Hierarchically structured nanocarbon electrodes for flexible solid lithium batteries

The ever increasing demand for storage of electrical energy in portable electronic devices and electric vehicles is driving technological improvements in rechargeable batteries. Lithium (Li) batteries have many advantages over other rechargeable battery technologies, including high specific energy and energy density, operation over a wide range of temperatures (-40 to 70. °C) and a low self-discharge rate, which translates into a long shelf-life (~10 years) [1]. However, upon release of the first generation of rechargeable Li batteries, explosions related to the shorting of the circuit through Li dendrites bridging the anode and cathode were observed. As a result, Li metal batteries today are generally relegated to non-rechargeable primary battery applications, because the dendritic growth of Li is associated with the charging and discharging process. However, there still remain significant advantages in realizing rechargeable secondary batteries based on Li metal anodes because they possess superior electrical conductivity, higher specific energy and lower heat generation due to lower internal resistance. One of the most practical solutions is to use a solid polymer electrolyte to act as a physical barrier against dendrite growth. This may enable the use of Li metal once again in rechargeable secondary batteries [2]. Here we report a flexible and solid Li battery using a polymer electrolyte with a hierarchical and highly porous nanocarbon electrode comprising aligned multiwalled carbon nanotubes (CNTs) and carbon nanohorns (CNHs). Electrodes with high specific surface area are realized through the combination of CNHs with CNTs and provide a significant performance enhancement to the solid Li battery performance. © 2013 Elsevier Ltd.

An integrated 2-D model of a lithium ion battery: The effect of material parameters and morphology on storage particle stress

An integrated 2-D model of a lithium ion battery is developed to study the mechanical stress in storage particles as a function of material properties. A previously developed coupled stress-diffusion model for storage particles is implemented in 2-D and integrated into a complete battery system. The effect of morphology on the stress and lithium concentration is studied for the case of extraction of lithium in terms of previously developed non-dimensional parameters. These non-dimensional parameters include the material properties of the storage particles in the system, among other variables. We examine particles functioning in isolation as well as in closely-packed systems. Our results show that the particle distance from the separator, in combination with the material properties of the particle, is critical in predicting the stress generated within the particle. © 2012 Springer-Verlag.

Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

Binder free three-dimensional sulphur/few-layer graphene foam cathode with enhanced high-rate capability for rechargeable lithium sulphur batteries.

A novel ultra-lightweight three-dimensional (3-D) cathode system for lithium sulphur (Li-S) batteries has been synthesised by loading sulphur on to an interconnected 3-D network of few-layered graphene (FLG) via a sulphur solution infiltration method. A free-standing FLG monolithic network foam was formed as a negative of a Ni metallic foam template by CVD followed by etching away of Ni. The FLG foam offers excellent electrical conductivity, an appropriate hierarchical pore structure for containing the electro-active sulphur and facilitates rapid electron/ion transport. This cathode system does not require any additional binding agents, conductive additives or a separate metallic current collector thus decreasing the weight of the cathode by typically ∼20-30 wt%. A Li-S battery with the sulphur-FLG foam cathode shows good electrochemical stability and high rate discharge capacity retention for up to 400 discharge/charge cycles at a high current density of 3200 mA g(-1). Even after 400 cycles the capacity decay is only ∼0.064% per cycle relative to the early (e.g. the 5th cycle) discharge capacity, while yielding an average columbic efficiency of ∼96.2%. Our results indicate the potential suitability of graphene foam for efficient, ultra-light and high-performance batteries.

Liquid salt cooled flexible conversion ratio fast reactor: Neutronic design

This paper presents the neutronic design of a liquid salt cooled fast reactor with flexible conversion ratio. The main objective of the design is to accommodate interchangeably within the same reactor core alternative transuranic actinides management strategies ranging from pure burning to self-sustainable breeding. Two, the most limiting, core design options with unity and zero conversion ratios are described. Ternary, NaCl-KCl-MgCl2 salt was chosen as a coolant after a rigorous screening process, due to a combination of favourable neutronic and heat transport properties. Large positive coolant temperature reactivity coefficient was identified as the most significant design challenge. A wide range of strategies aiming at the reduction of the coolant temperature coefficient to assure self-controllability of the core in the most limiting unprotected accidents were explored. However, none of the strategies resulted in sufficient reduction of the coolant temperature coefficient without significantly compromising the core performance characteristics such as power density or cycle length. Therefore, reactivity control devices known as lithium thermal expansion modules were employed instead. This allowed achieving all the design goals for both zero and unity conversion ratio cores. The neutronic feasibility of both designs was demonstrated through calculation of reactivity control and fuel loading requirements, fluence limits, power peaking factors, and reactivity feedback coefficients. © 2009 Elsevier B.V. All rights reserved.

The use of non-dimensional parameters to study stress in lithiumion battery electrode storage particles

Mechanical degradation is thought to be one of the causes of capacity fade within Lithium-Ion batteries. In this work we develop a coupled stress-diffusion model for idealized spherical storage particles, which is analogous to the development of thermal strains. We then non-dimensionalize the model and identify three important parameters that control the development of stress within these particles. We can therefore use a wide number of values for these parameters to make predictions about the stress responses of different materials. The maximum stress developed within the particle for different values of these parameters are plotted as stress maps. A two dimensional model of a battery was then developed, in order to study the effect of particle morphology. Copyright © 2012 by ASME.

Electrical properties of LiNbO3 (electrolyte)/Cu (anode) bi-layers

In this work specific film structures of Li-Nb-O/Li/Li-Nb-O are investigated by AC Impedance Spectroscopy measurements at different temperatures. This gives the opportunity to investigate properties of the material itself and, at the same time, to consider the influence of the grain boundaries on the ionic behavior of the polycrystalline Lithium Niobate. On the other hand, LiNbO3/Li/Cu multi-layers are studied as electrolyte/anode bi-layers and potential parts of "Li-free" microbatteries. The Li deficiency in the as deposited Li-Nb-O films is cured by forming a "sandwich" of Li-Nb-O/Li/Li-Nb-O, which after annealing becomes ionic conductor. The electrical behavior of an annealed film depends on two sources. The first is due to properties of the material itself and the second is based on the network of the grain boundaries. The average size of the grains is strongly influenced by the structure of the ohmic-contact/substrate. The electrical behavior of the electrolyte/anode interface of the "Li-free" structure LiNbO3/Li/Cu/Au is very similar to the impedance measurements of the single LiNbO3 single films. The whole multilayer structure, though, presents a third relaxation time which is consistent of a small resistance. This resistance is independent of temperature and it seems that is due to the metallic interface Li/Cu/Au. © 2010 Elsevier B.V. All rights reserved.