酞菁类配合物的合成及其对锂/亚硫酰氯电池催化活性研究
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摘要
本论文设计合成了四大系列二十二种酞菁类配合物,探讨了不同系列、不同金属对锂／亚硫酰氯(Li／SOCl2)电池放电性能的影响。
采用固相熔融法合成了氯代单核(MPcCl16)、双核(M2Pc2Cl24)金属酞菁及同核、异核双金属(M2Pc2)酞菁配合物,采用溶剂法合成了四-α-(8-喹啉氧基)酞菁锌(α-(QO)4PcZn)配合物,对所有配合物进行元素分析,红外吸收光谱、紫外吸收光谱表征并对部分配合物进行了热重分析。
对上述所有配合物进行电性能测试,并根据所得的电池放电电压与放电时间之间的关系,推导所对应的电池能量及电池容量等方面性能的变化,以及对部分酞菁类配合进行循环伏安测试,来分析催化反应特性,探讨中心金属对电池催化活性的影响。结果发现：对于不同系列的金属酞菁,即使同一中心金属对电池的催化活性也是不一样的,这与酞菁的取代基团、取代基团数目及酞菁环的共轭环境有关。
本论文通过对Li／SOCl2正极碳膜做扫描电镜,对比不同放大倍数下添加了酞菁类催化剂的与未添加的碳膜形貌,发现酞菁类配合物可以使碳膜变得疏松,一定程度上有利于提高电池放电电压,延长放电时间。同时,在酞菁对Li／SOCl2电池的催化机理方面做进一步完善,对于某一种酞菁配合物,当它具有足够数目的活性点并且这些活性点通过协同作用可达到一个恰当的状态时,才会具有良好的催化活性。
除此之外,本文还在培养酞菁晶体方面进行了尝试,期望得到更精确的酞菁配合物结构。
In this thesis, twenty-two phthalocyanine compounds which fall into four categories were designed and prepared. Besides, we discussed the effects of different series and different metals to the discharge characteristic of Li/SOCl2 battery.
Among these phthalocyanine compounds, chloride single-core and double-core metal phthalocyanines which include homonuclear and heteronuclear compounds were prepared by solide-phase melting method, and a-(QO)4PcZn was prepared in solvent. All of the compounds were characterized by Element Analyse, FT-IR, UV-vis and some of them were also characterized dy TGA.
The catalytic activity of all these prepared compounds were evaluated by electrical property test for Li/SOCl2 battery. Besides, some cyclic voltammetry experiments were completed to study the property of the catalystic reaction. As shown in the result, The different substitute group, the amount of substitute group and the conjugated circumstance all will effect the catalytic activity.
The SEM analyse were finished to study the morphology of carbon membrane, the result shown that the carbon membrane were loosen by phthalocyanine compounds, which could increase the discharge voltage of Li/SOCl2 battery. The catalytic mechanism of Li/SOCl2 battery was also investigated. Phthalocyanine compounds will act as efficient active catalyst when they have enough active sites and all these active sites reach a proper state by synergistic effect.
Besides, we designed a lot of experiments to obtain the crystal of the phthalocyanine compounds, which could study the accurate molecular structures of the catalysts.
采用固相熔融法合成了氯代单核(MPcCl16)、双核(M2Pc2Cl24)金属酞菁及同核、异核双金属(M2Pc2)酞菁配合物,采用溶剂法合成了四-α-(8-喹啉氧基)酞菁锌(α-(QO)4PcZn)配合物,对所有配合物进行元素分析,红外吸收光谱、紫外吸收光谱表征并对部分配合物进行了热重分析。
对上述所有配合物进行电性能测试,并根据所得的电池放电电压与放电时间之间的关系,推导所对应的电池能量及电池容量等方面性能的变化,以及对部分酞菁类配合进行循环伏安测试,来分析催化反应特性,探讨中心金属对电池催化活性的影响。结果发现：对于不同系列的金属酞菁,即使同一中心金属对电池的催化活性也是不一样的,这与酞菁的取代基团、取代基团数目及酞菁环的共轭环境有关。
本论文通过对Li／SOCl2正极碳膜做扫描电镜,对比不同放大倍数下添加了酞菁类催化剂的与未添加的碳膜形貌,发现酞菁类配合物可以使碳膜变得疏松,一定程度上有利于提高电池放电电压,延长放电时间。同时,在酞菁对Li／SOCl2电池的催化机理方面做进一步完善,对于某一种酞菁配合物,当它具有足够数目的活性点并且这些活性点通过协同作用可达到一个恰当的状态时,才会具有良好的催化活性。
除此之外,本文还在培养酞菁晶体方面进行了尝试,期望得到更精确的酞菁配合物结构。
In this thesis, twenty-two phthalocyanine compounds which fall into four categories were designed and prepared. Besides, we discussed the effects of different series and different metals to the discharge characteristic of Li/SOCl2 battery.
Among these phthalocyanine compounds, chloride single-core and double-core metal phthalocyanines which include homonuclear and heteronuclear compounds were prepared by solide-phase melting method, and a-(QO)4PcZn was prepared in solvent. All of the compounds were characterized by Element Analyse, FT-IR, UV-vis and some of them were also characterized dy TGA.
The catalytic activity of all these prepared compounds were evaluated by electrical property test for Li/SOCl2 battery. Besides, some cyclic voltammetry experiments were completed to study the property of the catalystic reaction. As shown in the result, The different substitute group, the amount of substitute group and the conjugated circumstance all will effect the catalytic activity.
The SEM analyse were finished to study the morphology of carbon membrane, the result shown that the carbon membrane were loosen by phthalocyanine compounds, which could increase the discharge voltage of Li/SOCl2 battery. The catalytic mechanism of Li/SOCl2 battery was also investigated. Phthalocyanine compounds will act as efficient active catalyst when they have enough active sites and all these active sites reach a proper state by synergistic effect.
Besides, we designed a lot of experiments to obtain the crystal of the phthalocyanine compounds, which could study the accurate molecular structures of the catalysts.
引文
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