Abstract The structural and interfacial stability of silicon-based and lithium metal anode materials is essential to their battery performance. Scientists are looking for a better inactive material to buffer strong volume change and suppress unwanted surface reactions of these anodes during cycling. Lithium silicates formed in situ during the formation cycle of silicon monoxide anode not only manage anode swelling but also avoid undesired interfacial interactions, contributing to the successful commercialization of silicon monoxide anode materials. Additionally, lithium silicates have been further utilized in the design of advanced silicon and lithium metal anodes, and the results have shown significant promise in the past few years. In this review article, we summarize the structures, electrochemical properties, and formation conditions of lithium silicates .Their applications in advanced silicon and lithium metal anode materials are also introduced.

Abstract All-solid-state batteries (ASSBs) are gaining traction in the arena of energy storage due to their promising results in producing high energy density and long cycle life coupled with their capability of being safe. The key challenges facing ASSBs are low conductivity and slow charge transfer kinetics at the interface between the electrode and the solid electrolyte. Garnet solid-state electrolyte has shown promising results in improving the ion conductivity but still suffers from poor capacity retention and rate performance due to the interfacial resistance between the electrodes. To im prove the interfacial resistance, we prepared a composite consisting of Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) garnet material as the ceramic, polyethylene oxide (PEO) as the polymer, and lithium hexafluorophosphate (LiPF6) as the salt. These compounds are mixed in a stoichiometric ratio and developed into a very thin disc-shaped solid electrolyte. The LLCZN provides a lithium-ion transport path to enhance the lithium-ion conduction during charging and discharging cycles, while the LiPF6 contributes more lithium ions via the transport path. The PEO matrix in the composite material aids in bonding the compounds together and creating a large contact area, thereby reducing the issue of large interfacial resistance. FESEM images show the porous nature of the electrolyte which promotes the movement of lithium ions through the electrolyte. The fabricated LLCZN/PEO/LiPF6 solid-state electrolyte shows outstanding electrochemical stability that remains at 130 mAh g−1 up to 150 charging and discharging cycles at 0.05 mA cm−2current. All the specific capacities were calculated based on the mass of the cathode material (LiCoO2). In addition, the coin cell retains 85% discharge capacity up to 150 cycles with a Coulombic efficiency of approximately 98% and energy efficiency of 90% during the entire cycling process.

Abstract Li-ion batteries as a support for future transportation have the advantages of high storage capacity, a long life cycle, and the fact that they are less dangerous than current battery materials. Li ion battery components, especially the cathode, are the intercalation places for lithium, which plays an important role in battery performance. This study aims to obtain the LiNixMnyCozO2 (NMC) cathode material using a simple flash coprecipitation method. As precipitation agents and pH regulators, oxalic acid and ammonia are widely available and inexpensive. The composition of the NMC mole ratio was varied, with values of 333, 424, 442, 523, 532, 622, and 811. As a comprehensive study of NMC, lithium transition-metal oxide (LMO, LCO, and LNO) is also provided. The crystal structure,functional groups, morphology, elemental composition and material behavior of the particles were all investigated during the heating process. The galvanostatic charge–discharge analysis was tested with cylindrical cells and using mesocarbon microbeads/graphite as the anode. Cells were tested at 2.7–4.25 V at 0.5 C. Based on the analysis results, NMC with a mole ratio of 622 showed the best characteristicd and electrochemical performance. After 100 cycles, the discharged capacity reaches 153.60 mAh/g with 70.9% capacity retention.

Abstract Graphite as a commercial anode for lithium-ion batteries has significant safety concerns owing to lithium dendrite growth at low operating voltages. Li4Ti5O12 is a potential candidate to replace graphite as the next-generation anode of lithium-ion batteries. In this work, fluoride-doped Li4Ti5O12 was successfully synthesized with a direct double coating of carbon and nitrogen using a solid-state method followed by the pyrolysis process of polyaniline. X-ray diffraction (XRD) results show that the addition of fluoride is successfully doped to the spinel-type structure of Li4Ti5O12 without any impurities being detected. The carbon and nitrogen coating are distributed on the surface of Li4Ti5O12 particles, as shown in the Scanning Electron Microscopy–Energy Dispersive X-ray Spectroscopy (SEM-EDS) image. The Transmission Electron Microscopy (TEM) image shows a thin layer of carbon coating on the Li4Ti5O12 surface. The fluoride-doped Li4Ti5O12 has the highest specific discharge capacity of 165.38 mAh g−1 at 0.5 C and capacity fading of 93.51% after 150 cycles compared to other samples, indicating improved electrochemical performance. This is attributed to the synergy between the appropriate amount of carbon and nitrogen coating, which induced a high mobility of electrons and larger crystallite size due to the insertion of fluoride to the spinel-type structure of Li4Ti5O12, enhancing lithium-ion transfer during the insertion/extraction process.

Abstract Both the binder and solid–electrolyte interface play an important role in improving the cycling stability of electrodes for Na-ion batteries. In this study, a novel tetrabutylammonium (TBA) alginate binder is used to prepare a Na0.67MnO2 electrode for sodium-ion batteries with improved electrochemical performance. The ageing of the electrodes is characterized. TBA alginate-based electrodes are compared to polyvinylidene fluoride- (PVDF) and Na alginate-based electrodes and show favorable electrochemical performance, with gravimetric capacity values of up to 164 mAh/g,which is 6% higher than measured for the electrode prepared with PVDF binder. TBA alginate-based electrodes also display good rate capability and improved cyclability. The solid–electrolyte interface of TBA alginate-based electrodes is similar to that of PVDF-based electrodes. As the only salt of alginic acid soluble in non-aqueous solvents, TBA alginate emerges as a good alternative to PVDF binder in battery applications where the water-based processing of electrode slurries is not feasible,such as the demonstrated case with Na0.67MnO2.

Abstract 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.

Abstract 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.

Abstract Lithium-ion batteries have been commonly employed as power sources in portable devices and are of great interest for large-scale energy storage. To further enhance the fundamental under standing of the electrode structure, we report on the use of multi-wavelength Raman spectroscopy for the detailed characterization of layered cathode materials for Li-ion batteries (LiCoO2, LiNixCo1−xO2,LiNi1/3Mn1/3Co1/3O2). Varying the laser excitation from the UV to the visible (257, 385, 515, 633 nm)reveals wavelength-dependent changes in the vibrational profile and overtone/combination bands,originating from resonance effects in LiCoO2. In mixed oxides, the influence of resonance effects on the vibrational profile is preserved but mitigated by the presence of Ni and/or Mn, highlight ing the influence of resonance Raman spectroscopy on electronic structure changes. The use of UV laser excitation (257, 385 nm) is shown to lead to a higher scattering efficiency towards Ni in LiNi1/3Mn1/3Co1/3O2 compared to visible wavelengths, while deep UV excitation at 257 nm allows for the sensitive detection of surface species and/or precursor species reminiscent of the synthesis. Our results demonstrate the potential of multi-wavelength Raman spectroscopy for the detailed char acterization of cathode materials for lithium-ion batteries, including phase/impurity identification and quantification, as well as electronic structure analysis.

Abstract Fast-switching semiconductors induce ripple currents on the high-voltage DC bus in the electric vehicle (EV). This paper describes the methods used in the project SiCWell and a new approach to investigate the influence of these overlaid ripples on the battery in EVs. The ripple current generated by the main inverter is demonstrated with a measurement obtained from an electric vehicle. A simulation model is presented which is based on an artificial reference DC bus, according to ISO 21498-2, and uses driving cycles in order to obtain current profiles relevant for battery cycling. A prototype of a battery cycling tester capable of high frequency and precise ripple current generation was developed and is used to cycle cells with superimposed ripple currents within an aging study. To investigate the impact of the frequency and the amplitude of the currents on the battery’s lifetime, these ripple parameters are varied between different test series. Cell parameters such as impedance and capacity are regularly characterized and the aging of the cells is compared to standard DC cycled reference cells. The aging study includes a total of 60 automotive-sized pouch cells. The evaluation of ripple currents and their impact on the battery can improve the state-of-health diagnosis and remaining-useful life prognosis. For the development and validation of such methods, the cycled cells are monitored with a measurement system that regularly measures current and voltage with a sampling rate of 2 MHz. The resulting dataset is suitable for the design of future ripplecurrent aging studies as well as for the development and validation of aging models and methods for battery diagnosis.

Abstract 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.

Abstract This paper addresses the thermal management of a solid polymer electrolyte battery system, which is currently the only commercialized solid-state battery chemistry. These batteries aim to increase the range of electric vehicles by facilitating a lithium metal anode but are limited by operational temperatures above 60 ◦C. The feasibility of a cold start procedure is examined, which would enable a solid polymer battery to be used, without preconditioning, in a wide variety of ambient temperatures. The proposed solution involves dividing the solid-state battery into smaller sub-packs, which can be heated and brought online more quickly. Thermal modelling shows a cold start procedure is theoretically feasible when using a small liquid electrolyte lithium battery at the start. The key bottlenecks are the rate at which the solid-state batteries can be heated, and the discharge rates they can provide. After resistive heating is used for the first solid-state module, all subsequent heating can be provided by waste heat from the motor and operating battery modules. Due to the insulation required, the proposed system has lower volumetric, but higher gravimetric energy density than liquid electrolyte systems. This work suggests that with suitable system-level design, solid-state batteries could be widely adopted despite temperature constraints.

Abstract Rapidly warming up batteries is an important challenge both for conventional lithium-ion batteries, which operate best over 15 ◦C, and for most solid-state batteries, which currently require operating temperatures over 60 ◦C. Internal heating using an alternating current (AC) has been proposed as a possible solution in automotive applications, with faster heating rates possible than conventional external heating methods. This paper investigates the performance of internal AC heating on cells of different sizes, for both cylindrical and pouch formats. A novel experimental arrangement is used in which two cells are tested in series while connected with opposing polarity to create a zero-voltage string, allowing the use of less expensive testing equipment. The results show that larger cells exhibit a considerably greater distribution of surface temperature than smaller format cells during internal heating. This is likely due to the more extreme spatial variation in current density in the current collectors, causing an uneven distribution of internal heat generation. This highlights a significant difference compared to external heating methods, which are not affected by this, and has important implications for temperature measurement and battery management if this type of internal heating is to be used, since temperature sensors must be placed in hot spots or supplemented by validated models to ensure all parts of the battery stay within safe temperature limits.

Abstract This paper shows the potential of artificial intelligence (AI) in Li-ion battery charging methods by introducing a new charging algorithm based on artificial neural networks (ANNs). The proposed charging algorithm is able to find an optimized charging current profile, through ANNs, considering the real-time conditions of the Li-ion batteries. To test and validate the proposed approach, a low-cost battery management system (BMS) was developed, supporting up to 168 cells in series and n cells in parallel. When compared with the multistage charging algorithm, the proposed charging algorithm revealed a shorter charging time (7.85%) and a smaller temperature increase (32.95%). Thus, the results show that the proposed algorithm based on AI is able to effectively charge and balance batteries and can be regarded as a subject of interest for future research.

Abstract The localisation and quantitative analysis of lithium (Li) in battery materials, components,and full cells are scientifically highly relevant, yet challenging tasks. The methodical developments of MeV ion beam analysis (IBA) presented here open up new possibilities for simultaneous elemental quantification and localisation of light and heavy elements in Li and other batteries. It describes the technical prerequisites and limitations of using IBA to analyse and solve current challenges with the example of Li-ion and solid-state battery-related research and development. Here, nuclear reaction analysis and Rutherford backscattering spectrometry can provide spatial resolutions down to 70 nm and 1% accuracy. To demonstrate the new insights to be gained by IBA, SiOx-containing graphite anodes are lithiated to six states-of-charge (SoC) between 0–50%. The quantitative Li depth profiling of the anodes shows a linear increase of the Li concentration with SoC and a match of injected and detected Li-ions. This unambiguously proofs the electrochemical activity of Si. Already at 50% SoC, we derive C/Li = 5.4 (< LiC6) when neglecting Si, proving a relevant uptake of Li by the 8 atom % Si (C/Si ≈ 9) in the anode with Li/Si ≤ 1.8 in this case. Extrapolations to full lithiation show a maximum of Li/Si = 1.04 ± 0.05. The analysis reveals all element concentrations are constant over the anode thickness of 44 µm, except for a ~6-µm-thick separator-side surface layer. Here, the Li and Si concentrations are a factor 1.23 higher compared to the bulk for all SoC, indicating preferential Li binding to SiOx. These insights are so far not accessible with conventional analysis methods and are a first important step towards in-depth knowledge of quantitative Li distributions on the component level and a further application of IBA in the battery community.

Abstract Commercial coin cells with LiNi0.6Mn0.2Co0.2O2 positive electrode material were investigated using an accelerating rate calorimeter and a Tian-Calvet calorimeter. After cycling and charging to the selected states of charge (SOCs), the cells were studied under thermal abuse conditions using the heat-wait-seek (HWS) method with the heating step of 5 K and a threshold for self-heating detection of 0.02 K/min. The onset temperature and the rate of the temperature rise, i.e., the selfheating rate for thermal runaway events, were determined. The morphology of the positive electrode, negative electrode and the separator of fresh and tested cells were compared and investigated with scanning electron microscopy (SEM). Furthermore, the microstructure and the chemical compositions of the individual components were investigated by X-ray diffraction (XRD) and inductively coupled plasma with optical emission spectrometry (ICP-OES), respectively. In the Tian-Calvet calorimeter, the coin cells with the selected SOCs and the individual components (positive electrode, negative electrode and separator) were heated up with a constant heating rate of 0.1 ◦C/min (ramp heating mode). Simultaneously, the heat flow signals were recorded to analyze the heat generation. The combination of the three different methods—the HWS method using the ES-ARC, ramp heating mode on both cells and the individual components using the Tian-Calvet calorimeter—together with a post-mortem analysis, give us a complete picture of the processes leading to thermal runaway.

Abstract A typical method for measuring the radial thermal conductivity of cylindrical objects is the pipe method. This method introduces a heating wire in combination with standard thermocouples and optical Fiber Bragg grating temperature sensors into the core of a cell. This experimental method can lead to high uncertainties due to the slightly varying setup for each measurement and the non-homogenous structure of the cell. Due to the lack of equipment on the market, researchers have to resort to such experimental methods. To verify the measurement uncertainties and to show the possible range of results, an additional method is introduced. In this second method the cell is disassembled, and the thermal conductivity of each cell component is calculated based on measurements with the laser flash method and differential scanning calorimetry. Those results are used to numerically calculate thermal conductivity and to parameterize a finite element model. With this model, the uncertainties and problems inherent in the pipe method for cylindrical cells were shown. The surprising result was that uncertainties of up to 25% arise, just from incorrect assumption about the sensor position. Furthermore, the change in radial thermal conductivity at different states of charge (SOC) was measured with fully functional cells using the pipe method.

Abstract Energy storage plays an important role in the adoption of renewable energy to help solve climate change problems. Lithium-ion batteries (LIBs) are an excellent solution for energy storage due to their properties. In order to ensure the safety and efficient operation of LIB systems, battery management systems (BMSs) are required. The current design and functionality of BMSs suffer from a few critical drawbacks including low computational capability and limited data storage. Recently, there has been some effort in researching and developing smart BMSs utilizing the cloud platform. A cloud-based BMS would be able to solve the problems of computational capability and data storage in the current BMSs. It would also lead to more accurate and reliable battery algorithms and allow the development of other complex BMS functions. This study reviews the concept and design of cloud based smart BMSs and provides some perspectives on their functionality and usability as well as their benefits for future battery applications. The potential division between the local and cloud functions of smart BMSs is also discussed. Cloud-based smart BMSs are expected to improve the reliability and overall performance of LIB systems, contributing to the mass adoption of renewable energy.

Abstract The alkali metal pyroxenes of the AVSi2O6 (A = Li and Na) family have attracted considerable interest as cathode materials for the application in Li and Na batteries. Computer modelling was carried out to determine the dominant intrinsic defects, Li and Na ion diffusion pathways and promising dopants for experimental verification. The results show that the lowest energy intrinsic defect is the V–Si anti-site in both LiVSi2O6 and NaVSi2O6 . Li or Na ion migration is slow, with activation energies of 3.31 eV and 3.95 eV, respectively, indicating the necessity of tailoring these materials before application. Here, we suggest that Al on the Si site can increase the amount of Li and Na in LiVSi2O6 and NaVSi2O6 , respectively. This strategy can also be applied to create oxygen vacancies in both materials. The most favourable isovalent dopants on the V and Si sites are Ga and Ge, respectively.

Abstract Lithium-ion batteries, which have high energy density, are the most suitable batteries for use in high-tech electromechanical applications requiring high performance. Because one of the important components that determines the efficiency of lithium-ion batteries is the electrode, the manufacturing process for this junction plays an important role in the entire production process. In particular, the process related to the resistance spot welding of the electrode is very important, directly affecting the safety of users, and greatly affecting the performance of the batteries. However, because the electrode tab is spot-welded onto the inner surface of the case, it is impossible to verify with visual testing (using the naked eye) whether the junction is well bonded. Therefore, it is very important to perform quality evaluation of the resistance welding of electrodes after completing the manufacturing process, using non-destructive testing methods. In this paper, a non-destructive ultrasonic testing technique was applied to examine the quality of lithium-ion batteries in which the negative electrode tabs were welded to the inner surface of the cell cans. The status of resistance spot welding between the electrode and the can was verified using deep-learning techniques with the experimentally acquired ultrasonic signal database.