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The chemical diffusion coefficient in LiNi1/3Mn1/3Co1/3O2 was determined via the galvanostatic intermittent titration technique in the voltage range 3 to 4.2 V. Calculated diffusion coefficients in these layered oxide cathodes during charging and discharging reach a minimum at the open-circuit voltage of 3.8 V and 3.7 V vs. Li/Li+, respectively. The observed minima of the chemical diffusion coefficients indicate a phase transition in this voltage range. The unit cell parameters of LiNi1/3Mn1/3Co1/3O2 cathodes were determined at different lithiation states using ex situ crystallographic analysis. It was shown that the unit cell parameter variation correlates well with the observed values for chemical diffusion in NMC cathodes; with a notable change in absolute values in the same voltage range. We relate the observed variation in unit cell parameters to the nickel conversion into the trivalent state, which is Jahn-Teller active, and to the re-arrangement of lithium ions and vacancies., Graphical Abstract

The end-of-life event of the battery system of an electric vehicle is defined by a fixed end-of-life threshold value. However, this kind of end-of-life threshold does not capture the application and battery characteristics and, consequently, it has a low accuracy in describing the real end-of-life event. This paper proposes a systematic methodology to determine the end-of-life threshold that describes accurately the end-of-life event. The proposed methodology can be divided into three phases. In the first phase, the health indicators that represent the aging behavior of the battery are defined. In the second phase, the application specifications and battery characteristics are evaluated to generate the end-of-life criteria. Finally, in the third phase, the simulation environment used to calculate the end-of-life threshold is designed. In this third phase, the electric-thermal behavior of the battery at different aging conditions is simulated using an electro-thermal equivalent circuit model. The proposed methodology is applied to a high-energy electric vehicle application and to a high-power electric vehicle application. The stated hypotheses and the calculated end-of-life threshold of the high-energy application are empirically validated. The study shows that commonly assumed 80 or 70% EOL thresholds could lead to mayor under or over lifespan estimations. The iModBatt project has received funding from the European Union’s Horizon 2020 Programme for research and innovation under Grant Agreement No. 770054.

Thanks to its exceptional performance in terms of high energy and power density as well as long lifespan, the lithium-ion secondary battery is the most relevant electrochemical energy storage technology to meet the requirements for partial or full electrification of vehicles (plug-in hybrids or pure electric vehicles), and thanks to decreasing cost and ongoing technical improvements, it will maintain this role in the near to mid-term future. This study benchmarks eight different (five 21700 and three 18650 format) high-energy cylindrical cells concerning their suitability for automotive applications and aims to give a holistic overview and comparison between them. Therefore, an ante-mortem material analysis, a benchmark of electrical and thermal values as well as a cycle life study were carried out. The results show that even when applying similar concepts like Nickel-rich cathodes with graphite-based anodes, the cells show wide variations in their performance under the same test conditions.

Lithium-sulfur (Li–S) batteries are considered promising candidates for next-generation energy storage devices due to their ultrahigh theoretical gravimetric energy density, cost-effectiveness, and environmental friendliness. However, the application of Li–S batteries remains challenging; mainly due to a lack of understanding of the complex chemical reactions and associated equilibria that occur in a working Li–S system. A new approach preparing graphene-based active cathode materials of Li-S battery with spatially confined lithium sulfides is reported. The starting graphene-embedded 2D-MoS2 was synthesized by a solvothermal method in organic solvents followed by the calcination of trapped organic solvent molecules at 800 °C to give graphene single sheets inside the 2D-MoS2 layers with 7 A distance (MoS2-Gr-32.51). Then, it was electrochemically reduced/lithiated at potential 0.01 V vs Li+/Li generating metallic molybdenum and lithium sulfides. As a result, the structure of MoS2 multi-layers collapsed. The graphene multi-layer (ML-Graphene) was left behind and shut the lithium sulfides between the layers. The sizes of Li2Sn (n = 4–6) are bigger than the inter-layer distance of ML-Graphene, and the escape of sulfur/sulfides from the cathode into the electrolyte is physically blocked alleviating shuttle effects. The specific capacity of ML-Graphene/lithium sulfides cathode was high of 1209 mAh/gMoS2-Gr at 0.1 C (1 C = 670 mA/g). The ML-Graphene exhibited the remarkable lithium intercalation capability, and the theoretical calculation has been carried out to give 2231.4 mAh/g. Such high capacity was hybridized with the theoretical capacity of sulfur (1675 mAh/g), and the ML-Graphene composite with dichalcogenides (2D-MoS2) became a promising platform for the cathode of Li-S batteries.

Tin (IV) sulfide is a promising anode active material for lithium ion batteries due to its relatively high reversible capacity of 644 mAh/g, which is more than one and a half times that of graphite. During lithiation of tin (IV) sulfide, an inert Li2S matrix is formed in the first discharge cycle, which serves to accommodate the mechanical stresses associated with the volume expansion of tin during the successive LixSn alloying and de-alloying reactions. In order to improve the electrochemical performance of tin (IV) sulfide further, fundamental understanding and insights into the thermodynamics, phase formation, and driving forces for the lithiation reactions are still required. Therefore, in this work, a computational thermodynamics approach was combined with ex-situ XRD investigations of electrodes during the discharge reaction as well as galvanostatic intermittent titration technique (GITT) experiments in order to clarify the lithiation thermodynamics of tin (IV) sulfide. Based on the experimental data, a one-phase mechanism was suggested for the intercalation of lithium into SnS2, a thermodynamic model was developed to describe the intercalation reaction and the expected open circuit voltages were calculated.

Lithium-Ion batteries are the key technology to power mobile devices, all types of electric vehicles, and for use in stationary energy storage. Much attention has been paid in research to improve the performance of active materials for Lithium-Ion batteries, however, for optimal, long and safe operation, detailed knowledge of -among others- the state-of-charge and the state-of-health of the battery is paramount both in laboratory use, as well as during application by the battery management system. Today’s systems often derive their estimators from data of the voltage, current and temperature measurements, which can lead to inaccurate estimations of values during operation. Mechanical based measurements became very popular recently to fill the gap in data by complementing conventional measurements and thus provide more accurate information about the internal state of Lithium-Ion batteries. This review aims to present the current state of this promising topic for both laboratory use and applications on non-destructive in-situ and in-operando methods for measurement of mechanical battery parameters like expansion, strain and force, experimental modal analysis, ultrasonic probing and acoustic emission technologies. The intention of this summary is to provide insights in this emerging topic by showing benefits, drawbacks, possibilities and applications of each technique and compare those to each other, thus providing the readers with a deep insight into the topic.

Surface degradation of Ni-enriched layered cathode material Li[Ni0.6Mn0.2Co0.2]O2 (NMC622) is the main reason that leads to large capacity decay during long-term cycling. In the frame of this research, an amorphous SiO2 coating was applied onto the surface of the commercially available NMC622 powder by a wet coating process, through the condensation reaction of tetraethyl orthosilicate. The chemical composition of the coating layer was analyzed by inductively-coupled plasma. The morphology was studied by scanning electron microscopy and transmission electron microscopy. Electrochemical properties, including cyclic voltammetry, galvanostatic cycling, and rate capability measurements in a half-cell configuration, were tested to compare the electrochemical behavior of the non-coated and coated NMC622 materials. It is shown that the rate performance of the NMC622 materials is not affected by the coating layer. After 700 cycles in the range of 3.0&ndash, 4.3 V at 2 C discharge, the cells with SiO2-coated NMC622 materials retained 80% of their initial capacity, which is higher than the uncoated ones (74%). Physicochemical characterizations, e.g., XRD and SEM, were performed post-mortem to reveal the stabilizing mechanism of the SiO2-coated NMC622 electrodes after long-term cycling. Based on these results, this is due to the shielding effect of the coating between the NMC622 particle surface and the liquid electrolyte, along with its scavenging effect on HF. SiO2 coating is therefore a facile surface modification method that results in potentially significant enhancement of the cyclic stability of Ni-rich NMC materials.

Development of future battery generations and quality control of current lithium-ion battery (LIB) systems require reliable techniques for the characterization of the complex dynamic processes in batteries. Electrochemical impedance spectroscopy (EIS) is an established tool for the electrochemical characterization of LIBs and the related ageing processes. Nevertheless, ensuring a reliable interpretation and validation of the impedance data remains challenging. Here we show how EIS complemented by microscopy data can be successfully used to follow battery ageing. We connect data from both methods in an electrochemical finite element model (FEM) to extract changes of intrinsic battery parameters, such as double layer capacitance, film resistance, exchange current density, and particle radii. Ageing mechanisms induced by cycling and temperature are investigated by EIS on commercial cells. Postmortem analysis of the anode and cathode electrodes is carried out to determine their initial micrometric and nanometric structure and to independently investigate morphological and electrical changes induced by ageing. While the obtained initial structural dimensions reduce drastically the number of adjustable parameters in the FEM model, which enables us to follow battery ageing processes noninvasively through the EIS spectra, the microscopy results of the aged cells prove independently the validity of the here presented approach.