WO2016124050A1 - 一种纳米陶瓷纤维管燃料电池质子交换膜及制备方法 - Google Patents

一种纳米陶瓷纤维管燃料电池质子交换膜及制备方法 Download PDF

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WO2016124050A1
WO2016124050A1 PCT/CN2015/099704 CN2015099704W WO2016124050A1 WO 2016124050 A1 WO2016124050 A1 WO 2016124050A1 CN 2015099704 W CN2015099704 W CN 2015099704W WO 2016124050 A1 WO2016124050 A1 WO 2016124050A1
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nano
fiber tube
ceramic fiber
proton
ceramic
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PCT/CN2015/099704
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French (fr)
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陈庆
曾军堂
叶任海
陈兵
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成都新柯力化工科技有限公司
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    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to the field of fuel cell proton exchange membranes, and in particular to a nano ceramic fiber tube fuel cell proton exchange membrane and a preparation method thereof.
  • Proton exchange membrane is one of the key components in proton exchange membrane fuel cells (PEMFC). It is a dense proton-selective membrane that acts as a separate fuel and oxidant to prevent their direct reaction; It also plays a role in conducting protons to electronic insulation, and its performance directly affects battery performance, energy conversion efficiency and service life.
  • PEMFC proton exchange membrane fuel cells
  • proton exchange membranes of polymer polymers such as perfluoroproton exchange membranes, non-fluorine proton exchange membranes, non-perfluorinated proton exchange membranes; although such proton exchange membranes It has the advantages of excellent proton conductivity, low methanol permeability and simple film formation, but the polymer polymer material itself has the characteristics of easy degradation, less raw material source, complicated synthesis process and more chemical properties, which leads to its preparation.
  • Proton exchange membranes have major defects such as high cost, high temperature resistance and short service life, which restrict the large-scale production and utilization of proton exchange membranes, and also limit the marketization and application of proton exchange membrane fuel cells.
  • Chinese Patent Publication No. CN101773792A discloses a fluorine-containing proton exchange membrane doped with an inorganic metal oxide for a fuel cell and a preparation method thereof.
  • the fluorine-containing proton exchange membrane wherein the inorganic metal ions are uniformly dispersed in the fluorine-containing ion exchange resin by using the ion conductive ceramic as a carrier, and the proton exchange membrane for the fuel cell prepared by the invention has high electrical conductivity and mechanical strength, and is favorable for improving fuel The performance of the battery, but due to the still used fluorine-containing ion exchange resin as the matrix resin of the proton exchange membrane, resulting in its use temperature and service life The life is not improved, so this method is not suitable for large-scale market applications.
  • Chinese Patent Publication No. CN102800881A discloses a method for preparing a fuel cell inorganic proton exchange membrane
  • the method utilizes a dispersant methyl cellulose ether to uniformly disperse Zr02 in the proton exchange membrane, thereby improving the operational stability of the battery, but is also limited by the short service life of the methyl cellulose ether under high temperature conditions. As a result, the service life of the inorganic proton exchange membrane is short, and thus the method cannot solve the defect that the polymer polymer proton exchange membrane has a short life.
  • the existing proton exchange membranes are all required to be assisted by the polymer polymer material, and thus cannot solve the defects of the high temperature and short service life of the exchange membrane of the polymer polymer, and the conventional ceramic protons.
  • the exchange membrane has the defects of low proton conductivity and poor toughness. Therefore, a new ceramic with high proton conductivity, good toughness, simple film formation, low cost, high working temperature and long working life has been developed. Proton exchange membranes have become the key to driving large-scale market applications of fuel cells. Summary of invention
  • the present invention provides a nano ceramic fiber tube fuel cell proton exchange membrane, compared with other fuel cell proton exchange membranes, due to the use of high temperature and stable performance of proton conductive nano ceramic fiber tube as a carrier material, and A variety of auxiliary materials are added, and a proton exchange membrane is obtained through multiple processes, thereby having the advantages of high temperature resistance, long service life, good toughness, and high proton conductivity.
  • a further object of the present invention is to provide a method for preparing a nano ceramic fiber tube fuel cell proton exchange membrane, which is prepared by a process of immersion, dispersion, molding, sintering, etc., and the proton exchange membrane has high temperature resistance. It has the advantages of long service life, good toughness and high proton conductivity. It can meet the application of proton exchange membrane on fuel cells, and can be produced in large-scale industrial production with stable quality. It is suitable for the promotion and application of fuel cell pairs.
  • a nano ceramic fiber tube fuel cell proton exchange membrane is characterized in that it comprises a nano ceramic proton conductive fiber body with a nano ceramic fiber tube as a sleeve and a proton conductive auxiliary agent as a core.
  • the nano ceramic fiber tube is SrCeO 3 nanometer having an outer diameter of 5-10 nm, an inner diameter of 2-6 nm, and a length of 20-100 nm.
  • the proton conductive auxiliary agent is one or more of phosphotungstic acid, silicotungstic acid, zirconium phosphate, phosphomolybdic acid, and bismuth hydrogen sulfate.
  • the invention discloses a preparation method of a nano ceramic fiber tube fuel cell proton exchange membrane, and the specific preparation steps thereof are as follows:
  • the nano-ceramic proton conductive fiber obtained in the step 1) is added to 15-30 parts by weight of the ceramic precursor sol solution, and uniformly dispersed in the solution to form a sol-like casting solution;
  • the casting solution obtained in the step 2) is formed into a film blank having a thickness of less than 1 mm by grouting or casting.
  • the ceramic precursor is an alumina ceramic precursor, a zirconia ceramic precursor, a magnesia ceramic precursor, a calcium oxide ceramic One of a precursor, a cerium oxide ceramic precursor, and a zinc oxide ceramic precursor.
  • the nano ceramic fiber tube is a nano-scale fiber tube prepared by proton conductive ceramics. Due to nanocrystallization and fiberization, the proton conductivity and toughness of the fiber tube are improved, and the proton exchange membrane can improve the proton exchange membrane. Conductivity and toughness; the invention is selected to have high temperature resistance, stable performance and proton conduction
  • the nano ceramic fiber tube is used as a carrier material, and the proton conductive auxiliary agent is deposited in the nano ceramic fiber tube through the adsorption, ultrasonic vibration and evaporation of the nano ceramic fiber tube to form a nano ceramic fiber tube as a sleeve.
  • the proton conductive auxiliary agent is a nano-ceramic proton conductive fiber body of the die, which provides a channel for rapid migration and conduction of protons, thereby effectively improving the proton conductivity of the material; and then mixing with the ceramic precursor sol solution to form a casting solution,
  • a proton exchange membrane with high temperature resistance, long service life, good toughness and high proton conductivity is prepared by molding and sintering process, and the method can be mass-produced industrially and has stable quality, and is suitable for the promotion and application of fuel cells.
  • the invention adopts a nano ceramic proton conductive fiber with high proton conductivity as a tube sleeve and a proton conductive auxiliary agent as a tube core, and is prepared as a proton conductive material prepared with a proton exchange membrane.
  • the proton exchange membrane has the advantages of good toughness and high proton conductivity.
  • the proton exchange membrane prepared by the invention is a pure inorganic material proton exchange membrane, which has the advantages of high temperature resistance and long service life. 3.
  • the preparation method of the invention is simple and convenient, low in cost, and can be mass-produced industrially, quality. Stable, suitable for the promotion and application of fuel cells.
  • the SrCeO 3 nano-ceramic proton conductive fiber obtained in the step 1) is added to 30 parts by weight of the alumina ceramic precursor sol solution, and uniformly dispersed in the solution to form a sol-like casting solution. :
  • the film blank having a thickness of 0. 8mm is formed by a grouting or casting.
  • the CaZrO 3 nano-ceramic proton conductive fiber obtained in the step 1) is added to 30 parts by weight of the zirconia ceramic precursor sol solution, and uniformly dispersed in the solution to form a sol-like casting solution. ;
  • the casting solution obtained in the step 2) is formed by grouting or casting to form a film blank having a thickness of lmm;
  • Embodiment 3 [0034] 1) 28 parts by weight of zirconium phosphate was completely dissolved in an evaporator with an appropriate amount of deionized water, 46 parts by weight of a SrZrO 3 nano ceramic fiber tube was added, stirred at a speed of 280 r/min, and an ultrasonic oscillator was used. for shock, while heating evaporation process, zirconium phosphate is deposited. 3 SrZrO nano ceramic fiber tube under the effect of suction. 3 SrZrO nano ceramic fiber tube, ultrasonic vibration, the three evaporation deposition, SrZrO formed having high proton conductivity 3 nanometer ceramic proton conductive fiber body;
  • the SrZrO 3 nano-ceramic proton conductive fiber obtained in the step 1) is added to 20 parts by weight of the cerium oxide ceramic precursor sol solution, and uniformly dispersed in the solution to form a sol-like casting solution. ;
  • the film blank having a thickness of 0. 5mm is formed by a grouting or casting.
  • the KTaO 3 nano-ceramic proton conductive fiber obtained in the step 1) is added to 20 parts by weight of the magnesia ceramic precursor sol solution, and uniformly dispersed in the solution to form a sol-like casting solution. ;
  • the film blank having a thickness of 0. 7mm is formed by a grouting or tape casting.
  • the LaScO 3 nano-ceramic proton conductive fiber obtained in the step 1) is added to 25 parts by weight of the calcium oxide ceramic precursor sol solution, and uniformly dispersed in the solution to form a sol-like casting solution. 6 ⁇ : [0046]
  • the film blank obtained by the step 2) is formed into a film thickness of 0. 6mm by grouting or casting.
  • the nano ceramic fiber tube is a nano-scale fiber tube prepared by proton conductive ceramics. Due to nanocrystallization and fibrosis, the proton conductivity and toughness of the fiber tube are improved, and the proton exchange membrane can improve the proton exchange membrane.
  • Conductivity and toughness The present invention selects a nano ceramic fiber tube having high temperature resistance, stable performance and proton conductivity as a carrier material, and proton conduction through the adsorption, ultrasonic oscillation and evaporation of the nano ceramic fiber tube.
  • the auxiliary agent is deposited in the nano ceramic fiber tube to form a nano ceramic proton conductive fiber body with a nano ceramic fiber tube as a sleeve and a proton conductive auxiliary agent as a core, which provides a channel for rapid migration and conduction of protons, thereby effectively
  • the proton conductivity of the material is improved: and the casting solution is formed by mixing with the ceramic precursor sol solution, and a proton exchange membrane having high temperature resistance, long service life, good toughness and high proton conductivity is prepared by molding and sintering process. And the method can be mass-produced industrially, with stable quality and suitable for burning Promotion and application of battery.

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Abstract

一种纳米陶瓷纤维管燃料电池质子交换膜及制备方法。本发明选取具有耐高温、性能稳定的且具有质子导电性的纳米陶瓷纤维管作为载体材料，形成以纳米陶瓷纤维管为管套，质子导电辅助剂为管芯的纳米陶瓷质子导电纤维体，为质子的快速迁移和传导提供了通道，从而有效地提高了材料的质子导电性；再与陶瓷前驱体溶胶溶液混合形成铸膜液，通过成型和烧结工艺制备得到一种耐高温，使用寿命长，韧性好，质子导电率高的的质子交换膜，且该方法能大规模工业化生产，质量稳定，适合燃料电池的推广应用。

Description

说明书 发明名称： 一种纳米陶瓷纤维管燃料电池质子交换膜及制备方法 技术领域
[0001] 本发明涉及燃料电池质子交换膜领域， 具体涉及一种纳米陶瓷纤维管燃料电池 质子交换膜及制备方法。
背景技术
[0002] 质子交换膜是质子交换膜燃料电池 (PEMFC)中的关键部件之一， 是一种致密的 质子选择透过的功能膜，起着分隔燃料和氧化剂 ，防止它们直接发生反应作用； 同时也起着传导质子对电子绝缘的作用，其性能的优劣直接影响电池的性能、 能 量转化效率和使用寿命。 现在广泛研宄和商业上使用的大部分都是聚合物高分 子类的质子交换膜， 如全氟质子交换膜、 非氟质子交换膜、 非全氟质子交换膜 ； 虽然这类的质子交换膜具有质子电导率优异、 甲醇透过率低、 成膜简单的优 点， 但聚合物高分子材料本身具有的易降解、 原材料来源少、 合成工艺复杂、 化学性能较活泼的性能， 因而导致其制备得到质子交换膜存在成本高昂、 不耐 高温和使用寿命短的重大缺陷， 从而制约了质子交换膜的大规模生产和利用， 也导致质子交换膜燃料电池的市场推广和应用受到限制。 虽然针对目前聚 合物高分子质子交换膜存在的问题， 在现有的聚合物高分子膜基础上进行了诸 多改进， 但却并不能很好的解决其存在的缺陷， 而具有的低廉的成本、 超高的 工作温度和长久的工作寿命等优点的陶瓷质子交换膜受到关注， 但传统的陶瓷 质子交换膜也存在其自身的缺陷， 如质子电导率低、 成膜困难、 易碎， 所以， 寻求一种新的改性技术或新型陶瓷质子交换膜成为改善或解决现今聚合物高分 子和传统陶瓷质子交换膜存在的缺陷具有重要意义。
[0003] 中国专利公开号 CN101773792A公开了一种燃料电池用无机金属氧化物掺杂含氟 质子交换膜及其制备方法。 该含氟质子交换膜， 其中无机金属离子以离子导电 陶瓷为载体均匀分散在含氟离子交换树脂中， 该发明制备的燃料电池用质子交 换膜具有较高的电导率和机械强度， 利于提高燃料电池的性能， 但由于依然采 用的含氟离子交换树脂作为质子交换膜的基体树脂， 导致其使用温度和使用寿 命均未得到提高， 因而该方法不适合大规模的市场应用。
[0004] 中国专利公开号 CN102800881A公开了一种燃料电池无机质子交换膜的制备方法
， 该方法由于采用了分散剂甲基纤维素醚使得 Zr02在质子交换膜中分散均匀， 从而提高了电池的运行稳定性， 但同样受到甲基纤维素醚在高温条件下的使用 寿命短的限制， 导致该无机质子交换膜的使用寿命短， 因而该方法也不能解决 目前聚合物高分子质子交换膜寿命短的缺陷。
[0005] 根据上述， 现有的质子交换膜都需要聚合物高分子材料的辅助， 因而并不能解 决聚合物高分子的交换膜存在的不耐高温和使用寿命短的缺陷， 且传统的陶瓷 质子交换膜存在质子电导率低， 韧性差的缺陷， 因此， 开发一种具有高质子电 导率、 韧性好， 成膜简单， 并且具有低廉的成本、 超高的工作温度和长久的工 作寿命的新型陶瓷质子交换膜成为推动燃料电池大规模市场应用的关键。 发明概述
技术问题
[0006] 目前高分子质子交换膜存在不耐高温和使用寿命短和传统的陶瓷质子交换膜存 在质子电导率低， 韧性差的缺陷。
问题的解决方案
技术解决方案
[0007] 本发明提出一种纳米陶瓷纤维管燃料电池质子交换膜， 与其它燃料电池质子交 换膜相比， 由于采用耐高温且性能稳定的具有质子导电性的纳米陶瓷纤维管作 为载体材料， 且添加多种辅助材料， 经过多重工艺处理制得质子交换膜， 因而 具有耐高温， 使用寿命长， 韧性好， 质子导电率高的优点。
[0008] 本发明进一步的目的是提供一种纳米陶瓷纤维管燃料电池质子交换膜的制备方 法， 该方法通过浸泡、 分散、 成型、 烧结等工艺制得质子交换膜， 该质子交换 膜具有耐高温， 使用寿命长， 韧性好， 质子导电率高的优点， 满足质子交换膜 在燃料电池上的应用， 且能大规模工业化生产， 质量稳定， 适合燃料电池对的 推广应用。
[0009] 本发明一种纳米陶瓷纤维管燃料电池质子交换膜， 其特征在于含有以纳米陶瓷 纤维管为管套， 质子导电辅助剂为管芯的纳米陶瓷质子导电纤维体。 [0010] 在上述一种纳米陶瓷纤维管燃料电池质子交换膜中， 其中所述的纳米陶瓷纤维 管为外径为 5-10nm， 内径为， 2-6nm, 长度为 20-100nm的 SrCeO 3纳米陶瓷纤维管 、 BaCeO 3纳米陶瓷纤维管、 CaZrO 3纳米陶瓷纤维管、 SrZrO 3
纳米陶瓷纤维管、 BaZrO 3纳米陶瓷纤维管、 KTaO 3纳米陶瓷纤维管、 LaScO 3纳 米陶瓷纤维管、 NdScO 3纳米陶瓷纤维管、 SmScO 3纳米陶瓷纤维管、 GdScO 3纳米 陶瓷纤维管中的一种或多种； 所说的质子导电辅助剂为磷钨酸、 硅钨酸、 磷酸 锆、 磷钼酸、 硫酸氢铯中的一种或多种。
[0011] 本发明一种纳米陶瓷纤维管燃料电池质子交换膜的制备方法， 其具体制备步骤 如下：
[0012] 1)将 20-30重量份的质子导电辅助剂用适量去离子水在蒸发器中完全溶解， 加 入 40-55重量份的纳米陶瓷纤维管， 采用 150-300r/min的速度进行搅拌， 并使用 超声波振荡器进行震荡， 同时加热进行蒸发处理， 使质子导电辅助剂在纳米陶 瓷纤维管的吸附、 超声波振荡、 蒸发析出三者的作用下沉积在纳米陶瓷纤维管 中， 形成具有高质子导电性的纳米陶瓷质子导电纤维体；
[0013] 2 ) 将步骤 1)得到的纳米陶瓷质子导电纤维体加入到 15-30重量份的陶瓷前驱体 溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜液；
[0014] 3 ) 将步骤 2) 得到的铸膜液采用注浆成型或流延成型制成厚度小于 lmm的膜坯
[0015] 4) 将步骤 3) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质子交换膜
[0016] 在上述一种纳米陶瓷纤维管燃料电池质子交换膜的制备方法中， 其中所述的陶 瓷前驱体为氧化铝陶瓷前驱体、 氧化锆陶瓷前驱体、 氧化镁陶瓷前驱体、 氧化 钙陶瓷前驱体、 氧化铍陶瓷前驱体、 氧化锌陶瓷前驱体中的一种。
[0017] 在上述一种纳米陶瓷纤维管燃料电池质子交换膜的制备方法中， 其中所述的热 压烧结中温度为 800-1200°C， 压力为 4-8个正常大气压。
[0018] 纳米陶瓷纤维管是由质子导电陶瓷制备得到的纳米级纤维管， 由于纳米化和纤 维化， 纤维管质子导电性和韧性都得到了提高， 用于质子交换膜， 能提高质子 交换膜的导电性和韧性； 本发明选取具有耐高温、 性能稳定的且具有质子导电 性的纳米陶瓷纤维管作为载体材料， 通过纳米陶瓷纤维管的吸附、 超声波振荡 、 蒸发析出三者的作用使质子导电辅助剂沉积在纳米陶瓷纤维管中， 形成以纳 米陶瓷纤维管为管套， 质子导电辅助剂为管芯的纳米陶瓷质子导电纤维体， 为 质子的快速迁移和传导提供了通道， 从而有效地提高了材料的质子导电性； 再 与陶瓷前驱体溶胶溶液混合形成铸膜液， 通过成型和烧结工艺制备得到一种耐 高温， 使用寿命长， 韧性好， 质子导电率高的的质子交换膜， 且该方法能大规 模工业化生产， 质量稳定， 适合燃料电池的推广应用。
[0019] 表一： 本发明与全氟磺酸燃料电池质子交换膜的性能对比
[] [表 1]
Figure imgf000005_0001
发明的有益效果
有益效果
[0020] 本发明突出的特点在于：
[0021] 1、 本发明采用以纳米陶瓷纤维管为管套， 质子导电辅助剂为管芯的， 具有高 质子导电性的纳米陶瓷质子导电纤维体作为备质子交换膜的质子导电材料， 制 备得到的质子交换膜具有韧性好， 质子导电率高的优点。
[0022] 2、 本发明制得质子交换膜为纯无机材料质子交换膜， 具有耐高温， 使用寿命 长的优点， 3、 本发明制备方法简单方便， 成本低廉， 且能大规模工业化生产， 质量稳定， 适合燃料电池的推广应用。 实施该发明的最佳实施例
本发明的最佳实施方式
[0023] 实施例 1
[0024] 1)将 20重量份的磷钨酸用适量去离子水在蒸发器中完全溶解， 加入 40重量份的 SrCeO 3纳米陶瓷纤维管， 采用 150r/min的速度进行搅拌， 并使用超声波振荡器 进行震荡， 同时加热进行蒸发处理， 使磷钨酸在 SrCeO 3纳米陶瓷纤维管的吸附 、 超声波振荡、 蒸发析出三者的作用下沉积在 SrCeO 3纳米陶瓷纤维管中， 形成 具有高质子导电性的 SrCeO 3纳米陶瓷质子导电纤维体；
[0025] 2) 将步骤 1)得到的 SrCeO 3纳米陶瓷质子导电纤维体加入到 30重量份的氧化铝 陶瓷前驱体溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜液：
[0026] 3) 将步骤 2) 得到的铸膜液采用注浆成型或流延成型制成厚度为 0. 8mm的膜坯
[0027] 4) 将步骤 3) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质子交换膜 发明实施例
本发明的实施方式
[0028] 实施例 2
[0029] 1)将 30重量份的硅钨酸用适量去离子水在蒸发器中完全溶解， 加入 55重量份 的 CaZrO 3纳米陶瓷纤维管， 采用 300r/min的速度进行搅拌， 并使用超声波振荡 器进行震荡， 同时加热进行蒸发处理， 使硅钨酸在 CaZrO 3纳米陶瓷纤维管的吸 附、 超声波振荡、 蒸发析出三者的作用下沉积在 CaZrO 3纳米陶瓷纤维管中， 形 成具有高质子导电性的 CaZrO 3纳米陶瓷质子导电纤维体；
[0030] 2) 将步骤 1)得到的 CaZrO 3纳米陶瓷质子导电纤维体加入到 30重量份的氧化锆 陶瓷前驱体溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜液；
[0031] 3) 将步骤 2) 得到的铸膜液采用注浆成型或流延成型制成厚度为 lmm的膜坯；
[0032] 4) 将步骤 3) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质子交换膜
[0033] 实施例 3 [0034] 1)将 28重量份的磷酸锆用适量去离子水在蒸发器中完全溶解， 加入 46重量份的 SrZrO 3纳米陶瓷纤维管， 采用 280r/min的速度进行搅拌， 并使用超声波振荡器 进行震荡， 同时加热进行蒸发处理， 使磷酸锆在 SrZrO 3纳米陶瓷纤维管的吸附 、 超声波振荡、 蒸发析出三者的作用下沉积在 SrZrO 3纳米陶瓷纤维管中， 形成 具有高质子导电性的 SrZrO 3纳米陶瓷质子导电纤维体；
[0035] 2) 将步骤 1)得到的 SrZrO 3纳米陶瓷质子导电纤维体加入到 20重量份的氧化铍 陶瓷前驱体溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜液；
[0036] 3) 将步骤 2) 得到的铸膜液采用注浆成型或流延成型制成厚度为 0. 5mm的膜坯
[0037] 4) 将步骤 3) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质子交换膜 [0038] 实施例 4
[0039] 1)将 25重量份的磷钼酸用适量去离子水在蒸发器中完全溶解， 加入 45重量份的 KTaO 3纳米陶瓷纤维管， 采用 250r/min的速度进行搅拌， 并使用超声波振荡器进 行震荡， 同时加热进行蒸发处理， 使磷钼酸在 KTaO 3纳米陶瓷纤维管的吸附、 超 声波振荡、 蒸发析出三者的作用下沉积在 KTaO 3纳米陶瓷纤维管中， 形成具有高 质子导电性的 KTaO 3纳米陶瓷质子导电纤维体；
[0040] 2) 将步骤 1)得到的 KTaO 3纳米陶瓷质子导电纤维体加入到 20重量份的氧化镁 陶瓷前驱体溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜液；
[0041] 3) 将步骤 2〕 得到的铸膜液采用注浆成型或流延成型制成厚度为 0. 7mm的膜坯
[0042] 4) 将步骤 3) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质子交换膜 [0043] 实施例 5
[0044] 1)将 30重量份的硫酸氢铯用适量去离子水在蒸发器中完全溶解， 加入 50重量份 的 LaScO 3纳米陶瓷纤维管， 采用 200r/min的速度进行搅拌， 并使用超声波振荡 器进行震荡， 同时加热进行蒸发处理， 使硫酸氢铯在 LaScO 3纳米陶瓷纤维管的 吸附、 超声波振荡、 蒸发析出三者的作用下沉积在 LaScO 3纳米陶瓷纤维管中， 形成具有高质子导电性的 LaScO 3纳米陶瓷质子导电纤维体；
[0045] 2 ) 将步骤 1)得到的 LaScO 3纳米陶瓷质子导电纤维体加入到 25重量份的氧化钙 陶瓷前驱体溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜液； [0046] 3 ) 将步骤 2) 得到的铸膜液采用注浆成型或流延成型制成厚度为 0. 6mm的膜坯
[0047] 4) 将步骤 3) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质子交换膜 工业实用性
[0048] 纳米陶瓷纤维管是由质子导电陶瓷制备得到的纳米级纤维管， 由于纳米化和纤 维化， 纤维管质子导电性和韧性都得到了提高， 用于质子交换膜， 能提高质子 交换膜的导电性和韧性： 本发明选取具有耐高温、 性能稳定的且具有质子导电 性的纳米陶瓷纤维管作为载体材料， 通过纳米陶瓷纤维管的吸附、 超声波振荡 、 蒸发析出三者的作用使质子导电辅助剂沉积在纳米陶瓷纤维管中， 形成以纳 米陶瓷纤维管为管套， 质子导电辅助剂为管芯的纳米陶瓷质子导电纤维体， 为 质子的快速迀移和传导提供了通道， 从而有效地提高了材料的质子导电性： 再 与陶瓷前驱体溶胶溶液混合形成铸膜液， 通过成型和烧结工艺制备得到一种耐 高温， 使用寿命长， 韧性好， 质子导电率高的的质子交换膜， 且该方法能大规 模工业化生产， 质量稳定， 适合燃料电池的推广应用。

Claims

权利要求书
一种纳米陶瓷纤维管燃料电池质子交换膜， 其特征在于含有以纳米陶 瓷纤维管为管套， 质子导电辅助剂为管芯的纳米陶瓷质子导电纤维体 根据权利要求 1所述的一种纳米陶瓷纤维管燃料电池质子交换膜， 其 特征在于所述的纳米陶瓷纤维管为外径为 5-10nm， 内径为 2-6nm, 长 度为 20-100nm的 SrCeO 3纳米陶瓷纤维管、 BaCeO 3
纳米陶瓷纤维管、 CaZrO 3纳米陶瓷纤维管、 SrZrO 3纳米陶瓷纤维管
、 BaZrO 3纳米陶瓷纤维管、 KTaO 3纳米陶瓷纤维管、 LaScO 3纳米陶 瓷纤维管、 NdScO 3纳米陶瓷纤维管、 SmScO 3纳米陶瓷纤维管、 GdScO
3纳米陶瓷纤维管中的一种或多种： 所说的质子导电辅助剂为磷钨酸
、 硅钨酸、 磷酸锆、 磷钼酸、 硫酸氢铯中的一种或多种。
一种纳米陶瓷纤维管燃料电池质子交换膜的制备方法， 其特征在于具 体制各步骤如下：
1)将 20-30重量份的质子导电辅助剂用适量去离子水在蒸发器中完全 溶解， 加入 40-55重量份的纳米陶瓷纤维管， 采用 150-300r/min的速 度进行搅拌， 并使用超声波振荡器进行震荡， 同时加热进行蒸发处理 ， 使质子导电辅助剂在纳米陶瓷纤维管的吸附、 超声波振荡、 蒸发析 出三者的作用下沉积在纳米陶瓷纤维管中， 形成具有高质子导电性的 纳米陶瓷质子导电纤维体；
2 ) 将步骤 1)得到的纳米陶瓷质子导电纤维体加入到 15-30重量份的陶 瓷前驱体溶胶溶液中， 并使其均匀分散在溶液中， 形成溶胶状的铸膜 液；
3 ) 将步骤 2 ) 得到的铸膜液采用注浆成型或流延成型制成厚度小于 lm m的膜坯；
4) 将步骤 3 ) 得到的膜胚在氮气的气氛条件下进行热压烧结， 得到质 子交换膜。
根据权利要求 3所述的一种纳米陶瓷纤维管燃料电池质子交换膜的制 备方法， 其特征在于所述的陶瓷前驱体为氧化铝陶瓷前驱体、 氧化锆 陶瓷前驱体、 氧化镁陶瓷前驱体、 氧化钙陶瓷前驱体、 氧化铍陶瓷前 驱体、 氧化锌陶瓷前驱体中的一种。
[权利要求 5] 根据权利要求 3所述的一种纳米陶瓷纤维管燃料电池质子交换膜的制 备方法， 其特征在于所述的热压烧结中温度为 800-1200°C， 压力为 4- 8个正常大气压。
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