CN114853747A - 一种有机热电材料及其制备方法与应用 - Google Patents
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Abstract
Description
技术领域
本发明涉及热电材料技术领域,尤其涉及一种有机热电材料及其制备方法与应用。
技术背景
热电材料是一种通过固体中载流子(电子和空穴)运动实现热能和电能之间直接相互转换的功能材料,在废热回收及绿色制冷领域中具有巨大的应用潜力。目前热电材料的商业化应用主要集中在热电偶控温和半导体制冷。尽管人们一直致力于把热电材料应用到余热发电,以达到节能减排和低碳环保的目的,但较低的热电转换效率仍然是其商业化的主要瓶颈。
目前研究的热电材料主要是掺杂的半导体以及半金属,包括无机和有机热电材料。无机材料由于具有较高的电导率和Seebeck系数,在热电材料领域得到快速发展,部分材料在热电偶控温和半导体制冷等领域已广泛应用。然而,无机材料的热导率普遍较高,且存在毒性、成本高以及难加工的缺点。与无机热电材料相比,有机热电材料具有资源丰富,成本低廉,易合成,易加工成型,环境友好且热导率低等特点而备受关注。然而,较低的热电性能是制约有机热电材料发展与应用的主要因素。通过设计合成具有新型结构的有机共轭分子,结合化学掺杂和物理复合手段是目前提高有机热电材料导电性的主要方法。通过化学掺杂可大幅提高有机材料的导电性,然而Seebeck系数也随之下降,精准控制掺杂程度来获得最优热电性能是一个重要难题。对于有机/无机复合体系,必需使两组分均匀分散、紧密接触从而实现杂化效果,否则复合体系的性能可能无法超越单独组分,难以体现复合体系的优势。有机-无机复合热电体系的关键在于提高两组分之间的相互作用来实现性能优化。研究表明,有机共轭化合物的化学结构(共轭体系、杂原子、侧链等)对热电性能的影响至关重要,通过合成具有新型结构的有机共轭分子,有望获得高性能的热电材料。
然而,目前有机分子的构性关系尚未明确,其设计合成与结构调控方面缺乏指导思想和策略,需要进一步研究。
因此,现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种有机热电材料及其制备方法与应用,旨在解决现有有机热电材料热电性能较差的问题。
本发明的技术方案如下:
中的一种。
一种有机热电材料的制备方法,其中,包括步骤:
在冰浴条件下,将4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基和4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基中的一种,含羧基的噻吩类共轭化合物以及4-二甲氨基吡啶溶解在二氯甲烷溶液中,充分搅拌,得到搅拌液;
再将1-(3-二甲基氨基丙基)-3-乙基碳二亚胺加入到所述搅拌液中,得到混合溶液,将所述混合溶液加热至室温并搅拌20-30h,制得有机热电材料。
一种有机热电材料的应用,其中,将所述有机热电材料用于制备热电器件的薄膜。
一种有机热电材料的应用,其中,将所述有机热电材料与无机热电材料结合用于制备热电器件的复合薄膜。
所述有机热电材料的应用,其中,所述无机热电材料为单壁碳纳米管。
有益效果:本发明设计了一种有机热电材料,所述有机热电材料为一类含氮氧稳定自由基的噻吩类有机共轭化合物,该化合物综合了共轭结构间的π-π相互作用、自由基间相互作用以及π-自由基作用,能促进有机分子间以及有机分子与碳纳米管间的电荷转移和传输,因此将其与单臂碳纳米管(SWCNT)进行物理复合能进一步提高有机复合材料的导电性和热电性能。
附图说明
图1为一种有机热电材料的反应原理图。
图2为本发明实施例1中化合物1的X-射线单晶衍射表征图。
图3为本发明实施例2中化合物2的X-射线单晶衍射表征图。
图4为本发明实施例3中化合物3的X-射线单晶衍射表征图。
图5为本发明实施例4中薄膜的电导率、塞贝克系数以及功率因子测试结果图。
图6为本发明实施例5中薄膜的电导率、塞贝克系数以及功率因子测试结果图。
图7为本发明实施例6中热电器件在不同温度梯度下的输出电压和输出功率图。
具体实施方式
本发明提供了一种有机热电材料及其制备方法与应用,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
有机热电材料具有资源丰富、结构多样、热导率低、可大面积生产且适用于柔性可穿戴电子器件等优点。然而,高导电性、高热电性能的有机热电材料体系依然有限,制约了有机热电材料的发展与商业化应用。
在本实施例中,所述有机热电材料为一类含氮氧稳定自由基的噻吩类有机共轭化合物,该化合物综合了共轭结构间的π-π相互作用、自由基间相互作用以及π-自由基作用,能促进有机分子间以及有机分子与碳纳米管间的电荷转移和传输,因此将其与单臂碳纳米管(SWCNT)进行物理复合能进一步提高有机复合材料的导电性和热电性。
中的一种,但不限于此。
在一些实施方式中,还提供一种有机热电材料的制备方法,其中,包括步骤:
在冰浴条件下,将4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基和4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基中的一种,含羧基的噻吩类共轭化合物以及4-二甲氨基吡啶溶解在二氯甲烷溶液中,充分搅拌,得到搅拌液;
再将1-(3-二甲基氨基丙基)-3-乙基碳二亚胺加入到所述搅拌液中,得到混合溶液,将所述混合溶液加热至室温并搅拌20-30h,制得有机热电材料。
具体来讲,所述有机热电材料的反应原理如图1所示,所述含羧基的噻吩类共轭化合物中的羧基与4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基中的羟基发生缩合反应制得所述有机热电材料,或者所述含羧基的噻吩类共轭化合物中的羧基与4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基中的氨基发生缩合反应制得所述有机热电材料。所述有机热电材料的制备方法简单易操作,且生产效率较高。
在一些实施方式中,还提供一种有机热电材料的应用,将所述有机热电材料用于制备热电器件的薄膜。
在另一实施方式中,还提供一种有机热电材料的应用,将所述有机热电材料与无机热电材料结合用于制备热电器件的复合薄膜。作为举例,所述无机热电材料为单壁碳纳米管。本发明所制备的含自由基侧基的噻吩类有机共轭化合物是一种潜在的有机热电材料,通过碳纳米管对其进行物理复合,可以得到较高的热电性能,实现高效的热电转换效率,有利于推广至热电领域中大规模使用。
下面通过具体实施例对本发明做进一步的解释说明:
实施例1
一种有机热电材料的制备方法,其化学反应过程为:
在0℃水浴中将1.0g噻吩-2-甲酸、2.0g TEMPO-OH、0.3g DMAP(4-二甲氨基吡啶)加到20ml二氯甲烷溶液中搅拌,再往搅拌液中加入1.2g EDC(1-(3-二甲基氨基丙基)-3-乙基碳二亚胺),然后把混合溶液加热至室温,继续搅拌24h。待反应完全后采用对反应液进行萃取,取有机层溶液用无水硫酸铜干燥后除去溶剂,所得残余物用石油醚/乙酸乙酯(5:1)作为洗脱剂通过硅胶柱色谱法纯化,得到1.71g化合物1,产率78%。
实施例2
一种有机热电材料的制备方法,其化学反应过程为:
在0℃水浴中将1.0g苯并[b]噻吩-3-甲酸、1.4g TEMPO-OH、0.2g DMAP加到20ml二氯甲烷溶液中搅拌,再往搅拌液中加入0.9g EDC,然后把混合溶液加热至室温,继续搅拌24h。待反应完全后采用对反应液进行萃取,取有机层溶液用无水硫酸铜干燥后除去溶剂,所得残余物用石油醚/乙酸乙酯(5:1)作为洗脱剂通过硅胶柱色谱法纯化,得到1.65g化合物2,产率87%。
实施例3
一种有机热电材料的制备方法,其化学反应过程为:
在0℃水浴中将1.0g 3,4-噻吩二羧酸、1.5g TEMPO-OH、0.2g DMAP加到20ml二氯甲烷溶液中搅拌,再往搅拌液中加入0.9g EDC,然后把混合溶液加热至室温,继续搅拌24h。待反应完全后采用对反应液进行萃取,取有机层溶液用无水硫酸铜干燥后除去溶剂,所得残余物用石油醚/乙酸乙酯(5:1)作为洗脱剂通过硅胶柱色谱法纯化,得到0.91g化合物3,产率22%。
实施例4
将8mg单壁碳纳米管(SWCNT)和8mL氯苯置于25mL圆底烧瓶中超声5~6h,继而磁力搅拌24h,得到均匀的SWCNT分散液。称取5mg化合物2完全溶解于2mL氯苯中,配置成浓度为2.5mg/mL化合物2溶液。将SWCNT分散液和化合物2溶液按照一定比例混合配置成化合物2的重量百分数分别为20%、40%、60%、80%的2/SWCNT复合材料溶液。采用滴涂的方式将约化合物2/SWCNT复合材料溶液滴到玻璃片上,待溶剂自然风干形成薄膜。测试薄膜的电导率(Electrical Conductivity)、塞贝克系数(Seebeck Coefficient)以及功率因子结果如图5所示,其中化合物2含量在40wt%时,薄膜功率因子(Power Factor)最高,为185.4μW m-1K-2。
实施例5
将8mg单壁碳纳米管(SWCNT)和8mL氯苯置于25mL圆底烧瓶中超声5~6h,继而磁力搅拌24h,得到均匀的SWCNT分散液。称取5mg化合物3完全溶解于2mL氯苯中,配置成浓度为2.5mg/mL化合物3溶液。将SWCNT分散液和化合物3溶液按照一定比例混合配置成化合物3的重量百分数分别为20%、40%、60%、80%的化合物2/SWCNT复合材料溶液。采用滴涂的方式将约化合物3/SWCNT复合材料溶液滴到玻璃片上,待溶剂自然风干形成薄膜。测试薄膜的电导率、塞贝克系数以及功率因子结果如图6所示,其中化合物3含量在40wt%时,薄膜功率因子(Power Factor)最高,为213.2μW m-1K-2。
实施例6
制备化合物3/SWCNT复合材料的热电器件:依次使用丙酮、异丙醇、乙醇将聚酰亚胺柔性衬底(厚度约为125μm)洗净。按照实施案例5中所述的步骤制备化合物3的含量为40wt%的化合物3/SWCNT混合溶液,以滴涂的方式在洗净的聚酰亚胺薄膜上成膜,在室温条件下等待溶剂的自然挥发制备成复合薄膜。将干燥的复合薄膜裁剪成3cm×1cm的矩形,采用铜箔以“头-尾”的方式将10片复合薄膜串联,并在连接处滴加少量银胶以降低接触电阻。通过加热器件的底部来制造温度梯度,采用温度控制器来监控温度,并使用半导体分析系统来测量热电器件在不同温度梯度下的输出电压和输出功率,结果如图7所示,其中温度梯度为60K时,热电器件的输出功率为1.35μW。
综上所述,本发明设计了一种有机热电材料,所述有机热电材料为一类含氮氧稳定自由基的噻吩类有机共轭化合物,该化合物综合了共轭结构间的π-π相互作用、自由基间相互作用以及π-自由基作用,能促进有机分子间以及有机分子与碳纳米管间的电荷转移和传输,因此将其与单臂碳纳米管(SWCNT)进行物理复合能进一步提高有机复合材料的导电性和热电性能。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (6)
3.一种如权利要求1-2任一有机热电材料的制备方法,其特征在于,包括步骤:
在冰浴条件下,将4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基和4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基中的一种,含羧基的噻吩类共轭化合物以及4-二甲氨基吡啶溶解在二氯甲烷溶液中,充分搅拌,得到搅拌液;
再将1-(3-二甲基氨基丙基)-3-乙基碳二亚胺加入到所述搅拌液中,得到混合溶液,将所述混合溶液加热至室温并搅拌20-30h,制得有机热电材料。
4.一种如权利要求1-2任一所述有机热电材料的应用,其特征在于,将所述有机热电材料用于制备热电器件的薄膜。
5.一种如权利要求1-2任一所述有机热电材料的应用,其特征在于,将所述有机热电材料与无机热电材料结合用于制备热电器件的复合薄膜。
6.根据权利要求5所述有机热电材料的应用,其特征在于,所述无机热电材料为单壁碳纳米管。
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