Lithiation Gradients and Tortuosity Factors in Thick NMC111-Argyrodite Solid-State Cathodes.

Achieving high energy density in all-solid-state lithium batteries will require the design of thick cathodes, and these will need to operate reversibly under normal use conditions. We use high-energy depth-profiling X-ray diffraction to measure the localized lithium content of Li1-xNi1/3Mn1/3Co1/3O2 (NMC111) through the thickness of 110 µm thick composite cathodes. The composite cathodes consisted of NMC111 of varying mass loadings mixed with argyrodite solid electrolyte Li6PS5Cl (LPSC). During cycling at C/10, substantial lithiation gradients developed, and varying the NMC111 loading altered the nature of these gradients. Microstructural analysis and cathode modeling showed this was due to high tortuosities in the cathodes. This was particularly true in the solid electrolyte phase, which experienced a marked increase in tortuosity factor during the initial charge. Our results demonstrate that current distributions are observed in sulfide-based composites and that these will be an important consideration for practical design of all-solid-state batteries.

Methods for Tomographic Segmentation in Pseudo-Cylindrical Coordinates for Bobbin-Type Batteries.

High-resolution X-ray computed tomography (CT) has become an invaluable tool in battery research for its ability to probe phase distributions in sealed samples. The Cartesian coordinates used in describing the CT image stack are not appropriate for understanding radial dependencies, like that seen in bobbin-type batteries. The most prominent of these bobbin-type batteries is alkaline Zn-MnO2, which dominates the primary battery market. To understand material radial dependencies within these batteries, a method is presented to approximate the Cartesian coordinates of CT data into pseudo-cylindrical coordinates. This is important because radial volume fractions are the output of computational battery models, and this will allow the correlation of a battery model to CT data. A selection of 10 anodes inside Zn-MnO2 AA batteries are used to demonstrate the method. For these, the pseudo-radius is defined as the relative distance in the anode between the central current collecting pin and the separator. Using these anodes, we validate that this method results in averaged one-dimensional material profiles that, when compared to other methods, show a better quantitative match to individual local slices of the anodes in the polar θ-direction. The other methods tested are methods that average to an absolute center point based on either the pin or the separator. The pseudo-cylindrical method also corrects for slight asymmetries observed in bobbin-type batteries because the pin is often slightly off-center and the separator often has a noncircular shape.

Tailoring Electrode-Electrolyte Interfaces in Lithium-Ion Batteries Using Molecularly Engineered Functional Polymers.

Electrode-electrolyte interfaces (EEIs) affect the rate capability, cycling stability, and thermal safety of lithium-ion batteries (LIBs). Designing stable EEIs with fast Li+ transport is crucial for developing advanced LIBs. Here, we study Li+ kinetics at EEIs tailored by three nanoscale polymer thin films via chemical vapor deposition (CVD) polymerization. Small binding energy with Li+ and the presence of sufficient binding sites for Li+ allow poly(3,4-ethylenedioxythiophene) (PEDOT) based artificial coatings to enable fast charging of LiCoO2. Operando synchrotron X-ray diffraction experiments suggest that the superior Li+ transport property in PEDOT further improves current homogeneity in the LiCoO2 electrode during cycling. PEDOT also forms chemical bonds with LiCoO2, which reduces Co dissolution and inhibits electrolyte decomposition. As a result, the LiCoO2 4.5 V cycle life tested at C/2 increases over 1700% after PEDOT coating. In comparison, the other two polymer coatings show undesirable effects on LiCoO2 performance. These insights provide us with rules for selecting/designing polymers to engineer EEIs in advanced LIBs.

In situ X-ray spatial profiling reveals uneven compression of electrode assemblies and steep lateral gradients in lithium-ion coin cells.

Coin cells are used extensively as test devices in battery research for evaluation of new materials and optimization of cycling protocols. In this study, in situ X-ray diffraction profilometry is used to characterize spatial distribution of the active materials, lithiation, and phase distribution in electrodes of NCM523/graphite coin cells. The X-ray data indicate uneven areal compression of the electrode assembly in such cells, which we trace to a specific design feature that leads to elastic deformation of a metal spacer. Steep lithiation gradients observed in the electrodes imply radially-dependent resistivity, for which uneven compression of the separator is a likely cause. Electrochemical model calculations suggest that variable porosity of the polymer separator would account for the salient features of spatial profiles observed in these coin cells.

Polymorphism in a high-entropy alloy.

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiation X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. As pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.

Quantifying the Nucleation and Growth Kinetics of Microwave Nanochemistry Enabled by in Situ High-Energy X-ray Scattering.

The fast reaction kinetics presented in the microwave synthesis of colloidal silver nanoparticles was quantitatively studied, for the first time, by integrating a microwave reactor with in situ X-ray diffraction at a high-energy synchrotron beamline. Comprehensive data analysis reveals two different types of reaction kinetics corresponding to the nucleation and growth of the Ag nanoparticles. The formation of seeds (nucleation) follows typical first-order reaction kinetics with activation energy of 20.34 kJ/mol, while the growth of seeds (growth) follows typical self-catalytic reaction kinetics. Varying the synthesis conditions indicates that the microwave colloidal chemistry is independent of concentration of surfactant. These discoveries reveal that the microwave synthesis of Ag nanoparticles proceeds with reaction kinetics significantly different from the synthesis present in conventional oil bath heating. The in situ X-ray diffraction technique reported in this work is promising to enable further understanding of crystalline nanomaterials formed through microwave synthesis.

In operando spatiotemporal study of Li(2)O(2) grain growth and its distribution inside operating Li-O(2) batteries.

Nanocrystalline lithium peroxide (Li2 O2 ) is considered to play a critical role in the redox chemistry during the discharge-charge cycling of the Li-O2 batteries. In this report, a spatially resolved, real-time synchrotron X-ray diffraction technique was applied to study the cyclic formation/decomposition of Li2 O2 crystallites in an operating Li-O2 cell. The evaluation of Li2 O2 grain size, concentration, and spatial distribution inside the cathode is demonstrated under the actual cycling conditions. The study not only unambiguously proved the reversibility of the Li2 O2 redox reaction during reduction and evolution of O2 , but also allowed for the concentration and dimension growths of the peroxide nanocrystallites to be accurately measured at different regions within the cathode. The results provide important insights for future investigation on mass and charge transport properties in Li2 O2 and improvement in cathode structure and material design.

Quantitative determination of fragmentation kinetics and thermodynamics of colloidal silver nanowires by in situ high-energy synchrotron X-ray diffraction.

Colloidal silver nanowires become instable and tend to fragment into shortened nanorods and nanoparticles at elevated temperatures. Such morphological variations are associated with the transformation of crystalline structures from the body-centered tetragonal (b.c.t.) lattices into the face-centered cubic (f.c.c.) ones. The crystalline phase transformation has been probed in real time with an in situ technique based on time-resolved high-energy synchrotron X-ray diffraction. Comprehensive analysis of the in situ measurements provides, for the first time, the quantitative understanding of kinetics and thermodynamics involved in the fragmentation of the colloidal silver nanowires.

Reversibility of anodic lithium in rechargeable lithium-oxygen batteries.

Non-aqueous lithium-air batteries represent the next-generation energy storage devices with very high theoretical capacity. The benefit of lithium-air batteries is based on the assumption that the anodic lithium is completely reversible during the discharge-charge process. Here we report our investigation on the reversibility of the anodic lithium inside of an operating lithium-air battery using spatially and temporally resolved synchrotron X-ray diffraction and three-dimensional micro-tomography technique. A combined electrochemical process is found, consisting of a partial recovery of lithium metal during the charging cycle and a constant accumulation of lithium hydroxide under both charging and discharging conditions. A lithium hydroxide layer forms on the anode separating the lithium metal from the separator. However, numerous microscopic 'tunnels' are also found within the hydroxide layer that provide a pathway to connect the metallic lithium with the electrolyte, enabling sustained ion-transport and battery operation until the total consumption of lithium.

Microfocused X-ray study on precipitate formation in the separator region of nonaqueous Li-O(2) batteries.

Using a microfocused synchrotron X-ray diffraction (µ-XRD) method, we systematically investigated the distributions of insoluble lithium precipitates, which formed through electrolyte decomposition, separately in all three regions (cathode, separator, and anode) of failed batteries with a spatial resolution of 20 µm. We found unexpectedly that there was a significantly higher concentration (almost twice as much) of precipitates in the separator than in the cathode. SEM revealed that the precipitates grew on the separator fiber surface, ultimately obstructing the pores serving as the ion-transport channel. A "refurbished" battery, which was composed of a spent separator from a failed battery, showed a much higher overpotential and shorter cycle life than that found in a new battery.

Ambient-stable tetragonal phase in silver nanostructures.

Crystallization of noble metal atoms usually leads to the highly symmetric face-centred cubic phase that represents the thermodynamically stable structure. Introducing defective microstructures into a metal crystal lattice may induce distortions to form non-face-centered cubic phases when the lateral dimensions of objects decrease down to nanometre scale. However, stable non-face-centered cubic phases have not been reported in noble metal nanoparticles. Here we report that a stable body-centred tetragonal phase is observed in silver nanoparticles with fivefold twinning even at ambient conditions. The body-centered tetragonal phase originates from the distortion of cubic silver lattices due to internal strains in the twinned nanoparticles. The lattice distortion in the centre of such a nanoparticle is larger than that in the surfaces, indicating that the nanoparticle is composed of a highly strained core encapsulated in a less-strained sheath that helps stabilize the strained core.

Layering of [BMIM]+-based ionic liquids at a charged sapphire interface.

The structure of two model room temperature ionic liquids, [BMIM](+)[PF(6)](-) and [BMIM](+)[BF(4)](-), near the solid/liquid interface with charged Al(2)O(3)(0001) (sapphire) was determined with subnanometer resolution by high energy (72.5 keV) x-ray reflectivity. [BMIM](+)[PF(6)](-) exhibits alternately charged, exponentially decaying, near-surface layering. By contrast, the smaller-anion compound, [BMIM](+)[BF(4)](-), shows only a single layer of enhanced electron density at the interface. The different layering behaviors, and their characteristic length scales, correspond well to the different bulk diffraction patterns, also measured in this study. Complementary measurements of the surface and interface energies showed no significant different between the two RTILs. The combined bulk-interface results support the conclusion that the interfacial ordering is dominated by the same electrostatic ion-ion interactions dominating the bulk correlations, with hydrogen bonding and dispersion interactions playing only a minor role.

Molecular layering of fluorinated ionic liquids at a charged sapphire (0001) surface.

Room-temperature ionic liquids (RTILs) are promising candidates for a broad range of "green" applications, for which their interaction with solid surfaces plays a crucial role. In this high-energy x-ray reflectivity study, the temperature-dependent structures of three ionic liquids with the tris(pentafluoroethyl)trifluorophosphate anion in contact with a charged sapphire substrate were investigated with submolecular resolution. All three RTILs show strong interfacial layering, starting with a cation layer at the substrate and decaying exponentially into the bulk liquid. The observed decay length and layering period point to an interfacial ordering mechanism, akin to the charge inversion effect, which is suggested to originate from strong correlations between the unscreened ions. The observed layering is expected to be a generic feature of RTILs at charged interfaces.

The controlled evolution of a polymer single crystal.

We present a method for controlling the initiation and kinetics of polymer crystal growth using dip-pen nanolithography and an atomic force microscope tip coated with poly-dl-lysine hydrobromide. Triangular prisms of the polymer epitaxially grow on freshly cleaved mica substrates, and their in-plane and out-of-plane growth rates can be controlled by raster scanning the coated tip across the substrate. Atomic force microscope images were concomitantly recorded, providing a set of photographic images of the process as it spans the nanometer- to micrometer-length scales as a function of environmental conditions.