CN102593466A - 用于燃料电池的基于纳米线的膜电极组件 - Google Patents
用于燃料电池的基于纳米线的膜电极组件 Download PDFInfo
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Abstract
本发明公开了在燃料电池中使用的纳米线,包括沉积在纳米线表面上的金属催化剂。公开了燃料电池的膜电极组件,它通常包括质子交换膜、阳极电极和阴极电极,其中阳极电极和阴极电极的至少一个或多个包括催化剂载体纳米线的互联网络。也公开了用于基于纳米线互联网络制备膜电极组件和燃料电池的方法。
Description
本申请是2005年12月6日提交的国际申请号为PCT/US2005/044068、国家申请号为200580042287.3、发明名称为“用于燃料电池的基于纳米线的膜电极组件”的发明专利申请的分案申请。
相关申请的交叉引用
本非临时申请要求2005年11月21日提交的题为“Stringed NanographiticCarbon(弦线化纳米石墨碳)”、律师备案号为01-007400的美国临时专利申请,以及2004年12月9日提交的美国临时专利申请No.60/634,472的优先权,这些申请通过引用整体结合于此。
技术领域
本发明一般涉及燃料电池,尤其涉及用于该燃料电池的基于纳米线的电极和膜电极组件。
背景技术
燃料电池是将诸如氢和甲醇的燃料的化学能直接转化成电能的装置。燃料电池的基本物理结构或构件由与两侧的多孔阳极和阴极接触的电解质层构成。图1示出具有反应物/产物气体的燃料电池和离子传导流穿过电池的方向的示意图。在图1所示的典型燃料电池中,燃料(例如甲醇或氢)被提供给可将燃料分子转化成质子(以及甲醇燃料电池的二氧化碳)的阳极催化剂,这些质子穿过质子交换膜到达电池的阴极一侧。在阴极催化剂处,质子(例如不带电子的氢原子)与氧离子反应形成水。通过将导电线从阳极连接到阴极一侧,从阳极侧的燃料、氢或甲醇剥除的电子可传播到阴极侧并与氧结合以形成氧离子,从而产生电。通过阳极的氢或甲醇燃料的电化学氧化与阴极的氧的减少而工作的燃料电池是诱人的电源,因为它转化效率高、污染低、重量轻以及能量密度高。
例如,在直接甲醇燃料电池(DMFC)中,在存在水的情况下液态甲醇(CH3OH)在阳极处被氧化从而产生CO2、氢离子和电子,电子作为燃料电池的电输出而传输通过外部电路。氢离子传输通过电解质并与来自空气的氧气和来自外部电路的电子反应以在阳极处形成水,从而完成电路。
阳极反应:CH3OH+H2O=>CO2+6H++6e-
阴极反应:3/2O2+6H++6e-=>3H2O
电池整体反应:CH3OH+3/2O2=>CO2+2H2O
最初在20世纪90年代早期开发时,DMFC因其低效率和功率密度以及其它问题而未被采用。催化剂的改进和近期的其它改进使功率密度增加20倍且效率可最终达到40%。在约50℃-120℃的范围内对这些电池进行测试。较低的工作温度和无需燃料重整器(reformer)使得DMFC成为诸如手机、膝上计算机、相机和其它消费品的极小尺寸到中等大小应用直到汽车功率设备的优秀候选。DMFC的缺点之一是甲醇低温氧化成氢离子和二氧化碳需要更加活性的催化剂,这通常说明需要更大量的昂贵铂(和/或钌)催化剂。
DMFC通常需要使用钌(Ru)作为催化剂成分,因为其较高的一氧化碳(CO)容耐和反应性。Ru分离水以产生便于将从甲醇产生的CO氧化成CO2的氧化物质。因为纳米尺寸的二金属Pt:Ru颗粒的高表面积与体积比率,一些现存的DFMC将其用作电氧化催化剂。Pt/Ru纳米颗粒通常设置在碳载体上(例如碳黑、富勒烯烟炱、脱硫碳黑)以形成堆积颗粒复合催化剂结构。用于产生Pt:Ru碳堆积颗粒复合物的最通用技术是在含有氯化铂和氯化钌的溶液中注入碳载体,之后进行热还原。
在多孔电极的区域中燃料电池反应物、电解质、活性Pt:Ru纳米颗粒和碳载体之间建立了多相界面或接触。该界面的性质在燃料电池的电化学性能中起关键作用。已经知道堆积颗粒复合物中只可使用一部分催化剂颗粒位置,因为其它位置不是反应物不能进入、就是未连接到碳载体网络(电子路径)和/或电解质(质子路径)。实际上,目前的堆积颗粒复合物只使用了催化剂颗粒的约20%或30%。因此,大多数使用堆积颗粒复合结构的DMFC是极没有效率的。
此外,由于颗粒之间和/或密堆颗粒之间燃料电池反应物的曲折扩散路径之间的较差接触,与阳极和/或阴极的连接性目前受限于现有的堆积颗粒复合结构。增加电解质或载体基质的密度能增加连接性,但是也会降低甲醇向催化剂位置的扩散。因此,在电极、电解质和多孔电极结构中的气相之间必须保持精确平衡,以便于在合理成本下最大化燃料电池的工作效率。最近对燃料电池技术改进的许多努力专注于在精制和改进电极结构和电解质物相的同时减小电池部件的厚度,旨在在降低成本的同时获得更高和更稳定的电化学性能。为了开发商用DFMC,必须改进催化剂的电催化活性。
本发明满足了这些需求以及其它需求。本发明总体上提供新型纳米线复合膜电极催化剂载体组装,该组装向极多孔的材料提供高表面积、高结构稳定性和连续结构。该复合结构可被设置为与电解质网络相互贯通的高度相互连接的纳米线载体的催化剂结构,以最大化催化剂利用、催化剂可进入性(accessibility)以及电连接性和离子连接性,从而在更低的成本等条件下改进燃料电池的总体效率。
发明内容
本发明提供具有纳米结构部件的质子交换膜燃料电池,尤其提供膜电极组件的一个或多个电极。纳米结构燃料电池比常规燃料电池具有更高的电极处催化剂金属利用率、更高的功率密度(kW/体积以及kW/质量)以及更低的成本。纳米结构燃料电池不仅对固定和移动应用具有吸引力,而且对用作诸如膝上计算机、手机、相机和其它电子装置的微电子的紧凑电源也具有吸引力。
根据本发明的第一方面,公开了在燃料电池的膜电极组件中使用的纳米线(例如无机纳米线),它通常包括沉积在纳米线表面上的金属催化剂。通过例如用标准表面化学反应官能化纳米线表面,该金属催化剂可在纳米线表面上沉积成薄膜,或者沉积成催化剂颗粒层。金属催化剂可从由铂(Pt)、钌(Ru)、铁(Fe)、钴(Co)、金(Au)、铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、锝(Tc)、铼(Re)、锇(Os)、铑(Rh)、铱(Ir)、镍(Ni)、钯(Pd)、铜(Cu)、银(Ag)、锌(Zn)、锡(Sn)、铝(Al)及其组合和合金(诸如二金属Pt:Ru纳米颗粒)的一个或多个组成的组中选择。纳米线可包括分支结构(例如侧结)以增加线的表面积与体积的比率,从而最大化燃料电池的催化效率。纳米线可由诸如RuO2、SiC、GaN、TiO2、SnO2、WCx、MoCx、ZrC、WNx、MoNx等的导电、半导电的金属碳化物、氮化物或氧化物材料制得。较佳地,纳米线可由在弱酸中抗降解的材料制得,从而该纳米线可与各种不同燃料电池的反应物相容。
纳米线可衍生成具有至少使用与金属催化剂颗粒结合的诸如硝酸基、羧酸基、羟基、胺基、磺酸基等的第一官能团或化学结合部分,或者催化剂可使用诸如电沉积、原子层沉积、等离子溅射等的其它沉积过程沉积成薄膜。纳米线也可衍生成具有有区别地结合于可直接沉积在纳米线上的薄的质子传导聚合物涂层(例如或其它磺化聚合物)的官能团。例如,可使用已知的标准化学反应用磺化烃、氟碳化合物或支链烃链官能化纳米线。或者,除了通过化学结合部分将离聚物结合到纳米线之外,纳米线可被官能化以使其传导质子。例如,纳米线可使用公知的官能化化学反应通过诸如全氟磺化烃的表面涂层来官能化。
这样,纳米线催化剂载体与聚合物壳之间的紧密关系确保大多数(如果不是全部的话)金属催化剂颗粒可位于三相接触点(例如,从而催化剂颗粒对燃料电池反应物、电解质和纳米线核而言可进入,以便于有效的电子和质子传导)。受控的纳米线表面化学可用于控制聚合物在复合纳米线结构中的浸润度、并确保催化剂颗粒暴露并可进入以便催化作用。
根据本发明的另一实施方式,公开了燃料电池膜电极组件的纳米结构催化剂载体,它通常包括各自具有沉积其上的金属催化剂的互连纳米线垫(mat)或网络。催化剂金属可包括上文公开的诸如铂的催化剂金属的任一种。催化剂金属可包括诸如铂和钌的金属的组合。在一个典型实施方式中,催化剂金属包括直径小于约50nm的纳米颗粒,例如小于约10nm、小于约5nm、在约1与5nm之间。在该实施方式中,纳米线网络中的各条纳米线通常物理和/或电连接于该纳米线网络中至少一条或多条其它纳米线以形成高度互连的纳米线网络。在其它实施方式中,纳米线可在阳极/阴极双极板与质子交换膜之间基本上排列成纳米线平行阵列,或者纳米线可随机取向。纳米线可各自涂敷有第一催化剂胶体涂层和/或第二质子传导聚合物薄涂层(例如)。膜电极组件可以是直接甲醇燃料电池、氢燃料电池或本领域中一般技术人员公知的任何其它燃料电池。
燃料电池可通过设置质子交换膜、阳极电极、阴极电极和第一与第二双极板而形成,其中阳极和阴极电极中的至少之一包括催化剂载体纳米线的互连网络。由于纳米线网络的卓越连接性,与常规燃料电池的情形一样燃料电池可能不需要质子交换膜与第一或第二双极板之间的气体扩散层。在一实施方式中,纳米线可在一个或多个燃料电池的双极板上和/或在质子交换膜上直接合成。纳米线也可以在单独的生长基底上生长,并获取之,然后转移(例如作为互连线的多孔片)并结合到燃料电池结构中(例如沉积到一个或多个燃料电池组件上,诸如一个或多个双极板和/或质子交换膜)。当在双极板和/或质子交换膜上原位生长时,纳米线可取向为基本上与双极板或质子交换膜表面垂直或正交,或者随机取向。
纳米线网络中的纳米线可较佳地物理和/或电连接于网络中的一条或多条其它线以形成开放、多分支、多孔、交织结构,该结构具有对反应物的较低的总扩散阻力以及电子的消耗扩散、高结构稳定性和高电连接性以确保高催化效率,从而得到高功率密度和较低的总成本。纳米线的复合电连接性确保:如果例如系统中的一条线断裂或者损坏,则沿该线的所有点依然沿其它路径(例如通过网络中的其它纳米线)连接于阳极(或阴极)电极。这提供了与先前堆积颗粒复合结构相比大大改进的电连接性和稳定性。对于燃料源催化剂极易进入以产生电子和质子,而电子可通过纳米线直接传导到双极板,且质子可通过聚合物直接传输到膜。
在纳米线与其它纳米线接触或接近的点处,纳米线网络中的纳米线可使用本文中要进一步描述的不同交叉连接或烧结方法交联或熔接在一起,以增加纳米线网络的连接性和结构稳定性。在另一实施方式中,交联或烧结的相同方案可用于改进纳米线、和与这些纳米线接触或接近的催化剂材料之间的电或结构连接性。
纳米线网络在网络中的纳米线之间限定了多个孔,其中该多个孔较佳地具有小于约10μm的有效孔尺寸,例如小于约5μm、小于约1μm、小于约0.2μm、小于0.02μm、在约0.002μm与0.02μm之间、在约0.005与0.01μm之间。分支纳米线结构的总孔隙率可大于约30%,例如在约30%与95%之间、在约40%与60%之间。纳米线可分散在诸如全氟磺酸/PTFE共聚物(例如)的多孔聚合物基质电解质材料中,该材料形成与分支纳米线网络中的纳米线相互贯通的连续网络以提供用于质子(例如H+)输运的充足接触点。
在本发明的另一实施方式中,公开了制备燃料电池膜电极的方法,该方法通常包括:(a)将从包含铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、锝(Tc)、铼(Re)、铁(Fe)、钌(Ru)、锇(Os)、钴(Co)、铑(Rh)、铱(Ir)、镍(Ni)、钯(Pd)、铂(Pt)、铜(Cu)、银(Ag)、金(Au)、锌(Zn)、锡(Sn)、铝(Al)及其组合的一种或多种的组中选择的催化剂金属与多条无机纳米线缔合,以形成具有缔合催化剂金属的多条无机纳米线;以及(b)形成包括具有缔合催化剂金属的多条无机纳米线的膜电极。
多条无机纳米线可衍生成具有与催化剂金属结合的诸如硝酸基、羧酸基、羟基、胺基、磺酸基等的至少第一官能团。缔合也可通过从包含化学气相沉积、电化学沉积、物理气相沉积、溶液注入和沉淀、胶体颗粒吸收和沉积、原子层沉积及其组合的组中选择的各种方法实现。例如,缔合可通过化学沉积诸如氯铂酸的催化剂金属前体或通过电沉积来自溶液中的前体盐的Pt而实现。催化剂金属前体可通过对催化剂金属前体进行金属还原来转化成催化活性金属,其中金属还原通过从包含氢还原、化学还原、电化学还原及其结合的组中选择的方法实现。催化活性金属可以是纳米线表面上的金属纳米颗粒形式。该形成可在质子交换膜上或一个或多个双极板上通过例如从包含喷漆/刷漆、溶液涂布、浇铸、电解沉积、过滤纳米线的悬浊液及其组合的组中选择的方法实现。纳米线也可在诸如一个或多个双极板的一个或多个燃料电池部件上和/或质子交换膜上直接生长。该方法还包括将离聚物树脂(例如全氟磺酸/PTFE共聚物、Nafion)与具有缔合催化剂金属的多条无机纳米线混合。多条无机纳米线可衍生成具有结合离聚物树脂的至少第二官能团(例如磺化烃基)。
在本发明的另一实施方式中,公开了一种制作燃料电池的膜电极组件的方法,它包括:在生长基底上形成纳米线;将纳米线从生长基底转移到悬浊液中;在纳米线上沉积一种或多种催化剂金属以形成纳米线载体催化剂;过滤纳米线悬浊液以构建互连纳米线的多孔片;用离聚物树脂渗入纳米线网络;以及将互连纳米线片与质子交换膜相结合以形成膜电极组件(MEA)。热压可用于将阳极和阴极电极中的电解质与质子交换膜相熔合以形成用于从阳极电极到阴极电极的有效质子传输的连续电解质物相。沉积一种或多种催化剂金属的步骤可包括例如沉积从包含铂、金、钌和其它金属及其组合的组中选择的金属。该方法还包括通过将第一和第二双极板组合在一起以形成质子交换膜燃料电池来形成利用所形成的MEA的质子交换膜燃料电池。
为了进一步理解本发明的特性和优点,可结合附图对以下描述进行参考。然而,应该明确理解各个附图仅为说明和描述目的而提供,并且并不旨在作为本发明的实施方式的限定。
附图说明
图1是示出阳极和阴极电极中的示例性反应的常规电化学燃料电池的示意图。
图2A是图1的燃料电池的阳极电极部分的展开图,示出包含设置在碳颗粒载体上的Pt/Ru纳米颗粒的常规堆积颗粒复合催化剂结构的细节。
图2B是图2A的堆积颗粒复合催化剂结构的展开图,示出气态反应物、电解质和电催化剂结构之间的示例性三相接触。
图3A是根据本发明示教制作的基于纳米线的电化学燃料电池的示意图。
图3B是根据本发明示教制作的基于纳米线的电化学燃料电池堆的示意图。
图4A是图3的燃料电池的阳极电极部分的展开图,示出横跨图3的燃料电池的质子交换膜和阳极电极之间的结的催化剂载体纳米线互连网络的一实施方式的细节。
图4B是燃料电池的基于纳米线的阳极部分的另一实施方式的展开图,示出横跨图3的燃料电池的质子交换膜与阳极电极之间的结的催化剂载体纳米线平行阵列的细节。
图5是用作根据本发明示教制作的燃料电池的阳极(和/或阴极)电极中的催化剂载体的纳米线互联网络的SEM图像。
图6是可用于实施本发明的方法的分支纳米线结构的示意图。
图7是包括具有从纳米线侧表面延伸的细小节结的多条分支纳米线的分支纳米线网络的SEM图像。
图8是如在本发明的某些方面中用来创建互连纳米线网络的交联或熔接纳米线的高倍放大SEM图像。
图9是示出沉积在互连纳米线网络上的Au催化剂颗粒的SEM图像。
具体实施方式
本发明的膜电极组件和燃料电池通过将纳米线结合在其部件结构中而获得显著独特的特性。术语“纳米线”通常指纵横比(长度∶宽度)大于10、较佳地大于100以及在很多情况下大于1000或更高的的细长结构。这些纳米线通常具有直径小于500nm且较佳地小于100nm以及在许多情况下小于50nm(例如大于1nm)的横截面尺寸。
本发明中使用的纳米线成分可改变。作为示例,纳米线可由有机聚合物、陶瓷、诸如碳化物和氮化物以及氧化物(诸如TiO2或ZnO)的无机半导体、碳纳米管、诸如纤维蛋白质的生物衍生化合物等组成。例如,在某些实施方式中,可使用诸如半导体纳米线的无机纳米线。半导体纳米线可由多个IV族、III-V族、或II-V族半导体及其氧化物组成。在一实施方式中,纳米线可包括导电、半导电的金属碳化物、氮化物或氧化物材料,诸如RuO2、SiC、GaN、TiO2、SnO2、WCx、MoCx、ZrC、WNx、MoNx等。较佳地,纳米线可由在弱酸中抗降解的材料制成,从而该纳米线与各种不同燃料电池的反应物相容。根据本发明的纳米线可明确地排除碳纳米管,且在某些实施方式中,排除“须线”或“纳米须线”,尤其是直径大于100nm或大于约200nm的须线。
通常,所使用的纳米线通过在基底表面上生长或合成这些细长结构而产生。作为示例,公开的美国专利申请No.US-2003-0089899-A1公开了使用气相外延生长从粘合在固体基底上的金胶体生长均匀分布的半导体纳米线的方法。Greene等人(“Low-temperature wafer scale production of ZnO nanowire arrays(ZnO纳米阵列的低温晶圆规模化生产)”,L.Greene,M.Law,J.Goldberger,F.Kim,J.Johnson,Y.Zhang,R.Saykally,P.Yang,Angew.Chem.Int.Ed.42,3031-3034,2003)公开了使用基于溶液的低温线生长工艺合成纳米线的另一方法。各种其它方法可用于合成其它细长纳米材料,包括美国专利No.5,505,928、6,225,198和6,306,736中公开的用于生产更短纳米材料的基于表面活性剂的合成方法,和用于生产碳纳米管的公知方法,参照例如Dai等人的US-2002/0179434以及在不使用生长基底的情况下生长纳米线的方法,参照例如Morales和Lieber,Science,V.279,208页(1998年1月9日)。如本文所示,这些不同材料的任一种或全部可用于生产本发明中使用的纳米线。对于一些应用,可使用各种III-V族、II-VI族和IV族半导体,这取决于制成的基底或物品的最终应用。通常,这种半导体纳米线在例如US-2003-0089899-A1中描述,该文献结合于此。在某些实施方式中,纳米线可从由Si、Ge、Sn、Se、Te、B、钻石、P、B-C、B-P(BP6)、B-Si、Si-C、Si-Ge、Si-Sn和Ge-Sn、SiC、BN/BP/BAs、AlN/AlP/AlAs/AlSb、GaN/GaP/GaAs/GaSb、InN/InP/InAs/InSb、BN/BP/BAs、AlN/AlP/AlAs/AlSb、GaN/GaP/GaAs/GaSb、InN/InP/InAs/InSb、ZnO/ZnS/ZnSe/ZnTe、CdS/CdSe/CdTe、HgS/HgSe/HgTe、BeS/BeSe/BeTe/MgS/MgSe、GeS、GeSe、GeTe、SnS、SnSe、SnTe、PbO、PbS、PbSe、PbTe、CuF、CuCl、CuBr、CuI、AgF、AgCl、AgBr、AgI、BeSiN2、CaCN2、ZnGeP2、CdSnAs2、ZnSnSb2、CuGeP3、CuSi2P3、(Cu,Ag)(Al,Ga,In,Tl,Fe)(S,Se,Te)2、Si3N4、Ge3N4、Al2O3、(Al,Ga,In)2(S,Se,Te)3、Al2CO以及两种或多种这样的半导体的适当组合组成的组中选择。
在半导体纳米线的情形中,纳米线可任选地包括掺杂物以增加纳米线催化剂载体的导电性。掺杂物可从由:来自周期表的III族的p-型掺杂物;来自周期表V族的n-型掺杂物;从由B、Al和In组成的组中选择的p-型掺杂物;从由P、As和Sb组成的组中选择的n-型掺杂物;来自周期表II族的p-型掺杂物;从由Mg、Zn、Cd和Hg组成的组中选择的p-型掺杂物;来自周期表IV族的p-型掺杂物;从由C和Si组成的组中选择的p-型掺杂物;或者从由Si、Ge、Sn、S、Se和Te组成的组中选择的n-型掺杂物组成的组中选择。
此外,这种纳米线可成分均一,包括单晶结构,或者它们可由不同材料的异质结构构成,例如沿其长度改变成分的纵向异质结构、或沿横截面或直径改变成分的同轴异质结构。这种同轴和纵向异质结构纳米线在例如公开的国际专利申请No.WO 02/080280中详细描述,为此该申请通过引用结合于此。
此外,如2005年11月21日提交的题为“Stringed Nanographitic Carbon(弦线化纳米石墨碳)”的律师备案号为01-007400的共同待批、共同授让临时专利申请(该申请通过引用整体结合于此)中更详细揭示的,可制造具有多壳的纳米线结构,例如导电内芯线(掺杂或未掺杂)(例如为电子传输提供必要的导电性)和为结合催化剂(和/或聚合物电解质)提供适当表面的一个或多个外壳层。例如在一实施方式中,可形成多层或多壁碳纳米管(MWNT),其中最外面的壳层转化成碳化硅以提供结合催化剂(和/或聚合物电解质)的表面(SiC)以及引入必要导电性的导电碳纳米管芯。在其它实施方式中,芯可由诸如掺杂硅的重掺杂材料组成,然后可在芯上形成碳化物、氮化物等材料(例如SiC)的壳。将硅用作芯材料可利用制造硅纳米线的各种广泛经验和基础结构。可使用受控表面反应围绕芯材料形成诸如SiC、WC、MoC或混合碳化物(例如WSiC)的碳化物壳。SiC、WC和MoC因其高导电率和化学稳定性而公知。此外,这些材料对于甲醇氧化已呈现具有与诸如Pt的贵金属类似的催化特性,从而进一步提供纳米线鸟巢MEA中的性能增强。壳的前体材料可通过原子层沉积(ALD)沉积在芯纳米线表面(例如硅),然后例如通过高温碳热还原转化成碳化物。
芯-壳纳米线(和其它纳米晶体)异质结构的合成在以下文献中描述:例如,Berkeley的美国专利申请公开No.20020172820;2005年8月29日提交的题为“Systems and methods for harvesting and integrating nanowires(获取和集成纳米线的系统和方法)”的共同授让和待批U.S.S.N.11/117,707;Peng等人的“Epitaxialgrowth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability andelectronic accessibility(具有光稳定性和电子可进入性的高发光CdSe/CdS芯/壳纳米晶体的外延生长)”J.Am.Chem.Soc.119,7019-7029,1997年;Dabbousi等人的“(CdSe)ZnS core-shell quantum dots:Synthesis and characterization of a size seriesof highly luminescent nanocrystallites((CdSe)ZnS芯-壳量子点:一系列尺寸的高发光纳米晶粒的合成和表征)”J.Phys.Chem.B 101,9463-9475,1997年;Manna等人的“Epitaxial growth and photochemical annealing of graded CdS/ZnS shells oncolloidal CdSe nanorods(胶体CdSe纳米棒上的分等级CdS/ZnS壳的外延生长和光化学退火)”J.Am.Chem.Soc.124,7136-7145,2002年,这些文献通过引用整体结合于此。类似的方法可用于生长包括纳米线的其它芯-壳纳米结构。
在本发明的一实施方式中,本发明的阳极(和/或阴极)电极的纳米线部分可在生长基底上合成,然后转移并结合到燃料电池的膜电极组件中。例如,在某些方面,可使用上述基于胶体催化剂的VLS合成方法在生长基底的表面上生长无机半导体或半导体氧化物纳米线。根据该合成技术,胶体催化剂(例如金、铂等颗粒)可沉积在基底的期望表面上。然后对包括胶体催化剂的基底进行合成处理,该处理产生附加于基底表面的纳米线。其它合成方法包括使用沉积在基底表面的例如50nm或以下的催化剂薄膜。然后VLS处理的热量将该薄膜熔化以形成可形成纳米线的催化剂小液滴。通常,该后一方法可在纤径均匀性对最终涂敷并不那么关键的情况下使用。通常,催化剂包括例如金或铂的金属,并且可电镀或蒸镀到基底表面或者用例如溅射等的其它许多众所周知的金属沉积技术之一沉积。在胶体沉积的情形中,胶体通常通过首先处理基底表面使胶体粘附于该表面而沉积。这些处理包括先前详细描述的那些处理,即多熔素处理等。然后,将具有经处理表面的基底浸入胶体悬浊液中。
在纳米线生长之后,从纳米线合成位置获取纳米线。然后,例如通过从喷涂/刷涂、浸液涂布、浇铸、电解质沉积、过滤纳米线悬浊液、及其组合,将独立(freestanding)纳米线引入到或沉积在诸如双极板或质子交换膜的燃料电池部件的相关表面上。例如,这种沉积可简单地包括将感兴趣的部件(例如一个或多个双极板或质子交换膜)浸入这种纳米线的悬浊液中,或者包括预处理该部件的全部或部分以官能化表面或表面部分来进行纳米线附加。如下所述,也可将纳米线引入到溶液(例如甲醇或水)中,过滤(例如通过聚偏二氟乙烯(PVDF)膜真空过滤)以给予其紧密、交织的衬垫或“鸟巢结构”,在干燥、清洗之后从滤器中取出,以及在高温下热处理(例如退火)。然后,所得的互连纳米线多孔片可结合到燃料电池的膜电极组件中。可使用各种其它沉积方法,例如2005年3月31日公开的美国专利申请公开No.20050066883和美国专利No.6,962,823,为所有目的这些文献通过引用整体结合于此。如下文进一步所述,纳米线也可以在诸如一个或多个双极板和/或质子交换膜的一个或多个燃料电池部件上直接生长。
通常,如图1所示,燃料电池100通常包括阳极电极102、阴极电极104和质子交换膜(PEM)106。这三个部件的组件通常称为膜电极组件(MEA)。如前所述,如果甲醇被用作燃料,则液态甲醇(CH3OH)在有水的情况下在阳极102被氧化,从而产生CO2、氢离子和通过外部电路108传输作为燃料电池电输出的电子。氢离子传输通过电解质膜106并与来自空气的氧和来自外部电路108的电子反应以在阴极形成水,从而完成该电路。阳极和阴极电极102、104分别与双极板110、112接触。双极板110、112通常在其表面具有将燃料和氧化剂分配到其相应催化剂电极、允许例如水和CO2的废物排出的沟道和/或凹槽,并且也可包含热转移的管道。通常,双极板具有高导电性并且由石墨、金属、导电聚合物及其合金和合成物制成。具有或不具有涂层的例如不锈钢、铝合金、碳和合成物的材料是PEM燃料电池中双极端板的较佳选择。双极板也可由包括结合在复合结构(例如金属、导电聚合物等)中的高度导电或半导体纳米线的复合材料形成。燃料电池部件的形状和尺寸可取决于特定设计而在较宽范围内改变。
在另一实施方式中,纳米线可沉积(例如生长)在一个或多个双极板上以提供对通过电极板的甲醇(或其它燃料电池气态或液态反应物)和废品具有较低流阻的高表面积电极板。对具有增强表面积的纳米线结构、以及这种纳米线和纳米线结构在各种高表面积应用中的使用的更完整描述在2004年3月2日提交的题为“Nanofiber Surfaces for use in Enhanced Surface Area Applications(用于增强表面积应用的纳米纤维表面)”的U.S.S.N.10/792,402中提供,该文献通过引用整体结合于此。
当前,最常用的电极催化剂是Pt或Pt:Ru颗粒202,它们由在如图2A中阳极102的放大图所示地分散在电介质膜206中的碳颗粒204(例如由碳黑制成)承载。商用化质子交换膜燃料电池(PEMFC)的挑战之一是用作催化剂(Pt或Ru)的贵重金属的高成本。通过增加Pt催化剂的利用率而减少PEMFC中Pt的用量是过去十年中主要关注点之一。为了有效地利用Pt催化剂,Pt应该同时与反应气体(或者反应溶液或液体)、电介质(例如质子传导膜)和碳颗粒(例如电子传导元件)同时接触。如图2B所示,燃料电池中的有效电极需要催化剂层中在反应气体/液体、活性金属颗粒、碳载体202、204和电解质206之间的4相接触208。较佳的催化剂层允许反应气体(例如甲醇、MeOH:H2O、氢气和/或氧气)、溶液或液体的流畅传输,去到/来自外部电路的电子以及去到/来自质子交换膜的质子的流畅传输。
碳颗粒传导电子且全氟磺酸盐离聚物(perfluorosulfonate inomer)(例如)传导质子。如前所述,在如图2A-B所示的常规堆积颗粒复合物系统中,存在与外部电路和/或PEM隔离的大部分Pt(或Pt:Ru),从而导致低Pt利用。例如,当前的堆积颗粒复合物仅利用约20至30%的催化剂颗粒。对一些催化剂位置的不可进入可归因于例如这样的事实:质子传输的增溶全氟代硫化离聚物(例如)的必要添加易于冲走或隔离催化剂层中的碳颗粒,从而导致较差的电子传输。因此,利用堆积颗粒复合结构的大多数DMFC是极低效的。
因其独特的机构、机械和电气特性,本申请的发明人发现纳米线可用于代替PEMFC中传统的碳颗粒作为催化剂载体和电子传导介质以制作MEA。由于例如SiC或GaN纳米线的纳米线上表面官能团的生成是相对直接的,所以诸如Pt和/或Pt:Ru(以及质子传导聚合物(例如Nafion))的催化剂纳米颗粒很容易在例如颗粒没有结块的情况下沉积在纳米线上。然后,各个催化剂颗粒可通过纳米线芯直接连接到阳极(和阴极)。互连纳米线的复合导电性确保从Pt到电子传导层的电子路径。使用纳米线以及所得的保障电子路径克服了常规PEMFC方案中质子传导介质(例如Nafion)可隔离电极层中的碳颗粒的上述问题。克服载体电极层的碳颗粒的隔离改进了Pt的利用率。
如参照图3A所示,示出基于纳米线的燃料电池,它包括阳极双极电极板302、阴极双极电极板304、质子交换膜306、阳极电极308、阴极电极310、以及夹在一侧的燃料电池阳极电极308和阴极电极310与另一侧的燃料电池质子交换膜306之间的纳米线互连网络312。通常,如图3A所示的多个燃料电池或MEA可结合以形成如图3B所示的具有分别由相应质子交换膜306和306’分开的分离阳极电极308、320和阴极电极310、322的燃料电池堆。电池堆中的电池可由双极板302、304、318和324串联连接,使得各个燃料电池的电压相加。
如图3A、4A所示以及在图5的SEM图像中,纳米线网络312中的纳米线316各自物理和/或电气地连接于网络中的一条或多条其它纳米线以形成开放、高度分支、多孔、交织结构,该结构具有对反应物和废物扩散的低的总扩散阻力、高结构稳定性和对电子的高导电性以确保高催化剂效率,从而获得高功率密度和低的总成本。重要的是,注意即使两条纳米线实际上彼此(或与催化剂颗粒)并未直接物理接触,也有可能在分开较小距离时它们仍然能转移变化(例如电接触)。较佳地,各条纳米线可物理和/或电气地连接于网络中至少一条或多条其它纳米线。纳米线的复合导电性确保:如果例如系统中的一条纳米线断裂或者损坏,则沿该纳米线的所有点仍可沿不同路径(例如经由网络中的其它纳米线)连接于阳极(和阴极)电极。与先前的堆积颗粒复合结构相比,这提供大大改进的电连接性和稳定性。纳米线可延伸阳极(和阴极)双极板与质子交换膜之间的所有路径(或仅仅部分路径)。在纳米线不延伸双极板和膜之间的所有路径的情况中,纳米线可从双极板向膜延伸,但是未到达该膜,并且聚合物电解质可从膜向双极板延伸,但并未到达双极板(但不是周围的另一路径)以确保电子有效地转移到阳极,且质子向阴极转移。
纳米线网络中的纳米线可任选地具有分支结构,并包括从如图6所示的和图7的SEM图像所示的纳米线侧面延伸的多个节结600。纳米线芯侧面上的节结600可进一步增加催化作用的可用表面积,而不显著影响纳米线网络的连接性或多孔性。
纳米线316分散在聚合物电解质材料315中(例如参照图4A),该材料315涂敷分支纳米线网络中纳米线的表面以提供质子(例如H+)传输的足够接触点。聚合物电解质可由包括例如聚环氧乙烷、聚丁二酸亚乙酯、聚(β-丙醇酸内酯)和诸如(可从Wilmington的DuPont Chemicals购得)的磺化含氟聚合物的各种聚合物制得。适当的阳离子交换膜在例如美国专利No.5,399,184中描述,该专利通过引用结合于此。或者,质子传导膜可以是具有多孔微结构的展开膜,其中离子交换材料注入该膜从而有效填充该膜的内部容积。通过引用结合于此的美国专利No.5,635,041描述了由展开聚四氟乙烯(PTFE)形成的这种膜。展开的PTFE膜具有由纤丝互连的节点微结构。类似的结构在美国专利No.4,849,311中描述,该专利通过引用结合于此。
互连纳米线网络的多孔结构为燃料电池反应物提供通向沉积在纳米线316上的催化剂(例如颗粒314)的畅通(非曲折)扩散路径,如下所述。互连纳米线之间的空隙形成高度多孔结构。有效孔径大小通常取决于纳米线群的密度和电解质层的厚度,以及在某种程度上取决于所用纳米线的宽度。所有这些参数都容易改变以生成具有期望有效多孔性的纳米线网络。例如,较佳的纳米线网络具有在保持足够的导电性和机械强度的同时足以提供均匀反应物流的多孔性。此外,纳米线网络的多孔性提供电池内的水管理。分支纳米线网络较佳地足够多孔,以使燃料气体和水汽从中穿过而无需设置可阻塞网络的孔并阻止水汽传输的水冷凝站。平均孔大小通常在从约0.002微米到约10.0微米范围内,例如小于约1微米、小于约0.2微米、小于约0.02微米、在0.002微米和0.02微米之间、在约0.005微米和0.01微米之间。分支纳米线结构的总多孔性可很容易地控制在约30%至95%之间,例如在40%至60%之间,同时仍然确保与阳极和阴极电极的电连接。
0054:形成互连纳米线网络312的纳米线316可任选地在不同纳米线彼此接触的点上熔合或交联以形成更加稳定、坚固和可能刚性的膜电极组件。纳米线也可包括可形成化学交联以交联下层纳米线的表面化学基。例如,纳米线可以通过在其交叉点上沉积少量导电或半导电材料而交联或熔合在一起。例如,SiC纳米线(或者例如具有SiC壳层的碳纳米管纳米线)可通过在其交叉点上沉积无定形或多晶SiC而交联。图8是示出在其交叉点使用沉积多晶硅而熔合在一起的多条硅纳米线的SEM微图像。本领域技术人员应该理解其它金属、半金属、半导体和半导体氧化物也可用于交联这些交叉点。
在参照图4B示出的本发明的另一方面中,纳米线316’可以设置成电解质315’散布在对齐纳米线之间的自由空间之间的对齐纳米线的平行阵列。在本发明的这个特定实现中,纳米线平行阵列较佳地例如在双极电极板302和/或304(和/或质子交换膜306)表面上原位合成。应该理解,如图3A、4A和5所示并如上所述的纳米线316的随机取向互联网络312也可使用本文所述技术在双极板302、304(和/或质子交换膜)上直接原位生长。例如,无机半导体或半导体氧化物纳米线可使用上述的基于胶体催化剂的VLS合成方法直接在电极板表面上生长。根据该合成技术,胶体催化剂被沉积在双极板的期望表面上。然后,对包括胶体催化剂的双极板进行合成处理,该处理产生附加于该板表面的纳米线。其它合成方法包括使用沉积在双极板表面上的例如50nm或以下的催化剂薄膜。然后,VLS处理的热量熔化该薄膜以形成可形成纳米线的催化剂小液滴。通常,后一种方法可在纳米线直径均匀性对最终涂敷不那么关键时使用。通常,催化剂包括例如金或铂的金属,并且可电镀或蒸镀到电极板表面上或者以诸如溅射等的多种其它公知金属沉积技术之一沉积。在胶体沉积的情形中,胶体通常可通过首先处理电极板表面使得胶体粘附于该表面而沉积。然后,将具有经处理表面的板浸入到胶体悬浊液中。
在本发明的另一方面,阳极电极308(和阴极电极310)可包括由例如诸如导电聚合物、碳片等的有机材料、诸如半导体的无机材料、诸如金的金属、半金属以及其中几种或全部的合成物的各种固体或半固体材料制成的导电栅格或栅网,其上可附加纳米线316,而其间存在孔隙。这种栅网提供具有定义明确的屏/孔和线号的商用格式的相对一致的表面。各种该屏/孔和线号的各种各样金属栅网很容易商用。或者,金属基板可设置为穿孔板,例如制作开孔的固体金属片。在金属板上制作开孔可通过多种方法之一完成。例如,诸如直径小于100微米的较小开孔可使用平板印刷以及较佳地光刻技术制作。类似地,这种开孔可使用例如烧蚀、激光钻孔等的基于激光的技术制作。对于较大的开孔,例如大于50-100微米的开孔,可使用更多的常规金属制作技术,例如冲压、钻孔等。在形成时,具有通过本文公开的方法形成或沉积其上的纳米线的金属栅格或栅网可沉积在质子交换膜、双极板上或者嵌入一个或多个电极层内以向多孔网络提供用于有效催化作用的附加其上的高表面积纳米线催化剂载体。可在本发明中使用的具有沉积其上的纳米线的各种栅格或栅网的其它示例在2004年9月15日提交的题为“Porous Substrates,Articles,Systemsand Compositions Comprising Nanofibers and Methods of Their Use and Production(包括纳米纤维的多孔基底、物品、系统和合成物及其使用和制作方法)”的序列号No.10/941,746的美国专利申请中完全公开,该申请通过引用整体结合于此。
因此,通过上述公开方法的任一种形成的纳米线网络用作可涂布或沉积例如在纳米线上的后续金属催化剂(例如铂、钌、金或其它下述金属)的载体。燃料电池的适当催化剂通常取决于所选反应物。例如,金属催化剂可从由铂(Pt)、钌(Ru)、铁(Fe)、钴(Co)、金(Au)、铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、锝(Tc)、铼(Re)、锇(Os)、铑(Rh)、铱(Ir)、镍(Ni)、钯(Pd)、铜(Cu)、银(Ag)、锌(Zn)、锡(Sn)、铝(Al)及其组合和合金(诸如二金属Pt:Ru纳米颗粒)的一个或多个组成的组中选择。用于氢或甲醇燃料氧化的适当催化剂材料具体包括诸如Pd、Pt、Ru、Rh及其合金的金属。
通过使用包括例如化学气相沉积、电化学沉积(例如电镀或无电镀化学镀)、物理气相沉积、溶液注入和沉淀、胶体颗粒吸收和沉积、原子层沉积及其组合的各种催化剂沉积技术,催化剂可在纳米线表面上沉积或以其它方式缔合为薄膜(例如厚度小于约10埃)(或者催化剂颗粒系列)。通过上述方法涂布的催化剂金属的量较佳地在重量比约10-85%(基于催化剂金属和纳米线材料的总量)的范围内,更佳地重量比为20-40%。
或者,在参照图3A和4A-B所示的一特定实施方式中,通过例如将纳米线外表面衍生成具有诸如一个或多个羧酸基、硝酸基、羟基、胺基、磺酸基等的一个或多个官能连接部分(例如化学反应基),催化剂可在溶液中的纳米线表面上沉积成多个纳米大小的金属催化剂颗粒314(例如直径在约1和50nm之间、直径小于约10nm、直径在约1和5nm之间)。催化剂颗粒(或膜)可均匀地或非均匀地附加于纳米线。催化剂颗粒可以是球形、半球形或非球形。催化剂颗粒可在纳米线表面形成岛,或者可在诸如芯-壳配置的纳米线表面上形成连续涂布或者沿纳米线长度形成条纹或环等。催化剂颗粒可在纳米线网络结合/沉积到燃料电池的MEA之前或之后附加于纳米线表面。在一实施方式中,催化剂颗粒可从具有小于约50%(例如小于约30%、小于约20%)的均匀大小分布的催化剂颗粒群中选择。
当化学连接分子用于将催化剂结合到纳米线,化学连接剂可选择成改进催化剂与纳米线之间的电连接,或者随后可移除化学连接剂以改进电连接。例如,热、真空、化学试剂或其组合可任选地施加到纳米线以移除连接分子,从而将催化剂置于直接与纳米线物理接触以在催化剂颗粒与纳米线之间形成坚固的电连接。也可加热该结构以退火催化剂与纳米线之间的界面以改进其间的电接触。
除了导电催化剂颗粒之外,可使用填充物来改变本发明中适用的纳米线复合结构的物理特性。适合的填充物包括例如二氧化硅(SiO2)、粉末状聚四氟乙烯和氟化石墨(CFn)。聚合物膜较佳地包括达到重量比约20%的填充物,最佳地重量比从约2%至约10%。填充物通常是颗粒状。
0062:在催化剂沉积之后,通过例如用优先地结合电解质或者改进一致和/或受控浸润的第二官能团(在使用时,与催化剂官能团不同)官能化纳米线表面,诸如Nafion的质子传导聚合物可任选地沉积在催化剂颗粒位置之间的纳米线表面上。聚合物可以是纳米线表面上的连续或者不连续膜。例如,聚合物电解质可在纳米线表面上均匀浸润,或者可沿纳米线长度形成电接触。纳米线可使用可经由硅烷化学反应附加于纳米线表面的磺化烃分子、碳氟化合物分子、两类分子的短链聚合物、或分子烃链官能化。本领域技术人员应该熟悉本文中任选使用的许多官能化和官能化技术(例如与分馏柱、生物测定等的构建中所使用的那些)。或者,除了通过化学结合部分将离聚物结合于纳米线之外,纳米线可直接官能化以使其传导质子。例如,纳米线可用熟知的官能化化学反应通过诸如全氟化磺化烃的表面涂层官能化。
例如,涉及相关部分和其它化学反应的细节、及其构建/使用方法可在例如Hermanson的Bioconjugate Techniques(生物共轭技术),Academic Press(1996);Kirk-Othmer的Concise Encyclopedia of Chemical Technology(化学技术简明全书)(1999),Crayson等人(编辑)第四版,John Wiley & Sons公司,纽约;和Kirk-Othmer的Encyclopedia of Chemical Technology(化学技术全书),Grayson等人(编辑)第四版(1998年和2000年),Wiley Interscience(印刷版)/John Wiley & Sons公司(电子格式)中找到。进一步的相关信息可在CRC Handbook of Chemistry and Physics (CRC化学和物理手册)(2003),CRC Press的83版中找到。同样可通过等离子体方法等结合在纳米线表面上的传导和其它涂层的细节可在H.S.Nalwa(编辑)的Handbook of Organic Conductive Molecules and Polymers(有机传导分子和聚合物手 册),John Wiley & Sons 1997中找到。也可参照题为“ORGANIC SPECIES THATFACILITATE CHARGE TRANSFER TO/FROM NANOCRYSTALS(便于去向/来自纳米晶体的电荷转移的有机物质)”美国专利6,949,206。涉及有机化学、有关例如熔附加部分耦联于官能化表面的细节可在例如Greene(1981)的Protective Groups in Organic Synthesis(有机合成中的保护基),John Wiley & Sons公司,纽约;以及Schmidt(1996)的Organic Chemistry(有机化学),Mosby,St Louis,MO和March的Advanced Organic Chemistry Reactions,Mechanisms and Structure(先进有机化学 反应、机制和结构),Smith和March的第5版(2000),Wiley Interscience New YorkISBN 0-471-58589-0,以及2005年8月18日公开的美国专利公开No.20050181195中找到。本领域技术人员应该熟悉适于本文的表面官能化的许多其它相关参考和技术。
聚合物电解质涂层可通过例如硅烷基直接连接于纳米线表面,或者可经由使用诸如取代硅烷、丁二炔、丙烯酸盐、丙烯酰胺、乙烯基、苯乙烯基、二氧化硅、氧化硼、氧化磷、N-(3-氨基丙基)3-巯基-苯甲酰胺、3-氨基丙基-三甲氧基硅烷、3-巯基丙基-三甲氧基硅烷、3-马来酰亚氨基丙基-三甲氧基硅烷、3-酰肼基(hydrazido)丙基-三甲氧基硅烷、三氯-全氟辛基硅烷、羟基琥珀酰亚胺、马来酰亚胺、卤代乙酰(haloacetyl)、肼、乙基二乙氨基碳二亚胺等的连接剂进行键合化学反应(衍生)的连接剂结合基团或其它适当化学反应基团来偶联。可使用诸如本领域技术人员公知的其它表面官能化化学反应。
此外,增溶全氟磺酸盐离聚物(例如)可置入纳米线之间的剩余空间。复合纳米线结构(例如由以下示例中描述的工艺制作的互连纳米线多孔片)在未在双极板和/或质子交换膜之一上原位生长的情况下,可置于质子交换膜两侧的双极板之间,且可对该组件进行热压以形成根据本发明的完整膜电极组件电池。热压温度被确定成质子交换膜在该温度范围内变软,例如对于Nafion的125摄氏度。压力大小约为200kgf/cm2。为了有效地向阳极/阴极电极308、310分配燃料/氧气,通常在常规燃料电池中在一侧的燃料电池阳极电极和双极板与另一侧的燃料电池阴极电极和双极板之间需要气体扩散层。通常,碳纤维织物用作气体扩散层。使用本发明的互连纳米线复合膜电极催化剂载体组件,该气体扩散层可因基于纳米线的电极的优越结构而得以消除。
示例:
以下非限制性示例描述了在根据本发明示教的膜电极组件中使用的用于在纳米线表面上沉积金(Au)纳米颗粒的示例性工艺。
0067:约10mg的Si纳米线通过声波降解而分散在乙醇中以形成纳米线悬浊液。互连纳米线网络通过在聚偏二氟乙烯(PVDF)膜上真空过滤纳米线悬浊液并真空干燥而制得,然后将2cc的0.1%多熔素溶液添加到过滤漏斗中以吸收纳米线表面上的多熔素。5分钟之后,将漏斗中的所有液体真空排除,且纳米线网络可与PVDF膜分离。100摄氏度下在烘箱中干燥15分钟之后,将纳米线网络浸入10cc的10nmAu胶体溶液中并浸泡20分钟,以吸收纳米线表面上的Au纳米颗粒。最后,纳米线网络可从Au胶体溶液取出,用异丙醇(IPA)漂洗,并在100摄氏度下干燥以获得涂布有金纳米颗粒的纳米线网络。图9示出沉积在互连纳米线网络上的Au催化剂纳米颗粒的SEM图像。
虽然以上已经相当详细地进行了描述,但是应该理解,可对上述发明进行各种更改同时仍然在如所附权利要求书所描绘地实施本发明。因此,本文所引用的所有出版物和专利文件通过引用结合于此,在一定程度上如同各个文献单独结合于此一样。
Claims (22)
1.一种复合物,其包括:
生长在支撑结构上的多个纳米线,所述支撑结构包括石墨、碳或碳复合物,所述纳米线包含晶体硅、多晶硅、无定形硅或它们的混合物;和
聚合物电解质。
2.如权利要求1所述的复合物,其特征在于,所述纳米线分散在所述聚合物电解质中。
3.如权利要求1所述的复合物,其特征在于,所述聚合物电解质的一部分附加于所述纳米线。
4.如权利要求1所述的复合物,其特征在于,所述聚合物电解质的一部分直接连接于所述纳米线表面。
5.如权利要求1所述的复合物,其特征在于,所述聚合物电解质的一部分形成覆盖在纳米线表面上的连续或者不连续聚合物膜。
6.如权利要求1所述的复合物,其特征在于,所述聚合物电解质的一部分在纳米线表面上均匀浸润。
7.如权利要求1所述的复合物,其特征在于,所述纳米线包括互连纳米线网络。
8.如权利要求1所述的复合物,其特征在于,所述纳米线包括在互连纳米线之间形成化学交联的至少一种表面化学基团。
9.如权利要求1所述的复合物,其特征在于,所述聚合物电解质包括离聚物、聚环氧乙烷、聚丁二酸亚乙酯、聚(β-丙醇酸内酯)或磺化含氟聚合物。
10.如权利要求1所述的复合物,其特征在于,所述纳米线表面是官能化的。
11.如权利要求1所述的复合物,其特征在于,所述纳米线用至少一种官能团进行官能化,所述官能团改进纳米线上聚合物电解质浸润。
12.如权利要求1所述的复合物,其特征在于,所述纳米线用至少一种官能团进行官能化,所述官能团将聚合物电解质与纳米线结合。
13.如权利要求1所述的复合物,其特征在于,所述纳米线用至少一种选自下组的分子进行官能化:短链聚合物、磺化烃、短链磺化烃、碳氟化合物、短链碳氟化合物和支链烃。
14.如权利要求1所述的复合物,其特征在于,所述纳米线用至少一种选自下组的官能团进行官能化:硝酸基、羧酸基、羟基、胺基、磺酸基或硅烷基。
15.如权利要求1所述的复合物,其特征在于,所述复合物是多孔的,所述多孔复合物包括设置在所述多个纳米线的纳米线之间的孔。
16.如权利要求16所述的复合物,其特征在于,所述聚合物电解质设置在所述多孔复合物的孔中。
17.如权利要求1所述的复合物,其特征在于,所述纳米线包含硅或碳化硅。
18.如权利要求1所述的复合物,其特征在于,所述纳米线包括芯和设置在所述芯上的一层或多层壳层。
19.如权利要求1所述的复合物,所述复合物还包含附加于所述纳米线的一种或多种金属催化剂颗粒,其特征在于,所述金属催化剂颗粒包括金、铜或其混合物或它们的合金。
20.如权利要求1所述的复合物,其特征在于,所述复合物具有导电性。
21.一种包括权利要求1所述的复合物的电极。
22.一种包括权利要求1所述的复合物的阳极。
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CN104362353A (zh) * | 2014-09-23 | 2015-02-18 | 杭州师范大学 | 一种直接甲醇燃料电池活性材料的制备方法与应用 |
CN104362353B (zh) * | 2014-09-23 | 2017-02-08 | 杭州师范大学 | 一种直接甲醇燃料电池活性材料的制备方法与应用 |
CN113471464A (zh) * | 2021-05-19 | 2021-10-01 | 深圳先进技术研究院 | 一种电池隔膜用材料、材料制备方法及电池隔膜 |
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AU2005314211B2 (en) | 2010-07-08 |
AU2005314211A1 (en) | 2006-06-15 |
EP1829141A2 (en) | 2007-09-05 |
WO2006062947A2 (en) | 2006-06-15 |
US20110229795A1 (en) | 2011-09-22 |
US20100233585A1 (en) | 2010-09-16 |
US7179561B2 (en) | 2007-02-20 |
JP5277451B2 (ja) | 2013-08-28 |
US20090017363A1 (en) | 2009-01-15 |
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CN101107737A (zh) | 2008-01-16 |
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