Origin of electrochemical activity in nano-Li2MnO3; Stabilization via a 'point defect scaffold'

Molecular dynamics (MD) simulations of the charging of Li2MnO3 reveal that the reason nanocrystalline-Li2MnO3 is electrochemically active, in contrast to the parent bulk-Li2MnO3, is because in the nanomaterial the tunnels, in which the Li ions reside, are held apart by Mn ions, which act as a pseudo 'point defect scaffold'. The Li ions are then able to diffuse, via a vacancy driven mechanism, throughout the nanomaterial in all spatial dimensions while the 'Mn defect scaffold' maintains the structural integrity of the layered structure during charging. Our findings reveal that oxides, which comprise cation disorder, can be potential candidates for electrodes in rechargeable Li-ion batteries. Moreover, we propose that the concept of a 'point defect scaffold' might manifest as a more general phenomenon, which can be exploited to engineer, for example, two or three-dimensional strain within a host material and can be fine-tuned to optimize properties, such as ionic conductivity

Environment-mediated structure, surface redox activity and reactivity of ceria nanoparticles

Nanomaterials, with potential application as bio-medicinal agents, exploit the chemical properties of a solid, with the ability to be transported (like a molecule) to a variety of bodily compartments. However, the chemical environment can change significantly the structure and hence properties of a nanomaterial. Accordingly, its surface reactivity is critically dependent upon the nature of the (biological) environment in which it resides. Here, we use Molecular Dynamics (MD) simulation, Density Functional Theory (DFT) and aberration corrected TEM to predict and rationalise differences in structure and hence surface reactivity of ceria nanoparticles in different environments. In particular we calculate reactivity 'fingerprints' for unreduced and reduced ceria nanoparticles immersed in water and in vacuum. Our simulations predict higher activities of ceria nanoparticles, towards oxygen release, when immersed in water because the water quenches the coordinative unsaturation of surface ions. Conversely, in vacuum, surface ions relax into the body of the nanoparticle to relieve coordinative unsaturation, which increases the energy barriers associated with oxygen release. Our simulations also reveal that reduced ceria nanoparticles are more active towards surface oxygen release compared to unreduced nanoceria. In parallel, experiment is used to explore the activities of ceria nanoparticles that have suffered a change in environment. In particular, we compare the ability of ceria nanoparticles, in an aqueous environment, to scavenge superoxide radicals compared to the same batch of nanoparticles, which have first been dried and then rehydrated. The latter show a distinct reduction in activity, which we correlate to a change in the redox chemistry associated with moving between different environments. The reactivity of ceria nanoparticles is therefore not only environment dependent, but is also influenced by the transport pathway or history required to reach the particular environment in which its reactivity is to be exploited. © 2013 The Royal Society of Chemistry

Mechanical properties of mesoporous ceria nanoarchitectures

Architectural constructs are engineered to impart desirable mechanical properties facilitating bridges spanning a thousand meters and buildings nearly 1 km in height. However, do the same 'engineering-rules' translate to the nanoscale, where the architectural features are less than 0.0001 mm in size? Here, we calculate the mechanical properties of a porous ceramic functional material, ceria, as a function of its nanoarchitecture using molecular dynamics simulation and predict its yield strength to be almost two orders of magnitude higher than the parent bulk material. In particular, we generate models of nanoporous ceria with either a hexagonal or cubic array of one-dimensional pores and simulate their responses to mechanical load. We find that the mechanical properties are critically dependent upon the orientation between the crystal structure (symmetry, direction) and the pore structure (symmetry, direction). This journal i

Amorphisation and recrystallisation study of lithium intercalation into TiO 2 nano-architecture.

Titanium dioxide is playing an increasingly significant role in easing environmental and energy concerns. Its rich variety of polymorphic crystal structures has facilitated a wide range of applications such as photo-catalysis, photo-splitting of water, photoelectrochromic devices, insulators in metal oxide, semiconductors devices, dye sensitized solar cells (DSSCs) (energy conversions), rechargeable lithium batteries (electrochemical storage). The complex structural aspects in nano TiO 2 , are elucidated by microscopic visualization and quantification of the microstructure for electrode materials, since cell performance and various aging mechanisms depend strongly on the appearance and changes in the microstructure. Recent studies on MnO 2 have demonstrated that amorphisation and recrystallisation simulation method can adequately generate various nanostructures, for Li-ion battery compounds. The method was also previously employed to produce nano-TiO 2 . In the current study, the approach is used to study lithiated nanoporous structure for TiO 2 which have been extensively studied experimentally, as mentioned above. Molecular graphic images showing microstructural features, including voids and channels have accommodated lithium’s during lithiation and delithiation. Preliminary lithiation of TiO 2 will be considered

Tuning the Properties of Nanoceria by Applying Force: Stress Induced Ostwald Ripening

The ionic conductivity and activity of a material, such as ceria, is central to its exploitation in applications such as fuel cells or catalysis. Grain Boundaries (GB) influence profoundly the ionic conductivity and activity of a material. Accordingly, the ability to control GB concentrations is pivotal to these applications. Here, we show that Oswald ripening can be induced by applying uniaxial force. In particular, grain-boundaries are purged to facilitate single nanocrystals from polycrystalline precursors. Our simulations thus predict mechanisms for strain-tunable properties

Mechanical properties of ceria nanorods and nanochains; The effect of dislocations, grain-boundaries and oriented attachment

We predict that the presence of extended defects can reduce the mechanical strength of a ceria nanorod by 70%. Conversely, the pristine material can deform near its theoretical strength limit. Specifically, atomistic models of ceria nanorods have been generated with full microstructure, including: growth direction, morphology, surface roughening (steps, edges, corners), point defects, dislocations and grain-boundaries. The models were then used to calculate the mechanical strength as a function of microstructure. Our simulations reveal that the compressive yield strengths of ceria nanorods, ca. 10 nm in diameter and without extended defects, are 46 and 36 GPa for rods oriented along [211] and [110] respectively, which represents almost 10% of the bulk elastic modulus and are associated with yield strains of about 0.09. Tensile yield strengths were calculated to be about 50% lower with associated yield strains of about 0.06. For both nanorods, plastic deformation was found to proceed via slip in the {001} plane with direction ã??110ã?? - a primary slip system for crystals with the fluorite structure. Dislocation evolution for the nanorod oriented along [110] was nucleated via a cerium vacancy present at the surface. A nanorod oriented along [321] and comprising twin-grain boundaries with {111} interfacial planes was calculated to have a yield strength of about 10 GPa (compression and tension) with the grain boundary providing the vehicle for plastic deformation, which slipped in the plane of the grain boundary, with an associated ã??110ã?? slip direction. We also predict, using a combination of atomistic simulation and DFT, that rutile-structured ceria is feasible when the crystal is placed under tension. The mechanical properties of nanochains, comprising individual ceria nanoparticles with oriented attachment and generated using simulated self-assembly, were found to be similar to those of the nanorod with grain-boundary. Images of the atom positions during tension and compression are shown, together with animations, revealing the mechanisms underpinning plastic deformation. For the nanochain, our simulations help further our understanding of how a crystallising ice front can be used to 'sculpt' ceria nanoparticles into nanorods via oriented attachment. © 2011 The Royal Society of Chemistry

The Structure of Surface Entrance Sites for Li-intercalation into TiO2Nanoparticles, Nanosheets and Mesoporous Architectures with Application for Li-ion Batteries

Power output is central to the viability of a Li-ion battery, and is, in part, dependent upon the activation energy barrier associated with Li intercalation/deintercalation into the host lattice (electrode). The lower the energy barrier, the faster the intercalation reaction rate and greater the power. The activation energy is governed by the atomistic structure(s) of the entrance sites for Li intercalation. Accordingly, a first step in optimising battery power via structural manipulation of entrance sites, is to understand the structure of these entrance sites. However, HRTEM is (presently) unable to characterise the structures of entrance sites with atomistic resolution. Accordingly, we generate models of the entrance sites using Molecular Dynamics. In particular, we simulate the synthetic protocol used to fabricate nanostructured TiO2 experimentally. The resulting atomistic models reveal a highly complex and diverse structural distribution of entrance sites, which emanate from the surface curvature of the nanostructured material. In particular, we show how nanostructuring can be used to change profoundly the nature and concentration of such entrance sites

Strongly Bound Surface Water Affects the Shape Evolution of Cerium Oxide Nanoparticles

The surface structure and composition of functional materials are well-known to be critically important factors controlling the surface reactivity. However, when doped the surface composition will change, and the challenge is to identify its impact on important surface processes and nanoparticle morphologies. We have begun to address this by using a combination of density functional theory and potential-based methods to investigate the effect of surface dopants on water adsorption and morphology of the technologically important material, CeO$_2$, which finds application as electrolyte in SOFCs, catalyst in soot combustion, and enzyme mimetic agents in biomedicine. We show that by mapping CeO$_2$ surface phase diagrams we can predict nanoparticle morphologies as a function of dopant, temperature, and water partial pressure. Our results show that low-temperature, undoped CeO$_2$ nanocubes with active {100} surface sites are thermodynamically stable, but at the typical high temperature, operating conditions favor polyhedra where {100} surfaces are replaced by less active {111} surfaces by surface ion migration. However, doping with trivalent cations, such as Gd$^{3+}$, will increase binding of water on the {100} surfaces and hence act to preserve the cuboidal architecture by capping the active surfaces. As surfaces tend to be decorated by impurities and dopants it is clear that their role should receive more attention and the approach we describe can be routinely applied to nanomaterials, morphologies, and associated active/inactive surfaces

Computer-Aided Design of Nanoceria Structures as Enzyme Mimetic Agents: The Role of Bodily Electrolytes on Maximising Their Activity

Nanoceria, typically used for ‘clean air’ catalytic converter technologies, is the same material that could also be used as a nanomedicine. Specifically, nanoceria, which can capture, store and release oxygen, for oxidative/reductive reactions, can also be used to control oxygen content in cellular environments; as a ‘nanozyme’, nanoceria mimics enzymes by acting as an antioxidant agent. The computational design procedures for predicting active materials for catalytic converters can therefore be used to design active ceria nanozymes. Crucially, the ceria nanomedicine is not a molecule; rather it is a crystal and exploits its unique crystal properties. Here, we use ab initio and classical computer modelling, together with experiment, to design structures for nanoceria that maximises its nanozymetic activity. We predict that the nanomaterial should have (truncated) polyhedral or cuboidal morphologies to expose (active) CeO2 {100} surfaces. It should also contain oxygen vacancies and surface –OH species. We also show that the surface structures strongly affects the biological activity of nanoceria. Analogous to catalyst poisoning, phosphorus 'poisoning' - the interaction of nanoceria with phosphate, a common bodily electrolyte – emanates from phosphate ions binding strongly to CeO2{100} surfaces, inhibiting oxygen capture and release and hence its ability to act as an nanozyme. Conversely, phosphate interaction with {111} surfaces is weak and therefore these surfaces protect the nanozyme against poisoning. The atom-level understanding presented here also illuminates catalytic processes and poisoning in ‘clean-air’ or fuel-cell technologies because the mechanism underpinning and exploited in each technology – oxygen capture, storage and release – is identical

Atomistic Simulation and Characterization of Spinel Li1+x_{1+x}Mn2_2O4_4 (0 ≤ x ≤ 1) Nanoparticles

Lithium-ion batteries, comprising nanoparticulate Ni–Mn–Co (NMC) cathodes that have been used to power electric vehicles, can be improved by blending NMC with Li–Mn–O (LMO). However, LMO undergoes a cubic to tetragonal phase change during charge cycling, which cracks and pulverizes the material, resulting in capacity fading. Structural characterization during the phase transition is the first step in mitigating capacity fading and can be challenging experimentally and computationally. Here, we use simulated amorphization and crystallization to generate atom-level models of the LMO nanoparticles. This simulation strategy does not require any structural information to be predetermined. Instead, the structures evolve “naturally” from amorphous precursors. Analysis of the model Li–Mn–O nanoparticles reveals that they comprise domains of defect-rich spinel, Mn$_3$O$_4$, layered Li$_2$MnO$_3$, and lithium-rich spinel Li$_{1+x}$Mn$_{2–x}$O$_4$ phases together with complex microstructural features. The discharge process was modeled by inserting surplus lithium atoms into the nanoparticles, resulting in structural changes, accompanied by a variety of constituent polymorphs. A transitional multigrained structure, between the cubic (Li$_1$Mn$_2$O$_4$) and tetragonal (Li$_2$Mn$_2$O$_4$) phases, is observed at Li$_{1.75}$Mn$_2$O$_4$. We also find that microstructural features, such as microtwinning and intrinsic dopants, vacancies, etc., result in a network of Li transport pathways, enabling Li mobility in all three spatial directions