起。
替换地，可以将碳或石墨粉加到碳纤维、未固化酚醛清漆纤维、临时粘合剂和可能地固化剂的混合物中以影响最终基质的性能。其它可交联的树脂体系是可接受的。树脂体系包括树脂和任意通用的固化剂。适宜树脂体系包括环氧化物、聚酰亚胺、聚酯、酚醛树脂、聚氨酯、蜜胺和脲醛。
酚醛清漆和可熔酚醛树脂由于它们在热处理过程期间大约50％的高碳产率而是优选的。
未固化酚醛清漆纤维与hexa的比例典型地为约10∶1～20∶1(重量)，但是可以调节该比例以容许在将该树脂在所选的温度-时间窗内固化之前该树脂的熔融和流动。对于连续层压工艺，小于5分钟、且甚至小于1分钟的固化时间是期望的。为了使固化时间最小化，更高的hexa含量和更高的固化温度是期望的。树脂必须在热压步骤期间固化以在随后热处理步骤期间保持期望的性能(厚度和孔隙率)。
临时粘合剂如聚乙烯醇优选为纤维形式，但是粉末形式也是可接受的，将其加到纤维和hexa的混合物中，临时粘合剂与碳纤维和未固化酚醛清漆树脂的总和的比例为约1∶10(重量)。但是，可以选择其它临时粘合剂和临时粘合剂浓度以在整个造纸过程中提供可接受的强度。临时粘合剂必须是在热处理过程期间分解或者转化为碳的粘合剂。
优选的方法包括，在高剪切混合机中形成斩碎碳纤维、斩碎未固化酚醛清漆纤维、和临时粘合剂如聚乙烯醇纤维活或粉末的含水悬浮体，使用或者不使用树脂固化剂如粉化hexa。随后通过湿法布置造纸工艺由该含水悬浮体形成无纺毡制品，通过重力除去水和通过相对于金属丝网筛抽真空除去水的组合使该毡制品脱水，并通过在充分低的毡制品温度(使得该树脂不发生交联)如75～125℃下加热该毡制品使其干燥。
如果含水悬浮体中不包括固化剂，那么通过传统在线式涂布机的方式在方法中在这一点上采用树脂固化剂溶液涂布该毡制品。随后，将一层或多层毡制品在足以熔融的温度如150～200℃下压制到期望的厚度和期望的孔隙率，并随后交联和固化该树脂约1分钟到约5分钟。例如，单层可以提供薄的、高多孔性基质，同时几个层可以提供更厚的多孔性基质或者低孔隙率的薄基质，取决于压力。依据既定应用来裁剪基质的厚度和孔隙率，如公知的那样。随后将基质在惰性气氛中在约750～1000℃的温度下进行热处理以使酚醛树脂转化为碳。可以将基质在惰性气氛中在约1000～约3000℃、或者优选约2500～约3000℃的温度下进一步进行热处理以使该材料部分石墨化，由此改进电导率和热导率以及耐腐蚀性。
但是，可以采用干法工艺，其中将斩碎碳纤维、斩碎可交联的树脂纤维、和临时粘合剂如聚乙烯醇粉、或优选聚乙烯醇纤维的干混物，使用或不使用固化剂如粉化hexa，在干法布置无纺毡制品形成工艺中由干燥粉末共混物的流化物流形成为无纺毡制品。如果该干混物中不存在固化剂，那么通过传统在线式涂布机的方式采用固化剂溶液涂布该毡制品。随后是在低于交联温度的温度下加热该毡制品、压制、和热处理的进一步步骤，如前所述。在湿法和干法工艺二者中，可以使用前面提及的各种可交联的树脂体系，但是酚醛清漆和可熔酚醛树脂由于它们在热处理过程期间大约50％的高碳产率而是优选的。

Claims (27)

1.一种制备电化学电池电极基质的方法，其特征在于：
(a)形成以下物质的含水或干混合物：(i)碳纤维、仍可熔化的可交联的树脂纤维和临时粘合剂，或者(ii)碳纤维、仍可熔化的可交联的树脂纤维、临时粘合剂和用于固化所述树脂纤维的可交联树脂的树脂固化剂；
(b)通过无纺湿法布置毡制品成型工艺或无纺干法布置毡制品成型工艺由含水混合物的含水悬浮体或者干混合物的空气悬浮体形成无纺毡制品；和
(c)如果所述步骤(a)中的混合物不含树脂固化剂，那么在所述步骤(b)之后采用用于固化所述树脂纤维的可交联树脂的树脂固化剂的溶液涂布所述毡制品；
(d)将一层或多层成型毡制品在足以使得所述仍可熔化的可交联的树脂熔融、交联且随后固化的温度下压制到控制的厚度和控制的孔隙率；和
(e)将压制毡制品在惰性的气氛中热处理。
2.权利要求1的方法，其进一步特征在于，所述步骤(a)包括形成碳纤维、仍可熔化的可交联的树脂纤维、临时粘合剂、和树脂固化剂的含水或干混合物，且不进行所述步骤(c)。
3.权利要求2的方法，其进一步特征在于，采用六亚甲基四胺作为树脂固化剂来进行所述步骤(a)。
4.权利要求1的方法，其进一步特征在于，所述步骤(a)包括形成碳纤维、仍可熔化的可交联的树脂纤维和临时粘合剂的含水或干混合物，且进行所述步骤(c)。
5.权利要求4的方法，其进一步特征在于，采用六亚甲基四胺作为树脂固化剂来进行所述步骤(c)。
6.权利要求1的方法，其进一步特征在于，在150～200℃的温度下进行所述步骤(d)。
7.权利要求1的方法，其进一步特征在于，所述步骤(d)持续1～5分钟。
8.权利要求1的方法，其进一步特征在于，在750～1000℃的温度下进行所述步骤(e)。
9.权利要求1的方法，其进一步特征在于，所述步骤(e)首先在750～1000℃的温度下进行以使被交联和固化的树脂转化为碳，并然后在1000～3000℃的温度下进行以使碳化树脂部分石墨化，其中所述树脂是酚醛树脂。
10.权利要求1的方法，其进一步特征在于，采用聚乙烯醇作为临时粘合剂来进行所述步骤(a)。
11.权利要求1的方法，其进一步特征在于，所述步骤(a)形成含水混合物；和所述步骤(b)包括使该混合物脱水。
12.权利要求11的方法，其进一步特征在于，所述步骤(b)包括通过选自(i)通过重力除去水和(ii)通过抽吸除去水的工艺或者(i)和(ii)二者使该混合物脱水。
13.权利要求1的方法，其进一步特征在于，所述仍可熔化的可交联的树脂选自未固化的酚醛清漆树脂、部分固化的酚醛清漆树脂、未固化的可熔酚醛树脂、在形成毡制品之后仍可熔化的其它酚醛树脂、环氧树脂、聚酰亚胺、聚酯、聚氨酯、蜜胺和脲醛。
14.权利要求1的方法，其进一步特征在于，在步骤(a)中采用碳粉作为添加剂形成所述混合物。
15.权利要求1的方法，其进一步特征在于，在步骤(a)中采用石墨粉作为添加剂形成所述混合物。
16.一种制备电化学电池电极基质的方法，其特征在于，
(a)形成(i)由碳纤维、未固化酚醛树脂纤维、临时粘合剂和用于固化所述树脂纤维的未固化酚醛树脂的树脂固化剂组成的含水悬浮体，或者(ii)由碳纤维、未固化酚醛树脂纤维和临时粘合剂组成的含水悬浮体；
(b)通过湿法布置造纸工艺由该悬浮体形成无纺毡制品；
(c)通过(i)通过重力除去水或(ii)通过抽吸除去水的工艺、或者(i)和(ii)二者，使该毡制品脱水；
(d)通过在不致于使所述未固化酚醛树脂交联的足够低的温度下加热该毡制品，使该毡制品干燥；
(e)如果所述步骤(a)中的混合物不含树脂固化剂，那么在所述步骤(b)之后采用用于固化所述树脂纤维的未固化酚醛树脂的树脂固化剂的溶液涂布所述毡制品；
(f)将一层或多层成型毡制品在150～200℃的温度下压制1～5分钟，由此交联和固化所述未固化酚醛树脂和提供期望的厚度和期望的孔隙率；和
(g)将压制毡制品在惰性气氛中热处理到750～1000℃以使至少一些被交联和固化的树脂转化为碳。
17.权利要求16的方法，其进一步特征在于，所述步骤(a)包括形成碳纤维、未固化酚醛树脂纤维、临时粘合剂、和树脂固化剂的含水悬浮体，且不进行所述步骤(e)。
18.权利要求17的方法，其进一步特征在于，采用六亚甲基四胺作为树脂固化剂来进行所述步骤(a)。
19.权利要求16的方法，其进一步特征在于，所述步骤(a)包括形成碳纤维、未固化酚醛树脂纤维和临时粘合剂的含水悬浮体，且进行所述步骤(e)。
20.权利要求19的方法，其进一步特征在于，采用六亚甲基四胺作为树脂固化剂来进行所述步骤(e)。
21.权利要求16的方法，其进一步特征在于，在步骤(g)之后，在惰性气氛中热处理到1000～3000℃以使碳化树脂纤维部分石墨化。
22.权利要求16的方法，其进一步特征在于，在所述步骤(a)中采用聚乙烯醇作为临时粘合剂形成所述悬浮体。
23.权利要求16的方法，其进一步特征在于，在所述步骤(a)中采用六亚甲基四胺作为树脂固化剂形成所述悬浮体。
24.权利要求16的方法，其进一步特征在于，在所述步骤(d)中在75～125℃的温度下使所述毡制品干燥。
25.权利要求16的方法，其进一步特征在于，在所述步骤(a)中采用碳粉作为添加剂形成所述悬浮体。
26.权利要求16的方法，其进一步特征在于，在所述步骤(a)中采用石墨粉作为添加剂形成所述悬浮体。
27.通过权利要求16的方法制得的电化学电池电极基质。
CN2007800393920A 2006-10-23 2007-03-29 由碳和可交联的树脂纤维形成的用于电化学电池的电极基质 Active CN101611509B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
USPCT/US2006/041494 2006-10-23
PCT/US2006/041494 WO2008051219A1 (en) 2006-10-23 2006-10-23 Electrode substrate for electrochemical cell from carbon and cross-linkable resin fibers
PCT/US2007/007554 WO2008051280A2 (en) 2006-10-23 2007-03-29 Electrode substrate for electrochemical cell from carbon and cross-linkable resin fibers

Publications (2)

Publication Number Publication Date
CN101611509A CN101611509A (zh) 2009-12-23
CN101611509B true CN101611509B (zh) 2013-09-25

Family

ID=39324875

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800393920A Active CN101611509B (zh) 2006-10-23 2007-03-29 由碳和可交联的树脂纤维形成的用于电化学电池的电极基质

Country Status (5)

Country Link
US (1) US8298725B2 (zh)
EP (1) EP2089925B1 (zh)
KR (1) KR20090082887A (zh)
CN (1) CN101611509B (zh)
WO (2) WO2008051219A1 (zh)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3021389B1 (en) * 2008-11-18 2018-07-11 Johnson Controls Technology Company Electrical power storage devices
DE102008062765A1 (de) 2008-12-18 2010-07-01 Vb Autobatterie Gmbh & Co. Kgaa Textiles flächiges Material für eine Batterieelektrode
GB0902312D0 (en) 2009-02-12 2009-04-01 Johnson Matthey Plc Gas diffusion substrate
KR101827528B1 (ko) 2009-02-26 2018-02-09 존슨 컨트롤스 테크놀러지 컴퍼니 배터리 전극 및 배터리 전극을 제조하는 방법
JP5643328B2 (ja) * 2009-11-23 2014-12-17 ユナイテッド テクノロジーズ コーポレイションＵｎｉｔｅｄ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏｒｐｏｒａｔｉｏｎ 多孔質物品の製造方法
DE102010005954B4 (de) * 2010-01-27 2020-11-19 Heraeus Quarzglas Gmbh & Co. Kg Poröses Kohlenstofferzeugnis
ITRM20120118A1 (it) * 2012-03-26 2013-09-27 Agenzia Naz Per Le Nuove Tecn Ologie L Ener Metodo per la realizzazione di feltri da fibre di carbonio di riciclo.
KR101715963B1 (ko) 2012-04-06 2017-03-27 삼성에스디아이 주식회사 이차 전지
CN103474676B (zh) * 2013-09-05 2015-08-26 大连理工大学 皮芯结构石墨毡电极材料的制备方法
US9524174B2 (en) 2013-09-16 2016-12-20 Axis Ab Configuration assistant for a control system within an operational environment
CN105874634B (zh) * 2013-12-09 2018-12-04 奥迪股份公司 制造干铺燃料电池前期衬底的方法和衬底
US10011535B2 (en) * 2014-09-02 2018-07-03 Honeywell International Inc. Sacrificial fibers to create channels in a composite material
US10370302B2 (en) 2014-09-02 2019-08-06 Honeywell International Inc. Facilitating pitch stabilization in densified carbon fiber preforms
DE102020213461A1 (de) 2020-10-26 2022-04-28 Sgl Carbon Se Elektrodenmaterial
CN112663189A (zh) * 2020-12-08 2021-04-16 中国科学院山西煤炭化学研究所 混合纱及其制造方法、炭纸及其制造方法
CN112670484B (zh) * 2020-12-25 2022-11-29 宁波杉杉新材料科技有限公司 锂离子电池负极材料、锂离子电池及其制备方法和应用
CN113555563B (zh) * 2021-05-31 2022-07-08 东华大学 一种质子交换膜燃料电池用气体扩散层及其制备方法
CN115536417A (zh) * 2022-09-26 2022-12-30 湖南纪璟新材料有限公司 一种硬质碳纤维保温毡及其制备方法
DE102023202453A1 (de) * 2023-03-20 2024-09-26 Phoenix Non Woven GmbH & Co. KG Vliesstoff, Elektrodenbauteil, Herstellungsverfahren hierfür sowie Vorrichtung zur Durchführung des Herstellungsverfahrens

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851304A (en) * 1987-04-10 1989-07-25 Toray Industries, Inc. Electrode substrate for fuel cell and process for producing the same
EP0439184A2 (en) * 1990-01-26 1991-07-31 PETOCA Ltd. Carbon fiber structure and process for producing the same
EP0892101A1 (en) * 1996-03-31 1999-01-20 Osaka Gas Co., Ltd. Three-dimensional structure of carbon fiber and method of manufacturing same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998058A (en) * 1998-04-29 1999-12-07 International Fuel Cells Corporation Porous support layer for an electrochemical cell
US6713034B2 (en) 2000-01-27 2004-03-30 Mitsubishi Rayon Co., Ltd. Porous carbon electrode material, method for manufacturing the same, and carbon fiber paper
GB0117212D0 (en) * 2001-07-16 2001-09-05 Mat & Separations Tech Int Ltd Filter element
WO2003087470A1 (fr) * 2002-04-17 2003-10-23 Mitsubishi Rayon Co., Ltd. Papier en fibre de carbone et substrat d'electrode en fibre de carbone poreux, destine aux piles
US7125624B2 (en) * 2002-04-08 2006-10-24 Nisshinbo Industries, Inc. Fuel cell separator and method of manufacture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851304A (en) * 1987-04-10 1989-07-25 Toray Industries, Inc. Electrode substrate for fuel cell and process for producing the same
EP0439184A2 (en) * 1990-01-26 1991-07-31 PETOCA Ltd. Carbon fiber structure and process for producing the same
EP0892101A1 (en) * 1996-03-31 1999-01-20 Osaka Gas Co., Ltd. Three-dimensional structure of carbon fiber and method of manufacturing same

Also Published As

Publication number Publication date
EP2089925A4 (en) 2011-06-29
US20100035126A1 (en) 2010-02-11
US8298725B2 (en) 2012-10-30
WO2008051219A1 (en) 2008-05-02
KR20090082887A (ko) 2009-07-31
CN101611509A (zh) 2009-12-23
EP2089925A2 (en) 2009-08-19
EP2089925B1 (en) 2014-10-01
WO2008051280A2 (en) 2008-05-02
WO2008051280A3 (en) 2009-04-09

Similar Documents

Publication Publication Date Title
CN101611509B (zh) 由碳和可交联的树脂纤维形成的用于电化学电池的电极基质
CA2405351C (en) Conductive sheet material
WO2001056103A1 (fr) Materiau d'electrode a base de carbone poreux, son procede de fabrication, et papier a fibres de carbone
WO2005124907A1 (ja) 多孔質電極基材およびその製造方法
JP3356534B2 (ja) 電解質保持板及びその製造方法
KR20100045501A (ko) 고 열전도도 전극 기판
CN102104152A (zh) 多孔质电极基材及其制造方法、使用了该基材的膜-电极接合体及固体高分子型燃料电池
JP6855843B2 (ja) レドックスフロー電池用電極とその製造方法、およびレドックスフロー電池
JP4266699B2 (ja) 固体高分子型燃料電池用多孔質電極基材及びその製造方法
JP2004259711A (ja) 炭素繊維紙および燃料電池用多孔質炭素電極基材
US4985316A (en) Corrosion resistant fuel cell substrates
CN113882186A (zh) 碳纤维纸及其制备方法和应用
JP5398297B2 (ja) 多孔質炭素電極基材の製造方法
JP4801354B2 (ja) 固体高分子型燃料電池用電極基材およびその製造方法
JPS63222080A (ja) 炭素繊維多孔体の製造方法
JP3437862B2 (ja) 多孔質電極基材及びその製造方法
US5026402A (en) Method of making a final cell electrode assembly substrate
JP2004134108A (ja) 多孔質炭素電極基材前駆体シート状物の製造方法
CA1320802C (en) Corrosion resistant fuel cell substrates
JPH0129891B2 (zh)
JP5336912B2 (ja) 多孔質電極基材の製造方法、それを用いた膜−電極接合体、および燃料電池
JPH06263558A (ja) 多孔質炭素板の製法および多孔質炭素電極材
CN113564749B (zh) 一种酚醛树脂/改性或未改性聚乙烯醇复合纤维粘合剂的制法
JPH052625B2 (zh)
JP2009117325A (ja) 多孔質電極基材及びそれを用いた燃料電池

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: UNITED TECHNOLOGIES CORP. (US) 1, FINANCIAL PLAZA

Free format text: FORMER OWNER: UTC POWER CORP.

Effective date: 20131213

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20131213

Address after: American Connecticut

Patentee after: United Technologies Corporation

Address before: American Connecticut

Patentee before: UTC Power Corp.

ASS Succession or assignment of patent right

Owner name: BALLARD POWER SYSTEMS

Free format text: FORMER OWNER: UNITED TECHNOLOGIES CORP. (US) 1, FINANCIAL PLAZA HARTFORD, CONNECTICUT 06101 U.

Effective date: 20150603

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20150603

Address after: Canadian British Columbia

Patentee after: Ballard Power Systems

Address before: American Connecticut

Patentee before: United Technologies Corporation

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160311

Address after: Germany Ingolstadt

Patentee after: Audi AG

Address before: Canadian British Columbia

Patentee before: Ballard Power Systems