Olbrich Lorenz F, Jagger Ben, Ihli Johannes, Pasta Mauro
Department of Materials, University of Oxford, Oxford OX1 3PH, U.K.
ACS Energy Lett. 2024 Jul 3;9(7):3636-3642. doi: 10.1021/acsenergylett.4c00954. eCollection 2024 Jul 12.
Transport and thermodynamic properties are integral parameters to understand, model, and optimize state-of-the-art and next-generation battery electrolytes. The accurate measurement of these properties is experimentally challenging as well as time- and resource-intensive, and consequently, reports are scarce. Their dependence on temperature is explored even less and is commonly limited to a few temperature points. Recently, we introduced an operando Raman gradient analysis (ORGA) tool to extract transport and thermodynamic properties. Here, we expand the capabilities of ORGA by incorporating a temperature-sensitive external reference into the design. With this enhancement, we are able to visualize the local concentration of any Raman-active species in the electrolyte and detect lithium filament nucleation. We demonstrate and validate this new functionality of ORGA via an examination of lithium bis(fluorosulfonyl)imide (LiFSI) in tetraethylene glycol dimethyl ether (G4) as a function of temperature. All transport properties and activation energies are reported, and the effect of temperature is discussed.
传输和热力学性质是理解、建模和优化现有及下一代电池电解质的重要参数。准确测量这些性质在实验上具有挑战性，而且耗费时间和资源，因此相关报道很少。对它们与温度的依赖关系的探索更少，通常仅限于少数几个温度点。最近，我们引入了一种原位拉曼梯度分析（ORGA）工具来提取传输和热力学性质。在此，我们通过在设计中纳入一个对温度敏感的外部参比物来扩展ORGA的功能。通过这一改进，我们能够可视化电解质中任何拉曼活性物种的局部浓度，并检测锂枝晶的成核。我们通过研究双（氟磺酰）亚胺锂（LiFSI）在四甘醇二甲醚（G4）中随温度的变化，展示并验证了ORGA的这一新功能。报告了所有传输性质和活化能，并讨论了温度的影响。
