CN103943869B - 一种石墨涂覆纸负载NiAu薄膜电极材料的制备方法 - Google Patents

一种石墨涂覆纸负载NiAu薄膜电极材料的制备方法 Download PDF

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CN103943869B
CN103943869B CN201410105310.XA CN201410105310A CN103943869B CN 103943869 B CN103943869 B CN 103943869B CN 201410105310 A CN201410105310 A CN 201410105310A CN 103943869 B CN103943869 B CN 103943869B
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王贵领
张栋铭
潘越
曹殿学
徐阳
闫鹏
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Heilongjiang hachang carbon material technology Co.,Ltd.
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Abstract

本发明提供的是一种石墨涂覆纸负载NiAu薄膜电极材料的制备方法。用粘土做固化剂，将粘土与石墨均匀混合后涂覆于普通纸张表面；将5～5.5g？NH4Cl及1～1.5g？NiCl2溶于50mL水中制成电沉积液；在电沉积液中将涂有石墨的纸在1.0V电压下保持20～30min，以活化涂覆的石墨，然后在-1.0V下电沉积Ni160～180min，得到纸-石墨-Ni薄膜电极；将纸-石墨-Ni薄膜电极在1mmol·L-1的HAuClO4溶液中静置2～4分钟，得到纸-石墨-NiAu薄膜电极。本发明用石墨涂覆纸，将Ni电沉积于导电的涂覆石墨的纸的表面，再以Au置换部分Ni制备铅笔涂覆纸负载NiAu催化剂，提高直接硼氢化物燃料电池阳极催化性能的方法。解决了硼氢化钠燃料电池阳极活性差的问题。

Description

一种石墨涂覆纸负载NiAu薄膜电极材料的制备方法
技术领域
本发明涉及的是一种薄膜电极材料的制备方法，具体地说是一种以石墨涂覆纸负载NiAu催化硼氢化物电氧化性能的方法。
背景技术
直接硼氢化钠燃料电池(DBFC)是以溶于碱性电解质溶液中的NaBH4直接作为燃料的燃料电池。硼氢化钠是含氢量很高（固体为11wt.%，饱和硼氢化钠溶液为7.4wt.%）的储氢材料。硼氢化钠比压缩氢和液化氢有较大体积的储氢能力。NaBH4比甲醇的氧化动力学快，能量密度和电池电压也优于甲醇。NaBH4不易燃、毒性低、无污染、不产生CO2，仅具有弱腐蚀性，所以装置简单、体积小、储运方便，可免除***的危险性，安全性能较为优越。硼氢化钠可用溶液或固体形式保存，在碱性溶液中可稳定存在数月。催化剂和反应产物可以循环使用，NaBH4水解的唯一副产物NaBO2对环境无毒害作用，并且还可以作为合成NaBH4的原材料，从而实现资源的循环利用。DBFC可在环境温度下工作，电池因而容易启动。从工程学角度考虑，NaBH4溶液能充当热交换介质来冷却电池而无须额外的冷却板；水的电渗拖曳可用做阴极反应物，而无须像氢气和空气那样需要润湿；这些特性对于燃料电池的设计是有益的。
理论上NaBH4的直接电氧化可为8e-反应，参见（1）式：
BH4 -+8OH-→BO2 -+4H2O+8e-(1)
DBFC理论上NaBH4可以使用非铂催化剂，NaBH4电氧化催化剂主要分为两大类，一类是Pt、Pd、Au、Ir等贵金属，其中Pt的电催化活性最高，但也易于发生NaBH4的水解反应，参见（2）式：
NaBH4+2H2O→4H2+NaBO2(2)
可参阅KuiCheng;DianxueCao;FanYang;DongmingZhang;PengYan;JinlingYin;guilingwang.Pddopedthree-dimensionalporousNifilmsupportedonNifoamanditshighperformancetowardsNaBH4electrooxidation.JournalofPowerSources,2013,242:141-147，以及CaoDianxue,GaoYinyi,WangGuiling,MiaoRongrong,LiuYao.AdirectNaBH4–H2O2fuelcellusingNifoamsupportedAunanoparticlesaselectrodes.InternationalJournalofHydrogenEnergy,2010,35:807–813.。
发明内容
本发明的目的在于提供一种能提高直接硼氢化物燃料电池阳极催化性能，解决硼氢化钠燃料电池阳极活性差的问题的石墨涂覆纸负载NiAu薄膜电极材料的制备方法。
本发明的目的是这样实现的：
本发明的目的是这样实现的：
（1）用粘土做固化剂，将粘土与石墨均匀混合后涂覆于普通纸张表面；
（2）将5～5.5gNH4Cl及1～1.5gNiCl2溶于50mL水中制成电沉积液；
（3）在电沉积液中将涂有石墨的纸在1.0V电压下保持20～30min，以活化涂覆的石墨，然后在-1.0V下电沉积Ni160～180min，得到纸-石墨-Ni薄膜电极；
（4）最后将纸-石墨-Ni薄膜电极在1mmolL-1的HAuClO4溶液中静置2～4分钟，得到纸-石墨-NiAu薄膜电极，即石墨涂覆纸负载NiAu催化剂。
本发明用石墨涂覆纸，将Ni电沉积于导电的涂覆石墨的纸的表面，再以Au置换部分Ni制备铅笔涂覆纸负载NiAu催化剂，提高直接硼氢化物燃料电池阳极催化性能的方法。克服了集流体价格高，以及硼氢化钠分解等缺点，解决了硼氢化钠燃料电池阳极活性差的问题。
本发明的实质是采用硼氢化钠燃料电池等的电池结构，以石墨涂覆纸负载NiAu为催化剂，构成燃料电池的阳极。
本发明的优点在于利用石墨涂覆纸负载NiAu催化剂作为硼氢化钠直接电氧化的催化剂，解决了硼氢化物燃料阳极放电电流小和易于水解等问题。本电极材料制备中不使用粘结剂，更重要的是在电场作用下石墨与粘土能与Ni和Au形成纸-石墨-粘土-NiAu的交联化合物，不仅导电性好，而且电催化活性高。纸负载NiAu催化剂不但石墨、粘土、Ni的储量极其丰富易得，价格低廉，大大降低了电极制备成本，而且其催化活性高，性能稳定，制备过程容易，适合工业化生产，具有工业应用前景与市场价值。
具体实施方式
为了更好地说明本发明工艺的效果，下面以具体实例加以说明。
（1）取普通纸一张，用粘土做固化剂与石墨均匀混合后涂覆于纸表面，取1×1cm-2作为研究电极；（2）将5gNH4Cl及1gNiCl2溶于50mL水中，用于恒电位法电沉积Ni。（3）将涂有石墨的纸在1.0V电压下保持20～30min，以活化涂覆的石墨，然后在-1.0V下电沉积Ni160～180min，得到纸-石墨-Ni薄膜电极。（4）最后将纸-石墨-Ni薄膜电极在1mmolL-1的HAuClO4溶液中静置2～4分钟，得到纸-石墨-NiAu薄膜电极，即石墨涂覆纸负载NiAu催化剂。
对纸-石墨-NiAu薄膜电极进行如下性能测试：
1、以纸-石墨-NiAu薄膜为工作电极，碳棒为对电极，以Ag/AgCl为参比电极，在1mol/L的NaOH和0.10mol/L的NaBH4的溶液中，-0.4Vvs.Ag/AgCl的电压下，计时电流密度达120mA/cm2。
2、以纸-石墨-NiAu薄膜为工作电极，碳棒为对电极，以Ag/AgCl为参比电极，在2M的NaOH和0.50M的NaBH4的溶液中，-0.4Vvs.Ag/AgCl的电压下，计时电流密度达350mA/cm2。
3、利用纸-石墨-NiAu薄膜催化NaBH4电氧化为阳极，3mol/L的KOH为阳极电解质溶液，1mol/L的硼氢化钠为燃料；以泡沫镍上负载的纳米Pd催化H2O2直接电还原为阴极，以3mol/L的KOH和0.6mol/L-1H2O2作为阴极电解液；Nafin-115质子交换摸作为隔膜；电池的最大功率密度为245mW/cm-2。

Claims (1)

1.一种纸-石墨-NiAu薄膜电极材料的制备方法，其特征是：
(1)用粘土做固化剂，将粘土与石墨均匀混合后涂覆于普通纸张表面得到涂有石墨的纸；
(2)将5～5.5gNH4Cl及1～1.5gNiCl2溶于50mL水中制成电沉积液；
(3)在电沉积液中将步骤(1)得到的涂有石墨的纸在1.0V电压下保持20～30min，以活化涂覆的石墨，然后在-1.0V下电沉积Ni160～180min，得到纸-石墨-Ni薄膜电极；
(4)最后将纸-石墨-Ni薄膜电极在1mmol·L-1的HAuClO4溶液中静置2～4分钟，得到纸-石墨-NiAu薄膜电极。
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