Hybrid Energy Storage Systems Based on Redox-Flow Batteries: Recent Developments, Challenges, and Future Perspectives

Recently, the appeal of Hybrid Energy Storage Systems (HESSs) has been growing in multiple application fields, such as charging stations, grid services, and microgrids. HESSs consist of an integration of two or more single Energy Storage Systems (ESSs) to combine the benefits of each ESS and improve the overall system performance, e.g., efficiency and lifespan. Most recent studies on HESS mainly focus on power management and coupling between the different ESSs without a particular interest in a specific type of ESS. Over the last decades, Redox-Flow Batteries (RFBs) have received significant attention due to their attractive features, especially for stationary storage applications, and hybridization can improve certain characteristics with respect to short-term duration and peak power availability. Presented in this paper is a comprehensive overview of the main concepts of HESSs based on RFBs. Starting with a brief description and a specification of the Key Performance Indicators (KPIs) of common electrochemical storage technologies suitable for hybridization with RFBs, HESS are classified based on battery-oriented and application-oriented KPIs. Furthermore, an optimal coupling architecture of HESS comprising the combination of an RFB and a Supercapacitor (SC) is proposed and evaluated via numerical simulation. Finally, an in-depth study of Energy Management Systems (EMS) is conducted. The general structure of an EMS as well as possible application scenarios are provided to identify commonly used control and optimization parameters. Therefore, the differentiation in system-oriented and application-oriented parameters is applied to literature data. Afterwards, state-of-the-art EMS optimization techniques are discussed. As an optimal EMS is characterized by the prediction of the system’s future behavior and the use of the suitable control technique, a detailed analysis of the previous implemented EMS prediction algorithms and control techniques is carried out. The study summarizes the key aspects and challenges of the electrical hybridization of RFBs and thus gives future perspectives on newly needed optimization and control algorithms for management systems

Lamination of Separators to Electrodes using Electrospinning.

This study shows the feasibility of the Electrospinning method as a process step for advanced and fast production Li ion cells. Lamination is a key technology for Lithium-ion battery production. It bares different advantages, such as a fast production line speed by fixing the separator to the electrodes. Unfortunately, this technology is inapplicable for separator and electrode formulations not based on thermoplastic binders. Using Electrospinning, this disadvantage can be overcome. In our study, beaded PVDF polymer nanofibres were spun onto a fibre-reinforced, inorganic-filled separator. This modified separator was then laminated onto a NMC111-cathode using a temperature profile of 110/110/120°C within the laminator. After Lamination, the separator was pulled-off again and placed in a SEM to see the adhesive behaviour of the applied polymer. The information gathered with SEM clearly shows a successful lamination of the separator to the electrode

Analyzing Experimental Design and Input Data Variation of a Vanadium Redox Flow Battery Model

Vanadium redox flow batteries (VRFB) are a fertile energy storage technology especially for customized storage applications with special energy and power requirements. The dimensioning and control of these storages is mostly calculated beforehand using battery models in embedded simulation structures. To cover various stack designs, chemistries, application strategies and system architectures, battery simulation models should be validated with different experimental input data and thus show universal functionality. In this study the functionality of a grey box VRFB model using current, voltage and state of charge (SOC) of a 10 kW/100 kWh VRFB as input data are validated for an adapted input data set using of a 5 kW/10 kWh VRFB. This model is designed for stationary applications of VRFB only. The contribution of this study is (i) to apply a suitable SOC conversion method to the raw data from the used 5 kW VRFB system, (ii) to adapt the modeling code for broader use and integration of the SOC conversion, (iii) to validate the functionality and (iv) to investigate the influence of constant current and constant voltage phases in the raw data on the accuracy of the model. A comparison of experimental data between different redox flow batteries shows that most VRFB measure the open circuit voltage (OCV) to calculate the SOC of the battery. Using the calculated SOC as an input data the proposed simulation model need to be adapted and a method is applied to use OCV input data for model validation. Although simulation models in general often assume linearity between SOC and OCV, the study showed sufficient accuracy using polynomic fitting of second order. Applying a parametrization process the results of the simulation model are compared to the raw data and the scope of application of the grey box VRFB model is defined. While using the dominant constant current phase for the charging and discharging cycle, the grey box simulation model has been sufficiently parametrized and validated for adapted input data

Study on Different Water-Based Binders for Li4Ti5O12 Electrodes

In this study, Li4Ti5O12 (LTO) electrodes with different types of water-soluble binders are successfully coated upon aluminum foil. Electrodes containing solely sodium alginate (SA) as a binder or a mixed PVDF/carboxymethyl cellulose (CMC) binder show the most stable performance in 1 M LiPF6 in EC/DMC 1:1 in half cell vs. Li, with respect to cycle stability over 100 cycles at 1 C. The electrodes processed with a mixture of PVDF/SA show considerable fading and slightly worse values for rate capability. Each one of the different binders used is eco-friendly, and the whole processing can be performed without the use of organic solvents. Further advantages covering the whole production and recycling process, as well as safety issues during operation, encourage deeper research in this area

Analyzing Experimental Design and Input Data Variation of a Vanadium Redox Flow Battery Model

Vanadium redox flow batteries (VRFB) are a fertile energy storage technology especially for customized storage applications with special energy and power requirements. The dimensioning and control of these storages is mostly calculated beforehand using battery models in embedded simulation structures. To cover various stack designs, chemistries, application strategies and system architectures, battery simulation models should be validated with different experimental input data and thus show universal functionality. In this study the functionality of a grey box VRFB model using current, voltage and state of charge (SOC) of a 10 kW/100 kWh VRFB as input data are validated for an adapted input data set using of a 5 kW/10 kWh VRFB. This model is designed for stationary applications of VRFB only. The contribution of this study is (i) to apply a suitable SOC conversion method to the raw data from the used 5 kW VRFB system, (ii) to adapt the modeling code for broader use and integration of the SOC conversion, (iii) to validate the functionality and (iv) to investigate the influence of constant current and constant voltage phases in the raw data on the accuracy of the model. A comparison of experimental data between different redox flow batteries shows that most VRFB measure the open circuit voltage (OCV) to calculate the SOC of the battery. Using the calculated SOC as an input data the proposed simulation model need to be adapted and a method is applied to use OCV input data for model validation. Although simulation models in general often assume linearity between SOC and OCV, the study showed sufficient accuracy using polynomic fitting of second order. Applying a parametrization process the results of the simulation model are compared to the raw data and the scope of application of the grey box VRFB model is defined. While using the dominant constant current phase for the charging and discharging cycle, the grey box simulation model has been sufficiently parametrized and validated for adapted input data

Modification of Battery Separators via Electrospinning to Enable Lamination in Cell Assembly

To meet the requirements of today’s fast-growing Li-ion battery market, cell production depends on cheap, fast and reliable methods. Lamination of electrodes and separators can accelerate the time-consuming stacking step in pouch cell assembly, reduce scrap rate and enhance battery performance. However, few laminable separators are available on the market so far. This study introduces electrospinning as a well-suited technique to apply thin functional polymer layers to common battery separator types, enabling lamination. The method is shown to be particularly appropriate for temperature resistant ceramic separators, for which stable interfaces between separator and electrodes were formed and capacity fading during 600 fast charging cycles was reduced by 44%. In addition, a straightforward approach to apply the method to other types of separators is presented, including separator characterization, coating polymer selection, mechanical tests on intermediates and electrochemical validation in pouch cells. The concept was successfully used for the modification of a polyethylene separator, to which a novel fluoroelastomer was applied. The stability of the electrode/separator interface depends on the polymer mass loading, lamination temperature and lamination pressure, whereas poorly selected lamination conditions may cause damage on the separator. Appropriate adhesion force of 8.3 N/m could be achieved using a polymer loading as low as 0.25 g/m2. In case separator properties, coating polymer, morphology of the fibrous coating and lamination conditions are well adjusted to each other, the implementation of electrospinning and lamination allows for faster, more flexible and robust pouch cell production at comparable or better electrochemical cell behaviour

Ageing and Water-Based Processing of LiFeMnPO4 Secondary Agglomerates and Its Effects on Electrochemical Characteristics

LiFeMnPO4 secondary agglomerates have been aged under different temperature and moisture conditions. The aged and pristine powder samples were then processed to water- and solvent-based cathodes. Structural studies by means of neutron and X-ray diffraction revealed that neither ageing nor water-based processing significantly modified the crystal structure of LiFeMnPO4 secondary agglomerates. Electrochemical characterization was carried out with full-cells. It was found that long-term cycling is similar independent of the solvent used for slurry preparation. Full-cells assembled with water-based cathodes show a better C-rate capability due to a more homogeneous distribution of cathode constituents compared to solvent-based ones. In no case was any negative effect of initial active material ageing on the electrochemical performance found. During ageing and processing, LiFeMnPO4 is effectively protected by carbon coating and water can be completely removed by drying since it is only reversibly bound. This contribution shows that LiFeMnPO4 secondary agglomerates allow simplified active material handling and have a high potential for sustainable water-based electrode manufacturing

Rheological Properties of Aqueous Sodium Alginate Slurries for LTO Battery Electrodes

Rheological properties of electrode slurries have been intensively studied for manifold different combinations of active materials and binders. Standardly, solvent-based systems are under use, but a trend towards water-based electrode manufacturing is becoming more and more important. The different solvent is beneficial in terms of sustainability and process safety but is also accompanied by some disadvantages such as extraction of residual humidity and a higher complexity concerning slurry stability. Li4Ti5O12 (LTO) active material provides good long-term stability and can be processed in aqueous solutions. Combining the LTO active material with sodium alginate (SA) as a promising biobased polymer binder reveals good electrochemical properties but suffers from bad slurry stability. In this work, we present a comprehensive rheological study on material interactions in anode slurries consisting of LTO and SA, based on a complex interaction of differentially sized materials. The use of two different surfactants—namely, an anionic and non-ionic one, to enhance slurry stability, compared with surfactant-free slurry

Influence of Particle Morphologies of LiFePO4 on Water- and Solvent-Based Processing and Electrochemical Properties

LiFePO4 (LFP) primary particles and secondary agglomerates have been processed into water- and solvent-based cathodes. By means of neutron and X-ray diffraction it was found that no structural changes of LiFePO4 occurred upon water- and solvent-based slurry preparation. Electrochemical characterization was carried out with full-cells and a distinct influence of particle morphology was observable. Water-based processing of primary particles leads to deficits in electrochemical performance while secondary agglomerates are non-sensitive to water during processing. In the presence of water, high mechanical stress during slurry preparation causes a partial detachment of carbon coating. However, this effect is negligible for secondary agglomerates since only surface particles are exposed to mechanical stress. Due to longer diffusion paths and the fact that secondary agglomerates represent a micro-heterogeneity in the cathode, the C-rate capability of secondary agglomerates is slightly lower than that of primary particles. This paper demonstrates that for any high energy application with moderate C-rates, secondary agglomerates hold a great potential for environmentally friendly and cost-efficient water-based cathode production