Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries

The electrochemical kinetics of battery electrodes at the single-particle scale are measured as a function of state-of-charge, and interpreted with the aid of concurrent transmission X-ray microscopy (TXM) of the evolving particle microstructure. An electrochemical cell operating with near-picoampere current resolution is used to characterize single secondary particles of two widely-used cathode compounds, NMC333 and NCA. Interfacial charge transfer kinetics are found to vary by two orders of magnitude with state-of-charge (SOC) in both materials, but the origin of the SOC dependence differs greatly. NCA behavior is dominated by electrochemically-induced microfracture, although thin binder coatings significantly ameliorate mechanical degradation, while NMC333 demonstrates strongly increasing interfacial reaction rates with SOC for chemical reasons. Micro-PITT is used to separate interfacial and bulk transport rates, and show that for commercially relevant particle sizes, interfacial transport is rate-limiting at low SOC, while mixed-control dominates at higher SOC. These results provide mechanistic insight into the mesoscale kinetics of ion intercalation compounds, which can guide the development of high performance rechargeable batteries

Evolution of the TGF-β Signaling Pathway and Its Potential Role in the Ctenophore, Mnemiopsis leidyi

The TGF-β signaling pathway is a metazoan-specific intercellular signaling pathway known to be important in many developmental and cellular processes in a wide variety of animals. We investigated the complexity and possible functions of this pathway in a member of one of the earliest branching metazoan phyla, the ctenophore Mnemiopsis leidyi. A search of the recently sequenced Mnemiopsis genome revealed an inventory of genes encoding ligands and the rest of the components of the TGF-β superfamily signaling pathway. The Mnemiopsis genome contains nine TGF-β ligands, two TGF-β-like family members, two BMP-like family members, and five gene products that were unable to be classified with certainty. We also identified four TGF-β receptors: three Type I and a single Type II receptor. There are five genes encoding Smad proteins (Smad2, Smad4, Smad6, and two Smad1s). While we have identified many of the other components of this pathway, including Tolloid, SMURF, and Nomo, notably absent are SARA and all of the known antagonists belonging to the Chordin, Follistatin, Noggin, and CAN families. This pathway likely evolved early in metazoan evolution as nearly all components of this pathway have yet to be identified in any non-metazoan. The complement of TGF-β signaling pathway components of ctenophores is more similar to that of the sponge, Amphimedon, than to cnidarians, Trichoplax, or bilaterians. The mRNA expression patterns of key genes revealed by in situ hybridization suggests that TGF-β signaling is not involved in ctenophore early axis specification. Four ligands are expressed during gastrulation in ectodermal micromeres along all three body axes, suggesting a role in transducing earlier maternal signals. Later expression patterns and experiments with the TGF-β inhibitor SB432542 suggest roles in pharyngeal morphogenesis and comb row organization

Chemical and Structural Mapping of Cathodes for Li-Ion Batteries From the Nano- to the Electrode-Scale

High-performance rechargeable batteries will play a key role in supplying our future energy needs. Electric vehicles, grid storage and portable devices place stringent demands on battery performance that cannot be fully satisfied with today's technologies. Bridging this gap requires an understanding of the chemistry occurring within a battery at multiple length-scales. The coupling of chemically sensitive spectroscopy and diffraction techniques with the spatial resolution provided by X-ray microscopy reveals heterogeneities at length-scales ranging from millimeters to nanometers, where kinetic limitations at one scale dictate the behavior at larger scales. Understanding the reaction inefficiencies underlying these heterogeneities is a key step in achieving next-generation battery performance. High-resolution ptychographic microscopy was used to probe the distribution of oxidation states within individual cathode particles, revealing incomplete oxidation unevenly distributed within particles, resulting in part from irreversible secondary reaction pathways. Reduced nickel states were found to dominate the outer atomic layer, even when the cell was subjected to highly oxidizing potentials. Full-field microscopy of secondary particles was conducted under applied current ("operando"), enabling observations that were not subject to relaxation effects but instead governed by the kinetic limitations present during real-world operation. Discrepancies between ensemble-average and particle-level measurements were found, demonstrating a high level of thermodynamic irreversibility in local redox reactions. Furthermore, a correlation was found between particle micro-structure and anomalous nickel reduction, clarifying the relationship between particle micro-structure and redox chemistry. A novel structural mapping technique was developed and used to measure heterogeneity within complete high energy density electrodes. The resulting maps reveal transport limitations through the solid matrix of the electrode and provide a comparison between solid and liquid diffusion. The multi-length-scale approach presented here provides a more detailed view of the underlying battery chemistry than is possible by conventional ensemble-averaged methods alone, and will provide a foundation for more targeted engineering solutions to performance limitations in Li-ion battery cathodes

3D Quantification of Elemental Gradients within Heterostructured Particles of Battery Cathodes

Heterogenous architectures with elemental gradients tailored within particles have been pursued to combat the instabilities limiting Ni-rich cathode materials for lithium-ion batteries. The growth of different compositional layers is accomplished during the synthesis of hydroxide precursors. However, the extent to which these concentration gradients are modified during high-temperature reactions is difficult to establish in their intact, spherical form. Here, we show the entire three-dimensional structure of a secondary particle can be resolved non-destructively with differential X-ray absorption spectroscopy (XAS) through transmission X-ray microscopy (TXM). The relationship between particle location and elemental content was fully quantified, with high statistical significance, for heterostructures possessing different compositional gradients in the precursors with 90:5:5 Ni:Mn:Co core compositions. Reduced elemental heterogeneity was observed after high-temperature synthesis, but gradients remained. The methodology presented should be used to guide synthesis while assuring that gains in electrochemical performance are linked to precise elemental distributions at the nanoscale

Origin of Rapid Delithiation In Secondary Particles Of LiNi0.8Co0.15Al0.05O2 and LiNiyMnzCo(1-y-z)O2 Cathodes

Most research on the electrochemical dynamics in materials for high-energy Li-ion batteries has focused on the global behavior of the electrode. This approach is susceptible to misleading analyses resulting from idiosyncratic kinetic conditions, such as surface impurities inducing an apparent two-phase transformation within LiNi 0.8Co0.15Al0.05O2 . Here, we use nano-focused X-ray probes to measure delithiation operando at the scale of secondary particle agglomerates in layered cathode materials during charge. After an initial latent phase, individual secondary particles undergo rapid, stochastic, and largely uniform delithiation, which is in contrast with the gradual increase in cell potential. This behavior reproduces across several layered oxides. Operando X-ray microdiffraction (µ-XRD) leverages the relationship between Li content and lattice parameter to further reveal that rate acceleration occurs between Li-site fraction (xLi) ~0.9 and ~0.4 for LiNi0.8Co0.15Al0.05O2 . Physics-based modeling shows that, to reproduce the experimental results, the exchange current density (i0) must depend on xLi , and that i0 should increase rapidly over three orders of magnitude at the transition point. The specifics and implications of this jump in i0 are crucial to understanding the charge-storage reaction of Li-ion battery cathodes