Development of a universal modeling tool for rechargeable lithium batteries

An interesting universal modeling tool for rechargeable lithium batteries is presented in this paper. The generic model is based on an equivalent circuit technique commonly used in electrochemical impedance characterization. Therefore, the parameters used in the model can be easily parameterized from the electrochemical impedance derivations, which provide a convenient integration with experimental cell characterizations. Such integration offers the universality in this modeling approach.     

Robust polynomial approach for state of charge estimation in NiMH batteries

In this work we estimate the state of charge (SOC) of NiMH rechargeable batteries using a robust optimal filter based on a simplified electrochemical model. The robust filter guarantees that the supremum of the error variance - difference between real and estimated SOC - with respect to all admissible uncertainties be minimum. The results are compared with those obtained using the linear Kalman filter. We conclude that both estimations have similar performance, although the robust filter is easier to tune. Experimental results with commercial batteries are provided to illustrate the estimation procedure and it performance.     

Influence of measurement procedure on quality of impedance spectra on lead-acid batteries

Many battery simulation models, but also electrochemical interpretations are based on impedance spectroscopy. However, the impedance of a battery is influenced by various factors, e.g. in the case of a lead-acid battery: state of charge (SOC), charging or discharging, superimposed dc current, short-term history or homogeneity of the electrolyte. This paper analyses the impact of those factors on impedance spectra of lead-acid batteries. The results show that very detailed information about the conditions during the measurement is crucial for the correct interpretation of a spectrum.     

Development of lithium batteries for energy storage and EV applications

The results of the Japanese national project of R&D on large-size lithium rechargeable batteries by Lithium Battery Energy Storage Technology Research Association (LIBES), as of fiscal year (FY) 2000 are reviewed. Based on the results of 10 Wh-class cell development in Phase I, the program of Phase II aims at further improvement of the performance of large-size cells and battery modules, and the formulation of roadmaps toward worldwide dissemination of large-size lithium secondary batteries. In addition to the above R&D programs, a new target was presented particularly for the near-term practical application of several kWh-class battery modules in FY 1998.

For the large-size battery modules, two types of 2 and 3 kWh-class battery modules have been developed for stationary device and electric vehicle applications, respectively. The battery modules for both types have achieved most of the targets other than cycle life. Currently, further improvements in the cycle life of the cells themselves are being pursued. For this purpose, the materials for cathodes and anodes, the shapes and structures for batteries and the methods for cell connection are being re-investigated.

The development of middle-size battery systems for mini-size electric vehicles (EVs), as well as for demand-side stationary device applications is under way. These battery systems have been fabricated and their fundamental performance confirmed. They are now being subjected to field tests.     

Transient-boundary voltage method for measurement of equivalent circuit components of rechargeable batteries

A method is presented for measuring the equivalent circuit components of rechargeable batteries. The temporal discharge-rest-charge-rest sequence of a rechargeable battery is described, using the principles of transient circuit analysis, to derive equations for the battery voltage as a function of time during voltage transients and at the boundaries at transitions between transient phases. The equations lead to a new measurement method for battery characterization. The equivalent circuit of the battery is described as an ideal voltage source in series with a resistor and the parallel combination of a resistor and a capacitor. The battery model uses different values of resistance and capacitance, in the parallel combination, during the different phases of the discharge-rest-charge-rest sequence. The method is used to measure the circuit parameters of a nickel-cadmium battery.     

Towards real-time (milliseconds) parameter estimation of lithium-ion batteries using reformulated physics-based models

In this paper, transport and kinetic parameters of lithium-ion batteries are estimated using a rigorous porous electrode theory based model. The rigorous model used in this investigation is reformulated using advanced mathematical techniques. Since batteries and other electrochemical devices are used in hybrid environments, which include devices with time constants less than a second (like supercapacitor), we need to develop parameter estimation codes with computation time less than a second or a few milliseconds. In this investigation, the computation time for parameter estimation measures between 100 and 300 ms since a reformulated battery model is devised especially for these purposes. Obtaining the numerical solution for battery model equations is very difficult towards the end of discharge and is usually neglected for parameter estimation purposes. However, in this paper the estimation takes into account the entire discharge data ranging from an initial potential of 4.2 V to a cut-off potential of 2.5 V. It is found from this investigation that the reformulated lithium-ion battery model is efficient and accurate in estimating parameters.     

Electrical and electrochemical studies of poly(vinylidene fluoride)-clay nanocomposite gel polymer electrolytes for Li-ion batteries

A study is conducted on the electrical and electrochemical properties of nanocomposite polymer electrolytes based on intercalation of poly(vinylidene fluoride) (PVdF) polymer into the galleries of organically modified montmorillonite (MMT) clay. A solution intercalation technique is employed for nanocomposite formation with varying clay loading from 0 to 4 wt.%. X-ray diffraction results show the β phase formation of PVdF on intercalation. Transmission electron microscopy reveals the formation of partially exfoliated nanocomposites. The nanocomposites are soaked with 1 M LiClO₄ in a 1:1 (v/v) solution of propylene carbonate (PC) and diethyl carbonate (DEC) to obtain the required gel electrolytes. The structural conformation of the nanocomposite electrolytes is examined by Fourier transform infrared spectroscopy analysis. Examination with a.c. impedance spectroscopy reveals that the ionic conductivity of the nanocomposite gel polymer electrolytes increases with increase in clay loading and attains a maximum value of 2.3 × 10⁻³ S cm⁻¹ for a 4 wt.% clay loading at room temperature. The same composition exhibits enhancement in the electrochemical and interfacial properties as compared with that of a clay-free electrolyte system.     

Experimental validation for Li-ion battery modeling using Extended Kalman Filters

The battery management systems (BMS) is an essential emerging component of both electric and hybrid electric vehicles (HEV) alongside with modern power systems. With the BMS integration, safe and reliable battery operation can be guaranteed through the accurate determination of the battery state of charge (SOC), its state of health (SOH) and the instantaneous available power. Therefore, undesired power fade and capacity loss problems can be avoided. Because of the electrochemical actions inside the battery, such emerging storage energy technology acts differently with operating and environment condition variations. Consequently, the SOC estimation mechanism should cope with the probable changes and uncertainties in the battery characteristics to ensure a permanent precise SOC determination over the battery lifetime.This paper aims to study and design the BMS for the Li-ion batteries. For this purpose, the system mathematical equations are presented. Then, the battery electrical model is developed. By imposing known charge/discharge current signals, all the parameters of such electrical model are identified using voltage drop measurements. Then, the extended kalman filter (EKF) methodology is employed to this nonlinear system to determine the most convenient battery SOC. This methodology is experimentally implemented using C language through micro-controller. The proposed BMS technique based on EKF is experimentally validated to determine the battery SOC values correlated to those reached by the Coulomb counting method with acceptable small errors.     

Aging model development based on multidisciplinary parameters for lithium-ion batteries

In this paper, a method composed of state of health (SOH) testing experiments and artificial intelligence simulation is proposed to carry out the study on the change of battery characteristic during its operation and generate mathematical models for the prediction of aging behaviour of battery. An experiment comprising of multidisciplinary parameters-based SOH detection is conducted to study the battery aging characteristics from several aspects (ie, electrochemistry, electric, thermal behaviour and mechanics). In total, 200 sets of data (corresponding 200 charging/discharging cycles) are collected from the experiment. The data obtained from the first 150 cycles are employed in generation of the models. The result of sensitivity analysis based on the obtained genetic programming models shows that it is better to apply voltage value at the end of charging step, charging time and cycle number to predict the operational performance of the battery. The average predicted accuracy of model (without stress) is 94.52%, whereas the average predicted accuracy of model (with stress effect) is 99.42%. The proposed models could be useful for defining the optimised charging strategy, fault diagnosis and spent batteries disposal strategies.     

Mathematical modeling of high-power-density insertion electrodes for lithium ion batteries

Theoretical calculations are compared with well-controlled experiments conducted on a high-surface area, small diameter lithiated-carbon electrodes. The electrodes are shown to yield very high current densities and exhibit little interfacial kinetics resistance or intercalate diffusion resistance. The mathematical treatment describes quantitatively a wide range of electrochemical experiments. The application of the model to the experimental data is facilitated by the use of a reference electrode. Initial cycling behavior of the high-surface-area electrode is elucidated, including clarification of the first-cycle coulombic inefficiency. Nitrogen absorbtion and scanning electron micrographs are utilized to ascertain the microstructural characteristics that distinguish the active electrode material. An asymptotic analysis is used to indicate when diffusion resistance within host particles is negligible; this fact simplifies model calculations and contributes to our overall understanding of insertion processes associated with host particles of very small dimensions.     

Three-dimensional conductivity model for porous electrodes in lead acid batteries

In this paper, the critical volume fraction (CVF) of electrodes having porosity is predicted with the help of a three-dimensional (3D) conductivity model. The model consists of a 3D lattice of nodes; which in this paper, are assumed to be identical spheres, which are in electrical contact with their neighbors. The porosity that exists between these spheres is referred to as “micro-porosity” while the porosity that occurs from having missing spheres is referred to as “macro-porosity”. The critical volume fraction is the maximum utilization of an electrode's active material and occurs when the electrode's conductivity changes from being conductive to nonconductive. Previous 3D conductivity models used to determine the CVF did not account for porosity. The porosity is modeled from porosity size distribution previously determined experimentally by other researchers.     

From single cell model to battery pack simulation for Li-ion batteries

A practical universal modeling and simulation approach is presented in this paper to show that accurate battery pack simulation can be achieved if cell-to-cell variations were taken into account. A generic equivalent circuit model was used in the approach with parameters deduced from cell testing with proper protocols, which could come from live cell monitoring in a control circuitry. Using a single cell model, which was validated against experimental data and demonstrated with validity of high accuracy in predicting cell performance, we showed that such a high accuracy in single cell model is essential for a high fidelity pack simulation. It is also important to derive statistical confidence intervals accurately from experiments to characterize intrinsic cell-to-cell variations in capacity and internal resistance, which need to be considered in the pack model. If parameters for each individual cell were correctly approximated and used in the pack model, the accuracy in the prediction of pack performance could be significantly improved.     

One-dimensional dynamic modeling and validation of maintenance-free lead-acid batteries emphasizing temperature effects

Lead acid batteries are still widely used for SLI (Starting-Lighting-Ignition) systems in vehicles because of the cost advantage. The batteries are frequently charged and discharged under different operation conditions, which continuously changes distribution of inner temperature of batteries. Variation of the temperature distributions significantly affects performance and durability of the battery. We developed a one-dimensional dynamic model based on the first principle of thermal dynamics and electrochemistry. The thermal model incorporates control volumes for each of the major constituents of the battery cells that is casing, electrolyte, and electrodes. The model was extended for a six-cell battery and used to analyze effects of discharging currents on the performances and temperature, compared with results from a three-dimensional finite element analysis and tested against experimental results obtained from a thermal chamber and using thermal imaging.     

Design modeling of lithium-ion battery performance

A computer design modeling technique has been developed for lithium-ion batteries to assist in setting goals for cell components, assessing materials requirements, and evaluating thermal management strategies. In this study, the input data for the model included design criteria from Quallion, LLC for Gen-2 18650 cells, which were used to test the accuracy of the dimensional modeling. Performance measurements on these cells were done at the electrochemical analysis and diagnostics laboratory (EADL) at Argonne National Laboratory. The impedance and capacity related criteria were calculated from the EADL measurements. Five batteries were designed for which the number of windings around the cell core was increased for each succeeding battery to study the effect of this variable upon the dimensions, weight, and performance of the batteries. The lumped-parameter battery model values were calculated for these batteries from the laboratory results, with adjustments for the current collection resistance calculated for the individual batteries.     

Thermal safety study of Li-ion batteries under limited overcharge abuse based on coupled electrochemical-thermal model

Many fire accidents of electric vehicles were reported that happened during the charging process. In order to investigate the reasons that lead to this problem, this paper studies the thermal safety of Li-ion batteries under limited overcharge abuse. A 3D electrochemical-thermal coupled model is developed for modeling thermal and electrochemical characteristics from normal charge to early overcharge state. This model is validated by experiment at charge rates of 0.5C, 1C, and 2C. The simulation results indicate that irreversible heat contributes most to temperature rise during the normal charge process, but the heat induced by Mn dissolution and Li deposition gradually dominates heat generation in the early overcharge period. Based on this, a threshold selection method for multistage warning of batteries overcharge is proposed. Among them, level 1 should be considered as a critical stage during the early overcharge process due to the deposited lithium starts to react with electrolyte at the end of level 1, where temperature rate increases to 0.5°C min⁻¹ for 1C charge. While the thresholds of levels depend on charge rate and composition of battery. Furthermore, several critical parameters are analyzed to figure out their effects on thermal safety. It is found that the temperature at the end of overcharge is significantly influenced by the change of positive electrode thickness and solid electrolyte interface (SEI) film resistance. The final temperature increases by 17.5°C and 7.9°C, respectively, with positive electrode thickness ranging from 50 to 80 μm and SEI film resistance increasing from 0.002 to 0.03 Ω.     

Thermal modeling of secondary lithium batteries for electric vehicle/hybrid electric vehicle applications

A major obstacle to the development of commercially successful electric vehicles (EV) or hybrid electric vehicles (HEV) is the lack of a suitably sized battery. Lithium ion batteries are viewed as the solution if only they could be “scaled-up safely”, i.e. if thermal management problems could be overcome so the batteries could be designed and manufactured in much larger sizes than the commercially available near-2-Ah cells.

Here, we review a novel thermal management system using phase-change material (PCM). A prototype of this PCM-based system is presently being manufactured. A PCM-based system has never been tested before with lithium-ion (Li-ion) batteries and battery packs, although its mode of operation is exceptionally well suited for the cell chemistry of the most common commercially available Li-ion batteries. The thermal management system described here is intended specifically for EV/HEV applications. It has a high potential for providing effective thermal management without introducing moving components. Thereby, the performance of EV/HEV batteries may be improved without complicating the system design and incurring major additional cost, as is the case with “active” cooling systems requiring air or liquid circulation.     

Discrimination of Li-ion batteries based on Hamming network using discharging-charging voltage pattern recognition for improved state-of-charge estimation

Differences in electrochemical characteristics among Li-ion batteries and factors such as temperature and ageing result in erroneous state-of-charge (SoC) estimation when using the existing extended Kalman filter (EKF) algorithm. This study presents an application of the Hamming neural network to the identification of suitable battery model parameters for improved SoC estimation. The discharging-charging voltage (DCV) patterns of ten fresh Li-ion batteries are measured, together with the battery parameters, as representative patterns. Through statistical analysis, the Hamming network is applied for identification of the representative DCV pattern that matches most closely of the pattern of the arbitrary battery to be measured. Model parameters of the representative battery are then applied to estimate the SoC of the arbitrary battery using the EKF. This avoids the need for repeated parameter measurement. Using model parameters selected by the proposed method, all SoC estimates (off-line and on-line) based on the EKF are within ±5% of the values estimated by ampere-hour counting.     

Recycling and reusing batteries: A significant way for effective sustainability of FCEVs and EVs

In the last 20 years, the transportation sector has enabled the technology to evolve in its direction with both environmental and energy efficiency in the use of electric and fuel cell vehicles. The two important components of these vehicles are the batteries and electric motors. The batteries are produced within a certain life cycle, and unfortunately it is not possible to use them without conversion/recycling. In this study, the crucial importance of battery recycling/reusing is underliying and last researches will be given about battery recycling, above next ten years. Recommendations and future forseen advices will be presented about the current state of battery recycling technology, how recycling systems exist in different batteries, and the future of battery recycling standart. As a result, battery recycling and reusing for fuel cell and electric vehicles is considered to be an important keypoint in terms of both envirenmontial, economical and technologial menner for the transportation sector in the next decades.     

Development and characterization of a bilayer separator for lithium ion batteries

A battery separator is placed between the positive and negative electrodes to prevent electric contact of the electrodes while maintaining good ionic flow. The most commonly used separators for lithium-ion batteries are porous polyolefin membranes. However, they generally do not have good dimentional stability at elevated temperatures. In this study, a bilayer separator has been formed directly on an anode. This bilayer separator comprised a ceramic layer and a porous polyvinylidene fluoride (PVDF) layer. Coin cells with this type of separators showed stable cycling performance at room temperature. They also showed significantly improved rate capabilities compared to the reference cell with a conventional polyolefin separator. An oven test has been used to characterize the cells thermal stability. Charged cells were kept in an oven at 150 °C and their voltage drop was recorded. The reference cell with a conventioal separator failed within about 50 min, while no noticeable voltage drop was observed for the cells with the new bilayer separator within the measured 2 h.