bluuebunny/crossref_metadata_2025_split huggingface dataset:
FeF2-Li Batteries in Ionic Liquid Electrolytes
Authors: Olbrich Lorenz Frank , Sanghadasa Mohan , Pasta Mauro 
Published: February 2024

The electrification of the aviation industry requires secondary batteries that meet strict technical specifications, which cannot be achieved by current lithium-ion cells. A step improvement in stack-level energy densities in addition to safer battery chemistries compatible with operations at temperatures up to 80°C are necessary to minimize water-cooling requirements and their adverse impact on energy density. [1]
Lithiation of transition metal fluorides (TMFs) cathodes occurs via a two- or three-electron transfer conversion mechanism, enabling an increase in theoretical energy density by 200% to 300% compared to conventional intercalation compounds. [2]
Ionic liquids (ILs) are characterized by their high thermal stability, little to no flammability, and low vapor pressure. [3]
Combining TMF cathodes with a lithium metal anode and an IL electrolyte results in a battery with a high energy density, safe cell operation, and high-temperature compatibility suitable for applications in electric aviation. [4, 5]
Here we present the progress we have made in the development of secondary FeF2-IL-lithium-metal batteries. Through a systematic investigation of active material particle morphology and carbon composite preparation techniques, we have been able to demonstrate stable capacity retention for over 500 cycles.
A post-mortem characterization analysis elucidates the role of the IL in forming stable interphases with both anode and cathode materials and on their ageing mechanism at room and elevated (80°C) temperatures.

Viswanathan, V. et al. The challenges and opportunities of battery-powered flight. Nature 601, 519–525 (2022).

Wang, L. et al. Li-free Cathode Materials for High Energy Density Lithium Batteries. Joule 3, 2086–2102 (2019).

Maton, C., De Vos, N. & Stevens, C. V. Ionic liquid thermal stabilities: Decomposition mechanisms and analysis tools. Chemical Society Reviews 42, 5963–5977 (2013).

Xiao, A. W. et al. Understanding the conversion mechanism and performance of monodisperse FeF2 nanocrystal cathodes. Nature Materials 19, 644–654 (2020).

Olbrich, L. F., Xiao, A. W. & Pasta, M. Conversion-type fluoride cathodes: Current state of the art. Current Opinion in Electrochemistry 30, 100779 (2021).

Figure 1
Metal(Pt, Pd)-Perovskite Oxide(Ba0.5Sr0.5Co0.8Fe0.2O3-δ) Hybrid Material As a Bifunctional Electrocatalyst for Lithium-Air Battery
Authors: Shin Seoyoon , Lee Seokhee , Shin Tae Ho 
Published: February 2024

The rapid depletion of fossil fuel resources and growing concerns over climate change have made the development of next-generation batteries a top priority. Among these, Li-O2 batteries have attracted significant interest due to their potential for much higher gravimetric energy storage density compared to other chemical batteries. However, efficient and cost-effective catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical for the efficient functioning of these batteries.
In recent years, complex perovskite oxides, such as Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), have been identified as promising candidates for bifunctional catalysts due to their defective structures and excellent oxygen mobility. However, while BSCF exhibits high OER activity, its ORR performance is poor. To address this issue, researchers have turned to metal-oxide composite catalysts, where nanosized metals are deposited on the surface of perovskite oxides, to increase activity and stability towards ORR due to the synergistic effect between metal and oxide support.
In this study, we report the development of bifunctional electrocatalysts with highly electrocatalytic activity for ORR and OER. We used a simple wet-chemical processing technique to deposit metal catalysts with superior ORR activity on perovskite oxide-based catalysts with high OER activity. The direct deposition method is an effective way to create a good distribution of metal catalysts, intimate contact between metal catalysts and BSCF perovskite oxide, which may contribute to the creation of a synergistic effect between them. Our results showed that the metal catalysts deposited on perovskite oxides of Pd@BSCF and Pt@BSCF exhibited better ORR activity than others and higher OER activity than the perovskite oxides alone, resulting in much-enhanced bifunctionality through a synergistic effect between the metal catalysts and perovskite oxides.
We further investigated the enhanced bifunctional electrocatalytic activity of the metal catalysts deposited perovskite oxides for Li-O2 batteries. The assembled Li-O2 batteries with Pd@BSCF cathode demonstrated lower discharge/charge overpotential (0.8 V at the cutoff capacity of 500 mAh gcat
-1) and improved cycling stability (over 70 cycles), indicating the effectiveness of our approach in enhancing the bifunctional activities of ORR and OER for application in electrochemical energy storage and conversion systems. The encouraging results obtained from this study might have been attributed to two mechanisms, namely, the synergistic effect of electronic transfer and RDS/spillover. Our study suggests that the deposition of metal catalysts on the surface of perovskite oxides (Pd@BSCF and Pt@BSCF) is an effective approach to enhance bifunctional activities of ORR and OER, making it a promising strategy for the development of next-generation batteries.

Figure 1
Zinc Slurry Electrodes for Double Flow Zinc-Nickel Batteries
Authors: Opitz Martin , Sörgel Seniz 
Published: February 2024

Lithium-based systems are still the major storage technology especially in mobile applications like electromobility and consumer electronics. However, in the field of stationary energy storage devices, redox-flow batteries exhibit significant advantages because energy and power can be scaled independently and the device can be discharged up to 20 h, in contrast to lithium-ion batteries.[1] In the field of redox-flow batteries, the main focus is placed on vanadium-based systems. However, vanadium-based systems have some drawbacks due to the low gravimetric energy densities, the toxicity [2] and the high price of vanadium [3], as well as the short life span of the membrane separating the half-cells.[4]
In our research project NiZi-Flow², a new concept of flow cells based on nickel and zinc is investigated, in which slurries of zinc and nickel-hydroxide particles are pumped through the flow battery, respectively. Our part in the project is the examination of the electrodeposition and dissolution of zinc under idealized conditions to obtain the influence of flow and current density parameters on the zinc surface morphology. To study the zinc half-cell, a stirred electrochemical cell was designed and cycling experiments with the zinc slurry were performed.

M. Skyllas-Kazacos, M.H. Chakrabarti, S.A. Hajimolana, F.S. Mjalli, M. Saleem, J. Electrochem. Soc., 158 (2011) R55.

A. Ciotola, M. Fuss, S. Colombo, W.-R. Poganietz, J. Energy Storage, 33 (2021) 102094.

T. Nguyen, R.F. Savinell, Electrochem. Soc. Interface, 19 (2010) 54–56.

A.Z. Weber, M.M. Mench, J.P. Meyers, P.N. Ross, J.T. Gostick, Q. Liu, J. Appl.
Electrochem., 41 (2011) 1137–1164.
Integrated Capture and Electrochemical Conversion of CO2 into CO
Authors: Xiao Yurou Celine , Gabardo Christine M. , Liu Shijie , Lee Geonhui , Zhao Yong , O'Brien Colin P. , Miao Rui Kai , Xu Yi , Edwards Jonathan P. , Fan Mengyang , Huang Jianan Erick , Li Jun , Papangelakis Panagiotis , Alkayyali Tartela , Sedighian Rasouli Armin , Zhang Jinqiang , Sargent Edward H. , Sinton David 
Published: February 2024

The capture and electrochemical conversion of CO2, powered by renewable electricity, is an attractive method of sustainably producing valuable chemicals and fuels (e.g. carbon monoxide (CO)), reducing atmospheric CO2, and storing intermittent renewable energy. Integrated capture and conversion (reactive capture) of CO2 presents a CO2-to-CO electrolysis pathway that eliminates most of the upstream capital and energy costs by releasing CO2 directly inside the electrolyzer using an internal pH-swing. The reactive capture system readily allows for the collection of produced gas products via phase separation, thus minimizing downstream separation costs.
Industrial-scale integration of reactive capture systems with upgrading processes require a pure and consistent product stream. Previous studies using bicarbonate electrolytes have demonstrated high selectivity towards CO. However, the limited CO2 capture capacity of bicarbonate electrolytes dilute the cathode product gas stream with excess CO2. This mandates a secondary CO2 capture unit and increases the cost of downstream separation. Other studies using carbonate or carbamate electrolyte as the inlet feed did not simultaneously achieve high CO selectivity and long-term stability.
This study sought to improve the Faradaic efficiency (FE) toward CO in our carbonate electrolysis system by engineering a novel membrane electrode assembly structure. We designed a composite CO2 diffusion layer (CDL) between the cathode and the membrane that attains high CO selectivity by simultaneously achieving high alkalinity and sufficient CO2 availability at the cathode. We determined that the thickness, wettability, and permeability of the CDL affected species transport and were important optimization parameters. Applying this strategy, we produced syngas, a mixture of CO and hydrogen (H2), with an industrial H2/CO ratio of 1.16 at 200 mA cm-2. This corresponded to a CO Faradaic efficiency (FE) of 46% and energy intensity of 52 GJ tsyngas-1. The syngas produced in this system was not diluted by CO2 and contained sufficient CO content to meet industrial standards. We further increased the FE towards CO by exploring different capture solutions and designing selective catalysts for energy efficient CO production. System parameters such as temperature and pressure effects were also investigated to improve the CO2 concentration at the cathode. This study illustrated the potential for the industrial implementation of an energy efficient and capital cost effective CO2-to-CO pathway via reactive capture.
Investigation of Aliovalent Substitution in the Solid Sodium Ion Electrolyte Na2ZrCl6
Authors: Guo Hao , Bianchini Matteo 
Published: February 2024

The research community is working hard on the development of solid-state batteries (SSB) as an alternative to commercialized lithium-ion batteries, due to their higher energy density and enhanced safety. One of the core research areas of SSBs is the solid-state electrolyte (SE), which should fit the demand for high ionic conductivity and electrochemical stability at the same time. Recently, halide SEs have emerged because they are mechanochemical processable, similar to sulfidic SEs, but halide SEs exhibit excellent electrochemical oxidation stability compared to sulfidic SEs [1,2].
However, the relatively low ionic conductivity at room temperature still hinders the application of halide SE in SSBs. Aliovalent substitution is a very widely used method to improve the ionic conductivity of SEs [3,4]. We are also motivated by the application of earth-abundance elements to reduce raw material costs.
Recently, significant focus has been gained by Zr-based compounds such as Na2ZrCl6. We investigate here such compounds, focusing on elemental substitutions to gain increased ionic conductivity and on gaining insight into the influence of synthesis on SE crystal structure and electrochemical properties.
In our work, different amounts of elemental substitutions are investigated, and the related materials are synthesized at different temperatures. In particular, the influence of a series of subsequent heating temperatures on the structure of the binary system is studied through XRD diffraction analysis and further refinement. The Ionic diffusion paths are also estimated through the band valence sum approach, in order to validate the electrochemical impedance spectroscopy (EIS) results.
In summary, we report our early results on the development of novel solid electrolytes for Na-based solid-state batteries.
REFERENCES
[1] Kwak, H.; Lyoo, J.; Park, J.; Han, Y.; Asakura, R.; Remhof, A.; Battaglia, C.; Kim, H.; Hong, S.-T.; Jung, Y. S. Na2ZrCl6 enabling highly stable 3 V all-solid-state Na-ion batteries. Energy Storage Mater. 2021, 37, 47−54.
[2] Tong Zhao, Alexander N. Sobolev, Roman Schlem, Bianca Helm, Marvin A. Kraft and Wolfgang G. Zeier. Synthesis-Controlled Cation Solubility in Solid Sodium Ion Conductors Na2+xZr1
-
xInxCl6.
ACS Appl. Energy Mater. 2023, XXXX, XXX, XXX-XXX.
[3] Schlem, R.; Banik, A.; Eckardt, M.; Zobel, M.; Zeier, W. G. Na3-xEr1-xZrxCl6-A Halide-Based Fast Sodium-Ion Conductor with Vacancy-Driven Ionic Transport. ACS Appl. Energy Mater. 2020, 3, 10164−10173.
[4] Wu, E. A.; Banerjee, S.; Tang, H.; Richardson, P. M.; Doux, J.M.; Qi, J.; Zhu, Z.; Grenier, A.;Li, Y.; Zhao, E.; Deysher, G.; Sebti, E.;Nguyen, H.; Stephens, R.; Verbist, G.; Chapman, K. W.; Clement, R.J.; Banerjee, A.; Meng, Y. S.; Ong, S. P. A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries. Nat. Commun. 2021, 12, 1256.
Binderless Sheet-Type Oxide-Sulfide Composite Solid Electrolyte for All-Solid-State Batteries
Authors: Kim A-yeon , Jung Hun-Gi , Shin Hyeon-Ji , Kim Jun tae 
Published: February 2024

Lithium-ion batteries have been used as energy sources not only for small electronic devices but also for high-capacity and high-energy-density applications such as electric vehicles. However, the use of flammable organic liquid electrolytes in lithium-ion batteries has raised safety concerns in various applications. Therefore, solid-state batteries using flame-retardant inorganic materials are considered a more reasonable direction for future energy sources due to their high safety and high energy density. Solid electrolytes(SEs) are divided into oxide-based, sulfide-based, and polymer-based. Each solid electrolyte has its own advantages and disadvantages. Oxide-based solid electrolytes (e.g., Li7La3Zr2O12 (LLZO), Li3xLa2/3-xTiO3 (LLTO), Li1.3Al0.3Ti1.7(PO4)3 (LATP)) are air-stable and exhibit excellent electrochemical properties over a wide potential range. However, their high interfacial resistance may limit their practical application as batteries. Sulfide-based solid electrolytes (e.g., Li6PS5X (X=Cl, Br, I), Li10GeP2S12, (100-x)Li2S-xP2S5)) have high ionic conductivity, ductile properties, low interfacial resistance, and good room temperature workability. However, they are vulnerable to atmospheric instability, which can produce toxic gases such as H2S, and are relatively electrochemically unstable with Li metal. Polymer-based solid electrolytes, such as those made from polymers like PEO, PVDF, PAN, etc. that are compounded with other solid electrolytes (oxides, sulfides, etc.), offer the advantage of being able to form solid electrolyte membranes over large areas. But they have low ionic conductivity and weak mechanical properties of the polymer itself, limiting their practical application.
To apply solid-state batteries to practical high-energy density energy storage devices such as electric vehicles, high ion conductivity, electrochemical stability, high mechanical properties, and large area formation of the electrolyte layer are essential. Solid electrolytes are mainly formed in powder form, and without a polymer binder, it is limited to apply as a film for large-capacity storage devices. Here, we fabricated a freestanding sheet-type Al-LLZO oxide-based solid electrolyte that forms a 3D network without a polymer material using an electrospinning method. In addition, we prepared a oxide-sulfide composite solid electrolyte membrane by impregnating LPSCl sulfide-based solid electrolyte into the Al-LLZO solid electrolyte sheet. As a result, This process removed the polymer and improved both the ionic conductivity and mechanical properties. Furthermore, it was possible to achieve both large-area and film characteristics without the need for a polymer.
Ceramic Composite Gel Polymer Electrolyte for Aqueous Zinc-Ion Battery
Authors: You Seungmin , Kang Chaeeun , Park Jooeun , Kim Jae-Kwang 
Published: February 2024

As the most extreme application of electrical energy storage devices, lithium-ion batteries (LIBs) not only have the high energy density, but also show long charge/discharge life cycles. Nevertheless, some inherent issues hinder its widespread application, such as the safety problems, lithium metal extrusion, dendrite growth, and the high cost, together with the limited resources of lithium metal. As one of the next-generation batteries, zinc-ion battery (ZIB) is a promising candidate to solve the above problems, due to their high theoretical capacity, low cost, high abundance, low potential, high energy density, and intrinsic safety. Three-types electrolytes, liquid-state, solid-state, and gel-state, are included in ZIBs. The aqueous ZIBs with liquid-state electrolytes are usually considered as ultra-intrinsic batteries. However, various side reactions of dendrite growth, oxygen evolution reaction, hydrogen evolution reaction, and metal Zn corrosion deteriorate the electrochemical reaction of ZIB.
Herein, ceramic composite gel polymer electrolytes preparing by electrospinning process were applied to improve the electrochemical properties of ZIB. The gel polymer electrolytes containing amounts of aqueous liquid electrolytes have the activity of water, which can extend the electrochemical stability window and provide good ﬂexibility and H+ insertion/extraction during charge/discharge process for high capacity and good cyclic stability.
Modelling Ca2+ Mobility and Dynamics in Solvent-Free Molten Salt Electrolytes for Calcium Batteries
Authors: Cruz Carolina , Johansson Patrik 
Published: February 2024

Multivalent elements based batteries using earth-abundant minerals is a route with promises, not only from a performance but also from a supply and cost point of view; this is not the last true for calcium (Ca) batteries since Ca is the fifth most abundant element in the Earth's crust [1,2,3]. There is, however, no functional electrolyte available yet for Ca batteries, calling for early modelling to be made to map the influence of different Ca-salts and salt concentrations on electrolyte physicochemical properties such as density, viscosity, ionic conductivity, charge carrier dynamics and diffusivity [3, 4].
One particular route little trodden is molten salt electrolytes (MSEs), materials that consist of ions with different valences in direct contact with each other due to the complete absence of any solvent. In practice, MSEs are multicomponent salt mixtures with reduced melting points with respect to the ingoing components and furthermore they also expand the operating temperature range upwards as compared to conventional liquid electrolytes. Moreover, MSEs have high ionic conductivities due to their intrinsically high ionic content and ionic mobility. Additionally, MSEs exhibit wide electrochemical stability windows, non-flammability, and non-toxicity [5, 6].
We have investigated MSEs composed of Ca(FSI)2, LiFSI, NaFSI, and KFSI, by molecular dynamics (MD) simulations. Apart from the basic properties, we focus on the relative dynamical properties of the different cations in the MSEs in order to obtain a fundamental understanding of the systems’ behaviour, both globally and locally, but for natural reasons with special emphasis on the Ca2+ ions.

References

[1] M. E. Arroyo-de Dompablo, A. Ponrouch, P. Johansson, and M. R. Palacín, “Achievements, Challenges, and Prospects of Calcium Batteries,” Chem. Rev., 120, 6331–6357 (2020). doi: 10.1021/acs.chemrev.9b00339.
[2] D. Monti, A. Ponrouch, R. B. Araujo, F. Barde, P. Johansson, and M. R. Palacín, “Multivalent Batteries—Prospects for High Energy Density: Ca Batteries,” Front. Chem., 7 (2019). doi: 10.3389/fchem.2019.00079.
[3] I. D. Hosein, “The Promise of Calcium Batteries: Open Perspectives and Fair Comparisons,” ACS Energy Lett., 6, 1560–1565 (2021). doi: 10.1021/acsenergylett.1c00593.
[4] M. Shakourian-Fard, G. Kamath, S. M. Taimoory, and J. F. Trant, “Calcium-Ion Batteries: Identifying Ideal Electrolytes for Next-Generation Energy Storage Using Computational Analysis,” J. Phys. Chem. C, 123, 15885–15896 (2019). doi: 10.1021/acs.jpcc.9b01655.
[5] K. Wang et al., “Molten salt electrolytes for electrochemical capacitors with energy densities exceeding 50 Wh kg−1,” Energy Environ. Sci., 15, 5229–5239 (2022). doi: 10.1039/D2EE01969H.
[6] P. Masset and R. A. Guidotti, “Thermal activated (thermal) battery technology,” J. Power Sources, 164, 397– 414 (2007). doi: 10.1016/j.jpowsour.2006.10.080.
Bridging Aqueous and Organic Electrolytes: Intercalation Mechanism of TiS2 in Sustainable Aqueous Li-Ion Batteries
Authors: Zhang Leiting , Kühling Franziska Maria , Mattsson Agnes-Matilda , Hou Xu , Zhang Chao , Brant William Robert , Edström Kristina , Berg Erik J. 
Published: February 2024

Aqueous Li-ion batteries (ALiBs) are a promising alternative for large-scale grid storage owing to water's non-flammability, low cost, and ease of purification. However, the narrow electrochemical stability window (ESW) of water (1.23 V) significantly limits the energy density of ALiBs, compared to their non-aqueous counterpart. The use of a highly concentrated electrolyte, such as 21 mol kg-1 (molality, m) of LiTFSI in water, known as the “water-in-salt” (WiS) electrolyte, can widen the water ESW to ~3 V, but its high cost and low environmental sustainability hinder the commercialization of ALiBs. Therefore, we explored the feasibility of cycling layered TiS2 anodes in ALiBs containing dilute electrolytes (i.e. 2 m LiTFSI in water).
We obtained a reversible discharge capacity of ca. 80 mAh g-1 at a current density of 50 mA g-1. By employing three-electrode cycling with online electrochemical mass spectrometry, we identified potential-dependent gas evolution from the cell triggered by multiple chemical/electrochemical reactions, such as (1) solvent co-intercalation, (2) partial TiS2 exfoliation, and (3) TiS2-catalyzed water splitting in dilute aqueous electrolytes. We also identified a completely different potential profile of TiS2, when cycled in an aqueous electrolyte, with two distinct redox plateaus at 2.95 V and 2.88 V, followed by a sloping region until 2.3 V (all vs. Li+/Li0). Recall that in classic non-aqueous electrolytes, TiS2 shows a characteristic sloping profile centered at ca. 2.2 V, the peculiar potential profile suggests a different intercalation mechanism of TiS2 in aqueous electrolytes.
In this presentation, we will share our latest findings from complementary physicochemical and computational methods to tackle the complex interfacial reactivity between layered anodes and aqueous electrolytes. Operando synchrotron X-ray diffraction data revealed the reversible uptake-release of water molecules between TiS2 layers, which was also confirmed energetically favorable by theoretical modeling. By introducing triethyl phosphate (TEP) as a co-solvent, we successfully tuned the electrochemical intercalation behavior of TiS2 from purely Li-intercalation (as in non-aqueous systems, when using only TEP as the solvent) to hydrated-Li-intercalation (as in concentrated and dilute aqueous electrolytes, when using water/TEP mixtures as the solvent). These findings suggest that solvent co-intercalation can be a promising strategy for ALiBs. The general implication of these results on the electrode-electrolyte interface and interphase in aqueous batteries will be systematically discussed in the talk. Overall, our work provides new perspectives on developing sustainable energy storage technologies.

Figure 1