bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thiocarbonyls as Performance Enhancing Additives for Lithium-Sulfur Batteries
Authors: Searle Joanne , Kibler Alexander , Walsh Darren Anthony , Johnson Lee R , Saywell Alexander , Newton Graham 
Published: December 2024

The lithium-ion battery (LIB) has been key to the electrification of the automotive sector. It is anticipated that electrification of sectors such as haulage and aerospace will require energy storage systems with capacities and performance beyond the capabilities of traditional LIB chemistries.[1] Lithium-sulfur (Li-S) batteries are a front-runner among next generation battery technologies, thanks to their high theoretical capacities (1675 mAh g-1) and impressive gravimetric energy densities (2,700 Wh kg-1).[2,3] Despite their potential, there are numerous chemical challenges (active material dissolution, polysulfide shuttle, dendrite formation etc.) that must be overcome before widespread adoption of the technology.[4] Electrolyte additives have been explored as a means to minimise active material loss within the cell and improve long-term cyclability and cell discharge capacity.[5]
Thiocarbonyl compounds are well known in the polymer science community, behaving as reversible addition fragmentation chain transfer (RAFT) agents.[6] The reactivity of the thiocarbonyl group in the presence of nucleophilic molecules such as polysulfides renders them promising additives for Li-S batteries. Here, we present our studies on ethyl 2-(4-methoxyphenylcarbonothioyl thio)acetate (EM), a thiocarbonyl derivative, as a new type of electrolyte additive that can improve the cycle life of Li-S batteries. A variety of electrochemical and analytical techniques, combined with computational density functional theory (DFT) calculations, have been employed to assess the suitability of EM as an additive in Li2S cells. We have built an understanding of its interactions with active materials in a Li-S cell, with results proving that EM chemically reacts with and aids the oxidation of Li2S. Galvanostatic cycling has allowed us to corroborate our electrochemical and computational findings with cell cycling performance. We observe a significant enhancement in long-term cycling capacity when the additive is introduced to the electrolyte.

Figure 1. A blot plot displaying the discharge capacities at specific cycle numbers for standard (light grey) and EM (dark grey) cells to provide a statistical comparison.
References:
[1] T. Kim, W. Song, D.-Y. Son, L. K. Ono and Y. Qi, J. Mater. Chem. A, 2019, 7, 2942–2964.
[2] A. Fotouhi, D. J. Auger, L. O’Neill, T. Cleaver and S. Walus, Energies, 2017, 10.
[3] S. Gifford and J. Robinson, Faraday Insights, 2020, 1-5.
[4] A. Manthiram, Y. Fu, S.-H. Chung, C. Zu and Y.-S. Su, Chem. Rev., 2014, 114, 11751–11787.
[5] J. M. Cameron, C. Holc, A. J. Kibler, C. L. Peake, D. A. Walsh, G. N. Newton and L. R. Johnson, Chem. Soc.
Rev., 2021, 50, 5863–5883.
[6] S. Perrier, Macromolecules
, 2017, 50, 7433–7447.

Figure 1
Binary Mixture–Based Electrolytes Using Imidazolium-Based Ionic Liquids for Enhanced Safety and Electrochemical Performance of Lithium-Ion Batteries
Authors: Kakibe Takeshi , Hirai Daichi , Matsuda Satoshi , Nakamura Tatsuya , Kishi Hajime 
Published: December 2024

In recent years, secondary lithium-ion batteries (LIBs) have become critical components for portable devices and large power source systems such as electric vehicles (EVs) and hybrid EVs (HEVs).[1],[2] However, conventional LIBs typically use flammable nonaqueous liquid electrolytes, posing a serious safety risk. Our previous study[3] demonstrated that one promising approach for safe LIBs involves using electrolytes based on a series of ionic liquids (ILs) with branched alkyl imidazolium cations. The introduction of bulky branched alkyl groups enhances charge delocalization in imidazolium cations, thereby improving the electrochemical reduction stability. Herein, we evaluated the compatibility and electrochemical performance of two types of ILs: branched alkyl functional and electrochemically polymerizable ILs. Moreover, binary mixture–based electrolytes based on their ILs were investigated for use in LIBs.
We synthesized two types of ILs: reduction-stable and polymerizable ILs (Fig. 1). An IL-based electrolyte was mixed with various compositions of reduction-stable and polymerizable ILs, with LiFSA (LiFSA molal concentration: ca. 1.5 mol/kg) serving as the Li ion source. The characteristics of the involved battery were examined using a graphite electrode | IL–LiFSA mixture–based electrolyte | Li metal half-cell configuration. The graphite electrode sheets comprised NMC powder (86 wt%) as the active material, acetylene black (7 wt%) as an electrically conductive additive, and poly(vinylidene fluoride) (7 wt%) as a binder. The graphite electrode sheet, separator, IL–LiFSA mixture–based electrolyte, and Li were assembled into a battery cell. Performance tests for charge–discharge rates were conducted at 303 K, with the involved rates varying from 0.1 to 0.5 C.
Fig. 2 shows the first charge–discharge profiles of the graphite | Li half-cells with [EPisoIm][FSA]–, [APisoIm][FSA]–, and [EPisoIm]0.8[APisoIm]0.2[FSA]–based electrolytes. During the first charge with the [APisoIm][FSA]– and [EPisoIm]0.8[APisoIm]0.2[FSA]–based electrolytes, a plateau was observed at approximately 0.5 V, attributed to the reduction decomposition and polymerization of [APisoIm] cations on graphite. The presence of [APisoIm] cations enabled the formation of a stable solid electrolyte interface, an electron-insulating, lithium-ion-conducting film.
[1] M. Wakihara, “Recent developments in lithium ion batteries”, Mater. Sci. Eng., R, 33, 109 (2001).
[2] D. D. Lecce, R. Verrelli, and J. Hassoun, “Lithium-ion batteries for sustainable energy storage: recent advances towards new cell configurations”, Green Chem., 19, 3442 (2017).

Figure 1
Understanding Interfacial Degradation in All Solid-State Lithium Batteries from Multiscale Simulations
Authors: Wan Liwen , Yuan Suyue , Wang Bo , Kim Kwangnam , Heo Tae Wook , Wood Brandon C. 
Published: December 2024

All solid-state battery technologies show great promises as next-generation energy storage solutions with opportunities to achieve higher energy density and improved safety features compared to the current liquid-based lithium-ion battery technologies. However, their practicality is limited by high interfacial impedance for ion transport and poor mechanical stability during cycles. In this talk, I will address the key chemo-mechanical coupling effect that critically defines the functionality of interfaces in all solid-state lithium batteries. I will consider the interface of garnet Li7La3Zr2O12 solid-electrolyte and LiCoO2 cathode as an example to demonstrate the powerfulness of multiscale modeling to identify degradation modes that can attribute to high interfacial resistance for Li-ion transport and mechanical failure. Mitigation strategies will be discussed based on manipulation of processing condition and the resulting microstructures to improve interfacial stability and thus enhance the cycling performance of catholyte.
This work was sponsored by the Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Next Generation Solid-State Batteries for Electric Aviation
Authors: Dornbusch Donald , Lin Yi , Huddleston William , Yamakov Vesselin I , Viggiano Rocco P. 
Published: December 2024

Energy storage will play a critical role in the success of future NASA missions that require batteries with higher energy density, higher power, and most critically improved safety. These performance requirements, which extend beyond those for electric automobile markets, must be satisfied to enable widespread adoption of electric aviation. One approach to improve battery safety and energy is to transition to non-volatile solid-state electrolytes (SSE) which promise many advantages over traditional flammable liquid electrolytes and may also be an enabling technology for next generation chemistries such as lithium-sulfur (Li-S). However, significant manufacturing challenges must be overcome before the adoption of such technology. This study will discuss development of solid electrolytes specifically designed to meet future NASA electric aviation targets. Separator films were processed with densified thickness between 20-30 microns using solvent processing techniques [1]. These films were produced 10-15 times thinner than comparable bulk pressed powder electrolytes and achieved thicknesses comparable to commercial polyolefin separators (25 micron) used in commercial liquid containing lithium-ion cells. Furthermore, design considerations and fabrication techniques of novel cathode composites optimized through the integration of experiment and particle dynamics modeling will be discussed [2] [3].
[1] Donald A. Dornbusch, Rocco P. Viggiano, John W. Connell, Yi Lin, Vadim F. Lvovich. Practical considerations in designing solid state Li-S cells for electric aviation, Electrochimica Acta, 2021, 139406, ISSN 0013-4686,
[2] Vesselin I. Yamakov, April A. Rains, Jin Ho Kang, Lopamudra Das, Rehan Rashid, Ji Su, Rocco P. Viggiano, John W. Connell, Yi Lin. Pressure Dependence of Solid Electrolyte Ionic Conductivity: A Particle Dynamics Study. ACS Applied Materials & Interfaces 2023, 15 (22) , 27243-27252.
[3] Elizabeth A. Barrios, April A. Rains, Yi Lin, Ji Su, John W. Connell, Rocco P. Viggiano, Donald A. Dornbusch, James J. Wu, and Vesselin Yamakov. Li-Ion Permeability of Holey Graphene in Solid State Batteries: A Particle Dynamics Study. ACS Appl. Mater. Interfaces 2022, 14, 18, 21363–21370.
(Invited) Revealing the Reaction Mechanism and Chemo-Mechanics of Solid-State Na-S Batteries
Authors: Nguyen Hung Quoc , Todt Juraj , Boles Steven T , Keckes Jozef , Rettenwander Daniel 
Published: December 2024

Solid-state sodium-sulfur batteries show great promise for energy storage applications due to their high energy density, cost-effectiveness, and abundance of raw materials. Despite these promising characteristics, challenges such as the phase evolution of (poly)sulfides and how it is linked to the significant volume expansion occurring in the cathode during cycling are still poorly understood.1,2

In this talk, I will showcase our recent progress in developing solid-state sodium-sulfur batteries using different solid electrolyte systems, namely Na3PS4 and closo-borates. I will discuss how tortuosity impacts sulfur utilization in the composite cathode and provide new insights into sulfur redox chemistry and associated kinetic limitations. Furthermore, I will examine the correlation between phase, volume, and stress evolution.
In summary, this study will offer unprecedented insights into the underlying mechanisms in solid-state sodium-sulfur batteries, which are of utmost importance for their further development towards commercialization.

References

Lei, Y. J., Liu, H. W., Yang, Z., Zhao, L. F., Lai, W. H., Chen, M., ... & Wang, Y. X. (2023). A Review on the Status and Challenges of Cathodes in Room‐Temperature Na‐S Batteries. Advanced Functional Materials, 33(11), 2212600.

Ma, J., Wang, M., Zhang, H., Shang, Z., Fu, L., Zhang, W., ... & Lu, K. (2023). Toward the Advanced Next‐Generation Solid‐State Na‐S Batteries: Progress and Prospects. Advanced Functional Materials, 33(20), 2214430.

Acknowledgment

D.R. acknowledge financial support from the Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology, and Development, and the Christian Doppler Research Association (Christian Doppler Laboratory for Solid-State Batteries). J.T., J.K., D.R. acknowledge funding from the European Union's Horizon Europe research and innovation program under Grant Agreement No 101103834 (OPERA).
Photoelectrochemical properties of Single walled and Double walled TiO2 nanotubes
Authors: Lee Ah-yeong , Jung Rin , Yoo JeongEun , Lee Kiyoung 
Published: December 2024

Titanium dioxide (TiO2) is one of the most studied materials to be applied in various filed due to its high environmental compatibility and corrosion resistance [1-2]. Among the nanostructures of TiO2 is including nanoparticles, nanorods, nanoplates, and nanotubes, nanotubular TiO2 acquires not only a high surface area but also rapid charge carrier transfer, providing higher efficiency for photocatalytic application such as, the degradation of organic contaminants and hydrogen production. Although various methods have been investigated to fabricate TiO2 nanotubes, the anodization technique is favored with its straightforward control over structure and direct growth on Ti substrates[3]. However, conventional anodic TiO2 nanotubes exhibit surface irregularities and double-walled structure consisting of carbon-rich inner and TiO2 out layer[4]. The inner layer of TiO2 nanotubes diminishes the photoelectrochemical efficiency owing to the carbon contamination.
In this study, double walled TiO2 nanotubes were synthesized by anodization with an applied voltage of 60 V for various periods. A piranha solution was utilized to eliminate the inner layer for double walled TiO2 nanotubes, achieving a single-walled TiO2 nanotube configuration. The morphological properties, crystallinity, and surface resistance of both single and double-walled TiO2 nanotubes were evaluated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Electrochemical Impedance Spectroscopy (EIS). In addition, the photoelectrochemical efficiencies of all TiO2 nanotubes were evaluated employing linear sweep voltammetry (LSV) and Incident photon-to-current efficiency (IPCE) measurements. As a result, the single-walled TiO2 nanotubes, produced under the specific conditions of 60 V for 7 min, showed the highest photoelectrochemical efficiencies at LSV and IPCE. The higher photoelectrochemical properties of the single walled nanotube are attributed to the enhancenment of surfave chage dynamics and environmental reactions as eliminating the inner layer.
[1] Fujishima A, Honda K, Electrochemical photolysis of water at semiconductor electrode. Nature 238 (1972) 37-38
[2]Lee K, Mazare A, Schmuki P, One-dimensional titanium dioxide nanomaterials: nanotubes, Chem. Rev, 114 (2014) 9385–9454,
[3] Yoo JE, Lee K, Altomare M, Selli E, Schmuki P, Self-organized arrays of single-metal catalyst particles in TiO2 cavities: a highly efficient photocatalytic system, Angew. Chem., Int. Ed, 52 (2013) 1002
[4] Liu N, Mirabolghasemia H, Lee K, Albua SP, Tighineanua A, Altomareab M, Schmuki P, Anodic TiO2 nanotubes: double walled vs. single walled. Faraday Discuss, 164 (2013) 107-116.
Physical and Electrochemical Properties of Zinc Chloride and Potassium Chloride Based Non-Aqueous Electrolytes
Authors: Mishra Arpita , P Manju , Sarkar Arindam , Suthar BharatKumar 
Published: December 2024

Ethylene glycol is a useful solvent which has applications in thermal, electrochemical and chemical systems as an antifreeze, dehydrating agent and corrosion preventor. Here, we have focused on some physical and electrochemical properties of the solvent which might help in determining a good performing electrolyte in a battery. We have added zinc chloride (ZnCl2) and potassium chloride (KCl) in ethylene glycol and made a ternary diagram of the three compounds according to which we have varied the concentrations of both salts. The mixtures were prepared in a glove box to not absorb moisture from the environment due to humidity. The electrochemical characterization of the solutions was done in zinc-zinc symmetric coin cells on which electrochemical impedance spectroscopy was performed at room temperature. This enabled the determination of the electrolyte resistance, exchange current density and activation energy. Additionally, ionic conductivity and viscosity were also measured using a conductivity meter and rheometer.
We observed that as ZnCl2 and KCl increased, conductivity increased, and it was maximum where both the salt concentrations were maximum. However, the exchange current density reached its maximum somewhere in the middle after which increasing the concentration resulted in its decrease. Viscosity increased slowly as the amount of ethylene glycol decreased and then it rose up steeply for the solution where no KCl was present and zinc chloride was maximum. These results showed a pattern of how the parameters depend on each species' concentration. The data trends were tried to be fitted by an equation model to predict its behavior at any arbitrary concentration. The conductivities of some concentrations were comparable to LiPF6 which is a common electrolyte used in lithium-ion batteries.
The findings contribute to understanding the solution’s performance in zinc or potassium ion batteries or capacitors as an electrolyte. These results can also be used for studying the electroplating attributes of zinc.
Advancements in Redox-Mediated Electrodialysis for Valorization of Biomolecules
Authors: Kim Nayeong , Aguda Aderiyike , Lee Jiho , Jeon Jemin , Elbert Johannes , Su Xiao 
Published: December 2024

In the chemical and biochemical manufacturing industry, separation processes are amongst the most energy-demanding processes, accounting for 50% of total operating costs.1, 2 Redox-mediated electrodialysis (redox-ED) has attracted attention as a process-intensified method for resource recovery, particularly selective recovery of organic molecules such as proteins and organic acids.2, 3 By replacing water-splitting reactions with reversible redox reactions, pH-sensitive biomolecules can be electrochemically recovered with reduced overall energy consumption. We demonstrated the valorization of proteins from whey waste via the redox-ED platform.2 Our system treated 99% of salt from the whey solution within a single step and recovered over 98% of various whey proteins (e.g., beta-lactoglobulin and alpha-lactalbumin). The preliminary techno-economic analysis confirmed the economic viability of redox-ED with 51−73% lower energy consumption compared to conventional ED.
Moreover, we mitigated the inherent limitation selectivity of ion-exchange membranes in discriminating among the same charged species (e.g., cations and anions), by employing a layer-by-layer (LBL) membrane functionalization approach.3 This LBL membrane modification enabled the recovery of organic acids from a multicomponent mixture, where there is a mixture of neutral and charged species. By tailoring the physicochemical properties of IEMs through the LBL polyelectrolyte layers, we achieved complete retention of succinic acid produced in the fermentation process, while enhancing the overall flux for inorganic ions.3 Redox-ED with LBL-functionalized membrane demonstrated the continuous up-concentration of succinate alongside the isolation of unreacted sugar and inorganic ions, opening avenues for modular multicomponent separations in biomanufacturing processes.

References

(1) Kim, N.; Jeon, J.; Chen, R.; Su, X. Electrochemical separation of organic acids and proteins for food and biomanufacturing. Chemical Engineering Research and Design
2022, 178, 267-288.
(2) Kim, N.; Jeon, J.; Elbert, J.; Kim, C.; Su, X. Redox-mediated electrochemical desalination for waste valorization in dairy production. Chemical Engineering Journal
2022, 428, 131082.
(3) Kim, N.; Lee, J.; Su, X. Precision Tuning of Highly Selective Polyelectrolyte Membranes for Redox‐Mediated Electrochemical Separation of Organic Acids. Advanced Functional Materials
2023, 33 (12), 2211645.
Model-Based Development of Control Strategies for a Fuel Cell Air Supply System and Experimental Verification at Flight-Relevant Conditions
Authors: Frank Daniel , Wazlawik Stefan , Brandao de Almeida Samara , Bauer Christiane , Willich Caroline 
Published: December 2024

The performance of hydrogen PEM fuel cell systems can be optimized by means of pressurization of the cathode air, especially in aviation, where at in-flight conditions the pressure of the ambient air is significantly lower as at on-ground conditions. To provide the inlet air at optimal conditions (p, T, rH) during flight, an air supply system is required and in an all-electric aircraft the compression should happen by means of an electric centrifugal compressor. A challenge for the operation of a pressurised fuel cell system at high altitudes is the control of the compression system. Any unstable operation like compressor surge has to be avoided, since it can damage both the fuel cell stack and the compressor itself. For the development of such an air supply system, a combined experimental and modeling approach was chosen.
A hydrogen PEM fuel cell system was characterized at nominal and at low cathode pressures to obtain the behavior at flight relevant conditions and an experimental air supply system containing electric compressor, intercooler, humidifier, cathode volume and throttle valve at the outlet has been set up and used for the development, parameterization, and validation of a model for the compression system. The model is based on the Greitzer model 1,2, and has been extended to also represent the additional components between the compressor and the throttle valve (intercooler, humidifier, and cathode volume) 3. It is now able to predict the transient response of the entire air supply system to changes in the reference values of compressor speed and valve opening angle and the resulting mass flow changes and pressures within the individual components.
The model and the data from the fuel cell system were used for the development of improved control strategies, that make it possible to operate the system safely in a wide range of operating conditions. Unstable situations, like compressor surge, are avoided by these control strategies even in the highly varying conditions during a flight. The developed control strategies are verified on the hardware of the experimental setup and tested under realistic flight conditions in a low-pressure climate chamber.
References

Greitzer, E. M. Surge and Rotating Stall in Axial Flow Compressors—Part I: Theoretical Compression System Model. Journal of Engineering for Power
98, 190–198 (1976).

Gravdahl, J. T. & Egeland, O. Compressor Surge and Rotating Stall. (Springer London, London, 1999). doi:10.1007/978-1-4471-0827-6.

Frank, D., Bauer, C. & Willich, C. Modeling of the cathode air supply for a pressurized hydrogen fuel cell system in airborne applications. Proceedings of the Aerospace Europe Conference 2023 (2023) doi:10.13009/EUCASS2023-218.