bluuebunny/crossref_metadata_2025_split huggingface dataset:
On the Chemomechanical Behavior in Solid-State Sodium Sulfur Batteries
Authors: Nguyen Hung Quoc , Todt Juraj , Keckes Jozef , Mehraj Ud Din Mir , Rettenwander Daniel 
Published: February 2024

Sodium-sulfur batteries are promising for grid energy storage applications thanks to their high theoretical capacity, their abundance in the Earth’s crust and raw materials being cost effective. Unfortunately, their practical application is limited by several technical challenges, especially polysulfide shuttling phenomenon and accompanied volume expansion, which can lead to serious capacity degradation [1]. In this case, solid-state sodium-sulfur battery (S4B) can effectively suppress the shuttle phenomenon [2]. However, the poor triple-phase contact among active material, solid electrolytes and electroconductive agent limits the battery performance. During cycling, the complete conversion of one mole S8 into eight mole Na2S expands its volume by 260 %, and contracts upon dissociation [1].This phenomenon causes the chemo-mechanical failure, results in contact lost within the cathode composite and decreases the reversible capacity. In contrast to solid-state Li-S batteries [3][4], the understanding in case of S4B is lacking. In this study, the battery using composite cathode preparing by ball milling achieved the first discharge capacity of 1640 mAh/g and 50 mA/g current density which is close to the theoretical capacity of sulfur. This is owing to the homogeneous distribution of sulfur within the electrode and intimate contact of sulfur, solid electrolyte, and conductive carbon. Upon cycling the chemo-mechanical impact on the global performance of S4B has been studied using operando XRD, SAXS, WAXS, and electrochemical dilatometry.

References

[1] Wang, L., Wang, T., Peng, L., Wang, Y., Zhang, M., Zhou, J., ... & Duan, X. (2022). The promises, challenges, and pathways to room-temperature sodium-sulfur batteries. Nat Sci Rev, 9(3), nwab050.
[2] Tanibata, N., Deguchi, M., Hayashi, A., & Tatsumisago, M. (2017). All-solid-state Na/S batteries with a Na3PS4 electrolyte operating at room temperature. Chem Mater, 29(12), 5232-5238.
[3] Ohno, S., Koerver, R., Dewald, G., Rosenbach, C., Titscher, P., Steckermeier, D., ... & Zeier, W. G. (2019). Observation of chemomechanical failure and the influence of cutoff potentials in all-solid-state Li–S batteries. Chem Mater, 31(8), 2930-2940.
[4] Ohno, S., & Zeier, W. G. (2021). Toward Practical Solid-State Lithium–Sulfur Batteries: Challenges and Perspectives. Acc Mater Res, 2(10), 869-880.

Acknowledgement

We acknowledge financial support by Norwegian University of Science and Technology, the National Foundation for Research, Technology and Development and the Christian Doppler Research Association (Christian Doppler Laboratory for Solid-State Batteries).
Molten Salt Based High Entropy Electrolytes for Calcium Batteries
Authors: Timhagen Johanna , Weidow Jonathan , Johansson Patrik 
Published: February 2024

Calcium (Ca) is in principle a very attractive metal anode for rechargeable batteries due to the large abundance of calcium in the Earth’s crust, its low electrochemical potential, and its low cost1. Until rather recently2, however, stable plating and stripping of Ca and hence rechargeability of Ca-batteries was deemed impossible, due to the stable phases formed at the electrolyte/electrode interface, completely blocking Ca2+ transfer3.Since this pivotal breakthrough, Ca-batteries have attracted more interest, but they are still in their very infancy and new battery designs – such as using novel electrolyte concepts – are needed to achieve stable cycling of Ca metal anodes, and this preferably at room temperature.
Here we report on the use of molten salt electrolytes, i.e. binary and multi-component systems of inorganic cations and anions, and more specifically on their physico-chemical and electrochemical properties as a function of composition with special emphasis on the compositional entropy. By using completely solvent-free electrolytes issues associated with organic electrolytes and solvents, such as the blocking of Ca2+ transfer and electrolyte flammability3, are avoided. Furthermore, they should/do not induce any large polarization, as opposed to ionic liquid-based electrolytes4.
In more detail, using the Ca(FSI)2 salt in combination with the analogous Li-, Na-, and KFSI salts in equimolar compositions, all with melting temperatures (significantly) above 100 °C, we can create electrolytes melting at ca. 60-75 °C for the ternary systems, which is further reduced to ca. 55 °C for the quaternary system. These lowered melting temperatures are achieved by increased entropy of mixing, reducing the Gibbs free energy. This can for example be illustrated by Raman spectroscopy via comparing the spectra of “as cast” electrolytes with the spectra for the ones “aged” for one week (Figure 1). Here the FSI anion band at 772 cm-1 (νsS-N-S)5 shows that the electrolytes partially (re-)crystallize/micro-separate for the ternary systems, but stay more stable for the quaternary system, which we, at least partially, attribute to an entropy effect.

Reference
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Figure 1
Tight-Binding Modelling of Deep Eutectic Solvent Based Electrolytes
Authors: Alhanash Mirna , Johansson Patrik 
Published: February 2024

Deep eutectic solvents (DES) have in recent years gained momentum in the development of new electrolytes for lithium-ion batteries (LiBs)1. Due to their easy creation, tuning possibilities, wide electrochemical stability windows, and low vapor pressures, they are not only able to create safer LiB electrolytes as compared to traditional organic electrolytes, but more importantly, they may enable high voltage LIB cells2. One aspect not yet fully understood is the connection between the symmetry and entropy of the DES local structure and their macroscopic properties. Exploring this connection could assist in rational design of more performant electrolytes, including controlled electrochemical properties, by symmetry and entropy tuning.
Herein, we have studied in detail a few simple DES electrolytes created using the hydrogen bond donor N-methyl-acetamide (MAc) combined with each of the three different lithium salts: LiBF4, LiDFOB, and LiBOB, in 1:4 molar ratios – as previously shown advantageous 3. We chose these salts as they exhibit pseudospherical (BF4-), asymmetrical linear (DFOB), and symmetric linear (BOB) anion geometries and thus are plausible to introduce local symmetry differences. Molecular dynamic simulations were run using DFTB+ 4 and the xTB method 5, and as a first level geometrical analysis we look at the (partial) coordination and solvation numbers of the lithium ions.
References:
1. A. M. Navarro-Suarez and P. Johansson, J. Electrochem. Soc. 167 (2020) 070511.
2. H. Ogawa et al., Phys. Chem. Chem. Phys. 22 (2020) 8853-8863.
3. B. Bang et al., Korean J. Chem. Eng. 33 (2016) 1441–1446.
4. H. B. Aradi et al., J. Phys. Chem. A 111 (2007) 5678–5684.
5. S. Grimme et al., J. Chem. Theory Comp. 13 (2017) 1989-2009.
Li1.3Al0.3Ti1.7(PO4)3 /PEO Polymer Double-Layer Electrolyte to Improve Electrochemical Properties of Li-CO2 Battery
Authors: Lim HakBeom , Kim Jae-Kwang 
Published: February 2024

Li−CO2 batteries are explored as promising power systems to alleviate environmental issues and to implement space applications. However, sluggish cathode kinetics of CO2 reduction/evolution result in low round-trip efficiency and poor cycling stability of the fabricated energy-storage devices.
Herein, we design a double-layer solid electrolyte to decrease interfacial resistance. Li-CO2 battery with high stability and energy density was developed using Li1.3Al0.3Ti1.7(PO4)3 (LATP) as the solid-state electrolyte and a polyethylene oxide (PEO) polymer electrolyte film together. The oxide solid electrolyte LATP has temperature stability and physical solidity, but it has a metal substitution reaction with lithium metal and a low interfacial stability with the electrode. However, this drawback can be solved by using the polymer electrolyte PEO to avoid direct contact between the lithium metal electrode and LATP. The mechanism of the Li-CO2 battery, a carbon capture technology, is used, and the characteristics of the oxide solid electrolyte and polymer electrolyte are combined to suggest a new solution for improving the stability and performance of the battery.
Formation of N-Rich Solid Electrolyte Interphase with LiNO3 Solution for Lithium Metal Powder Batteries
Authors: Kang Dongyoon , Dzakpasu Cyril Bubu Bubu , Ryou Sun-Yul , Lee Hongkyung , Lee Yong Min 
Published: February 2024

Conventional manufacturing process of Li metal anodes employs extrusion-pressing or deposition methods resulting in sheet or film-types, respectively. Considering the demands for high-gravimetric energy density, thinner Li metal is crucial for realizing the desired weight ratio of anode in Li metal batteries (LMBs). However, during the manufacturing process at high rate, there could be limitations such as Li damage or dendritic growth caused by excessive pressure or non-uniform deposition. Li metal powders (LMPs) are beneficial for fabricating thin Li anodes within a short time via a slurry coating process. Despite the advantages of LMP, the Li2CO3 passivation layer unevenly covering the LMP surface results in dendritic Li growth. Thus, modification of the passivation layer is very crucial to control the Li plating/stripping behavior.
Here, we suggest a LiNO3 solution-treated LMP electrode for securing robust cyclability with low overpotential in LMBs. The dissolved LiNO3 in the LMP slurry can effectively modify the passivation layer into an N-rich SEI, enabling a uniform Li+ flux. Additionally, the well-distributed LiNO3 in the LMP anode could continuously repair the SEI during cycling via a slow-release mechanism into the carbonate-based electrolyte system. As a result, the LiNO3-treated LMP electrode effectively enhances the performance and stability of LMBs. Therefore, LiNO3 solution treatment of Li metal is an attractive approach to achieving a stable and robust SEI in LMBs.
Calcium – Oxygen Batteries: Challenges and Possibilities
Authors: Slim Zaher , Šekularac Gavrilo , Mihalinec Grgur , Johansson Patrik , Panić Vladimir , Mandic Zoran 
Published: February 2024

The present lithium-ion battery technology has a hard time keeping pace with the ever-increasing demands and requirements of various applications and markets. To enable continuous and sustainable growth of society, we need to develop new less expensive and less environmentally unfriendly energy storage solutions, and preferably also with higher gravimetric and volumetric energy densities, high power densities, and long(er) cycle-life. In this context, rechargeable metal–oxygen batteries are often considered the “Holy Grail” – this as the cathode of conventional metal-ion batteries most often is the most expensive component and at the same time the most challenging from both environmental and resource perspectives. An oxygen/air cathode, especially when used with a multivalent metal anode, can thus be a path to secure reliable energy storage for the future with significantly fewer concerns.
Herein we describe the efforts made in the framework of our NATO-funded project: “High-energy Ca–O2 batteries”. The overall objective is to overcome the challenges of both a reversible oxygen cathode and the passivation of calcium metal via a proper selection of Ca metal, electrolyte design, and oxygen reduction catalysts/oxygen evolution mediators. We do this by developing two compatible half-cells with full cell KPIs in mind.
Initially, we have explored, mainly via cyclic voltammetry, standard style organic electrolytes based on either Ca(TFSI)2 or Ca(OTf)2 and a boron-based additive, showing the latter to significantly enhance the Ca plating/stripping at room temperature. For the Ca(OTf)2 salt we create electrolytes using a tailored mixture of organic solvents, which not only allows for higher salt concentrations but also a wide ranges of additives possible.
At the cathode/electrolyte interface a novel bi-functional multi-component catalyst has been employed to create gas-diffusion electrode (GDE) assemblies based on transition metal (Co, Mn) oxides as interactive supports for Ir and Pt in few-monolayer sizes. These are first tested using model aqueous solutions before turning to the organic electrolytes. Preliminary tests indicate controlled kinetics of the hydrothermal oxide generation and the electrochemical deposition/galvanic replacement, which could result in adequate bi-functional activity.

Figure 1
Modelling Interfaces for Solid Electrolytes
Authors: Dippell Jan , Danner Timo , Latz Arnulf 
Published: February 2024

All-solid-state batteries (ASSBs) are candidates for the next-generation of battery electric vehicles. They potentially enable the use of lithium metal as an anode material thereby highly improving the energy density of the battery. Among the most promising candidates for solid electrolytes are polycrystalline materials such as LLZO, due to their high ionic conductivity and chemical stability. Lithium dendrites form above a critical current density (CDC) of as low as 0.6 mA/cm² [1], however. While some explanations where suggested, the underlying mechanisms are not yet understood. In a recent paper a more viable CDC of 5 mA/cm² was reported, which was achieved by protonating the interfaces and grain boundaries [2], this shows that understanding both external and internal interfaces is crucial for the successful development of ASSBs.
One often used tool in battery analysis is Electrochemical Impedance Spectroscopy (EIS). We developed a continuum scale model [3] in order to compare experimental impedance data with simulated impedances for a range of possible interface configurations. Space charge layers and their effects are resolved in the model and material properties are informed by atomistic simulations.
In our contribution we simulate impedances at ASSB internal and external interfaces. The comparison to experiment helps us validate the model while better understanding the effect that different interface configurations have on resistance and capacitance. The gained understanding can inform the development and manufacturing of future ASSBs.

Acknowledgements

This work contributes to the research performed at CELEST (Center for Electrochemical Energy Storage Ulm-Karlsruhe). The authors thank the German Ministry of Education and Research (BMBF) for funding of the project CatSE II under grant number 03XP0223E.

Han, F., Westover, A. S. et al. Nature Energy 2019, 4(3), 187-196. DOI: 1038/s41560-018-0312-z

Kim, S., Kim, J. S. et al. Nature Commun 2022, 13(1), 1-12. DOI: 10.1038/s41467-022-29531-x

Becker-Steinberger, K., Schardt, S. et al. arXiv 2021 DOI: 10.48550/arXiv.2101.10294
(Invited) Different Designs for Ta-Doped Llzo Based Solid State Battery Prepared By Tape-Casting
Authors: Vestli Mihkel , Pateli Ioanna , Irvine John 
Published: February 2024

One pathway for moving forward from current Li-ion battery technology based on organic liquid electrolytes to next-generation battery design can be implementation of solid state electrolyte along with Li metal based negative electrode. This step would result in a battery with higher energy density and improved safety.
One promising candidate material for ceramic electrolyte is garnet-type oxide LLZO (Li7La3Zr2O12) due to its relatively good chemical stability which allows relaxed requirements for processing and handling. Additionally, the doped LLZO has sufficiently good Li+ ionic conductivity (0.1 – 1 mS/cm at room temperature) and exhibits (electro-)chemical stability with the electrode materials currently under focus. To achieve low resistance values, the LLZO electrolyte needs to be prepared as a thin layer with high density. In order to integrate fabrication of LLZO electrolyte into industrial manufacturing, tape-casting can be considered as one of the low-cost scalable method for producing ceramic layers.
In this study tape-casting was used to produce Ta-doped LLZO electrolyte layers with relative density of 98% and total conductivity of 0.3 mS/cm at room temperature. In order to obtain Li/LLZO/Li symmetrical cells, interfacial treatment was used for surface of LLZO to achieve good contact and low interfacial resistance with Li metal electrode. Current densities up to 300 µA/cm2 were achieved during galvanostatic cycling for flat LLZO pellet sample at 40 °C. The cell was galvanostatically cycled with high stability for long term at current density of 100 µA/cm2.
Another design that can be considered for LLZO-based solid state battery is porous-dense-porous multilayers. This architecture has the advantage to provide support for electrolyte layer allowing to reduce its thickness and also increases the interfacial surface area which will reduce interfacial resistance. The described design allows to obtain lower resistance for the solid state battery with higher accessible current densities (>1mA/cm2), thus providing higher performance.
Towards Totally Aqueous Membrane-Free Flow Batteries: Fundamentals and Challenges
Authors: Navalpotro Paula , Ibañez Santiago Enrique , Pedraza Eduardo , Marcilla Rebeca 
Published: February 2024

The implementation of renewable energies (solar, wind, etc) is driven the development of new energy storage systems that can mitigate their inherent intermittency solving the mismatch between the energy demand and production. Among different systems, electrochemical energy storage devices stand out due to their efficiency, flexibility and modularity. Specifically, Redox Flow Batteries (RFB) are the unique type of battery able to decouple energy and power densities which makes them versatile and adaptable to different applications. Nevertheless, although they are commercially available, their implementation is limited by the high cost and issues associated with some components such as the vanadium-based electrolytes and Nafion ion-exchange membranes. In this regard, our approach to overcome these limitations is the development of a membrane-free flow battery based on immiscible/biphasic electrolytes with organic active species1,2. In this talk, we will present a totally aqueous membrane-free battery based on a sustainable and safe aqueous biphasic system with near neutral pH and highly soluble organic active species. The aqueous biphasic electrolytes allow a selective thermodynamic separation of the active species instead of using any membrane or physical barrier. Thanks to a new flow-cell design3, it becomes the first example of aqueous membrane-free flow battery (Figure 1). The results show high coulombic efficiency (94%), capacity utilization (98%), and stable long-term performance over 250 cycles4. The fundamental aspects and the last advances in this innovative concept will be discussed.
Figure 1 Schematic representation of the development of a membrane-free flow battery based on two aqueous biphasic electrolytes with organic active species.
References:
[1] Navalpotro, P.; Palma, J.; Anderson, M.; Marcilla, R.. Angew. Chemie - Int. Ed. 2017, 56 (41), 12460–12465.
[2] Navalpotro, P.; Trujillo, C.; Montes, I.; Neves, C. M. S. S.; Palma, J.; Freire, M. G.; Coutinho, J. A. P.; Marcilla, R.. Energy Storage Mater. 2020, 26, 400–407.
[3] Montes, I.; Marcilla, R.; Palma, J.; Ventosa, E.; Vera, M.; Sánchez Sanz, M.; Ibañez, S.E.. Redox flow Battery with immiscible electrolyte and flow through electrode, WO2021209585A1.
[4] Navalpotro, P.; Ibañez, S. E.; Pedraza, E.; Marcilla, R.. Energy Storage Mater. 2023, 56, 403-411.

Figure 1
Towards Semi-Solid Organic Redox Flow Batteries: Material Screening, Electrochemical Performance, and Reactor Design Optimization
Authors: Zaffaroni Riccardo , Alfonso Villanueva Angel , van der Willige Nolan , Brandt Nathanael , Brentjes Antoni , Dussi Simone , Tedesco Michele 
Published: February 2024

As our society transitions to cleaner sources of energy, the need for stationary electricity storage becomes increasingly important. In this context, redox flow batteries (RFBs) have emerged as a promising solution to provide electricity storage at full scale, due to their high scalability and flexibility. However, despite the growing research interest, there is still a urgent need of novel batteries, which are able to operate at high energy densities while relying on sustainable, abundant, and cost-effective electrolytes.
In this work we report the development of novel semi-solid RFBs based on cost-effective and environmentally friendly organic materials. We have systematically screened different classes of organic molecules, to identify suitable redox couples that can operate under stable conditions (i.e., >5,000 cycles) in a wide pH range. Therefore, we have experimentally investigated the most promising redox couples in a 10-cm2 electrochemical cell, to understand the behavior of the systems under different carbon and active molecule loadings. Finally, we have simulated the performance of the battery under dynamic and steady-state conditions, aiming to quantify the influence of fluid dynamics and rheological properties of the carbon slurry on the electrochemical performance. Based on our simulations results, we have identified new reactor designs for the RFB, aiming to optimize both fluid dynamics and electrochemical performance of the battery. Such designs represent an important first step towards future upscaling strategies.
Study of the Properties of Iron/Iron Redox Flow Batteries
Authors: Challuri Sai Venkata Akhil Kumar , Noack Jens 
Published: February 2024

New energy storage technologies are needed to offset the erratic power supply of renewable energy sources due to the rising global energy demand and the urgency of climate change action. Even if there are still concerns with operational parameters and efficiency, the Iron/Iron redox flow battery is a viable contender for large-scale energy storage. Iron is a highly affordable active material, making it possible to create inexpensive energy storage systems and possibly batteries with very low initial investment costs due to the positive electrode's moderate pH and relatively low voltage, maintaining minimal toxicity and aggression. Many challenges have been faced in the experiments on iron/iron redox flow batteries. For example, hydrogen formation and its impacts on the system must be minimized to ensure long-term use as an energy storage device. Iron hydroxides quickly form in response to elevated pH levels or contact with ambient oxygen, which restricts the battery's effectiveness.
For each series, various iron/iron redox flow batteries were assembled, and their functional properties were studied as a sustainability factor. The functional properties of the battery, such as an increase in electrolyte volume, an increase in charge/discharge times, the addition of a break time between charge/discharge cycles, varied charge cut-off voltages, varied discharge cut-off voltages and IU charge/discharge were investigated. It was also possible to complete more than 50 cycles with 8 hours of charging time and calculate and compare efficiencies and other performance values. The 8 hours of charge/discharge parameter proved to be the most suitable for conducting long-term cycling experiments because of the increased CE and EE trendline over 25 cycles. The 60 minutes rest time recorded a delay of charge voltage with a maximum of 35 minutes starting from the third cycle because of the blockage of the membrane and polarization effects. An optimized battery achieved up to 62% energy efficiency at 25 mA/cm2 with 4 hours of charging time and 8.01 Ah maximum theoretical capacity.

Figure 1