Differences in the Interfacial Mechanical Properties of Thiophosphate and Argyrodite Solid Electrolytes and Their Composites.

Interfacial mechanics are a significant contributor to the performance and degradation of solid-state batteries. Spatially resolved measurements of interfacial properties are extremely important to effectively model and understand the electrochemical behavior. Herein, we report the interfacial properties of thiophosphate (Li3PS4)- and argyrodite (Li6PS5Cl)-type solid electrolytes. Using atomic force microscopy, we showcase the differences in the surface morphology as well as adhesion of these materials. We also investigate solvent-less processing of hybrid electrolytes using UV-assisted curing. Physical, chemical, and structural characterizations of the materials highlight the differences in the surface morphology, chemical makeup, and distribution of the inorganic phases between the argyrodite and thiophosphate solid electrolytes.

Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes.

One of the most challenging aspects of developing high-energy lithium-based batteries is the structural and (electro)chemical stability of Ni-rich active cathode materials at thermally-abused and prolonged cell cycling conditions. Here, we report in situ physicochemical characterizations to improve the fundamental understanding of the degradation mechanism of charged polycrystalline Ni-rich cathodes at elevated temperatures (e.g., ≥ 40 °C). Using multiple microscopy, scattering, thermal, and electrochemical probes, we decouple the major contributors for the thermal instability from intertwined factors. Our research work demonstrates that the grain microstructures play an essential role in the thermal stability of polycrystalline lithium-based positive battery electrodes. We also show that the oxygen release, a crucial process during battery thermal runaway, can be regulated by engineering grain arrangements. Furthermore, the grain arrangements can also modulate the macroscopic crystallographic transformation pattern and oxygen diffusion length in layered oxide cathode materials.

Structural Evolution and Transition Dynamics in Lithium Ion Battery under Fast Charging: An Operando Neutron Diffraction Investigation.

Fast charging (<15 min) of lithium-ion batteries (LIBs) for electrical vehicles (EVs) is widely seen as the key factor that will greatly stimulate the EV markets, and its realization is mainly hindered by the sluggish diffusion of Li+ . To have a mechanistic understanding of Li+ diffusion within LIBs, in this study, structural evolutions of electrodes for a Ni-rich LiNi0.6 Mn0.2 Co0.2 O2 (NMC622) || graphite cylindrical cell with high areal loading (2.78 mAh cm-2 ) are developed for operando neutron powder diffraction study at different charging rates. Via sequential Rietveld refinements, changes in structures of NMC622 and Lix C6 are obtained during moderate and fast charging (from 0.27 C to 4.4 C). NMC622 exhibits the same structural evolution regardless of C-rates. For phase transitions of Lix C6 , the stage I (LiC6 ) phase emerges earlier during the stepwise intercalation at a lower state of charge when charging rate is increased. It is also found that the stage II (LiC12 ) → stage I (LiC6 ) transition is the rate-limiting step during fast charging. The LiC12 → LiC6 transition mechanism is further analyzed using the Johnson-Mehl-Avrami-Kolmogorov model. It is concluded as a diffusion-controlled, 1D phase transition with decreasing nucleation kinetics under increasing chargingrates.

Lithium Iron Aluminum Nickelate, LiNix Fey Alz O2 -New Sustainable Cathodes for Next-Generation Cobalt-Free Li-Ion Batteries.

In recent years, cobalt has become a critical constraint on the supply chain of the Li-ion battery industry. With the ever-increasing projections for electric vehicles, the dependency of current Li-ion batteries on the ever-fluctuating cobalt prices poses serious environmental and sustainability issues. To address these challenges, a new class of cobalt-free materials with general formula of LiNix Fey Alz O2 (x + y + z = 1), termed as the lithium iron aluminum nickelate (NFA) class of cathodes, is introduced. These cobalt-free materials are synthesized using the sol-gel process to explore their compositional landscape by varying aluminum and iron. These NFA variants are characterized using electron microscopy, neutron and X-ray diffraction, and Mössbauer and X-ray photoelectron spectroscopy to investigate their morphological, physical, and crystal-structure properties. Operando experiments by X-ray diffraction, Mössbauer spectroscopy, and galvanostatic intermittent titration have been also used to study the crystallographic transitions, electrochemical activity, and Li-ion diffusivity upon lithium removal and uptake in the NFA cathodes. NFA compositions yield specific capacities of ≈200 mAh g-1 , demonstrating reasonable rate capability and cycling stability with ≈80% capacity retention after 100 charge/discharge cycles. While this is an early stage of research, the potential that these cathodes could have as viable candidates in next-generation cobalt-free lithium-ion batteries is highlighted here.

Bulk and surface structural changes in high nickel cathodes subjected to fast charging conditions.

A layered oxide cathode, LiNi0.6Mn0.2Co0.2O2, undergoes noticeable crystal expansion by losing significantly higher amounts of Li+ at the end of fast charging cycles. However, the bulk structure of the cycled NMC622 is restored back to its pristine discharged state when intercalated with enough lithium ions during an electrochemical process.

Effect of Binder Architecture on the Performance of Silicon/Graphite Composite Anodes for Lithium Ion Batteries.

Although significant progress has been made in improving cycling performance of silicon-based electrodes, few studies have been performed on the architecture effect on polymer binder performance for lithium-ion batteries. A systematic study on the relationship between polymer architectures and binder performance is especially useful in designing synthetic polymer binders. Herein, a graft block copolymer with readily tunable architecture parameters is synthesized and tested as the polymer binder for the high-mass loading silicon (15 wt %)/graphite (73 wt %) composite electrode (active materials >2.5 mg/cm2). With the same chemical composition and functional group ratio, the graft block copolymer reveals improved cycling performance in both capacity retention (495 mAh/g vs 356 mAh/g at 100th cycle) and Coulombic efficiency (90.3% vs 88.1% at first cycle) than the physical mixing of glycol chitosan (GC) and lithium polyacrylate (LiPAA). Galvanostatic results also demonstrate the significant impacts of different architecture parameters of graft copolymers, including grafting density and side chain length, on their ultimate binder performance. By simply changing the side chain length of GC-g-LiPAA, the retaining delithiation capacity after 100 cycles varies from 347 mAh/g to 495 mAh/g.

Synthesis and characterization of hollow alpha-Fe2O3 spheres with carbon coating for Li-ion battery.

Carbon coated hollow alpha-Fe2O3 spheres were prepared via a facile two-step hydrothermal method. The appearance and crystalline structure of the samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The morphology showed that the hollow spheres were composed of well crystallized nanoparticles after the first hydrothermal reaction and subsequent calcinations. A thin carbon film was coated on each Fe2O3 nanoparticles after the second hydrothermal procedure. This carbon coating was probably beneficial to maintain the microstructure of the active material during repeatable lithiation and delithiation. Afterwards, the samples were assembled into half-cells to investigate the electrochemical properties. The electrode delivered relatively high initial discharge/charge capacities of 1291/890 mA h g(-1) at the rate of 0.3 C. The reversible capacity maintained very well in a prolonged 140 cycles. The capacity retention was 89% after 70 cycles, and that was 81% after 140 cycles. This exceptional lithium storage property was probably attributed to the porous and hollow structure which allowed the penetration of electrolyte to the inner of the electrode, the nanoscale Fe2O3 particles which shortened the migration pathway for lithium ion, and the carbon coating which kept the active materials structure intact. The attractive electrochemical performance suggested the carbon coated hollow Fe2O3 spheres would be the potential anode material for future lithium ion battery.