Production Of Lithium-ion Batteries Research Articles

Optimization of a Pyrometallurgical Process to Efficiently Recover Valuable Metals from Commercially Used Lithium-Ion Battery Cathode Materials LCO, NCA, NMC622, and LFP

With an ever-growing demand for critical raw materials for the production of lithium-ion batteries and a price increase of respective commodities, an ever louder call from the industry for efficient recycling technologies can be noticed. So far, state-of-the-art industry-scaled pyrometallurgical recycling technologies all suffer from the same bottleneck of lithium slagging. At the Chair of Thermal Processing Technology at Montanuniversitaet Leoben, a novel reactor was developed to recover lithium and phosphorus via the gas phase in a pyrometallurgical process. Critical elements such as Li, Ni, Co, and Mn of the commercially used cathode materials LCO (LiCoO2), LFP (LiFePO4), NCA (LiNi0.8Co0.15Al0.05O2), and NMC622 (LiNi0.6Mn0.2Co0.2) were analyzed in a batch version of the so-called InduRed reactor concept. The analyses underline that the reactor concept is highly suitable for an efficient recovery for the metals Ni and Co and that slagging of Li can not only be largely prohibited, but the elements lithium and phosphorous can even be recovered from the gas phase. Plant engineering issues were also considered for further development toward a continuous process. The MgO crucible used shows significant diffusion of various elements from the battery material, which is why the choice of crucible material still requires in-depth research.

Pressure Leaching of Copper Slag Flotation Tailings in Oxygenated Sulfuric Acid Media.

In this study, a hydrometallurgical method for the recovery of copper, cobalt, and zinc from copper slag flotation tailings (SFT) was investigated. SFT contains large amounts of valuable metallic compounds, such as copper, cobalt, and zinc. A representative SFT sample containing 0.50% Cu, 0.148% Co, 3.93% Zn, and 39.50% Fe was used in experimental studies. High-pressure oxidative acid leaching of SFT was carried out to assess the effects of sulfuric acid concentration, oxygen partial pressure, reaction time, solid/liquid ratio, and temperature on the extraction of copper, cobalt, zinc, and iron. The dissolution of metals from the SFT sample increased with temperature and sulfuric acid concentration. However, high acid concentrations and high solid/liquid (S/L) ratios led to gel formation that caused filtration problems and inhibited metal dissolution. The optimum leaching conditions were found to be a leaching time of 90 min, an acid concentration of 250 kg/t, a temperature of 220 °C, an S/L ratio of 1:5, and an oxygen partial pressure of 0.7 MPa. Under these conditions, 93.1 ± 1.1% Cu, 96.3 ± 1.8% Co, and 92.3 ± 1.7% Zn were extracted. Iron dissolution was only 0.5 ± 0.1%. This hydrometallurgical process almost completely recovers valuable metals. In particular, cobalt, which is of great importance in the production of lithium-ion batteries, has been declared a critical metal by the United States, Canada, and the EU and was taken into solution with very high extraction efficiency (>95%). Additionally, oxygen partial pressure enhanced copper, cobalt, and zinc dissolution. When O2 was not introduced into the leaching system, the extraction efficiencies of Co, Cu, and Zn were approximately 24.5, 5.3, and 26.3%, respectively, after 2 h of leaching treatment.

In-situ preparation of gel polymer electrolytes in a fully-assembled lithium ion battery through deeply-penetrating high-energy electron beam irradiation

Several in-situ preparation methods of gel polymer electrolytes (GPEs) to develop long-lasting and safe lithium ion batteries (LIBs) recently have been reported. However, the reported in-situ methods still have technical gaps for practical industrial uses in terms of processing time, integrity with the current production line, and scalability. Here, we report an in-situ method to prepare crosslinked poly(vinylene carbonate-co-cyanoethyl acrylate) (PVCEA) GPEs using 10 MeV electron beam (EB) irradiation in a fully-assembled metallic housing LIB that can be processed in a short time without any initiator or thermal treatment. The successful in-situ formation of PVCEA GPEs was achieved at absorbed doses above 16 kGy (irradiation time of 56 s), leading to intimately integrated GPEs with the electrodes, while ensuring stable charge and discharge performance. The prepared PVCEA GPE exhibited a higher transference number (tLi+ = ca. 0.53) and a wider electrochemical operation window (up to 5.0 V) than those of a liquid electrolyte (LE), while providing good ionic conductivity (1.17 mS/cm at 20 °C). Furthermore, the PVCEA GPE-based LIB prepared at an optimized dose of 16 kGy showed comparable retention capacity of 83 % at 0.5C to the conventional LE-based LIB after 300 cycles at 25 °C, and more importantly, better cycling durability at elevated temperature of 60 °C in comparison to the LE-based LIB. This study suggests that the combination of radiation-sensitive precursor formulation and high-energy EB with high penetration ability can provide a promising solution for industrial production of high-performing and safe LIBs.

The Role of the Government in the Development of the Rechargeable Battery Industry in Korea

Abstract This article discusses the role of the government in the development of the rechargeable battery, particularly the lithium-ion battery, industry in Korea. The Korean government aimed to promote the small-sized rechargeable batteries in the late 1990s and early 2000s. It began to emphasize support of the middle- to large-sized lithium-ion batteries in the early 2010s. The policy measures have comprised enhancing infrastructure such as human capital and establishment of a rechargeable battery testing center, increasing R&D expenditure, and promoting the electric vehicle (EV) industry through tax and financial incentives, public procurement, and increasing the number of EV charging facilities. Korea has become one of the leading lithium-ion battery producers in the world. The three large Korean companies, i.e. LG Chem, Samsung SDI, and SK Innovation, have come to share more than one-third of the global production of lithium-ion batteries in 2020. Korea’s experience provides policy implications to other countries intending to develop technology-intensive industries. It would be needed for the WTO system to modify the provisions in the sense of providing policy space for development of technology-intensive industries of developing countries.

Analysis of Trace Elements as Impurities in Materials Used for Lithium-Ion Battery Production

The continuous development of lithium-ion battery technology is a key step in moving away from the combustion of fossil fuels at point of use. Lithium-based batteries are the most promising alternative because they combine high capacity and good cycle stability while being moderately inexpensive. To achieve the intended performance and test for purity of the raw materials used, including cathode materials (like binary or ternary alloys containing lithium, cobalt, manganese and nickel) and electrolytes (lithium hexafluorophosphate) is highly important. For analyzing trace elements at the required levels, techniques based on inductively coupled plasmas (ICP) are the ideal choice, especially ICP–optical emission spectroscopy (ICP-OES) and also increasingly ICP–mass spectrometry (ICP-MS).

Regionalized life cycle assessment of present and future lithium production for Li-ion batteries

While many different lithium carbonate production routes have been developed, existing life cycle assessments (LCA) of lithium carbonate production from brines are mainly based on a single brine operation site. Hence, current life cycle inventories do not capture the variability of brine sites and misestimate life cycle impacts. This study presents a systematic approach for LCA of existing and future lithium carbonate production from brines, which can furthermore be applied to geothermal brines or seawater. It has been used to model life cycle inventories of three existing and two upcoming brine operations in Argentina, Chile, and China, and is combined with regionalized life cycle impact assessment. Impacts on climate change, particulate matter human health impacts, and water scarcity from lithium carbonate production differ substantially among sites. Existing life cycle inventories for lithium-ion battery production underestimate climate change impacts by up to 19% compared to one from our study.

Investigating greenhouse gas emissions and environmental impacts from the production of lithium-ion batteries in China

Greenhouse gas (GHG) emissions and environmental burdens in the lithium-ion batteries (LIBs) production stage are essential issues for their sustainable development. In this study, eleven ecological metrics about six typical types of LIBs are investigated using the life cycle assessment method based on the local data of China to assess the ecological impacts and the possibility of carbon neutralization of battery production. Furthermore, the GHG emissions from battery production under electricity mixes in China in the next 40 years are predicted. The results are summarized as follows: (1) The GHG emissions in the production of ternary battery production in China are from 114.3 kg CO2-eq/kWh to 137.0 kg CO2-eq/kWh, which are greater than those of the lithium iron phosphate (LFP) batteries (82.5 kg CO2-eq/kWh). It is found that the carbon emission from cathode production dominates the whole battery production, followed by battery assembly. (2) Almost all ecological indexes of LFP batteries are better than those of ternary batteries. It is beneficial to reduce environmental damage by prioritizing LFP batteries. (3) Under the electricity mixes in China in 2030 and 2060, GHG emissions from battery production will be reduced by at least 30% and 90% compared with 2020, respectively. Green energy is a powerful path to realizing carbon neutralization in battery production.

Life cycle assessment of recycling options for automotive Li-ion battery packs

Ramping up automotive lithium-ion battery (LIB) production volumes creates an imperative need for the establishment of end-of-life treatment chains for spent automotive traction battery packs. Life Cycle Assessment (LCA) is an essential tool in evaluating the environmental performance of such chains and options. This work synthesises publicly-available data to expand upon previously reported LCA studies for LIB recycling and holistically model end-of-life treatment chains for spent automotive traction battery packs with lithium nickel cobalt manganese oxide positive electrodes. The study provides an in-depth analysis of unit process contributions to the environmental benefits and burdens of battery recycling options and integrates these with the battery production impacts to estimate the net environmental benefit achieved by the introduction of recycling in the value chain. The attributional LCA model accounts for the whole recycling chain, from the point of end-of-life LIB collection to the provision of secondary materials for battery manufacturing. Pyrometallurgical processing of spent automotive traction battery cells is predicted to have a larger Global Warming Potential (GWP), due to its higher energy intensity, while hydrometallurgical processing is shown to be more environmentally beneficial, due to the additional recovery of lithium as hydroxide. The majority of the environmental benefits arise from the recovery of aluminium and copper fractions of battery packs, with important contributions also arising from the recovery of nickel and cobalt from the battery cells. Overall, the LCA model presented estimates a net benefit in 11 out of 13 environmental impact categories based on the ReCiPe characterisation method, as compared to battery production without recycling. An investigation of the effect of geographic specificity on the combined production and recycling indicates that it is as a key source of GWP impact variability and that the more climate burdening chains offer a significantly higher potential for GWP reductions through battery recycling. The sensitivity analysis carried out shows that impacts related to air quality are higher when recovering lower grade materials. This study provides a quantitative and replicable inventory model which highlights the significance of the environmental benefits achieved through the establishment of circular automotive battery value chains.

Corn-like Si derived from sepiolite as anode for advanced lithium-ion batteries

Low initial coulombic efficiency (ICE) and poor long-term cycling performance are key issues of silicon (Si) anode for lithium-ion batteries (LIBs), due to the irreversible consumption of Li ion. Herein, Si with corn-like structure is synthesized by a simple and low cost magnesiothermic reduction method from pre-treated sepiolite ore. The ICE of corn-like Si reaches 75.1 % and can be increased to almost 100 % by a simple surface prelithiated engineering, meanwhile the charge capacity remains 788 mA h·g-1 (0.56 mAh·cm-2) after 500 cycles at 1 A·g-1(0.71 mA·cm-2). Further SEM observation reveals that the prelithiated Si electrode keeps the original corn-like structure during cycling, confirming that available-Si from natural clay is applicable for the production of LIBs.

Direct regeneration and performance of spent LiFePO4 via a green efficient hydrothermal technique

With the quick development of electric vehicles and grid energy storage, the demand and production of lithium ion batteries (LIBs) are rapidly increasing, and the problem of lithium resource shortage becomes more and more serious. Both in terms of economic value and environmental protection, the recycling and regeneration of the spent lithium batteries is extremely urgent. Herein, a green and efficient hydrothermal technique for direct regeneration of spent lithium iron phosphate (LiFePO4 or LFP) was proposed. LFP loses the partial lithium during the long cycle and converts to FePO4 (FP), therefore, the replacement of the lost lithium is crucial for the regeneration of spent LFP. Herein, the effects of hydrothermal conditions such as reaction temperature, Li+ concentration and reducing agent concentration on the performance of product are systemically studied. Besides, it has been found that the control of hydrothermal condition is conductive to the supplement of Li and the enhancement of electrochemical performance of the product. Under hydrothermal conditions of 200 °C for 3 h, the regenerated LFP shows the optimal electrochemical performance of 165.9, 151.93, 145.92, 133.11 and 114.96 mAh g−1 at 0.1, 0.5, 1, 2, and 5 C, respectively. In addition, the capacity retention is as high as 99.1% after 200 cycles at 1 C. Therefore, this work provides a new idea for the direct regeneration of spent LFP cathode materials.

Application of Roasting Flotation Technology to Enrich Valuable Metals from Spent LiFePO4 Batteries.

The application of lithium-ion batteries (LIBs) in electric vehicles has attracted wide attention in recent years, especially LiFePO4 batteries that have been extensively used in large electric buses and cars. The increased demand for LIBs has greatly stimulated lithium-ion battery production, which subsequently has led to greatly increased quantities of spent LIBs. From the perspective of environmental protection and resource recovery, the recycling of spent LIBs is of great significance. In this study, the roasting flotation technology was applied to enrich valuable metals from the mixed electrode powder of spent LiFePO4 batteries. Roasting could thoroughly remove the organic outer layer coated on the surface of electrode-active materials, which improved the flotation enrichment efficiency of valuable metals in the mixed electrode powder of spent LiFePO4 batteries. Under the optimum conditions of roasting at 500 °C for 1 h, the enrichment efficiency of Li and Fe reached the best. The recovery and the enrichment ratio of Li were 95.87% and 1.37, respectively, while the recovery and the enrichment ratio of Fe were 95.25% and 1.36, respectively. Roasting flotation was an efficient process to enrich valuable metals from spent LiFePO4 batteries without wasting graphite resources.

Decomposition of PVDF to delaminate cathode materials from end-of-life lithium-ion battery cathodes

The growing demand of electric vehicles and rapid consumption of rechargeable lithium-ion batteries (LIBs) require recycling of spent cathode active materials (CAMs) to reduce hazardous wastes and supply raw materials to LIB production. To separate CAMs from the cathode, direct calcination of polyvinylidene fluoride (PVDF) binder is widely applied, which leads to high energy consumption and release of toxic hydrogen fluoride. It is desirable to have an environmentally friendly and effective alternative to traditional direct calcination. In this study, five lithium salts, LiOAc (lithium acetate), LiNO3, LiCl, Li2CO3, and Li2SO4, were deployed and compared for their performance in recycling CAMs. A peel-off efficiency of up to 98.5% was achieved at a LiOAc to LiNO3 molar ratio of 3:2, salt to cathode mass ratio of 10:1, and temperature of 300 °C at a holding time of 30 min. This system avoids corrosive chemicals and minimizes particle agglomeration of recycled products. Compared with sodium salt systems (NaOAc-NaNO3) or direct calcination, the LiOAc-LiNO3 system prevented high reaction temperature or further lithium loss, and minimized crystal structure and morphological changes. A decomposition mechanism of PVDF through adsorption of HF and fluorine substitution was proposed.

Automated Data Gathering, Classification, Standardization and Evaluation Connected with AI in Smart Li-ion Battery Cell Production

The production of lithium-ion batteries is characterized by high scrap rates. With material costs of 70-80% of the cell price, these are a significant cost factor. By using AI, correlations of process data and cell properties can be determined and particularly quality-relevant process steps can be identified.However, the prerequisite for the use of AI is a clean collection, description and allocation of data which is very time-consuming.In the BMBF-funded projects “KontElPro”, for solvent-free electrode production and “AgiloBat2”, for the agile production of format-flexible cells, software is being developed to solve this problem.The corresponding software system "Batalyse" is capable of automatically collecting, categorizing, linking and evaluating test, analysis and production data. Quality-relevant parameters of the produced (lab) cells such as capacity, resistance and power can thus be directly correlated with process parameters and data. The complete process chain of input materials, (intermediate) products, sensors, equipment, process parameters and all evaluated result data of the produced cells is stored in the database. All data, correlations and logic is provided by this database via an interface for AI applications.The aim is to use this data to generate digital twins of each individual process step and to optimize them step by step. Later, the processes are to be controlled autonomously by AI applying optimized process parameters to avoid or at least to reduce scrap.In the talk we present the structure, status and use of the software for research data management and in the use of in the research production of Li-ion cells.

Life Cycle Comparison of Battery Recycling and Conventional Material Refining

Background: The rise of renewable energy generation and vehicle electrification has created exponential growth in lithium-ion battery (LIB) production, particularly for electric vehicles.1 However, the limited supply of raw materials needed for prominent battery chemistries has exacerbated concerns linked to economic, environmental, national security, and human rights dimensions.2 For example, raw materials necessary for LIB production are not equally distributed, and current supply chains are insufficient for projected demand. For countries with natural reserves of critical LIB elements, the mining of ore for battery production often involves the destruction of natural ecosystems and sometimes employs child labor under harsh working conditions.3 Further, many small LIBs in consumer electronics are carelessly disposed of in garbage or recycling bins at end-of-life. Because these disposal streams are not designed to process energized batteries, LIBs have caused fires and millions of dollars in damage to waste management and recycling centers.4 Taken together, these concerns underscore the need for robust recycling programs for LIBs and their components. Methods: We performed a comparative environmental assessment of the gate-to-gate refinement process of battery material production based on conventional battery material refining versus LIB recycling by Redwood Materials. Two- and three-step recycling processes were assessed for battery feedstocks that included production scrap and mixed spent lithium-ion batteries. Data detailing energy, water, and consumables usage were provided by Redwood and normalized to elemental mass flows and products of interest. The system boundary does not include other operations at Redwood Materials outside of the direct refinement processes nor the embodied resources in the capital equipment used for material refinement.The functional unit employed in the analysis was a 1 kg of active nickel, cobalt, aluminum oxide (NCA) battery material. The primary LCA criteria evaluated included global warming potential (CO2eq), primary energy demand, and water consumption. Data for conventional material refining were adapted from the Argonne National Laboratory’s Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET®) 2020 model. GREET was also employed to acquire the life cycle parameters for producing consumables used in both conventional metal refining and Redwood Materials’ recycling processes to provide common scaling factors. Transportation between stages was not included in this analysis because it was not consistently available in the GREET model. The environmental metrics for each metal pathway were normalized by the mass of the individual element of interest within the final product and then normalized again by the mass of that element in the functional unit. Results and Implications: The goal of this study was to compare environmental metrics of two scenarios: (1) conventional refining of raw battery materials and (2) recycling of batteries by Redwood Materials. Relative to conventional refining, the Redwood Materials recycling processes reduced both water (by 70–80%) and energy consumption (by 81–87%) per kg of NCA battery active material. The Redwood processes lowered CO2 emissions by 67–68% compared to conventional ore refining. The output products of each recycling process were dependent on the battery feedstock and recycling efficiency. In the case of Ni-rich feedstock, the CO2 emissions by mass of Ni were 30–45 times lower for recycling versus conventional refining when considering only nickel as the output product.In addition to comparing recycling processes to conventional refining, we also conducted a prospective life-cycle assessment to identify optimization opportunities at Redwood. Among the three process steps (mechanical processing, low-temperature calcination, and hydrometallurgy), the hydrometallurgical process was the most resource- and carbon-intensive, counter to popular opinion. This was due to the embodied resources required to produce the input consumables Ca(OH)2, H2O2, and electricity from the Nevada electrical grid. The addition of a low-temperature calcination step prior to hydrometallurgy slightly reduced overall resource consumptions and emissions because fewer input consumables were needed for the hydrometallurgical step. Overall, this study identified value propositions and optimization opportunities for battery recycling as it reaches a much-needed scale to support the burgeoning LIB market. This assessment will guide battery recyclers on environmental targets, and inform several stakeholders (e.g., public, policymakers, electrochemists and electrochemical engineers) regarding the tradeoffs and opportunities for a circular battery economy relative to conventional battery manufacturing. References Electric Vehicles are starting to buoy the global metals market. https://www.bloombergquint.com/technology/the-relentless-march-toward-an-ev-future-is-good-news-for-miners.National Blueprint for Lithium Batteries; U. S. Department of Energy: 2021.Findings on the Worst Forms of Child Labor: Democratic Republic of the Congo. https://www.dol.gov/agencies/ilab/resources/reports/child-labor/congo-democratic-republic-drc.Staub, C. MRF operator: Lithium-ion batteries are ‘ticking time bombs’. https://resource-recycling.com/recycling/2021/04/13/mrf-operator-lithium-ion-batteries-are-ticking-time-bomb.

Circular Economy Insights: Sustainable Reuse of Aged Li-Ion LiFePO4 Cathodes within Na-Ion Cells

Lithium-ion batteries (LIBs) are today considered as one of the best solutions towards an energy model based on renewable sources and zero-emission electric vehicles. However, the increased production of LIBs raises concerns regarding cost and availability of key materials such as lithium, cobalt or graphite. Indeed, after almost 20 years of cost decrease, the price of lithium-ion batteries is slowing down [1]. This is related to the fact that a lot of raw materials and metals (mainly copper, aluminum and cobalt) that are used in LiBs have increased relentlessly their prices because of its continuous demand. In this sense, are needed better performing, more price competitive and sustainable battery storage solutions beyond lithium that take into consideration the overall value chain, from access to raw material, innovative advanced materials, production, recycling and second life.In this context, disposal and recycling are essential for the sustainability of this market and new recycling processes for LIBs are needed. Today there are processes that can recover high-value raw materials from LIBs (mainly copper, aluminum, and cobalt) but direct recycling of materials such as LiFePO4 (LFP) that has less economic value and are environmentally much more sustainable represents an economic challenge for the battery market and future research.NaFePO4 (NFP) has been indeed proposed as one of the cheapest and most sustainable sodium-ion (Na-ion) cathode materials, [2-3] but it is not a thermodynamically stable phase and it is necessary to obtain it from LFP through redox reactions usually using expensive, toxic and hazardous reagents, cutting down its commercialization.[3-5] LFP recovering from spent LIBs can contribute to reducing the manufacturing costs of the NFP and increase the interest to recycle Li-ion batteries based on LFP cathodes.In the perspective of a circular economy market, we propose in this work to explore the recovery of aged LFP electrodes and their reuse in new Na-ion batteries.

Modeling Approaches for the Description of the Carbon Black Particle Size in Batch and Continuous Dispersion Processes for Lithium-Ion Battery Slurries

Energy storage is a key technology for alternative power trains like electric and hybrid electric vehicles. Lithium-ion batteries (LIB) are widely used for this purpose due to their high energy density and elaborated developmental state. Also, the increasing usage of electrified transportation leads to ever-increasing demands on LIBs in terms of fast charging ability and power density. The fragmentation of carbon black (CB) aggregates and agglomerates, respectively, has high impact on the resulting microstructure and mechanical integrity as well as conductivity of electrodes and furthermore, the electrochemical performance of LIBs [1]. To achieve optimized cell performances and to reduce the process times or increase throughputs while conserving the slurry quality, a method to predict the CB particle sizes based on simulations and experiments has been developed.This work demonstrates how the dispersion process can be modelled, thus laying the foundation for an optimized microstructure of the electrode right at the beginning of the process chain. For this purpose, a high-intensity batch process in a planetary mixer is investigated and modelled for the description of the CB fragmentation, and the approach is then applied to a continuous twin-screw extruder. Through the use of computational fluid dynamics, theoretical equations and considerations, and experimentally obtained data, the models are parametrized and can be used to predict the result of the dispersion process in form of the CB particle size. The critical values here are the shear rate in the laminar flow and the viscosity of the slurry, which determine the transferred energy onto the particles during the process. By appropriately modelling these characteristic values, it is possible to transfer the models to machines of different types and designs.Furthermore, it is shown how the predicted particle size of CB affects the microstructure of the electrodes. For this purpose, an innovative structural parameter is calculated from mercury intrusion measurements of manufactured electrodes, which expresses the internal porosity of the CB particles, or of the conductive microstructure, respectively. Based on the modelled CB particle size, this parameter can already be used to estimate the developing microstructure of the electrodes depending on the selected process parameters during dispersion. Such an approach is the basis for further work in order to holistically depict and digitalize the entire process chain of the LIB production and its counteracting influences.The experimental process data (power uptake of dispersion machines, viscosities, CB particle sizes), electrode structures, electrode properties (adhesive tensile strengths, spec. resistances) and cell performance data are shown to illustrate the approaches and the value of the created models. All LIB cathodes investigated consist of industrially relevant formulations (> 95 wt% active material NMC622, < 2.5 wt% CB). Reference s : [1] Mayer, J. , Almar, L., Asylbekov, E., Haselrieder, W., Kwade, A., Weber, A. and Nirschl, H., Influence of the Carbon Black Dispersing Process on the Microstructure and Performance of Li‐ion Battery Cathodes, Energy Technol. (2019)

Acidic Chloride Leaching of NMC Cathodes Combined with Solvent Extraction for the Production of Value Metals from Spent Lithium-Ion Battery

Lithium-ion battery is the technology of choice in the development of electric vehicles. This technology is now mature although there are still many challenges to increase their energy density while ensuring an irreproachable safety of use. For this goal, it is necessary to develop new cathodic materials that can be cycled at higher voltages and electrolytes compatible with these materials. But the challenge does not only concern the production of efficient batteries for the electrochemical storage of energy since lithium-ion battery technology relies on the use of critical and/or strategic value resources. It is therefore crucial to include Lithium-ion batteries development in a circular economy approach very early. In particular, optimized recycling and reuse of battery components must both minimize their impact on the environment and limit geopolitical issues related to tensions on the mineral resources necessary for lithium-ion battery production. Although recycling will never replace mining, it reduces resource dependence by ensuring the presence of exploitable resources in the territory, which is particularly important for countries like France where exploited or exploitable resources are limited.This conference addresses the development of a new hydrometallurgical process combining leaching of cathodic material from spent lithium-ion battery in acidic chloride media and solvent extraction process. Most of recycling processes reported in the literature rely on the sulphate route and a few studies investigate the potentialities of the chloride route despite many advantages and the possibility to develop new chemistry, which could get easier the metal separation. The leaching mechanisms and the solvent extraction equilibria will be presented in this conference. Based on the comprehension of the physicochemistry of leaching and solvent extraction, the present study will introduce a new hydrometallurgical process for the production of cobalt, nickel, manganese and lithium from spent cathodic materials.

Evaluation of Electrochemical Performance Tuning By Laser Structuring of Electrodes and Its Impact on Cell Degradation Mechanisms

Tuning of electrochemical properties of lithium-ion batteries by using ultrafast laser structuring of electrodes is a rather new technical approach. At Karlsruhe Institute of Technology (KIT) this technology was developed and established for the first time. However, quite recently, other research groups and institutions worldwide also recognized the high potential of this technology for lithium-ion battery production. Lately, a roll-to-roll laser processing infrastructure for structuring large footprint electrode materials for high capacity pouch cells and cylindrical cells was installed at KIT in order to push this technology to demonstrator level, namely technology readiness level 6. The high rate capability of the produced high energy battery cells were significantly improved and twice lifetime of cells could be achieved in comparison to cells with unstructured electrodes. In frame of research, cooperative, and industrial projects the impact of laser structuring for small and large footprint electrodes was studied with regard to lithium distribution caused electrochemical cycling. Hereby, different types of LiNixMnyCo1-x-yO2 (NMC) as a cathode material and graphite as well as silicon-graphite as an anode material with areal capacities up to 4 mAh/cm2 were investigated. Quantitative lithium distribution along entire electrodes were measured by laser-induced breakdown spectroscopy (LIBS). From the 3D elemental mapping starting points for electrochemical degradation could be identified. In cathode materials the local increase of lithium indicated the formation of electrical short cuts which were most related to electrode material inhomogeneity, e.g., by a macroscopic change in porosity or macroscopic film defects. The compressive stress applied to electrodes and separator during cycling has also a significant influence on lithium distribution and subsequent cell degradation. The appropriate type of laser generated patterns such as holes, lines or grids strongly depends on the application scenario as well as type of materials. For silicon-graphite anodes the huge volume expansion during lithium silicide needs to be considered and more rectangular and broader structure features become relevant. Laser structuring of electrodes showed in all cases, for small and large footprint cathodes and anodes, a rather homogenized lithium distribution along the surface and electrode thickness. For full cells elemental mapping of electrodes facing each other was performed indicating the mutual influence on lithium distribution. It can be concluded that the laser-based 3D electrode concept is beneficial regarding a reduced cell degradation. In addition, it could be proven by LIBS that for the 3D battery concept new lithium diffusion pathways were generated which becomes activated at elevated C-rates. Those new lithium diffusion pathways counteract the increase of diffusion overpotential leading to a higher capacities also for high power operation.

Transition Metal Oxides and Li2CO3 as Precursors for the Synthesis of Ni-Rich Single-Crystalline NCM for Sustainable Lithium-Ion Battery Production

Single-crystalline Ni-rich LiNi1-x-y Co x Mn y O2 (SC-NCM) cathode active materials promise to increase the lifetime of high energy Li-ion batteries. SC-NCM consist of large primary particles that offer low surface area, limiting detrimental chemical reactions while exhibiting high morphological stability. A typical SC-NCM synthesis starts from the same Ni1-x-y Co x Mn y (OH)2 and LiOH∙H2O precursors commonly used for conventional spherical poly-crystalline NCM (PC-NCM), but requires higher temperatures and additional post-processing. Consequently, the cost and environmental impact of the production of Ni-rich SC-NCM is higher compared to the production of PC-NCM. In this study, we demonstrate a synthesis of SC-NCM that does not require the same highly engineered precursors as used for PC-NCM. We propose a more energy-efficient and cost-effective route that involves simple blending of NiO, MnO, Co3O4 and Li2CO3 which yields single-crystalline LiNi0.83Co0.11Mn0.06O2 with 2–3 μm particle size and good structural quality. It is shown by in situ XRD during synthesis that—while the reaction suffers from slow kinetics—the elevated temperature and longer reaction time, which are in any case required for the crystal growth, are sufficient to also complete the reaction. Furthermore, it is shown that this material is structurally and electrochemically equivalent to the material commonly synthesized from hydroxide-based precursors.

Towards the lithium-ion battery production network: Thinking beyond mineral supply chains

The increasing role of electricity as an energy carrier in decarbonising economies is driving a growing demand for electrical energy storage in the form of battery systems. Two battery applications driving demand growth are electric vehicles and stationary forms of energy storage. Consequently, established battery production networks are increasingly intersecting with – and being transformed by – actors and strategies in the transport and power sectors, in ways that are important to understand. Most analyses of battery production adopt a supply chain approach, focussing on the flow and transformation of materials from primary production via manufacturing to final assembly. They pay only limited attention to organisational and geographical relations, and they overlook critical areas of intersection between battery production and OEM manufacturing for automotive and power sectors. As a result, supply chain approaches do not fully account for emergent properties of battery production networks.To remedy this, we deploy a global production network (GPN) approach that highlights the increasing intersection of battery manufacturing with the automotive and power sectors, informed by original research with key respondents in battery R&D and commercialization at the collaborative interfaces of academia, industry and government. Our GPN approach augments conventional supply chain accounts based on battery manufacturing in two ways: it identifies the economic and non-economic actors, network relations and multiple locations that constitute the global battery production network; and focuses on firm strategies of innovation, cooperation and competition through which this network acquires its organisationally and geographically dynamic character, (specifically increasing inter-industry intersections), and the multifaceted role of the state. The paper concludes by reflecting on the implications of this alternative account for understanding key areas of policy concern, and for analyses of the geopolitical economy of energy system transformation.