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The accurate diagnosis of state of charge (SOC) and state of health (SOH) is of utmost importance for battery users and for battery manufacturers. State diagnosis is commonly based on measuring battery current and using it in Coulomb counters or as input for a current-controlled model. Here we introduce a new algorithm based on measuring battery voltage and using it as input for a voltage-controlled model. We demonstrate the algorithm using fresh and pre-aged lithium-ion battery single cells operated under well-defined laboratory conditions on full cycles, shallow cycles, and a dynamic battery electric vehicle load profile. We show that both SOC and SOH are accurately estimated using a simple equivalent circuit model. The new algorithm is self-calibrating, is robust with respect to cell aging, allows to estimate SOH from arbitrary load profiles, and is numerically simpler than state-of-the-art model-based methods.
Lithium-ion batteries exhibit a well-known trade-off between energy and power, which is problematic for electric vehicles which require both high energy during discharge (high driving range) and high power during charge (fast-charge capability). We use two commercial lithium-ion cells (high-energy [HE] and high-power) to parameterize and validate physicochemical pseudo-two-dimensional models. In a systematic virtual design study, we vary electrode thicknesses, cell temperature, and the type of charging protocol. We are able to show that low anode potentials during charge, inducing lithium plating and cell aging, can be effectively avoided either by using high temperatures or by using a constant-current/constant-potential/constant-voltage charge protocol which includes a constant anode potential phase. We introduce and quantify a specific charging power as the ratio of discharged energy (at slow discharge) and required charging time (at a fast charge). This value is shown to exhibit a distinct optimum with respect to electrode thickness. At 35°C, the optimum was achieved using an HE electrode design, yielding 23.8 Wh/(min L) volumetric charging power at 15.2 min charging time (10% to 80% state of charge) and 517 Wh/L discharge energy density. By analyzing the various overpotential contributions, we were able to show that electrolyte transport losses are dominantly responsible for the insufficient charge and discharge performance of cells with very thick electrodes.
Ziel der Investitionsmaßnahme Enerlab 4.0 war die Bereitstellung einer umfangreichen in-operando und post-mortem Diagnostik für dezentrale Energieerzeuger und -Speicher, z. B. Batteriezellen und Photovoltaikzellen. Diese sind wichtige Komponenten für verschiedene Bereiche der Industrie 4.0 – von autonomen Sensoren über energieautarke Produktion bis hin zur Qualitätskontrolle. Zu diesem Zweck wurde die apparative Ausstattung der Hochschule Offenburg erweitert, und zwar sowohl für in-operando Diagnostik (elektrische Zyklierer, Impedanzspektrometer, Temperaturprüfschränke) als auch für post-mortem Diagnostik (Glovebox, Probenpräparationen für vorhandene Werkstoffanalytik und chemische Analytik). Be-reits vorhandene Geräte aus anderen laufenden oder abgeschlossenen Projekten wurden in die neue Infrastruktur integriert. Im Ergebnis entstand ein modernes und leistungsfähiges Batterie- und Photovoltaiklabor, welches in zahlreichen laufenden und neuen Vorhaben genutzt wird.
Die Erfindung betrifft ein Verfahren und eine Vorrichtung zur Bestimmung des Ladezustandes (SOC) einer aufladbaren Batterie (106) eines vorgegebenen Batterietyps oder eines damit in einem physikalischen Zusammenhang stehenden Parameters, insbesondere einer in der Batterie enthaltenen Restladungsmenge Q, wobei das Verfahren mittels eines spannungsgeführten Batteriemodells (102) arbeitet, welches für die betreffende Batterie (106) oder einen entsprechenden Batterietyp parametriert wird. Es muss lediglich die Batteriespannung Umess gemessen und dem Batteriemodell (102) als Eingangsgröße zur Verfügung gestellt werden. Weiterhin betrifft die Erfindung ein Verfahren und eine Vorrichtung zur Bestimmung des Gesundheitszustandes (SOH) einer Batterie (102), wobei das Batteriemodell (102), das auch zur Bestimmung des SOC verwendet wird, einen modellierten Batteriestrom Imodliefert. Aus diesem können modellierte Ladungsmengen während Lade- und Entladephasen der Batterie (106) bestimmt und mit gemessenen Ladungsmengen, die aus dem gemessenen Batteriestrom Imessbestimmt werden, verglichen werden. Da das Batteriemodell (102) nicht altert, kann hierdurch der SOH der Batterie bestimmt werden.
The invention relates to a method and to a device for determining the state of charge (SOC) of a rechargeable battery (106) of a specified battery type or a parameter physically related thereto, in particular a remaining charge amount Q contained in the battery, the method operating by means of a voltage-controlled battery model (102), which is parameterized for the battery (106) in question or a corresponding battery type. It is merely necessary to measure the battery voltage Umess and to provide said battery voltage to the battery model (102) as an input variable. The invention further relates to a method and to a device for determining the state of health (SOH) of a battery (102), wherein the battery model (102) also used to determine the SOC provides a modeled battery current Imod. Modeled charge amounts during charging and discharging phases of the battery (106) can be determined from said modeled battery current and can be compared with measured charge amounts, which are determined from the measured battery current Imess. Because the battery model (102) does not age, the SOH of the battery can thereby be determined.
Die Erfindung betrifft ein Verfahren und eine Vorrichtung zur Bestimmung des Ladezustandes (SOC) einer aufladbaren Batterie (106) eines vorgegebenen Batterietyps oder eines damit in einem physikalischen Zusammenhang stehenden Parameters, insbesondere einer in der Batterie enthaltenen Restladungsmenge Q, wobei das Verfahren mittels eines spannungsgeführten Batteriemodells (102) arbeitet, welches für die betreffende Batterie (106) oder einen entsprechenden Batterietyp parametriert wird. Es muss lediglich die Batteriespannung Umess gemessen und dem Batteriemodell (102) als Eingangsgröße zur Verfügung gestellt werden. Weiterhin betrifft die Erfindung ein Verfahren und eine Vorrichtung zur Bestimmung des Gesundheitszustandes (SOH) einer Batterie (102), wobei das Batteriemodell (102), das auch zur Bestimmung des SOC verwendet wird, einen modellierten Batteriestrom Imodliefert. Aus diesem können modellierte Ladungsmengen während Lade- und Entladephasen der Batterie (106) bestimmt und mit gemessenen Ladungsmengen, die aus dem gemessenen Batteriestrom Imessbestimmt werden, verglichen werden. Da das Batteriemodell (102) nicht altert, kann hierdurch der SOH der Batterie bestimmt werden.
Ziel des LiBaLu-Teilprojekts Modellierung und Simulation war die Unterstützung der Elektroden- und Zellentwicklung mit Hilfe umfangreicher Computersimulationen im Sinne des computergestützten Engineering (CAE). Zwei verschiedene Schwerpunkte standen im Mittelpunkt der Untersuchungen. Zum einen wurde das mechanistische Verständnis der komplexen Elektrochemie in Lithium-Luftbatterien durch mikrokinetische Modelle aufgeklärt. Auf Basis von postulierten Mehrschrittmechanismen wurden makroskopische Eigenschaften (Entlade-/Ladekennlinien, Zyklovoltammogramme) vorhergesagt und mit experimentellen Daten der Projektpartner verglichen. Zum anderen wurde das Design der Prototypzelle mit Hilfe numerischer Simulationen untersucht und optimiert. So konnten z. B. optimale Schichtdicken oder die Rolle von Gastransportlimitierungen identifiziert werden.
Ziel des Projekts STABIL war die Vorhersage der Alterung und Verbesserung der Lebensdauer von mobilen und stationären Lithium-Ionen-Batterien. Batterien sind zentrale Komponenten der Elektromobilität und der stationären Speicherung von regenerativem Strom. Die im Stand der Technik unzureichende Lebensdauer der Batterie ist heute wesentlicher Kostentreiber. Im Projekt wurde daher in einem skalenübergreifenden und interdisziplinären Ansatz das Verhalten von einzelnen Batteriezellen und ganzen Batteriesystemen unter zwei unterschiedlichen systemischen Randbedingungen untersucht.
Passive hybridization refers to a parallel connection of photovoltaic and battery cells on the direct current level without any active controllers or inverters. We present the first study of a lithium-ion battery cell connected in parallel to a string of four or five serially-connected photovoltaic cells. Experimental investigations were performed using a modified commercial photovoltaic module and a lithium titanate battery pouch cell, representing an overall 41.7 W-peak (photovoltaic)/36.8 W-hour (battery) passive hybrid system. Systematic and detailed monitoring of this system over periods of several days with different load scenarios was carried out. A scaled dynamic synthetic load representing a typical profile of a single-family house was successfully supplied with 100 % self-sufficiency over a period of two days. The system shows dynamic, fully passive self-regulation without maximum power point tracking and without battery management system. The feasibility of a photovoltaic/lithium-ion battery passive hybrid system could therefore be demonstrated.
Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.
Silicon (Si) has turned out to be a promising active material for next‐generation lithium‐ion battery anodes. Nevertheless, the issues known from Si as electrode material (pulverization effects, volume change etc.) are impeding the development of Si anodes to reach market maturity. In this study, we are investigating a possible application of Si anodes in low‐power printed electronic applications. Tailored Si inks are produced and the impact of carbon coating on the printability and their electrochemical behavior as printed Si anodes is investigated. The printed Si anodes contain active material loadings that are practical for powering printed electronic devices, like electrolyte gated transistors, and are able to show high capacity retentions. A capacity of 1754 mAh/gSi is achieved for a printed Si anode after 100 cycles. Additionally, the direct applicability of the printed Si anodes is shown by successfully powering an ink‐jet printed transistor.
Die Erfindung betrifft eine Photovoltaik-Stromversorgungsvorrichtung, insbesondere vom öffentlichen Stromnetz unabhängige Photovoltaik-Stromversorgungsvorrichtung, mit einem positiven (204) und einem negativen (206) Lastanschluss für den Anschluss einer elektrischen Last, mit einer Mehrzahl von photovoltaischen Zellen (104) und einer wiederaufladbaren Batterie (5), welche wenigstens zwei in Serie geschaltete Batteriezellen (112) umfasst. Nach der Erfindung sind die photovoltaischen Zellen (104) zu einer der Anzahl der Batteriezellen (112) entsprechenden Anzahl von seriell verbundenen Teilstrings (108) verschaltet und jeder Teilstring (108) ist mit einem positiven Teilstringanschluss mit einem Pluspol und mit einem negativen Teilstringanschluss mit einem Minuspol einer zugeordneten Batteriezelle (112) oder mehreren zugeordneten parallel geschalteten Batteriezellen (112) verbunden. Dabei kann jeder Teilstring (108) zwischen dem positiven und negativen Teilstringanschluss eine maximale Leerlaufspannung erzeugen, die kleiner oder gleich einer vorgegebenen Ladeschlussspannung der zugeordneten Batteriezelle (112) oder der zugeordneten parallel geschalteten Batteriezellen (112) ist. Weiterhin betrifft die Erfindung eine Schaltungsanordnung zum Laden einer wiederaufladbaren Batterie, die zur Realisierung einer derartigen Photovoltaik-Stromversorgungsvorrichtung geeignet ist.
Modeling and simulation play a key role in analyzing the complex electrochemical behavior of lithium-ion batteries. We present the development of a thermodynamic and kinetic modeling framework for intercalation electrochemistry within the open-source software Cantera. Instead of using equilibrium potentials and single-step Butler-Volmer kinetics, Cantera is based on molar thermodynamic data and mass-action kinetics, providing a physically-based and flexible means for complex reaction pathways. Herein, we introduce a new thermodynamic class for intercalation materials into the open-source software. We discuss the derivation of molar thermodynamic data from experimental half-cell potentials, and provide practical guidelines. We then demonstrate the new class using a single-particle model of a lithium cobalt oxide/graphite lithium-ion cell, implemented in MATLAB. With the present extensions, Cantera provides a platform for the lithium-ion battery modeling community both for consistent thermodynamic and kinetic models and for exchanging the required thermodynamic and kinetic parameters. We provide the full MATLAB code and parameter files as supplementary material to this article.
Oxidation of the nickel electrode is a severe aging mechanism of solid oxide fuel cells (SOFC) and solid oxide electrolyzer cells (SOEC). This work presents a modeling study of safe operating conditions with respect to nickel oxide formation. Microkinetic reaction mechanisms for thermochemical and electrochemical nickel oxidation are integrated into a 2D multiphase model of an anode‐supported solid oxide cell. Local oxidation propensity can be separated into four regimes. Simulations show that the thermochemical pathway generally dominates the electrochemical pathway. As a consequence, as long as fuel utilization is low, cell operation considerably below electrochemical oxidation limit of 0.704 V is possible without the risk of reoxidation.
In this article the high-temperature behavior of a cylindrical lithium iron phosphate/graphite lithium-ion cell is investigated numerically and experimentally by means of differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), and external short circuit test (ESC). For the simulations a multi-physics multi-scale (1D+1D+1D) model is used. Assuming a two-step electro-/thermochemical SEI formation mechanism, the model is able to qualitatively reproduce experimental data at temperatures up to approx. 200 °C. Model assumptions and parameters could be evaluated via comparison to experimental results, where the three types of experiments (DSC, ARC, ESC) show complementary sensitivities towards model parameters. The results underline that elevated-temperature experiments can be used to identify parameters of the multi-physics model, which then can be used to understand and interpret high-temperature behavior. The resulting model is able to describe nominal charge/discharge operation behavior, long-term calendaric aging behavior, and short-term high-temperature behavior during extreme events, demonstrating the descriptive and predictive capabilities of physicochemical models.
Model-based analysis of Electrochemical Pressure Impedance Spectroscopy (EPIS) for PEM Fuel Cells
(2019)
Electrochemical impedance spectroscopy (EIS) is a widely-used diagnostic technique to characterize electrochemical processes. It is based on the dynamic analysis of two electrical observables, that is, current and voltage. Electrochemical cells with gaseous reactants or products, in particular fuel cells, offer an additional observable, that is, the gas pressure. The dynamic coupling of current or voltage with gas pressure gives rise to a number of additional impedance definitions, for which we have previously introduced the term electrochemical pressure impedance spectroscopy (EPIS) [1,2]. EPIS shows a particular sensitivity towards transport processes of gas-phase or dissolved species, in particular, diffusion coefficients and transport pathway lengths. It is as such complementary to standard EIS, which is mainly sensitive towards electrochemical processes. First EPIS experiments on PEM fuel cells have recently been shown [3].
We present a detailed modeling and simulation analysis of EPIS of a PEM fuel cell. We use a 1D+1D continuum model of a fuel/air channel pair with GDL and MEA. Backpressure is dynamically varied, and the resulting simulated oscillation in cell voltage is evaluated to yield the ▁Z_( V⁄p_ca ) EPIS signal. Results are obtained for different transport situations of the fuel cell, giving rise to very complex EPIS shapes in the Nyquist plot. This complexity shows the necessity of model-based interpretation of the complex EPIS shapes. Based on the simulation results, specific features in the EPIS spectra can be assigned to different transport domains (gas channel, GDL, membrane water transport).
The measurement of the active material volume fraction in composite electrodes of lithium-ion battery cells is difficult due to the small (sub-micrometer) and irregular structure and multi-component composition of the electrodes, particularly in the case of blend electrodes. State-of-the-art experimental methods such as focused ion beam/scanning electron microscopy (FIB/SEM) and subsequent image analysis require expensive equipment and significant expertise. We present here a simple method for identifying active material volume fractions in single-material and blend electrodes, based on the comparison of experimental equilibrium cell voltage curve (open-circuit voltage as function of charge throughput) with active material half-cell potential curves (half-cell potential as function of lithium stoichiometry). The method requires only (i) low-current cycling data of full cells, (ii) cell opening for measurement of electrode thickness and active electrode area, and (iii) literature half-cell potentials of the active materials. Mathematical optimization is used to identify volume fractions and lithium stoichiometry ranges in which the active materials are cycled. The method is particularly useful for model parameterization of either physicochemical (e.g., pseudo-two-dimensional) models or equivalent circuit models, as it yields a self-consistent set of stoichiometric and structural parameters. The method is demonstrated using a commercial LCO–NCA/graphite pouch cell with blend cathode, but can also be applied to other blends (e.g., graphite–silicon anode).
Multi-phase management is crucial for performance and durability of electrochemical cells such as batteries and fuel cells. In this paper we present a generic framework for describing the two-dimensional spatiotemporal evolution of gaseous, liquid and solid phases, as well as their interdependence with interfacial (electro-)chemistry and microstructure in a continuum description. The modeling domain consists of up to seven layers (current collectors, channels, electrodes, separator/membrane), each of which can consist of an arbitrary number of bulk phases (gas, liquid, solid) and connecting interfaces (two-phase or multi-phase boundaries). Bulk and interfacial chemistry is described using global or elementary kinetic reactions. Multi-phase management is coupled to chemistry and to mass and charge transport within bulk phases. The functionality and flexibility of this framework is demonstrated using four application areas in the context of post-lithium-ion batteries and fuel cells, that is, lithium-sulfur (Li-S) cells, lithium-oxygen (Li-O) cells, solid oxide fuel cells (SOFC) and polymer electrolyte membrane fuel cells (PEFC). The results are compared to models available in literature and properties of the generic framework are discussed.