Preliminary List of Abstracts (Alphabetical Order)

1ST INTL. SYMP. ON SUSTAINABLE SECONDARY BATTERY MANUFACTURING AND RECYCLING

Through mesoscale design of a 3D current collector, high power density and high energy density primary and secondary (rechargeable) batteries were fabricated. At the most fundamental level, mesostructuring enables optimization of the trade-off between energy and power density in energy storage systems due to unavoidable ohmic and other losses that occur during charge or discharge. Of course, it is at fast charge and discharge, where these effects are most important. By efficient design of the ion and electron transport pathways, we and others have shown it is possible to significantly improve the power-energy relationship. We have found a particularly effective way to provide these pathways is to use a colloidal-based template to form a mesostructured 3D current collector. The electrochemically active material is then deposited on this current collector. Using this approach, Li-ion batteries which could be discharged at up to 300C with 75% capacity retention were formed. The combination of a high surface area and short solid-state diffusion lengths offers a number of unique opportunities for both high energy and high power chemistries. As examples, we have formed conventional form-factor and microbattery high power cells based on a lithiated manganese oxide cathode and carbon or NiSn anodes, and high energy cells based on a silicon anode. Time permitting, I will also describe how such engineering can also provide benefits to supercapacitor systems.

Li-O2 battery is regarded as one of the most promising energy storage systems for future applications. However, its energy efficiency is greatly undermined by the large over potentials of the discharge (formation of Li2O2) and charge (oxidation of Li2O2) reactions. The parasitic reactions of electrolyte and carbon electrode induced by the high charging potential cause the decay of capacity and limit the battery life. Here, a K-O2 battery is reported as using K+ ions to capture O2- to form the thermodynamically stable KO2 product. This allows the battery to operate through the one-electron redox process of O2/O2. Our studies confirm the formation and removal of KO2 in the battery cycle test. Furthermore, without the use of catalysts, the battery shows a low discharge/charge potential gap of less than 50 mV at a modest current density, which is the lowest one that has ever been reported in metal-oxygen batteries.

The ability to store large amounts of electrical energy is of increasing importance with the growing fraction of electricity generation from intermittent renewable sources such as wind and solar. Solid-electrode batteries are drained far too soon, when discharged at full power, to economically fill the gaps in photovoltaic or wind temporal power profiles. Flow batteries show promise because the designer can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all electro-active species in fluids. Wide-scale utilization of flow batteries is limited by the abundance and cost of these materials, particularly those utilizing redox-active metals and precious metal electrocatalysts. We have developed a flow battery based on the aqueous redox chemistry of small organic molecules called quinones. The redox active materials contain no metals and can be very inexpensive. Electrochemical studies show that these molecules undergo fast and reversible two-electron two-proton reduction on carbon electrodes without the addition of electrocatalyst. At the time this abstract is being written, an aqueous flow battery involving the quinone/hydroquinone couple has achieved a peak power density exceeding 0.6 W/cm2 and has undergone over 100 deep discharge cycles with 99.986% capacity retention per cycle. The absence of active metal components in both redox chemistry and catalysis represents a significant shift away from the direction modern battery R&D has been taking. This new approach may enable massive electrical energy storage at greatly reduced cost.

The mechanisms and efficiency of charge transport in lithium peroxide (Li2O2) are key factors in understanding the performance of non-aqueous Li-air batteries. Towards revealing these mechanisms, we use first-principles calculations to predict the concentrations and mobilities of charge carriers in Li2O2 as a function of cell voltage. Our calculations reveal that changes in the charge state of O2 dimers control the defect chemistry and conductivity of Li2O2. Negative lithium vacancies and small hole polarons are identified as the dominant charge carriers. The electronic conductivity associated with polaron hopping (10-20 S/cm) is comparable to the ionic conductivity arising from the migration of Li-ions (10-19 S/cm), suggesting that charge transport in Li2O2 occurs through a mixture of ionic and polaronic contributions. These data indicate that the bulk regions of crystalline Li2O2 are insulating, with appreciable charge transport occurring only at moderately high charging potentials that drive partial delithiation. The implications of limited charge transport on discharge and recharge mechanisms are discussed, and a two-stage charging process linking charge transport, discharge product morphology, and overpotentials are described. We conclude that achieving both high discharge capacities and efficient charging will depend upon access to mechanisms that bypass bulk charge transport.

Highly distributed metal/alloy nanoparticles in carbon matrices is the promising anode microstructure that can enhance both energy density and cycle life for the next generation lithium-ion battery. In this report, high theoretical capacity metal/alloys such as Sn, SnSb, and SnS nanoparticles can simply be synthesized on carbon surface via chemical method at low temperature. Sn-C and SnSb-C were obtained from the reduction reaction of metal ions with sodium borohydride in ethylene glycol solvent; While SnS-C was prepared from a reflux method at 200°C in ethylene glycol. The carbon surface area affected by the amount and size of metal/alloy formation was studied by using different types of carbon materials, which were natural graphite (NG), artificial graphite (AG), mesocarbonmicrobead (MCMB) and graphene. The amount of Sn varied from 10-20% by weight in Sn-C and SnS-C, and 10-40% in SnSb-C, while the amount of Sb was maintained at 10% and S varied from 10-20%. Materials characterization by XRD and TEM techniques revealed Sn, SnSb, SnS phases appeared along with C phase. The highest Sn content and lowest Sn particles size were obtained from Sn-graphene samples. The preferred SnSb phase with ratio Sn:Sb of 1:1 was obtained when the weight of the reactants was 10 %wt of Sb, 20 %wt of Sn, and 70%wt of artificial graphite. SnS-C shows different morphology as high surface area flower like microstructure.

Electrochemical conversion is an important path through which realizes high specific storage capacity of, for example, lithium ions. Such reactions were supposed to be reversible and have been observed in compounds of transition metals. This report will show that the reaction paths and products are highly dependent on the kinetic as well as thermodynamic properties of the electrode, such as particle size and conductivity of the material. In addition, we will demonstrate that conversion reaction is also an important method to obtain high-performance electrode materials that are difficult to synthesize by conventional chemical reactions. By selecting the starting materials and optimizing the reaction conditions, some inert metals can be oxidized and, therefore, provide high reversible lithium storage capacities. In some other cases, novel lithium storage materials can be electrochemically synthesized that deliver very high lithium storage capacities.

Rechargeable lithium ion batteries are widely used in portable electronic devices. There are several advantages to replacing the organic liquid electrolyte with one based on a polymeric material, most notably the ability to use lithium metal as the anode material. Such "solid polymer electrolytes" or SPEs suffer from low conductivity with significant contribution of the anion. In this talk, the latter issue is addressed by considering a single ion conductor, in which the anion is incorporated in the polymer backbone. The single ion conductor contains a PEO spacer, punctuated by an anion-bearing isophalate group. In "traditional" SPEs, the ion motion is coupled to segmental mobility of the polymer, and a significant fraction of the lithium ions are solvated by the polymer backbone [single ions] with limited pairing and aggregation. The behavior of the single ion conductors is more complex: Single ions, ion pairs, and temperature-dependent aggregation are observed. The polymer mobility is influenced by the amounts of single ions and aggregates, both of which form temporary cross links with the polymer chains. The polymer relaxes in two stages: One related to single ions and corresponding to the spacer midpoint, and one related to ionic aggregates. The slow regions are spatially correlated, leading to "dynamic phase separation". In some cases, ionic aggregation occurs within the slow regions. Manipulating the single ion conductor to create more single ions does not increase ion mobility, in contrast to the expectation that single ions are the main contributors to conductivity. Instead, most highly mobile ions hop between pair states or along the edges of ion clusters. Within string-like aggregates, mechanisms that move charge without similar movement of ion position are observed.

Tin/graphene (Sn/graphene) composites are prepared in nano-dimensions to be used as anode materials in lithium-ion batteries. The objectives of this research are enhancing both the energy density and mechanical stability of anodic electrodes from high theoretical capacity of Sn and graphene supported material, respectively. The chemical reduction method, which is the simple and low cost method, is used to prepare Sn on graphene. Sn particles are prepared by using SnCl2*2H2O, NaBH4 and ethylene glycol as Sn precursor, reducing agent and solvent, respectively. The effect of reducing SnCl2*2H2O precursor concentration in ethylene glycol solvent and the solvent viscosity on tin particle sizes is studied in this research. The solvent viscosity is varied by adding methanol to ethylene glycol solvent. The result from X-ray diffraction (XRD) technique shows that Sn phase contains the prepared products. The phase of products will be confirmed by transmission electron microscopy (TEM) technique. The results from scanning electron microscopy (SEM) technique will give the information about size and morphology of Sn particles. The condition of that smallest size of Sn obtained will be used to prepare 10 and 20%weight Sn on graphene composites. The charge-discharge voltage and the cycling performance of the products will be investigated. The results of the characterization will be discussed in the symposium.

In the past decades, micro emulsion synthesis has been demonstrated to be efficient soft colloidal templates in preparing nanopowders of metal oxides for its feasible and precise control of size, shape and crystallinity. For most soft colloidal-template syntheses of nanoparticles are confined in the water phase, water-in-oil namely reverse micelles or micro emulsions have attracted much more attention. Water-in-oil (W/O) micro emulsion is an isotropic, thermodynamically stable dispersion of water phase wrapped by surfactant and co-surfactant in a continuous oil phase, which has been extensively employed as soft template for the synthesis of nanoparticles or nanostructure materials. Typically, for the soft-colloidal template synthesis of target materials, usually two different reverse micelles or micro emulsion droplets containing two types of reaction precursors are first prepared. The reaction is enabled once two different droplets fluctuate and collide with each other. Then followed by a complicated separation step. Here, we extend this kind of novel electrolyte to an electrochemical cell, in situ assemblies of metal oxide and applied to an electrode of super capacitor. The results showed that the metal oxides are in uniform morphologies and an outstanding capacitive performance was obtained.

Plug in vehicles and many other electronic devices are limited by the performance of secondary batteries. In addition, the battery should also be safe. This presentation will feature nanocomposite materials that improve performance or reduce the risk of failure or fire. Titania and other nanocomposites will be discussed for their structural stability, long cycling life, low cost, wide availability, decent charging/discharging capacity and environmental benignity. Latest results on fabrication and electrochemical performance of nanofibers synthesized via electrospinning will be presented. Fibers with diameters well below 200 nm can be achieved. The impact of calcination condition on material structure and activity are reported.

The large-scale commercialization of new energy storage technologies is essential to the development of electric vehicles, as well as to distributed renewable electric power generation. To achieve the necessary transformational advances, Argonne has continued to build upon its historical leadership in battery research to create a broad research, development, and demonstration program centered on advanced energy storage materials and systems for both mobile and stationary applications.Argonne is currently focusing on the development of more robust, safer, and higher-energy density lithium-ion batteries and the processes to manufacture them. In the near future, Argonne will make use of its fundamental science capabilities to develop storage materials that go beyond current lithium technology to dramatically increase storage capacity and power densities for electrification of the transportation sector.In this presentation we will describe some of the highlights of the work currently underway targeted to provide the scientific basis for the discovery and implementation of new technologies to yield translational solutions to energy storage in support of DOE's mission.

There is no doubt that the concentration of carbon dioxide in the earth's atmosphere has risen steadily since the onset of the Industrial Revolution in the late 18th century. The moderation of climate change is perhaps the most important long-term challenge that confronts the world today and, as long as uncertainty over its origins prevails, it is prudent to work towards limiting the emissions of carbon dioxide. The International Energy Agency estimates that, in order to limit the average rise in global temperature to 2°C, it will be necessary to cut global emission of carbon dioxide by 50% from its 2009 level by 2050.Batteries based on lead acid chemistry are likely to remain the lowest cost option for some time to come and thus represent the best hope of large-scale uptake of new schemes aimed at reduction of carbon dioxide emissions provided that such batteries are able to perform the necessary function for an acceptable life. Despite the antiquity of the system, it has been possible to modify the design of lead acid batteries in a relatively simple manner to allow them to cope with all of the challenges of novel vehicles and the storage of renewable energy. The key is to make use of appropriate forms of carbon in the construction of the negative plate. This can be accomplished in several ways with the result that so-called lead carbon batteries are able to maintain a high level of dynamic charge acceptance in order to accommodate regenerative braking energy and, in at least one embodiment, for the individual cells of a long string to remain in-balance for a long service life without the need for intrusive battery management.

The rechargeable Li-ion battery market was approximately $11.8 billion in 2010 and it is expected to grow to $53.7 billion in 2020. In the past few years, however, millions of Li-ion batteries were recalled by various manufacturers (e.g., Sony and GM) due to safety concerns, which also led the U.S. Battery company A123 Systems to file for bankruptcy in 2012. The most recent Li-ion battery fires on the Boeing 787 Dreamliner airplane have drawn even more attention to the battery safety issue. Currently, the highest priority for manufacturers has been switched from the energy density and cost of Li-ion batteries to their thermal safety, reliability, and durability. As the major components of a Li-ion battery, the cathode and anode are responsible for most heat generation and it is thus of significance to better understand the associated heat generation and transport processes within these regions. In the literature, however, sufficient details for electrode thermal properties were only available for LiCoO2/C batteries (Sony US-18650) used for portable devices and inconsistencies still existed in these data due to the employed measurement technique. On the other hand, large divergence was also found in different heat generation tests of Li-ion batteries. In this work, we carry out systematic thermal conductivity measurements for LiCoO2 and LiFePO4 cathodes and equally important heat generation studies on various Li-ion batteries. These new experimental data will be compared with those previously used for Li-ion battery thermal simulations to better guide the future thermal designs of Li-ion batteries.

The demand for the full implementation of lithium-ion batteries (LIBs) in powering applications such as electric vehicles has promoted vast research towards new materials with higher capacities and longer lifetimes. Commercialized graphite anodes stand far from achieving this goal due to their capped specific capacity of 372 mAh g-1. The search for new anode materials capable of reversibly retaining large amounts of lithium is a necessity in creating advanced LIBs. One such material is silicon (Si), which is naturally abundant and able to form LixSi compounds, where x can reach a value of 3.75 at room temperature corresponding to a specific capacity of 3579 mAh g-1. However, the alloying of lithium into Si leads to an increase in its specific volume of about 300%, creating a number of challenges that have retracted the implementation of Si as a LIB anode material. The stress induced by large volume changes of the Si anodes causes material degradation and major problems for electrochemical performance. In addition to the material degradation, the inherent volume change of Si also induces composite electrode thickness expansion and external cell deformation. From a practical point of view, cell deformation is as important as electrochemical performance and it is the critical factor limiting the commercialization of Si-based anode materials. In this work, we present the manufacturing of a scalable and low-cost material that attains a lowest electrode deformation ever reported.

Among new anode materials, tin oxide, silicon, and titanate nanostructures are promising anode materials because of their energy capacity and safer performance for Li-ion batteries. The major obstacle for these new materials is the lack of scientific knowledge on the electrochemical reactions that happen inside a battery under charging and discharging conditions. This presentation focuses on the in-situ observation of lithiation and delithiation inside an aberration-corrected STEM. The electrochemical testing of these low dimensional structures was conducted inside a transmission electron microscope equipped with a novel in-situ electrical probing holder. The intercalation of Li-ions in Si and SnO2 nanorods was monitored during charging and the fracture of nanorods was quantified in terms of size. In addition, the intercalation of crystalline anatase and amorphous TiO2 was studied and their fracture events were monitored in real time.

For large-scale application of lithium-ion batteries in electric vehicles and grid-scale storage, it has been of great interest to develop cost-effective hydrothermal/solvothermal synthesis methods for preparing high-energy electrodes. But solution-based reactions are mostly carried out in a sealed autoclave and therefore the reactor is a black box - the inputs and outputs are known, but little is known about intermediate phases and reaction pathways. Real-time probing of synthesis reactions can provide the details of reaction process, elucidating intermediate phases and how temperature, pressure, time and the precursor concentration affect the reaction pathways, and eventually the final product. To this end, new in-situ reactors and relevant techniques have been developed and applied for studying solvothermal synthesis of high-energy cathodes, olivines (LiFexMn1-xPO4), copper vanadates (Cu-V-O), and V-based phosphates (Li-V-PO4), using time-resolved synchrotron X-ray diffraction (XRD). Quantitative analysis of XRD patterns was performed via a rigorous Rietveld refinement procedure to extract the structural parameters, such as lattice constants, bond lengths and effective coordination numbers of crystalline phases, and their evolution as a function of reaction time and temperature. In addition, structural and electrochemical characterization were performed, via XRD, XAS and TEM-EELS, for gaining insights into lithium reaction mechanisms and possible limitations to the cycling stability of the synthesized electrodes. We show the development of in-situ methods provides access to a wide range of solvothermal synthesis reactions, and in a combination with structure-property characterization of synthesized materials, eventually enables rational design and synthesis of battery electrodes of desired phases and material properties.

The intensively growing Li-ion battery research area places high demands in the establishing of the long- and short-range structure of the electrodes after or during Li intercalation. The low crystallinity of the electrode materials and the weak scattering of the X-rays by Li atoms make these systems crystallographically challenging. To understand the processes occurring in tin pnictides electrodes, we have synthesized ternary Li-Sn-Pn (Pn = P, As) compounds. We hypothesize that the formation of Li1-xSn2+xPn2 is the first stage of Li intercalation into Sn4Pn3. To fully characterize the long-range and local structure, a combination of powder and single crystal X-ray diffraction, neutron and synchrotron X-ray PDF analysis, 7Li NMR and 119Sn Mossbauer spectroscopies, as well as high resolution TEM were applied. An observed local ordering of Sn and Li atoms was further probed by quantum-chemical calculations which indicate strong anisotropy of the properties of Li1-xSn2+xPn2. An investigation of the resistivity and thermal conductivity performed on the large single crystals confirmed anisotropic transport properties of Li1-xSn2+xPn2.

Despite quite a good power density of currently 1 - 3 kW/kg upon discharge, lithium ion batteries suffer of a low energy density of not more than 0,15 kWh/kg. This is a factor of 80 below the one of hydrocarbons, and even with "5 Volt cathode materials", the energy density will hardly exceed 0,3 kWh/kg. Especially for electric cars, there is a need of batteries with a higher energy density if the cruising range of a mass market electric car shall not be limited to only 100 - 200 km. In this context, new battery designs are needed. It will be shown in this lecture that zinc/air batteries with ionic liquid based electrolytes have few promising properties, especially as the dendritic growth of Zn can be avoided. Furthermore, it is shortly discussed that Al/air and Si/air batteries might be the batteries of the future as both elements are abundant and comparably cheap. The challenges for rechargeable Al/air and Si/air batteries will be shortly discussed.

Silicon-based alloys, composites and nanostructures have received great attention as a possible replacement of conventional carbon-based anodes due to their higher lithium storage capacity. However, still fundamental aspects of lithiation processes and properties in Si-based nanomaterials remain largely ambiguous, despite their importance in overcoming many technical hurdles faced in practical use. Using first principles-based atomistic modeling, we have explored lithiation mechanisms in various Si-based nanosystems including nanowires, composites, oxides, and alloys. In this talk, I will present our recent progress in understanding the impacts of surfaces, interfaces and alloying elements on the properties and performance of Si-based anode materials for Li-ion batteries. Our first principles study shows that the lithiation behavior of Si nanostructures and composites is considerably different from the case of bulk Si because of surface and interface effects. For instance, the mobility of Li along the surface or interface tends to be significantly enhanced by several factors. We also find that by alloying Si with certain metal (M) elements, the theoretical capacity is compromised slightly, but in return the Si-M network may help stabilize the lithiated host matrix and therefore contributes to the improved cycling performance. I will also briefly touch on the importance of alloy composition and local atomic environment in determining the lithiation properties and performance. The improved understanding can contribute to the rational design of Si-based anode materials to maximize capacity retention and rate performance.

In this talk I will present recent work exploring the use of metastable materials having the calcium ferrite structure as electrodes in Li-ion batteries. By using low temperature ion-exchange reactions it is possible to make Li-analogues of NaFeTiO4 and Na2Fe3SbO8 with Li-ions replacing Na in the one dimensional channels within the Fe-Ti/Sb-O polyhedral framework. The anomalous changes to the structure when Na is replaced with Li and possible origins of this will be discussed, as will the electrochemical properties of both the Li and Na materials. The divergence in the properties will be discussed in relation to the crystal structure and chemical properties of Na and Li ions.

In this paper, we study the fracture behaviour and associated crack patterns that develop in Si thin film anodes of lithium ion batteries. In order to account for the ~300% volume expansions that the Li-ion exchange results in, a coupled deformation-diffusion problem is considered. The non-linear equations are solved using the extended finite element method, allowing for numerical simulations that are in good agreement with the experimentally observed crack patterns. In the simulations, the derived stress and strain fields are obtained independently of the mesh within the framework of the extended finite element method and linear elastic fracture mechanics. The advancing front is represented by the level sets with the stress distribution and the fracture parameters being estimated to assess damage development during lithiation. The fracture is simulated based on the maximum principal stress criterion. The stress fields ahead of the crack tip are modelled by a semi-analytical approach, which facilitates the computation of the fracture parameters, i.e., the stress intensity factors and the T-stress. The numerical results are compared with available experimental observations. The proposed framework will provide guidelines for designing crack free thin-film electrodes. The influence of the particle size and shape on the fracture parameters and the stress distribution is also investigated.

Li-ion batteries are the most promising energy sources for electric vehicles and biomedical implantable devices. They have therefore attracted the significant attention of the materials science and chemistry communities for over fifteen years. Before, however, we can fully utilize the most promising materials, such as Si and Sn, as next generation anodes. We must understand their mechanical behavior during the Li-intercalation and de-intercalation processes. The present talk will elaborate on advances that have been made, thus far in this area, and illustrate how they can be used to develop design criteria. It is shown that the theoretical predictions are in very good agreement with experimental data.

Surface modification on electrode has been reported to be an effective way to improve the cycling stability, coulombic efficiency, and abuse tolerance. However, less work has been done to fundamentally understand its role on the formation of solid electrolyte interphase (SEI) and lithium transport. In this talk, we reported some important findings on the effect of surface coating on SEI formation. We found that the oxide coating can suppress electrolyte decomposition, therefore significantly reduced the SEI thickness (from around 20 nm thick without coating down to 1nm). Al2O3 coating also went through the structural changes which better facilitate charge transfer. We have demonstrated that the self-modified coating served as an artificial SEI layer which not only stabilized the interface between electrolyte and electrode, but also mitigated the mechanical degradation of electrode and improved the cycling stability. We will discuss a few examples to show how surface coating can help improve the battery performance from different aspects.

The production of nano-structured carbon materials is a subject of large scientific and technological interest. A less prominent way of accomplishing this is by the conversion of graphite directly into nanocarbon through the application of molten salt electrochemistry. In this method, alkali metal ions from a molten chloride salt are intercalated into cathodically polarised graphite at a high rate, such that the graphite microstructure is destabilised and various nano-structured carbon species are formed which then detach from the graphite bulk. However, due to the heterogeneous product composition and the low yields, this method has hitherto been regarded as inferior.This presentation will summarise research and development work that may have the potential to change this view. By rigorously optimising the process parameters and implementing a novel type of process control, it has now become possible to prepare in gramme quantities nano-structured carbon material with nanotube contents as high as 70 to 80%. Through a variation of the process, it is also feasible to prepare carbon species filled with tin metal. A key application of this material is as the anode in lithium ion batteries. A first set of independently performed successful battery tests will be presented.

Graphite has been the traditional anode material in lithium ion batteries but this material cannot possibly meet the expectations for high energy and high power batteries. Disordered and especially nanostructured forms of carbon offer the possibility of higher reversible capacity. However, a much greater capacity can be achieved by using tin and silicon anodes but these suffer from large volume changes on charge and discharge which need to be controlled. Containing the metals inside carbon nanotubes and nanoparticles is one way of overcoming this problem. Other solutions include nanostructured materials based upon carbon, metal oxides and metal phosphides/nitrides/sulphides, all offering high surface areas, low diffusion coefficients coupled with high electrical and ionic conductivities. This paper reviews the progress towards the production and characterisation of these novel nanostructured materials for use as novel anodes in lithium ion batteries.

The past three decades have seen the remarkable success of lithium-ion batteries as power source for portable electronic devices. Furthermore, Lithium ion batteries can and will find applications to power hybrid and pure electric vehicle for land, water and air, as well as for stationary power system, back-up system, integrated with renewable energy production facilities (e.g. Solar, wind, biomass), and with smart grid. Their possible use for the most disparate applications has rendered lithium-ion the greatest key energy storage technology to help us with the transition to a more sustainable society.Constant research & development, high quality production of advanced materials for lithium ion batteries and cutting edge cells manufacturing process technologies are the recipes to be a master in today and future lithium ion battery industry. Why are different types of lithium ion active materials suitable only for certain industrial applications today? Which type of limitations has today the lithium ion battery industry? How is it possible to overcome the limit of today technology? These questions will be answered by over-viewing the advanced active materials (anode and cathode) and electrolytes currently employed for cutting edge lithium ion technology, by describing current lithium ion cells manufacturing industry technology, and by envisioning research directions to overcome today lithium ion batteries technology constraints.

A new process of recovering lead directly from spent battery paste as PbO precursor for making new paste has been developed. In this new environmentally sound paste to paste process, the net-carbon, SO2 and lead dust emissions are very low towards making new batteries without the use of high temperature pyrometallurgy or the energy-intensive electrowinning processes. By reacting spent lead battery paste with organic reagents and then combusting the organic crystallites, high surface area PbO is directly available for making pastes for new batteries.

Among the various electrochemical storage systems, lithium-ion batteries (LIBs) appear as a flagship technology able to power an increasing range of applications because of their high energy density values. Consequently, the world production of LIBs is expected to keep on growing. However, faced with a production of several billion a year one has also to consider their environmental burden from "cradle-to-grave" like other goods. A main brake in making "greener" batteries is probably related to the chemistry used itself, which is typically based on non-renewable redox-active inorganic components. In this context, a possible parallel research to inorganic-based batteries consists in developing organic electrode materials. Basically, organic materials are composed of quite naturally abundant chemical elements (C, H, N, O, in particular) giving them the true possibility of being prepared from renewable resources and eco-friendly processes coupled with a simplified recycling management. Nevertheless, in practice, the development of efficient organic electrodes is clearly in its early stages, and much remains to be done. One significant issue of organic electrode materials is their tendency to dissolve in common liquid electrolytes used in batteries, which automatically ruins the cyclability of a promising redox-active species. Another limitation lies in the difficulty in finding robust lithiated organic cathode materials capable of being reversibly delithiated (charged) at a high enough potential, similar to that of common inorganic insertion compounds.In this context, pi-conjugated enolate/C=O-based structures appear as highly interesting since the redox system is most often reversible whereas the dissolution phenomenon can be suppressed thanks to chemical tricks. For the past few years, we have been revisiting selected organic structures and we created a reliable experimental database of model chemical structures. Robust organic electrode materials able to react at both high and low potentials vs. Li have been identified and synthesized. The challenge is now the fabrication of efficient all-organic Li-ion cells.

This research aims to prepare nanostructral lead oxides used as active materials in HEVs, with a green hydrometallurgy recovery method from spent batteries via a homemade low-temperature. The nanostructral products were prepared by lead citrate precursor, which was synthesized through leaching of spent lead acid battery paste in citrate salt aqueous system. The nanostructral products were characterized by X-ray diffraction, scanning electron microscopy and thermo gravimetric-differential thermal analysis. The results show that the product comprise orthorhombic phase B-PbO, metallic Pb and elemental C in N2 atmosphere, while B-PbO with a small part of -PbO and Pb in air atmosphere. The PbO/Pb ratio of product can be controlled by modifying temperature, calcination time and air amount. And the battery testing results show that initial capacity of novel lead oxide is better than traditional oxides, and nanostructural lead oxides could be used as active materials in HEVs.

In this study, lead acid battery paste was recycled to be used as anode for lithium ion batteries (LIB). First, lead-acid battery paste was leached with citrus acids to transform into lead citrate following calcination-combustion reaction. Then, the product was used as an electrode material for lithium ion batteries. Used lead acid battery pastes contain typically 55-60 % PbSO4, 20-25 % PbO and 1-5 % PbO2. The reaction among PbO and C6H8O7.H2O, PbO2, the mixture of C6H8O7.H2O and H2O2, PbSO4 and the mixture of C6H5Na3O7.H2O and C6H8O7.H2O caused lead citrate to form. Reaction time, temperature and concentration were important parameters. In leaching step, the effects of poly-hydroxyl alcohol addition as grain refiner was investigated to synthesize lead based powder having submicron particles after the combustion-calcination process. Chemical and morphological characterization of battery paste and products were made. Galvanostatic half-cell electrochemical measurements conducted between 0.2-1.2V using lithium counter electrode was conducted to understand the electrochemical behavior of the anodes produced.

Lithium-ion batteries are attractive candidates as energy storage devices for solar power, wind power, and electric vehicle applications; However, their capacities and energy densities are still not enough to meet the industry standards. Although replacing the existing electrode materials with higher performance materials could address the capacity issue to some extent, it poses other challenges. These new anode materials (such as Si, Sn, Al etc.) undergo large volume changes (~100-270%) upon reacting with lithium which induces significant amount of stresses in the electrodes during battery operation. These stresses cause fracture and mechanical damage, which also promotes chemical degradation. Both of these processes lead to rapid capacity fade. Although cathode materials do not undergo significant volume changes, mechanical degradation, due to stresses, is still a major issue. Hence, there is a need to understand the mechanical behavior of electrode materials and coupling between electrochemistry and mechanics to be able to design efficient, durable, and higher-energy density batteries.Stress evolution in Si and Al thin films during electrochemical cycling was measured by monitoring substrate curvature using the multi beam optical sensor method. Strain rate sensitivity, fracture properties, and biaxial modulus of Si were also measured as a function of state of charge. After reacting with lithium, Si becomes ductile and undergoes plastic deformation. In contrast to graphite, elastic modulus of Si decreases with Li concentration. Further, a continuum mechanics model was developed to simulate the mechanical response of the Si electrodes during electrochemical cycling. Model predictions agreed very well with the experimental data. Finally, stress measurements were conducted on composite anode (based on graphite) and cathode (based on Li1.2Ni0.15Mn0.55Co0.1O2). The stress data from these composite electrodes was then used in an approximate semi-analytical method to estimate the pressure that the casing of a commercial (jelly roll configuration) Li-ion battery will undergo as a function of state of charge.

The need for higher capacity clean, portable, wearable energy storage devices has enormously incremented in recent decades. Additional functionality and thus, enhanced energy consumption characterizes the development of new portable devices. Likewise, higher driving ranges are needed for wider adaptability of electrical vehicles. Whereas evolutionary improvements in energy density can be anticipated in Li-ion technology, the most advanced battery device currently in the market, its chemistry limits the attainable capacity in such devices. Alternative lithium-air battery systems provide a theoretical energy density rivaling that of liquid fuels.There remains, however, significant technical challenges to be solved for the realization of safe, fully recyclable, high-energy capacity Li-Air batteries. These include the reactivity of high capacity Li metal anodes, the propensity when employing said anodes for incremental dendrite formation. In addition, during cycling of rechargeable lithium-ion cells, lithium can buildup in the electrolyte, resulting in thermal runoff, rapid discharge, ultimately failure of the cell. Engineering an electrolyte to better interface with lithium metal and easily cycle lithium ions, is essential for making energy storage systems such as lithium-air a reality. In this presentation I will discuss our efforts in the development of solid-state electrolytes that will provide solutions to these problems.

Metallic lithium embodies a large amount of energy. In order to improve sustainable use of this reactive element, it is crucial to harness this energy effectively. A lithium/sulfur (Li/S) battery has been regarded as one of the candidates for next generation battery because of high theoretical capacity at 1672 mAh per g, low cost of the materials, and environmentally benign nature of elemental sulfur. By using novel 3-D scaffolds based on nano-structured carbon infiltrated with sulfur, great improvements in energy density and cycle life have been demonstrated. Novel Concepts for scaffold to scaffold recovery from spent batteries for enhancing sustainability is discussed.

A nanoscale and pure olivine structure LiFePO4 (triphylite) and NaFePO4 (maricite) were synthesized at low temperature (from 300°C) using an organic-inorganic steric entrapment solution, from precursor chemicals of LiNO3, NaNO3, Fe(NO3)3*9H2O and (NH4)2HPO4 stoichiometrically dissolved in distilled water. A long-chain polymer, such as polyvinyl alcohol (-[CH2-CHOH]-n or PVA), having a degree of polymerization corresponding to a molecular weight of 9,000 to 10,000, was used as the organic carrier for the precursors, which served for the physical entrapment of the metal ions in the dried network. Normally, when calcined and crystallized in air, this method leads to the synthesis of compounds where the cations in their highest oxidation state. However, in this study we found a way to make compounds having lower oxidation states (e.g. Fe+2 versus Fe+3), which may have wider applications in the synthesis of other compounds having variable oxidation states, with potential applications in electronic ceramics of complex chemistry. The resulting LiFePO4 or (Li2O*2FeO*P2O5) and NaFePO4 or (Na2O*2FeO*P2O5) powders were characterized by TG/DTA thermal analysis, X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) nitrogen absorption and particle size analysis.

Lithium-sulfur batteries are among the most attractive candidates for next generation battery systems, offering both high theoretical capacities and thus high energy densities (1675 mAh/g and 3518 Wh/kg, respectively), despite a relatively low operating voltage (~2.1 V).However, they suffer from numerous severe challenges such as the so-called internal polysulfide shuttle: The sulfur active material dissolves in the course of the electrochemical reactions and the polysulfide intermediates can diffuse to and directly react with the metallic lithium anode. This severely lowers the Coulombic charge efficiency of the cells and results in a loss of active material.Moreover, the electrolyte is slowly consumed in reduction reactions continuously taking place on the anode surface. These side reactions lead to the formation and growth of surface layers (SEI). However, they are not stable upon cycling, as lithium is deposited in mossy and dendritic structures. The growth of lithium dendrites between the electrodes can lead to short-circuits and poses severe safety issues. It will be shown that an addition of excess amounts of electrolyte results in a considerable improvement of the cycle life (on the expense of the energy density of the cells under consideration), showing that the drying out of the cells due to electrolyte decomposition is one of the major reasons for cell failure upon long-term cycling. In addition, the degradation of the electrolyte solvents leads to gas formation, which can be monitored by means of differential electrochemical mass spectrometry (DEMS) and ex situ gas analysis.However, also the sulfur active material content exerts a strong influence on the overall cell performance and its cycle life, which is discussed in this presentation.Given that the major failure mechanisms involve reactions with the metallic lithium, it can be expected that only protected anodes have the potential to extend the cycle life of lithium-sulfur batteries far enough to become commercially of interest.

Lead Acid batteries (PbA) exemplify the cutting edge in environment stewardship and resource recovery. Currently, over 98% of all end-of-life lead acid batteries are collected and successfully recycled. An analysis of the energy balance for general smelter based recycling reveals that primary Pb production requires 7,000 - 20,000 Mj/t while secondary production 5,000 - 10,000 Mj/t. Direct recycling methodologies for the active material from PbA batteries, i.e. Paste, indicate that a 10 to 30% energy requirement reduction 3,500 - 4,500 Mj/t is possible. Although in early development stages this technology is a promising route to reduction of energy consumption and greenhouse gas emissions in the recycling of the world's dominant rechargeable battery technology.

Recycling is an important issue in the lifecycle and environmental management of electrochemical systems, i.e. Batteries & capacitors, in advanced automotive technology. The issues, opportunities and requirements of electrochemical system recycling need to be addressed in a way which is uncertain to the chemistries involved. In conjunction, this places a high demand for the development of technologies, which can address both the technical and legislative issues surrounding either waste mitigation or resource recovery from "End of Life" electrochemical systems. The SAE Battery Recycling Committee has brought together the producers of end products, the full complement of other SAE groups working on battery applications and the battery recyclers to address the complex matrix of issues. We will discuss the complex interrelationships and how the structures are being developed to lead to consolidated technical information, recommended practices and industry standards. This is a particularly daunting task as the structures developed must be applicable and acceptable across multiple political and product lines.

As a new energy storage system, sodium-ion batteries have attracted much attention due to their low cost and abundance of sodium raw materials. Herein, we report a detailed study of transition metal oxides as new energy storage materials for sodium-ion batteries. In virtue of the variable valence and the distinctive structure of the transition metal oxides, the sodium cations can easily and rapidly intercalate and deintercalate in the unit cell of the as-synthesized materials. The electrochemical performance and the energy storage mechanism have been investigated by XRD, TEM, XPS, galvanostatic charge/discharge test and first-principle simulations. The results show high specific capacity, superior cyclability and excellent rate capability. With a simple synthetic method and cost-effective chemicals, the transition metal oxides exhibit promising materials in large-scale applications for rechargeable sodium-ion batteries.

Li-O2 ("Li-air") batteries have been intensely studied as a future technology for energy storage due to high theoretical capacities, up to ten times that of existing Li-ion battery materials. There are significant technological challenges before Li-O2 batteries can be practical, such as the large overpotential and slow kinetics. In order to reduce the overpotential and hence improve the energy efficiency, and improve the reaction kinetics, transition metal oxides (MOx) such as Mn and Fe oxides have been used as electrocatalysts. In addition, we have recently proposed using lithium transition metal oxides (nLi2O.MOx) as hybrid all-in-one materials that can perform as both electrodes in Li-ion and electrocatalysts in Li-O2 batteries. A fundamental understanding of these MOx and nLi2O.MOx materials require collaborative efforts between electrochemical experiments, in situ and ex situ characterization, and computational modeling. In this talk, I will discuss the use of first principles density functional theory modeling in conjunction with synchrotron characterization to understand the reaction mechanisms of these materials and the possible impact of different materials on battery performance.

With the anticipation of a higher penetration of intermittent renewable technologies into electrical grids, energy storage technologies will be necessary to allow for load levelling and use of excess energy that would otherwise be wasted. Two methods of renewable energy storage that are currently being researched are: Vanadium redox flow batteries (VRFB) and hydrogen storage along with the use of electrolysers and fuel cells (FC). Both technologies show promising characteristics for energy storage with many test applications already operating. The comparison of both technologies will be completed by the development of a system dynamic model using Vensim. The model will allow energy storage characteristics including storage capacity (kWh), power capacity (kW), estimated total costs, efficiencies and response time of the storage system to be compared to allow for an analysis of the feasibility of the storage systems. Different scenarios will be developed to indicate the response of the energy stored in the system over time with regard to wind power and how effective it is in meeting demand. The model will investigate the feasibility and suitability of both energy storage technologies.

Sodium-ion batteries (SIB) are considered as an attractive alternative to lithium-ion batteries (LIB) as they could potentially be much less expensive, safer, and sustainable. Clearly, one of the major concerns that we are currently faced with consists in determining to what extent the results gathered over the past twenty years in the Li battery field, can be transferred to the Na one. Our research directly addresses this issue by highlighting two facts: 1- The Na intercalation process in FePO4 is significantly different from the Li one with the existence of an intermediate Na2/3FePO4 phase. By combining TEM, synchrotron XRD as well as Mossbauer and NMR, we proved Na2/3FePO4 as being a fully ordered composition showing vacancy ordering. Ab initio DFT calculations confirmed a very good agreement between all analytical methods. 2- Contrary to what has hitherto been observed for Li batteries, the thermodynamic phase diagram of FePO4 needs thorough reassessment as far as the dynamic intercalation/deintercalation of Na ions within a cycling battery is concerned. Indeed, based on operando synchrotron X-Ray diffraction, we show that structural phase transformation does not proceed at constant composition. This striking result, hitherto unseen in material science, to our knowledge, results in Na batteries having an enormous advantage over Li ones, since the lattice volume mismatch during phase transformation is greatly reduced. Such kinetically controlled structural behavior could clearly compensate for the less efficient Na-related SEI, as well as the larger size of Na ions compared to Li ones.

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