CN104022295B - 一种直接甲醇燃料电池PdAg/TiO2纳米管电极的制备方法 - Google Patents

一种直接甲醇燃料电池PdAg/TiO2纳米管电极的制备方法 Download PDF

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CN104022295B
CN104022295B CN201410188912.6A CN201410188912A CN104022295B CN 104022295 B CN104022295 B CN 104022295B CN 201410188912 A CN201410188912 A CN 201410188912A CN 104022295 B CN104022295 B CN 104022295B
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CN104022295A (zh
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鞠剑峰
石玉军
高强
吴东辉
苏广均
华平
李建华
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Nantong University
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    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • H01M4/8803—Supports for the deposition of the catalytic active 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
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Abstract

本发明公开了直接甲醇燃料电池纳米PdAg/TiO2纳米管电极及制备方法，产品由钛板阳极氧化先在表面形成纳米管，然后电镀沉积纳米PdAg合金而成。钛板阳极氧化焙烧后在钛板表面形成一薄层高比表面的TiO2纳米管，TiO2纳米管表面电镀沉积的PdAg合金能提高TiO2纳米管的导电性以及PdAg合金对TiO2的协同作用提高TiO2对甲醇的催化氧化性能，同时，甲醇氧化产生的CO等中间产物被吸附、转移到PdAg/TiO2纳米管表面，并被深度氧化为最终产物CO2，可以提高催化剂的抗CO毒化能力，由于PdAg的价格远低于Pt、Ru等贵金属，且在PdAg/TiO2纳米管中量较小，因此可以大大降低催化剂的成本，PdAg/TiO2纳米管电极用作直接甲醇燃料电池阳极，可以提高电池性能。

Description

一种直接甲醇燃料电池PdAg/TiO2纳米管电极的制备方法
技术领域
本发明涉及直接甲醇燃料电池PdAg/TiO2纳米管电极的制备方法。
背景技术
直接甲醇燃料电池(Direct Methanol Fuel Cell,DMFC)具有能耗少、能量密度高、甲醇来源丰富、价格便宜、***简单、运行便捷和噪声低等优点，被认为是未来汽车动力和其它交通工具最有希望的化学电源，引起人们的广泛关注。DMFC最关键的材料之一是电极催化剂，它直接影响电池的性能、稳定性、使用寿命及制造成本。贵金属Pt在低温条件下(小于80℃)具有优异的催化性能，目前DMFC的电极催化剂均以Pt为主要成分，其中PtRu催化剂比纯Pt具有更强的抗CO中毒性能和更高的催化活性，被认为是目前DMFC最佳的催化剂，但是由于其价格昂贵、Ru易溶等缺陷，在DMFC中的利用率还达不到商业化的要求。人们进行了大量研究制备多元复合催化剂以提高其催化活性，提高抗CO毒化能力。TiO2掺杂如PtRuTiOX/C和Au/TiO2PtRu催化剂或作为载体如PtNi/TiO2、PdNi/TiO2、PdAg/TiO2等，可以减少催化剂中贵金属Pt的用量或制备非铂催化剂，降低催化剂制造成本，提高催化性能和抗CO毒化能力，具有应用前景。PdAg/TiO2纳米管电极可作为传感器或直接甲醇燃料电池阳极，对甲醇具有良好的催化性能和抗CO毒化性能，还未见报道。
发明内容
本发明的目的在于提供一种可用作直接甲醇燃料电池阳极，降低直接甲醇燃料电池催化剂成本，提高其催化活性和抗CO毒化能力的直接甲醇燃料电池PdAg/TiO2纳米管电极及制备方法。
本发明的技术解决方案是：
本发明以钛板阳极氧化先在表面形成纳米管，然后电镀沉积纳米 PdAg合金而成。钛板阳极氧化焙烧后在钛板表面形成一薄层高比表面的TiO2纳米管，TiO2纳米管表面电镀沉积的PdAg合金能提高TiO2纳米管的导电性以及PdAg合金对TiO2的协同作用提高TiO2对甲醇的催化氧化性能，同时，甲醇氧化产生的CO等中间产物被吸附、转移到PdAg/TiO2纳米管表面，并被深度氧化为最终产物CO2，可以提高催化剂的抗CO毒化能力，由于PdAg的价格远低于Pt、Ru等贵金属，且在PdAg/TiO2纳米管中量较小，因此可以大大降低催化剂的成本，PdAg/TiO2纳米管电极用作直接甲醇燃料电池阳极，可以提高电池性能。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1：
(1)钛板的前处理：钛板用金相砂纸打磨，丙酮中超声除油15分钟，甲醇或乙醇清洗，1mol/L的HF处理10分钟，二次蒸馏水超声清洗3次，烘干。
(2)TiO2纳米管/Ti的制备：将处理好的钛板在电解液中进行阳极氧化。电解液的组成：0.5％-1％的HF，1mol/L的H2SO4。电解电位20V，电解时间30分钟。电解完毕，去离子水洗涤，烘干，马弗炉中500-600℃焙烧3小时得TiO2纳米管/Ti。
(3)PdAg/TiO2纳米管电极的制备：将制备好的TiO2纳米管/Ti作为阴极进行电镀，镀液的体积为50mL。电镀液的组成：
电镀完毕，去离子水洗涤，烘干，得PdAg/TiO2纳米管电极。
实施例2：
(1)钛板的前处理：钛板用金相砂纸打磨，丙酮中超声除油15分 钟，甲醇或乙醇清洗，1mol/L的HF处理10分钟，二次蒸馏水超声清洗3次，烘干。
(2)TiO2纳米管/Ti的制备：将处理好的钛板在电解液中进行阳极氧化。电解液的组成：0.5％-1％的HF，1mol/L的H2SO4。电解电位20V，电解时间120分钟。电解完毕，去离子水洗涤，烘干，马弗炉中500-600℃焙烧3小时得TiO2纳米管/Ti。
(3)PdAg/TiO2纳米管电极的制备：将制备好的TiO2纳米管/Ti作为阴极进行电镀，镀液的体积为50mL。电镀液的组成：
电镀完毕，去离子水洗涤，烘干，得PdAg/TiO2纳米管电极。
实施例3：
(1)钛板的前处理：钛板用金相砂纸打磨，丙酮中超声除油15分钟，甲醇或乙醇清洗，1mol/L的HF处理10分钟，二次蒸馏水超声清洗3次，烘干。
(2)TiO2纳米管/Ti的制备：将处理好的钛板在电解液中进行阳极氧化。电解液的组成：0.5％-1％的HF，1mol/L的H2SO4。电解电位20V，电解时间60分钟。电解完毕，去离子水洗涤，烘干，马弗炉中500-600℃焙烧3小时得TiO2纳米管/Ti。
(3)PdAg/TiO2纳米管电极的制备：将制备好的TiO2纳米管/Ti作为阴极进行电镀。电镀液的组成：
电镀完毕，去离子水洗涤，烘干，得PdAg/TiO2纳米管电极。

Claims (1)

1.一种直接甲醇燃料电池PdAg/TiO2纳米管电极的制备方法，其特征在于，所述的制备方法包括下列步骤：
(1)钛板的前处理：钛板用金相砂纸打磨，丙酮中超声除油15分钟，甲醇或乙醇清洗，1mol/L的HF处理10分钟，二次蒸馏水超声清洗3次，烘干；
(2)TiO2纳米管/Ti的制备：将处理好的钛板在电解液中进行阳极氧化；电解液的组成：0.5％-1％的HF，1mol/L的H2SO4，电解电位20V，电解时间30-120分钟；电解完毕，去离子水洗涤，烘干，马弗炉中500-600℃焙烧3小时得TiO2纳米管/Ti；
(3)PdAg/TiO2纳米管电极的制备：将制备好的TiO2纳米管/Ti作为阴极进行电镀，镀液的体积为50mL，电镀液的组成：
电镀完毕，去离子水洗涤，烘干，得PdAg/TiO2纳米管电极。
CN201410188912.6A 2014-05-07 2014-05-07 一种直接甲醇燃料电池PdAg/TiO2纳米管电极的制备方法 Expired - Fee Related CN104022295B (zh)

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