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CN1166019C - 质子交换膜燃料电池纳米电催化剂的制备方法 - Google Patents

质子交换膜燃料电池纳米电催化剂的制备方法 Download PDF

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CN1166019C
CN1166019C CNB011182539A CN01118253A CN1166019C CN 1166019 C CN1166019 C CN 1166019C CN B011182539 A CNB011182539 A CN B011182539A CN 01118253 A CN01118253 A CN 01118253A CN 1166019 C CN1166019 C CN 1166019C
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���Ρ�˹����
邢巍
杜荣兵
陆天虹
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Changchun Institute of Applied Chemistry of CAS
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    • H—ELECTRICITY
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Abstract

本发明属于质子交换膜燃料电池纳米电催化剂的制备方法。提供了一种方便的制备纳米级高活性的直接甲醇质子交换膜燃料电池和氢/氧质子交换膜燃料电池阳极催化剂的方法和有效化学成分及其化学计量。本方法制备的催化剂粒度均匀，粒径约4±0.5纳米，电化学性能优于国际上同类型的商品。

Description

质子交换膜燃料电池纳米电催化剂的制备方法
本发明是关于制备高活性质子交换膜燃料电池电催化剂的方法。
质子交换膜燃料电池是一种新型的直接将化学能转化为电能的装置。由于无转动部件的内能消耗、不经过燃烧，能量转化效率不受卡诺循环限制；采用清洁能源，如氢气、甲醇等，无硫氧化物和氮氧化物排放，无环境危害；适合于移动电源的应用领域，是发展电动车的首选电源。目前，由于技术的不断提高，工业化和实用化日益明朗。它的关键材料之一是电催化剂，其活性直接影响电池性能。E-TEK公司出品的催化剂，是电催化活性和贵金属用量比最佳的商业化催化剂之一。实验室中人们通常用化学还原法制备催化剂，催化剂性能随不同方法有很大区别。(1)浸渍法是制备载体金属催化剂的最常用方法[J.B.Goodenough，A.Hamnett，B.J.Kemmedy，ETC.ElectrochimicaActa，Vol 15，No.1 pp.199-207，1990]。其基本操作过程为，将载体放入金属盐的溶液中充分浸渍，然后加入还原剂还原金属离子。该法主要依靠毛细管作用使液体渗透到载体内部空隙中，使液体中的活性组分在载体上吸附。因此，液体中活性组分在载体上的吸附特性对催化剂的性能有很大影响。(2)金属蒸汽法[吴世华，杨树军，王序昆等，石油化工，18(6)，361，1989]是先将金属汽化，再使金属凝聚到载体表面上，这样可以制备出金属分散度更高，活性更好的催化剂。但该法对设备的要求较高，不易大量制备。(3)金属离子配合物氧化还原法[Masahiro Watanabe，Makoto Uchida，Satoshi Motoo，J.Electroanal.Chem.229(1987)395-406]是将金属离子与还原态配位离子形成配合物，然后加入氧化剂，氧化配体和金属离子，形成亚稳态溶液。一定条件下，加入载体，金属在载体上沉积，形成金属分散度较好，颗粒大小较均一的催化剂。但该法较为繁琐。(4)纳米金属簇合成法是一种全新的方法[Schmidt，M.Noeske，H.A.Gasteiger，R.J.Behm，J.Electrochem.Soc.，Vol.145，No.3，March 1998]，在合适的有机相中，金属离子和还原剂反应，在稳定剂存在条件下，生成纳米金属簇。然后加入载体吸附金属簇，用该法制得的金属催化剂粒径较小，但该法反应条件过于苛刻。一般认为铂微粒应在4纳米范围，呈非晶体状态，催化剂表现的电化学活性最好[MasahiroWatanabe，Makoto Uchida，Satoshi Motoo，J.Electroanal.Chem.229(1987)395-406]。但制备时由于条件控制很苛刻，常规方法一般很难制备微观状态均匀的催化剂。通常由于吸附平衡存在，溶液中的贵金属先被还原，吸附平衡向液相移动，被吸附的贵金属脱附，实际上大部分贵金属的还原是在液相中进行的，这样还原得到的催化剂必然产生金属粒子的聚集、均匀度下降和活性炭承载不佳。
本发明的目的是提供一种质子交换膜燃料电池纳米电催化剂的制备方法，通过控制活性炭对贵金属的吸附，获得贵金属催化剂最佳粒径和晶态，解决了上述方法中的缺陷，在同等条件下进行电化学测试，性能超过E-TEK公司同类商品。
本发明以含有铂或铂和钌的水溶液为原料，铂或铂和钌是以二价或四价离子的铂卤化合物或铂卤化合物和钌卤化合物及其盐的形式存在，加入活性炭吸附贵金属；用一种碱保持原料液的pH值，控制此pH值下的特定吸附状态，用一种化学物质作为还原剂，还原铂和钌金属离子，使还原的金属离子与活性炭沉积复合在一起。确保金属颗粒及其表面状态具有优越的催化活性。
本发明选择的铂卤化合物、钌卤化合物分别是氯化物、溴化物或碘化物。最佳为氯化合物，氯铂酸钠、氯钌酸钠、氯铂酸钾、氯钌酸钾、氯亚铂酸钠、氯亚钌酸钠、氯亚铂酸钾或氯亚钌酸钾的水溶液。
本发明选择铂卤化合物水溶液或铂和钌卤化合物水溶液为原料，其中铂和钌摩尔比为1∶0.2-1，将活性炭用二次蒸馏水配成悬浮液，搅拌，加热到50-65℃；将贵金属溶液加入活性炭悬浮液进行吸附，贵金属含量0.5-10g/l，活性炭量为0.05-2g/l，并用碱溶液调整pH值2.5-10.5，碱为氢氧化钠、氢氧化钾或氢氧化铵之中二种碱的混合溶液，配比均为1∶1；向贵金属活性炭混合液中滴注加入相对贵金属摩尔数过量2.5-5倍的还原剂，还原剂的化学物质为水合肼、硼氢化钠、甲酸中之一的水溶液或氢气，保持温度继续搅拌1小时；温度降到室温时将液体过滤，洗涤，直到其中无Cl-时为止；在60-80℃下真空干燥，得到粒径4±0.5纳米的活性炭载贵金属催化剂。
本方法制备的催化剂与E-TEK催化剂相比，对甲醇和氢的氧化反应的催化活性具有明显的提高。氧化极化曲线测试得知：在相同氧化反应电流密度下，对甲醇氧化的起始电势E负移约110mV，表明本发明催化剂对甲醇氧化反应的活化能大大降低，为提高电池总工作电压提供了110mV的潜力。实际用此催化剂组装的DMFC在同样电流密度下工作，电压比用E-TEK催化剂组装的电池高100mV。催化剂晶体结构X-衍射图表明，自制催化剂和E-Tek催化剂中金属铂的结晶度较小，铂的衍射峰更矮、更宽。表明催化剂中铂的结晶度较低，以晶体形式存在的铂较少。铂表面的活性位多，所以其催化活性更好。高分辨电子显微镜像图表明本发明制备的纳米催化剂粒径均匀，尺度分布在4±0.5纳米，呈非晶态。
本发明中的化合物配方与方法专门适用于制备直接甲醇质子交换膜燃料电池电催化剂。具体地说，本发明的方法包括配备合适的铂或铂/钌水溶液，加入活性炭进行吸附，然后调节其pH值，控制还原温度，逐步加入还原剂，制备成活性炭载的铂或铂/钌纳米微粒。
本发明提供的实施例如下：
实施例1：取0.05g活性炭 用二次蒸馏水配成悬浮液1升，搅拌，加热悬浮液使其达到50℃。滴注氯铂酸溶液，使其铂含量为5g/l，保持1小时后使之被活性炭吸附并达到平衡，用氢氧化钾/氢氧化铵水溶液调节pH值到7.5，将悬浊液搅拌30分钟；加入1g硼氢化钠，保持温度20℃，至活性炭相可以沉淀并溶液相呈无色。将温度降到室温时将液体过滤，并用热水多次洗涤活性炭载还原产物，用氯化银测试，直到其中无Cl-时为止；最后在60℃真空干燥，得到质子交换膜燃料电池用一元电催化剂，催化剂中铂粒径为4±0.5纳米，呈非晶态。
实施例2：其他条件同实施例1，仅改变pH＝10.5，铂含量0.5g/l，以0.25g水合肼为还原剂，反应温度为60℃，得到对H2的氧化反应的一元阳极催化剂。
实施例3：其他条件同实施例1，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝7.0，铂含量5g/l，还原反应过程在连续通氢气下进行，还原反应温度为0℃，得对甲醇的氧化反应的一元催化剂，催化剂中铂粒径为4±0.5纳米，呈非晶态。
实施例4：其他条件同实施例1，仅改变采用氯铂酸/氯钌酸水溶液，其中铂/钌摩尔比为1∶0.5，铂、钌含量为5g/l，用2.5g水合肼为还原剂，得到对甲醇的氧化反应的高催化活性的二元催化剂，与E-TEK催化剂相比，在相同氧化反应电流密度下，对甲醇氧化的起始电位负移110mV。
实施例5：其他条件同实施例4，仅改变用氢氧化钾/氢氧化钠水溶液调节pH＝2.5，采用氯亚铂酸/氯亚钌酸水溶液，其中铂/钌摩尔比为1∶0.2，铂、钌含量0.5g/l，以连续通入的氢气为还原剂，还原反应温度为0℃，得到对甲醇的氧化反应的高催化活性的二元催化剂，与E-TEK催化剂相比，在相同氧化反应电流密度下，对甲醇氧化的起始电势E负移约100mV。
实施例6：其他条件同实施例4，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝5，铂、钌含量10g/l，其中铂/钌摩尔比为1∶0.5，还原剂为12g甲酸，还原反应温度为40℃，得到对甲醇氧化反应的高催化活性的二元催化剂，与E-TEK催化剂相比，在相同氧化反应电流密度下，对甲醇氧化的起始电势E负移约105mV。
实施例7：其他条件同实施例4，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝6.8，采用氯铂酸/氯钌酸水溶液，其中铂/钌摩尔比为1∶1，铂、钌含量5g/l，以连续通入的氢气为还原剂，还原反应温度为40℃，得对H2的氧化反应的高催化活性的二元催化剂，组装成氢/氧燃料电池，与E-TEK催化剂相比，在相同工作电流密度下，工作电压提高80mV。
实施例8：其他条件同实施例4，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝7.5，采用溴铂酸/溴钌酸水溶液，铂、钌含量2g/l，还原剂0.6g硼氢化钠，还原反应温度为30℃，得到对氢的氧化反应的高催化活性的二元催化剂，与E-TEK催化剂相比，组装成氢/氧燃料电池，在相同工作电流密度下，工作电压提高80mV。
实施例9：其他条件实施例4，同仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝8.5，采用溴亚铂酸钠/溴亚钌酸钠水溶液，铂、钌含量1g/l，还原剂为1.2克甲酸，还原反应温度为50℃，得到对氢的氧化反应的高催化活性的二元催化剂，组装成氢/氧燃料电池，与E-TEK催化剂相比，在相同工作电流密度下，工作电压提高80mV。
实施例10：其他条件同实施例4，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝10.5，采用碘铂酸/碘钌酸水溶液，其中铂/钌摩尔比为1∶0.2，铂、钌含量7g/l，还原剂为6g甲酸，还原反应温度为40℃，得到对氢的氧化反应的高催化活性的二元催化剂，组装成氢/氧燃料电池，与E-TEK催化剂相比，在相同工作电流密度下，工作电压提高80mV。
实施例11：其他条件同实施例4，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝6.5，采用碘铂酸钠/亚钌酸钠水溶液，铂、钌含量8g/l，还原剂为6克甲酸，还原反应温度为70℃，得到对氢的氧化反应的高催化活性二元催化剂，组装成氢/氧燃料电池，与E-TEK催化剂相比，在相同工作电流密度下，工作电压提高80mV。
实施例12：其他条件同实施例4，仅改变用氢氧化钠/氢氧化铵水溶液调节pH＝10.5，采用碘亚铂酸钠/碘亚钌酸钠水溶液，铂、钌含量7g/l，还原剂为4.5克甲酸，还原反应温度为50℃，得到对氢的氧化反应的高催化活性的二元催化剂，组装成氢/氧燃料电池，与E-TEK催化剂相比，在相同工作电流密度下，工作电压提高80mV。
实施例13：其他条件同实施例4，仅改变氢氧化钾/氢氧化铵用水溶液调节pH＝10.5，铂、钌含量10g/l，还原剂为8g水合肼，还原反应温度为65℃，得到对甲醇和氢的氧化反应的高催化活性的二元催化剂，组装成氢/氧燃料电池，与E-TEK催化剂相比，在相同工作电流密度下，工作电压提高80mV。
实施例14：其他条件同实施例4，仅改变用氢氧化钾/氢氧化铵水溶液调节pH＝9.5，一边搅拌一边加入氯铂酸/氯钌酸溶液，铂、钌含量8g/l，还原剂为4g水合肼，还原反应温度为65℃，得到对甲醇和氢的氧化反应的高催化活性的二元催化剂，与E-TEK催化剂相比，在相同氧化反应电流密度下，对甲醇氧化的起始电势E负移约100mV。
实施例15：其他条件同实施例4，仅改变用氢氧化钾/氢氧化铵水溶液调节pH＝9.0，一边搅拌一边加入氯铂酸/氯钌酸溶液，铂、钌含量8g/l，还原剂为8克水合肼，还原反应温度为55℃，得到对甲醇和氢的氧化反应的高催化活性的二元催化剂，与E-TEK催化剂相比，在相同氧化反应电流密度下，对甲醇氧化的起始电势E负移约100mV。

Claims (2)

1.一种质子交换膜燃料电池纳米电催化剂的制备方法，其特征在于选择铂卤化合物水溶液或铂卤化合物和钌卤化合物水溶液为原料，其中铂和钌摩尔比为1∶0.2-1，将活性炭用二次蒸馏水配成悬浮液，搅拌，加热到50-65℃；将上述贵金属水溶液加入活性炭悬浮溶液中进行吸附，活性炭量为0.05-2g/l，上述贵金属含量0.5-10g/l；用碱性溶液调整其pH值2.5-10.5，碱为氢氧化钠、氢氧化钾或氢氧化铵之中二种碱的混合溶液，配比为1∶1；向上述贵金属水溶液活性炭混合液中滴注加入相对贵金属摩尔数过量2.5-5倍的还原剂，还原剂的化学物质为水合肼、硼氢化钠、甲酸中之一的水溶液或氢气，保持温度继续搅拌1小时；温度降到室温时对还原后的悬浮溶液进行过滤，洗涤，直到其中无Cl-时为止；在60-80℃下真空干燥，得到粒径4±0.5纳米的活性炭载贵金属催化剂。
2 如权利要求1所述的质子交换膜燃料电池纳米电催化剂的制备方法，其特征在于铂卤化合物、钌卤化合物水溶液分别是氯铂酸和氯钌酸及其碱金属盐氯铂酸钠、氯钌酸钠、氯铂酸钾、氯钌酸钾、氯亚铂酸钠、氯亚钌酸钠、氯亚铂酸钾或氯亚钌酸钾的水溶液。
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