To advance the progress of miniatured energy conversion and storage devices, several promising new advanced functional materials have been systematically investigated in past few years. In this talk, I will discuss various potential electrode materials for energy and sensing devices (1-3). This talk provides a broad spectrum of the state-of-the-art research activities that focus on the functional metal-oxide nanostructured (MOXN) systems, 2D and 3D nanoarchitectures materials and their characterizations by diverse techniques. It commences with the synthetic methods and possible mechanisms that have been employed to form these nanostructures. A wide range of remarkable characteristics will be presented, organized into sections covering a numerous type of functional materials. The talk will also focus on high temperature gel polymer electrolytes (GPE) for lithium ion battery applications (4). Finally, an overview of challenges, frontiers and opportunities of materials for renewable energy conversion and storage systems will be conversed.
Keywords:Lithium based batteries have come to represent paradigm shift in energy storage in electrification of transportation and in supporting power generation from renewable energy technologies. Looking into the near future, many other battery chemistries are staking their claims within a mix of battery chemistry portfolios. Given the massive shifts facing the future energy-environment paradigm, it is pertinent to evaluate the progress of various battery chemistries within this nexus in the evolving scenario. Several factors including future research trajectories with respect to low-carbon resources become matters of paramount interest. Understanding battery chemistry basics is critical to unlocking the issues of energy, power, costs, safety, resources, and sustainability, as this Tutorial will explore. In addition to Lithium chemistries, fundamentals of Sodium, Zinc, Aluminium, Potassium, Magnesium, Lead, Solid-State and Redox battery systems will be introduced.
Keywords:Aqueous Zn-ion battery has been getting much attention because of the ready availability and low cost of zinc relative to lithium [1]. The battery is also much safer to manufacture, use and dispose as they use water-based electrolyte and non-flammable electrode materials [2]. As a cathode, hollow shelled MOOH (M = V, Fe) has been considered as a good cathode as it produces high capacity, stability, and long-life [3]. In this study, the morphology of the VOOH material has been altered into hollow double shell sphere structure to achieve a stable cathode with high internal surface area[3][4]. The effects on capacity with respect to a single-shelled VOOH will be investigated and analyzed. The double shelled VOOH was prepared using a 2-step hydrothermal process [4] and was made into a slurry to be pasted onto a stainless steel SS304 current collector. The battery was then assembled using current collectors, a metallic anode, a separator soaked with electrolyte and the cathode in a Swagelock Cell for testing. The results showed that the capacity of the cathode was similar to the single-shelled VOOH with a capacity of 479, 426, 414, 374, and 284 mAh g-1, at current densities of 0.01, 0.1, 0.2, 0.5 and 1 A g-1, respectively. Effects of each battery component was also analyzed in this study by using different anodes (Zn and Cu), electrolytes (Zn(CF3SO3)2 (aq, 3M) and ZnSO4 (aq, 2M)), separators (glass fiber and polypropylene), and current collectors SS304, Al, and Cu. An oxidized version of VOOH was also tested as a cathode to analyze the difference between the two cathodes. Structural and morphological characterization methods used in this study were XRD and SEM, and the electrochemical methods deployed were battery performance Charge-discharge cycle tests, Cyclic Voltammetry, and Electrochemical Impedance Spectroscopy. The result showed that the optimal component for the battery were VOOH as the cathode, Zn as the anode, Zn(CF3SO3)2 3M as the electrolyte, glass fiber as the separator and SS 304 as the current collector.
Keywords:Li-S batteries are likely to have a promising role to play in the next generation of energy storage technology. The interest arises from several favorable factors: high specific capacity of sulfur at 1670 mAh g-1; abundance in nature and from desulfurised waste dumps; low-cost; and non-toxicity. The practical applications are still hampered by several issues: extremely low conductivity of S and the final discharge product Li2S; shuttling of soluble intermediate polysulfides between electrodes; poor utilization of S; low coulombic efficiency; large volume change of S upon lithiation; and low cycle life from fast capacity fade.
Strategies that promise to offer solutions to deal with the above technical barriers are presented.
The invention of 14C-based solid state diamond power-cells offers unique opportunities for demonstrating a circular economy in relation to fissile energy production; and closed-loop recycling of these 14C Diamond Betavoltaic Batteries (C14-DBB). The extremely long half-life of the radioisotope 14C on a human time scale, 5730 ± 40 years, means that the power output of a C14-DBB is constant from any practical power engineering perspective. The durability of a diamond crystal on geological time scales is quite long and is the result of strong covalent bonds between carbon atoms. 14C as a beta emitter has a maximum decay energy of 156 keV and a weighted mean energy of 49.5 keV, insufficient to break the covalent bonds and therefore preserving integrity of the crystal over the entire “discharge” period/half-life of the C14-DBB.
Whether as back-up cells for real-time clocks (RTC), volatile memory, infrastructural health monitoring, medical implants, or any other use case, this class of betavoltaics will outlive any foreseeable engineering application they are used in. An examination of the socio-economic, ecological, and regulatory interplay in relation to the use and life cycle of a 14C-based diamond is meant to demonstrate the applicability of closed-loop circular economy as applied to the nuclear sector as a first of a kind demonstrator of how fissile energy production can operate in a closed-loop circular economy, not just as a means of producing energy with a significant waste stream, but a holistically integrated cycle. As a part of this cycle we demonstrate the utility of harvesting feedstock for radiovoltaics. In the next step we demonstrate the incentive to collect and recycle 14C-based C14-DBB’s thus completing a closed-loop economic cycle wherein the derivative waste stream from fissile energy production is reutilised and recycled. Though this approach is not a panacea solution for how to deal with the end state waste from fissile energy production, it is our hope that this first demonstration will evince new investigations along similar lines to make maximum use of every part of the process thus converting the entire value chain to a wholly integrated and cyclical ‘value constellation’ relating to fissile energy production.
In this work, we specifically present a novel process flow to identify and recover C14-DBB’s from Waste Electrical and Electronic (WEE) appliances repurposing the 14C-diamond into new C14-DBBs. The process uses machine vision to detect C14-DBBs on Printed Circuit Boards (PCB) using inspection cameras, and fiducial marks from the SMD assembly process to calculate the exact location of the C14-DBB on the PCB. It is then recovered using selective hot air de-soldering. Electrical contacts and package are removed in a nitric acid bath to expose the C14-DBB and recover it in a controlled environment. The 14C-diamond is packaged inside a layer of non-active 12C-diamond, so no radioactivity is exposed at any point in the recycling process. It is inspected using surface analysis techniques before new ohmic contacts are applied and an electrical check is performed using a flying probe tester. The recovered diamond is finally repackaged as a repurposed C14-DBB device, and valuable metals are recovered from the nitric acid solution for re-used after electro-filtration and purification.
Treatment and adequate disposal of slaughterhouse wastewater (SWW) is a worldwide economy and public health necessity. SW contains elevated amounts of organic matter and salts. Typical parametrical analyses include pH, chemical oxygen demand (COD), biochemical oxygen demand (BOD), total nitrogen (TN), total phosphorous (TP), total organic carbon (TOC) and total suspended solids (TSS) [2]. After preliminary treatment, the electrochemical processes such anodic oxidation (AO) and electrocoagulation (EC) have been considered an alternative technology for the treatment of SWW.
In this study, a real beef slaughterhouse wastewater presented the following characteristics: TOC (1150 mg L–1), COD (4320 mg L–1), TP (25 mg L–1), TN (72.28 mg L–1), TSS (1433 mg L–1) at pH 7.18 and conductivity of 2.79 mS cm–1. Bright red color was observed at 416 nm (1.24 A.U.) and the presence of coliform bacteria was confirmed (> 1600 MPN). AO and EC tests were carried out in a single open cell compartment in batch operation mode with constant stirring to ensure mass transport of the oxidant specie towards/from the anode to the bulk. AO was assessed using two different dimensionally stable anodes (DSA) type anodes: i) Ti/IrO2/Ta2O5 coating (DSA-O2) ii) Ti/Ru0,3Ti0,7O2 (DSA-Cl2). AISI 304 stainless steel plate was used as cathode. EC was evaluated using iron and aluminum electrodes (anode and cathode).
The best operating conditions were found at current density of 20 mA cm–2 without supporting electrolyte. TOC, COD and TP removal efficiency were 79.77% and 78.62 %; 89.22% and 79.4%; 96.0% and 64% using DSA-Cl2 (Ti/Ru0,3Ti0,7O2) and DSA-O2 (Ti/IrO2/Ta2O5), respectively. Moreover, a complete discoloration and disinfection were achieved.
Electrochemical oxidation test at best operating conditions gave energy consumption and specific energy consumption values for TOC, COD and TP using DSA-Cl2 and DSA-O2 of 24.5- and 26.5-kW h m–3-, 27.1- and 28.9-kW h kgTOC–1-, 7.14- and 6.88-kW h kgCOD–1 and, 1531.25- and 1104.17-kW h kgTP–1, respectively.
As a low cost and mature clean energy source, solar PV generation currently has a high penetration rate especially in sunshine-rich states like California. Battery energy storage systems (BESSs) are frequently incorporated with PV systems as a standard approach to buffer the volatile nature of the PV output. Household small PV and storage systems are popular products in the market. For commercial buildings, similar technology is also available, but normally featuring large centralized battery stacks and consequently high cost.
Electric vehicles (EVs) started to enjoy a booming market share since the last decade. The number of EVs on roads is enormous and keeps growing rapidly, and so is the quantity of EV batteries. It is estimated that the first huge wave of EV battery retirement in California will hit in 2025, and retired batteries will keep coming thereafter. EV batteries today, almost exclusively lithium-ion based, cost heavily in both production and recycling. Economically dealing with retired EV batteries is an important topic.
Retired EV batteries, though no longer roadworthy, still have considerable capacity for stationary applications where the requirement for energy and power density is not as stringent. As an abundant byproduct from the road, these second-life EV batteries cost much less than new products. Meanwhile, the high cost of (new) batteries in storage systems could be a major discouragement for potential clients, especially small/medium owners. Thus, developing proper technologies to bridge the supply and demand has great significance.
The aim of this research is to validate that using second-life EV batteries in BESS for PV and storage system for small/medium sized commercial buildings will reduce the overall cost over serviceable life compared to using new batteries. To achieve this, we are conducting thorough multi-scale analysis and modeling of the second-life EV battery aging process and building degradation models, accordingly developing optimized energy management strategy considering PV and load profiles, and building customized electrical and control systems for site pilot testing.
Downscaled lab test bench for electrical and control system and battery cycling lab test system are established in San Diego State University (SDSU), and tests are being conducted. Two pilot testing sites, both with existing solar PV systems but different penetration rate, have been selected and the respective BESSs designing processes are ongoing. Through pilot testing, we aim to achieve overall cost reduction and no less than 35% reduction in initial installation cost, and also to establish the supply chain for similar projects in the future.
Li-Ion batteries are the technology of choice for most of today’s applications, especially those demanding high energy densities. Large part of this success is due to intercalation electrodes, like graphite in the negative electrode and lamellar oxides in the positive electrode, which constitute a limit in term of energy density and power. Renewable energy and especially electric mobility demand a considerably higher energy density, which is unlikely to be met with the current technology. Therefore, investigating new materials to overcome these limits is fundamental. In this presentation, both cathode and anode developments will be considered. In the first part, we will concentrate on overlithiated rock salts that are promising cathode materials for Li ion high energy applications. Despite the earlier results, these materials can offer much higher capacities (>250 mAh/g) than the stoichiometric compositions. This high capacity is associated to Li rich content that forms a good percolation network along the Li diffusion channels [1]. Lithium titanium sulfide (Li2TiS3), which has been reported by Sakuda et al. [2], demonstrated excellent capacity owing to the multielectron redox reactions. Upon cycling, more than two lithium ions were reversibly intercalated through the structure and the capacity reached 425 mAh/g. Besides these promising results, low electronic conductivity as well as poor cycling stability were also reported. To eliminate such disadvantages, doping or substitution can be an effective solution. Here, we propose new patented selenium substituted lithium titanium sulfide materials [3-4], which have been prepared by high energy ball milling. New materials showed better cycling stability than the current material. For a comparison, we will also provide a comprehensive study of these materials through fine characterization tools (XRD, SEM, EDX, voltammetry, XPS, ex situ and in situ XRD) in order to examine electrochemical and structural properties as well as the degradation mechanism. In the second part, we will focus on Lithium metal that represents the ultimate candidate for the negative electrode, due to its high energy density and low potential. The major drawback of this technology is the formation of dendrites, which are structures that are formed on the surface of the metal electrode during the cycles of dissolution/precipitation. They cause loss of cyclable lithium, therefore they are responsible for the limited lifetime of this technology and may cause short-circuit and thus battery failures. Therefore, it is fundamental to understand the formation of these structures. The proposed model lies on the solid theoretical basis provided by Newman and Monroe [5], in which they proposed a steady-state model that considers the effect of the mechanical properties on the lithium deposition. On the other hand, the presented model is time-dependent and it adds the study of a pseudo-2D Solid Electrolyte Interface (SEI) component, starting from the work of Liu and Lu [6] in which both SEI creation, due to side reactions, and SEI fractures, due to change in geometry, are considered. Different from it, the effect of the mechanical properties of the SEI on the reaction kinetics is taken into account in this work. The surface of the electrode changes in shape due the electrodeposition of the lithium, which is proportional to the current on the surface, modeled with a modified Butler-Volmer kinetics. The model, with an example of results given in figure 2, is designed to be integrated with parameters that are found with a consistent set of experiments. Electrochemical Impedance Spectroscopy (EIS) and Atomic Force Microscopy (AFM) are conducted to find electrochemical and mechanical properties of the SEI. The proposed model has the goal of guiding the experiment in finding ways to avoid or curtail dendrites formation, being able to simulate the effect on dendrites growth depending on operative condition, SEI and electrolyte composition, electrode surface defect and coating.
Keywords:[1] J. Lee, G. Ceder et al., Science, 343, 519-521 (2014) [2] A. Sakuda, Sci. Rep, 4, 4883 (2014) [3] Y. Celasun, D. Peralta, J.F. Colin, S. Martinet. European Patent EP3626682 (2018) [4] Y. Celasun, D. Peralta, J.F. Colin, S. Martinet. European Patent EP3626681 (2018) [5] C. Monroe, J. Newman; Journal of the Electrochemical Society (2004) [6] G. Liu, W. Lu; Journal of the Electrochemical Society (2017)
Many practical systems at micro- and nanoscale can be represented as arrays of active sites distributed randomly [1]. As shown previously these systems can be efficiently addressed theoretically by using Voronoi diagrams [2, 3] which allows facile tessellation of the system into the unit cells around each active sites. The overall current flowing in the system can then be evaluated by modelling diffusion-reaction processes inside every unit cell and summing the contributions from individual active sites. Although this approach is tempting by its simplicity and efficiency [3] one should bear in mind that Voronoi diagram representing the unit cells by polygonal prisms remains approximation and as each approximation remains valid only under certain conditions. In this work [4] we show that even for the case of diffusion limited electron transfer (ET) the actual shapes of the unit cells are more complicated and depend on the local configuration of the neighbouring active sites. This was exemplified on the small patches of the random arrays with band-like and disk-like active sites via simulations and in the case of band-like active sites confirmed by analytical derivations.
Importantly, by comparing the total array current obtained by employing Voronoi tessellation and simulation of the system without any approximations we found that they agree well (relative error ca. 5% or less). At the same time, the individual contributions from the active sites are reproduced with a much larger relative error [4]. The latter suggests that in the case of kinetic control or reaction mechanisms that are more complicated than simple ET the diffusion-reaction competition between the active sites may become even stronger eventually leading to significant deviations from the total current predicted on the basis of the Voronoi approximation. This is currently investigated in our team.
Red phosphorus (RP) has aroused growing concern as a promising anode material for Li-ion and Na-ion batteries due to its high theoretical capacity of 2596 mAhg-1 and appropriately low redox potential of ~0.4 V. However, the poor electronic conductivity of RP and its large volume expansion during lithiation lead to rapid capacity fading after first several cycles [1]. It is known, that threatment of electrodes by irradiation can possitively affect their performances.
In this work, the commercial RP powder with an average particle size 20-30 μm was ball milled until the nano- and mesosize 140 nm - 5 μm. In order to improve the capacity retention, the milled RP particles were coated by carbon black. A water-soluble sodium alginate was used as a binder [2]. The anodes were fabricated using the ratio RP:CB:SA (6:3:1). The electrodes were irradiated by 0,5 MeV proton pulsed beam. To analyze the structure and composition of the investigated XRD, Raman spectroscopy and SEM were carried out before and after irradiation.
The electrochemical tests of the nontreated and treated electrodes were performed in the coin-type 2032 cell, soaked in a few drops of 1M LiPF6 in ethyl, diethyl, ethyl methyl carbonates (EC:DEC:EMC 1/1 by vol.) + 5% fluoroethylene carbonate (FEC) as electrolyte with the Celgard 2400 separator and Li metal as the opposite and reference electrode. The experimental results and characterization details will be discussed at the conference.
The study of surfaces and interfaces is one of the main fields of material science. This domain requires specific techniques of surface analysis such as X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Secondary Ion Mass spectrometry (TOF-SIMS) or Scanning Probe Microscopies (AFM – STM). In this field, redox processes and surface and interface phenomena (usually linked) occurring in Li(Na, Mg, K….) batteries during cycling (including liquid or solid electrolyte) play a key role for their performances as well. Solid Electrolyte Interphase (SEI) formed upon cycling leads to a double-edged problematic: its formation lowers the coulombic efficiency and causes irreversible capacity loss, but it also passivates the electrode from the electrolyte and prevents further aging processes.
Several systems were considered in this keynote to illustrate the relevance of such surface analyses in the understanding of redox phenomena in batteries:
First is the study of Full cells as Li4Ti5O12(LTO)/LiNi3/5Co1/5Mn1/5O2 (NMC) and LTO/LiMn2O4 (LMO). The interactions between the two electrodes during cycling are investigated, especially the deposition and insertion of metallic compounds within the LTO electrode, which can directly influence on the stability of the cells and their electrochemical performances. More specifically, we focus this presentation on the results obtained by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) which could give in-depth elemental and molecular information about the interfacial layers through sputter-depth-profiling experiments. Thanks to a high sensitivity and 2 D and 3D imaging capability, it will be particularly useful to follow the deposition of low amounts of metallic species and especially manganese within the SEI layer. Moreover, the evolution of the SEI chemical composition and spatial distribution upon cycling is also reported to better understand the protective role of the SEI.
Secondly, innovative K-ion batteries were considered; potassium is a promising alternative to lithium as K i) is much more abundant than lithium in the earth's crust and concomitantly much cheaper ; ii) has a low redox potential in non-aqueous solvent so that high voltage is expected and iii) has the lowest Lewis acidity and desolvation energy (compared to Na+ and Li+), which should lead to higher ionic conductivity and faster electrode/electrolyte interface diffusion kinetics so that high power potassium-ion batteries (KIBs) are expected.
However, for the practical use of KIBs, high energy density cathode materials are required. In that direction, polyanionic compounds offer various structural frameworks working at high voltage. Among them, KVPO4F showed reversible capacity up to 105 mAh.g-1 with an average discharge potential of 4.3 V vs. K+/K with excellent rate performance. However, the exact electrochemical redox processes of KxVPO4F remains to be better understood, especially above 4.5 V (i.e. from x=0.5 to x=0), to further improve its electrochemical performance.To fill this gap, the carbon-coating impact of the KVPO4F material on the electrolyte reactivity and the polarization will first be presented. Then, the vanadium average oxidation state of KxVPO4F-C was followed upon charge/discharge in half cell using X-ray photoelectron spectroscopy. Importantly, it will be shown that the obtained results not only validate the occurrence of a redox process from x=0.5 to x=0 but also provide the extent of this process, which was never reported before. Also, a severe electrolyte degradation issue above 4.5 V was observed.
IPREM-UPPA (FRANCE) Contributors : N.Gauthier, C. Courrèges, L. Madec, L.Caracciolo
Reliance Industries focuses on using clean energy to become a net-zero carbon emissions company by 2035.
The aim is to establish and enable 100GW of solar energy by 2030. To achieve this goal, Reliance Industries will establish four Giga factories to produce photovoltaic panels, energy storage solutions, green hydrogen, and fuel cell systems. Reliance Industries will also be building a Giga factory to produce power electronics, one of the critical components to affect the transition. The factory will bring together power electronics and software capabilities to create affordable solutions at scale.
As a part of this plan, energy storage has been identified as the key technology of the company's plans to replace fossil fuels with renewable alternatives and make the transaction more sustainable. Reliance sees batteries as integral to providing long-duration energy storage for grid-scale renewable energy. It also aims to create an end-to-end battery ecosystem—from battery materials to cell manufacturing, leading to the development of battery packs and battery management systems (BMS).
Reliance entered partnerships with Lithium Werks (producer of Lithium Iron Phosphate based battery technologies for advanced applications), Faradion (world-leading technology provider of Sodium-ion batteries), and Ambri (developing liquid metal batteries for storage applications), each of them being an industry disruptor and offering superior chemistry and better performance.
Reliance will set up a new energy manufacturing ecosystem in the Jamnagar complex to meet its captive energy requirement. Most importantly, Reliance aspires to make India a world leader in new energy manufacturing and a credible alternative to China.
Three-dimensional (3D) configuration of battery provides a large active surface area of the electrodes to store and utilize more active material, enabling a remarkable increase of capacity. This work reports a perfect conformal coating of a unique 3D structured NiO/Ni anode synthesized by a simple thermal oxidation process with PAA-PVA polymer multi-layers. The coating of the 3D structure with a polymer was carried out by electrophoretic deposition (EPD). EPD is an attractive colloidal method for the obtaining polymer and composite films. The EPD mechanism includes the electrophoretic movement of charged polymer molecules and the formation of a film on the electrode surface under the influence of an electric field. An aqueous solution of 2 wt% polyvinyl alcohol (PVA) was prepared by dissolving PVA in deionized water with vigorous stirring at 80 °C for several hours until the mixture turned into a homogeneous viscous solution. After cooling, isopropyl alcohol was added into the solution to suppress water decomposition in the EPD process. Then, 0.2 wt% SiO2 powder was added to the solution, which was subjected to 10 minutes of magnetic stirring followed by 20 minutes of sonication. A 2 wt% aqueous-alcoholic solution of polyacrylic acid (PAA) with 0.2 wt% LiCl was prepared similarly to the PVA solution. SEM and EDS-SEM analysis confirmed a uniform polymer deposition and distribution elements throughout the coating structure.
Keywords:Insufficient areal energy density from planar micro batteries has inspired a search for three-dimensional micro batteries. The power output of a three-dimensional micro battery is expected to be higher than that of a two-dimensional battery of equal size, as a result of the higher ratio of electrode-surface-area to volume and lower Ohmic losses. Within a battery electrode, the 3D architecture provides large surface area, increasing power by reducing the diffusion path for Li ions. Some proposed 3D architectures used in micro batteries include vertical rods, foams and interdigitated networks [1]. However, even three-dimensional micro batteries are restricted by the shape meaning the need for a new concept.
Additive manufacturing, also known as 3D printing, has appeared as a novel class of free form fabrication technologies that have a variety of possibilities for the rapid creation of complex architectures at lower cost than conventional methods. 3D printing enables the controlled creation of functional materials with three-dimensional architectures, representing a promising approach for the fabrication of next-generation electrochemical energy-storage devices and has many unique advantages over conventional manufacturing methods. Moreover, sequential 3D printing of battery electrodes and the solid electrolyte layer meets the need for intimate contact between the electrodes and electrolytes. The exclusive capabilities of the 3D-printing technology enable the design of different shapes and high-surface-area structures, which no other manufacturing method can easily do. Therefore, the use of 3D printing will provide an ideal opportunity to design high-power micro batteries with well-designed arrangements of microelectrodes [2].
This work targets the creation of a 3D printed micro-battery with small dimensions with outstanding electrochemical performance on the base of MXenes combined with high capacity active materials. Ink s were formulated and the rheology were studied with the consequent printing of electrodes. Challenges of electrolyte preparation and incapsulation of full-cell micro-battery will be discussed.
KEYWORDS: 3D printing, MXene, micro-battery, energy
Energy storage is one of the most important challenges for the 21st century. The improvement of the electrochemical performances implies the development of new class of electrode materials, allowing higher energy density, longer cycle life, moderate cost, etc. In this context, nano-fluoride materials may occupy a noticeable place in both primary and secondary batteries.
1) Nano-CFx in primary Li batteries - The electrochemical performances of primary Li-battery, can be improved by developing new materials with higher potential and energy density values [1-4]. New kinds of carbon-fluorine nanoparticles are suitable since they allow combining the physical properties of CFx with the effect of nanosized particles. These materials allow having higher OCV and suppressing the potential delay, generally observed during the first time of the discharge reaction in commercial graphite fluorides.
2) CoF3-based materials in secondary Li batteries
In reversible Li batteries, several types of transition metal trifluorides and derived (MX3, with M=Ti, Mn, Fe, Co) have been tested for increasing the electrochemical performances because these compounds may incorporate three electrons per 3d-metal during the process, thus delivering higher energy density, and exhibiting longer cycle life
Nano-CoF3 have been synthesized by direct fluorination (with F2-gas) of cobalt nanoparticles at various temperatures (up to 300°C). When handled in very dry atmospheres, CoF3-based samples are stable vs. traces of humidity and can be used to prepare electrodes in fairly good conditions for batteries. The best electrochemical performances were obtained with nano-CoF3 powders prepared at TF2 = 100 °C, for which a reversible capacity of about 390 mAh/g was obtained after subsequent cycles [5]. More recently, high-energy X-ray data, showed that in fact CoF3 decomposes during the discharge process into an intermediate compound with a new structure/composition [6]. Using the pair distribution function, the structure was elucidated to correspond to a defect corundum phase exhibiting Co vacancies, i.e., Co1.26IICo0.16III0.58F3.
Separator and current collectors are fundamental components of every Li-Ion battery; they contribute to the safety, performance, longevity, weight, and volume of a cell without directly participating in the kinetics of the electrochemistry. Decreasing the weight or volume of such passive components, without negatively affecting their functionalities, can directly improve the cell gravimetric or volumetric energy and power density.
In this article we propose a new approach to improving the safety and performance of Li-Ion batteries of various sizes and chemistries by utilizing two next generation, smart passive components: a metallized plastic “COATED” Current Collector (CCC) and a thin nanoporous ceramic Separator (NPORE®). CCC is a 6 μm PET film coated with Cu on both sides by a proprietary PLASMAfusion™ process that operates as a fuse when the internal temperature of the cell exceeds 250° C, preventing dangerous runaway events. NPORE® is a proprietary, thin and robust ceramic separator with sub-100nm pores and narrow pore-size distribution that does not shrink even at very high temperatures, further improving the inherent safety of a cell. Further, we discuss the expected benefits in terms of manufacturing cost, environmental impact and supply chain.
An assessment of current efforts to design next-generation renewable batteries is provided. Mechanics and electrochemistry aspects are presented on materials, geometry/topology, and size of both electrodes and binder. The feasibility of current laboratory research to be transferred to pilot and industrial scale is discussed.An assessment of current efforts to design next-generation renewable batteries is provided. Mechanics and electrochemistry aspects are presented on materials, geometry/topology, and size of both electrodes and binder. The feasibility of current laboratory research to be transferred to pilot and industrial scale is discussed.
Keywords:The markets for portable devices and electric vehicles are constantly expanding, which generates a great need for cutting-edge battery technologies. However, current Li-ion batteries (LIBs) still cannot meet such a huge demand due to charge/discharge rate and service life. Moreover, the sluggish low temperature performance of LIBs restricts their application in mountainous regions and cold climates. The majority of the low-temperature restrictions are caused by features of the graphite anode. To solve this issue, numerous investigations have been conducted to develop composite anode materials. Although low-temperature performance of LIBs has improved, the process for synthesizing these materials is complex and expensive to commercialize. Therefore, we propose low cost biomass derived N-doped carbon as alternative anode material with enhanced low temperature performance of LIBs. The carbonaceous material was prepared by facile annealing date seeds with urea in the inert atmosphere. The as-obtained carbon material was characterized by X-ray diffractometry, scanning electron microscopy, and X-ray photoelectron spectroscopy. The electrochemical characteristics of the prepared anode show 6 times higher and more stable capacity than commercial graphite at -20 °C. The improved properties can be attributed to the porous structure of the prepared N-doped carbon, which shortens the diffusion path and provides excellent anodic properties.
Keywords:Hybrid organic-inorganic perovskites have attracted significant attention in the past two decades owing to their enormous application potential in energy. Like their oxide counterparts, these hybrid organic-inorganic systems exhibit abundant phase transitions which can often lead to significant changes in the electrical, magnetic, and optical properties that are of vital importance for the design and fabrication of functional devices. However, the atomistic driving forces and underlying mechanism need to be well understood for these hybrid perovskite systems. In this talk, I shall present our recent advances in the thermally and pressure-driven phase transitions and their microscopic mechanisms of some three-dimensional and two-dimensional hybrid organic-inorganic perovskites. At the same time, I shall discuss the symmetry alternation at the interface and corresponding atomic origin of some two-dimensional hybrid organic-inorganic perovskites.
Keywords:The expansion of the electric vehicle market is expected to lead to the rapid growth of the lithium-ion battery market [1]. Accordingly, the amount of scrap is also expected to increase, so various attempts are being made to recover valuable metals (nickel, cobalt, etc.) from the scrap [2]. The methods include the pyrometallurgical process, hydrometallurgical process, and direct recycling process, and comparison of each process is also being discussed [3]. However, process development, such as mutual complement of the process, continues. We have investigated the continuous pilot testing of a solvent extraction process to recover nickel and cobalt from secondary battery scrap for the production of high purity nickel sulfate and cobalt sulfate for secondary batteries.
The solvent extraction process is composed of three different solvent extraction processes, and each solvent extraction process is generally composed of extraction, scrubbing, and stripping step. The continuous process was operated for about 200 hours, and the steady state of the process was confirmed through pH observation and quantitative analysis of components, and stability of the process was secured through continuous operation.
[1] GLOBE NEWSWIRE report, "Global electric vehicles battery market 2017–2026: EV battery market to reach $93.94 billion" (2018).
[2] K. Richa, "Sustainable management of lithium-ion batteries after use in electric vehicles" (2016), PhD Thesis.
[3] M. Chen, X. Ma, B. Chen, R. Arsenault, P. Karlson, N. Simon, Y. Wang, Joule (2019) 1-25.
Nowadays lithium metal is considered as one of the key elements in modern industry. Its usages range from pharmacy to aeronautics including energy storage devices and glass-ceramics. However, since 2005, Lithium-ion Batteries (LiBs) have taken over, as they play a major role in the development of the electronic and green industries [1]. LiBs show the highest growth rate and are expected to take an even bigger part in the lithium industry. The expected growth rate for lithium carbonate and lithium hydroxide is respectively 10% and 14.5% until 2025 [2], since they are two of the raw materials used for LiBs. In 2016, lithium carbonate prices were reported to range from 10,000 US$ to 16,000 US$ while lithium hydroxide prices were reported to range from 14,000 US$ to 20,000 US$ [3].
The lithium production was, until recently, dominated by the Salt Lake brines, because of their cheaper production cost. The ever-growing demand in lithium compounds led to the regaining of interest for another source, after the lithium price increased. This other source, lithium rich minerals, now account for 50% of the world’s lithium production [4]. Lithium minerals are numerous and include spodumene, eucryptite, petalite, bikitaite, etc. [5].
Among those minerals, spodumene LiAlSi2O6 is the most common and the most studied. It offers a theoretical Li2O content of 8 wt %, whereas raw minerals in nature typically offer 1 to 2 wt % Li2O.
In Kazakhstan, all known lithium reserves are associated with spodumene and according to U.S. Geological Survey, Mineral Commodity Summaries made in January 2020, Kazakhstan has approximately 50000 tons of lithium [6]. And according to the Kazakh National Technical University, lithium in the process of operation is usually not separately extracted and all goes into the waste "tailings" of the deposits.
In this work preliminary results on the development of the optimal leaching process of lithium composites from Kazakhstani spodumene will be presented. The new process offers a fast throughput, direct leach process for spodumene concentrates to produce battery grade lithium hydroxide and / or lithium carbonate monohydrate products. The process is also environmentally sustainable. The leach process is totally sulfate and acid free and the refining process does not involve any crystallization of unnecessary by-product salts.
E+R Group ( Emerson and Renwick ) a world leading desinger of manufacturing equipment since 1918 established in Lancashire in England.
E+R Mission to be recognised for innovative and sustainable manufacturing solutions that consume fewer resources while meeting the needs of our clients in a demanding and developing world and Vision to be Enable and optimise production of life-changing products.
As E+R Group, we have grown and developed across a number of market sectors including Print, Forming, Vacuum and Coating and we are proud to be a leading manufacturer of sophisticated roll-to-roll production machinery.
We have built a reputation for innovation in engineering, technology and process, and use
our experience gained across a diverse range of application ( batteries, solar, photovoltaics, electrochromic films, medical grade, touch screen applications ) to develop ever more
demanding processes and products.
More than 80% of our sales are exported to customer locations all over the world and we
remain committed to being a UK-based business at the forefront of our industry.
The need for high-performance and sustainable energy storage systems is rising, and lithium-ion batteries are one of the promising technologies. The Li-Ion battery technology market size is projected to reach USD 135.1 billion in 2031 from 48.6 billion in 2023 [1]. To address this increase in demand, companies across the globe are focusing on setting up giga factories for cell manufacturing. This paper aims to provide a complete overview of the cell manufacturing process and an overview of building a gigafactory for cell manufacturing, including the stepwise scale-up, establishing a stable supply chain, and utility requirements. In addition, the paper discusses the challenges and opportunities involved with developing a gigafactory and its potential effect on the energy storage market. It is a helpful resource for individuals and companies interested in setting up a giga factory.
Nanostructured materials have triggered a great excitement in the area of energy sector due to both fundamental interest and technological impact. [1,2] Size reduction in nanocrystals leads to a variety of unexpected exciting phenomena due to enhanced surface-to-volume ratio and reduced length for the transport of ions and electrons. We will consider some of those anomalous phenomena restricting our discussions to the nano-size effects on (a) transport, (b) thermodynamics and (c) storage behaviour with a few examples to illustrate material challenges for advanced energy storage devices.
(a) Mesoscopic electrical conduction occurs due to overlap of space charges at reduced interfacial spacings. Unlike microcrystalline SrTiO3, having both bulk as well as semi-infinite interfacial contributions to the electrical conduction, nanocrystalline SrTiO3 exhibits only interfacial conduction. [3]
(b) Size reduction of materials affects thermodynamic properties and hence their energetics due to excess surface contributions causing stabilization of meta-stable phases at nano-size. [4] Increase in cell voltage due to nanosizing or amorphization will be highlighted. [5]
(c) In the context of storage behaviour, nanocrystalline materials exhibit high capacity as well as high coulombic efficiency (reversible storage). We will consider a few case studies on lithium storage. [6-8]
The lead-acid battery was invented in the 1850s, before the commercial distribution of electric power which started in 1882. How did a product invented in the 19th Century, before global warming and recycling had entered the mainstream, become the world’s most successfully recycled commodity item? What will it take for the emerging lithium-ion battery recyclers to replicate the success of lead-acid?
In this seminar we will discuss the success story of lead-acid battery recycling; the reasons this industry is polluting despite its impressive recycling rates; and what it would take for lithium-ion battery recycling to emulate its success.
The lead-acid battery was invented in the 1850s, before the commercial distribution of electric power which started in 1882. How did a product invented in the 19th Century, before global warming and recycling had entered the mainstream, become the world’s most successfully recycled commodity item? What will it take for the emerging lithium-ion battery recyclers to replicate the success of lead-acid?
In this seminar we will discuss the success story of lead-acid battery recycling; the reasons this industry is polluting despite its impressive recycling rates; and what it would take for lithium-ion battery recycling to emulate its success.
Since the number of electric vehicles has raised substantially, the market for Lithium- Ion battery (LiB) has also a vast expansion. Industry is using state of health to indicate the reliability of LiB and its associated system. However, this cannot provide proper prediction to the LiB pack reliability according to the system reliability theory that has long been established without considering the sharing current effect in the parallel sub-structure and the cell diversities in a pack. This work illustrates a statistical modelling procedure of Lithium-Ion battery pack useful life based on the experiments of cell degradation and physical effects of parallel sub-structure in a pack. The suggested statistical capacity fading (SCF) model with fixed and random coefficients (mixed effect) was based on a simplification of the electrochemistry- based electrical (ECBE) model which had a strong support from electrochemistry theory. Our method demonstrated that less than 50% of their entire life cycle data is sufficient for its distribution determination. Several scenarios of structure
connections in a LiB pack were illustrated for the computation of the corresponding reliability and life span. The critical condition to prolong the lifetime of a LiB pack was the similar discharge current rates of cells in the pack.
For four decades, the development of biointerfaces has been the subject of increasing research efforts in the field of analytical chemistry and energy conversion. In particular, the functionalization of electrodes by biomaterials based on electrogenerated polymers, carbon nanotubes and / or nano-objects, is widely used for the design of biosensors and biofuel cells [1,2].
Some new approaches for developing nanostructured biomaterials like buckypapers based on functionalized carbon nanotubes, will be illustrated with enzymes as biosensing element or for energy conversion. Composite bioelectrodes by compression of enzymes and carbon nanotube mixtures and creation of microcavities, will be reported [3]. The development of glyconanoparticles resulting from the self-assembly of block copolymers composed of polystyrene and cyclodextrin as an inclusion site will be also reported. These glyconanoparticles allow a post-functionalization by hydrophobic molecules through host-guest interactions [4,5]. It appears that it is possible to modulate the site density of βCD at the surface of the shell of the hybrid glyconanoparticles while maintaining its inclusion properties. They were used in solution or immobilized for fixing redox mediators or enzymes modified by adamantane groups. Moreover, the anchoring of glyconanoparticles to the surface of electrodes has been carried out by host-guest interactions with electrogenerated polymers. Fluorescent nanoparticles were thus spatially addressed on surfaces. The efficient immobilization of the nanoparticles allows the anchoring of multilayers of biotinylated glucose oxidase [6]. This innovative approach will be applied to the elaboration of solubilized enzymatic fuel cell or biosensors [7].
Secondary Li ion batteries have become an indispensable source of energy for portable appliances and they are presently establishing themselves as the energy source of choice for electric vehicles. While lithium ion batteries have matured and are produced at an industrial scale, they continue to suffer from a range of shortcomings, one of which is the comparatively low energy and power densities of the anode (negative electrode) materials presently in use.
This contribution will present routes towards the preparation of new anode materials with higher capacities than the current ones. The strict overriding premise in the experimental approaches has been to exclusively employ earth-abundant commodity reactants and known-to-be-scalable processes. Two such approaches will be highlighted. One is based on the anodic decomposition of graphite in a molten LiCl/SnCl2 electrolyte, resulting in the formation of Sn-filled nanocarbons [1-4]. The other is based on the cathodic deoxidation of SiO2/C in a molten CaCl2 electrolyte, yielding nano-structured SiC [5,6]. The synthesis methods will be described and the products characterised in detail. Advantages and limitations of the approaches will be discussed.
Lithium-ion batteries (LIB) will play a major role in the future energy transition owing to
outstanding performances in energy, power, lifespan, costs, and environment friendliness [1].
Electric vehicles are among the most LIB using systems since most of the automobile
manufacturers will stop producing internal combustion engine vehicles (ICV) by 2030-35 to
move to hybrid and full electric vehicles (EV). Accordingly, LIB should offer the same
conveniences to the end-user of EV as for current ICV, which includes ultra-fast charging
(full charge below 15 min), long driving range between charges (>500 km), long life (>10
years), affordable prize (<10% premium vs. ICV) and high safety (reduced thermal
runaway’s events).
Current LIB charging protocols based on constant current (CC) fall short to fully charge an
LIB EV pack in less than 60 min due to overheating. To overcome this limitation, we have
developed a voltage-controlled charging protocol coined as “Non-Linear Voltammetry”
(NLV). By tuning the NLV parameters to the battery characteristics (chemistry, state of
heath, design, engineering…) ultra-fast charging has been successfully achieved at both the
cell and pack levels enabling from 0 to 100% state of charge to be complete below 20
minutes in most cases and below 10 min in specially designed LIB. Artificial intelligence
methods [2] are used to adjust the NLV parameters as the LIB ages to ensure safety and life
span owing to temperature control. Other applications of NLV such as enhanced energy
density will be presented and discussed.
With the increasing demand for advanced energy storage devices in portable electronics and electrical vehicles, nikel-rich LiNixCoyMn1-x-yO2 (with x ≥ 0.8) layered cathode materials, which are low cost, have low toxicity, high practical specific capacity (> 200 mAh/g), and a relatively high operating voltage, are attracting increasing attention for their promising applications in next-generation cathode materials.[1] However, Ni-rich cathode materials have poor electrochemical performance, particularly during cycling at elevated temperatures, which significantly limits their application.
X-ray nano-computed tomography (nano-CT) and deep learning combined with Cs- corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy were employed to investigate the atomic to microscopic structural evolution of LiNi0.8Co0.1Mn0.1O2 (NCM) upon cycling at 55 ◦C.[2] Two types of intergranular cracks were clearly distinguished by nano-CT for cycled cathode particles; denoted open and closed cracks depending on whether or not the cracks reach the surface of the NCM secondary particles. The volume of high-temperature cycling-induced cracks quantified by deep learning increased drastically, particularly for the open cracks, and this phenomenon was accompanied by rapid degradation of capacity retention. Further precise STEM analysis of the crack regions revealed that
migration of transition metal (TM) ions to the Li layer forms a rocksalt-like structure, and the associated reduction of TM ions, e.g., Ni3+ to Ni2+, predominately occurred in the open crack regions in the presence of penetrated electrolyte, even for regions extending to the center of the secondary particle. In contrast, in the closed crack regions, no significant atomic-scale structure distortion and limited reduction of TM
ions was observed.