Carbon Nitrides: Metal-free Materials for Energy Applications

氮化碳：用于能源应用的无金属材料

• 批准号: EP/L017091/1
• 负责人: Paul McMillan
• 金额: $ 107.01万
• 依托单位: University College London
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2014
• 资助国家: 英国
• 起止时间: 2014 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FL017091%2F1
• 关键词: Carbon; Nitrides; Metal; free; Materials

Our project aims to develop and optimise a new class of metal-free electroactive graphitic carbon nitride materials (gCNMs) as lithium ion battery (LIB) electrodes, supercapacitors (SC) and fuel cell catalyst supports. These are important energy-related applications. gCNMs are based on layers of sp2-bonded carbon and nitrogen atoms similar to C-graphite or graphene, but they contain voids or channels within and between the layers giving a 3-dimensional character that we will develop here for reversible Li+ intercalation and LIB applications. During proof-of-concept studies supported by a 12-month award from UCL Enterprise we found that the Li+ storage capacity of gCNMs could be competitive with C-graphite (patent application 1311742.9, filed 1/7/13). In this project we will apply a systematic approach combining synthetic chemistry, ab initio theoretical prediction, advanced characterisation and electrochemical testing to control and optimise the potential of gCNMs as LIB electrode materials.The gCNM layers are built from triazine (C3N3) or heptazine (C6N7) units linked by -N= or -NH- groups. Fully condensed structures have composition C3N4: the number of -NH- linkages increases for incomplete polymerisation and this controls the electronic properties as well as voids and channels within and between layers. Non-bonded electron pairs and exchangeable H atoms attached to nitrogen provide charge storage capabilities for metal-free supercapacitors. A second area of our project will optimise gCNMs for SC applications.We will systematically tune the synthesis and processing to control the layer condensation and void arrangements optimised for each application. We will use templates to produce hierarchical structures with controlled porosity and incorporate the materials in electrochemical test devices. We will also build on our observation that gCNMs show promise as catalyst support materials for fuel cell applications. We will optimise the microstructure, surface chemistry and electronic properties to produce a new family of robust and efficient support materials that remain stable over many hundreds of cycles.Our project combines chemistry and chemical engineering approaches leading to design and construction of demonstrator devices. We will work with industrial partners to test and optimise the materials and devices under realistic operating conditions to provide a rapid route to commercialisation. Our gCNMs are physically and chemically compatible with C-based materials in current use and so are compatible with present-day technology. However because of their superior performance they will represent a major step forward in terms of application potential. Our project is designed so that there is constant feedback between prediction-synthesis-testing components of the research to permit efficient and informed identification and optimisation of key materials and properties targets for each application.Our team of researchers is at the forefront of synthesis, characterisation and electrochemical testing of gCNMs and they have patented the first result showing superior performance over C-graphite as LIB electrode materials. They have also observed excellent stability of gCNMs as Pt catalyst support materials for methanol oxidation fuel cells and predicted their action as metal-free supercapacitors. We wish to take advantage of this unique opportunity to build the UK lead in this new area of developing gCNMs for electrochemical applications. The PIs work closely together on several projects that integrate fundamental to applied science and are involved in commercialising products and devices for energy-related applications.

我们的项目旨在开发和优化一种新型的无金属电活性石墨化碳氮化物材料(GCNMs)，作为锂离子电池(Lib)电极、超级电容器(SC)和燃料电池催化剂载体。这些都是与能源相关的重要应用。GCNM是基于类似于C-石墨或石墨烯的sp2键合的碳和氮原子层，但它们在层内和层之间包含空洞或通道，从而提供了我们将在这里开发的用于可逆Li+嵌入和LiB应用的三维特征。在UCL企业公司为期12个月的奖励支持的概念验证研究中，我们发现gCNM的Li+存储容量可以与C-石墨竞争(专利申请1311742.9,2013年1月7日提交)。在这个项目中，我们将应用合成化学、从头算理论预测、高级表征和电化学测试相结合的系统方法来控制和优化作为LiB电极材料的gCNM的电位。gCNM层由三嗪(C3N3)或七嗪(C6N7)单元通过-N=或-NH-基团连接而成。完全凝聚的结构由C3N4组成：由于不完全聚合，-NH-键的数量增加，这控制了层内和层之间的电子性质以及空穴和沟道。无键电子对和氮上可交换的氢原子为无金属超级电容器提供了电荷存储能力。我们项目的第二个领域将优化适用于SC应用的gCNM。我们将系统地调整合成和处理，以控制针对每种应用优化的层冷凝和空穴排列。我们将使用模板来生成孔隙率可控的分层结构，并将这些材料整合到电化学测试设备中。我们还将基于我们的观察结果，即gCNMs在燃料电池应用中显示出作为催化剂载体材料的前景。我们将优化微结构、表面化学和电子性能，以生产一种新的坚固高效的支撑材料家族，这些材料在数百个循环中保持稳定。我们的项目结合了化学和化学工程方法，导致了演示设备的设计和建造。我们将与工业合作伙伴合作，在现实的操作条件下测试和优化材料和设备，以提供一条快速实现商业化的途径。我们的gCNM与当前使用的碳基材料在物理和化学上都是兼容的，因此也与当今的技术兼容。然而，由于它们的卓越性能，它们将在应用潜力方面向前迈进一大步。我们的项目旨在使研究的预测-合成-测试组件之间有持续的反馈，以允许有效和知情地识别和优化每个应用的关键材料和性能目标。我们的研究团队处于gCNM合成、表征和电化学测试的前沿，他们已经为第一个显示出性能优于C-石墨的锂电极材料申请了专利。他们还观察到了作为甲醇氧化燃料电池铂催化剂载体材料的gCNMs的优异稳定性，并预测了它们作为无金属超级电容器的作用。我们希望利用这一独特的机会，在开发用于电化学应用的gCNM这一新领域建立英国的领先地位。PIS在几个项目上密切合作，这些项目整合了应用科学的基础，并参与了能源相关应用的产品和设备的商业化。

项目成果

Electrochemical properties of graphitic carbon nitrides

• DOI: 10.1504/ijnt.2014.063784
• 发表时间: 2014-07
• 期刊: International Journal of Nanotechnology
• 影响因子: 0.5
• 作者: A. B. Jorge;F. Corà;A. Sella;P. McMillan;D. Brett

Pharaoh's Serpents: New Insights into a Classic Carbon Nitride Material

• DOI: 10.1002/zaac.201700268
• 发表时间: 2017-11
• 期刊: Zeitschrift für anorganische und allgemeine Chemie
• 作者: T. Miller;Anita D'Aleo;T. Suter;A. Aliev;A. Sella;P. McMillan

Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging

通过框架充电实现二维晶体氮化碳的快速剥离和功能化

• DOI: 10.1002/ange.201800875
• 发表时间: 2018
• 期刊: Angewandte Chemie
• 作者: Jia J

Graphitic Carbon Nitride Supported Catalysts for Polymer Electrolyte Fuel Cells.

石墨碳支持聚合物电解质燃料电池的催化剂。

• DOI: 10.1021/jp412501j
• 发表时间: 2014-04-03
• 期刊: The journal of physical chemistry. C, Nanomaterials and interfaces
• 作者: Mansor N;Jorge AB;Corà F;Gibbs C;Jervis R;McMillan PF;Wang X;Brett DJ
• 通讯作者: Brett DJ

The Use of Graphitic Carbon Nitride Based Composite Anodes for Lithium-Ion Battery Applications

• DOI: 10.1002/elan.201500205
• 发表时间: 2015-11-01
• 期刊: ELECTROANALYSIS
• 影响因子: 3
• 作者: Miller, Thomas S.;Jorge, Ana Belen;McMillan, Paul F.
• 通讯作者: McMillan, Paul F.