Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes

The discovery of facile Li transport in disordered, Li-excess rocksalt materials has opened a vast new chemical space for the development of high energy density, low cost Li-ion cathodes. We develop a strategy for obtaining optimized compositions within this class of materials, exhibiting high capacity and energy density as well as good reversibility, by using a combination of low-valence transition metal redox and a high-valence redox active charge compensator, as well as fluorine substitution for oxygen. Furthermore, we identify a new constraint on high-performance compositions by demonstrating the necessity of excess Li capacity as a means of counteracting high-voltage tetrahedral Li formation, Li-binding by fluorine and the associated irreversibility. Specifically, we demonstrate that 10–12% of Li capacity is lost due to tetrahedral Li formation, and 0.4–0.8 Li per F dopant is made inaccessible at moderate voltages due to Li–F binding. We demonstrate the success of this strategy by realizing a series of high-performance disordered oxyfluoride cathode materials based on Mn²+/⁴+ and V⁴+/⁵+ redox.Vehicle Technologies Program (U.S.) (Contract No. DE-AC02-05CH11231)United States. Department of Energy. Office of Energy Efficiency and Renewable Energy. Advanced Battery Materials Research Program (Subcontract No. 7056411)National Science Foundation (U.S.) (Reward No. OCI-1147503)National Science Foundation (U.S.) (grant number ACI- 105357)National Science Foundation (U.S.) (NSF DMR 172025)United States. Department of Energy (Contract No. DE-AC02-06C H11357)United States. Department of Energy. Office of Science (contract no. DE-AC02-05CH11231

Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries

This work was supported by the Robert Bosch Corporation, Umicore Specialty Oxides and Chemicals, and the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 under the Advanced Battery Materials Research (BMR) Program. The research conducted at the NOMAD Beamline at ORNL’s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U.S. Department of Energy. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The computational analysis was performed using computational resources sponsored by the Department of Energy’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, as well computational resources provided by Extreme Science and Engineering Discovery Environment (XSEDE), which was supported by the National Science Foundation grant number ACI-1053575.Structure plays a vital role in determining materials properties. In lithium ion cathode materials, the crystal structure defines the dimensionality and connectivity of interstitial sites, thus determining lithium ion diffusion kinetics. In most conventional cathode materials that are well-ordered, the average structure as seen in diffraction dictates the lithium ion diffusion pathways. Here, we show that this is not the case in a class of recently discovered high-capacity lithium-excess rocksalts. An average structure picture is no longer satisfactory to understand the performance of such disordered materials. Cation short-range order, hidden in diffraction, is not only ubiquitous in these long-range disordered materials, but fully controls the local and macroscopic environments for lithium ion transport. Our discovery identifies a crucial property that has previously been overlooked and provides guidelines for designing and engineering cation-disordered cathode materials.Publisher PDFPeer reviewe

Head-to-Head Comparison of Flow Reduction between Fibered and Non-Fibered Pushable Coils

Purpose To compare the embolization effects of a non-fibered pushable coil with a conventional fibered pushable coil in an in vitro bench-top experiment. Materials and Methods A simplified vascular phantom with 4 channels (1 for the non-fibered coil, 1 for the fibered coil, and 2 for continuous circuit flow) was used. A single coil of the longest length was inserted to evaluate the effect of single-coil embolization, and 3 consecutive coils were inserted to assess the effect of multiple-coil embolization. Post-embolization angiography was performed to obtain flow variables (time to peak [TTP], relative peak intensity [rPI], and angiographic flow reduction score [AFRS]) from time density curves. The packing densities of the two coil types were calculated, and the AFRS of each channel was determined by dividing the TTP by the rPI. Results When inserting a single coil, the conventional fibered coil demonstrated better flow reduction, as indicated by a higher AFRS (25.6 vs. 17.4, P=0.034). However, the non-fibered coil exhibited a significantly higher packing density (12.9 vs. 2.4, P=0.001). Similar trends were observed with multiple coils. Conclusion The conventional fibered pushable coil showed better flow reduction efficiency, while the non-fibered pushable coil had a higher packing density, likely due to the flexibility of the coil loops. A better understanding of the distinct characteristics of different pushable coils can enhance the outcomes of various vascular embolization

Electrochemical properties and structural evolution of O3-type layered sodium mixed transition metal oxides with trivalent nickel

The electrochemical properties of NaNi0.5Co0.5O2 and NaNi0.5Fe0.5O2 and their structural transitions as a function of Na extraction associated with redox reactions are investigated in this work. Synthesized in the O3-type layered structure, both materials show reasonable electrochemical activities at room temperature, delivering approximately 0.5 Na per formula unit at C/10 discharge. More Na can be reversibly cycled in NaNi0.5Co0.5O2 at elevated temperature and/or in an extended voltage window, while NaNi0.5Fe0.5O2 shows significant capacity fading at a high voltage cutoff which is likely due to Fe4+ migration. In situ X-ray diffraction shows that the structural changes in the two materials upon desodiation are very different. NaNi0.5Co0.5O2 goes through many different two-phase reactions including three different O3-type and three different P3-type structures during cycling, producing a voltage profile with multiple plateau-like features. In contrast, NaNi0.5Fe0.5O2 has a smooth voltage profile and shows the typical O3-P3 phase transition without lattice distortion seen in other materials. This different structural evolution upon desodiation and re-sodiation can be explained by the electronic structure of the mixed transition metals and how it perturbs the ordering between Na ions differently