Tadhg Kennedy

High-Performance Germanium Nanowire-Based Lithium-Ion Battery Anodes Extending over 1000 Cycles Through in Situ Formation of a Continuous Porous Network

Here we report the formation of high-performance and high-capacity lithium-ion battery anodes from high-density germanium nanowire arrays grown directly from the current collector. The anodes retain capacities of ∼ 900 mAh/g after 1100 cycles with excellent rate performance characteristics, even at very high discharge rates of 20-100C. We show by an ex situ high-resolution transmission electron microscopy and high-resolution scanning electron microscopy study that this performance can be attributed to the complete restructuring of the nanowires that occurs within the first 100 cycles to form a continuous porous network that is mechanically robust. Once formed, this restructured anode retains a remarkably stable capacity with a drop of only 0.01% per cycle thereafter. As this approach encompasses a low energy processing method where all the material is electrochemically active and binder free, the extended cycle life and rate performance characteristics demonstrated makes these anodes highly attractive for the most demanding lithium-ion applications such as long-range battery electric vehicles.

Advances in the Application of Silicon and Germanium Nanowires for High‐Performance Lithium‐Ion Batteries

Li-alloying materials such as Si and Ge nanowires have emerged as the forerunners to replace the current, relatively low-capacity carbonaceous based Li-ion anodes. Since the initial report of binder-free nanowire electrodes, a vast body of research has been carried out in which the performance and cycle life has significantly progressed. The study of such electrodes has provided invaluable insights into the cycling behavior of Si and Ge, as the effects of repeated lithiation/delithiation on the material can be observed without interference from conductive additives or binders. Here, some of the key developments in this area are looked at, focusing on the problems encountered by Li-alloying electrodes in general (e.g., pulverization, loss of contact with current collector etc.) and how the study of nanowire electrodes has overcome these issues. Some key nanowire studies that have elucidated the consequences of the alloying/dealloying process on the morphology of Si and Ge are also considered, in particular looking at the impact that effects such as pore formation and lithium-assisted welding have on performance. Finally, the challenges for the practical implementation of nanowire anodes within the context of the current understanding of such systems are discussed.

Nanowire Heterostructures Comprising Germanium Stems and Silicon Branches as High-Capacity Li-Ion Anodes with Tunable Rate Capability.

Here we report the rational design of a high-capacity Li-ion anode material comprising Ge nanowires with Si branches. The unique structure provides an electrode material with tunable properties, allowing the performance to be tailored for either high capacity or high rate capability by controlling the mass ratio of Si to Ge. The binder free Si-Ge branched nanowire heterostructures are grown directly from the current collector and exhibit high capacities of up to ∼1800 mAh/g. Rate capability testing revealed that increasing the Ge content within the material boosted the performance of the anode at fast cycling rates, whereas a higher Si content was optimal at slower rates of charge and discharge. Using ex-situ electron microscopy, Raman spectroscopy and energy dispersive X-ray spectroscopy mapping, the composition of the material is shown to be transient in nature, transforming from a heterostructure to a Si-Ge alloy as a consequence of repeated lithiation and delithiation.

A Rapid, Solvent-Free Protocol for the Synthesis of Germanium Nanowire Lithium-Ion Anodes with a Long Cycle Life and High Rate Capability

A rapid synthetic protocol for the formation of high-performance Ge nanowire-based Li-ion battery anodes is reported. The nanowires are formed in high density by the solvent-free liquid deposition of a Ge precursor directly onto a heated stainless steel substrate under inert conditions. The novel growth system exploits the in situ formation of discrete Cu3Ge catalyst seeds from 1 nm thermally evaporated Cu layers. As the nanowires were grown from a suitable current collector, the electrodes could be used directly without binders in lithium-ion half cells. Electrochemical testing showed remarkable capacity retention with 866 mAh/g achieved after 1900 charge/discharge cycles and a Coulombic efficiency of 99.7%. The nanowire-based anodes also showed high-rate stability with discharge capacities of 800 mAh/g when cycled at a rate of 10C.

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.

Behavior of Germanium and Silicon Nanowire Anodes with Ionic Liquid Electrolytes

The electrochemical behavior of binder-free, germanium and silicon nanowires as high-capacity anode materials for lithium-ion battery systems is investigated in an ionic liquid electrolyte. Cyclic voltammetry, cycling tests, and impedance spectroscopy reveal a highly reversible lithium alloying/dealloying process, as well as promising compatibility between the Ge and Si materials and the electrolyte components. Reversible capacities of 1400 and 2200 mA h g-1 are delivered by the Ge and Si anodes, respectively, matching the values exhibited in conventional organic solutions. Furthermore, impressive extended cycling performance is obtained in comparison to previous research on Li alloying anodes in ionic liquids, with capacity retention overcoming 50% for Si after 500 cycles and 67% for Ge after 1000 cycles, at a current rate of 0.5C. This stable long-term cycling arises due to the ability of the electrolyte formulation to promote the transformation of the nanowires into durable porous network structures of Ge or Si nanoligaments, which can withstand the extreme volume changes associated with lithiation/delithiation. Remarkable capacity is exhibited also by composite Ge and Si nanowire electrodes. Preliminary tests with lithium cobalt oxide cathodes clearly demonstrate the feasibility of Ge and Si nanowires in full batteries.

Direct Synthesis of Alloyed Si1–xGex Nanowires for Performance-Tunable Lithium Ion Battery Anodes

Here we report the formation of high capacity Li-ion battery anodes from Si1-xGex alloy nanowire arrays that are grown directly on stainless steel current collectors, in a single-step synthesis. The direct formation of these Si1-xGex nanowires (ranging from Si0.20Ge0.80 to Si0.67Ge0.33) represents a simple and efficient processing route for the production of Li-ion battery anodes possessing the benefits of both Si (high capacity) and Ge (improved rate performance and capacity retention). The nanowires were characterized through SEM, TEM, XRD and ex situ HRSEM/HRTEM. Electrochemical analysis was conducted on these nanowires, in half-cell configurations, with capacities of up to 1360 mAh/g (Si0.67Ge0.33) sustained after 250 cycles and in full cells, against a commercial cathode, where capacities up to 1364 mAh/g (Si0.67Ge0.33) were retained after 100 cycles.

High density and patternable growth of silicon, germanium and alloyed SiGe nanowires by a rapid anneal protocol

We report the formation of silicon, germanium and alloyed Si1−xGex nanowires by direct pyrolysis of liquid precursors on a heated substrate in an inert environment. The nanowires form in high density on the substrate with a fast reaction time. We use SEM, HRTEM, EDX-STEM, and Raman spectroscopy to carry out an in depth study into the population distribution of Si1−xGex nanowires. The method was sufficiently adaptable to pattern the nanowire growth using standard dry film lithography techniques. Additionally, we further show that direct writing with a copper metal pen deposited sufficient catalyst to allow localised nanowire growth constrained to the treated areas.

Solution synthesis of lead seeded germanium nanowires and branched nanowire networks and their application as Li-ion battery anodes

Herein, we report the high density growth of lead seeded germanium nanowires (NWs) and their development into branched nanowire networks suitable for application as lithium ion battery anodes. The synthesis of the NWs from lead seeds occurs simultaneously in both the liquid zone (solution-liquid-solid (SLS) growth) and solvent rich vapor zone (vapor-liquid-solid (VLS) growth) of a high boiling point solvent growth system. The reaction is sufficiently versatile to allow for the growth of NWs directly from either an evaporated catalyst layer or from pre-defined nanoparticle seeds and can be extended to allowing extensive branched nanowire formation in a secondary reaction where these seeds are coated onto existing wires. The NWs are characterized using TEM, SEM, XRD and DF-STEM. Electrochemical analysis was carried out on both the single crystal Pb-Ge NWs and the branched Pb-Ge NWs to assess their suitability for use as anodes in a Li-ion battery. Differential capacity plots show both the germanium wires and the lead seeds cycle lithium and contribute to the specific capacity that is approximately 900 mAh g-1 for the single crystal wires, rising to approximately 1100 mAh g-1 for the branched nanowire networks.

GREENLION Project: Advanced Manufacturing Processes for Low Cost Greener Li-Ion Batteries

GREENLION is a Large Scale Collaborative Project within the FP7 (GC.NMP.2011-1) leading to the manufacturing of greener and cheaper Li-Ion batteries for electric vehicle applications via the use of water soluble, fluorine-free, high thermally stable binders, which would eliminate the use of VOCs and reduce the cell assembly cost. The project has 6 key objectives: (i) development of new active and inactive battery materials viable for water processes (green chemistry); (ii) development of innovative processes (coating from aqueous slurries) capable of reducing electrode production cost and avoid environmental pollution; (iii) development of new assembly procedures (including laser cutting and high temperature pre-treatment) capable of substantially reduce the time and the cost of cell fabrication; (iv) lighter battery modules with easier disassembly through eco-designed bonding techniques; (v) waste reduction, which, by making use of the water solubility of the binder, allows the extensive recovery of the active and inactive battery materials; and (vi) development of automated process and construction of fully integrated battery module for electric vehicle applications with optimized electrodes, cells, and other ancillaries. Achievements during the first 18 months of the project, especially on materials development and water-based electrode fabrication are reported herein.