Research in Li-S battery is recently becoming very popular and the potential applicability of the Li-S battery as a power source had been mentioned more than two decades ago. Its development was mainly impeded by the difficulty in the safe use of pure Li as an anode on one hand and even more critically the electrochemical use of S without encountering charge transfer problems. Furthermore, the formation of Li dendrites on the Li-anode during re-charge and the loss of available S at the cathode resulted in a rapid fade of the capacity. A summary of recent progress in Li-S battery is presented. Current development of Li-S batteries have led to > 400 Wh per Kg of energy densities, but the capacity fade with cycling is still an issue requiring scientific and technological solutions, however one can cautiously predict that the strides can prove to be more rapid than Li-ion batteries after take-off.

Recycling the major components of the spent lithium-ion batteries (LIBs), such as lithium and cobalt and other hazardous materials, appears to be a useful method to inhibit environmental contamination and raw material utilization. In this work, a novel pyrometallurgical process is developed for separation and recovery of cobalt and lithium from spent lithium-ion batteries. The main material used in cathode is LiCoO2 in the form of ground fraction principally containing cobalt and lithium. The ground fraction is mixed with carbon and pressed into pellets for the reduction reaction to take place. The carbon used in this reaction is chosen from carbon produced in a waste tire recycling process. The characterization of the reaction products shows that cobalt can be recovered as metallic cobalt and lithium as Li2CO3. This pyrometallurgical process is adequate and easy for recovery of cobalt and lithium from spent lithium-ion batteries.

Carbon nanomaterials including carbon nanotubes and graphene will play a crucial role in the next-generation of energy storage devices. In lithium ion batteries, graphite is the traditional anode material due to its excellent cycle life. However, graphite has a theoretical maximum capacity of 372 mAh/g which is not enough for high energy Li-ion batteries. Metallic and intermetallic anode materials can provide much higher theoretical capacity than graphite, but suffer from high volume changes during battery cycling, leading to premature degradation of the anode after a few cycles. In order to overcome this problem, new classes of hybrid metal-carbon nanostructures have been developed and evaluated as anode active materials, and some of them have shown promising results. In lithium-sulfur batteries, sulfur serves as the active cathode material with a theoretical specific capacity of 1672mAh/g. However, various challenges are associated with sulfur electrode including low electrical conductivity of sulfur, dissolution of polysulfides in electrolyte and volume expansion of sulphur during discharge, causing poor cycle life, low specific capacity and low energy efficiency. The successful incorporation of carbon nanomaterials into the cathode structure can improve the electroconductivity, and also provides an effective electron conduction path and structural integrity. This paper reviews the achievements in utilisation of carbon nanomaterials in energy storage devices. Moreover, the activities carried out in the Materials Chemistry Group at Cambridge towards scalable synthesis of carbon nanotubes, graphene and metal filled carbon nanostructures, and their application in energy storage devices are presented.

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 and dendrite formation on recharge. Dendrites can be prevented if the material is stiff, however, attempts to stiffen the polymer will decrease conductivity because fast conduction requires the polymer to be flexible. To make progress, we must decouple conductivity and mechanical properties. We address this issue by the use of large aspect ratio nanofillers. Spherical nanopolymers have been known to improve conductivity for the past 10 years. Their influence depends on surface chemistry. If the surface is acidic (in the sense that it is an electron acceptor), conductivity is improved more than if it is basic. This talk will demonstrate that high aspect ratio fillers, tunable surface chemistry and whisker alignment lead to significant gains in conductivity. We propose that these fillers serve as nucleation sites for (polyethylene oxide)6(ClO4)1, the crystalline structure with fast conduction. At the eutectic composition, (polyethylene oxide)10(ClO4)1, multiple layers are formed, further enhancing conductivity. There are many demonstrations of nanofillers significantly increasing stiffness in polymers without salt. We expect the same result with Li salts, and thus we decouple conductivity and mechanical properties.

The main aim of the work reported here is to explore the feasibility of competing ligand exchange-adsorptive stripping voltammetry (CLE-AdSV) technique to study speciation of Ni(II) in Pb-rich solution. A general introduction of competing ligand exchange (CLE) and adsorptive stripping voltammetry (AdSV) techniques are presented. Cyclam, a Ni(II) complex ligand, and its redox properties is investigated in different solution conditions. The complex formation equilibrium of NiCy is then investigated. Its competition with metal ions (Fe(III), Cu(II), Zn (II) and Pb(II)) and citrate ion is simulated based on complex formation equilibrium. Then attention is brought to the optimisation of the stripping parameters to achieve maximisation of sensitivity and selectivity. Finally some of these experimental results are explained with the application of aqueous solution theory.

Energy (production, storage and utilization) constitutes one of the most important and challenging issues in the United States and no single solution will be able to provide the required answer to this gigantic problem we face.
In order to help DOE to advance technologies, the Chemical Sciences and Engineering Division at Argonne National Laboratory is conducting cutting edge research in the following fields:
-Reverse engineering photosynthesis for bio-inspired solar energy conversion
-Vertically integrated experimental and theoretical combustion chemistry
-Atomic and molecular-scale control of catalytic reactions for energy technologies
-Fundamental mechanisms for photons to fuels conversion
-Atomic and molecular-scale chemistry of heavy elements and fission products
-New Tailored Interfaces for Electrical Energy Storage.
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 in support of DOE's mission.

Infiltration of small amount of CuO into La0.6Sr0.4Co0.2Fe0.8O3 (LSCF)/ Ce0.1Gd0.9O2 (CGO) to modify the surface activity of the cathode has been conducted in this work. The ASR of LSCF/CGO at 500oC was significantly reduced by more than 5 times from 27.6Ωcm2 to 5.2Ωcm2 by the CuO infiltration. It has been found that the reduction of ASR may be attributed to the formation of La0.6Sr0.4Cu0.2Fe0.8O3 (LSCuF) or other Cu-containing oxides. However, this kind of composite is not stable which will degrade during aging. Also, Cu2+ will cause internal strain inside the lattice arising from the Jahn Teller effect. This will cause segregation of other elements, such as Sr, and as a consequence, the catalytic property becomes worse. More studies are needed to stabilize the CuO infiltrated cathode. Ability to produce infiltrated electrodes are relevant for energy devices ranging from fuel cells to batteries and supercapacitors.

The feasibility of the inkjet printing technique for fabrication and modification of electrode and electrolyte coatings for energy applications was studied. A variety of suspension (ceramic, metal) and solution inks was optimised for direct inkjet printing of functional coatings and patterns (2D/3D) as well as infiltration of the electrodes' backbone structures. Electromagnetic print-heads were utilized to reproducibly dispense droplets at rates of several kHz on demand. Printing parameters including line pressure, nozzle opening time and droplet overlapping percentage were studied in order to optimize the jetting and the uniformity of ink delivery. Special attention was paid to finding working windows without satellite droplets formation in order to maximise the printing resolution. Droplet volumes of order of nano-litters and jetting velocities of order of several meters per second were achieved without accompanying splashing effects. The technology allowed easy modification of the coatings, including thickness control, composition and porosity graduation. Scanning electron microscopy revealed highly conformal coatings produced on rigid and flexible substrates with thickness resolution below 10 µm. The effect of microstructure on the electrochemical and electrical performance was investigated. Drop-on-demand inkjet printing infiltration was explored in order to achieve controllable loading of active elements via variation of Reynolds and Weber numbers of the impinging ink droplets. The inkjet printing was proven to be environmentally friendly by allowing a substantial reduction of the expensive precursor materials usage.

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.

Lithium ion batteries have become critical energy storage devices, not only for the plethora of consumer electronics that we depend on daily, but also for electric vehicles and utility energy storage systems that will be essential for combating climate change and enabling clean energy. Consequently, substantial investments have been made in both manufacturing capacity and research programs globally. However, the manufacturing processes used to produce lithium ion batteries are neither inexpensive nor environmentally benign.
Current manufacturing processes employ a solvent based slurry mixing/coating method with N-Methyl-2-pyrrolidone (NMP) as the solvent of choice. NMP has recently been identified as a known reproductive toxicant, and as a result, its use is increasingly restricted in the E.U, North America and Japan. In addition to escalating the potential liability and environmental repercussions for its use, the use of NMP is partially responsible for the high of the costs of lithium ion batteries, where it can be responsible for over 50% of the processing costs. NMP-free production processes would not only offer a truly 'green' lithium ion battery, but they would also enable a breakthrough in cost reductions which could have massive beneficial global consequences.
Recently, Electrovaya launched its second generation coating technology that avoids the use of NMP altogether, while also enhancing the quality of the electrode coating. A comparison of the microstructure and performance of electrodes produced with Electrovaya's process and conventional NMP methods is shown. This includes both SEM/TEM analysis in addition to novel TOF-SIMS analysis methods. Finally, the new process also allows the use of sensitive additives, which will further enhance the performance and energy density of lithium ion batteries.

Lithium-sulphur (Li-S) electrochemical system has attracted great interest because of its high theoretical specific energy of 2500-2700 Wh/kg. However, there are still many challenges ahead. The prototypes of lithium-sulphur batteries provide practical specific energy of 200-300 Wh/kg and can suffer fast capacity depletion during charge-discharge cycling. A key issue to address in a Li-S battery arises from lithium electrodes. Metallic lithium has high reactivity and can react with electrolyte systems during cycling of the batteries and can cause electrolyte destruction that is one of the reasons restricting the cycle life of Li-S batteries. Moreover, fine dispersed lithium precipitations can be formed on the negative electrode during electrochemical plating. This negatively affects the safety and the cycle life of Li-S batteries. We report on our study of chemical and physicochemical processes on a lithium electrode during both stripping and plating in selected electrolyte system of a Li-S battery by electrochemical impedance spectroscopy, electrochemical dilatometry, electrochemical isothermal calorimetry, galvanostatic cycling and scanning electron microscopy. The performed study shows that presence of lithium polysulphides in the electrolyte systems of lithium-sulphur batteries can reduce the rate of accumulation of fine dispersed lithium on the lithium electrodes during galvonastatic cycling of lithium-sulphur and half lithium cells. It was estimated that in presence of lithium polysulphide, corrosion activity of fine dispersed lithium decreases because of formation of a sulphide protective layer on the surface of lithium. This serves to increase the cycle life of lithium electrodes.

Robust, scalable and low cost stationary energy storage is needed to stabilize the electric grid against the intermittency common to solar and wind-generated power, thus improving grid reliability and thereby enabling the broader use of renewable resources. Redox flow batteries are well-suited to storing megawatt-hours of electrical energy that is meant to be discharged over the course of hours. While a large number of aqueous flow batteries have been developed, a number of technical and economic challenges have prevented widespread commercial success. Transitioning from aqueous to non-aqueous electrolytes offers a wider window of electrochemical stability that enables operation at higher cell voltage (> 4 V) leading to higher energy density. Moreover, a greater selection of redox materials may be available due to either the wider potential window or the variety of non-aqueous solvents. Together, these benefits promise to reduce the cost of energy as well as to shrink the system footprint, enabling storage in confined spaces. However, this promise must be balanced with the challenges associated with non-aqueous electrolytes including increased solvent cost, reduced ionic conductivity and other undesirable physical properties. Furthermore, as compared to their aqueous counterparts, non-aqueous flow batteries are in their infancy and many unknowns still exist. Understanding and balancing these competing factors will be key to determining the true prospects for non-aqueous flow batteries.
Here, we will present the challenges and opportunities in the science and engineering of non-aqueous flow batteries capable of meeting US Department of Energy established grid storage costs. Specifically, we will describe system-level techno-economic analyses which yield materials-level benchmarks to guide molecular discovery. We will then highlight the development of several promising new materials which begin to lay a credible pathway to low cost electrochemical technologies.

Transition metal oxides (TMOs), such as TiO2, NiO2, SnO2, and Co3O4, have been considered as the potential anode material substitutes for graphite in rechargeable lithium-ion batteries (LIBs), due to their high theoretical capacities, high volumetric energy densities and improved safety in comparison with conventional graphite. However, the practical applications of TMOs have been suffered from poor electronic conduction, large volume change followed by disintegration or pulverization during charging-discharging.
In our work, three main types of strategies have proved more effective to deal with these problems. One favourable method is based upon preparing nano-sized metal oxides with hollow, mesoporous and hierarchical structures, which can potentially buffer the large volume changes while simultaneously decreasing the diffusion length for lithium ions, leading to improvement in cycling capacity retention upon extended cycling. The other approach is to combine the metal oxides nanostructures with flexible conductive matrix such as carbon nanotubes (CNTs), CMK-3 and graphene which can also accommodate the mechanical strain during the lithiation/delithiation process while inhibiting agglomeration and enhancing conductivity. Another method is based upon using mixed transition metal oxides (MTMOs) as a suitable electrode material on account of their higher electrochemical activities and higher electrical conductivities than simple TMOs. These results indicate promising innovative designs for battery electrodes with improved electrochemical performance.

In recent years, lithium-ion batteries are important for a wide variety of applications. Battery performance depends critically on the materials used, so the development of advanced materials is important for advancing battery technology. Lithium niobate (LN) is a ferroelectric material widely used in electro-optics but recent studies have been carried out on Li-ion batteries, where LN is used as a negative electrode or buffer layer material. In this study, nanopowders of lithium niobate (LiNbO3, LN) were synthesized using a simple and effective method via Pechini-type reaction from the mixture of water–soluble compounds including Li2CO3, a new Nb source, ammonium niobate (v) oxalate hydrate, citric acid (CA) and ethylene glycol (EG). Heating the mixture to 80 °C produced a white gelatinous precursor without any precipitation, which was calcined at various temperatures in air. The thermal behavior of the precursor gel has been studied by thermal gravimetric (TG) and differential thermal analysis (DTA) and the products derived from calcination of the gel at various temperatures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM).

Both tin (Sn) and sulfur (S) can act as hosts for lithium-ions and, therefore, Sn/C and SnS/C nanocomposites, prepared by the solution method, have the potential to be used as anodes in next-generation Li-ion batteries. One of the key factors in the design of promising anodes is the ability of their microstructure to accommodate the Li-insertion and de-insertion; hence, in the present study, various carbon types were employed, and the metal volume fractions (S and Sn) were varied in order to determine the most promising microstructures. Particularly, the types of carbons, which were considered in this study, were artificial graphite (AG), mesocarbonmicrobeads (MCMB), and graphene (GC). To prepare Sn/graphene composites, the amount of Sn was made to vary between 10 wt.% and 20 wt.%. As for the SnS/C materials, the Sn and S ratios were 10:10 and 20:20, and the types of carbon used were MCMB and AG. X-ray diffraction showed that Sn and SnS phases develop within graphite, and scanning electron microscopy revealed that these phases disperse well in graphite. Furthermore, transmission electron microscopy allowed for a better observation of the nanometer dimensions of the particle size in all the samples.

Energy storage is the key enabling technology for exploitation of alternative energy and the vast deployment will help the transaction from a fossil fuel based economy to a more sustainable society. In the field of energy storage, lithium ion rechargeable batteries (LIB) play a significant role thanks to their high gravimetric and volumetric energy, long cycle's life, high efficiency and low self- discharge properties. The LIBs have proven to be the solution for portable devices like smart phones, tablets, personal computers, cameras, however for consistent application as a power source in electric vehicles they need from five to ten times more energy density than present state of the art technology can offer (150Wh/Kg) and higher power density. Furthermore, for the massive application of smart grid and stationary power projects, the production cost should be reduced and cycle life substantially increased.
The path to LIB with improved energy density and reduced cost of manufacturing led to the development of advanced materials originally designed for application in LIB. Among the materials used in LIB, the active material for the fabrication of the negative electrode is an important component of the LIB. Soft carbons materials (graphitizable carbons), where crystallites are stacked almost in the same direction, are the standard active materials for anode used in today lithium ion batteries industry. Soft carbon (i.e. graphite) shows an appropriate reversible capacity of around 370 mAh/gr, long cycle durability and a columbic efficiency higher than 90%. However, these type of materials are suffering for many drawback such as low energy density, low power density, and safety issues related to Solid Electrolyte Interface formation as well as lithium plating phenomena during the charging and discharging of LIBs.
The development of alternative anode materials is mandatory for LIBs with improved electrochemical performance. For the sake of simplicity, anodes materials can be divided in three categories based on their working mechanism: 1) intercalation / de-intercalation 2) alloy / de-alloy 3) conversion materials. Carbon Nanotubes, Graphene, Silicium based material, Germanium based materials, Titanium based materials, Transition Metal Oxide, Metal Sulphides, Phosphides, and Nitrides are currently under investigation. Nano-structuring these materials represents the feature capable of leading these innovative materials from being theoretically relevant to an effective technological breakthrough. Recent research outcomes and outstanding results on nanostructured alternative anodes materials will be overviewed.

Reversible solid oxide cells (SOC) could potentially contribute to electrical energy storage in the future. SOCs are expected to be capable of producing electricity using stored fuels and in reverse mode of producing hydrogen or syngas that can be stored or processed further to produce easily storable fuels. Their potential use for energy storage will be influenced by the efficiencies, economic benefits, demand for large scale energy storage and the development of competing technologies. The paper will present the current status of the technology, system thermodynamics and a comparison with competing energy storage options.

The lithium ion batteries consist of positive (inorganic lithium-intercalating compound and negative (lithium-intercalating carbon) electrodes and have an organic liquid electrolyte (a lithium salt in an organic liquid). They store lots of energy in a small and light package. Lithium-ion batteries are widely used in cordless communication technologies and equipment such as laptops, cell phones, and other mobile devices.
Despite lithium ion batteries are produced with the high safety standards, plenty of incidents have been reported because of fire and explosion of lithium ion batteries in electronic devices or large vehicles and facilities. Therefore, lithium-ion batteries are optimized to store and release energy with respect to environmental, health, and safety issues. This work summarizes potential hazards and safety recommendations for their commercialization.

Ultra-thin 2D materials have emerged as promising candidates for a variety of applications ranging from information to energy technologies. Often, such materials and structures offer superior scalability to 1D and 0D materials, and for energy applications, such scalability is a strong pre-requisite for making a significant impact on this grand-challenge problem. For example, graphene offers straightforward processing routes and useful properties for a variety of energy-related devices such as solar cells, supercapacitors and lithium ion batteries. This presentation will discuss the major synthesis techniques that have been employed to obtain single-, bi- and few-layer graphene, as well as vertical 'petal' versions and the subsequent scale-up of the plasma synthesis process to a roll-to-roll nanomanufacturing platform. We also consider prospects for the use of biorenewable feedstocks that transform into graphene in the plasma synthesis process. Subsequent coating of the graphene with electrochemically active material can produce extremely high levels of energy storage via electrical charge in form factors that are highly durable and flexible. The remainder of the talk will consider such coatings, such as metal oxides derived preferably from abundant and recyclable elements, and the assembly of these materials into electrical storage devices including symmetric and asymmetric supercapacitors with battery-like pseudocapacitive behavior. For these, a broad range of functional performance metrics exist and will be discussed in the context of the state of the art.

Lead acid battery can be recycled by adapting a sustainable hydrometallurgy process with carboxylic acids for directly producing lead oxide from lead pastes to make new batteries. However, impurities in the lead paste can easily contaminate the lead oxide product thus affecting the battery performance.
In order to investigate the behavior of three typical impurities, antimony, tin and barium sulphate during the hydrometallurgical recycling of lead acid battery, we report on the dissolution behavior of these elements in citric acid/sodium citrate solution (CS) and acetic acid/sodium citrate solution (AS) under varying temperature, time and atmosphere. In a CS solution, tin and barium sulphate can achieve higher dissolution, while dissolution of antimony can be promoted in an AS solution. This work has also shown that oxygen in air can dramatically accelerate the dissolution of both antimony and tin in CS solutions. The performance of tin and antimony during recycling of real lead paste was also studied in this work.

The effect of using ammonia based reagent was investigated in the newly developed citric acid hydrometallurgical method for recycling spent lead-acid batteries. The pH of leaching solution was adjusted with varying additions of ammonia, while monitoring the observed change in temperature. The desulphurization ratio of spent lead paste reached up to 90%, with the addition of 20 wt% ammonia for a reaction time of 1 h. The effect of experimental factors, mole ratio of citric acid to lead, leaching time, leaching temperature, initial solution pH on desulphurization efficiency of spent lead paste were studied. The XRD patterns of the crystals formed after leaching were studied whose chemical formula was shown to be Pb(C6H6O7)*H2O at a pH of 3.3 and Pb3(C6H5O7)2*3H2O at a pH of 6.2. The crystal structure of the lead citrate crystal was also studied using the single crystal method. The crystals obtained at different pH crystallize in the triclinic crystal system, with space group P-1. This attractive study shed light on the recycling of spent lead paste via this new method.

Nanostructured carbon composites can play important roles in lithium and other batteries. Preparation and characterisation of such composites are therefore important in further development of batteries.
Carbon nanostructures including carbon nanotubes, nanoparticles and graphene can economically be produced in molten lithium chloride. The present work reports the influence of the molten salt synthesised carbon nanostructure filler and commercial graphite on the properties of epoxy resin. The carbon materials were incorporated into the polymer matrix to make composites. The carbon-epoxy composites produced were then characterized by a variety of techniques including scanning electron microscopy, x-ray diffractometry, and dynamic mechanical analysis. The thermal and mechanical properties of the nanocomposites were also measured. It was found that addition of carbon materials can enhance the properties of the epoxy matrix considerably.

The Italian legislation anticipated the implementation of the guide lines of the European Directive 91/157 through a law (issued in 1988) ruling waste management and specifically scrapped lead-acid accumulators collection and recycling and providing one single, mandatory, non-profit Consortium with members of the Board of Directors representing all of the categories of operators taking part to the life-cycle of the batteries (batteries producers or importers, smelters operators, retailers, collectors, car-repair shops, etc). The Consortium became fully operating in 1991, and, as a result, the collection rate ramped up immediately (1992) to 120 kt/year, and, throughout the 90s and 2000s increased up to 200 kt/year, achieving one of the highest recovery efficiency in Europe, regardless of any lead price fluctuations. <br />The key factors of success were: 1) responsibility and control shared among all of the categories taking part to the life-cycle of the batteries 2) viability and efficiency of the financial scheme, granting to all categories adequate profitability 3) viability of the centralized control system, ensuring effective management of collection and recycling operation as a whole.<br />The paper gives also details of two original Information Systems that are conditional to design and master the collection and recycling network. The technical project of the collection network was supported by an original software developed by Texeco Engineering srl (now Texeco Consulting) with the scope of calculating the potential flow of scrap batteries arising from the various geographical areas of the Italian territory, together with relevant forecast of collection cost. Another software was implemented by the Consortium for processing all data transferred by collectors, so to master and optimize handling, storage, and transfer of collected scrap batteries to smelters. Such Information system was capable of monitoring a network consisting of about 80 collectors and 7 smelters, with a yearly output of 150-190,000 tpy of scrap batteries.

In this paper, we study the effects of stress-diffusion interactions on the fracture behaviour and the crack growth of Lithium ion battery electrodes. A coupled mechanical equilibrium and Lithium diffusion accounting for the effect of stress on diffusion and the effect of advancement of the front to the crack growth is considered. The discontinuous fields are represented independent of the mesh within the framework of the XFEM and linear elastic fracture mechanics. The advancing front is represented by the level sets and the stress distribution and the fracture parameters are estimated to understand the stress development during lithiation. The fracturing is simulated based on the maximum principal stress criterion. The numerical results are compared with available experimental results. The proposed framework will provide insights into understanding the failure and degradation of the electrodes under potentiostatic and galvanostatic conditions. The influence of the particle size and shape on the fracture parameters and the stress distribution is also investigated.

At the beginning of its operation, the Italian Mandatory Consortium for collection and recycling of waste lead acid battery had to carry out an assessment of already existing recycling facilities in Italy, as to smelting capacity and to environmental performance as well. The Consortium entrusted Texeco Engineering s.r.l. (now Texeco Consulting) to perform an independent audit of the different existing recycling plants because of its long lasting experience in secondary lead operation. The entirety of Italian secondary smelters is based on the operation of short rotary furnaces (SRF) that generally are the production bottleneck. In order to carry out such commitment, Texeco developed a thermodynamic model of the SRF, based on the general thermodynamic software HSC Chemistry by Outokumpu Technology, thus creating a standard and indisputable tool, suitable to grant a reliable and accepted assessment of the SRF capacity, on the basis of a given lead charge and additives receipt, as stated by each plant operator and furnaces size. The model output provides equilibrium compositions of each phase (bullion, slag, gas), fuel and air/oxygen requirements, temperature and composition of process gases, required time length of one batch. The model was experienced and field-validated in 7 Italian recycling plants, equipped with 14 SRF with nominal capacities ranging from 4000 to 8000 lt. Of course the application of the Texeco model is not limited to assessment of existing capacities, but it has been successfully applied to engineering design of new furnaces and relevant process gas treatment unit in different projects. The model has a broad application for different heating systems (air or oxygen, oil or natural gas) and different charges that is why the model is also a powerful tool in evaluating new secondary lead projects feasibility, as well as expansion and/or retrofitting of existing installation, optimization of performance of any existing operation.

The work deals with the thermodynamics of leaching of the active mass from spent Li-ion batteries (LiBs) in acidic media - in sulfuric acid and hydrochloric acid. The active mass contains oxide phases of cobalt, lithium, manganese and nickel in the form of LiCoO2, LiNiO2, LiMn2O4, graphite and others. In the active mass, other phases of cobalt and lithium can be present as a result of decomposition of the constituents during the discharge or overcharging of LiBs in their life cycle. Thermodynamic study was carried out by software HSC Chemistry 6.1. I”Go was calculated for the predicted chemical reactions in the temperature range 20-80 A°C and E-pH diagrams were constructed. It was found that I”G0 reached the negative values almost for all reactions in the monitored temperature range in both of leaching media. It means that the expected chemical reactions can proceed during the leaching in the direction of product formation. For the design of E-pH diagrams, the acidic pH range was considered. According to the E-pH diagrams, cobalt is present in ionic form in both leaching agents throughout the whole water stability area to the pH ~ 5-7, depending on the temperature. At higher pH, cobalt can precipitate from solution as CoSO4.7H2O (only in sulfate medium) or Co(OH)2. Lithium is present in ionic form throughout the whole water stability area in the whole acid pH range. Thermodynamic study confirmed the viability of cobalt and lithium leaching from spent LiBs in the sulfuric acid and hydrochloric acid as well.

The requirement for easy and low-cost access to energy storage technologies is increasing with the continued growth of renewable energy in the attempt of reducing fossil fuels consumption and greenhouse gas emissions. Advanced energy storage capabilities are necessary for load levelling and maximising the penetration of renewable energy into the grid. Hydrogen is a well-known energy carrier that can be used for energy storage. The strong synergy between natural gas and hydrogen anticipates that new efficient methods of hydrogen production such as microwave plasma and solar/thermal processing of natural gas will have a leading role. Furthermore, these novel approaches will allow added value from the hydrogen production path to be achieved. The aforementioned processes can produce valuable carbon allotropes that can have different applications including conductive and high-strength composites, hydrogen storage media etc. Redox-flow batteries (RFB) have promising storage characteristics and, as the power and energy capacity of the battery are independent, they can be optimised to maximise performance and minimise cost. A technical and economic comparison of vanadium and all-iron flow batteries will be explored within the present study. Selective carbon allotropes from microwave plasma processing can be used as an integral part of low-cost large-scale energy storage in RFB functionalised electrodes, providing a valuable link between two different methods where one can also supply materials for the other technology. Here, this link will be investigated by looking at the system economics and by comparing all-iron and vanadium redox flow batteries with regard to technical performances. The manuscript will also look into the carbon allotropes value within hydrogen production pathways.

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