4.2 Article

Li+/H+ exchange of Li7La3Zr2O12 single and polycrystals investigated by quantitative LIBS depth profiling

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MATERIALS ADVANCES
卷 3, 期 23, 页码 8760-8770

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d2ma00845a

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  1. Austrian Science Fund (FWF) [W 1243-N16, P 31437-N36, P 31165-N37]

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LLZO garnets are potential solid electrolytes for solid-state Li batteries, but suffer from chemical interaction with air and humidity. This study investigates the kinetics of Li+/H+ exchange and its dependence on microstructural features, revealing the importance of microstructure in determining the exchange kinetics of LLZO.
Li7La3Zr2O12 (LLZO) garnets are highly attractive to be used as solid electrolyte in solid-state Li batteries. However, LLZO suffers from chemical interaction with air and humidity, causing Li+/H+ exchange with detrimental implication on its performance, processing and scalability. To better understand the kinetics of the detrimental Li+/H+ exchange and its dependence on microstructural features, accelerated Li+/H+ exchange experiments were performed on single crystalline and polycrystalline LLZO, exposed for 80 minutes to 80 degrees C hot water. The resulting chemical changes were quantified by analytical methods, i.e. inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser induced breakdown spectroscopy (LIBS). From the time dependence of the Li+ enrichment in the water, measured by ICP-OES, a bulk interdiffusion coefficient of Li+/H+ could be determined (7 x 10(-17) m(2) s(-1) at 80 degrees C). Depth dependent concentrations were obtained from the LIBS data for both ions after establishing a calibration method enabling not only Li+ but also H+ quantification in the solid electrolyte. Short interdiffusion lengths in the 1 mu m range are found for the single crystalline Ga:LLZO, in accordance with the measured bulk diffusion coefficient. In polycrystalline Ta:LLZO, however, very long diffusion tails in the 20 mu m range and ion exchange fractions up to about 70% are observed. Those are attributed to fast ion interdiffusion along grain boundaries. The severe compositional changes also strongly affect the electrical properties measured by impedance spectroscopy. This study highlights that microstructural effects may be decisive for the Li+/H+ ion exchange kinetics of LLZO.

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