RESUMEN
Thiophosphate-based all-solid-state batteries (ASSBs) are considered the most promising candidate for the next generation of energy storage systems. However, thiophosphate-based ASSBs suffer from fast capacity fading with nickel-rich cathode materials. In many reports, this capacity fading is attributed to an increase of the charge transfer resistance of the composite cathode caused by interface degradation and/or chemo-mechanical failure. The change in the charge transfer resistance is typically determined using impedance spectroscopy after charging the cells. In this work, we demonstrate that large differences in the long-term cycling performance also arise in cells, which exhibit a comparable charge transfer resistance at the cathode side. Our results confirm that the charge transfer resistance of the cathode is not necessarily responsible for capacity fading. Other processes, such as resistive processes on the anode side, can also play a major role. Since these processes usually depend on the state of charge, they may not appear in the impedance spectra of fully charged cells; i.e., analyzing the impedance spectra of charged cells alone is insufficient for the identification of major resistive processes. Thus, we recommend measuring the impedance at different potentials to get a complete understanding of the reasons for capacity fading in ASSBs.
RESUMEN
Solid-state batteries (SSBs) with high-voltage cathode active materials (CAMs) such as LiNi1-x-y Cox Mny O2 (NCM) and poly(ethylene oxide) (PEO) suffer from "noisy voltage" related cell failure. Moreover, reports on their long-term cycling performance with high-voltage CAMs are not consistent. In this work, we verified that the penetration of lithium dendrites through the solid polymer electrolyte (SPE) indeed causes such "noisy voltage cell failure". This problem can be overcome by a simple modification of the SPE using higher molecular weight PEO, resulting in an improved cycling stability compared to lower molecular weight PEO. Furthermore, X-ray photoelectron spectroscopy analysis confirms the formation of oxidative degradation products after cycling with NCM, for what Fourier transform infrared spectroscopy is not suitable as an analytical technique due to its limited surface sensitivity. Overall, our results help to critically evaluate and improve the stability of PEO-based SSBs.
RESUMEN
Lithium argyrodite-type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li6 PS5 Cl and Li5.5 PS4.5 Cl1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time-of-flight secondary ion mass spectrometry indicate that the Li5.5 PS4.5 Cl1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance.
RESUMEN
All-solid-state batteries are intensively investigated, although their performance is not yet satisfactory for large-scale applications. In this context, the combination of Li10GeP2S12 solid electrolyte and LiNi1-x-yCoxMnyO2 positive electrode active materials is considered promising despite the yet unsatisfactory battery performance induced by the thermodynamically unstable electrode|electrolyte interface. Here, we report electrochemical and spectrometric studies to monitor the interface evolution during cycling and understand the reactivity and degradation kinetics. We found that the Wagner-type model for diffusion-controlled reactions describes the degradation kinetics very well, suggesting that electronic transport limits the growth of the degradation layer formed at the electrode|electrolyte interface. Furthermore, we demonstrate that the rate of interfacial degradation increases with the state of charge and the presence of two oxidation mechanisms at medium (3.7 V vs. Li+/Li < E < 4.2 V vs. Li+/Li) and high (E ≥ 4.2 V vs. Li+/Li) potentials. A high state of charge (>80%) triggers the structural instability and oxygen release at the positive electrode and leads to more severe degradation.
RESUMEN
Dye-sensitized solar cells (DSSCs) based on ZnO photoanodes have, despite extensive research, lagged behind cells based on TiO2, which is due to generally lower open-circuit voltages VOC and fill factors. Here, DSSCs have been prepared using Mg-doped ZnO (MZO) photoanodes based on nanoparticles, thin films or ZnO-MZO core-shell-type nanoparticles with varying Mg-concentration. The cells were studied in detailed photoelectrochemical and photoluminescence experiments. It was confirmed that VOC was significantly increased by Mg-doping. A clear influence of the Mg-concentration was also revealed on the transport and recombination of electrons in MZO, leading to a higher cell performance at low and lower cell performance at high concentrations of Mg in MZO. Nanoparticles with a pure ZnO core and an MZO shell offered a way to lower the influence of increased transport resistance in MZO and to capitalize on the significantly improved VOC.
RESUMEN
Fast recombination of electrons from semiconductors with the oxidized redox species in the electrolyte represents a major bottleneck in the improvement of ZnO-based dye-sensitized solar cells (DSSCs). While processes at the semiconductor-electrolyte interface are well studied on TiO2 electrodes, the interactions of the ZnO surface with the electrolyte solution in DSSCs are less explored. This work aims at clarifying the different impact of the two contrasting redox couples I3-/I- or [Co(bpy-pz)2]3+/2+ (bpy-pz = bis(6-(1H-pyrazol-1-yl)-2,2'-bipyridine)) in electrolytes containing either no additives or Li+ ions and/or 4-tert-butlypyridine (TBP) in DSSCs using screen-printed nanoparticulate TiO2 (NP-TiO2) or electrodeposited ZnO (ED-ZnO) photoanodes sensitized with the indoline dye DN216. A detailed photoelectrochemical study is performed to investigate light absorption, charge transfer and mass transport in these cells. We demonstrate that the chemical nature of the semiconductor directly influences the affinity of adsorbates. This drastically influences the energy levels and recombination kinetics at the semiconductor-electrolyte interface, electron and ion transport in the porous system as well as light absorption of dye molecules by the Stark effect. The present investigation reveals the origin of major performance losses in DSSCs based on ED-ZnO photoanodes as well as the relevance of ionic interactions with NP-TiO2 photoanodes that can both serve as the starting point for rationally guided improvement of their conversion efficiencies.
RESUMEN
Thin films of the methylammonium lead halides CH3 NH3 Pb(I1-x Brx )3 are prepared on fluorine-doped tin oxide substrates and exposed to humid air in the dark and under illumination. To characterize the stability of the materials, UV/Vis spectra are acquired at fixed intervals, accompanied by XRD, energy-dispersive X-ray spectroscopy, SEM, and confocal laser scanning microscopy. Different degradation mechanisms are observed depending on the environmental conditions. It is found that bromide can successfully suppress the transformation of the perovskite into the monohydrate, presumably owing to stronger hydrogen-bonding interactions with the organic cation. However, under illumination in humid air, rather rapid decomposition of the perovskites was still observed, which is due to phase segregation. The use of increased bromide content in methylammonium lead halide absorbers is discussed in terms of their application in perovskite solar cells.