Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe<inf>x</inf>Co<inf>1-x</inf>PO<inf>4</inf>

The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data, and supporting ex situ 31P NMR spectra. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1-xPO4 for 0 Fe3+) and Li2/3FexCo1-xPO4 for 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, are affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system.This is the final version of the article. It first appeared from The American Chemical Society via https://doi.org/10.1021/acs.chemmater.6b0031

Local Structure Evolution and Modes of Charge Storage in Secondary Li-FeS2_{2} Cells

In the pursuit of high-capacity electrochemical energy storage, a promising domain of research involves conversion reaction schemes, wherein electrode materials are fully transformed during charge and discharge. There are, however, numerous difficulties in realizing theoretical capacity and high rate capability in many conversion schemes. Here we employ operando studies to understand the conversion material FeS$_{2}$, focusing on the local structure evolution of this relatively reversible material. X-ray absorption spectroscopy, pair distribution function analysis, and first-principles calculations of intermediate structures shed light on the mechanism of charge storage in the Li-FeS$_{2}$ system, with some general principles emerging for charge storage in chalcogenide materials. Focusing on second and later charge/discharge cycles, we find small, disordered domains that locally resemble Fe and Li$_{2}$S at the end of the first discharge. Upon charge, this is converted to a Li-Fe-S composition whose local structure reveals tetrahedrally coordinated Fe. With continued charge, this ternary composition displays insertion-extraction behavior at higher potentials and lower Li content. The finding of hybrid modes of charge storage, rather than simple conversion, points to the important role of intermediates that appear to store charge by mechanisms that more closely resemble intercalation.M.M.B. acknowledges support by the Fletcher Jones and Peter J. Frenkel Foundation Fellowships. V.V.T.D.-N. is supported by the University of California President’s Postdoctoral Fellowship and the UCSB California NanoSystems Institute Elings Prize Fellowship. V.V.T.D.-N. gratefully acknowledges the Southern California Electrochemical Energy Storage Alliance (SCEESA), supported by the UCSB CNSI. Experiments at UCSB made use of MRL facilities, supported by the MRSEC Program of the NSF under Grant No. NSF-DMR 1121053. M.A.L. was supported by the RISE program through Grant No. NSF-DMR 1121053. This work was partially supported by the IMI Program of the National Science Foundation under Award No. DMR 08-43934. M.M. and A.J.M. acknowledge the support from the Winton Programme for the Physics of Sustainability. C.P.G. and S.B. thank EPSRC for financial support. This research made use of resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. X-ray absorption experiments were performed at APS 20-BM-B under GUP-41555. Sector 20 operations are supported by the U.S. DOE and the Canadian Light Source. X-ray scattering experiments were performed at APS 11-ID-B under GUP-42128 and GUP-45245

Stable amorphous georgeite as a precursor to a high-activity catalyst .

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored1—georgeite. The first three of these minerals are widely used as catalyst precursors2, 3, 4 for the industrially important methanol-synthesis and low-temperature water–gas shift (LTS) reactions5, 6, 7, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase2, 3, 8, 9, 10 is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite11; with few exceptions12 it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts

Study of the nature and mechanism of the rhombohedral-to-cubic phase transition in alpha-AlF3 with molecular dynamics simulations

α-AlF3, which adopts a rhombohedrally distorted form of the ReO3 structure at room temperature, undergoes a phase transition to the cubic ReO3 structure at 466°C. The phase transition has been studied using molecular dynamics (MD) simulations performed with a polarizable ion model (PIM). The results are compared to information obtained from experimental diffraction data, and analogies to the tilting schemes of the structurally related perovskite phases are made. The cubic phase can be distinguished from the rhombohedral phase by following the Al-F-Al bond angles that describe the tilting of the AlF6 corner sharing octahedra as a function of temperature. The Al-F-Al chains are still bent in the so-called cubic phase, but the direction of tilting of the AlF6 octahedra varies continuously during the MD run, so that the time-averaged symmetry of the system is nearly cubic. The motion of the octahedra primarily involves a 360° rotation of the vector that describes the displacement of the F atom from its ideal position in a linear Al-F-Al chain. It is this 360° motion that distinguishes the cubic from the rhombohedral phase. The high-temperature phase is also associated with increased vibrations of the Al-F-Al chains. The results provide an explanation for the large thermal parameters observed experimentally for fluorine (in structures refined from diffraction data) above the phase transition. The simulation results suggest the possible existence of a third (orthorhombic) form of α-AlF3, which is energetically very similar to the rhombohedral phase at room temperature but differs in its octahedral tilting scheme

Lithiation thermodynamics and kinetics of the TiO2 (B) nanoparticles.

TiO2 (B) has attracted considerable attention in recent years because it exhibits the largest capacity among all studied titania polymorphs, with high rate performance for Li intercalation being achieved when this material is nanostructured. However, due to the complex nature of its lithiation mechanism and practical challenges in probing Li structure in nanostructured materials, a definitive understanding of the lithiation thermodynamics has yet to be established. A comprehensive mechanistic investigation of the TiO2 (B) nanoparticles is therefore presented using a combination of in situ/operando X-ray pair distribution function (PDF) and electrochemical techniques. The discharge begins with surface reactions in parallel with Li insertion into the subsurface of the nanoparticles. The Li bulk insertion starts with a single-phase reaction into the A2 site, a position adjacent to the b-channel. A change of the Li diffusion pathway from that along this open channel to that along the c-direction is likely to occur at the composition of Li0.25TiO2 until Li0.5TiO2 is attained, leading to a two-step A2-site incorporation with one step kinetically distinct from the other. Subsequent Li insertion involves the C' site, a position situated inside the channel, and follows a rapid two-phase reaction to form Li0.75TiO2. Due to the high diffusion barrier associated with the further lithiation, Li insertion into the A1 site, another position adjacent to the channel neighboring the A2 sites, is kinetically restricted. This study not only explores the lithiation reaction thermodynamics and mechanisms of nanoparticulate TiO2 (B) but also serves as a strong reference for future studies of the bulk phase, and for future calculations to study the Li transport properties of TiO2 (B)