Anton Van der Ven

Understanding Li Diffusion in Li-Intercalation Compounds

Intercalation compounds, used as electrodes in Li-ion batteries, are a fascinating class of materials that exhibit a wide variety of electronic, crystallographic, thermodynamic, and kinetic properties. With open structures that allow for the easy insertion and removal of Li ions, the properties of these materials strongly depend on the interplay of the host chemistry and crystal structure, the Li concentration, and electrode particle morphology. The large variations in Li concentration within electrodes during each charge and discharge cycle of a Li battery are often accompanied by phase transformations. These transformations include order-disorder transitions, two-phase reactions that require the passage of an interface through the electrode particles, and structural phase transitions, in which the host undergoes a crystallographic change. Although the chemistry of an electrode material determines the voltage range in which it is electrochemically active, the crystal structure of the compound often plays a crucial role in determining the shape of the voltage profile as a function of Li concentration. While the relationship between the voltage profile and crystal structure of transition metal oxide and sulfide intercalation compounds is well characterized, far less is known about the kinetic behavior of these materials. For example, because these processes are especially difficult to isolate experimentally, solid-state Li diffusion, phase transformation mechanisms, and interface reactions remain poorly understood. In this respect, first-principles statistical mechanical approaches can elucidate the effect of chemistry and crystal structure on kinetic properties. In this Account, we review the key factors that govern Li diffusion in intercalation compounds and illustrate how the complexity of Li diffusion mechanisms correlates with the crystal structure of the compound. A variety of important diffusion mechanisms and associated migration barriers are sensitive to the overall Li concentration, resulting in diffusion coefficients that can vary by several orders of magnitude with changes in the lithium content. Vacancy clusters, groupings of vacancies within the crystal lattice, provide a common mechanism that mediates Li diffusion in important intercalation compounds. This mechanism emerges from specific crystallographic features of the host and results in a strong decrease of the Li diffusion coefficient as Li is added to an already Li rich host. Other crystallographic and electronic factors, such as the proximity of transition metal ions to activated states of hops and the occurrence of electronically induced distortions, can result in a strong dependence of the Li mobility on the overall Li concentration. The insights obtained from fundamental studies of ionic diffusion in electrode materials will be instrumental for physical chemists, chemical engineers, synthetic chemists, and materials and device designers who are developing these technologies.

Tracking lithium transport and electrochemical reactions in nanoparticles

Expectations for the next generation of lithium batteries include greater energy and power densities along with a substantial increase in both calendar and cycle life. Developing new materials to meet these goals requires a better understanding of how electrodes function by tracking physical and chemical changes of active components in a working electrode. Here we develop a new, simple in-situ electrochemical cell for the transmission electron microscope and use it to track lithium transport and conversion in FeF(2) nanoparticles by nanoscale imaging, diffraction and spectroscopy. In this system, lithium conversion is initiated at the surface, sweeping rapidly across the FeF(2) particles, followed by a gradual phase transformation in the bulk, resulting in 1-3 nm iron crystallites mixed with amorphous LiF. The real-time imaging reveals a surprisingly fast conversion process in individual particles (complete in a few minutes), with a morphological evolution resembling spinodal decomposition. This work provides new insights into the inter- and intra-particle lithium transport and kinetics of lithium conversion reactions, and may help to pave the way to develop high-energy conversion electrodes for lithium-ion batteries.

Ab initio structure search and in situ 7Li NMR studies of discharge products in the Li-S battery system.

The high theoretical gravimetric capacity of the Li–S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li–S phase diagram using computational techniques and complement this with an in situ 7Li NMR study of the cell during discharge. Both the computational and experimental studies are consistent with the suggestion that the only solid product formed in the cell is Li2S, formed soon after cell discharge is initiated. In situ NMR spectroscopy also allows the direct observation of soluble Li+-species during cell discharge; species that are known to be highly detrimental to capacity retention. We suggest that during the first discharge plateau, S is reduced to soluble polysulfide species concurrently with the formation of a solid component (Li2S) which forms near the beginning of the first plateau, in the cell configuration studied here. The NMR data suggest that the second plateau is defined by the reduction of the residual soluble species to solid product (Li2S). A ternary diagram is presented to rationalize the phases observed with NMR during the discharge pathway and provide thermodynamic underpinnings for the shape of the discharge profile as a function of cell composition.

Mg Intercalation in Layered and Spinel Host Crystal Structures for Mg Batteries

We investigate electrochemical properties of Mg in layered and spinel intercalation compounds from first-principles using TiS2 as a model system. Our calculations predict that Mg(x)TiS2 in both the layered and spinel crystal structures exhibits sloping voltage profiles with steps at stoichiometric compositions due to Mg-vacancy ordering. Mg ions are predicted to occupy the octahedral sites in both layered and spinel TiS2 with diffusion mediated by hops between octahedral sites that pass through adjacent tetrahedral sites. Predicted migration barriers are substantially higher than typical Li-migration barriers in intercalation compounds. The migration barriers are shown to be very sensitive to lattice parameters of the host crystal structure. We also discuss the possible role of rehybridization between the transition metal and the anion in affecting migration barriers.

Dynamic Stereochemical Activity of the Sn2+ Lone Pair in Perovskite CsSnBr3

Stable s(2) lone pair electrons on heavy main-group elements in their lower oxidation states drive a range of important phenomena, such as the emergence of polar ground states in some ferroic materials. Here we study the perovskite halide CsSnBr3 as an embodiment of the broader materials class. We show that lone pair stereochemical activity due to the Sn(2+) s(2) lone pair causes a crystallographically hidden, locally distorted state to appear upon warming, a phenomenon previously referred to as emphanisis. The synchrotron X-ray pair distribution function acquired between 300 and 420 K reveals emerging asymmetry in the nearest-neighbor Sn-Br correlations, consistent with dynamic Sn(2+) off-centering, despite there being no evidence of any deviation from the average cubic structure. Computation based on density functional theory supports the finding of a lattice instability associated with dynamic off-centering of Sn(2+) in its coordination environment. Photoluminescence measurements reveal an unusual blue-shift with increasing temperature, closely linked to the structural evolution. At low temperatures, the structures reflect the influence of octahedral rotation. A continuous transition from an orthorhombic structure (Pnma, no. 62) to a tetragonal structure (P4/mbm, no. 127) is found around 250 K, with a final, first-order transformation at 286 K to the cubic structure (Pm3̅m, no. 221).

Water-Free Titania-Bronze Thin Films With Superfast Lithium Ion Transport

Using pulsed laser deposition, TiO2 (-) B and its recently discovered variant Ca:TiO2 (-) B (CaTi5O11) are synthesized as highly crystalline thin films for the first time by a completely water-free process. Significant enhancement in the Li-ion battery performance is achieved by manipulating the crystal orientation of the films, used as anodes, with a demonstration of extraordinary structural stability under extreme conditions.

Main-Group Halide Semiconductors Derived from Perovskite: Distinguishing Chemical, Structural, and Electronic Aspects

Main-group halide perovskites have generated much excitement of late because of their remarkable optoelectronic properties, ease of preparation, and abundant constituent elements, but these curious and promising materials differ in important respects from traditional semiconductors. The distinguishing chemical, structural, and electronic features of these materials present the key to understanding the origins of the optoelectronic performance of the well-studied hybrid organic-inorganic lead halides and provide a starting point for the design and preparation of new functional materials. Here we review and discuss these distinguishing features, among them a defect-tolerant electronic structure, proximal lattice instabilities, labile defect migration, and, in the case of hybrid perovskites, disordered molecular cations. Additionally, we discuss the preparation and characterization of some alternatives to the lead halide perovskites, including lead-free bismuth halides and hybrid materials with optically and electronically active organic constituents.

Elucidating the origins of phase transformation hysteresis during electrochemical cycling of Li–Sb electrodes

We investigate the origins of phase transformation hysteresis in electrodes of Li-ion batteries, focusing on the alloying reaction of Li with Sb. Electrochemical measurements confirm that the reaction path followed during Li insertion into Sb electrodes differs from that followed upon subsequent Li extraction. Results from first-principles calculations and NMR measurements indicate that Li3Sb is capable of tolerating high Li-vacancy concentrations. An unusually high Li mobility in Li3Sb facilitates over potentials during charging, which leads to a substantially larger driving force for the nucleation of Sb compared to that of Li2Sb. The differences in nucleation driving forces arise from a lever effect that favors phases with large changes in Li concentration over phases that are closer in composition along the equilibrium path. These properties provide an explanation for the observed path hysteresis between charge and discharge in the Li–Sb system and likely also play a role in intercalation compounds and other alloying reactions exhibiting similar phase transformation hysteresis.

Mechanochemical spinodal decomposition: A phenomenological theory of phase transformations in multi-component, crystalline solids

We present a phenomenological treatment of diffusion-driven martensitic phase transformations in multi-component crystalline solids that arise from non-convex free energies in mechanical and chemical variables. The treatment describes diffusional phase transformations that are accompanied by symmetry-breaking structural changes of the crystal unit cell and reveals the importance of a mechanochemical spinodal, defined as the region in strain–composition space, where the free-energy density function is non-convex. The approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. The governing equations describing mechanochemical spinodal decomposition are variationally derived from a free-energy density function that accounts for interfacial energy via gradients of the rapidly varying strain and composition fields. A robust computational framework for treating the coupled, higher-order diffusion and nonlinear strain gradient elasticity problems is presented. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. An evaluation of available experimental phase diagrams and first-principles free energies suggests that mechanochemical spinodal decomposition should occur in metal hydrides such as ZrH2−2c. The rich physics that ensues is explored in several numerical examples in two and three dimensions, and the relevance of the mechanism is discussed in the context of important electrode materials for Li-ion batteries and high-temperature ceramics. A treatment to describe structural phase transformations in materials has been developed by researchers in the USA. Under favorable energetic conditions, some multicomponent solids such as lithium-ion battery electrodes can decompose from a uniform phase into two co-existing phases having different compositions. This spinodal decomposition affects the properties of a range of structural and electronic materials. Now, Krishna Garikipati at the University of Michigan and colleagues have modeled spinodal decomposition triggered by instabilities and variations in either strain or composition throughout a material. The model requires solving a system of complex nonlinear interactions through a computational framework, and represents a new phenomenological description of spinodal decomposition that could potentially be extended to other phase-transformation phenomena. The model may play a role in the study and development of practically relevant materials such as battery electrodes or nanoelectronics.

First-principles Investigation of B-site Ordering in Ba(MgxTa1-x)O3 Microwave Dielectrics with the Complex Perovskite Structure

The B-site cation ordering of Ba(Mg1/3Ta2/3)O3 microwave dielectrics with the complex perovskite structure has been studied using a combination of first-principles calculations, a cluster expansion technique, and Monte Carlo simulations. Our calculations confirm the experimentally observed hexagonal superstructure with space group P3m1 (D33d) as the ground state. The order-disorder transition between the low-temperature 1:2 ordered hexagonal phase (P3m1) and high-temperature simple perovskite phase (Pm3m) is predicted to occur at ~3770 K. This indicates that Ba(Mg1/3Ta2/3)O3 in equilibrium should be fully ordered at all practical temperatures. Sintering at high temperature for a long time or prolonging the anneal should therefore be effective in enhancing the degree of cation order in Ba(Mg1/3Ta2/3)O3. The charge density distribution and one electron density of states (DOS) for the 1:2 ordered structure indicate that Ta and O atoms possess some degree of covalency with some overlap between the O-2p orbitals and the Ta-5d orbitals.