ABSTRACT
The role of cobalt deficiency on the crystal structure, surface chemistry, and electrochemical performance of Ni-rich layered LiNi0.8Co0.1Mn0.1O2 (NCM811) positive electrode materials was experimentally studied possibly for the first time. We synthesized pristine and cobalt-deficient NCM811 samples by solid-state reaction. Using a variety of characterization techniques and electrochemical measurements, we show that cobalt nonstoichiometry can suppress Ni2+/Li+ cation mixing, but can simultaneously promote the formation of oxygen vacancies, leading to rapid capacity fade and inferior rate capability compared to pristine NCM811. This study provides new insights into the effects of cobalt deficiency on the cation mixing and electrochemical performance of a Ni-rich layered NCM compound.
ABSTRACT
Garnet-type cubic Li7La3Zr2O12 exhibits one of the highest lithium-ion conductivity values amongst oxides (up to â¼2 mS cm-1 at room temperature). This compound has also emerged as a promising candidate for solid electrolytes in all-solid-state lithium batteries, due to its high ionic conductivity, good chemical stability against lithium metal, and wide electrochemical stability window. Defect chemistry of this class of materials, although less studied, is critical to the understanding of the nature of ionic conductivity and predicting the properties of grain boundaries and heterogeneous solid interfaces. In this study, the electrical properties of nominally undoped cubic Li7La3Zr2O12 are characterized as a function of temperature and pO2 using a suite of AC impedance and DC polarization techniques. The formation of ionic defects and defect pairs as well as their impact on the transport properties are discussed, and a Brouwer-type diagram is constructed.
ABSTRACT
Composite electrodes consisting of cathode particles and an ion-conducting phase can address the limited ion accessibility of the cathode in high-energy all-solid-state lithium batteries. In this Letter, we discuss the microstructure-conductivity relationship in an electronic-ionic composite with a focus on lithium ion conductivity. This study is the first step toward further understanding of electrochemical reactions in all solid multiphase systems.
ABSTRACT
The microstructural and compositional evolution at the solid/aqueous solution interfaces are investigated to monitor the electrical properties of superionic conducting phosphates and the electrochemical failure of aqueous sodium-ion batteries.
ABSTRACT
Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g. changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g. on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.
Subject(s)
Electric Power Supplies , Electrodes , Lithium/chemistry , Sodium/chemistry , Cations, Monovalent/chemistry , Synchrotrons , X-Ray Absorption Spectroscopy/methods , X-Ray Diffraction/methodsABSTRACT
Conductivity measurements were performed on microcrystalline and nanocrystalline ceria (undoped and doped) in dry as well as wet atmosphere. Below 200-250 °C, the nanocrystalline samples exhibit an enhanced total conductivity under wet conditions, which increases with decreasing temperature. In addition, thermo-gravimetric analysis revealed a strong water uptake below 200 °C. DC-polarization measurements confirm the ionic character of conductivity in the nanocrystalline samples at low temperatures. The role of both grain boundaries and residual porosity on the enhanced conductivity below 200 °C is discussed.
