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A balcony photovoltaic (PV) system, also known as a micro-PV system, is a small PV system consisting of one or two solar modules with an output of 100–600 Wp and a corresponding inverter that uses standard plugs to feed the renewable energy into the house grid. In the present study we demonstrate the integration of a commercial lithium-ion battery into a commercial micro-PV system. We firstly show simulations over one year with one second time resolution which we use to assess the influence of battery and PV size on self-consumption, self-sufficiency and the annual cost savings. We then develop and operate experimental setups using two different architectures for integrating the battery into the micro-PV system. In the passive hybrid architecture, the battery is in parallel electrical connection to the PV module. In the active hybrid architecture, an additional DC-DC converter is used. Both architectures include measures to avoid maximum power point tracking of the battery by the module inverter. Resulting PV/battery/inverter systems with 300 Wp PV and 555 Wh battery were tested in continuous operation over three days under real solar irradiance conditions. Both architectures were able to maintain stable operation and demonstrate the shift of PV energy from the day into the night. System efficiencies were observed comparable to a reference system without battery. This study therefore demonstrates the feasibility of both active and passive coupling architectures.
Im Batterielabor der Hochschule Offenburg wurde ein neues Verfahren zur Bestimmung von Ladezustand und Gesundheitszustand von Lithium-Ionen-Batterien entwickelt. Es beruht auf der Auswertung von Spannungs- und Strommessungen mit einem mathematischen Batteriemodell. Das Verfahren ist genauer und robuster als Standardverfahren, die auf Ladungszählung beruhen. Zudem ist es numerisch einfacher umzusetzen als andere modellbasierte Verfahren. Wir demonstrieren die Methode mit einer Heimspeicherzelle und einer Elektrofahrzeugzelle.
Fast charging of lithium-ion batteries remains one of the most delicate challenges for the automotive industry, being seriously affected by the formation of lithium metal in the negative electrode. Here we present a physicochemical pseudo-3D model that explicitly includes the plating reaction as side reaction running in parallel to the main intercalation reaction. The thermodynamics of the plating reaction are modeled depending on temperature and ion concentration, which differs from the often-used assumption of a constant plating condition of 0 V anode potential. The reaction kinetics are described with an Arrhenius-type rate law parameterized from an extensive literature research. Re-intercalation of plated lithium was modeled to take place either via reverse plating (solution-mediated) or via an explicit interfacial reaction (surface-mediated). At low temperatures not only the main processes (intercalation and solid-state diffusion) become slow, but also the plating reaction itself becomes slower. Using this model, we are able to predict typical macroscopic experimental observables that are indicative of plating, that is, a voltage plateau during discharge and a voltage drop upon temperature increase. A spatiotemporal analysis of the internal cell states allows a quantitative insight into the competition between intercalation and plating. Finally, we calculate operation maps over a wide range of C-rates and temperatures that allow to assess plating propensity as function of operating condition.
Batteries typically consist of multiple individual cells connected in series. Here we demonstrate single-cell state of charge (SOC) and state of health (SOH) diagnosis in a 24 V class lithium-ion battery. To this goal, we introduce and apply a novel, highly efficient algorithm based on a voltage-controlled model (VCM). The battery, consisting of eight single cells, is cycled over a duration of five months under a simple cycling protocol between 20 % and 100 % SOC. The cell-to-cell standard deviations obtained with the novel algorithm were 1.25 SOC-% and 1.07 SOH-% at beginning of cycling. A cell-averaged capacity loss of 9.9 % after five months cycling was observed. While the accuracy of single-cell SOC estimation was limited (probably owed to the flat voltage characteristics of the lithium iron phosphate, LFP, chemistry investigated here), single-cell SOH estimation showed a high accuracy (2.09 SOH-% mean absolute error compared to laboratory reference tests). Because the algorithm does not require observers, filters, or neural networks, it is computationally very efficient (three seconds analysis time for the complete data set consisting of eight cells with approx. 780.000 measurement points per cell).
Lithium-ion batteries exhibit a dynamic voltage behaviour depending nonlinearly on current and state of charge. The modelling of lithium-ion batteries is therefore complicated and model parametrisation is often time demanding. Grey-box models combine physical and data-driven modelling to benefit from their respective advantages. Neural ordinary differential equations (NODEs) offer new possibilities for grey-box modelling. Differential equations given by physical laws and NODEs can be combined in a single modelling framework. Here we demonstrate the use of NODEs for grey-box modelling of lithium-ion batteries. A simple equivalent circuit model serves as a basis and represents the physical part of the model. The voltage drop over the resistor–capacitor circuit, including its dependency on current and state of charge, is implemented as a NODE. After training, the grey-box model shows good agreement with experimental full-cycle data and pulse tests on a lithium iron phosphate cell. We test the model against two dynamic load profiles: one consisting of half cycles and one dynamic load profile representing a home-storage system. The dynamic response of the battery is well captured by the model.
Lithium-ion batteries exhibit slow voltage dynamics on the minute time scale that are usually associated with transport processes. We present a novel modelling approach toward these dynamics by combining physical and data-driven models into a Grey-box model. We use neural networks, in particular neural ordinary differential equations. The physical structure of the Grey-box model is borrowed from the Fickian diffusion law, where the transport domain is discretized using finite volumes. Within this physical structure, unknown parameters (diffusion coefficient, diffusion length, discretization) and dependencies (state of charge, lithium concentration) are replaced by neural networks and learnable parameters. We perform model-to-model comparisons, using as training data (a) a Fickian diffusion process, (b) a Warburg element, and (c) a resistor-capacitor circuit. Voltage dynamics during constant-current operation and pulse tests as well as electrochemical impedance spectra are simulated. The slow dynamics of all three physical models in the order of ten to 30 min are well captured by the Grey-box model, demonstrating the flexibility of the present approach.
Grey-box modelling combines physical and data-driven models to benefit from their respective advantages. Neural ordinary differential equations (NODEs) offer new possibilities for grey-box modelling, as differential equations given by physical laws and neural networks can be combined in a single modelling framework. This simplifies the simulation and optimization and allows to consider irregularly-sampled data during training and evaluation of the model. We demonstrate this approach using two levels of model complexity; first, a simple parallel resistor-capacitor circuit; and second, an equivalent circuit model of a lithium-ion battery cell, where the change of the voltage drop over the resistor-capacitor circuit including its dependence on current and State-of-Charge is implemented as NODE. After training, both models show good agreement with analytical solutions respectively with experimental data.
Lithium-ion batteries show strongly nonlinear behaviour regarding the battery current and state of charge. Therefore, the modelling of lithium-ion batteries is complex. Combining physical and data-driven models in a grey-box model can simplify the modelling. Our focus is on using neural networks, especially neural ordinary differential equations, for grey-box modelling of lithium-ion batteries. A simple equivalent circuit model serves as a basis for the grey-box model. Unknown parameters and dependencies are then replaced by learnable parameters and neural networks. We use experimental full-cycle data and data from pulse tests of a lithium iron phosphate cell to train the model. Finally, we test the model against two dynamic load profiles: one consisting of half cycles and one dynamic load profile representing a home-storage system. The dynamic response of the battery is well captured by the model.
The lifetime of a battery is affected by various aging processes happening at the electrode scale and causing capacity and power fade over time. Two of the most critical mechanisms are the deposition of metallic lithium (plating) and the loss of lithium inventory to the solid electrolyte interphase (SEI). These side reactions compete with reversible lithium intercalation at the graphite anode. Here we present a comprehensive physicochemical pseudo-3D aging model for a lithium-ion battery cell, which includes electrochemical reactions for SEI formation on graphite anode, lithium plating, and SEI formation on plated lithium. The thermodynamics of the aging reactions are modeled depending on temperature and ion concentration, and the reactions kinetics are described with an Arrhenius-type rate law. The model includes also the positive feedback of plating on SEI growth, with the presence of plated lithium leading to a higher SEI formation rate compared to the values obtained in its absence at the same operating conditions. The model is thus able to describe cell aging over a wide range of temperatures and C-rates. In particular, it allows to quantify capacity loss due to cycling (here in % per year) as function of operating conditions. This allows the visualization of aging colormaps as function of both temperature and C-rate and the identification of critical operation conditions, a fundamental step for a comprehensive understanding of batteries performance and behavior. For example, the model predicts that at the harshest conditions (< –5 °C, > 3 C), aging is reduced compared to most critical conditions (around 0–5 °C) because the cell cannot be fully charged.
This article presents the development, parameterization, and experimental validation of a pseudo-three-dimensional (P3D) multiphysics aging model of a 500 mAh high-energy lithium-ion pouch cell with graphite negative electrode and lithium nickel manganese cobalt oxide (NMC) positive electrode. This model includes electrochemical reactions for solid electrolyte interphase (SEI) formation at the graphite negative electrode, lithium plating, and SEI formation on plated lithium. The thermodynamics of the aging reactions are modeled depending on temperature and ion concentration and the reactions kinetics are described with an Arrhenius-type rate law. Good agreement of model predictions with galvanostatic charge/discharge measurements and electrochemical impedance spectroscopy is observed over a wide range of operating conditions. The model allows to quantify capacity loss due to cycling near beginning-of-life as function of operating conditions and the visualization of aging colormaps as function of both temperature and C-rate (0.05 to 2 C charge and discharge, −20 °C to 60 °C). The model predictions are also qualitatively verified through voltage relaxation, cell expansion and cell cycling measurements. Based on this full model, six different aging indicators for determination of the limits of fast charging are derived from post-processing simulations of a reduced, pseudo-two-dimensional isothermal model without aging mechanisms. The most successful aging indicator, compared to results from the full model, is based on combined lithium plating and SEI kinetics calculated from battery states available in the reduced model. This methodology is applicable to standard pseudo-two-dimensional models available today both commercially and as open source.
This article presents the development, parameterization, and experimental validation of a pseudo-three-dimensional (P3D) multiphysics model of a 350 mAh high-power lithium-ion pouch cell with graphite anode and lithium cobalt oxide/lithium nickel cobalt aluminum oxide (LCO/NCA) blend cathode. The model describes transport processes on three different scales: Heat transport on the macroscopic scale (cell), mass and charge transport on the mesoscopic scale (electrode pair), and mass transport on the microscopic scale (active material particles). A generalized description of electrochemistry in blend electrodes is developed, using the open-source software Cantera for calculating species source terms. Very good agreement of model predictions with galvanostatic charge/discharge measurements, electrochemical impedance spectroscopy, and surface temperature measurements is observed over a wide range of operating conditions (0.05C to 10C charge and discharge, 5°C to 35°C). The behavior of internal states (concentrations, potentials, temperatures) is discussed. The blend materials show a complex behavior with both intra-particle and inter-particle non-equilibria during cycling.
Lithium-ion batteries show a complex thermo-electrochemical performance and aging behavior. This paper presents a modeling and simulation framework that is able to describe both multi-scale heat and mass transport and complex electrochemical reaction mechanisms. The transport model is based on a 1D + 1D + 1D (pseudo-3D or P3D) multi-scale approach for intra-particle lithium diffusion, electrode-pair mass and charge transport, and cell-level heat transport, coupled via boundary conditions and homogenization approaches. The electrochemistry model is based on the use of the open-source chemical kinetics code CANTERA, allowing flexible multi-phase electrochemistry to describe both main and side reactions such as SEI formation. A model of gas-phase pressure buildup inside the cell upon aging is added. We parameterize the model to reflect the performance and aging behavior of a lithium iron phosphate (LiFePO4, LFP)/graphite (LiC6) 26650 battery cell. Performance (0.1–10 C discharge/charge at 25, 40 and 60°C) and calendaric aging experimental data (500 days at 30°C and 45°C and different SOC) from literature can be successfully reproduced. The predicted internal cell states (concentrations, potential, temperature, pressure, internal resistances) are shown and discussed. The model is able to capture the nonlinear feedback between performance, aging, and temperature.
We present an electrochemical model of a lithium iron phosphate/graphite (LFP/C6) cell that includes combined aging mechanisms: (i) Electrochemical formation of the solid electrolyte interphase (SEI) at the anode, leading to loss of lithium inventory, (ii) breaking of the SEI due to volume changes of the graphite particles, causing accelerated SEI growth, and (iii) loss of active material due to of loss percolation of the liquid electrolyte resulting from electrode dry-out. The latter requires the introduction of an activity-saturation relationship. A time-upscaling methodology is developed that allows to simulate large time spans (thousands of operating hours). The combined modeling and simulation framework is able to predict calendaric and cyclic aging up to the end of life of the battery cells. The aging parameters are adjusted to match literature calendaric and cyclic aging experiments, resulting in quantitative agreement of simulated nonlinear capacity loss with experimental data. The model predicts and provides an interpretation for the dependence of capacity loss on temperature, cycling depth, and average SOC. The introduction of a percolation threshold in the activity-saturation relationship allows to capture the strong nonlinearity of aging toward end of life (“sudden death”).
One of the practical bottlenecks associated with commercialization of lithium-air cells is the choice of an appropriate electrolyte that provides the required combination of cell performance, cyclability and safety. With the help of a two-dimensional multiphysics model, we attempt to narrow down the electrolyte choice by providing insights into the effect of the transport properties of electrolyte, electrode saturation (flooded versus gas diffusion), and electrode thickness on a single discharge performance of a lithium-air button cell cathode for five different electrolytes including water, ionic liquid, carbonate, ether, and sulfoxide. The 2D distribution of local current density and concentrations of electrochemically active species (O2 and Li+) in the cathode is also discussed w.r.t electrode saturation. Furthermore, the efficacy of species transport in the cathode is quantified by introducing two parameters, firstly, a transport efficiency that gives local insight into the distribution of mass transfer losses, and secondly, an active electrode volume that gives global insight into the cathode volume utilization at different current densities. A detailed discussion is presented toward understanding the design-induced performance limitations in a Li-air button cell prototype.
Lithium‐ion battery cells are multiscale and multiphysics systems. Design and material parameters influence the macroscopically observable cell performance in a complex and nonlinear way. Herein, the development and application of three methodologies for model‐based interpretation and visualization of these influences are presented: 1) deconvolution of overpotential contributions, including ohmic, concentration, and activation overpotentials of the various cell components; 2) partial electrochemical impedance spectroscopy, allowing a direct visualization of the origin of different impedance features; and 3) sensitivity analyses, allowing a systematic assessment of the influence of cell parameters on capacity, internal resistance, and impedance. The methods are applied to a previously developed and validated pseudo‐3D model of a high‐power lithium‐ion pouch cell. The cell features a blend cathode. The two blend components show strong coupling, which can be observed and interpreted using the results of overpotential deconvolution, partial impedance spectroscopy, and sensitivity analysis. The presented methods are useful tools for model‐supported lithium‐ion cell research and development.
Electrochemical pressure impedance spectroscopy (EPIS) is an emerging tool for the diagnosis of polymer electrolyte membrane fuel cells (PEMFC). It is based on analyzing the frequency response of the cell voltage with respect to an excitation of the gas-phase pressure. Several experimental studies in the past decade have shown the complexity of EPIS signals, and so far there is no agreement on the interpretation of EPIS features. The present study contributes to shed light into the physicochemical origin of EPIS features, by using a combination of pseudo-two-dimensional modeling and analytical interpretation. Using static simulations, the contributions of cathode equilibrium potential, cathode overpotential, and membrane resistance on the quasi-static EPIS response are quantified. Using model reduction, the EPIS responses of individual dynamic processes are predicted and compared to the response of the full model. We show that the EPIS signal of the PEMFC studied here is dominated by the humidifier. The signal is further analyzed by using transfer functions between various internal cell states and the outlet pressure excitation. We show that the EPIS response of the humidifier is caused by an oscillating oxygen molar fraction due to an oscillating mass flow rate.
Electrochemical pressure impedance spectroscopy (EPIS) has recently been developed as a potential diagnosis tool for polymer electrolyte membrane fuel cells (PEMFC). It is based on analyzing the frequency response of the cell voltage with respect to an excitation of the gas-phase pressure. We present here a combined modeling and experimental study of EPIS. A pseudo-twodimensional PEMFC model was parameterized to a 100 cm2 laboratory cell installed in its test bench, and used to reproduce steady-state cell polarization and electrochemical impedance spectra (EIS). Pressure impedance spectra were obtained both in experiment and simulation by applying a harmonic pressure excitation at the cathode outlet. The model shows good agreement with experimental data for current densities ⩽ 0.4 A cm−2. Here it allows a further simulative analysis of observed EPIS features, including the magnitude and shape of spectra. Key findings include a strong influence of the humidifier gas volume on EPIS and a substantial increase in oxygen partial pressure oscillations towards the channel outlet at the resonance frequency. At current densities ⩾ 0.8 A cm−2 the experimental EIS and EPIS data cannot be fully reproduced. This deviation might be associated with the formation and transport of liquid water, which is not included in the model.
Lithium-ion battery cells exhibit a complex and nonlinear coupling of thermal, electrochemical,and mechanical behavior. In order to increase insight into these processes, we report the development of a pseudo-three-dimensional (P3D) thermo-electro-mechanical model of a commercial lithium-ion pouch cell with graphite negative electrode and lithium nickel cobalt aluminum oxide/lithium cobalt oxide blend positive electrode. Nonlinear molar volumes of the active materials as function of lithium stoichiometry are taken from literature and implemented into the open-source software Cantera for convenient coupling to battery simulation codes. The model is parameterized and validated using electrical, thermal and thickness measurements over a wide range of C-rates from 0.05 C to 10 C. The combined experimental and simulated analyses show that thickness change during cycling is dominated by intercalation-induced swelling of graphite, while swelling of the two blend components partially cancel each other. At C-rates above 2 C, electrochemistry-induced temperature increase significantly contributes to cell swelling due to thermal expansion. The thickness changes are nonlinearly distributed over the thickness of the electrode pair due to gradients in the local lithiation, which may accelerate local degradation. Remaining discrepancies between simulation and experiment at high C-rates might be attributed to lithium plating, which is not considered in the model at present.
This article presents a comparative experimental study of the electrical, structural and chemical properties of large‐format, 180 Ah prismatic lithium iron phosphate (LFP)/graphite lithium‐ion battery cells from two different manufacturers. These cells are particularly used in the field of stationary energy storage such as home‐storage systems. The investigations include (1) cell‐to‐cell performance assessment, for which a total of 28 cells was tested from each manufacturer, (2) electrical charge/discharge characteristics at different currents and ambient temperatures, (3) internal cell geometries, components, and weight analysis after cell opening, (4) microstructural analysis of the electrodes via light microscopy and scanning electron microscopy, (5) chemical analysis of the electrode materials using energy‐dispersive X‐ray spectroscopy, and (6) mathematical analysis of the electrode balances. The combined results give a detailed and comparative insight into the cell characteristics, providing essential information needed for system integration. The study also provides complete and self‐consistent parameter sets for the use in cells models needed for performance prediction or state diagnosis.
The significant market growth of stationary electrical energy storage systems both for private and commercial applications has raised the question of battery lifetime under practical operation conditions. Here, we present a study of two 8 kWh lithium-ion battery (LIB) systems, each equipped with 14 lithium iron phosphate/graphite (LFP) single cells in different cell configurations. One system was based on a standard configuration with cells connected in series, including a cell-balancing system and a 48 V inverter. The other system featured a novel configuration of two stacks with a parallel connection of seven cells each, no cell-balancing system, and a 4 V inverter. The two systems were operated as part of a microgrid both in continuous cycling mode between 30% and 100% state of charge, and in solar-storage mode with day–night cycling. The aging characteristics in terms of capacity loss and internal resistance change in the cells were determined by disassembling the systems for regular checkups and characterizing the individual cells under well-defined laboratory conditions. As a main result, the two systems showed cell-averaged capacity losses of 18.6% and 21.4% for the serial and parallel configurations, respectively, after 2.5 years of operation with 810 (serial operation) and 881 (parallel operation) cumulated equivalent full cycles. This is significantly higher than the aging of a reference single cell cycled under laboratory conditions at 20 °C, which showed a capacity loss of only 10% after 1000 continuous full cycles.