bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mechanism of Charge Transfer Via Dielectric Interfaces in Li Ion Battery
Authors: Higaki Yusuke , Teranishi Takashi , Kondo Shinya , Kishimoto Akira , Sasaoka Chinatsu , Hirabaru Hikaru , Katayama Shingo 
Published: December 2024

Lithium-ion batteries (LIBs) are utilized into the power source of the electric vehicles (EVs) due to their relatively high energy density (~200 Whkg-1), originating from high theoretical capacity of the bulk oxide electrodes. In order to deliver both excellent acceleration and better fuel efficiency, LIBs is required to achieve a good balance between high power density (low cell resistance) and high electric capacity. The high-rate capability of LIBs is generally limited by the slow charge transfer at the electrolyte–electrode interface. In particular, the slow Li diffusion through the solid electrolyte interfaces (SEIs), namely an undesirable byproduct, attributing to the electrolyte decomposition during cycling, severely increase the charge transfer resistance (R
ct) of the cell. Oxide-layer decoration of the active material, e.g., Al2O3, can act as barrier layers to prevent undesirable side reactions at the electrolyte–active material interface, thus preventing the evolution of mentioned native SEIs [1]. Nanoscale coating of such protection layers, regarded as an artificial SEI, also allows a faster Li transfer at the electrolyte–cathode interface, rather than the Li diffusion via native SEIs, resulting in better high-rate characteristics.
We have been proposing the partial surface decoration onto the active materials by dielectric nanoparticles as an artificial SEI, which enables faster charge transfer architecture via the surface Li diffusion of the dielectric layer [2]. For instance, incorporating BaTiO3 (BTO) nanoparticles into the surface of LiCoO2 (LCO) led to drastically enhanced high-rate capabilities. A series of experimental results and calculations utilizing density functional theory and molecular dynamics (DFT-MD) implied the improved activity at interfacial charge transfer is responsible for the faster Li adsorption and subsequent desolvation process at the dielectric surfaces. In this study, the dominant factors determining the adsorption and desolvation activities, which are strongly affecting high rate capability, were elucidated. The cell evaluations of the cathodes modified with various metal oxides SEIs, in addition to the conventional BTO based compounds, were performed as a function of the local chemical structure as well as the surface polarization between cation and neighborhood anions.
[1] L. Daheron, R. Dedryvere, H. Martinez, D. Flahaut, M. Menetrier, C. Delmas, and D. Gonbeau, Chem. Mater, 21, (2009), 5607–5616.
[2] T. Teranishi, K. Kozai, S. Yasuhara, S. Yasui, N. Ishida, K. Ishida, M. Nakayama, A. Kishimoto, Journal of Power Sources, 494, (2021) 229710.
Investigating the Morphological Evolution of Lithium Plating/Stripping in Concentrated Electrolyte by Operando X-Ray Computed Tomography
Authors: Liu Xiaoyu , Watanabe Toshiki , Orikasa Yuki , Yamada Yuki , Kanamura Kiyoshi , Uchimoto Yoshiharu 
Published: December 2024

Lithium metal is expected to be next-generation anode because of its low redox potential (-3.04 V vs SHE.) and high specific capacity (3860 mAh g-1), which can achieve high energy density by matching with sulfur or oxygen cathode.1 However, Li metal anode is not viable until now due to the uncontrollable morphology and high activity during Li plating/stripping.2 Especially the growth of Li dendrites, the formation of dead Li, and the broken of unstable SEI (solid electrolyte interphase), result in significant safety risk and low coulombic efficiency. Therefore, to obtain the stable Li metal anode, it’s important to investigate the behavior of Li plating/stripping and the properties of SEI.
In recent years, concentrated electrolyte has received great attention as an effective means to improve the performance of lithium anode.3 With the development of these electrolytes, new insights into lithium morphology and SEI composition have also emerged. Compared with that in dilute electrolytes, the solvation structures of Li ions in concentrated electrolytes are changed, thus the SEI components are also changed from solvent derived to lithium salt anion derived.4 As a result, the morphology of Li and the performance of lithium metal anode are effectively improved.5 However, how these changes in solvation structure and SEI composition affect lithium morphology during cycling, which is helpful to gain more information about the basic Li behavior, remains unclear.
This study endeavors to elucidate the Li plating/stripping behaviors in concentrated electrolyte by operando X-ray computed tomography. The morphological evolution of Li on Cu current collector surface is investigated. In particular, the growth of Li dendrites and the formation of dead Li, as well as the evolution process between them, have received special attention. These results are helpful to understand basic Li plating/stripping behaviors during cycling and provide guidance to lithium metal anode improvement.

Acknowledgment

This work was financially supported by the JST, GteX Project (Grant Number: JPMJGX23S3).

References

[1] Y. Cui et al., Nat. Nanotechnol.
2017, 12 (3), 194-206.
[2] Q. Zhang et al., Chem. Rev.
2017, 117, 10403−10473
[3] G. M. Hobold et al., Nat. Energy,
2021, 6, 951-960.
[4] Y. Yamada et al., J. Am. Chem. Soc., 2014, 136, 5039.
[5] J. G. Zhang et al., Nat. Commun.,2015, 6(1), 6362.
Optimization of an Aqueous Zn-Mn Redox Flow Battery System
Authors: Natale Eleonora , Lissandrello Federico , Gibertini Eugenio , Magagnin Luca 
Published: December 2024

Zinc-based negative electrodes are chosen for their cost-effectiveness, low equilibrium potential, and high electrochemical reversibility, making them widely utilized in redox flow batteries. To achieve a high cell voltage, zinc electrodes are usually paired with positive half-cells featuring high equilibrium potentials, such as Zn-air and Zn-Br systems [1]. The work investigates the feasibility of an alkaline redox flow battery with high energy density and operating voltage involving Zn/ Zn(OH)₄2- and MnO₄⁻/MnO₄²⁻ redox couples. The study focuses on the less-explored permanganate half-cell, which offers a high equilibrium potential (+0.55 V vs SHE) and excellent solubility in alkaline conditions (~3.6 M). These properties make it a promising candidate for positive electrolytes with high energy density [2]. In the study, the electrolytes of the two cells were optimized separately to increase conductivity and avoid side reactions. Cyclic voltammetry experiments at different scan rates confirm the excellent reversibility of electrochemical reactions in both the zinc and permanganate-based electrolytes, characterized by high faradic efficiency. Subsequently, a prototype flow battery is assembled and subjected to galvanostatic charge/discharge tests to assess stability and performance. The cell is evaluated at varying catholyte concentrations and different current densities to determine rate performance. The galvanostatic tests demonstrate remarkable cycling stability and notable cell potential compared to other aqueous systems. The battery exhibits high energetic efficiency (EE > 75%) and Coulombic efficiency (CE) and voltage efficiency (VE) both around 85%. Capacity tests at full charge reveal stable electrochemical reactions throughout the charging and discharging processes. Additionally, ex-situ UV-vis spectroscopy is employed to investigate the mechanism of the manganate/permanganate redox reaction and evaluate the permeability of permanganate ions through membranes during cycling. Overall, the study provides significant insights into the development of high-voltage aqueous batteries. The alkaline Zn-MnO₄⁻ flow battery described in this work emerges as a promising candidate for energy storage applications, offering enhanced stability, high energy efficiency, and energy density.

References:

[1] J. Ren, Z. Wang, B. Liu, al -, J.D. Milshtein, J.L. Barton, T.J. Carney, G. Wang, H. Zou, X. Zhu, M. Ding, C. Jia, Recent progress in zinc-based redox flow batteries: a review, J Phys D Appl Phys 55 (2021) 163001. https://doi.org/10.1088/1361-6463/AC4182.
[2] A.N. Colli, P. Peljo, H.H. Girault, High energy density MnO4
- /MnO4
2− redox couple for alkaline redox flow batteries, Chemical Communications 52 (2016) 14039–14042. https://doi.org/10.1039/C6CC08070G.
Development of Coal-Derived Graphite for Lithium-Ion Batteries
Authors: Paul Abigail , Baca Isabel , Magee Regan , Wilczewski Warren , Wichert Nathan , Wolfe Kody D , Lowe Jeffrey , Trembly Jason , Staser John A. , Garrick Taylor R. 
Published: December 2024

The demand for graphite is expected to increase considerably as the demand for lithium-ion batteries grows. Much of the graphite used in the United States is imported from other countries.1 Because of this supply chain, there is a desire to develop a domestic supply of graphite. One potential feedstock that shows promise is coal because of its abundance and chemical structure. Coal-derived graphite has been successfully utilized in lithium-ion batteries.2

In this poster, the characterization and electrochemical performance of multiple coal-derived graphites will be presented. A focus will be placed on linking electrochemical performance to the microstructure of each material. Electrochemical performance data such as initial capacity loss, gravimetric capacity and columbic efficiency will be presented for both coin and pouch cells. The application of the Multi-Species, Multi-Reaction model on coal-derived graphite will also be presented.
References:

Mineral Commodity Summaries, (2021), p. 82–83.

A. Paul et al., Journal of The Electrochemical Society, 171, 039001 (2024)
Investigating Reduction Intermediates of Fluoroethylene Carbonate
Authors: Ramesh Sapna L , Krzyaniak Matthew D , Wasielewski Michael R , Lopez Jeffrey 
Published: December 2024

Lithium-ion batteries are integral to the clean energy transition due to the important role of electric vehicles in lowering transportation sector emissions. As electrification continues to play a key role in mitigating climate change, there is a need for lithium-ion batteries with energy densities exceeding 500 Wh/kg. Among energy storage technologies, lithium metal batteries (LMBs) offer great potential due to lithium’s high theoretical specific capacity and low electrochemical potential, enabling batteries with energy densities surpassing current state of the art lithium-ion batteries.1 However, the highly reductive lithium metal anode reacts with the electrolyte during cycling, resulting in capacity loss and forming a solid electrolyte interphase (SEI). Electrolyte engineering has emerged as a successful strategy in tuning these reactions to form mechanically and chemically stable SEI, while preventing further parasitic reactions between the lithium metal anode and electrolyte.
In this work, we investigate the reduction mechanism of fluoroethylene carbonate (FEC), a highly effective electrolyte solvent in LMBs.2 We probe the mechanism by which FEC and other similar fluorinated solvents are reduced to form an SEI in order to identify key reduction intermediates that underpin the high performance of these electrolytes and their interphases. In the case of FEC, LiF is commonly identified as a crucial SEI component that results in a stable SEI, but recent research has demonstrated that a preformed SEI comprised solely of LiF breaks down during cycling, illustrating that bulk chemical and mechanical properties of individual SEI components may not translate to their function within the SEI.3 In this work, we employ electron paramagnetic resonance (EPR) spectroscopy to study radical reaction intermediates formed during FEC reduction within an electrochemical cell. We identify these reaction intermediates by employing a spin trap, which stabilizes these intermediates and enables their characterization at room temperature. Using this approach, we have identified two distinct radical species formed during FEC reduction. We further analyze these species with a combination of density functional theory (DFT) calculations and nuclear magnetic resonance (NMR) spectroscopy. Ultimately, this framework will expand the tools available to the field of electrolyte engineering to design stable and effective interphases for lithium metal batteries, enabling the next generation of electrolyte design.
References

K. G. Gallagher et al., Energy Environ. Sci., 7, 1555–1563 (2014).

X.-Q. Zhang, X.-B. Cheng, X. Chen, C. Yan, and Q. Zhang, Advanced Functional Materials, 27, 1605989 (2017).

M. He, R. Guo, G. M. Hobold, H. Gao, and B. M. Gallant, Proceedings of the National Academy of Sciences, 117, 73–79 (2020).
Highly-Coordinated Iron Complex with Multidentate Ligands for Aqueous Redox Flow Battery Electrolytes
Authors: Soshi Kodama , Kawai Kosuke , Atsushi Okazawa , Okubo Masashi 
Published: December 2024

Redox flow batteries (RFBs) possess a longer cycle life than other secondary batteries owing to their limited electrode deterioration upon charge/discharge cycling. Commercial RFBs use vanadium ions as active materials, resulting in a high cost. Therefore, more abundant and less expensive iron-based complexes are desirable as catholyte active materials for RFBs. However, to develop stable iron-based aqueous electrolytes, precipitation of ferric hydroxides under a mild alkaline condition should be suppressed. One potential strategy is to use polydentate ligands that stabilizes the iron coordination structure owing to a chelating effect. For example, a heptadentated [Fe(DTPA)]2
− (DTPA: diethylenetriaminepentaacetate) shows an excellent cycle stability of 0.029% per cycle as an RFB posolyte.[2] In this study, we further improve the cycle stability of iron-based complexes using an octadentate tetraazacyclododecatetraacetate (DOTA) ligand.
The target complex, K[Fe(DOTA)], was prepared by adding FeCl3•6H2O to an aqueous solution of deprotonated DOTA. Single-crystal X-ray structural analysis reveals an eight-coordinated structure of the iron complex. Cyclic voltammetry shows a redox peak at 0.37 V (vs. SHE) for K[Fe(DOTA)], which is higher by 0.088 V than that for K2[Fe(DTPA)] and by 0.12 V than that for K[Fe(EDTA)] (Figure 1). Levich plots obtained by rotating desk electrode measurements reveal the diffusion coefficient of 9.9×10−7 cm2 s−1 and the electron transfer rate constant of 5.0×10−3 cm s−1 for K[Fe(DOTA)] , which are comparable to those of K2[Fe(DTPA)]. UV-Vis spectroscopy shows the aqueous solubility of 0.57 mol L−1 for K[Fe(DOTA)], which is lower than that of K2[Fe(DTPA)] (1.3 mol L−1). The low solubility of K[Fe(DOTA)] should arise from large lattice energy owing to its symmetric structure. Charge/discharge measurements using an H-type cell with 0.10 mol L−1 KCl aqueous solution reveal that K[Fe(DOTA)] exhibits a greater capacity retention rate of 99.973% per cycle than K2[Fe(DTPA)] (99.333%/cycle) (Figure 2).

Reference:

[1] H. J. Schugar, C. Walling, R. B. Jones, H. B. Gray, J. Am. Chem. Soc.
1967, 89, 3712.
[2] S. E. Waters, B. H. Robb, M. P. Marshak, ACS Energy Lett.
2020, 5, 1758.

Figure 1
Utilizing Advanced Spectroscopy Techniques to Investigate Mn-Ligand Bonding Environments in Disordered Rocksalt Oxyfluorides
Authors: Sunariwal Neelam , Kumar Khagesh , Cabana Jordi 
Published: December 2024

Li-rich disordered rock-salt oxyfluorides (DRS) stand out as a promising class of cathode materials due to their exceptional electrochemical performance [1-3]. The substitution of oxygen (O) with fluorine (F) within DRS compounds has demonstrated a significant enhancement in reversible discharge capacity, making them highly desirable candidates for next-generation high-energy Li-ion batteries with enhanced capacity. Despite considerable research into the structural and electrochemical characteristics of these materials, the metal-fluorine (M-F) bonding in DRS oxyfluorides has received limited attention [4,5]. To address this gap in knowledge, we synthesized oxyfluorides based on manganese (Mn) with a composition of Li2MO2F. Employing advanced spectroscopy techniques, we sought to unravel the intricate details of Mn-F bonding in DRS materials. Specifically, we utilized Kβ X-ray emission spectroscopy (XES) to examine the Mn bonding environment and performed fluorine Resonant Inelastic X-ray Scattering (RIXS) measurements to gain insights into the F bonding perspective. Kβ XES has therefore been established as a probe of both metal and ligand properties and RIXS of F enables a direct investigation of Mn-F bonding dynamics by identifying alterations in emission features corresponding to various excitation energies in the F XAS pre-edge region upon charging [6-8]. Furthermore, Kβ XES analysis offers valuable information on the oxidation states and covalency trends of Mn-ligand interactions comparing with the end-member Mn oxides and fluorides.
References:

D. Chen, J. Ahn, and G. Chen, ACS Energy Lett., 6, 1358–1376 (2021).

X. Xu et al., J. Electrochem. Soc., 168, 080521 (2021).

D. A. Kitchaev et al., Energy Environ. Sci., 11, 2159–2171 (2018).

I. Roy et al., Chem. Mater.(2023), 35, 5, 2107–2113

N. Sunariwal et al., Adv. Funct. Mater.2024,34, 2312010

C. J. Pollock et al, J. Am. Chem. Soc. (2014), 136, 9453−9463

S. Limandri et al. Chemical Physics 367 (2010) 93–98

D. J. Higley et al., Communications Physics volume 5, Article number: 83 (2022)
Soaking Tests to Understand and Mitigate Electrolyte Decomposition Products Etching on Li- and Mn- Rich Cathode Materials
Authors: Wang Bingning , Liao Chen , Garcia Juan , Iddir Hakim , Qin Yang , Zhu Qijia , Liu Qian , Tornheim Adam P. 
Published: December 2024

A series of soaking experiments were conducted to investigate electrolyte decompositions etching on the 5 V cobalt-free spinel LiNi0.5Mn1.5O4 (LNMO) cathode, revealing that intense electrode/electrolyte reactions between LNMO and Gen2 electrolyte could lead to significant corrosion and delamination of electrode laminates.1 In this study, similar soaking tests are performed for 0.3Li2MnO3
·0.7LiMn0.5Ni0.5O2 (LMR-NM), a promising cathode material for next-generation high-energy-density and cobalt-free lithium-ion batteries, to assess its stability with respect to the electrolyte and its aging byproducts resulting from extended storage at elevated temperature.
The acidic electrolyte decomposition generated at 55 oC can result in undesirable transition metal (TM) dissolution, which is considered as a main cause for lithium inventory loss and cells degradation. However, lithium difluoro(oxalato)borate (LiDFOB) can act as a scavenger type additive by reacting with early-stage electrolyte decomposition products, forming a thermal stable salt of lithium tetrafluoro oxalato phosphate (LiF4OxP), and preventing further electrolyte decompositions.2 Additionally, modifications involving Co-doping and Al(NO3)3 surface coating for LMR-NM can also alleviate these electrode/electrolyte interactions. The role of cathode electrolyte interphase (CEI) in mitigating such etching is also examined.

Wang, Bingning, et al. "Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi0. 5Mn1. 5O4." Batteries9 (2023): 435.

Liu, Minghong, et al. "Improved electrolyte and its application in LiNi1/3Mn1/3Co1/3O2–Graphite full cells." Journal of Power Sources268 (2014): 37-44.
Innovative Dual Cross-Link Hydrogel for Enhanced Stability and Performance of Zinc-Ion Batteries
Authors: Wang Peng , Andrei Petru 
Published: December 2024

Zinc-ion batteries (ZIBs) are emerging as promising contenders in the realm of energy storage due to their potential for cost-effectiveness, environmental sustainability, high safety. However, the formation of dendrites on Zn anodes, alongside hydrogen evolution and side reactions, represent notable disadvantages in the performance of zinc-ion batteries. These challenges hinder their long-term stability and efficiency, necessitating further research and development efforts to overcome them. Strategies to overcome challenges in zinc-ion batteries include improving Zn anode construction to mitigate dendrite formation and adjusting electrolyte composition to suppress hydrogen evolution and side reactions. Additionally, the use of solid-state or gel polymer electrolytes can enhance ion transport and reduce dendrite formation.
In this presentation, we introduce a rapid and effective method for constructing a dual cross-link hydrogel directly onto current collectors, such as Carbon Fiber Paper (CFP) and Carbon Nanotube (CNT) film, utilizing polyacrylamide and aramid nano fiber (ANF). The resulting hydrogel exhibits high ionic conductivity and improved mechanical properties, mitigating the formation of Zn dendrites and enhancing cycling stability in Zn/Zn symmetric cells (stable after 1000 hours of plating/stripping). Additionally, in-situ polymerization on cathode current collectors enhances electrolyte-cathode active material contact, particularly beneficial for porous cathodes like CFP. Furthermore, combined with in-situ electrochemical deposition of MnO2 active material, this approach facilitates the production of practical winding batteries using conventional winding machines. This research provides an efficient approach to assembling practical, flexible and stable AZIBs pouch cells with high capacity and cycling stability.