富锂反钙钛矿固态电解质缺陷调控及其全固态电池应用研究

近年来随着新能源汽车市场的快速发展，人们对储能设备的性能要求越来越高。传统的锂离子电池基于液态有机电解液，在受到撞击或针刺时容易漏液，发生燃烧甚至爆炸事故，存在着较大的安全隐患。全固态锂电池（All-Solid-State Lithium Metal Batteries，ASSLMBs）因其能量密度高、安全性好等优势，有望成为新一代储能电池。固态电解质（Solid Electrolyte，SE）是全固态锂电池的关键组分之一，近年来，以Li₂OHX（X=Cl或Br）为代表的富锂反钙钛矿型（Li-Rich Anti-perovskite，LiRAP）SE因优异的性能和低廉的价格引起人们的密切关注。然而，目前的研究对Li₂OHX中H组分和肖特基缺陷对锂离子传输和全固态电池性能的影响等基础科学问题尚未搞清。本文围绕着LiRAP SE材料，通过精准调控H含量和引入肖特基缺陷，研究缺陷对LiRAP SE中的锂离子传输动力学以及综合电化学性能的影响。研究成果可为后期设计和开发新型SE材料提供思路。概括内容如下：

（1）采用高温煅烧熔融盐法制备了LiRAP SE材料Li_2+aOH_1−aX（a=0、0.05、0.1和0.15）。本工作结合实验和理论计算结果发现了H会影响Li₂OHX的锂离子输运、晶体稳定性、电化学稳定性和电子电导率。调控H含量后的Li₂OHCl与完全不含H的Li₃OCl相比，发现虽然H有助于产生类似空位的缺陷，但是H与锂离子之间的库伦排斥力会导致活化能和扩散距离（空间补偿效应）的增加，这导致锂离子沿Li−O面的特殊输运轨迹。H含量的减少增加了Li₂OHX的锂离子电导率，降低了电子电导率，提高了抗还原能力，从而提升了Li/Li₂OHX/Li对称电池的临界电流密度（Critical Current Density，CCD）和长循环性能，进而增强了ASSLMBs的循环稳定性和倍率性能。

（2）采用高温煅烧熔融盐法制备了含Li−X肖特基缺陷的LiRAP材料Li_2−aOHCl_1−a（a=0、0.03、0.05、0.09和0.13），和Li_2−bOHBr_1−b（b=0、0.09、0.17、0.23和0.29）。本工作发现，Li−X肖特基缺陷影响了LiRAP的晶体稳定性、电化学稳定性、离子电导率和电子电导率。低浓度的肖特基缺陷有利于提升LiRAP的晶体稳定性和离子电导率，而高浓度肖特基缺陷会引起LiRAP晶格发生畸变调整，不利于锂离子传输。除此之外，低浓度的肖特基缺陷降低了Li₂OHX的电子电导率，改善了Li−Li对称电池的循环稳定性和CCD，增强了ASSLMBs的循环和倍率性能。

In recent years, with the rapid development of new energy vehicle markets, it demands lithium−ion batteries with higher energy density and higher safety. The current commercial lithium−ion batteries are based on liquid organic electrolyte. The fire or explosion accidents easily occur under collision or penetration, which threatens people's safety. All−solid−state lithium metal batteries (ASSLMBs) are considered as one of the most ideal new−generation energy storage batteries due to their advantages such as high energy density, good safety performance. Solid electrolyte (SE) is one of the key components of ASSLMBs. In recent years, Li−rich antiperovskite (LiRAP) SEs, represented by Li₂OHX (X=Cl, Br), have attracted wide attention due to their excellent performance and low cost. However, fundamental scientific issues such as the influence of H component and Schottky defects in Li₂OHX on lithium ion transport and battery performance are still not clear. In this thesis, by regulating the H content and schottky defects, influence of these defects on the Li ions dynamics and electrochemical performance of the LiRAP SEs are systematically investigated. The research results can serve as theoretical guidelines for the design and development of new SE materials. The findings are summarized as follows:

(1)  The LiRAP SE, Li_2+aOH_1−aX (X=Cl and Br, a=0, 0.05, 0.1, 0.15), are prepared by high temperature calcination molten salt method. Combining the experimental and theoretical results, it is found that H would affect the Li−ion transport, crystal stability, electrochemical stability and electronic conductivity of Li₂OHX. Comparing Li₂OHCl with Li₃OCl, it is found that although H contributes to the generation of vacancy−like defects, the coulombic repulsion force between H and Li ions leads to an increase in activation energy and diffusion distance (termed as “space compensation effect”), resulting in a special transport trajectory of Li ions along the Li−O plane. Decreasing H content increases the conductivity of lithium ions, reduces the electronic conductivity and enhances the reduction−resistant ability of Li₂OHX, promoting the cycling stability and CCD of Li/Li₂OHX/Li symmetric cells, thereby improving the cycle and rate performance of ASSLMBs.

(2)  The LiRAP SE materials, Li_2−aOHCl_1−a (a=0, 0.03, 0.05, 0.09, 0.13) and Li_2−bOHBr_1−b (b=0, 0.09, 0.17, 0.23, 0.29) containing Li−X (X=Cl,Br) schottky defect, are prepared by high temperature calcination molten salt method. It is found that Li−X schottky defects affect the crystal stability, electrochemical stability, ionic conductivity and electronic conductivity of LiRAP. Low concentration of schottky defects improves the crystal stability and enhances the ionic conductivity of LiRAP, while high concentration of schottky defects cause "distortion adjustment" of LiRAP lattice and counts against Li−ion transport. In addition, low concentration of schottky defects reduces the electronic conductivity of Li₂OHX, improves the cycle stability and critical current density of Li−Li symmetric batteries, and enhances the cycle and rate performance of ASSLMBs.

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