Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge.

Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior of LiNi0.6Mn0.2Co0.2O2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors or oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials.

Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials.

Redox phase transformations are relevant to a number of metrics pertaining to the electrochemical performance of batteries. These phase transformations deviate from and are more complicated than the conventional theory of phase nucleation and propagation, owing to simultaneous changes of cationic and anionic valence states as well as the polycrystalline nature of battery materials. Herein, we propose an integrative approach of mapping valence states and constructing chemical topographies to investigate the redox phase transformation in polycrystalline layered oxide cathode materials under thermal abuse conditions. We discover that, in addition to the three-dimensional heterogeneous phase transformation, there is a mesoscale evolution of local valence curvatures in valence state topographies. The relative probability of negative and positive local valence curvatures alternates during the layered-to-spinel/rocksalt phase transformation. The implementation of our method can potentially provide a universal approach to study phase transformation behaviors in battery materials and beyond.

Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties.

Layered lithium transition metal oxides, in particular, NMCs (LiNixCoyMnzO2) represent a family of prominent lithium ion battery cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety for electric vehicles and grid storage. Our work has focused on various strategies to improve performance and to understand the limitations to these strategies, which include altering compositions, utilizing cation substitutions, and charging to higher than usual potentials in cells. Understanding the effects of these strategies on surface and bulk behavior and correlating structure-performance relationships advance our understanding of NMC materials. This also provides information relevant to the efficacy of various approaches toward ensuring reliable operation of these materials in batteries intended for demanding traction and grid storage applications. In this Account, we start by comparing NMCs to the isostructural LiCoO2 cathode, which is widely used in consumer batteries. Effects of changing the metal content (Ni, Mn, Co) upon structure and performance of NMCs are briefly discussed. Our early work on the effects of partial substitution of Al, Fe, and Ti for Co on the electrochemical and bulk structural properties is then covered. The original aim of this work was to reduce the Co content (and thus the raw materials cost) and to determine the effect of the substitutions on the electrochemical and bulk structural properties. More recently, we have turned to the application of synchrotron and advanced microscopy techniques to understand both bulk and surface characteristics of the NMCs. Via nanoscale-to-macroscale spectroscopy and atomically resolved imaging techniques, we were able to determine that the surfaces of NMC undergo heterogeneous reconstruction from a layered structure to rock salt under a variety of conditions. Interestingly, formation of rock salt also occurs under abuse conditions. The surface structural and chemical changes affect the charge distribution, the charge compensation mechanisms, and ultimately, the battery performance. Surface reconstruction, cathode/electrolyte interface layer formation, and oxygen loss are intimately related, making it difficult to disentangle the effects of each of these phenomena. They are driven by the different redox activities of Ni and O on the surface and in the bulk; there is a greater tendency for charge compensation to occur on oxygen anions at particle surfaces rather than on Ni, whereas the Ni in the bulk is more redox active than on the surface. Finally, our latest research efforts are directed toward understanding the thermal properties of NMCs, which is highly relevant to their safety in operating cells.

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries.

Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage. The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials. There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications. Further progress with rechargeable batteries may require new chemistries (lithium ion batteries and beyond) and better understanding of materials electrochemistry in the various battery technologies. In the past decade, advancement of battery materials has been complemented by new analytical techniques that are capable of probing battery chemistries at various length and time scales. Synchrotron X-ray techniques stand out as one of the most effective methods that allow for nearly nondestructive probing of materials characteristics such as electronic and geometric structures with various depth sensitivities through spectroscopy, scattering, and imaging capabilities. This article begins with the discussion of various rechargeable batteries and associated important scientific questions in the field, followed by a review of synchrotron X-ray based analytical tools (scattering, spectroscopy, and imaging) and their successful applications (ex situ, in situ, and in operando) in gaining fundamental insights into these scientific questions. Furthermore, electron microscopy and spectroscopy complement the detection length scales of synchrotron X-ray tools and are also discussed toward the end. We highlight the importance of studying battery materials by combining analytical techniques with complementary length sensitivities, such as the combination of X-ray absorption spectroscopy and electron spectroscopy with spatial resolution, because a sole technique may lead to biased and inaccurate conclusions. We then discuss the current progress of experimental design for synchrotron experiments and methods to mitigate beam effects. Finally, a perspective is provided to elaborate how synchrotron techniques can impact the development of next-generation battery chemistries.

A spongy nickel-organic CO2 reduction photocatalyst for nearly 100% selective CO production.

Solar-driven photocatalytic conversion of CO2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H2 evolution during photocatalytic CO2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO2 to CO, with a production rate of ~1.6 × 104 µmol hour-1 g-1. No measurable H2 is generated during the reaction, leading to nearly 100% selective CO production over H2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO2 reduction reactions generate formic acid and acetic acid. Achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy.

Intermediate selectivity in the oxidation of phenols using plasmonic Au/ZnO photocatalysts.

Tunable reaction selectivity on a single catalyst is a continual goal in chemical syntheses. Herein, we report an unexpected light-directed intermediate selectivity using well-known plasmonic photocatalysts. We observed distinct intermediate selectivity behaviors between using UV and visible light irradiations. Chemical computations and quenching experiments suggest that the radicals generated by the plasmonic excitation govern the light-directed selectivity. The broader impact of this work ranges from selective yield of desirable intermediates for subsequent syntheses without tedious separation procedures, to arousing interest in examining new opportunities for plasmonic photocatalysts.

In Situ Engineering of the Electrode-Electrolyte Interface for Stabilized Overlithiated Cathodes.

The first-ever demonstration of stabilized Si/lithium-manganese-rich full cells, capable of retaining >90% energy over early cycling and >90% capacity over more than 750 cycles at the 1C rate (100% depth-of-discharge), is made through the utilization of a modified ionic-liquid electrolyte capable of forming a favorable cathode-electrolyte interface.

Surface Modification of Gd Nanoparticles with pH-Responsive Block Copolymers for Use As Smart MRI Contrast Agents.

Despite recent advances in the understanding of fundamental cancer biology, cancer remains the second most common cause of death in the United States. One of the primary factors indicative of high cancer morbidity and mortality and aggressive cancer phenotypes is tumors with a low extracellular pH (pHe). Thus, the ability to measure tumor pHe in vivo using noninvasive and accurate techniques that also provide high spatiotemporal resolution has become increasingly important and is of great interest to researchers and clinicians. In an effort to develop a pH-responsive magnetic resonance imaging (MRI) contrast agent (CA) that has the potential to be used to measure tumor pHe, well-defined pH-responsive polymers, synthesized via reversible addition-fragmentation chain transfer polymerization, were attached to the surface of gadolinium-based nanoparticles (GdNPs) via a "grafting to" method after reduction of the thiocarbonylthio end groups. The successful modification of the GdNPs was verified by transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and dynamic light scattering. The performance of the pH-responsive polymer modified GdNPs was then evaluated for potential use as smart MRI CAs via monitoring the relaxivity changes with changing environmental pH. The results suggested that the pH-responsive polymers can be used to effectively modify the GdNPs surface to prepare a smart contrast agent for MRI.

Poly(acrylic acid) Bridged Gadolinium Metal-Organic Framework-Gold Nanoparticle Composites as Contrast Agents for Computed Tomography and Magnetic Resonance Bimodal Imaging.

Imaging contrast agents for magnetic resonance imaging (MRI) and computed tomography (CT) have received significant attention in the development of techniques for early stage cancer diagnosis. Gadolinium (Gd)(III), which has seven unpaired electrons and a large magnetic moment, can dramatically influence the water proton relaxation and hence exhibits excellent MRI contrast. On the other hand, gold (Au), which has a high atomic number and high X-ray attenuation coefficient, is an ideal contrast agent candidate for X-ray-based CT imaging. Gd metal-organic framework (MOF) nanoparticles with tunable size, high Gd(III) loading and multivalency can potentially overcome the limitations of clinically utilized Gd chelate contrast agents. In this work, we report for the first time the integration of GdMOF nanoparticles with gold nanoparticles (AuNPs) for the preparation of a MRI/CT bimodal imaging agent. Highly stable hybrid GdMOF/AuNPs composites have been prepared by using poly(acrylic acid) as a bridge between the GdMOF nanoparticles and AuNPs. The hybrid nanocomposites were then evaluated in MRI and CT imaging. The results revealed high longitudinal relaxivity in MRI and excellent CT imaging performance. Therefore, these GdMOF/AuNPs hybrid nanocomposites potentially provide a new platform for the development of multimodal imaging probes.

Immunostimulatory properties and enhanced TNF- alpha mediated cellular immunity for tumor therapy by C60(OH)20 nanoparticles.

Publications concerning the mechanism of biological activity, especially the immunological mechanism of C(60)(OH)(20) nanoparticles, are relatively limited. However, the structure and characteristics of this carbon allotrope have been widely investigated. In this paper, we have demonstrated that water-soluble C(60)(OH)(20) nanoparticles have an efficient anti-tumor activity in vivo, and show specific immunomodulatory effects to the immune cells, such as T cells and macrophages, both in vivo and in vitro. For example, C(60)(OH)(20) nanoparticles can increase the production of T-helper cell type 1 (Th1) cytokines (IL-2, IFN- gamma and TNF-alpha), and decrease the production of Th2 cytokines (IL-4, IL-5 and IL-6) in serum samples. On the other hand, C(60)(OH)(20) nanoparticles show almost no adverse effect to the viability of immune cells in vitro but stimulate the immune cells to release more cytokines, in particular TNF- alpha, which plays a key role in the cellular immune process to help eliminate abnormal cells. TNF- alpha production increased almost three-fold in treated T lymphocytes and macrophages. Accordingly, we conclude that C(60)(OH)(20) nanoparticles have an efficient anti-tumor activity and this effect is associated with an increased CD(4)(+)/CD(8)(+) lymphocyte ratio and the enhancement of TNF- alpha production. The data suggest that C(60)(OH)(20) nanoparticles can improve the immune response to help to scavenge and kill tumor cells.