All-Solid-State Batteries Using Rationally Designed Garnet Electrolyte Frameworks

Functioning bulk-type all-solid-state batteries in a practical form factor with composite positive electrodes, using Al-substituted Li7La3Zr2O12 (LLZO) as the solid electrolyte, have been demonstrated for the first time. The devices incorporate bilayers composed of dense LLZO membranes and porous LLZO scaffolds infiltrated with LiNi0.6Mn0.2Co0.2O2 and other components as positive electrodes, combined with lithium anodes. The porous scaffolds are prepared using an easily scaled freeze-tape-casting method. The unidirectional pores of the scaffold facilitate infiltration of cathode components and shorten lithium ion diffusion path lengths, while the addition of a soft ionically conductive solid to the scaffold ensures good contact among the components

Thermal stress-induced charge and structure heterogeneity in emerging cathode materials

Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi0.8Mn0.1Co0.1O2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode's thermal robustness for battery performance and safety

CRADA: Synthesis and Evaluation of NMC Cathode Materials

Ni-rich NMCs, technologically important cathode materials for lithium-ion batteries were synthesized and studied for this project. Electrodes were also harvested from cycled and/or aged commercial Li-ion cells and examined using high-throughput, ensemble average synchrotron soft x-ray absorption techniques developed at LBNL to observe surface reconstruction in NMC materials (see F. Lin et al. Nature Commun. 5:3529, (2014)). A goal was to observe which cycling and storage conditions lead to degradation of cathode materials, a process that has been implicated in premature failure of the devices in some cases. VW provided pristine electrodes to use as baselines. Cells containing electrodes synthesized at LBNL were cycled or subjected to various storage conditions at LBNL, and VW also provided cycled or aged electrodes from commercial cells with histories of interest

CRADA: Analysis of Cathode Material with a Study of Effects of Battery Cycling and Aging Regimes on Cathodes

Ni-rich NMCs, technologically important cathode materials for lithium-ion batteries were synthesized and studied for this project. Electrodes were also harvested from cycled and/or aged commercial Li-ion cells and examined using high-throughput, ensemble average synchrotron soft x-ray absorption techniques developed at LBNL to observe surface reconstruction in NMC materials (see F. Lin et al. Nature Commun. 5:3529, (2014)). A goal was to observe which cycling and storage conditions lead to degradation of cathode materials, a process that has been implicated in premature failure of the devices in some cases. VW provided pristine electrodes to use as baselines. Cells containing electrodes synthesized at LBNL were cycled or subjected to various storage conditions at LBNL, and VW also provided cycled or aged electrodes from commercial cells with histories of interest

Solid Electrolytes in the Spotlight

10.1021/acs.chemmater.1c03770CHEMISTRY OF MATERIALS342463-467complete

Synthesis and characterization of metastable, 20 nm-sized Pna21-LiCoPO4 nanospheres

The majority of research activities on LiCoPO are focused on the phospho-olivine (space group Pnma), which is a promising high-voltage cathode material for Li-ion batteries. In contrast, comparably little is known about its metastable Pna2 modification. Herein, we present a comprehensive study on the structure–property relationships of 15–20 nm Pna2 -LiCoPO nanospheres prepared by a simple microwave-assisted solvothermal process. Unlike previous reports, the results indicate that the compound is non-stoichiometric and shows cation-mixing with Co ions on the Li sites, which provides an explanation for the poor electrochemical performance. Co L -edge X-ray absorption spectroscopic data confirm the local tetrahedral symmetry of Co . Comprehensive studies on the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and in situ powder X-ray diffraction show an exothermic phase transition to olivine Pnma-LiCoPO at 527 °C. The influence of the atmosphere and the particle size on the thermal stability is also investigated. 4 1 1 4 2,3 4 2

A review of Ni-based layered oxides for rechargeable Li-ion batteries

The portable electronic market, vehicle electrification (electric vehicles or EVs) and grid electricity storage impose strict performance requirements on Li-ion batteries, the energy storage device of choice, for these demanding applications. Higher energy density than currently available is needed for these batteries, but a limited choice of materials for cathodes remains a bottleneck. Layered lithium metal oxides, particularly those with high Ni content, hold the greatest promise for high energy density Li-ion batteries because of their unique performance characteristics as well as for cost and availability considerations. In this article, we review Ni-based layered oxide materials as cathodes for high-energy Li-ion batteries. The scope of the review covers an extended chemical space, including traditional stoichiometric layered compounds and those containing two lithium ions per formula unit (with potentially even higher energy density), primarily from a materials design perspective. An in-depth understanding of the composition-structure-property map for each class of materials will be highlighted as well. The ultimate goal is to enable the discovery of new battery materials by integrating known wisdom with new principles of design, and unconventional experimental approaches (e.g., combinatorial chemistry)