ABSTRACT
Numerous sophisticated diagnostic techniques have been designed to monitor electrode-electrolyte interfaces that mainly govern the lifetime and reliability of batteries. Among them is the electrochemical quartz crystal microbalance (EQCM) that offers valuable insights of the interfaces once the required conditions of the deposited film in terms of viscoelastic and hydrodynamic properties are fulfilled. Herein, we propose a friendly protocol that includes the elaboration of a homogeneous deposit by spray coating followed by QCM measurements at multiharmonic frequencies to ensure the film flatness and rigidity for collecting meaningful data. Moreover, for easiness of the measurements, we report the design of a versatile and airtight EQCM cell setup that can be used either with aqueous or non-aqueous electrolytes. We also present, using a model battery material, LiFePO4, how dual frequency and motional resistance monitoring during electrochemical cycling can be used as a well-suitable indicator for achieving reliable and reproducible electrogravimetric measurements. We demonstrate through this study the essential role of the solvent assisting lithium-ion insertion at the LiFePO4 interface with a major outcome of solvent-dependent interfacial behavior. Namely, in aqueous media, we prove a near-surface desolvation of lithium ions from their water solvation shell as compared with organic molecules. This spatial dissimilarity leads to a smoother Li-ion transport across the LFP-H2O interface, hence accounting for the difference in rate capability of LFP in the respective electrolytes. Overall, we hope our analytical insights on interfacial mechanisms will help in gaining a wider acceptance of EQCM-based methods from the battery community.
ABSTRACT
Great hopes are placed on all-solid-state Li-metal batteries (ASSBs) to boost the energy density of the current Li-ion technology. However, these devices still present a number of unresolved issues that keep them far from commercialization; such as interfacial instability, lithium dendrite formation, and lack of mechanical integrity during cycling. To mitigate these limiting aspects, the most advanced ASSB systems presently combine a sulfide- or oxide-based solid electrolyte (SE) with a coated Li-based oxide as the positive electrode and a lithium anode. Through this work, we propose a different twist by switching from layered oxides to layered sulfides as active cathode materials. Herein, we present the performance of a Li-rich layered sulfide of formula Li1.13Ti0.57Fe0.3S2 (LTFS) in room temperature operating all-solid-state batteries, using ß-Li3PS4 as SE and both InLi and Li anode materials. These batteries exhibit good cyclability, small polarization and, in the case of the Li anode, no initial irreversible capacity. We also suggest the possibility of using this Li-rich sulfide mixed with oxide cathode materials as part of the positive electrode in ASSBs in order to improve the cathode/sulfide SE interface. Our proof of concept using LiNi0.6 Mn0.2Co0.2O2 (NMC 622) showed that the addition of a small amount of LTFS had a direct positive impact in the battery performance.
ABSTRACT
Recently, because of sustainability issues dictated by societal demands, more importance has been given to aqueous systems and especially to proton-based batteries. However, the mechanisms behind the processes leading to energy storage in such systems are still not elucidated. Under this scope, our study is structured on the selection of a model electrode material, the protonic phase HxIrO4, and the scrutiny of the interfacial processes through suitable analytical tools. Herein, we employed operando electrochemical quartz crystal microbalance (EQCM) combined with electrochemical impedance spectroscopy (EIS) to provide new insights into the mechanism intervening at the electrode-electrolyte interface. First, we demonstrated that not only the surface or near surface but the whole particle participates in the cationic redox process. Second, we proved that the contribution of the proton on the overall potential window together with the incorporation of water at low potentials solely. This is explained by the fact that water molecules permit a further insertion of protons in the material by shielding the proton charge but at the expense of the proton kinetic properties. These findings shed a new light on the importance of water molecules in the ion-insertion mechanisms taking place at the electrode-electrolyte interface of aqueous proton-based batteries. Overall, the present results further highlight the richness of the EQCM-based methods for the battery field in offering mechanistic insights that are crucial for the understanding of interfaces and charge storage in insertion compounds.
ABSTRACT
The search for high Li-ion conducting ceramics has regained tremendous interest triggered by the renaissance of the all-solid-state battery. Within this context we herein reveal the impact of structural polymorphism of lithium copper pyroborate Li6CuB4O10 on its ionic conductivity. Using combined in situ synchrotron X-ray and neutron powder diffraction, a structural and synthetic relationship between α- and ß-Li6CuB4O10 could be established and its impact on ionic conductivity evolution was followed using electrochemical impedance spectroscopy. We show that the high temperature form of Li6CuB4O10 exhibits a high Li-ion conductivity (2.7 mS cm-1 at 350 °C) and solve its crystal structure for the first time. Our results emphasize the significant impact of structural phase transitions on ionic conductivity and show possible high Li-ion mobility within borate based compounds.
ABSTRACT
In the search for new cathode materials for Li-ion batteries, borate (BO3(3-)) based compounds have gained much interest during the last two decades due to the low molecular weight of the borate polyanions which leads to active materials with increased theoretical capacities. In this context we herein report the electrochemical activity versus lithium and the ionic conductivity of a diborate or pyroborate B2O5(4-) based compound, Li6CuB4O10. By combining various electrochemical techniques with in situ X-ray diffraction, we show that this material can reversibly insert/deinsert limited amounts of lithium (â¼0.3 Li(+)) in a potential window ranging from 2.5 to 4.5 V vs. Li(+)/Li(0). We demonstrate, via electron paramagnetic resonance (EPR), that such an electrochemical activity centered near 4.25 V vs. Li(+)/Li(0) is associated with the Cu(3+)/Cu(2+) redox couple, confirmed by density functional theory (DFT) calculations. Another specificity of this compound lies in its different electrochemical behavior when cycled down to 1 V vs. Li(+)/Li(0) which leads to the extrusion of elemental copper via a conversion type reaction as deduced by transmission electron microscopy (TEM). Lastly, we probe the ionic conductivity by means of AC and DC impedance measurements as a function of temperature and show that Li6CuB4O10 undergoes a reversible structural transition around 350 °C, leading to a surprisingly high ionic conductivity of â¼1.4 mS cm(-1) at 500 °C.
