Batteries

The safety requirements in vehicles continuously increase due to more automated functions using electronic components. Besides the reliability of the components themselves, a reliable power supply is crucial for a safe overall system. Different architectures for a safe power supply consider the lead battery as a backup solution for safety-critical applications. Various ageing mechanisms influence the performance of the battery and have an impact on its reliability. In order to qualify the battery with its specific failure modes for use in safety-critical applications, it is necessary to prove this reliability by failure rates. Previous investigations determine the fixed failure rates of lead batteries using data from teardown analyses to identify the battery failure modes but did not include the lifetime of these batteries examined. Alternatively, lifetime values of battery replacements in workshops without knowing the reason for failure were used to determine the overall time-dependent failure rate. This study presents a method for determining reliability models of lead batteries by investigating individual failure modes. Since batteries are subject to ageing, the analysis of lifetime values of different failure modes results in time-dependent failure rates of different magnitudes. The failure rates of the individual failure modes develop with different shapes over time, which allows their ageing behaviour to be evaluated. 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

Increasingly stringent emission regulations and environmental concerns have propelled the development of electrification technology in the transport industry. Yet, the greatest hurdle to developing fully electric vehicles is electrochemical energy storage, which struggles to achieve profitable specific power, specific energy and cost targets. Hybrid energy storage systems (HESSs), which combine energy- and power-optimised sources, seem to be the most promising solution for improving the overall performance of energy storage. The potential for gravimetric and volumetric reduction is strictly dependent on the overall power-to-energy ratio (PE ratio) of the application, packaging factors, the minimum and maximum PE ratio achievable for the system’s energy- and power-optimised sources and the performance of power electronics. This paper presents a simple optimisation methodology that considers these factors and identifies the optimal HESS requirements that may present new opportunities for a variety of vehicles where low weight and volume are of high importance. The simplicity of the method means that decisions relating to a HESS can be made earlier in the system design process. This method of analysis showed that a battery HESS has the potential to reduce cell mass and volume by over 30% for applications that are well suited to optimal HESS characteristics. Full article

The distribution of relaxation times (DRT) analysis of impedance spectra is a proven method to determine the number of occurring polarization processes in lithium-ion batteries (LIBs), their polarization contributions and characteristic time constants. Direct measurement of a spectrum by means of electrochemical impedance spectroscopy (EIS), however, suffers from a high expenditure of time for low-frequency impedances and a lack of general availability in most online applications. In this study, a method is presented to derive the DRT by evaluating the relaxation voltage after a current pulse. The method was experimentally validated using both EIS and the proposed pulse evaluation to determine the DRT of automotive pouch-cells and an aging study was carried out. The DRT derived from time domain data provided improved resolution of processes with large time constants and therefore enabled changes in low-frequency impedance and the correlated degradation mechanisms to be identified. One of the polarization contributions identified could be determined as an indicator for the potential risk of plating. The novel, general approach for batteries was tested with a sampling rate of 10 Hz and only requires relaxation periods. Therefore, the method is applicable in battery management systems and contributes to improving the reliability and safety of LIBs. Full article

A unified evaluation framework for stochastic tools is developed in this paper. Firstly, we provide a set of already existing quantitative and qualitative metrics that rate the relevant aspects of the performance of a stochastic prognosis algorithm. Secondly, we provide innovative guidelines to detect and minimize the effect of side aspects that interact on the algorithms’ performance. Those aspects are related with the input uncertainty (the uncertainty on the data and the prior knowledge), the parametrization method and the uncertainty propagation method. The proposed evaluation framework is contextualized on a Lithium-ion battery Remaining Useful Life prognosis problem. As an example, a Particle Filter is evaluated. On this example, two different data sets taken from NCA aged batteries and two semi-empirical aging models available in the literature fed up the Particle Filter under evaluation. The obtained results show that the proposed framework gives enough details to take decisions about the viability of the chosen algorithm. Full article

The present study aimed to evaluate the factors that influence the formation of sodium hydroxide (NaOH) by means of an electrolytic cell with ion exchange membranes. To achieve this experiment, the NaOH production cell had to be designed and built inexpensively, using graphite electrodes. The operational parameters in our study were: initial NaOH concentration, applied voltage, and temperature. All experiments were carried out using model NaCl solutions with a concentration of 40 g/L for 150 min. The results of the experiment were that the NaOH concentration, conductivity, and pH presented an increasing linear trend with the electrolysis time. Finally, it was possible to obtain the efficiency level of the electric current in our investigation, which was an average of 80.2%, that indicated good performance of the built cell. Full article

In this study, the importance of the preparation technique of Li₄Ti₅O₁₂ (LTO) anode on its performance in a lithium-ion capacitor (LIC) application was investigated. These desired characteristics include energy density, rate capability, and cycle life. The samples were prepared using three approaches, and the same sol-gel synthesis procedure is applied to obtain phase-pure samples and keep the structural properties similar. The influence of these methods on the LTO anodes was then explored in both half-cell and full-cell LIC devices with an activated carbon (AC) cathode. It was observed that the samples had similar specific capacities and energy densities at low specific currents. However, significant differences were observed in the samples’ morphological properties, the rate capability, and the full-cell cycle life performance. Electrochemical impedance spectroscopy was used to identify the electrochemical kinetics and revealed that the LIC with the best performance was influenced by the LTO anode having the least charge transfer and diffusion resistances prepared using a surfactant. This was due to the small particle size, good particle dispersion, and high specific surface area of the LTO anode. This result points to the importance of the choice of synthesis technique in LIC material’s overall performance. Full article

The reuse and repurposing of lithium-ion batteries for transportation in stationary energy systems improve the economic value of batteries. A precise suitability test at the beginning of the second life is therefore necessary. Common methods such as electrochemical impedance spectroscopy (EIS) and current interrupt (CI) analysis, as well as capacity analysis, can be used for testing. In this paper, these methods are studied from the aspects of test duration, sensitivity and acquisition costs of the measuring instruments. For this purpose, tests are carried out on battery modules, which were used for transportation. It is shown that subtle differences are better detected with EIS and less accurately with the CI method. The test duration is fastest with the CI method, followed by EIS and the capacity test. Strongly aged modules are reliably detected with all methods. Full article

Novel intelligent battery systems are gaining importance with functional hardware on the cell level. Cell-level hardware allows for advanced battery state monitoring and thermal management, but also leads to additional thermal interactions. In this work, an electro-thermal framework for the modeling of these novel intelligent battery cells is provided. Thereby, a lumped thermal model, as well as a novel neural network, are implemented in the framework as thermal submodels. For the first time, a direct comparison of a physics-based and a data-driven thermal battery model is performed in the same framework. The models are compared in terms of temperature estimation with regard to accuracy. Both models are very well suited to represent the thermal behavior in novel intelligent battery cells. In terms of accuracy and computation time, however, the data-driven neural network approach with a Nonlinear AutoregRessive network with eXogeneous input (NARX) shows slight advantages. Finally, novel applications of temperature prediction in battery electric vehicles are presented and the applicability of the models is illustrated. Thereby, the conventional prediction of the state of power is extended by simultaneous temperature prediction. Additionally, temperature forecasting is used for pre-conditioning by advanced cooling system regulation to enable energy efficiency and fast charging. Full article

A low-pressure drop stack design with minimal shunt losses was explored for vanadium redox flow batteries, which, due to their low energy density, are used invariably in stationary applications. Three kilowatt-scale stacks, having cell sizes in the range of 400 to 1500 cm², were built with thick graphite plates grooved with serpentine flow fields and external split manifolds for electrolyte circulation, and they were tested over a range of current densities and flow rates. The results show that stacks of different cell sizes have different optimal flow rate conditions, but under their individual optimal flow conditions, all three cell sizes exhibit similar electrochemical performance including stack resistivity. Stacks having larger cell sizes can be operated at lower stoichiometric factors, resulting in lower parasitic pumping losses. Further, these can be operated at a fixed flow rate for power variations of ±25% without any significant changes in discharge capacity and efficiency; this is attributed to the use of serpentine flow fields, which ensure uniform distribution of the electrolyte over a range of flow rates and cell sizes. Full article

Due to the increasing demand for battery electric vehicles (BEVs), the need for vehicle battery raw materials is increasing. The traction battery (TB) of an electric vehicle, usually a lithium-ion battery (LIB), represents the largest share of a BEV’s CO₂ footprint. To reduce this carbon footprint sustainably and to keep the raw materials within a closed loop economy, suitable and efficient recycling processes are essential. In this life cycle assessment (LCA), the ecological performance of a waterjet-based direct recycling process with minimal use of resources and energy is evaluated; only the recycling process is considered, waste treatment and credits for by-products are not part of the analysis. Primary data from a performing recycling company were mainly used for the modelling. The study concludes that the recycling of 1 kg of TB is associated with a global warming potential (GWP) of 158 g CO₂ equivalents (CO₂e). Mechanical removal using a water jet was identified as the main driver of the recycling process, followed by an air purification system. Compared to conventional hydro- or pyrometallurgical processes, this waterjet-based recycling process could be attributed an 8 to 26 times lower GWP. With 10% and 20% reuse of recyclate in new cells, the GWP of TBs could be reduced by 4% and 8%, respectively. It has been shown that this recycling approach can be classified as environmentally friendly. 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

Although lithium-sulfur (Li-S) batteries are one of the promising candidates for next-generation energy storage, their practical implementation is limited by rapid capacity fading due to lithium polysulfide (LiPSs) formation and the low electronic conductivity of sulfur. Herein, we report a high-performance lithium-sulfur battery based on multidimensional cathode architecture consisting of nanosulfur, graphene nanoplatelets (2D) and multiwalled carbon nanotubes (1D). The ultrasonic synthesis method results in the generation of sulfur nanoparticles and their intercalation into the multilayered graphene nanoplatelets. The optimized multidimensional graphene-sulfur-CNT hybrid cathode (GNS58-CNT10) demonstrated a high specific capacity (1067 mAh g⁻¹ @ 50 mA g⁻¹), rate performance (539 @ 1 A g⁻¹), coulombic efficiency (~95%) and cycling stability (726 mAh g⁻¹ after 100 cycles @ 200 mA g⁻¹) compared to the reference cathode. Superior electrochemical performances are credited to the encapsulation of nanosulfur between the individual layers of graphene nanoplatelets with high electronic conductivity, and effective polysulfide trapping by MWCNT bundles. 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

During the operation of the negative electrode, some critical processes take place, which are limiting factors for the operation of lead–acid batteries. To improve the efficiency of the negative active material and minimize these processes, external application of multivector field is proposed. Two applications of the multivector field are studied: during negative paste preparation and during formation. It is established that, when applying multivector field during negative paste preparation, the chemical processes proceed more efficiently. The results are better phase composition and crystallinity of the cured paste, thus increasing the capacity of the consequently built lead batteries by 12% on average. The application of a multivector field during the formation of negative active materials in lead batteries has a positive effect on the skeletal structure, the size and shape of the Pb crystals. This ensures longer service life, which is confirmed by the 17.5% Depth of Discharge continuous tests on 12 V/75 Ah batteries. The batteries formed under the influence of external multivector field showed 20% longer cycle life. Based on the experimental result, a most probable mechanism of the influence of the multivector field on the chemical and electrochemical processes in lead batteries during negative paste preparation and formation of negative active masses is proposed. 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

Float currents are steady-state self-discharge currents after a transient phase—caused by anode overhang, polarization, etc.—is accomplished. The float current is measured in this study with a standard test bench for five 18650 cells (Samsung 25R) at potentiostatic conditions while the temperature is changed in 5 K steps from 5 °C to 60 °C. The entire test is performed in about 100 days resulting in 12 measurement points per cell potential for an Arrhenius representation. The float current follows the Arrhenius law with an activation energy of about 60 kJ/mol. The capacity loss measured at reference condition shows a high correlation to the results of float currents analysis. In contrast to classical calendar aging tests, the performed float current analysis enables determining the aging rate with high precision down to at least 10 °C. Returning from higher temperatures to 30 °C reference temperature shows reducing float currents at 30 °C for increasing temperature steps that may originate from an hysteresis effect that has to be investigated in future publications. Full article

A structural model of LiPON solid electrolyte, containing elements that simulate drift conductivity, diffusion conductivity, and leakage current was proposed. The dependence of the impedance of the structural model on frequency was calculated, and the parameters of the model at which the theoretical curve best approximates the experimental Nyquist diagrams were determined. Based on these data, the ion diffusion coefficient and conductivity of LiPON were calculated, which are D₁ = 1.5 × 10⁻¹¹ cm²/s and σ = 1.9 × 10⁻⁶ S/cm, respectively. Full article