Editor’s Choice Articles

The process chain of electrode production includes calendering as a crucial process step to enhance the volumetric energy density as well as to influence the particle-pore-structure and simultaneously the mechanical and electrochemical properties of the electrode coating. A further way to improve the volumetric energy density is the usage of other materials with higher specific capacity, such as silicon instead of graphite as the active material for anodes. In this study, both opportunities, calendering and using silicon-containing composites, are combined to investigate the relations between material, process and performance. The applied line loads for the compaction are correlated with the silicon mass fraction and lead to a silicon-dependent mathematical model to estimate further line loads for silicon-graphite-composite electrodes. On the basis of established analyzing methods for adhesion strength and deformation behavior, it is shown that with increasing silicon content, the elastic deformation of the electrode coating rises. In addition, the overall porosity of the electrodes is less affected by silicon than the pore size distribution compared to graphite electrodes. Furthermore, the electrical conductivity decreases at higher silicon contents independent of coating density. Moreover, the long-term electrochemical stability deteriorates with increasing silicon content and coating density. Full article

We characterize for the first time the performances of IBM quantum chips as quantum batteries, specifically addressing the single-qubit Armonk processor. By exploiting the Pulse access enabled to some of the IBM Quantum processors via the Qiskit package, we investigate the advantages and limitations of different profiles for classical drives used to charge these miniaturized batteries, establishing the optimal compromise between charging time and stored energy. Moreover, we consider the role played by various possible initial conditions on the functioning of the quantum batteries. As the main result of our analysis, we observe that unavoidable errors occurring in the initialization phase of the qubit, which can be detrimental for quantum computing applications, only marginally affect energy transfer and storage. This can lead counter-intuitively to improvements of the performances. This is a strong indication of the fact that IBM quantum devices are already in the proper range of parameters to be considered as good and stable quantum batteries comparable to state-of-the-art devices recently discussed in the literature. Full article

In recent years, research on lithium–ion (Li-ion) battery safety and fault detection has become an important topic, providing a broad range of methods for evaluating the cell state based on voltage and temperature measurements. However, other measurement quantities and close-to-application test setups have only been sparsely considered, and there has been no comparison in between methods. In this work, the feasibility of a multi-sensor setup for the detection of Thermal Runaway failure of automotive-size Li-ion battery modules have been investigated in comparison to a model-based approach. For experimental validation, Thermal Runaway tests were conducted in a close-to-application configuration of module and battery case—triggered by external heating with two different heating rates. By two repetitions of each experiment, a high accordance of characteristics and results has been achieved and the signal feasibility for fault detection has been discussed. The model-based method, that had previously been published, recognised the thermal fault in the fastest way—significantly prior to the required 5 min pre-warning time. This requirement was also achieved with smoke and gas sensors in most test runs. Additional criteria for evaluating detection approaches besides detection time have been discussed to provide a good starting point for choosing a suitable approach that is dependent on application defined requirements, e.g., acceptable complexity. Full article

Fast charging of lithium-ion batteries is often related to accelerated cell degradation due to lithium-plating on the negative electrode. In this contribution, an advanced electrode equivalent circuit model is used in order to simulate fast-charging strategies without lithium-plating. A novel parameterization approach based on 3-electrode cell measurements is developed, which enables precise simulation fidelity. An optimized fast-charging strategy without evoking lithium-plating was simulated that lasted about 29 min for a 0–80% state of charge. This variable current strategy was compared in experiments to a conventional constant-current–constant-voltage fast-charging strategy that lasted 20 min. The experiments showed that the optimized strategy prevented lithium-plating and led to a 2% capacity fade every 100 fast-charging cycles. In contrast, the conventional strategy led to lithium-plating, about 20% capacity fade after 100 fast-charging cycles and the fast-charging duration extended from 20 min to over 30 min due to increased cell resistances. The duration of the optimized fast charging was constant at 29 min, even after 300 cycles. The developed methods are suitable to be applied for any given lithium-ion battery configuration in order to determine the maximum fast-charging capability while ensuring safe and durable cycling conditions. Full article

Lithium-ion batteries (LIBs) have been widely used in various fields. In order to ensure the safety of LIBs, it is necessary to accurately estimate of the state of health (SOH) of the LIBs. This paper proposes a SOH hybrid estimation method based on incremental capacity (IC) curve and back-propagation neural network (BPNN). The voltage and current data of the LIB during the constant current (CC) charging process are used to convert into IC curves. Taking into account the incompleteness of the actual charging process, this paper divides the IC curve into multiple voltage segments for SOH prediction. Corresponding BP neural network is established in multiple voltage segments. The experiment divides the LIBs into five groups to carry out the aging experiment under different discharge conditions. Aging experiment data are used to establish the non-linear relationship between the decline of SOH and the change of IC curve by BP neural network. Experimental results show that in all voltage segments, the maximum mean absolute error does not exceed 2%. The SOH estimation method proposed in this research makes it possible to embed the SOH estimation function in battery management system (BMS), and can realize high-precision SOH online estimation. Full article

Stationary battery systems are becoming more prevalent around the world, with both the quantity and capacity of installations growing at the same time. Large battery installations and uninterruptible power supply can generate a significant amount of heat during operation; while this is widely understood, current thermal management methods have not kept up with the increase of stationary battery installations. Active cooling has long been the default approach of thermal management for stationary batteries; however, there is no academic research or comparative studies available for this technology. The present work presents assessment of different active cooling methods through an experimentally validated computational fluid dynamics simulation. Following model validation, several cooling system configurations were analyzed, including effects from implementing either a perforated vent plate or vortex generators. The vent plate was observed to greatly increase cooling performance while simultaneously promoting temperature uniformity between batteries. Vortex generators were shown to marginally increase cooling performance, yet, future research is recommended to study the effects and improvement of the design. The average battery temperature for the vented model is reduced by approximately 5.2 °C, while the average temperature differential among the batteries was only 2.7 °C, less than the recommend value (3 °C) by ASHRAE/IEEE Standards. Full article

Surface modified reduced graphene oxide (rGO) aerogels were synthesized using the hydrothermal method. Ethylene diamine (EDA) and α-cyclodextrin (CD) were used to functionalize the surface of the graphene oxide layers. The oxygen reduction and surface modification occurred in-situ during the hydrothermal self-assembly process. The chemical functionality and structure of the resulting ethylene diamine modified (rGO-EDA) and cyclodextrin modified (rGO-CD) aerogels as well as of the pristine unmodified rGO aerogel were studied using XPS, SEM, XRD, and SANS techniques. The overall surface composition showed a significant decrease in the oxygen content for all synthesized aerogels. The surface modified aerogels were characterized by a disordered stacking of the assembled rGO layers. The surface functionalities resulted in a broad distribution of the interlayer spacing and introduced structural heterogeneities. Such disordered structures can enable a better adsorption mechanism of the sodium ions. Coin cells based on the synthesized aerogels and sodium metal were assembled and tested at several charge and discharge rates. The correlation between the surface functionality of the rGO, the induced structural heterogeneities due to the disordered stacking, and the electrochemical performance of sodium-ion batteries were investigated. Operando XRD measurements were carried out during the battery cycling to investigate the adsorption or intercalation nature of the sodiation mechanism. Full article

Circular business models for batteries have been revealed in earlier research to achieve economic viability while reducing total resource consumption of raw materials. The objective of this study is to measure the economic performance of the preferred business model by creating different scenarios comparing second life (spent) and new battery investment for seven different European regions and four energy management strategies. Findings reveal levels of economic ability for a total of 34 scenarios simulated, including direct savings per kWh, a total change in energy costs per year, battery charge/discharge cycles, and comparative breakeven analyses. Regional effects are also measured based on day-ahead electricity prices and solar irradiation. The minimum payback time is 7 years before battery system investment costs are covered. The most viable energy management strategies also had the highest number of charge/discharge cycles, which decreases battery lifetime. Investment in a second life battery compared to a new battery reduced the payback time by 0.5 to 2 years due to lower investment costs. However, the estimated lifetime range (3 to 10 years) is lower compared to a new battery (5 to 15 years), which questions the circular business model viability for the scenarios studied. Energy management strategies should be combined and customized to increase economic benefits. Full article

Lithium-ion battery cells not only show different behaviors depending on degradation and charging states, but also overcharge and overdischarge of cells shorten battery life and cause safety problems, thus studies aiming to provide an accurate state of a cell are required. Measurements of battery cell impedance are used for cell SoH and SoC estimation techniques, but it generally takes a long time for a cell in each state to be prepared and cell voltage response is measured when charging and discharging under each condition. This study introduces an electrical equivalent circuit model of lithium-ion cells developed in the MATLAB/Simulink environment. Cell SoC, SoH, temperature, and C-rate are considered for more accurate cell impedance prediction, and the simulation results are verified with the measurement results. The developed model is suitable for use in cell SoC and SoH monitoring studies by successfully outputting cell impedance through real-time prediction of cell voltage during discharge. Full article

Various studies show that electrification, integrated into a circular economy, is crucial to reach sustainable mobility solutions. In this context, the circular use of electric vehicle batteries (EVBs) is particularly relevant because of the resource intensity during manufacturing. After reaching the end-of-life phase, EVBs can be subjected to various circular economy strategies, all of which require the previous disassembly. Today, disassembly is carried out manually and represents a bottleneck process. At the same time, extremely high return volumes have been forecast for the next few years, and manual disassembly is associated with safety risks. That is why automated disassembly is identified as being a key enabler of highly efficient circularity. However, several challenges need to be addressed to ensure secure, economic, and ecological disassembly processes. One of these is ensuring that optimal disassembly strategies are determined, considering the uncertainties during disassembly. This paper introduces our design for an adaptive disassembly planner with an integrated disassembly strategy optimizer. Furthermore, we present our optimization method for obtaining optimal disassembly strategies as a combination of three decisions: (1) the optimal disassembly sequence, (2) the optimal disassembly depth, and (3) the optimal circular economy strategy at the component level. Finally, we apply the proposed method to derive optimal disassembly strategies for one selected battery system for two condition scenarios. The results show that the optimization of disassembly strategies must also be used as a tool in the design phase of battery systems to boost the disassembly automation and thus contribute to achieving profitable circular economy solutions for EVBs. Full article

Lithium-ion batteries are a key technology for electromobility; thus, quality control in cell production is a central aspect for the success of electric vehicles. The detection of defects and poor insulation behavior of the separator is essential for high-quality batteries. Optical quality control methods in cell production are unable to detect small but still relevant defects in the separator layer, e.g., pinholes or particle contaminations. This gap can be closed by executing high-potential testing to analyze the insulation performance of the electrically insulating separator layer in a pouch cell. Here, we present an experimental study to identify different separator defects on dry cell stacks on the basis of electric voltage stress and mechanical pressure. In addition, finite element modeling (FEM) is used to generate physical insights into the partial discharge by examining the defect structures and the corresponding electric fields, including topographical electrode roughness, impurity particles, and voids in the separator. The test results show that hard discharges are associated with significant separator defects. Based on the study, a voltage of 350 to 450 V and a pressure of 0.3 to 0.6 N/mm² are identified as optimum ranges for the test methodology, resulting in failure detection rates of up to 85%. Full article

Sustainable battery production with low environmental footprints requires a systematic assessment of the entire value chain, from raw material extraction and processing to battery production and recycling. In order to explore and understand the variations observed in the reported footprints of raw battery materials, it is vital to re-assess the footprints of these material value chains. Identifying the causes of these variations by combining engineering and environmental system analysis expands our knowledge of the footprints of these battery materials. This article disaggregates the value chains of six raw battery materials (aluminum, copper, graphite, lithium carbonate, manganese, and nickel) and identifies the sources of variabilities (levers) for each process along each value chain. We developed a parametric attributional process-based life cycle model to explore the effect of these levers on the greenhouse gas (GHG) emissions of the value chains, expressed in kg of CO₂e. The parametric life cycle inventory model is used to conduct distinct life cycle assessments (LCA) for each material value chain by varying the identified levers within defined engineering ranges. 570 distinct LCAs are conducted for the aluminum value chain, 450 for copper, 170 for graphite, 39 for lithium carbonate via spodumene, 20 for lithium carbonate via brine, 260 for manganese, and 440 for nickel. Three-dimensional representations of these results for each value chain in kg of CO₂e are presented as contour plots with gradient lines illustrating the intensity of lever combinations on the GHG emissions. The results of this study convey multidimensional insights into how changes in the lever settings of value chains yield variations in the overall GHG emissions of the raw materials. Parameterization of these value chains forms a flexible and high-resolution backbone, leading towards a more reliable life cycle assessment of lithium-ion batteries (LIB). Full article

Carbon monoliths were tested as electrodes for vanadium redox batteries. The materials were synthesised by a hard-templating route, employing sucrose as carbon precursor and sodium chloride crystals as the hard template. For the preparation process, both sucrose and sodium chloride were ball-milled together and molten into a paste which was hot-pressed to achieve polycondensation of sucrose into a hard monolith. The resultant material was pyrolysed in nitrogen at 750 °C, and then washed to remove the salt by dissolving it in water. Once the porosity was opened, a second pyrolysis step at 900 °C was performed for the complete conversion of the materials into carbon. The products were next characterised in terms of textural properties and composition. Changes in porosity, obtained by varying the proportions of sucrose to sodium chloride in the initial mixture, were correlated with the electrochemical performances of the samples, and a good agreement between capacitive response and microporosity was indeed observed highlighted by an increase in the cyclic voltammetry curve area when the S_BET increased. In contrast, the reversibility of vanadium redox reactions measured as a function of the difference between reduction and oxidation potentials was correlated with the accessibility of the active vanadium species to the carbon surface, i.e., was correlated with the macroporosity. The latter was a critical parameter for understanding the differences of energy and voltage efficiencies among the materials, those with larger macropore volumes having the higher efficiencies. Full article

Calcium-ion batteries represent a promising alternative to the current lithium-ion batteries. Nevertheless, calcium-ion intercalating materials in nonaqueous electrolytes are scarce, probably due to the difficulties in finding suitable host materials. Considering that research into calcium-ion batteries is in its infancy, discovering and characterizing new host materials would be critical to further development. Here, we demonstrate FeV₃O₉∙1.2H₂O as a high-performance calcium-ion battery cathode material that delivers a reversible discharge capacity of 303 mAh g⁻¹ with a good cycling stability and an average discharge voltage of ~2.6 V (vs. Ca/Ca²⁺). The material was synthesized via a facile co-precipitation method. Its reversible capacity is the highest among calcium-ion battery materials, and it is the first example of a material with a capacity much larger than that of conventional lithium-ion battery cathode materials. Bulk intercalation of calcium into the host lattice contributed predominantly to the total capacity at a lower rate, but became comparable to that due to surface adsorption at a higher rate. This stimulating discovery will lead to the development of new strategies for obtaining high energy density calcium-ion batteries. Full article

Progress in renewable energy production has directed interest in advanced developments of energy storage systems. The all-vanadium redox flow battery (VRFB) is one of the attractive technologies for large scale energy storage due to its design versatility and scalability, longevity, good round-trip efficiencies, stable capacity and safety. Despite these advantages, the deployment of the vanadium battery has been limited due to vanadium and cell material costs, as well as supply issues. Improving stack power density can lower the cost per kW power output and therefore, intensive research and development is currently ongoing to improve cell performance by increasing electrode activity, reducing cell resistance, improving membrane selectivity and ionic conductivity, etc. In order to evaluate the cell performance arising from this intensive R&D, numerous physical, electrochemical and chemical techniques are employed, which are mostly carried out ex situ, particularly on cell characterizations. However, this approach is unable to provide in-depth insights into the changes within the cell during operation. Therefore, in situ diagnostic tools have been developed to acquire information relating to the design, operating parameters and cell materials during VRFB operation. This paper reviews in situ diagnostic tools used to realize an in-depth insight into the VRFBs. A systematic review of the previous research in the field is presented with the advantages and limitations of each technique being discussed, along with the recommendations to guide researchers to identify the most appropriate technique for specific investigations. Full article

Equivalent circuit models (ECMs) are a widely used modeling approach for lithium-ion batteries in engineering applications. The RC elements, which display the dynamic loss processes of the cell, are usually parameterized by fitting the ECM to experimental data in either the time-domain or the frequency-domain. However, both types of data have limitations with regard to the observable time constants of electrochemical processes. This work proposes a method to combine time-domain and frequency-domain measurement data for parameterization of RC elements by exploiting the full potential of the distribution of relaxation times (DRT). Instead of using only partial information from the DRT to supplement a conventional fitting algorithm, we determine the parameters of an arbitrary number of RC elements directly from the DRT. The difficulties of automated deconvolution of the DRT, including regularization and the choice of an optimal regularization factor, is tackled by using the L-curve criterion for optimized calculation of the DRT via Tikhonov regularization. Three different approaches to merge time- and frequency-domain data are presented, including a novel approach where the DRT is simultaneously calculated from electrochemical impedance spectoscropy (EIS) and pulse relaxation measurements. The parameterized model for a commercial 18650 NCA cell was validated during a validation cycle consisting of constant current and real-world automotive cycling and yields a relative improvement of over 40% compared to a conventional EIS-fitting algorithm. Full article

Lithium-ion (Li-ion) batteries are an important component of energy storage systems used in various applications such as electric vehicles and portable electronics. There are many chemistries of Li-ion battery, but LFP, NMC, LMO, and NCA are four commonly used types. In order for the battery applications to operate safely and effectively, battery modeling is very important. The equivalent circuit model (ECM) is a battery model often used in the battery management system (BMS) to monitor and control Li-ion batteries. In this study, experiments were performed to investigate the performance of three different ECMs (1RC, 2RC, and 1RC with hysteresis) on four Li-ion battery chemistries (LFP, NMC, LMO, and NCA). The results indicated that all three models are usable for the four types of Li-ion chemistries, with low errors. It was also found that the ECMs tend to perform better in dynamic current profiles compared to non-dynamic ones. Overall, the best-performed model for LFP and NCA was the 1RC with hysteresis ECM, while the most suited model for NMC and LMO was the 1RC ECM. The results from this study showed that different ECMs would be suited for different Li-ion battery chemistries, which should be an important factor to be considered in real-world battery and BMS applications. Full article

In this paper, tests and analysis of thermal runaway propagation for commercial modules consisting of four 41 Ah Li-ion pouch cells are presented. Module samples were tested at 100% state-of-charge and mechanically constrained between two steel plates to provide thermal and mechanical contact between the parts. Voltage and temperature of each cell were monitored during the whole experiment. The triggering of the exothermal reactions was obtained by overheating one cell of the stack with a flat steel heater. In preliminary studies, the melting temperature of the separator was measured (from an extracted sample) with differential scanning calorimetry and thermogravimetric analysis techniques, revealing a tri-layers separator with two melting points (≈135 °C and ≈170 °C). The tests on module level revealed 8 distinct phases observed and analyzed in the respective temperature ranges, including smoking, venting, sparkling, and massive, short circuit condition. The triggering temperature of the cells resulted to be close to the melting temperature of the separator obtained in preliminary tests, confirming that the violent exothermal reactions of thermal runaway are caused by the internal separator failure. Postmortem inspections of the modules revealed the internal electrical failure path in one cell and the propagation of the internal short circuit in its active material volume, suggesting that the expansion of the electrolyte plays a role in the short circuit propagation at the single cell level. The complete thermal runaway propagation process was repeated on 5 modules and ended on average 60 s after the first thermal runaway triggered cell reached a top temperature of 1100 °C. Full article

Driven by the rise of the electric automotive industry, the Li-ion battery market is in strong expansion. This technology does not only fulfill the requirements of electric mobility, but is also found in most portable electric devices. Even though Li-ion batteries are known for their numerous advantages, they undergo serious performance degradation during their aging, and more particularly when used in specific conditions such as at low temperature or high charging current rates. Depending on the operational conditions, different aging mechanisms are favored and can induce physical and chemical modifications of the internal components, leading to performance decay. In this article, the identification of the degradation mechanisms was carried out thanks to an in-depth ante- and post mortem study on three high power and high energy commercial 18,650 cells. Li-ion cells were aged using a battery electric vehicle (BEV) aging profile at −20 °C, 0 °C, 25 °C, and 45 °C in accordance with the international standard IEC 62-660, and in calendar aging mode at 45 °C and SOC 100%. Internal components recovered from fresh and aged cells were investigated through different electrochemical (half-coin cell), chemical (EDX, GD-OES, NMR), and topological (SEM) characterization techniques. The influence of power and energy cells’ internal design and Si content in the negative electrode on cell aging has been highlighted vis-à-vis the capacity and power fade. Full article

The widespread use of electric vehicles is nowadays limited by the “range anxiety” of the customers. The drivers’ main concerns are related to the kilometric range of the vehicle and to the charging time. An optimized fast-charge profile can help to decrease the charging time, without degrading the cell performance and reducing the cycle life. One of the main reasons for battery capacity fade is linked to the Lithium plating phenomenon. This work investigates two methodologies, i.e., three-electrode cell measurement and internal resistance evolution during charging, for detecting the Lithium plating conditions. From this preliminary analysis, it was possible to develop new Multi-Stage Constant-Current profiles, designed to improve the performance in terms of charging time and cells capacity retention with respect to a reference profile. Four new profiles were tested and compared to a reference. The results coming from the new profiles demonstrate a simultaneous improvement in terms of charging time and cycling life, showing the reliability of the implemented methodology in preventing Lithium plating. Full article

To better asses the ageing and to reduce the hazards involved in the use of Lithium-Ion Batteries, multi-measurand monitoring units and strategies are urged. In this paper, a Cell Management Unit, based on the SENSIPLUS chip, a recently introduced multichannel, multi-mode sensor interface, is described. SENSIPLUS is a single System on a Chip combined with a reduced number of external components, resulting in a highly miniaturized device, built on 20 × 8 mm² printed circuit board. Thanks to SENSIPLUS’ versatility, the proposed system is capable of performing direct measurements (EIS, cell voltage) on the cell it is applied to, and reading different kinds of sensors. The SENSIPLUS versatile digital communication interface, combined with a digital isolator, enable connection of several devices to a single bus for parallel monitoring a large number of cells connected in series. Experiments performed by connecting the proposed system to a commercial Lithium-Ion Battery and to capacitive and resistive sensors are described. In particular, the capability of measuring the cell internal impedance with a resolution of 120 μΩ is demonstrated. Full article

Direct observation of the lithiation and de-lithiation in lithium batteries on the component and microstructural scale is still difficult. This work presents recent advances in MeV ion-beam analysis, enabling quantitative contact-free analysis of the spatially-resolved lithium content and state-of-charge (SoC) in all-solid-state lithium batteries via 3 MeV proton-based characteristic x-ray and gamma-ray emission analysis. The analysis is demonstrated on cross-sections of ceramic and polymer all-solid-state cells with LLZO and MEEP/LIBOB solid electrolytes. Different SoC are measured ex-situ and one polymer-based operando cell is charged at 333 K during analysis. The data unambiguously show the migration of lithium upon charging. Quantitative lithium concentrations are obtained by taking the physical and material aspects of the mixed cathodes into account. This quantitative lithium determination as a function of SoC gives insight into irreversible degradation phenomena of all-solid-state batteries during the first cycles and locations of immobile lithium. The determined SoC matches the electrochemical characterization within uncertainties. The presented analysis method thus opens up a completely new access to the state-of-charge of battery cells not depending on electrochemical measurements. Automated beam scanning and data-analysis algorithms enable a 2D quantitative Li and SoC mapping on the µm-scale, not accessible with other methods. Full article

To investigate the influence of cell formats during a cell development programme, lithium-ion cells have been prepared in three different formats. Coin cells, single layer pouch cells, and stacked pouch cells gave a range of scales of almost three orders of magnitude. The cells used the same electrode coatings, electrolyte and separator. The performance of the different formats was compared in long term cycling tests and in measurements of resistance and discharge capacities at different rates. Some test results were common to all three formats. However, the stacked pouch cells had higher discharge capacities at higher rates. During cycling tests, there were indications of differences in the predominant degradation mechanism between the stacked cells and the other two cell formats. The stacked cells showed faster resistance increases, whereas the coin cells showed faster capacity loss. The difference in degradation mechanism can be linked to the different thermal and mechanical environments in the three cell formats. The correlation in the electrochemical performance between coin cells, single layer pouch cells, and stacked pouch cells shows that developments within a single cell format are likely to lead to improvements across all cell formats. Full article

The lifetime of the battery significantly influences the acceptance of electric vehicles. Calendar aging contributes to the limited operating lifetime of lithium-ion batteries. Therefore, its consideration in addition to cyclical aging is essential to understand battery degradation. This study consequently examines the same graphite/NCA pouch cell that was the subject of previously published cyclic aging tests. The cells were aged at different temperatures and states of charge. The self-discharge was continuously monitored, and after each storage period, the remaining capacity and the impedance were measured. The focus of this publication is on the correlation of the measurements. An aging correlation is obtained that is valid for a wide range of temperatures and states of charge. The results show an accelerated capacity fade and impedance rise with increasing temperature, following the law of Arrhenius. However, the obtained data do also indicate that there is no path dependency, i.e., earlier periods at different temperature levels do not affect the present degradation rate. A large impact of the storage state of charge at 100% is evident, whereas the influence is small below 80%. Instead of the commonly applied square root of the time function, our results are in excellent agreement with an exponential function. Full article

The temperature and the temperature gradient within the battery pack of an electric vehicle have a strong effect on the life time of the battery cells. In the case of automotive applications, a battery thermal management (BTM) system is required to maintain the temperature of the cells within a prescribed and safe range, and to prevent excessively high thermal gradients within the battery pack. This work documents the assessment of a thermal management system for a battery pack for an electric van, which adopts a combination of active/passive solutions: the battery cells are arranged in a matrix or composite made of expanded graphite and a phase change material (PCM), which can be actively cooled by forced air convection. The thermal dissipation of the cells was predicted based on an equivalent circuit model of the cells (LG Chem MJ1) that was empirically calibrated in a previous study. It resulted that, in order to keep the temperature of the battery pack at or below 40 °C during certain charge/discharge cycles, a purely passive BTM would require a considerable amount of PCM material that would unacceptably increase the battery pack weight. Therefore, the passive solution was combined with an air cooling system that could be activated when necessary. To assess the resulting hybrid BTM concept, CFD simulations were performed and an experimental test setup was built to validate the simulations. In particular, PCM melting and solidification times, the thermal discrepancy among the cells and the melting/solidification temperatures were examined. The melting time experimentally observed was higher than that predicted by the CFD model, but this discrepancy was not observed during the solidification of the PCM. This deviation between the CFD model results and the experimental data during PCM melting can be attributed to the thermal losses occurring through the mock-up casing as the heating elements are in direct contact with the external walls of the casing. Moreover, the temperature range over which the PCM solidifies was 6 °C lower than that estimated in the numerical simulations. This occurs because the simple thermodynamic model cannot predict the metastable state of the liquid phase which occurs before the onset of PCM solidification. The mockup was also used to emulate the heat dissipation of the cells during a highway driving cycle of the eVan and the thermal management solution as designed. Results showed that for this mission of the vehicle and starting from an initial temperature of the cells of 40 °C, the battery pack temperature could be maintained below 40 °C over the entire mission by a cooling air flow at 2.5 m/s and at a temperature of 30 °C. Full article

Safety for automotive lithium-ion battery (LIB) applications is of crucial importance, especially for electric vehicle applications using batteries with high capacity and high energy density. In case of a defect inside or outside the cell, serious safety risks are possible including extensive heat generation, toxic and flammable gas generation, and consequently fire and explosion. New regulations (GB 38031-2020) require a warning for passengers at least five minutes before serious incidents. This regulation can hardly be fulfilled with state-of-the-art battery monitoring. In this study, gases produced during battery failure before and during a thermal runaway (TR) are investigated in detail and the use of different gas sensors as early detectors of battery incidents is tested and proposed. The response of several commercially available gas sensors is tested in four battery failure cases: unwanted electrolysis of voltage carrying parts, electrolyte vapor, first venting of the cell and the TR. The experiments show that battery failure detection with gas sensors is possible but depends highly on the failure case. The chosen gas sensor can detect H₂ produced by unwanted electrolysis and electrolyte vapor and gases produced by degassing of state-of-the-art LIBs. The results may contribute significantly to failure detection and improvement of battery safety. Full article

Lithium-ion batteries (LIBs) are a dominant state-of-the-art energy storage system and have importance in the automotive sector. Still, LIBs suffer from aging effects and serious hazards from failing batteries are possible. These failures can lead to exothermic chemical reactions inside the cell, ending up in thermal runaway (TR). TR has caused most electric vehicle (EV) fires. Since statistically most accidents with EVs happen after about one year of vehicle usage, in particular, the failing behavior of aged cells needs to be investigated. Little information is available in open literature about the influence of aging paths on the failing behavior and especially on the degassing behavior of large automotive LIBs. Therefore, this study investigates the influence of three different aging paths (cyclic at −10 °C and at 45 °C and calendric at 60 °C) on the thermal behavior, the vent gas emission, and the vent gas composition. The results show a clear effect of aging on the failing behavior. The aged cells showed a less violent failing reaction, reduced maximal temperatures, lower amount of produced gas, significantly lower amount of CO in the vent gas, and lower mass loss than fresh cells in the same overtemperature experiments. The results are valuable for the scientific and industrial community dealing with LIBs. Full article

Electrolytes are key components in electrochemical storage systems, which provide an ion-transport mechanism between the cathode and anode of a cell. As battery technologies are in continuous development, there has been growing demand for more efficient, reliable and environmentally friendly materials. Solid-state lithium ion batteries (SSLIBs) are considered as next-generation energy storage systems and solid electrolytes (SEs) are the key components for these systems. Compared to liquid electrolytes, SEs are thermally stable (safer), less toxic and provide a more compact (lighter) battery design. However, the main issue is the ionic conductivity, especially at low temperatures. So far, there are two popular types of SEs: (1) inorganic solid electrolytes (InSEs) and (2) polymer electrolytes (PEs). Among InSEs, sulfide-based SEs are providing very high ionic conductivities (up to 10⁻² S/cm) and they can easily compete with liquid electrolytes (LEs). On the other hand, they are much more expensive than LEs. PEs can be produced at less cost than InSEs but their conductivities are still not sufficient for higher performances. This paper reviews the most efficient SEs and compares them in terms of their performances and costs. The challenges associated with the current state-of-the-art electrolytes and their cost-reduction potentials are described. Full article

For lithium iron phosphate batteries (LFP) in aerospace applications, impedance spectroscopy is applicable in the flat region of the voltage-charge curve. The frequency-dependent pseudocapacitance at 0.15 Hz is presented as useful state-of-charge (SOC) and state-of-health (SOH) indicator. For the same battery type, the prediction error of pseudocapacitance is better than 1% for a quadratic calibration curve, and less than 36% for a linear model. An approximately linear correlation between pseudocapacitance and Ah battery capacity is observed as long as overcharge and deep discharge are avoided. We verify the impedance method in comparison to the classical constant-current discharge measurements. In the case of five examined lithium-ion chemistries, the linear trend of impedance and SOC is lost if the slope of the discharge voltage curve versus SOC changes. With nickel manganese cobalt (NMC), high impedance modulus correlates with high SOC above 70%. Full article

Over the last decade, the demand for safer batteries with excellent performance and lower costs has been intensively increasing. The abundantly available precursors and environmental friendliness are generating more and more interest in sodium ion batteries (SIBs), especially because of the lower material costs compared to Li-ion batteries. Therefore, significant efforts are being dedicated to investigating new cathode materials for SIBs. Since the thermal characterization of cathode materials is one of the key factors for designing safe batteries, the thermophysical properties of a commercial layered P2 type structure Na_0.53MnO₂ cathode material in powder form were measured in the temperature range between −20 and 1200 °C by differential scanning calorimetry (DSC), laser flash analysis (LFA), and thermogravimetry (TG). The thermogravimetry (TG) was combined with mass spectrometry (MS) to study the thermal decomposition of the cathode material with respect to the evolved gas analysis (EGA) and was performed from room temperature up to 1200 °C. The specific heat (C_p) and the thermal diffusivity (α) were measured up to 400 °C because beyond this temperature, the cathode material starts to decompose. The thermal conductivity (λ) as a function of temperature was calculated from the thermal diffusivity, the specific heat capacity, and the density. Such thermophysical data are highly relevant and important for thermal simulation studies, thermal management, and the mitigation of thermal runaway. Full article

Li-ion battery packs are the heart of modern electric vehicles. Due to their perishable nature, it is crucial to supervise them closely. In addition to on-board supervision over safety and range, insights into the battery’s degradation are also becoming increasingly important, not only for the vehicle manufacturers but also for vehicle users. The concept of digital twins has already emerged on the field of automotive technology, and can also help to digitalize the vehicle’s battery. In this work, we set up a data pipeline and digital battery twin to track the battery state, including State of charge (SOC) and State of Health (SOH). To achieve this goal, we reverse-engineer the diagnostics interface of a 2014 e-Golf to query for UDS messages containing both battery pack and cell-individual data. An OBD logger records the data with edge-processing capability. Pushing this data into the cloud twin system using IoT-technology, we can fit battery models to the data and infer for example, cell individual internal resistance from them. We find that the resistances of the cells differ by a magnitude of two. Furthermore, we propose an architecture for the battery twin in which the twin fleet shares resources like models by encapsulating them in Docker containers run on a cloud stack. By using web technology, we present the analyzed results on a web interface. Full article

The increasing use of electric vehicle batteries in the world has a significant impact on both society and the environment. Thus, there is a need for the availability of transparent information on resource allocation. Battery manufacturing process details in this regard are not available in academia or the public. The available energy data on manufacturing has a high variation. Furthermore, different process steps have different energy and material demands. A process model can benchmark the energy usage, provide detailed process data, and compare various cell productions which in turn can be used in life-cycle assessment studies to reduce the variation and provide directions for improvements. Therefore, a cell manufacturing model is developed for the calculation of energy and material demands for different battery types, plant capacities, and process steps. The model consists of the main process steps, machines, intermediate products and building service units. Furthermore, the results are validated using literature values. For a case study of a 2 GWh plant that produces prismatic NMC333 cells, the total energy requirement on a theoretical and optimal basis is suggested to be $44.6\mathrm{W}{\mathrm{h}}_{\mathrm{in}\mathrm{production}}/\mathrm{W}{\mathrm{h}}_{\mathrm{cell}\mathrm{capacity}}$. This energy consumption in producing batteries is dominated by electrode drying, and dry room. Energy usage for a variety of cell types for a similar plant capacity shows that the standard deviation in the results is low ($47.23\pm 13.03\mathrm{W}\mathrm{h}/\mathrm{W}\mathrm{h}$). Full article

We report a new process technique for electrode manufacturing for all solid-state batteries. Porous electrodes are manufactured by a tape casting process and subsequently infiltrated by a plastic crystal polymer electrolyte (PCPE). With a following isostatic lamination process, the PCPE was further integrated deeply into the porous electrode layer, forming a composite electrode. The PCPE comprises the plastic crystal succinonitrile (SN), lithium conductive salt LiTFSI and polyacrylonitrile (PAN) and exhibits suitable thermal, rheological (ƞ = 0.6 Pa s @ 80 °C 1 s⁻¹) and electrochemical properties (σ > 10⁻⁴ S/cm @ 45 °C). We detected a lowered porosity of infiltrated and laminated electrodes through Hg porosimetry, showing a reduction from 25.6% to 2.6% (NCM infiltrated to laminated) and 32.9% to 4.0% (LTO infiltrated to laminated). Infiltration of PCPE into the electrodes was further verified by FESEM images and EDS mapping of sulfur content of the conductive salt. Cycling tests of full cells with NCM and LTO electrodes with PCPE separator at 45 °C showed up to 165 mAh/g at 0.03C over 20 cycles, which is about 97% of the total usable LTO capacity with a coulomb efficiency of between 98 and 99%. Cycling tests at 0.1C showed a capacity of ~128 mAh/g after 40 cycles. The C-rate of 0.2C showed a mean capacity of 127 mAh/g. In summary, we could manufacture full cells using a plastic crystal polymer electrolyte suitable for NCM and LTO active material, which is easily to be integrated into porous electrodes and which is being able to be used in future cell concepts like bipolar stacked cells. Full article

Internal short-circuit tests were carried out in a battery safety investigation chamber to determine the behavior of batteries during the nail penetration test. So far, systematic investigations regarding the test setup and its influence are rarely found in the literature. Especially, to improve the comparability of the multitude of available results, it is essential to understand the effects of the geometric, operating and ambient parameters. In this study commercial lithium ion batteries with a capacity of 5.3 and 3.3 Ah were used to study the influence of the varied parameters on the voltage drop, the development of surface temperatures and of infrared active gas species. We studied both the influence of the geometry of the penetrating nail and concentration of water in the inert atmosphere especially on the quantities of the reaction products under variation of cell capacity. It could be shown that the geometry of the nail, within certain limits, has no influence on the processes of the thermal runaway of high energy density lithium ion batteries (LIBs). However, a change in capacity from 5.3 to 3.3 Ah shows that in particular the gaseous reaction products differ: The standardized gas concentrations show a higher measurable concentration of all gases except CO for the 3.3 Ah LIBs. This circumstance can be explained by the intensity of the reactions due to the different battery capacities: In the 5.3 Ah cells a larger amount of unreacted material is immediately discharged from the reaction center, and by the different available amounts of oxidizing reaction partners. An increase of the water content in the surrounding atmosphere during the thermal runaway leads to a reduction of the measurable gas concentrations of up to 36.01%. In general, all measured concentrations decrease. With increased water content more reaction products from the atmosphere can be directly bound or settle as condensate on surfaces. Full article

Lithium ion cells that can be quickly charged are of critical importance for the continued and accelerated penetration of electric vehicles (EV) into the consumer market. Considering this, the U.S. Department of Energy (DOE) has set a cell recharge time goal of 10–15 min. The following study provides an investigation into the effect of cell design, specifically negative to positive matching ratio (1.2:1 vs. 1.7:1) on fast charging performance. By using specific charging procedures based on negative electrode performance, as opposed to the industrial standard constant current constant voltage procedures, we show that the cells with a higher N:P ratio can be charged to ~16% higher capacity in the ten-minute time frame. Cells with a higher N:P ratio also show similar cycle life performance to those with a conventional N:P ratio, despite the fact that these cells experience a much higher irreversible capacity loss, leading to a lower reversible specific capacity. Full article

The temperature and heat produced by lithium-ion (Li-ion) batteries in electric and hybrid vehicles is an important field of investigation as it determines the power, performance, and cycle life of the battery pack. This paper presented both laboratory data and simulation results at C-rates of 1C, 2C, 3C, and 4C at an ambient temperature of approximately 23 °C. During experiment thermocouples were placed on the surface of the battery. The thermal model assumed constant current discharge and was experimentally validated. It was observed that temperature increased with C-rates at both the surface and the tabs. We note that at 4C the battery temperature increased from 22 °C to 47.40 °C and the tab temperature increased from 22 °C to 52.94 °C. Overall, the simulation results showed that more heat was produced in the cathode than the anode, the primary source of heat was the electrolyte resistance, and the battery temperature was the highest near the tabs and in the internal space of the battery. Simulation of the lithium concentration within the battery showed that the lithium concentration was more uniform in the anode than in the cathode. These results can help the accurate thermal design and thermal management of Li-ion batteries. Full article

A hermetic dense polymer-carbon composite-based current collector foil (PCCF) for lithium-ion battery applications was developed and evaluated in comparison to state-of-the-art aluminum (Al) foil collector. Water-processed LiNi_0.5Mn_1.5O₄ (LMNO) cathode and Li₄Ti₅O₁₂ (LTO) anode coatings with the integration of a thin carbon primer at the interface to the collector were prepared. Despite the fact that the laboratory manufactured PCCF shows a much higher film thickness of 55 µm compared to Al foil of 19 µm, the electrode resistance was measured to be by a factor of 5 lower compared to the Al collector, which was attributed to the low contact resistance between PCCF, carbon primer and electrode microstructure. The PCCF-C-primer collector shows a sufficient voltage stability up to 5 V vs. Li/Li⁺ and a negligible Li-intercalation loss into the carbon primer. Electrochemical cell tests demonstrate the applicability of the developed PCCF for LMNO and LTO electrodes, with no disadvantage compared to state-of-the-art Al collector. Due to a 50% lower material density, the lightweight and hermetic dense PCCF polymer collector offers the possibility to significantly decrease the mass loading of the collector in battery cells, which can be of special interest for bipolar battery architectures. Full article

In this work, optimal siting and sizing of a battery energy storage system (BESS) in a distribution network with renewable energy sources (RESs) of distribution network operators (DNO) are presented to reduce the effect of RES fluctuations for power generation reliability and quality. The optimal siting and sizing of the BESS are found by minimizing the costs caused by the voltage deviations, power losses, and peak demands in the distribution network for improving the performance of the distribution network. The simulation results of the BESS installation were evaluated in the IEEE 33-bus distribution network. Genetic algorithm (GA) and particle swarm optimization (PSO) were adopted to solve this optimization problem, and the results obtained from these two algorithms were compared. After the BESS installation in the distribution network, the voltage deviations, power losses, and peak demands were reduced when compared to those of the case without BESS installation. Full article

Temperature heavily affects the behavior of any energy storage chemistries. In particular, lithium-ion batteries (LIBs) play a significant role in almost all storage application fields, including Electric Vehicles (EVs). Therefore, a full comprehension of the influence of the temperature on the key cell components and their governing equations is mandatory for the effective integration of LIBs into the application. If the battery is exposed to extreme thermal environments or the desired temperature cannot be maintained, the rates of chemical reactions and/or the mobility of the active species may change drastically. The alteration of properties of LIBs with temperature may create at best a performance problem and at worst a safety problem. Despite the presence of many reports on LIBs in the literature, their industrial realization has still been difficult, as the technologies developed in different labs have not been standardized yet. Thus, the field requires a systematic analysis of the effect of temperature on the critical properties of LIBs. In this paper, we report a comprehensive review of the effect of temperature on the properties of LIBs such as performance, cycle life, and safety. In addition, we focus on the alterations in resistances, energy losses, physicochemical properties, and aging mechanism when the temperature of LIBs are not under control. Full article

Lithium-ion batteries (LIBs) are gaining importance in the automotive sector because of the potential of electric vehicles (EVs) to reduce greenhouse gas emissions and air pollution. However, there are serious hazards resulting from failing battery cells leading to exothermic chemical reactions inside the cell, called thermal runaway (TR). Literature of quantifying the failing behavior of modern automotive high capacity cells is rare and focusing on single hazard categories such as heat generation. Thus, the aim of this study is to quantify several hazard relevant parameters of a failing currently used battery cell extracted from a modern mass-produced EV: the temperature response of the cell, the maximum reached cell surface temperature, the amount of produced vent gas, the gas venting rate, the composition of the produced gases including electrolyte vapor and the size and composition of the produced particles at TR. For this purpose, overtemperature experiments with fresh 41 Ah automotive lithium NMC/LMO—graphite pouch cells at different state-of-charge (SOC) 100%, 30% and 0% are performed. The results are valuable for firefighters, battery pack designers, cell recyclers, cell transportation and all who deal with batteries. Full article

The accumulation of solid electrolyte interphases (SEI) in graphite anodes related to elevated formation rates (0.1C, 1C and 2C), cycling rates (1C and 2C), and electrode-separator lamination is investigated. As shown previously, the lamination technique is beneficial for the capacity aging in graphite-LiNi_1/3Mn_1/3Co_1/3O₂ cells. Here, surface resistance growth phenomena are quantified using electrochemical impedance spectroscopy (EIS). The graphite anodes were extracted from the graphite NMC cells in their fully discharged state and irreversible accumulations of lithium in the SEI are revealed using neutron depth profiling (NDP). In this post-mortem study, NDP reveals uniform lithium accumulations as a function of depth with lithium situated at the surface of the graphite particles thus forming the SEI. The SEI was found to grow logarithmically with cycle number starting with the main formation in the initial cycles. Furthermore, the EIS measurements indicate that benefits from lamination arise from surface resistance growth phenomena aside from SEI growth in superior anode fractions. Full article

Temperature has a significant influence on the behavior of batteries and their lifetime. There are several studies in literature that investigate the aging behavior under electrical load, but are limited to homogeneous, constant temperatures. This article presents an approach to quantifying cyclic aging of lithium-ion cells that takes into account complex thermal boundary conditions. It not only considers different temperature levels but also spatial and transient temperature gradients that can occur despite-or even due to-the use of thermal management systems. Capacity fade and impedance rise are used as measured quantities for degradation and correlated with the temperature boundary conditions during the aging process. The concept and definition of an equivalent aging temperature (EAT) is introduced to relate the degradation caused by spatial and temporal temperature inhomogeneities to similar degradation caused by a homogeneous steady temperature during electrical cycling. The results show an increased degradation at both lower and higher temperatures, which can be very well described by two superimposed exponential functions. These correlations also apply to cells that are cycled under the influence of spatial temperature gradients, both steady and transient. Only cells that are exposed to transient, but spatially homogeneous temperature conditions show a significantly different aging behavior. The concluding result is a correlation between temperature and aging rate, which is expressed as degradation per equivalent full cycle (EFC). This enables both temperature-dependent modeling of the aging behavior and its prediction. Full article

Driven by the increasing plea for greener transportation and efficient integration of renewable energy sources, Ni-rich metal layered oxides, namely NMC, Li [Ni_1−x−yCo_yMn_z] O₂ (x + y ≤ 0.4), and NCA, Li [Ni_1−x−yCo_xAl_y] O₂, cathode materials have garnered huge attention for the development of Next-Generation lithium-ion batteries (LIBs). The impetus behind such huge celebrity includes their higher capacity and cost effectiveness when compared to the-state-of-the-art LiCoO₂ (LCO) and other low Ni content NMC versions. However, despite all the beneficial attributes, the large-scale deployment of Ni-rich NMC based LIBs poses a technical challenge due to less stability of the cathode/electrolyte interphase (CEI) and diverse degradation processes that are associated with electrolyte decomposition, transition metal cation dissolution, cation–mixing, oxygen release reaction etc. Here, the potential degradation routes, recent efforts and enabling strategies for mitigating the core challenges of Ni-rich NMC cathode materials are presented and assessed. In the end, the review shed light on the perspectives for the future research directions of Ni-rich cathode materials. Full article

As storage technology in electric vehicles, lithium-ion cells are subject to a continuous aging process during their service life that, in the worst case, can lead to a premature system failure. Battery manufacturers thus have an interest in the aging prediction during the early design phase, for which semi-empirical aging models are often used. The progress of aging is dependent on the application-specific load profile, more precisely on the aging-relevant stress factors. Still, a literature review reveals a controversy on the aging-relevant stress factors to use as input parameters for the simulation models. It shows that, at present, a systematic and efficient procedure for stress factor selection is missing, as the aging characteristic is cell-specific. In this study, an accelerated sensitivity analysis as a prior step to aging modeling is proposed, which is transferable and allows to determine the actual aging-relevant stress factors for a specific lithium-ion cell. For the assessment of this accelerated approach, two test series with different acceleration levels and cell types are performed and evaluated. The results show that a certain amount of charge throughput, 100 equivalent full cycles in this case, is necessary to conduct a statistically significant sensitivity analysis. Full article

To draw reliable conclusions about the thermal characteristic of or a preferential cooling strategy for a lithium–ion battery, the correct set of thermal input parameters and a detailed battery layout is crucial. In our previous work, an electrochemical model for a commercially-available, 40 $\mathrm{Ah}$ prismatic lithium–ion battery was validated under heuristic temperature dependence. In this work the validated electrochemical model is coupled to a spatially resolved, three dimensional (3D), thermal model of the same battery to evaluate the thermal characteristics, i.e., thermal barriers and preferential heat rejection patterns, within common environment layouts. We discuss to which extent the knowledge of the batteries’ interior layout can be constructively used for the design of an exterior battery thermal management. It is found from the study results that: (1) Increasing the current rate without considering an increased heat removal flux at natural convection at higher temperatures will lead to increased model deviations; (2) Centralized fan air-cooling within a climate chamber in a multi cell test arrangement can lead to significantly different thermal characteristics at each battery cell; (3) Increasing the interfacial surface area, at which preferential battery interior and exterior heat rejection match, can significantly lower the temperature rise and inhomogeneity within the electrode stack and increase the batteries’ lifespan. Full article