Eileen Armstrong

Structuring materials for lithium-ion batteries: advancements in nanomaterial structure, composition, and defined assembly on cell performance

This review outlines the developments in the structure, composition, size, and shape control of many important and emerging Li-ion battery materials on many length scales, and details very recent investigations on how the assembly and programmable order in energy storage materials have not only influenced and dramatically improved the performance of some Li-ion batteries, but offered new routes toward improved power densities. This review also describes and discusses material aspects of hybrid and multiphasic materials including silicon, germanium, a wide range of metal oxides, alloys and crystal structures, carbons and other important materials. Methods including engineered porosity that offer the energy density of Li-ion batteries and the power density of pseudocapacitors are also highlighted. Recent developments in the analytical methods, electrochemical response, and the structure, composition, size, shape and defined assembly of active materials for a wide range of Li-ion cathodes and anodes are compared and assessed with respect to cell performance. Perspectives on the future development of energy storage materials based on structure as well as chemistry are also outlined.

Artificial opal photonic crystals and inverse opal structures – fundamentals and applications from optics to energy storage

Photonic crystals (PhCs) influence the propagation of light by their periodic variation in dielectric contrast or refractive index. This review outlines the attractive optical qualities inherent to most PhCs namely the presence of full or partial photonic band gaps and the possibilities they present towards the inhibition of spontaneous emission and the localization of light. Colloidal self-assembly of polymer or silica spheres is one of the most favoured and low cost methods for the formation of PhCs as artificial opals. The state of the art in growth methods currently used for colloidal self-assembly are discussed and the use of these structures for the formation of inverse opal architectures is then presented. Inverse opal structures with their porous and interconnected architecture span several technological arenas – optics and optoelectronics, energy storage, communications, sensor and biological applications. This review presents several of these applications and an accessible overview of the physics of photonic crystal optics that may be useful for opal and inverse opal researchers in general, with a particular emphasis on the recent use of these three-dimensional porous structures in electrochemical energy storage technology. Progress towards all-optical integrated circuits may lie with the concepts of the photonic crystal, but the unique optical and structural properties of these materials and the convergence of PhC and energy storage disciplines may facilitate further developments and non-destructive optical analysis capabilities for (electro)chemical processes that occur within a wide variety of materials in energy storage research.

Electrodeposited Structurally Stable V2O5 Inverse Opal Networks as High Performance Thin Film Lithium Batteries.

High performance thin film lithium batteries using structurally stable electrodeposited V2O5 inverse opal (IO) networks as cathodes provide high capacity and outstanding cycling capability and also were demonstrated on transparent conducting oxide current collectors. The superior electrochemical performance of the inverse opal structures was evaluated through galvanostatic and potentiodynamic cycling, and the IO thin film battery offers increased capacity retention compared to micron-scale bulk particles from improved mechanical stability and electrical contact to stainless steel or transparent conducting current collectors from bottom-up electrodeposition growth. Li(+) is inserted into planar and IO structures at different potentials, and correlated to a preferential exposure of insertion sites of the IO network to the electrolyte. Additionally, potentiodynamic testing quantified the portion of the capacity stored as surface bound capacitive charge. Raman scattering and XRD characterization showed how the IO allows swelling into the pore volume rather than away from the current collector. V2O5 IO coin cells offer high initial capacities, but capacity fading can occur with limited electrolyte. Finally, we demonstrate that a V2O5 IO thin film battery prepared on a transparent conducting current collector with excess electrolyte exhibits high capacities (∼200 mAh g(-1)) and outstanding capacity retention and rate capability.

Ordered 2D Colloidal Photonic Crystals on Gold Substrates by Surfactant‐Assisted Fast‐Rate Dip Coating

EA and MO acknowledge the support of the Irish Research Council under awards RS/2010/2920 and RS/2010/2170. WK and CMST acknowledge support from the Spanish National I+D Plan projects TAPHOR (MAT-2012–31392) and CONSOLIDER nanoTHERM (CSD2010–00044). COD acknowledges support from Science Foundation Ireland under award no. 07/SK/B1232a-STTF11, the UCC Strategic Research Fund, and from the Irish Research Council New Foundations Award.

Core−Shell Tin Oxide, Indium Oxide, and Indium Tin Oxide Nanoparticles on Silicon with Tunable Dispersion: Electrochemical and Structural Characteristics as a Hybrid Li-Ion Battery Anode

Tin oxide (SnO2) is considered a very promising material as a high capacity Li-ion battery anode. Its adoption depends on a solid understanding of factors that affect electrochemical behavior and performance such as size and composition. We demonstrate here, that defined dispersions and structures can improve our understanding of Li-ion battery anode material architecture on alloying and co-intercalation processes of Lithium with Sn from SnO2 on Si. Two different types of well-defined hierarchical Sn@SnO2 core-shell nanoparticle (NP) dispersions were prepared by molecular beam epitaxy (MBE) on silicon, composed of either amorphous or polycrystalline SnO2 shells. In2O3 and Sn doped In2O3 (ITO) NP dispersions are also demonstrated from MBE NP growth. Lithium alloying with the reduced form of the NPs and co-insertion into the silicon substrate showed reversible charge storage. Through correlation of electrochemical and structural characteristics of the anodes, we detail the link between the composition, areal and volumetric densities, and the effect of electrochemical alloying of Lithium with Sn@SnO2 and related NPs on their structure and, importantly, their dispersion on the electrode. The dispersion also dictates the degree of co-insertion into the Si current collector, which can act as a buffer. The compositional and structural engineering of SnO2 and related materials using highly defined MBE growth as model system allows a detailed examination of the influence of material dispersion or nanoarchitecture on the electrochemical performance of active electrodes and materials.

2D and 3D vanadium oxide inverse opals and hollow sphere arrays

High quality 2D and 3D inverse opals and hollow sphere arrays of vanadium oxide are grown on conductive substrates from colloidal polymer sphere templates formed by electrophoretic deposition or surfactant-assisted dip-coating. Inverse opals (IOs) are formed using variants of solution drop-casting, N2-gun assisted infiltration and high-rate (200 mm min−1) iterative dip-coating methods. Through Raman scattering, transmission electron microscopy and optical diffraction, we show how the oxide phase, crystallinity and structure are inter-related and controlled. Opal template removal steps are demonstrated to determine the morphology, crystallinity and phase of the resulting 2D and 3D IO structures. The ability to form high quality 2D IOs is also demonstrated using UV Ozone removal of PMMA spheres. Rapid hydrolysis of the alkoxide precursor allows the formation of 2D arrays of crystalline hollow spheres of V2O5 by utilizing over-filling during iterative dip-coating. The methods and crystallinity control allow 2D and 3D hierarchically structured templates and inverse opal vanadium oxides directly on conductive surfaces. This can be extended to a wide range of other functional porous materials for energy storage and batteries, electrocatalysis, sensing, solar cell materials and diffractive optical coatings.

High performance inverse opal Li-ion battery with paired intercalation and conversion mode electrodes

Structured porous materials have provided several breakthroughs that have facilitated high rate capability, better capacity retention and material stability in Li-ion batteries. However, most advances have been limited to half cells or lithium batteries, and with a single mode of charge storage (intercalation, conversion, or alloying etc.). The use of dual-mode charge storage with non-traditional material pairings, while maintaining the numerous benefits of nanoscale materials, could significantly improve the capacity, energy density, stability and overall battery safety considerably. Here, we demonstrate an efficient, high capacity full inverse opal Li-ion battery with excellent cycle life, where both the cathode and anode binder-free electrodes are composed of 3D nanocrystal assemblies as inverse opal (IO) structures of intercalation-mode V2O5 IO cathodes and conversion-mode Co3O4 IO anodes. Electrochemically charged Co3O4 IOs function as Li-ion anodes and the full V2O5/Co3O4 cell exhibits superior performance compared to lithium batteries or half cells of either IO material, with voltage window compatibility for high capacity and energy density. Through asymmetric charge–discharge tests, the V2O5 IO/Co3O4 IO full Li-ion cell can be quickly charged, and discharged both quickly and slowly without any capacity decay. We demonstrate that issues due to the decomposition of the electrolyte with increased cycling can be overcome by complete electrolyte infiltration to remove capacity fading from long term cycling at high capacity and rate. Lastly, we show that the V2O5 IO/Co3O4 IO full Li-ion cells cycled in 2 and 3-electrode flooded cells maintain 150 mA h g−1 and remarkably, show no capacity fade at any stage during cycling for at least 175 cycles. The realization of an all-3D structured anode and cathode geometry with new mutually co-operative dual-mode charge storage mechanisms and efficient electrolyte penetration to the nanocrystalline network of material provides a testbed for advancing high rate, high capacity, stable Li-ion batteries using a wide range of materials pairings.

Linking Precursor Alterations to Nanoscale Structure and Optical Transparency in Polymer Assisted Fast-Rate Dip-Coating of Vanadium Oxide Thin Films

Solution processed metal oxide thin films are important for modern optoelectronic devices ranging from thin film transistors to photovoltaics and for functional optical coatings. Solution processed techniques such as dip-coating, allow thin films to be rapidly deposited over a large range of surfaces including curved, flexible or plastic substrates without extensive processing of comparative vapour or physical deposition methods. To increase the effectiveness and versatility of dip-coated thin films, alterations to commonly used precursors can be made that facilitate controlled thin film deposition. The effects of polymer assisted deposition and changes in solvent-alkoxide dilution on the morphology, structure, optoelectronic properties and crystallinity of vanadium pentoxide thin films was studied using a dip-coating method using a substrate withdrawal speed within the fast-rate draining regime. The formation of sub-100 nm thin films could be achieved rapidly from dilute alkoxide based precursor solutions with high optical transmission in the visible, linked to the phase and film structure. The effects of the polymer addition was shown to change the crystallized vanadium pentoxide thin films from a granular surface structure to a polycrystalline structure composed of a high density of smaller in-plane grains, resulting in a uniform surface morphology with lower thickness and roughness.

MBE Growth and Structural and Electrochemical Characterization of Tin Oxide and Indium Tin Oxide Nanoparticles Grown on Silicon for Li-ion Battery Anodes

Irish Research Council (RS/2010/2170 and RS/2010/2920); University College Cork (UCC Strategic Research Fund);