Engineering Solution-Processed Non-Crystalline Solid Electrolytes for Li Metal Batteries.
Engineering Solution-Processed Non-Crystalline Solid Electrolytes for Li Metal Batteries.
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DOI：
10.1021/acs.chemmater.2c03071
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发表时间：
2023-02-14
影响因子：
8.6
通讯作者：
Miller, Thomas S.
中科院分区：
文献类型：
--
作者：
Rettie, Alexander J. E.;Vadhva, Pooja;Gill, Thomas E.;Cruddos, Joshua H.;Said, Samia;Siniscalchi, Marco;Narayanan, Sudarshan;Pasta, Mauro;Miller, Thomas S.
非晶态锂离子固体电解质（SE），如锂磷氮氧化物，可以独特地实现薄膜形式的数千次循环的高速率固态电池操作。然而，它们通常通过昂贵且低通量的真空沉积来生产，限制了它们的广泛应用和研究。在这里，我们报告的非晶态SE的组成Li-Al-P-O（LAPO）的离子电导率> 10-7 S cm-1，在室温下通过旋涂从水溶液和随后在空气中退火制成。在低至230 °C的温度下可以合成亚微米厚度的均匀、致密、平坦的层。控制的组合物被示出显着影响的离子电导率，与增加的锂和减少的P含量是最佳的，而较高的退火温度导致在降低的离子电导率。活化能分析揭示了一个锂离子跳跃势垒为10.4 eV。此外，这些SE表现出低的室温电子电导率（< 10-11 S cm-1）和1.54 GPa的中等杨氏模量，这可能有利于防止Li枝晶形成。与Li金属接触时，发现LAPO形成由Al金属、Li-P和Li-O物质组成的稳定但高阻抗的钝化层。这些发现在为具有高能量和功率密度的锂金属电池设计非结晶SE时应该是有价值的。
Non-crystalline Li-ion solid electrolytes (SEs), such as lithium phosphorus oxynitride, can uniquely enable high-rate solid-state battery operation over thousands of cycles in thin film form. However, they are typically produced by expensive and low throughput vacuum deposition, limiting their wide application and study. Here, we report non-crystalline SEs of composition Li–Al–P–O (LAPO) with ionic conductivities > 10–7 S cm–1 at room temperature made by spin coating from aqueous solutions and subsequent annealing in air. Homogenous, dense, flat layers can be synthesized with submicrometer thickness at temperatures as low as 230 °C. Control of the composition is shown to significantly affect the ionic conductivity, with increased Li and decreased P content being optimal, while higher annealing temperatures result in decreased ionic conductivity. Activation energy analysis reveals a Li-ion hopping barrier of ≈0.4 eV. Additionally, these SEs exhibit low room temperature electronic conductivity (< 10–11 S cm–1) and a moderate Young’s modulus of ≈54 GPa, which may be beneficial in preventing Li dendrite formation. In contact with Li metal, LAPO is found to form a stable but high impedance passivation layer comprised of Al metal, Li–P, and Li–O species. These findings should be of value when engineering non-crystalline SEs for Li-metal batteries with high energy and power densities.
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影响因子：
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