福州大学李亚峰研究组近日取得一项新成果。经过不懈努力，他们的研究开发出了全固态锂电池用阳离子-阴离子工程改性氯化氧锆基锂超离子导体。相关论文发表在2025年4月1日出版的《德国应用化学》杂志上。

课题组人员提出了一种新的阳离子和阴离子亚晶格工程策略，称为CASE，以增加非晶含量并增强离子电导率。Cu²⁺和O^2-的掺入在Li₂ZrCl₆中引起了明显的结构修饰。通过x射线吸收光谱、中子衍射和从头算分子动力学的分析数据证实了这一结构。结果表明，在25℃时，非晶Li_2.1Zr_0.95Cu_0.05Cl_4.4 O_0.8的离子电导率提高到2.05 mS cm^-1。

此外，以无定形Li_2.1Zr_0.95Cu_0.05Cl_4.4 O_0.8为电解质，以LiNi_0.83Co_0.11Mn_0.06O₂为阴极的全固态锂电池表现出优异的长期循环稳定性，在室温下2℃下循环1000次后仍保持90.3%的容量，远高于文献中报道的Zr基卤化物电解质。这样的结果可能会刺激在CASE策略中更多具有高离子电导率的无定形结构的发展。

据悉，在卤化物固体电解质（SEs）家族中，Li₂ZrCl₆具有较高的氧化稳定性，成本效益和机械变形性，使其成为有前途的SEs候选者。然而，Li₂ZrCl₆在室温下离子电导率较低，阻碍了其作为SEs的应用。目前提高Li₂ZrCl₆离子电导率的策略主要集中在单阳离子或阴离子亚晶格工程上，每种方法都有各自的优势和局限性。

附：英文原文

Title: Cation-Anion-Engineering Modified Oxychloride Zr-Based Lithium Superionic Conductors for All-Solid-State Lithium Batteries

Author: Zongnan Li, Yongbiao Mu, Kunxi Lü, Guojian Kang, Ting Yang, Shuping Huang, Mingdeng Wei, Lin Zeng, Yafeng Li

Issue&Volume: 2025-04-01

Abstract: Within the family of halide solid electrolytes (SEs), Li2ZrCl6 demonstrates high oxidative stability, cost-effectiveness, and mechanical deformability, positioning it as a promising candidate for SEs. However, the application of Li2ZrCl6 as a SEs was hindered by its low ionic conductivity at room temperature. Current strategies to enhance the ionic conductivity of Li2ZrCl6 primarily are focused on single cation or anion sublattice-engineering, each with distinct advantages and limitations. Here, we propose a novel cation and anion-sublattice-engineering strategy, termed CASE, to increase the amorphous content and thus enhance ionic conductivity. The incorporation of Cu2+ and O2- induces distinctive structural modifications within Li2ZrCl6. This structure corroborated through analytic data of X-ray absorption spectroscopy, the neutron diffraction, and ab initio molecular dynamics. Consequently, the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 achieves an enhanced ionic conductivity of 2.05 mS cm-1 at 25 °C. Furthermore, all-solid-state lithium batteries utilizing the amorphous Li2.1Zr0.95Cu0.05Cl4.4O0.8 as an electrolyte and LiNi0.83Co0.11Mn0.06O2 as a cathode exhibit a superior long-term cycling stability retaining 90.3% of capacity after 1000 cycles at 2 C under room temperature, which are much higher than those of Zr-based halide electrolytes in publications. Such a result might stimulate the development of more amorphous structures with high ionic conductivity in the CASE strategy.

DOI: 10.1002/anie.202501749

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202501749