166 research outputs found
Quasi-homogenous photocatalysis of quantum-sized Fe-doped TiO in optically transparent aqueous dispersions
In this study, the preparation of anatase TiO2 nanocrystals via a facile non-aqueous sol–gel route and their characterization are reported. The 3–4 nm particles are readily dispersable in aqueous media and show excellent photoreactivity in terms of rhodamine B degradation. The catalytic performance can be further increased considerably by doping with iron and UV-light irradiation as a pre-treatment. The effect of surface ligands (blocked adsorption sites, surface defects etc.) on the photoreactivity was thoroughly probed using thermogravimetric analysis combined with mass spectrometry. Photoelectrochemical characterization of thin-film electrodes made from the same TiO2 nanocrystals showed the opposite trend to the catalytic experiments, that is, a strong decrease in photocurrent and quantum efficiency upon doping due to introduction of shallow defect states
Influence of synthesis parameters on crystallization behavior and ionic conductivity of the LiPSI solid electrolyte
Superionic solid electrolytes are key to the development of advanced solid-state Li batteries. In recent years, various materials have been discovered, with ionic conductivities approaching or even exceeding those of carbonate-based liquid electrolytes used in high-performance Li-ion batteries. Among the different classes of inorganic solid electrolytes under study, lithium thiophosphates are one of the most promising due to their high Li-ion conductivity at room temperature and mechanical softness. Here, we report about the effect of synthesis parameters on the crystallization behavior and charge-transport properties of LiPSI. We show that thermally induced crystallization of LiPSI (P4/nmm), starting from the glassy phase 1.5LiS–0.5PS–LiI, adversely affects the material’s conductivity. However, both conductivity and crystallization temperature can be significantly increased by applying pressure during the preparation
Ordered mesoporous metal oxides for electrochemical applications: correlation between structure, electrical properties and device performance
Ordered mesoporous metal oxides with a high specific surface area, tailored porosity and engineered interfaces are promising materials for electrochemical applications. In particular, the method of evaporation-induced self-assembly allows the formation of nanocrystalline films of controlled thickness on polar substrates. In general, mesoporous materials have the advantage of benefiting from a unique combination of structural, chemical and physical properties. This Perspective article addresses the structural characteristics and the electrical (charge-transport) properties of mesoporous metal oxides and how these affect their application in energy storage, catalysis and gas sensing
Operando acoustic emission monitoring of degradation processes in lithium-ion batteries with a high-entropy oxide anode
In recent years, high-entropy oxides are receiving increasing attention for electrochemical energy-storage applications. Among them, the rocksalt (CoCuMgNiZn)O (HEO) has been shown to be a promising high-capacity anode material. Because high-entropy oxides constitute a new class of electrode materials, systematic understanding of their behavior during ion insertion and extraction is yet to be established. Here, we probe the conversion-type HEO material in lithium half-cells by acoustic emission (AE) monitoring. Especially the clustering of AE signals allows for correlations of acoustic events with various processes. The initial cycle was found to be the most acoustically active because of solid-electrolyte interphase formation and chemo-mechanical degradation. In the subsequent cycles, AE was mainly detected during delithiation, a finding we attribute to the progressive crack formation and propagation. Overall, the data confirm that the AE technology as a non-destructive operando technique holds promise for gaining insight into the degradation processes occurring in battery cells during cycling
Investigations into the superionic glass phase of LiPSI for improving the stability of high-loading all-solid-state batteries
In recent years, investigations into improving the performance of bulk-type solid-state batteries (SSBs) have attracted much attention. This is due, in part, to the fact that they offer an opportunity to outperform the present Li-ion battery technology in terms of energy density. Ni-rich Li(NiCoMn)O (NCM) and lithium-thiophosphate-based solid electrolytes appear to be a promising material combination for application at the cathode side. Here, we report about exploratory investigations into the 1.5LiS/0.5PS/LiI phase system and demonstrate that a glassy solid electrolyte has more than an order of magnitude higher room-temperature ionic conductivity than the crystalline counterpart, tetragonal LiPSI with the P4/nmm space group (∼1.3 versus ∼0.2 mS cm). In addition, preliminary results show that usage of the glassy 1.5LiS–0.5PS–LiI in pellet stack SSB cells with an NCM622 (60% Ni content) cathode and a LiTiO anode leads to enhanced capacity retention when compared to the frequently employed argyrodite LiPSCl solid electrolyte. This indicates that, apart from interfacial instabilities, the stiffness (modulus) of the solid electrolyte and associated mechanical effects may also impact significantly the long-term performance. Moreover, SSB cells with the glassy 1.5LiS–0.5PS–LiI and high-loading cathode (∼22 mg cm) manufactured using a slurry-casting process are found to cycle stably for 200 cycles at C/5 rate and 45 °C, with areal capacities in excess of 3 mA h cm
In situ analysis of gas evolution in liquid- and solid-electrolyte-based batteries with current and next-generation cathode materials
The operation of combined mass spectrometry and electrochemistry setups has recently become a powerful approach for the in situ analysis of gas evolution in batteries. It allows for real-time insights and mechanistic understanding into different processes, including battery formation, operation, degradation, and behavior under stress conditions. Important information is gained on the safety and stability window as well as on the effect of protecting strategies, such as surface coatings, dopings, and electrolyte additives. This review primarily aims at summarizing recent findings on the gassing behavior in different kinds of liquid- and solid-electrolyte-based batteries, with emphasis placed on novel cathode-active materials and isotope labeling experiments, to highlight the relevance of in situ gas analysis for elucidation of reaction mechanisms. Various instrumental and experimental approaches are presented to encourage and inspire both novices and experienced scientists in the field
Acoustic Emission Monitoring of High-Entropy Oxyfluoride Rock-Salt Cathodes during Battery Operation
The Sound of Batteries: An Operando Acoustic Emission Study of the LiNiO Cathode in Li–Ion Cells
The development of advanced Li‐ion batteries relies on the implementation of high‐capacity Ni‐rich layered oxide cathode materials, such as NCM and NCA, among others. However, fast performance decay because of intrinsic chemical and structural instabilities hampers their practical application. Hence, thoroughly understanding degradation processes is crucial to overcome current limitations. To monitor instabilities of electrode materials under realistic operating conditions, the application of nondestructive operando techniques is required. While structural changes of crystalline phases can be studied by X‐ray diffraction, microstructural changes (e. g., particle fracture) cannot be easily accessed in situ and are therefore mostly investigated ex situ. Here, we use acoustic emission (AE) measurements to probe a potential next‐generation cathode material in real‐time. Specifically, we focus on LiNiO(LNO) and demonstrate that AE events in different frequency ranges can be correlated with the formation of the cathode solid‐electrolyte interphase and the mechanical degradation during electrochemical cycling
Single versus poly-crystalline layered oxide cathode materials for solid-state battery applications - a short review article
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