Understanding the Role of Overpotentials in Lithium Ion Conversion Reactions: Visualizing the Interface.

Oxide conversion reactions are known to have substantially higher specific capacities than intercalation materials used in Li-ion batteries, but universally suffer from large overpotentials associated with the formation of interfaces between the resulting nanoscale metal and Li2O products. Here we use the interfacial sensitivity of operando X-ray reflectivity to visualize the structural evolution of ultrathin NiO electrodes and their interfaces during conversion. We observe two additional reactions prior to the well-known bulk, three-dimensional conversion occurring at 0.6 V: an accumulation of lithium at the buried metal/oxide interface (at 2.2 V) followed by interfacial lithiation of the buried NiO/Ni interface at the theoretical potential for conversion (at 1.9 V). To understand the mechanisms for bulk and interfacial lithiation, we calculate interfacial energies using density functional theory to build a potential-dependent nucleation model for conversion. These calculations show that the additional space charge layer of lithium is a crucial component for reducing energy barriers for conversion in NiO.

Mechanistic Analysis of Oxygen Vacancy-Driven Conductive Filament Formation in Resistive Random Access Memory Metal/NiO/Metal Structures.

Electrically switchable resistive random access memories have drawn much interest as nonvolatile memory device candidates based on metal-insulator-metal (MIM) structure concepts. However, atomic level mechanisms that lead to conductive filament (CF) formation in MIM structures are often lacking, such as for the system with NiO as the oxide layer, which was found promising for resistive random access memory (RRAM) device applications. In this work, using density functional theory with a Hubbard-type on-site Coulomb correction, which we carefully benchmarked, we analyzed the intrinsic propensity toward CF formation in NiO upon introduction of oxygen vacancies, including interfacial effects of Ag or Pt electrodes. First, for stoichiometric MIM structural models, contributions from metal-induced gap states to the electronic density of states (DOS) were identified, accommodating oxygen vacancy states and showing that the interface region is reduced more easily than the bulklike region, for example, for the Ag/NiO/Ag structure. Moreover, a tendency toward oxygen vacancy clustering was demonstrated, important for CF formation. Indeed, by introducing ordered oxygen vacancies into the oxide layer for both MIM models, several extended defect states within the forbidden gap have resulted, which lead to defect-assisted transport. These were shown to be influenced by the spatial distribution and number of oxygen vacancies in the filament, where the degree of reduction of Ni atoms changes based on the immediate surroundings. Projected electronic DOS for individual Ni atoms in regions near and away from oxygen vacancies indicated that those Ni close to oxygen vacancies contribute most to the conductivity. Interestingly, based on charge analyses, these atoms are revealed to undergo significant reduction, generating a locally conductive region in the oxide layer that consists of metallic/near-metallic Ni (Ni0), formed through local reduction.

Cyano-Functionalized Triarylamines on Coinage Metal Surfaces: Interplay of Intermolecular and Molecule-Substrate Interactions.

The self-assembly of cyano-functionalized triarylamine derivatives on Cu(111), Ag(111) and Au(111) was studied by means of scanning tunnelling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy and density functional theory calculations. Different bonding motifs, such as antiparallel dipolar coupling, hydrogen bonding and metal coordination, were observed. Whereas on Ag(111) only one hexagonally close-packed pattern stabilized by hydrogen bonding is observed, on Au(111) two different partially porous phases are present at submonolayer coverage, stabilized by dipolar coupling, hydrogen bonding and metal coordination. In contrast to the self-assembly on Ag(111) and Au(111), for which large islands are formed, on Cu(111), only small patches of hexagonally close-packed networks stabilized by metal coordination and areas of disordered molecules are found. The significant variety in the molecular self-assembly of the cyano-functionalized triarylamine derivatives on these coinage metal surfaces is explained by differences in molecular mobility and the subtle interplay between intermolecular and molecule-substrate interactions.

First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF.

The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively. The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0-4 V, corresponding to conditions relevant to both anode and cathode SEI's. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O, the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. The results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.

First-principles analysis of defect-mediated Li adsorption on graphene.

To evaluate the possible utility of single layer graphene for applications in Li ion batteries, an extensive series of periodic density functional theory (DFT) calculations are performed on graphene sheets with both point and extended defects for a wide range of lithium coverages. Consistent with recent reports, it is found that Li adsorption on defect-free single layer graphene is not thermodynamically favorable compared to bulk metallic Li. However, graphene surfaces activated by defects are generally found to bind Li more strongly, and the interaction strength is sensitive to both the nature of the defects and their densities. Double vacancy defects are found to have much stronger interactions with Li as compared to Stone-Wales defects, and increasing defect density also enhances the interaction of the Stone-Wales defects with Li. Li interaction with one-dimensional extended defects on graphene is additionally found to be strong and leads to increased Li adsorption. A rigorous thermodynamic analysis of these data establishes the theoretical Li storage capacities of the defected graphene structures. In some cases, these capacities are found to approach, although not exceed, those of graphite. The results provide new insights into the fundamental physics of adsorbate interactions with graphene defects and suggest that careful defect engineering of graphene might, ultimately, provide anode electrodes of suitable capacity for lithium ion battery applications.

localized order-disorder transitions induced by Li segregation in amorphous TiO2 nanoparticles.

Li segregation and transport characteristics in amorphous TiO2 nanoparticles (NPs) are studied using molecular dynamics (MD) simulations. A strong intraparticle segregation of Li is observed, and the degree of segregation is found to correlate with Li concentration. With increasing Li concentration, Li diffusivity and segregation are enhanced, and this behavior is tied to the structural response of the NPs with increasing lithiation. The atoms in the amorphous NPs undergo rearrangement in the regions of high Li concentration, introducing new pathways for Li transport and segregation. These localized atomic rearrangements, in turn, induce preferential crystallization near the surfaces of the NPs. Such rich, dynamical responses are not expected for crystalline NPs, where the presence of well-defined lattice sites leads to limited segregation and transport at high Li concentrations. The preferential crystallization in the near-surface region in amorphous NPs may offer enhanced stability and fast Li transport for Li-ion battery applications, in addition to having potentially useful properties for other materials science applications.

Defect evolution in graphene upon electrochemical lithiation.

Despite rapidly growing interest in the application of graphene in lithium ion batteries, the interaction of the graphene with lithium ions and electrolyte species during electrochemical cycling is not fully understood. In this work, we use Raman spectroscopy in a model system of monolayer graphene transferred on a Si(111) substrate and density functional theory (DFT) to investigate defect formation as a function of lithiation. This model system enables the early stages of defect formation to be probed in a manner previously not possible with commonly used reduced graphene oxide or multilayer graphene substrates. Using ex situ and Ar-atmosphere Raman spectroscopy, we detected a rapid increase in graphene defect level for small increments in the number of lithiation/delithiation cycles until the I(D)/I(G) ratio reaches ∼1.5-2.0 and the 2D peak intensity drops by ∼50%, after which the Raman spectra show minimal changes upon further cycling. Using DFT, the interplay between graphene topological defects and chemical functionalization is explored, thus providing insight into the experimental results. In particular, the DFT results show that defects can act as active sites for species that are present in the electrochemical environment such as Li, O, and F. Furthermore, chemical functionalization with these species lowers subsequent defect formation energies, thus accelerating graphene degradation upon cycling. This positive feedback loop continues until the defect concentration reaches a level where lithium diffusion through the graphene can occur in a relatively unimpeded manner, with minimal further degradation upon extended cycling. Overall, this study provides mechanistic insight into graphene defect formation during lithiation, thus informing ongoing efforts to employ graphene in lithium ion battery technology.

On the role of long range interactions for the adsorption of sexithiophene on Ag(110) surface.

The adsorption characteristics of the sexithiophene (6T) molecule on Ag(110) are studied using density functional theory with the inclusion of van der Waals (vdW) interactions. The stable adsorption configurations on 6T on Ag(110) as well as the nature of bonding the Ag substrate are evaluated. We also assess the performance of the vdW-DF method in describing the adsorption, energetics, heights, as well as the interface characteristics with the Ag(110) surface. We find two lowest adsorption energy configurations, at which the 6T molecule aligns with its molecular long axis parallel and perpendicular to the [001] direction, to be energetically close to each other, suggesting that they may coexist. Our findings indicate a significant increase in the 6T adsorption energies upon the inclusion of vdW interactions with the highest increase obtained using the opt-type functionals, in particular with the optB86b-vdW functional. The revPBE-vdW and rPW86-vdW2 functionals lead to less enhancement in adsorption energies that is attributed to the strong repulsive nature of these functionals, in agreement with earlier predictions. Upon adsorption of the 6T molecule, the changes in the atomic and electronic structures of the 6T molecule and Ag surface are found to be negligible; there is no charge transfer, and no interface state is observed. The work function is reduced upon adsorption with the largest change is ~0.6 eV obtained using the optB88-vdW functional. The results are in good agreement with the available experimental observations of the adsorption configurations and the work function changes. Based on our results, we conclude that the nature of bonding for 6T on Ag(110) can be classified as strong physisorption.

Compositional tuning of structural stability of lithiated cubic titania via a vacancy-filling mechanism under high pressure.

Experimental and theoretical studies on the compositional dependence of stability and compressibility in lithiated cubic titania are presented. The crystalline-to-amorphous phase transition pressure increases monotonically with Li concentration (from ∼17.5 GPa for delithiated to no phase transition for fully lithiated cubic titania up to 60 GPa). The associated enhancement in structural stability is postulated to arise from a vacancy filling mechanism in which an applied pressure drives interstitial Li ions to vacancy sites in the oxide interior. The results are of significance for understanding mechanisms of structural response of metal oxide electrode materials at high pressures as well as emerging energy storage technologies utilizing such materials.

The effect of concentration on Li diffusivity and conductivity in rutile TiO2.

Li transport characteristics are studied by means of density functional theory (DFT) and molecular dynamics (MD) simulations in order to investigate concentration effects on Li chemical diffusivity and conductivity in TiO(2) rutile. Our MD simulations predict one-dimensional diffusion of Li ions via jumps between the octahedral sites along the channels parallel to the c-axis. The diffusion barrier and diffusion coefficient (at room temperature) for the isolated Li, determined by means of DFT calculations, correspond to 60 meV and 9.1 × 10(-6) cm(2) s(-1), respectively. Such a small barrier suggests rapid mass transport along the channels. MD simulations are performed to evaluate the concentration dependent diffusivity profiles. The changes in Li energetics and dynamics are studied as a function of Li content, which is varied primarily between 10% and 50%. In addition, we consider a couple of compositions over 50% although this is above the intercalation limit. Our results suggest that Li diffusivity is strongly dependent on the Li ∶ TiO(2) ratio, and it decreases with increasing Li concentration. For instance, at room temperature, we find Li diffusivity for high concentrations (50% Li) to be three orders of magnitude slower than that for lower concentrations (10% Li). Our analyses on the energetics and dynamics suggest that the changes in the diffusivities originate from successive increases in the barriers with increasing concentration. The decrease in diffusivity as a function of increasing Li content is attributed to the fact that additional Li ions successively block the energetically preferred vacant sites along the channels. Our analyses also show that increasing Li concentration enhances the Li-Li repulsion within the channels, and as a result, diffusion is hindered. We also compare concentration-dependent diffusivities for Li diffusion in anatase, rutile and amorphous TiO(2). Interestingly, we find differing concentration dependence of the diffusivity in these chemically identical but structurally non-equivalent TiO(2) polymorphs. Our study suggests that these differences result from intrinsic structural characteristics of TiO(2) polymorphs, which ultimately contribute to intercalation limit, diffusivity, ionic conductivity, and the electrochemical performance in energy storage applications.

Off-lattice self-learning kinetic Monte Carlo: application to 2D cluster diffusion on the fcc(111) surface.

We report developments of the kinetic Monte Carlo (KMC) method with improved accuracy and increased versatility for the description of atomic diffusivity on metal surfaces. The on-lattice constraint built into our recently proposed self-learning KMC (SLKMC) (Trushin et al 2005 Phys. Rev. B 72 115401) is released, leaving atoms free to occupy 'off-lattice' positions to accommodate several processes responsible for small-cluster diffusion, periphery atom motion and heteroepitaxial growth. This technique combines the ideas embedded in the SLKMC method with a new pattern-recognition scheme fitted to an off-lattice model in which relative atomic positions are used to characterize and store configurations. Application of a combination of the 'drag' and the repulsive bias potential (RBP) methods for saddle point searches allows the treatment of concerted cluster, and multiple- and single-atom, motions on an equal footing. This tandem approach has helped reveal several new atomic mechanisms which contribute to cluster migration. We present applications of this off-lattice SLKMC to the diffusion of 2D islands of Cu (containing 2-30 atoms) on Cu and Ag(111), using the interatomic potential from the embedded-atom method. For the hetero-system Cu/Ag(111), this technique has uncovered mechanisms involving concerted motions such as shear, breathing and commensurate-incommensurate occupancies. Although the technique introduces complexities in storage and retrieval, it does not introduce noticeable extra computational cost.

Structural, vibrational and thermodynamic properties of Ag(n)Cu(34-n) nanoparticles.

We report results of a systematic study of structural, vibrational and thermodynamical properties of 34-atom bimetallic nanoparticles from the Ag(n)Cu(34-n) family using model interaction potentials as derived from the embedded atom method and invoking the harmonic approximation of lattice dynamics. Systematic trends in the bond length and dynamical properties can be explained largely from arguments based on local coordination and elemental environment. Thus an increase in the number of silver atoms in a given neighborhood introduces a monotonic increase in bond length, while an increase of the copper content does the reverse. Moreover, for the bond lengths of the lowest-coordinated (six and eight) copper atoms with their nearest neighbors (Cu atoms), we find that the nanoparticles divide into two groups with the average bond length either close to (∼2.58 Å) or smaller than (∼2.48 Å) that in bulk copper, accompanied by characteristic features in their vibrational density of states. For the entire set of nanoparticles, we find vibrational modes above the bulk bands of copper/silver. We trace a blue shift in the high-frequency end of the spectrum that occurs as the number of copper atoms increases in the nanoparticles, leading to shrinkage of the bond lengths from those in the bulk. The vibrational densities of states at the low-frequency end of the spectrum scale linearly with frequency as for single-element nanoparticles, with a more pronounced effect for these nanoalloys. The Debye temperature is found to be about one-third of that of the bulk for pure copper and silver nanoparticles, with a non-linear increase as copper atoms increase in the nanoalloy.