Refine
Year of publication
Document Type
- Article (reviewed) (62)
- Conference Proceeding (37)
- Article (unreviewed) (6)
- Part of a Book (5)
- Book (2)
- Doctoral Thesis (2)
- Patent (1)
Conference Type
- Konferenzartikel (26)
- Konferenz-Abstract (10)
- Konferenz-Poster (1)
Language
- English (115) (remove)
Has Fulltext
- no (115) (remove)
Is part of the Bibliography
- yes (115)
Keywords
- Lithiumbatterie (9)
- Brennstoffzelle (6)
- Batterie (5)
- Haustechnik (5)
- Elektrochemie (4)
- Energieversorgung (4)
- Fotovoltaik (4)
- Hochtemperaturbrennstoffzelle (3)
- Lithium-Ionen-Akkumulator (3)
- Lithium-ion battery (3)
Institute
- INES - Institut für nachhaltige Energiesysteme (115) (remove)
Open Access
- Closed Access (45)
- Open Access (30)
- Closed (14)
- Diamond (4)
- Gold (2)
- Bronze (1)
One of the major challenges impeding the energy transition is the intermittency of solar and wind electricity generation due to their dependency on weather changes. The demand-side energy flexibility contributes considerably to mitigate the energy supply/demand imbalances resulting from external influences such as the weather. As one of the largest electricity consumers, the industrial enterprises present a high demand-side flexibility potential from their production processes and on-site energy assets. In this direction, methods are needed with a focus on enabling the energy flexibility and ensure an active participation of such enterprises in the electricity markets especially with variable prices of electricity. This paper presents a generic model library for an industrial enterprise implemented with optimal control for energy flexibility purposes. The components in the model library represent the typical technical units of an industrial enterprise on material, media, and energy flow levels with their operative constraints. A case study of a plastic manufacturing plant using the generic model library is also presented, in which the results of two simulation with different electricity prices are compared and the behavior of the model can be assessed. The results show that the model provides an optimal scheduling of the manufacturing system according to the variations in the electricity prices, and ensures an optimal control for utilities and energy systems needed for the production.
Solar energy plays a central role in the energy transition. Clouds generate locally large fluctuations in the generation output of photovoltaic systems, which is a major problem for energy systems such as microgrids, among others. For an optimal design of a power system, this work analyzed the variability using a spatially distributed sensor network at Stuttgart Airport. It has been shown that the spatial distribution partially reduces the variability of solar radiation. A tool was also developed to estimate the output power of photovoltaic systems using irradiation time series and assumptions about the photovoltaic sites. For days with high fluctuations of the estimated photovoltaic power, different energy system scenarios were investigated. It was found the approach can be used to have a more realistic representation of aggregated PV power taking spatial smoothing into account and that the resulting PV power generation profiles provide a good basis for energy system design considerations like battery sizing.
With recent developments in the Ukrainian-Russian conflict, many are discussing about Germany’s dependency on fossil fuel imports in its energy system, and how can the country proceed with reducing that dependency. With its wide-ranging consumption sectors, the electricity sector comes as the perfect choice to start with. Recent reports showed that the German federal government is already intending to have a fully renewable electricity by 2035 while exploiting all possible clean power options. This was published in the federal government’s climate emergency program (Easter Package) in early 2022. The aim of this package is to initiate a rapid transition and decarbonization of the electricity sector. The Easter Package expects an enormous growth of renewable energies to a completely new level, with already at least 80% renewable gross energy consumption, with extensive and broad deployment of different generation technologies on various scales. This paper will discuss this ambitious plan and outline some insights into this huge and rapidly increasing step, and show how much will Germany need in order to achieve this huge milestone towards a fully green supply of the electricity sector. Different scenarios and shares of renewables will be investigated in order to elaborate on preponed climate-neutral goal of the electricity sector by 2035. The results pointed out some promising aspects in achieving a 100% renewable power, with massive investments in both generation and storage technologies.
Soiling is an important issue in the renewable energy sector since it can result in significant yield losses, especially in regions with higher pollution or dust levels. To mitigate the impact of soiling on photovoltaic (PV) plants, it is essential to regularly monitor and clean the panels, as well as develop accurate soiling predictions that can affect cleaning strategies and enhance the overall performance of PV power plants. This research focuses on the problem of soiling loss in photovoltaic power plants and the potential to improve the accuracy of soiling predictions. The study examines how soiling can affect the efficiency and productivity of the modules and how to measure and predict soiling using machine learning (ML) algorithms. The research includes analyzing real data from large-scale ground-mounted PV sites and comparing different soiling measurement methods. It was observed that there were some deviations in the real soiling loss values compared to the expected values for some projects in southern Spain, thus, the main goal of this work is to develop machine learning models that could predict the soiling more accurately. The developed models have a low mean square error (MSE), indicating the accuracy and suitability of the models to predict the soiling rates. The study also investigates the impact of different cleaning strategies on the performance of PV power plants and provides a powerful application to predict both the soiling and the number of cleaning cycles.
Passive solar elements for both direct and indirect gains, are systems used to maintain a comfortable living environment while saving energy, especially in the building energy retrofit and adaptation process. Sunspaces, thermal mass and glazing area and orientation have been often used in the past to guarantee adequate indoor conditions when mechanical devices were not available. After a period of neglect, nowadays they are again considered as appropriate systems to help face environmental issues in the building sector, and both international and national legislation takes into consideration the possibility of including them in the building planning tools, also providing economic incentives. Their proper design needs dynamic simulation, often difficult to perform and time consuming. Moreover, results generally suffer from several uncertainties, so quasi steady-state procedures are often used in everyday practice with good results, but some corrections are still needed. In this paper, a comparative analysis of different solutions for the construction of verandas in an existing building is presented, following the procedure provided by the slightly modified and improved Standard EN ISO 13790:2008. Advantages and disadvantages of different configurations considering thermal insulation, windows typology and mechanical ventilation systems are discussed and a general intervention strategy is proposed. The aim is to highlight the possibility of using sunspaces in order to increase the efficiency of the existing building stock, considering ease of construction and economic viability.
Energy Performance of Verandas in the Building Retrofit Process (PDF Download Available). Available from: https://www.researchgate.net/publication/303093420_Energy_Performance_of_Verandas_in_the_Building_Retrofit_Process [accessed Jul 5, 2017].
Experimental Investigation of the Air Exchange Effectiveness of Push-Pull Ventilation Devices
(2020)
The increasing installation numbers of ventilation units in residential buildings are driven by legal objectives to improve their energy efficiency. The dimensioning of a ventilation system for nearly zero energy buildings is usually based on the air flow rate desired by the clients or requested by technical regulations. However, this does not necessarily lead to a system actually able to renew the air volume of the living space effectively. In recent years decentralised systems with an alternating operation mode and fairly good energy efficiencies entered the market and following question was raised: “Does this operation mode allow an efficient air renewal?” This question can be answered experimentally by performing a tracer gas analysis. In the presented study, a total of 15 preliminary tests are carried out in a climatic chamber representing a single room equipped with two push-pull devices. The tests include summer, winter and isothermal supply air conditions since this parameter variation is missing till now for push-pull devices. Further investigations are dedicated to the effect of thermal convection due to human heat dissipation on the room air flow. In dependence on these boundary conditions, the determined air exchange efficiency varies, lagging behind the expected range 0.5 < εa < 1 in almost all cases, indicating insufficient air exchange including short-circuiting. Local air exchange values suggest inhomogeneous air renewal depending on the distance to the indoor apertures as well as the temperature gradients between in- and outdoor. The tested measurement set-up is applicable for field measurements.
A two-dimensional single-phase model is developed for the steady-state and transient analysis of polymer electrolyte membrane fuel cells (PEMFC). Based on diluted and concentrated solution theories, viscous flow is introduced into a phenomenological multi-component modeling framework in the membrane. Characteristic variables related to the water uptake are discussed. A Butler–Volmer formulation of the current-overpotential relationship is developed based on an elementary mechanism of electrochemical oxygen reduction. Validated by using published V–I experiments, the model is then used to analyze the effects of operating conditions on current output and water management, especially net water transport coefficient along the channel. For a power PEMFC, the long-channel configuration is helpful for internal humidification and anode water removal, operating in counterflow mode with proper gas flow rate and humidity. In time domain, a typical transient process with closed anode is also investigated.
The state-of-the-art electrochemical impedance spectroscopy (EIS) calculations have not yet started from fully multi-dimensional modeling. For a polymer electrolyte membrane fuel cell (PEMFC) with long flow channel, the impedance plot shows a multi-arc characteristic and some impedance arcs could merge. By using a step excitation/Fourier transform algorithm, an EIS simulation is implemented for the first time based on the full 2D PEMFC model presented in the first part of this work. All the dominant transient behaviors are able to be captured. A novel methodology called ‘configuration of system dynamics’, which is suitable for any electrochemical system, is then developed to resolve the physical meaning of the impedance spectra. In addition to the high-frequency arc due to charge transfer, the Nyquist plots contain additional medium/low-frequency arcs due to mass transfer in the diffusion layers and along the channel, as well as a low-frequency arc resulting from water transport in the membrane. In some case, the impedance spectra appear partly inductive due to water transport, which demonstrates the complexity of the water management of PEMFCs and the necessity of physics-based calculations.
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.
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.
Optimal microgrid scheduling with peak load reduction involving an electrolyzer and flexible loads
(2016)
This work consists of a multi-objective mixed-integer linear programming model for defining optimized schedules of components in a grid-connected microgrid. The microgrid includes a hydrogen energy system consisting of an alkaline electrolyzer, hydrogen cylinder bundles and a fuel cell for energy storage. Local generation is provided from photovoltaic panels, and the load is given by a fixed load profile combined with a flexible electrical load, which is a battery electric vehicle. The electrolyzer has ramp-up constraints which are modeled explicitly. The objective function includes, besides operational costs and an environmental indicator, a representation of peak power costs, thus leading to an overall peak load reduction under optimized operation. The model is used both for controlling a microgrid in a field trial set-up deployed in South-West Germany and for simulating the microgrid operation for defined period, thus allowing for economic system evaluation. Results from defined sample runs show that the energy storage is primarily used for trimming the peak of electricity drawn from the public grid and is not solely operated with excess power. The flexible demand operation also helps keeping the peak at its possible minimum.
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 play a vital role in a society more and more affected by the spectre of climate change: hence the need of lowering CO2 emissions and reducing the fossil fuel consumption. At the moment, lithium-ion batteries appear as the ideal candidates for this challenge but further research and development is required to understand their behaviour, predict their issues and therefore improve their performance. In this regard, mathematical modelling and numerical simulation have become standard techniques in lithium-ion battery research and development and have proven to be highly useful in supporting experimental work and increasing the predictability of model-based life expectancy.
This study focuses on the electrochemical ageing reactions at the anode, especially on the topic of lithium plating and its interaction with the solid electrolyte interface (SEI). The purpose of this work is a deeper understanding of these degradation processes through the construction of refined modelling frameworks and the analysis of simulations carried out over a wide range of operating conditions. The governing equations are implemented in the in-house multiphysics software package DENIS, while the electrochemistry model is based on the use of the open-source chemical kinetics code CANTERA.
The development, parameterisation and experimental validation of a comprehensive pseudo-three-dimensional multiphysics model of a commercial lithium-ion cell with blend cathode and graphite anode is presented. This model is able to describe and simulate both multiscale heat and mass transport and complex electrochemical reaction mechanisms, including also as extra feature the capability of reproducing a composite electrode where multiple active materials are subject to intercalation/deintercalation reaction.
A further extension to include reversible lithium plating process and predict ageing behaviour over a wide range of conditions, with a focus on the high currents and low temperatures particularly interesting for the fast charging topic, follows. This extended model is verified by comparison with published experimental data showing voltage plateau and voltage drop as plating indicators and optionally includes an explicit re-intercalation reaction that is shown to suppress macroscopic plating hints in the specific case of a cell not showing evident plating signs. This model is used to create degradation maps over a wide range of conditions and an in-depth spatiotemporal analysis of the anode behaviour at the mesoscopic and microscopic scales, demonstrating the dynamic and nonlinear interaction between the intercalation and plating reactions.
A deeper outlook on the SEI formation and growth is presented, together with the qualitative description of three different 1D-models with a decreasing level of detail, developed with the purpose of ideally being included in future in more comprehensive multiscale frameworks.
Finally, the extended model is successfully coupled with a previously developed SEI model to result in an original modelling framework able to simulate both degradation processes and their continuous positive feedback.
The current methods used to assess the energy performance of ventilation devices do not consider all the aspects necessary for a comprehensive evaluation of decentralised ventilation concepts and can only be partially adapted to their needs. In order to improve the energy evaluation and to ensure the comparability of different systems, a calorimetric method was developed and implemented in test facilities for the evaluation of two decentralised devices: one equipped with a recuperative counter flow heat exchanger and one with a regenerative heat exchanger. This method, based on direct measurements of the heating load in an insulated test room, includes the effect of the electrical consumption of the fans on the energy performance of the ventilation devices. The calorimetric evaluation method was extended to a seasonal evaluation on the basis of a heating-degree-day method implemented for a warm, a cool and a moderate location in Europe: Athens, Strasbourg and Copenhagen. All the results are above 50% efficiency for both devices, even in Athens where the use of heat recovery ventilation is not usual.
In this paper we report on further success of our work to develop a multi-method energy optimization which works with a digital twin concept. The twin concept serves to replicate production processes of different kinds of production companies, including complex energy systems and test market interactions to then use them for model predictive optimizing. The presented work finally reports about the performed flexibility assessment leading to a flexibility audit with a list of measures and the impact of energy optimizations made related to interactions with the local power grid i.e., the exchange node of the low voltage distribution grid. The analysis and continuous exploration of flexibilities as well as the exchange with energy markets require a “guide” leading to continuous optimization with a further tool like the Flexibility Survey and Control Panel helping decision-making processes on the day-ahead horizon for real production plants or the investment planning to improve machinery, staff schedules and production
infrastructure.
The PHOTOPUR project aims to develop a photocatalytic process as a type of AOPs (Advanced Oxidation Processes) for the elimination of plant protection products (PPP) of the cleaning water used to wash sprayers. At INES a PV based energy supply for the photocatalytic cleaning system was developed within the framework of two bachelor theses and assembled as a demonstration unit. Then the system was step by step extended with further process automation features and pushed to a remote operating device. The final system is now available as a mobile unit mounted on a lab table. The latest step was the photocatalytic reactor module which completed the first PHOTOPUR prototype. The system is actually undergoing an intensive testing phase with performance checks at the consortium partners. First results give an overview about the successful operation.
The twin concept is increasingly used for optimization tasks in the context of Industry 4.0 and digitization. The twin concept can also help small and medium-sized enterprises (SME) to exploit their energy flexibility potential and to achieve added value by appropriate energy marketing. At the same time, this use of flexibility helps to realize a climate-neutral energy supply with high shares of renewable energies. The digital twin reflects real production, power flows and market influences as a computer model, which makes it possible to simulate and optimize on-site interventions and interactions with the energy market without disturbing the real production processes. This paper describes the development of a generic model library that maps flexibility-relevant components and processes of SME, thus simplifying the creation of a digital twin. The paper also includes the development of an experimental twin consisting of SME hardware components and a PLC-based SCADA system. The experimental twin provides a laboratory environment in which the digital twin can be tested, further developed and demonstrated on a laboratory scale. Concrete implementations of such a digital twin and experimental twin are described as examples.
Aqueous lithium–oxygen batteries are promising candidates for electric energy storage. In this paper we present and discuss a multiphase continuum model of an aqueous lithium–oxygen single cell including reactions and transport in a porous gas diffusion electrode (GDE). The model is parameterized using in-house half-cell experiments and available literature data on aqueous electrolytes. We validate our transport model with cyclic voltammetry and electrochemical impedance spectroscopy measurements over a wide range of temperatures (25, 40, 55 °C) and electrolyte concentrations (0.1–2 M). We observe very good agreement between simulations and measurements during oxygen reduction conditions. A sensitivity analysis of the validated model demonstrates the influence of the porous structure on GDE performance and gives directions for the future development of electrodes.
On the Fundamental and Practical Aspects of Modeling Complex Electrochemical Kinetics and Transport
(2018)
Numerous technologies, such as batteries and fuel cells, depend on electrochemical kinetics. In some cases, the responsible electrochemistry and charged-species transport is complex. However, to date, there are essentially no general-purpose modeling capabilities that facilitate the incorporation of thermodynamic, kinetic, and transport complexities into the simulation of electrochemical processes. A vast majority of the modeling literature uses only a few (often only one) global charge-transfer reactions, with the rates expressed using Butler–Volmer approximations. The objective of the present paper is to identify common aspects of electrochemistry, seeking a foundational basis for designing and implementing software with general applicability across a wide range of materials sets and applications. The development of new technologies should be accelerated and improved by enabling the incorporation of electrochemical complexity (e.g., multi-step, elementary charge-transfer reactions and as well as supporting ionic and electronic transport) into the analysis and interpretation of scientific results. The spirit of the approach is analogous to the role that Chemkin has played in homogeneous chemistry modeling, especially combustion. The Cantera software, which already has some electrochemistry capabilities, forms the foundation for future capabilities expansion.
The present work describes an extension of current slope estimation for parameter estimation of permanent magnet synchronous machines operated at inverters. The area of operation for current slope estimation in the individual switching states of the inverter is limited due to measurement noise, bandwidth limitation of the current sensors and the commutation processes of the inverter's switching operations. Therefore, a minimum duration of each switching state is necessary, limiting the final area of operation of a robust current slope estimation. This paper presents an extension of existing current slope estimation algorithms resulting in a greater area of operation and a more robust estimation result.
Private households constitute a considerable share of Europe's electricity consumption. The current electricity distribution system treats them as effectively passive individual units. In the future, however, users of the electricity grid will be involved more actively in the grid operation and can become part of intelligent networked collaborations. They can then contribute the demand and supply flexibility that they dispose of and, as a result, help to better integrate renewable energy in-feed into the distribution grids.
During pyrolysis, biomass is carbonised in the absence of oxygen to produce biochar with heat and/or electricity as co-products making pyrolysis one of the promising negative emission technologies to reach climate goals worldwide. This paper presents a simplified representation of pyrolysis and analyses the impact of this technology on the energy system. Results show that the use of pyrolysis can allow getting zero emissions with lower costs by making changes in the unit commitment of the power plants, e.g. conventional power plants are used differently, as the emissions will be compensated by biochar. Additionally, the process of pyrolysis can enhance the flexibility of energy systems, as it shows a correlation between the electricity generated by pyrolysis and the hydrogen installation capacity, being hydrogen used less when pyrolysis appears. The results indicate that pyrolysis, which is available on the market, integrates well into the energy system with a promising potential to sequester carbon.
This paper presents the use of model predictive control (MPC) based approach for peak shaving application of a battery in a Photovoltaic (PV) battery system connected to a rural low voltage gird. The goals of the MPC are to shave the peaks in the PV feed-in and the grid power consumption and at the same time maximize the use of the battery. The benefit to the prosumer is from the maximum use of the self-produced electricity. The benefit to the grid is from the reduced peaks in the PV feed-in and the grid power consumption. This would allow an increase in the PV hosting and the load hosting capacity of the grid.
The paper presents the mathematical formulation of the optimal control problem
along with the cost benefit analysis. The MPC implementation scheme in the
laboratory and experiment results have also been presented. The results show
that the MPC is able to track the deviation in the weather forecast and operate
the battery by solving the optimal control problem to handle this deviation.
Energy efficiency and hygrothermal performance of hemp clay walls for Moroccan residential buildings
(2023)
Hemp-based building envelopes have gained significant popularity in developed countries, and now the trend of constructing houses with hemp-clay blocks is spreading to developing countries like Morocco. Investigating the hygrothermal behavior of such structures under actual climate conditions is essential for advancing and promoting this sustainable practice. This paper presents an in-depth experimental characterization of a commercial hemp-clay brick that has been exposed to the outdoor environment for four years, in addition to field measurements on a building scale demonstration prototype. Additionally, the study simulates 17 representative cities to assess the hygrothermal performance and energy-saving potential in each of Morocco's six existing climate zones, using the EnergyPlus engine. The experimental campaign's findings demonstrate excellent indoor air temperature and relative humidity regulation within the hemp-clay wall building, leading to satisfactory levels of thermal comfort within hemp-clay wall buildings. This is attributed to the material's good thermal conductivity and excellent moisture buffering capacity (found to be 0.31 W/mK and 2.25 g/m2%RH), respectively). The energy simulation findings also point to significant energy savings, with cooling and heating energy reductions ranging from 27.7% to 47.5% and 33.7% to 79.8%, respectively, as compared to traditional Moroccan buildings.
To improve the building’s energy efficiency many parameters should be assessed considering the building envelope, energy loads, occupation, and HVAC systems. Fenestration is among the most important variables impacting residential building indoor temperatures. So, it is crucial to use the most optimal energy-efficient window glazing in buildings to reduce energy consumption and at the same time provide visual daylight comfort and thermal comfort. Many studies have focused on the improvement of building energy efficiency focusing on the building envelope or the heating, ventilation, and cooling systems. But just a few studies have focused on studying the effect of glazing on building energy consumption. Thus, this paper aims to study the influence of different glazing types on the building’s heating and cooling energy consumption. A real case study building located under a semi-arid climate was used. The building energy model has been conducted using the OpenStudio simulation engine. Building indoor temperature was calibrated using ASHRAE’s statistical indices. Then a comparative analysis was conducted using seven different types of windows including single, double, and triple glazing filled with air and argon. Tripleglazed and double-glazed windows with argon space offer 37% and 32% of annual energy savings. It should be stressed that the methodology developed in this paper could be useful for further studies to improve building energy efficiency using optimal window glazing.
Micronization of biochar (BC) may ease its application in agriculture. For example, fine biochar powders can be applied as suspensions via drip-irrigation systems or can be used to produce grnulated fertilizers. However, micronization may effect important physical biochar properties like the water holding capacity (WHC) or the porosity.
Lithium-oxygen cells with organic electrolyte suffer high overpotentials during charge, indicating asymmetric charge/discharge reaction mechanisms. We present a multi-physics dynamic modeling and simulation study of the Li/O2 cell cycling behavior. We present three different multi-step mechanisms of the 2 Li + O2 ⇄ Li2O2 cell reaction, (A) a reversible 5-step mechanism, (B) a partially irreversible 6-step mechanism, and (C) a partially irreversible 8-step mechanism that includes reactions of a redox mediator. Model predictions are compared to experimental galvanostatic cycling data of Swagelok cells without and with 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) as redox mediator. All mechanisms are able to predict the discharge behavior in good agreement to the experimental results. The experimentally observed high charge overpotentials as well as their reduction by using a redox mediator can be qualitatively reproduced with the irreversible reaction mechanisms. However, the particular shape of the experimental charge curve with continuously increasing charge overpotential cannot be reproduced with the present mechanisms.
Lithium–oxygen cells with nonaqueous electrolyte show high overpotentials during charge, indicating asymmetric charge/discharge reaction mechanisms. We present a kinetic modeling and simulation study of the lithium–oxygen cell cycling behavior. The model includes a multistep reaction mechanism of the cell reaction (2Li + O2 ⇄ Li2O2) forming lithium peroxide by precipitation, coupled to a 1D porous-electrode transport model. We apply the model to study the asymmetric discharge/charge characteristics and analyze the influence of a redox mediator dissolved homogeneously in the liquid electrolyte. Model predictions are compared to experimental galvanostatic cycling data of cells without and with 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) as redox mediator. The predicted discharge behavior shows good agreement with the experimental results. A spatiotemporal analysis of species concentrations reveals inhomogeneous distributions of dissolved oxygen and reaction products within the cathode during discharge. The experimentally observed charge overpotentials as well as their reduction by using a redox mediator can be qualitatively reproduced with a partially irreversible reaction mechanism. However, the proposed models fail to reproduce the particular shape of the experimental charge curve with continuously increasing charge overpotential, which implies that part of the reaction mechanism is still open for investigation in future work.
Seven cell design concepts for aqueous (alkaline) lithium–oxygen batteries are investigated using a multi-physics continuum model for predicting cell behavior and performance in terms of the specific energy and specific power. Two different silver-based cathode designs (a gas diffusion electrode and a flooded cathode) and three different separator designs (a porous separator, a stirred separator chamber, and a redox-flow separator) are compared. Cathode and separator thicknesses are varied over a wide range (50 μm–20 mm) in order to identify optimum configurations. All designs show a considerable capacity-rate effect due to spatiotemporally inhomogeneous precipitation of solid discharge product LiOH·H2O. In addition, a cell design with flooded cathode and redox-flow separator including oxygen uptake within the external tank is suggested. For this design, the model predicts specific power up to 33 W/kg and specific energy up to 570 Wh/kg (gravimetric values of discharged cell including all cell components and catholyte except housing and piping).
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 (e.g., fuel cells, metal/air cells, electrolyzers) offer an additional observable, that is, the gas pressure. The dynamic coupling of current and/or voltage with gas pressure gives rise to a number of additional impedance definitions, for which we use the term electrochemical pressure impedance. It also gives rise to different experimental probing approaches. In this article we present a model-based study of electrochemical pressure impedance spectroscopy (EPIS). Possible quantifications and realizations of EPIS are discussed. The study of generic cell geometries consisting of gas reservoir, diffusion layer(s) and electrochemically active layer(s) reveals distinct spiral-shaped features in the Nyquist plot. Using the example of a sodium/oxygen (Na/O2) cell, the dynamic spatiotemporal behavior of the state variables is quantified and interpreted. Results are compared to first experimental EPIS measurements by Hartmann et al. [J. Phys. Chem. C118, 1461, 2014]. A sensitivity analysis highlights the properties of EPIS with respect to geometric, transport, and kinetic parameters. We demonstrate that EPIS is sensitive to transport parameters that are not well-accessible with standard EIS.
Lithium-ion pouch cells with lithium titanate (Li4Ti5O12, LTO) anode and lithium nickel cobalt aluminum oxide (LiNi0.8Co0.15Al0.05O2, NCA) cathode were investigated experimentally with respect to their electrical (0.1C…4C), thermal (5 °C…50 °C) and long-time cycling behavior. The 16 Ah cell exhibits an asymmetric charge/discharge behavior which leads to a strong capacity-rate effect, as well as a significantly temperature-dependent capacity (0.37 Ah ∙ K−1) which expresses as additional high-temperature feature in the differential voltage plot. The cell was cycled for 10,000 cycles inbetween the nominal voltage limits (1.7–2.7 V) with a symmetric 4C constant-current charge/discharge protocol, corresponding to approx. 3400 equivalent full cycles. A small (0.192 mΩ/1000 cycles) but continuous increase of internal resistance was observed. Using electrochemical impedance spectroscopy (EIS), this could be identified to be caused by the NCA cathode, while the LTO anode showed only minor changes during cycling. The temperature-corrected capacity during 4C cycling exhibited a decrease of 1.28%/1000 cycles. The 1C discharge capacity faded by only 4.0% for CC discharge and 2.3% for CCCV discharge after 10,000 cycles. The cell thus exhibits very good internal-resistance stability and excellent capacity retention even under harsh (4C continuous) cycling, demonstrating the excellent stability of LTO as anode material.
Nickel cobalt aluminum oxide (NCA) based lithium-ion battery electrodes exhibit a distinct asymmetry in discharge/charge behavior towards high bulk stoichiometry (low state of charge). We show that basic electrochemical relationships, that is, the Nernst equation and the Butler-Volmer equation, are able to reproduce this behavior when a two-step reaction mechanism is assumed. The two-step mechanism consists of (1) lithium-ion adsorption from the electrolyte onto the active material particle surface under electron transfer, and (2) intercalation of surface-adsorbed lithium atoms into the bulk material. The asymmetry of experimental half-cell data of an NCA electrode cycled at 0.1 C-rate can be quantitatively reproduced with this simple model. The model parameters show two alternative solutions, predicting either a saturated (highly-covered) or a depleted surface for high bulk lithiation.
Pressure dynamics in metal-oxygen (metal-air) batteries: a case study on sodium superoxide cells
(2014)
Electrochemical reactions in metal–oxygen batteries come along with the consumption or release of gaseous oxygen. We present a novel methodology for investigating electrode reactions and transport phenomena in metal–oxygen batteries by measuring the pressure dynamics in an enclosed gas reservoir above the oxygen electrode. The methodology is exemplified by a room-temperature sodium–oxygen battery forming sodium superoxide (NaO2) in an electrolyte of diethylene glycol dimethyl ether (diglyme) and sodium trifluoromethanesulfonate (NaOSO2CF3, NaOTf). The experiments are supported by microkinetic simulations with a one-dimensional multiphysics continuum model. During galvanostatic cycling over 30 cycles, a constant oxygen consumption/release rate is observed upon discharge/charge. The number of transferred electrons per oxygen molecule is calculated to 1.01 ± 0.02 and 1.03 ± 0.02 for discharge and charge, respectively, confirming the nature of the oxygen reaction product as superoxide O2–. The same ratio is observed in cyclic voltammetry experiments with low scan rate (<1 mV/s). However, at higher scan rates, the ratio increases as a result of oxygen transport limitations in the electrolyte. We introduce electrochemical pressure impedance spectroscopy (EPIS) for simultaneously analyzing current, voltage, and pressure of electrochemical cells. Pressure recording significantly increases the sensitivity of impedance toward oxygen transport properties of the porous electrode systems. In addition, we report experimental data on the diffusion coefficient and solubility of oxygen in electrolyte solutions as important parameters for the microkinetic models.
Autonomous humanoid robots need high torque actuators to be able to walk and run. One problem in this context is the heat generated. In this paper we propose to use water evaporation to improve cooling of the motors. Simulations based on thermodynamic calculations as well as measurements on real actuators show that, under the assumption of the load of a soccer game, cooling can be considerably improved with relatively small amounts of water.
Lithium–sulfur (Li/S) cells are promising candidates for a next generation of safe and cost-effective high energy density batteries for mobile and stationary applications. At present, most Li/S cells still suffer from relatively poor cyclability, capacity loss under moderate current densities and self-discharge. Furthermore, the underlying chemical mechanisms of the general discharge/charge behavior as well as Li/S-specific phenomena like the polysulfide shuttle are not yet fully understood. Here we present a thermodynamically consistent, fully reversible continuum model of a Li/S cell with simplified four-step electrochemistry, including a simple description of the polysulfide shuttle effect. The model is parameterized using experimental discharge curves obtained from literature and reproduces behavior at various current densities with fairly high accuracy. While being instructively simple, the presented model can still reproduce distinct macroscopic Li/S-cell features caused by the shuttle effect, e.g., seemingly infinite charging at low charge current densities, and suboptimal coulombic efficiency. The irreversible transport of active material from the cathode to the anode results in a voltage drop and capacity loss during cycling, which can also be observed experimentally.