ABSTRACT
Garnet-type Li7La3Zr2O12 (LLZO) is a potential electrolyte material for all-solid-state Li-ion batteries mainly because of its reported excellent chemical stability in contact with Li metal. But good wettability of LLZO and 100% surface coverage of lithium are still a challenge. This study elucidated the suitability of magnetron-sputtered indium in Li(In)/LLZO/Li(In) symmetrical model cells as one of the promising interfacial modifications reported in the literature. Importance was given to the impact of preparation parameters on the surface coverage of Li(In)/LLZO interfaces and the consequences of impedance, cycling stability, and critical current density. SEM and EDXS analyses of In layers of thickness 100 nm to 1 µm revealed complete dissolution of indium in the lithium anode after annealing; 300 nm In layers annealed at 220 °C/10 h provided a surface coverage of >80%, best reproducibility, and a supreme interface resistance Rint of 12.4 Ω·cm2. Presuming a surface coverage of 100%, an ultimate interface resistance close to 1 Ω·cm2 can be expected. The critical current density was determined as 200-500 µA/cm2 at a charge of 100-250 µAh, whereas 500 µA/cm2 and above affected cell stability. The increasing voltage plateau was assigned to the increase of the interface resistance Rint and the electrolyte resistance RG+GB. SEM, EDXS, and X-ray microtomography analyses after voltage breakdown confirmed Li-dendrite growth along grain boundaries into LLZO, often curved parallel to the interface, indicating short-circuiting of the solid electrolyte. Grain boundary characteristics are supposed to be decisive for lithium deposition in and failure of garnet-type solid electrolytes after cycling.
ABSTRACT
This article presents a literature review and new results on experimental and theoretical investigations of the electrochemistry of solid oxide fuel cell (SOFC) model anodes, focusing on the nickel/yttria-stabilized zirconia (Ni/YSZ) materials system with operation under H(2)/H(2)O atmospheres. Micropatterned model anodes were used for electrochemical characterization under well-defined operating conditions. Structural and chemical integrity was confirmed by ex situ pre-test and post-test microstructural and chemical analysis. Elementary kinetic models of reaction and transport processes were used to assess reaction pathways and rate-determining steps. The comparison of experimental and simulated electrochemical behaviors of pattern anodes shows quantitative agreement over a wide range of operating conditions (p(H(2)) = 8×10(2) - 9×10(4) Pa, p(H(2)O) = 2×10(1) - 6×10(4) Pa, T = 400-800 °C). Previously published experimental data on model anodes show a strong scatter in electrochemical performance. Furthermore, model anodes exhibit a pronounced dynamics on multiple time scales which is not reproduced in state-of-the-art models and which is also not observed in technical cermet anodes. Potential origin of these effects as well as consequences for further steps in model anode and anode model studies are discussed.
ABSTRACT
The oxygen incorporation reaction in undoped SrTiO(3) was investigated by electrical measurements (pressure modulation technique) in the temperature range from 650-920 degrees C and by means of tracer exchange experiments in the temperature range from 458-600 degrees C. The surface of the undoped SrTiO(3) single crystals was modified by alkaline earth metal compounds leading to a tremendous enhancement of the effective surface exchange rate for oxygen incorporation as compared to the uncoated surface.
