CN107665998B - 一种电催化触媒及其燃料电池 - Google Patents
一种电催化触媒及其燃料电池 Download PDFInfo
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Abstract
本发明提供的电催化触媒,包括:含Pd的金属氮化物,且金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合,且Pd与金属的摩尔比大于0且小于或等于0.8。本发明另提供包含上述电催化触媒的燃料电池。
Description
技术领域
本发明涉及电催化触媒及其燃料电池。
背景技术
在能源短缺的现今,寻求替代能源势在必行,其中燃料电池因具备洁净能源的特色而受到各方注目。燃料电池的性能取决于所使用的电催化触媒,因此高性能的电催化触媒材料将是提升燃料电池效能的关键之一。由于现行燃料电池技术所使用的电解质分为酸性、中性与碱性三种环境,在酸性或中性环境下,大多数的金属材料会有被腐蚀的问题,必须要使用抗蚀性较佳且较昂贵的贵金属作为电极,因此降低了电极材料的选择性。而在众多电极材料中,白金(Pt)一直是耐腐蚀性及催化活性佳的电极材料之一,但是其价格相当昂贵,不利于商业化的要求。与之相比,虽然在碱性环境中金属电极较没有腐蚀的问题,选择性也增加许多,但现行非白金电催化触媒材料虽然可具有低成本的优势,但其催化活性及起始氧化电位(Onset potential)却仍不及白金(Pt)。
因此,目前极需开发一种非白金且具有较高起始氧化电位及催化活性的电催化触媒,以提升燃料电池发电效率。
发明内容
本发明一实施例提供的电催化触媒,包括:含Pd的金属氮化物,其中金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合,且金属与Pd的摩尔比大于0且小于或等于0.8。
本发明一实施例提供的燃料电池,包括:阳极;阴极;电解质,设置在阳极及阴极中间;以及电催化触媒层,设置于该阴极与该电解质之间,其中该电催化触媒,包括:含Pd的金属氮化物,其中金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合,且金属与Pd的摩尔比大于0且小于或等于0.8。
具体实施方式
本发明的一实施例为一种电催化触媒,利用钯(Pd)与白金(Pt)的活性相当但价格较为便宜,并结合经ab initio计算模拟选择过的过渡金属,并以组合化学实际验证形成Pd合金氮化反应,设计出具备导电度、电化学活性的电催化触媒,上述电催化触媒,包括含Pd的金属氮化物,其中金属与Pd的摩尔比大于0且小于或等于0.8,且金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合。因为上述电催化触媒具较高的起始氧还原电位及活性,因此在燃料电池运作中受欧姆阻抗及过电位(Overpotential)影响会较小,所产生的额外能量消耗较少,对燃料电池操作效能提升有实质的帮助,可应用于燃料电池领域中。
在一实施例中,上述的电催化触媒,其中金属为Co,且且Ni与Pd的摩尔比大于0且小于或等于0.115。在一实施例中,所述的电催化触媒,其中金属为Fe,且Fe与Pd的摩尔比大于0且小于或等于0.083。在一实施例中,所述的电催化触媒,其中金属为Y,且Y与Pd的摩尔比大于0且小于或等于0.065。在一实施例中,所述的电催化触媒,其中金属为Lu,且Lu与Pd的摩尔比大于0且小于或等于0.034。在一实施例中,所述的电催化触媒,其中金属为Sc,且Sc与Pd的摩尔比大于0且小于或等于0.079。在一实施例中,所述的电催化触媒,其中金属为Ti,且Ti与Pd的摩尔比大于0且小于或等于0.107。在一实施例中,所述的电催化触媒,其中金属为V,且V与Pd的摩尔比大于0且小于或等于0.290。在另一实施例中,所述的电催化触媒,其中金属为Cu,且Cu与Pd的摩尔比大于0且小于或等于0.615。在另一实施例中,所述的电催化触媒,其中金属为Ni,且Ni与Pd的摩尔比大于0且小于或等于0.652。
在电催化触媒的一实施例中,更包括一载体,承载该电催化触媒,上述电催化触媒的材料是以层状或膜状方式形成在该载体之上。在一实施例中,电催化触媒层例如是以干式沉积或湿式沉积形成在载体之上,其中,若以干式沉积,其催化触媒层的组成成分比例较容易控制。
在一实施例中,上述载体材料包括石墨、纳米碳管、碳纤维、碳微球,或其材料的组合。而在另一实施例中,上述载体材料包括金属、导电氧化物、导电氮化物,或其材料的组合。在又一实施例中,上述载体材料包括金属、导电氧化物、导电氮化物的纳米线、纳米微球或其材料的组合。
本发明的另一实施例为一种燃料电池,包括:阳极;阴极;电解质,设置在阳极及阴极中间;以及一电催化触媒层,设置于该阴极与电解质之间;其中,该电催化触媒层包括含Pd的金属氮化物,其中金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合,且金属与Pd的摩尔比大于0且小于或等于0.8。
在燃料电池的一实施例中,上述电催化触媒层形成在该阴极之上。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例作详细说明如下:
【实施例】
实施例1(含Pd的氮化钴电催化触媒的制作及活性测量)
本实施例采用反应磁控溅镀的方法在玻璃碳(glassy carbon,厂商:Pineresearch instrumentation,尺寸:5mm ODx4mm H)上沉积含Pd的氮化钴电催化触媒,其中含Pd的氮化钴触媒是以Pd靶材(厂商:邦杰材料科技股份有限公司)及Co靶材(厂商:邦杰材料科技股份有限公司)共溅镀并通入N2/(Ar+N2)=50%的气体,形成反应式溅镀,并针对Co靶材改变溅镀功率,以获得不同Co/Pd的组成比例,并沉积含Pd的氮化钴电催化触媒层在玻璃碳上,其中氩气及氮气两者相加的总流量为20sccm,溅镀压力控制于20mtorr,制程温度控制为室温,镀膜时间为5-6分钟,控制镀膜厚度约100nm。经EDS的组成分析所得到的含Pd的氮化钴电催化触媒层的Co/Pd原子比为0.005-0.682。
再者,将其不同原子比的含Pd的氮化钴电催化触媒层,进行电化学活性测试,其作法为在0.1M KOH溶液中,使用的参考电极为可逆氢电极(Reversible hydrogenelectrode),扫瞄电压范围:0.079~0.979V,Scan speed:50mV/s,扫瞄次数:10次,然后再进行氧还原反应(ORR:oxygen reduction reaction)的CV及LSV测量,在CV测量部分,在扫瞄电压范围:0.079~0.979V,Scan speed:10mV/s,扫瞄次数:5次;在LSV测量部分,旋转电极设定的转速为1600rpm,在扫瞄电压范围:0.079~1.179V,使用扫瞄速度:10mV/s,扫瞄次数:3次,不同Co/Pd原子比的组成下,含Pd的氮化钴电催化触媒的起始氧还原电位(Ewe(V)vs RHE)与操作电压0.8V下的活性(Activity,mA/mg)整理如表一。
表一(含Pd的氮化钴)
实施例2(含Pd的氮化铁电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Fe靶材(厂商:邦杰材料科技股份有限公司),并针对Fe靶材改变溅镀功率,以获得不同Fe/Pd的组成比例,并沉积含Pd的氮化铁电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化铁电催化触媒的Fe/Pd原子比为0.008-0.377。
再者,将其不同原子比的含Pd的氮化铁电催化触媒,进行与实施例1相同的电化学活性测试,整理如表二。
表二(含Pd的氮化铁)
实施例3(含Pd的氮化钇电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Y靶材(厂商:邦杰材料科技股份有限公司),并针对Y靶材改变溅镀功率,以获得不同Y/Pd的组成比例,并沉积含Pd的氮化钇电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化钇电催化触媒的Y/Pd原子比为0.010-0.188。
再者,将其不同原子比的含Pd的氮化钇电催化触媒,进行与实施例1相同的电化学活性测试,整理如表三。
表三(含Pd的氮化钇)
实施例4(含Pd的氮化镥电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Lu靶材(厂商:邦杰材料科技股份有限公司),并针对Lu靶材改变溅镀功率,以获得不同Lu/Pd的组成比例,并沉积含Pd的氮化镥电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化镥电催化触媒的Lu/Pd原子比为0.010-0.390。
再者,将其不同原子比的含Pd的氮化镥电催化触媒,进行与实施例1相同的电化学活性测试,整理如表四。
表四(含Pd的氮化镥)
实施例5(含Pd的氮化钪电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Sc靶材(厂商:邦杰材料科技股份有限公司),并针对Sc靶材改变溅镀功率,以获得不同Sc/Pd的组成比例,并沉积含Pd的氮化钪电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化钪电催化触媒的Sc/Pd原子比为0.030-0.192。
再者,将其不同原子比的含Pd的氮化钪电催化触媒,进行与实施例1相同的电化学活性测试,整理如表五。
表五(含Pd的氮化钪)
实施例6(含Pd的氮化钛电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Ti靶材(厂商:邦杰材料科技股份有限公司),并针对Ti靶材改变溅镀功率,以获得不同Ti/Pd的组成比例,并沉积含Pd的氮化钛电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化钛电催化触媒的Ti/Pd原子比为0.043-0.408。
再者,将其不同原子比的含Pd的氮化钛电催化触媒,进行与实施例1相同的电化学活性测试,整理如表六。
表六(含Pd的氮化钛)
实施例7(含Pd的氮化钒电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为V靶材(厂商:邦杰材料科技股份有限公司),并针对V靶材改变溅镀功率,以获得不同V/Pd的组成比例,并沉积含Pd的氮化钒电催化触媒层在glassy carbon上,经EDS的组成分析所得到的含Pd的氮化钒电催化触媒的V/Pd原子比为0.013-0.290。
再者,将其不同原子比的含Pd的氮化钒电催化触媒,进行与实施例1相同的电化学活性测试,整理如表七。
表七(含Pd的氮化钒)
实施例8(含Pd的氮化铜电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Cu靶材(厂商:邦杰材料科技股份有限公司),并针对Cu靶材改变溅镀功率,以获得不同Cu/Pd的组成比例,并沉积含Pd的氮化铜电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化铜电催化触媒的Cu/Pd原子比为0.034-0.777。
再者,将其不同原子比的含Pd的氮化铜电催化触媒,进行与实施例1相同的电化学活性测试,整理如表八。
表八(含Pd的氮化铜)
实施例9(含Pd的氮化镍电催化触媒的制作及活性测量)
本实施例采用与上述实施例1相同的电催化触媒的制作方法,差异在于将Co靶材更换为Ni靶材(厂商:邦杰材料科技股份有限公司),并针对Ni靶材改变溅镀功率,以获得不同Ni/Pd的组成比例,并沉积含Pd的氮化镍电催化触媒层在玻璃碳上,经EDS的组成分析所得到的含Pd的氮化镍电催化触媒的Cu/Pd原子比为0.005-0.915。
再者,将其不同原子比的含Pd的氮化镍电催化触媒,进行与实施例1相同的电化学活性测试,整理如表九。
表九(含Pd的氮化镍)
比较例1,Pt/C触媒制作及电化学活性测量:
本比较例采用商品料Pt/C(Pt 50wt%;C 50wt%,型号:TEC10V50E,厂商:Tanaka),将其滴定玻璃碳(5mm ODx4mm H)上烘干成Pt/C触媒层,进行与实施例1相同的电化学活性测试,整理如表九,其结果显示Pt/C触媒具有起始氧还原电位为1.04V,操作电压0.8V下的活性为15.2mA/mg。
比较例2,Pd触媒制作及电化学活性测量:
本比较例采用商品料Pd(厂商:邦杰材料科技股份有限公司),沉积Pd层在玻璃碳(5mm ODx4mm H),进行与实施例1相同的电化学活性测试,整理如表九,其结果显示Pd触媒具有起始氧还原电位为0.94V,操作电压0.8V下的活性为24mA/mg。
比较例3,PdN触媒制作及电化学活性测量:
本比较例采用与上述实施例1相同的Pd靶材,通入N2/(Ar+N2)=50%的气体,形成反应式溅镀,并沉积PdN电催化触媒层在玻璃碳上。进行与实施例1相同的电化学活性测试,整理如表九,其结果显示PdN触媒具有起始氧还原电位为0.97V,操作电压0.8V下的活性为27.4mA/mg。
比较例4,FeN触媒制作及电化学活性测量:
本比较例采用与上述实施例2相同的Fe靶材,通入N2/(Ar+N2)=50%的气体,形成反应式溅镀,并沉积FeN电催化触媒层在玻璃碳上。进行与实施例1相同的电化学活性测试,整理如表九。
比较例5(TiN触媒制作及电化学活性测量)
本比较例采用与上述实施例6相同的Ti靶材,通入N2/(Ar+N2)=50%的气体,形成反应式溅镀,并沉积TiN电催化触媒层在玻璃碳上。进行与实施例1相同的电化学活性测试,整理如表十。
表十(上述实施例1-9及比较例1-5的整理)
从表一至表九显示含Pd的金属氮化物电催化触媒在碱性的环境中,不同金属/Pd原子比的组成下,实施例中含Pd的金属氮化物电催化触媒的电化学的起始氧化电位值随金属含量减低而增加,这是因为Pd-N-金属的电子云及电子组态的变化原因所造成。电子云及电子组态的d轨域中心位置(d-band center position)代表触媒与氧间的键结强弱,如果我们将d轨域中心位置(d-band center position)产生有效地往下调降(downshift),代表可以使整个氧与触媒表面的键结变弱,使氧还原反应(ORR反应)有效进行,有利整个活性向上提升,另外依据the Brewer金属间键结理论(the Brewer intermetallic bondingtheory),通过前期与后期过渡金属的d电子轨域混成(hypo-hyper-d-electronictransition metal),使d电子轨域间增益作用,形成增效作用效应(Synergistic effect),进一步使整个活性有效向上提升,因此可以从不同的金属/Pd原子比的组成下,找出起始氧还原的电位与商用材料Pt/C差不多,但催化活性大于商用材料Pt/C的含Pd的金属氮化物电催化触媒,并整理如表十一。
表十一(催化活性大于商用材料Pt/C的含Pd的金属氮化物电催化触媒)
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (11)
1.一种电催化触媒,为:
Pd与其他金属所形成的氮化物,
其中其他金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合,且其他金属与Pd的摩尔比大于0且小于或等于0.8;
当其他金属为Co时,Co与Pd的摩尔比大于0且小于或等于0.115;
当其他金属为Fe时,Fe与Pd的摩尔比大于0且小于或等于0.083;
当其他金属为Ti时,Ti与Pd的摩尔比大于0且小于或等于0.107;
当其他金属为V时,V与Pd的摩尔比大于0且小于或等于0.290;以及
当其他金属为Ni时,Ni与Pd的摩尔比大于0且小于或等于0.652。
2.如权利要求1所述的电催化触媒,其特征在于,其他金属为Y,且Y与Pd的摩尔比大于0且小于或等于0.065。
3.如权利要求1所述的电催化触媒,其特征在于,其他金属为Lu,且Lu与Pd的摩尔比大于0且小于或等于0.034。
4.如权利要求1所述的电催化触媒,其特征在于,其他金属为Sc,且Sc与Pd的摩尔比大于0且小于或等于0.079。
5.如权利要求1所述的电催化触媒,其特征在于,其他金属为Cu,且Cu与Pd的摩尔比大于0且小于或等于0.615。
6.如权利要求1所述的电催化触媒,其特征在于,其中该电催化触媒承载于一载体上。
7.如权利要求6所述的电催化触媒,其特征在于,该电催化触媒的材料是以层状或膜状方式形成在该载体之上。
8.如权利要求6所述的电催化触媒,其特征在于,该载体材料包括石墨、纳米碳管、碳纤维、碳微球,或其材料的组合。
9.如权利要求6所述的电催化触媒,其特征在于,该载体材料包括金属、导电氧化物、导电氮化物,或其材料的组合。
10.一种燃料电池,包括:
阳极;
阴极;
电解质,设置在阳极及阴极中间;以及
电催化触媒层,设置于该阴极与该电解质之间,其中该电催化触媒,包括:
Pd与其他金属所形成的氮化物,
其中其他金属是Co、Fe、Y、Lu、Sc、Ti、V、Cu、Ni、或上述的组合,且其他金属与Pd的摩尔比大于0且小于或等于0.8;
当其他金属为Co时,Co与Pd的摩尔比大于0且小于或等于0.115;
当其他金属为Fe时,Fe与Pd的摩尔比大于0且小于或等于0.083;
当其他金属为Ti时,Ti与Pd的摩尔比大于0且小于或等于0.107;
当其他金属为V时,V与Pd的摩尔比大于0且小于或等于0.290;
当其他金属为Ni时,Ni与Pd的摩尔比大于0且小于或等于0.652。
11.如权利要求10所述的燃料电池,其特征在于,该电催化触媒层形成在该阴极之上。
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