Scholarlink

<p>Currently, lithium all-solid-state batteries are in great demand. Lithium-ion conducting liquid electrolytes LiPF<sub>6</sub> and LiClO<sub>4</sub>, dissolved in organic solvents (mixture of carbonates), are considered promising buffer layers for cathode | solid electrolyte interface modification. However, their stability in contact with solid electrolytes should be investigated. Thus, the study of the stability of solid electrolytes based on Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (LLZ) in contact with organic solvents, as well as liquid electrolytes, is the aim of the presented work. The formation of an intermediate phase was observed by scanning electron microscopy on the ceramic surface after exposure of the solid electrolyte in LiClO<sub>4</sub> and LiPF<sub>6</sub>, dissolved in a mixture of carbonates. According to X-ray diffraction analysis and Raman spectroscopy, LiF and LaOCl are present on the surface of Al-doped LLZ after its exposure to LiPF<sub>6</sub> and LiClO<sub>4</sub> liquid electrolytes, respectively. It was established that an increase in the holding time leads to a decrease in the conductivity of the solid electrolyte (from 1.4·10<sup>−4</sup> to 3.9·10<sup>−5</sup> S cm<sup>−1</sup> after exposure to LiClO<sub>4</sub> liquid electrolytes), which is especially noticeable for LiPF<sub>6</sub> liquid electrolyte (to 2.1·10<sup>−8</sup> S cm<sup>−1</sup>). Despite the decrease in the total resistance of the electrochemical cells modified by LiClO<sub>4</sub> liquid electrolyte, the resistance at the modified cathode | solid electrolyte interface increased over time (from 3 to 180 kΩ cm<sup>2</sup>) and after galvanostatic cycling (up to tens of MΩ cm<sup>2</sup>). Thus, the modification of the cathode | LLZ interface cannot be performed by such liquid electrolytes as LiClO<sub>4</sub> and LiPF<sub>6</sub> dissolved in the mixture of carbonates due to their interaction with solid electrolytes based on LLZ and the formation of a low-conductivity layer. The search for lithium-ion conducting liquid electrolytes that are stable in contact with solid electrolytes with a garnet-like structure for cathode | solid electrolyte interface optimization in all-solid-state batteries is an important task for further research.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Stability of Li7La3Zr2O12 solid electrolyte versus conventional liquid electrolytes based on LiClO4 and LiPF6

  • 期刊论文

  • 发表日期：

    2025年11月20日

查看全文
  • E. A. Il’ina,
  • K. V. Druzhinin,
  • V. A. Elterman,
  • A. V. Tkachuk

摘要

Currently, lithium all-solid-state batteries are in great demand. Lithium-ion conducting liquid electrolytes LiPF6 and LiClO4, dissolved in organic solvents (mixture of carbonates), are considered promising buffer layers for cathode | solid electrolyte interface modification. However, their stability in contact with solid electrolytes should be investigated. Thus, the study of the stability of solid electrolytes based on Li7La3Zr2O12 (LLZ) in contact with organic solvents, as well as liquid electrolytes, is the aim of the presented work. The formation of an intermediate phase was observed by scanning electron microscopy on the ceramic surface after exposure of the solid electrolyte in LiClO4 and LiPF6, dissolved in a mixture of carbonates. According to X-ray diffraction analysis and Raman spectroscopy, LiF and LaOCl are present on the surface of Al-doped LLZ after its exposure to LiPF6 and LiClO4 liquid electrolytes, respectively. It was established that an increase in the holding time leads to a decrease in the conductivity of the solid electrolyte (from 1.4·10−4 to 3.9·10−5 S cm−1 after exposure to LiClO4 liquid electrolytes), which is especially noticeable for LiPF6 liquid electrolyte (to 2.1·10−8 S cm−1). Despite the decrease in the total resistance of the electrochemical cells modified by LiClO4 liquid electrolyte, the resistance at the modified cathode | solid electrolyte interface increased over time (from 3 to 180 kΩ cm2) and after galvanostatic cycling (up to tens of MΩ cm2). Thus, the modification of the cathode | LLZ interface cannot be performed by such liquid electrolytes as LiClO4 and LiPF6 dissolved in the mixture of carbonates due to their interaction with solid electrolytes based on LLZ and the formation of a low-conductivity layer. The search for lithium-ion conducting liquid electrolytes that are stable in contact with solid electrolytes with a garnet-like structure for cathode | solid electrolyte interface optimization in all-solid-state batteries is an important task for further research.