Novel boron-nitrogen coordinated polymers as next-generation n-type thermoelectric materials

新型硼氮配位聚合物作为下一代n型热电材料

• 批准号: 2763714
• 金额: --
• 依托单位: University of Nottingham
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2763714
• 关键词: Novel; boron; nitrogen; coordinated; polymers

Despite the high interest in new, greener energy sources, we are not using our current energy sources efficiently: the amount of waste heat generated in the UK in 2019 equals approximately 10% of the national electricity demand in the same year. In addition to finding new energy sources, recycling unused energy, especially waste heat which is attributed to the majority of the energy loss, is also vital for a more sustainable world in the future. Thermoelectric generators can capture the waste heat and convert it to electricity, hence their importance in contributing to sustainability has been highlighted in recent years. Organic thermoelectric generators, which are built up with organic polymeric p-type and n-type thermoelectric material couples, are more favoured over conventional heavy-metal materials concerning sustainability. Although many good p-type thermoelectric materials are established, a lack of good n-type materials lags the development of organic thermoelectric generators. This is because good n-type materials require low-lying HOMO/LUMO energies and narrow band gaps for effective charge transfers and decent air stabilities. So far only a few groups of compounds meet the criteria. This project will work on a new group of n-type organic thermoelectric materials: boron-nitrogen coordinated polymers. The B-N coordination unit has been applied in several families of electronic materials as an effective way to boost up the electron affinities but has almost not been exploited in the thermoelectric field. Introducing the B-N coordination unit to organic thermoelectric materials may allow us to discover more high-performance n-type thermoelectric materials.This project aims to develop conjugated polymers bearing boron units within the structures that are either novel or yet to be studied as n-type thermoelectric materials. In general, the identified targets will be synthesised, characterised and made into thin films. Intrinsic thermoelectric properties will be measured to determine if targets display good n-type performance. When possible, the developed materials will be paired up with commercially available, high-performance p-type thermoelectric materials, such as PEDOT:PSS, to build proof-of-concept thermoelectric generators to showcase energy harvesting abilities. Approaches towards the targets will be the following four routes, with target novelties and technical difficulties gradually increasing from Route 1 to Route 4:Route 1: Thermoelectric performance of known boron-nitrogen based polymers. Initially published n-type B-N coordinated polymers that have been exploited in fields other than thermoelectric materials but show promising properties (e.g. low-lying frontier orbitals, narrow band gaps) that fit the requirements for good n-type thermoelectric materials will be trialled.Route 2: B-N decoration on known n-type thermoelectric polymers. This route will focus on known examples of n-type thermoelectric polymers and discover the extent of enhancement on the n-type thermoelectric performance by incorporating B-N coordination units into the structures.Route 3: Optimisation on developed targets. Optimisation methods like adding electron-withdrawing groups and extending the length of sidechains are commonly used on n-type thermoelectric materials. Therefore, this route will further optimise the compounds developed from Route 1 and 2 to maximise their performance. Computational calculations (e.g. DFT) will evaluate the design, particularly the HOMO/LUMO levels, before targets are synthesised.Route 4: Polymers bearing other coordination units. In addition to B-N coordination, other types of coordination units, such as B-O, might do a better job than B-N in n-type thermoelectric materials. Likewise, calculations in silico will be done as a proof of concept before synthesis.

尽管对新的，更绿色的能源感兴趣，但我们并未有效地使用我们当前的能源：2019年英国产生的废热量与同年大约10％的国家电力需求相当。除了找到新的能源外，回收未使用的能源，尤其是归因于大部分能源损失的废热，对未来更可持续的世界也至关重要。热电发电机可以捕获废热并将其转换为电力，因此近年来强调了它们在为可持续性促进可持续性方面的重要性。用有机聚合物P型和N型热电材料夫妇构建的有机热电发电机更受到有关可持续性的常规重金属材料的青睐。尽管建立了许多良好的P型热电材料，但缺乏良好的N型材料会落后有机热电发生器的发展。这是因为良好的N型材料需要低洼的均匀/Lumo能量和狭窄的带隙，才能有效地传输和体面的空气稳定性。到目前为止，只有几组化合物符合标准。该项目将在一组新的N型有机热电材料上使用：硼氮协调聚合物。 B-N协调单元已在几种电子材料家族中应用，作为增强电子亲和力的有效方法，但在热电场几乎没有被利用。将B-N协调单元引入有机热电材料可能使我们能够发现更多高性能的N型热电材料。该项目旨在开发具有新颖的结构中的硼隆单元，或者尚未研究为N型PE热电学材料。通常，确定的目标将被合成，表征并制成薄膜。将测量固有的热电特性，以确定目标是否显示出良好的N型性能。在可能的情况下，开发的材料将与市售的高性能P型热电材料（例如PEDOT：PSS）配对，以构建概念验证热电发电机以展示能量收集能力。目标的方法将是以下四个途径，目标新闻和技术困难从1号公路1逐渐增加到4号公路：1号公路：已知的基于硼氮的聚合物的热电性能。最初发表的N型B-N协调聚合物在热电材料以外的其他领域被利用，但显示出有希望的特性（例如，低洼边界轨道，狭窄的频带间隙），这些特性符合良好的N型热电学材料的要求。该路线将重点放在已知的N型热电聚合物的示例上，并通过将B-N配位单元纳入结构3：对已发达目标的优化，发现N型热电性能增强的程度。诸如添加电子吸引电子组和延长Sidechains的长度之类的优化方法通常用于N型热电材料。因此，该路线将进一步优化从1和2公路2开发的化合物，以最大程度地提高其性能。在合成目标之前，计算计算（例如DFT）将评估设计，尤其是HOMO/LUMO水平。ROUTE4：具有其他协调单元的聚合物。除了B-N协调外，其他类型的协调单元（例如B-O）在N型热电材料中的工作可能比B-N更好。同样，在合成之前，计算中的计算将作为概念证明。