Batteries, Volume 3, Issue 2 (June 2017) – 9 articles

In this work, we investigated the effects of heat treatment on the microstructure, hydrogen storage characteristics and corrosion rate of a Ti₃₄V₄₀Cr₂₄Fe₂ alloy. The arc melted alloy was divided into three samples, two of which were separately quartz-sealed under vacuum and heated to 1000 °C for 1 h; one of these samples was quenched and the other furnace-cooled to ambient temperature. The crystal structures of the samples were studied via X-ray diffractometry and scanning electron microscopy. Hydrogenation/dehydrogenation characteristics were investigated using a Sievert apparatus. Potentiostat corrosion tests on the alloys were performed using an AutoLab^® corrosion test apparatus and electrochemical cell. All samples exhibited a major body-center-cubic (BCC) and some secondary phases. An abundance of Laves phases that were found in the as-cast sample reduced with annealing and disappeared in the quenched sample. Beside suppressing Laves phase, annealing also introduced a Ti-rich phase. The corrosion rate, maximum absorption, and useful capacities increased after both heat treatments. The annealed sample had the highest absorption and reversible capacity. The plateau pressure of the as-cast alloy increased after quenching. The corrosion rate increased from 0.0004 mm/y in the as-cast sample to 0.0009 mm/y after annealing and 0.0017 mm/y after quenching. Full article

The number of Stationary Battery Systems (SBS) connected to various power distribution networks across the world has increased drastically. The increase in the integration of renewable energy sources is one of the major contributors to the increase in the number of SBS. SBS are also used in other applications such as peak load management, load-shifting, voltage regulation and power quality improvement. Accurately modeling the charging/discharging characteristics of such SBS at various instances (charging/discharging profile) is vital for many applications. Capacity loss due to the aging of the batteries is an important factor to be considered for estimating the charging/discharging profile of SBS more accurately. Empirical modeling is a common approach used in the literature for estimating capacity loss, which is further used for estimating the charging/discharging profiles of SBS. However, in the case of SBS used for renewable integration and other grid related applications, machine-learning (ML) based models provide extreme flexibility and require minimal resources for implementation. The models can even leverage existing smart meter data to estimate the charging/discharging profile of SBS. In this paper, an analysis on the performance of different ML approaches that can be applied for lithium iron phosphate battery systems and vanadium redox flow battery systems used as SBS is presented for the scenarios where the aging of individual cells is non-uniform. Full article

The demand for batteries for energy storage is growing with the rapid increase in photovoltaics (PV) and wind energy installation as well as electric vehicle (EV), hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV). Electrochemical batteries have emerged as the preferred choice for most of the consumer product applications. Cost reduction of batteries will accelerate the growth in all of these sectors. Lithium-ion (Li-ion) and solid-state batteries are showing promise through their downward price and upward performance trends. We may achieve further performance improvement and cost reduction for Li-ion and solid-state batteries through reduction of the variation in physical and electrical properties. These properties can be improved and made uniform by considering the electrical model of batteries and adopting novel manufacturing approaches. Using quantum-photo effect, the incorporation of ultra-violet (UV) assisted photo-thermal processing can reduce metal surface roughness. Using in-situ measurements, advanced process control (APC) can help ensure uniformity among the constituent electrochemical cells. Industrial internet of things (IIoT) can streamline the production flow. In this article, we have examined the issue of electrochemical battery manufacturing of Li-ion and solid-state type from cell-level to battery-level process variability, and proposed potential areas where improvements in the manufacturing process can be made. By incorporating these practices in the manufacturing process we expect reduced cost of energy management system, improved reliability and yield gain with the net saving of manufacturing cost being at least 20%. Full article

Na₂Ti₃O₇ is a promising negative electrode for rechargeable Na-ion batteries; however, its good properties in terms of insertion voltage and specific capacity are hampered by the poor capacity retention reported in the past. The interfacial and ionic/electronic properties are key factors to understanding the electrochemical performance of Na₂Ti₃O₇. Therefore, its study is of utmost importance. In addition, although rather unexplored, the use of metallic Na in half-cell studies is another important issue due to the fact that side-reactions will be induced when metallic Na is in contact with the electrolyte. Hence, in this work the interfacial and transport properties of full Na-ion cells have been investigated and compared with half-cells upon electrochemical cycling by means of X-ray photoelectron spectroscopy (conventional XPS and Auger parameter analysis) and electrochemical impedance spectroscopy. The half-cell has been assembled with C-coated Na₂Ti₃O₇ against metallic Na whilst the full-cell uses C-coated Na₂Ti₃O₇ as negative electrode and NaFePO₄ as positive electrode, delivering 112 Wh/kg_{anode+cathode} in the 2nd cycle. When comparing both types of cells, it has been found that the interfacial properties, the OCV (open circuit voltage) and the electrode–-electrolyte interphase behavior are more stable in the full-cell than in the half-cell. The electronic transition from insulator to conductor previously observed in a half-cell for Na₂Ti₃O₇ has also been detected in the full-cell impedance analysis. Full article

The archival value of this paper is the investigation of novel methods to recover lead (II) ions from spent lead acid battery electrodes to be used directly as electrolyte for a soluble lead flow battery. The methods involved heating electrodes of spent lead acid batteries in methanesulfonic acid and hydrogen peroxide to dissolve solid lead and lead dioxide out of the electrode material. The processes yielded lead methanesulfonate, which is an electrolyte for the soluble lead acid battery. The lead (II) ions in the electrolyte were identified using Inductively Coupled Plasma Mass Spectroscopy and their electrochemistry confirmed using cyclic voltammetry. The concentration of lead (II) ions was determined and it was found that using the higher concentration of hydrogen peroxide yielded the highest concentration of lead (II) ions. The method was therefore found to be sufficient to make electrolyte for a soluble lead cell. Full article

In this work, commercial 18650 lithium-ion cells with LiMn₂O₄, LiFePO₄, and Li(Ni_0.33Mn_0.33Co_0.33)O₂ cathodes were exposed to external heating in an accelerating rate calorimeter (es-ARC, Thermal Hazard Technology (THT), Bletchley, UK), to investigate the thermal behavior under abuse conditions. New procedures for measuring the external and internal pressure change of cells were developed. The external pressure was measured utilizing a gas-tight cylinder inside the calorimeter chamber, in order to detect the venting of the cells. For internal pressure measurements, a pressure line connected to a pressure transducer was directly inserted into the cell. During the thermal runaway experiments, three stages (low rate, medium rate, and high rate reactions) were observed. Both the pressure and temperature change indicated different stages of exothermic reactions, which produced gases or/and heat. The onset temperature of the thermal runaway was estimated according to the temperature and pressure changes. Moreover, the different activation energies for the exothermic reactions could be derived from Arrhenius plots. Full article

Power management strategies have impacts on fuel economy, greenhouse gasses (GHG) emission, as well as effects on the durability of power-train components. This is why different off-line and real-time optimal control approaches are being developed. However, real-time control seems to be more attractive than off-line control because it can be directly implemented for managing power and energy flows inside an actual vehicle. One interesting illustration of these power management strategies is the model predictive control (MPC) based algorithm. Inside a MPC, a cost function is optimized while system constraints are validated in real time. The MPC algorithm relies on dynamic models of the vehicle and the battery. The complexity and accuracy of the battery model are usually neglected to benefit the development of new cost functions or better MPC algorithms. The contribution of this manuscript consists of developing and evaluating a high-fidelity battery model of a plug-in hybrid electric vehicle (PHEV) that has been used for MPC. Via empirical work and simulation, the impact of a high-fidelity battery model has been evaluated and compared to a simpler model in the context of MPC. It is proven that the new battery model reduces the absolute voltage, state of charge (SoC), and battery power loss error by a factor of 3.2, 1.9 and 2.1 on average respectively, compared to the simpler battery model. Full article

Online estimation techniques are extensively used to determine the parameters of various uncertain dynamic systems. In this paper, online estimation of the open-circuit voltage (OCV) of lithium-ion batteries is proposed by two different adaptive filtering methods (i.e., recursive least square, RLS, and least mean square, LMS), along with an adaptive observer. The proposed techniques use the battery’s terminal voltage and current to estimate the OCV, which is correlated to the state of charge (SOC). Experimental results highlight the effectiveness of the proposed methods in online estimation at different charge/discharge conditions and temperatures. The comparative study illustrates the advantages and limitations of each online estimation method. Full article

A density functional theory (DFT) study has been carried out on transition metal phosphates with olivine structure and formula LiMPO4 (M = Fe, Mn, Co, Ni) to assess their potential as cathode materials in rechargeable Li-ion batteries based on their chemical and structural stability and high theoretical capacity. The investigation focuses on LiMnPO4, which could offer an improved cell potential (4.1 V) with respect to the reference LiFePO4 compound, but it is characterized by poor lithium intercalation/de-intercalation kinetics. Substitution of cations like Co and Ni in the olivine structure of LiMnPO4 was recently reported in an attempt to improve the electrochemical performances. Here the electronic structure and lithium intercalation potential of Ni- and Co-doped LiMnPO4 were calculated in the framework of the Hubbard U density functional theory (DFT+U) method for highly correlated materials. Moreover, the diffusion process of lithium in the host structures was simulated, and the activation barriers in the doped and pristine structures were compared. Our calculation predicted that doping increases Li insertion potential while activation barriers for Li diffusion remain similar to the pristine material. Moreover, Ni and Co doping induces the formation of impurity states near the Fermi level and significantly reduces the band gap of LiMnPO4. Full article