晶相锂离子导体Li-O-H-X (X = Cl, Br) 的高温高压制备及电化学性能研究

能源是社会和经济发展的基础，近些年来，全球对传统化石能源的消耗不断增加，导致了一系列资源耗尽、环境污染和生态破坏等关系到社会持续发展和人 类生存的严重问题，因此我们需要最大程度地利用好地球上的可再生能源并且开 发新型绿色能源。然而，这些能源具有很大的不可控性，而且它们的高效储存也是一大挑战，所以开发新的储能技术迫在眉睫。在电化学储能技术中，固态锂离子电池是一类十分有应用前景的新型电池技术，具有十分可靠的安全性、较长的使用寿命以及优异的离子传输能力等优势。固态电池的性能主要取决于固态电解 质的性能，发展高性能固态电解质是当前固态电池领域亟待解决的问题。其中， 具有反钙钛矿结构的超离子导体Li₃OX和Li₂OHX（X = Cl, Br）被认为是一种极 具潜力的固态电解质，但是在合成制备、室温锂离子电导率等方面仍有较大的缺陷。本论文采用高温高压的方法制备Li₃OBr和Li₂OHCl(Br)，并对Li₂OHCl(Br)进行S元素和F元素的掺杂取代。结果表明，高压下仍然很难得到立方Li₃OBr纯相， 并且在高温下会催生出Li-O-Br体系中的两种新型结构相Li₄OBr2（四方相）和 Li₅OBr₃（六方相）。通过改变压力和温度会导致Li₃OBr-Li₄OBr₂-Li₅OBr₃之间的相转变，进一步研究了不同温压条件对于Li-O-Br体系中化合物相平衡的影响。 Li₂OHCl在高温下呈现立方相，但在27 ℃~37 ℃之间会存在立方相到正交相的转变，导致室温离子导率大幅度降低。而在高温高压和元素掺杂的作用下， Li₂OHCl的相转变温度大大降低，在0 ℃仍然保持立方相结构，导致离子导率相比于文献中提升了4个数量级，活化能也有较大程度的改善。由于Li₂OHBr室温不发生相转变，S元素掺杂后离子导率提升近1个量级，但迁移势垒都有改善。 在高温高压和元素掺杂的作用下，Li₃OBr和Li₂OHCl的结构均有所变化，由此对离子传输提供了良好的通道，促进锂离子扩散和迁移。

Energy powers social and economic development. In recent years, the global consumption of traditional fossil fuel has been rapidly increasing, leading to series of problems such as resource depletion, environmental pollution and ecological destruction. Therefore, it is imperative to harvest the renewable energy on earth and develop novel green energy. However, these energy sources are highly uncontrollable, and their efficient storage is also a major challenge, so the development of new energy storage technologies is much desired. In electrochemical energy storage technology, solid-state lithium-ion battery has become a promising new technology because of its high security and durability and excellent energy density. The overall performance of solid-state battery strongly depends on the properties of solid electrolytes, and there is an urgent need to develop solid-state electrolyte materials with excellent performance. Among them, Li₃OX and Li₂OHX (X = Cl, Br) with anti-perovskite structure are regarded as promising solid electrolytes, but their preparation procedure and room-temperature lithium-ion conductivity remain unsatisfactory. In this paper, crystalline phases Li₃OX and Li₂OHX (X = Cl, Br) were prepared by high-pressure synthesis method. In addition, the halogen elements in Li₂OHX were partially replaced by sulfur and fluorine to improve their ionic conductivities. Results show that it is still difficult to obtain the pure phase of cubic Li₃OX under high pressure and relatively low temperature. Raising temperature at high pressure led to the formation of two new crystalline phases Li₄OBr₂ (tetragonal structure) and Li₅OBr₃ (hexagonal structure) in Li-O-Br system. By changing pressure and temperature, the phase transitions among Li₃OBr, Li₄OBr₂, and Li₅OBr₃ were examined. I further studied the influence of different P-T conditions on the thermodynamic equilibrium of various crystalline compounds in Li-O-Br system. It has been reported that Li₂OHCl adopts a cubic structure (Pm3m) at high temperature and changes to an orthorhombic structure (Pmc2) between 27 ℃ and 37 ℃, leading to a large decrease in its room-temperature ionic conductivity. However, with high-pressure synthesis and elemental doping, the transition temperature of Li₂OHCl is greatly reduced, and the cubic structure is maintained at 0 ℃. As a result, the ionic conductivity at room temperature is 4 orders of magnitude higher than the reported value for Li₂OHCl with an orthorhombic structure, and the activation energy is also greatly improved. In contrast, though Li₂OHBr does not undergo structural transformation at room temperature, the ionic conductivity is also significantly improved after doping with S, and so is the migration barrier. The cell parameters for both Li₃OBr and Li₂OHCl has undergone significant changes after S doping, thus providing good pathways for ion transport and facilitating the diffusion and migration of lithium ions.

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