bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Analysis of the Cathode/Electrolyte Interface in Li-Ion Batteries by Scanning Electrochemical Microscopy (SECM)
Authors: He Rong , Zhou Meng , Luo Hongmei , Tenent Robert 
Published: December 2024

Lithium ion battery (LIB) performance degradation is a complex process involving multiple overlapping, but still poorly understood mechanisms. Processes occurring at the anode-electrolyte interphase, commonly known as the “solid-electrolyte interphase” (SEI) in LIBs are known to stabilize cell performance and have been extensively studied. Similar processes occurring at the cathode-electrolyte interphase (CEI) are less well studied, however, CEI processes are known to form products which drive cell degradation. How these products form, and hence, how they can be controlled remains an active area of research. Multiple processes are known to occur at the CEI including oxidation of the electrolyte, dissolution of transition metals and gas evolution both from electrolyte decomposition as well as decomposition of the cathode material itself. Recent work has shown that electrolyte oxidation processes in the presence of metal oxide cathode materials may occur through multiple mechanisms including direct electron transfer from the electrolyte to the electrode as well as the potential chemical oxidation of the electrolyte by reactive species leaving the cathode at high voltage.
Scanning electrochemical microscopy (SECM) is a powerful scanning probe technique that can be used to characterize near surface electrochemical processes under steady state conditions. The technique is particularly well suited to study short-lived reactive species as well as the presence of chemical reactions coupled to electron transfer processes. Our work uses these capabilities to help unravel some of the complex processes occurring as part of the electrolyte oxidation process at the CEI. We use SECM to explore electrolyte oxidation processes occurring at non-intercalating electrodes (Pt and glassy carbon) and compare to companion studies using model metal oxide cathode materials. This allows isolated study of direct electron transfer between the electrode and electrolyte and potential chemical oxidation processes that may occur at the metal oxide surface. Studies of these two processes appear to show both similarities and differences between apparent chemical and electrochemical oxidation routes for the LIB and results will be shared in this presentation.
Pyrochlore Structure Enables Stable Cycling Performance of Iron Fluoride Cathodes
Authors: Baumgartner Julian F. , Stoian Dragos C. , Marshall Kenneth P. , Jafarpour Mohammad , Klimpel Matthias , van Beek Wouter , Abdolhosseinzadeh Sina , Kravchyk Kostiantyn V. , Kovalenko Maksym V. 
Published: December 2024

Iron (III) fluorides are appealing low-cost cathode materials for next-generation lithium-ion batteries due to the virtually unlimited supply of the constituting elements and high energy densities.[1] However, the lack of sufficiently large Li-ion diffusing channels in the thermodynamically stable rhombohedral iron fluoride modification impede fast Li-ion conduction, while also inducing phase transformations of the active material during lithiation, ultimately causing contact loss with the conductive network, and resulting in rapid capacity fade. Meanwhile, the pyrochlore modification of iron fluoride may enable fast Li-ion diffusion due to its 3D interconnected channels, as well as significantly improved cycling stability.[2] Inspired by the synthesis of porous materials, such as metal organic frameworks, zeolithes and Prussian blue analogues, which often employ dissolved precursor building blocks that condense into the desired porous structure in the presence of a suitable templating agent, we recently reported on the synthesis of pyrochlore iron hydroxy fluoride (Pyr-IHF) from soluble iron (III) fluoride precursors at ambient conditions.[3] This facile dissolution-precipitation synthesis allows the production of Pyr-IHF particles with narrow particle size distribution at low costs (10-20 $ kg-1), competitive with Lithium iron phosphate. Moreover, we demonstrated excellent rate capability up to 1 A g-1 (4 C) with a capacity retention of > 80% after 600 cycles, and provided the first experimental evidence for Li-ion diffusion occurring through the 3D channels of Pyr-IHF, by studying the electrochemical performance of Pyr-IHF samples with varying contents of zeolithic water within the 3D channels.
Herein, we extend our work on the lithiation mechanism of Pyr-IHF. We demonstrate its outstanding structural stability during cycling with almost no volume change or morphological changes to the particles, challenging the notion of iron fluorides as conversion-type materials. Using operando spectroscopy, and X-ray total scattering, we study the lithiation mechanism of Pyr-IHF on an atomic level. Without the need for elaborate cathode designs, we demonstrate outstanding cycling stability for 500 cycles at 100 mA g-1 (0.4 C), with a high cumulative discharge capacity close to 60.000 mA h g-1.
[1] F. Wu, G. Yushin, Energy Environ. Sci.
2017, 10, 435.
[2] C. Li, C. Yin, L. Gu, R. E. Dinnebier, X. Mu, P. A. van Aken, J. Maier, J. Am. Chem. Soc.
2013, 135, 11425.
[3] J. F. Baumgärtner, M. Wörle, C. P. Guntlin, F. Krumeich, S. Siegrist, V. Vogt, D. C. Stoian, D. Chernyshov, W. van Beek, K. V. Kravchyk, M. V. Kovalenko, Adv. Mater.
2023, 35, 2304158.

Figure 1
Electrochemical Behavior Variation of Graphite/LiNi0.6Co0.2Mn0.2O2 Cells during Overdischarge
Authors: Kim Bong Jin , Yoon Geon Woo , Ryu Ji Heon 
Published: December 2024

As the demand for secondary batteries surges with the growth of the electric vehicle market, challenges related to the disposal and recycling of used batteries are escalating. Proper recycling of lithium-ion batteries (LIBs) necessitates the implementation of an efficient discharge process to deplete their stored energy. Successful disposal and disassembly hinge on conducting a thorough discharge, including deep overdischarge, to effectively eliminate stored energy.
This study aims to provide a thorough comparative analysis of the electrochemical behavior of lithium-ion batteries during overdischarge. Coin-type full cells were fabricated using the commonly employed graphite negative electrode and LiNi0.6Co0.2Mn0.2O2 (NCM622) positive electrode, and their electrochemical behavior during overdischarge and forced discharge was evaluated by constant current, constant current/voltage discharge, and galvanostatic intermittent titration technique (GITT).
Cells were manufactured with varying electrode compositions, N/P ratios, degrees of deterioration, etc., and their electrochemical behavior during overdischarge was compared. Additionally, the evaluation was conducted using various current magnitudes, application methods, and temperature conditions. While minor discrepancies in electrochemical characteristics emerged during spontaneous discharge up to 0 V, variations in cell configuration and evaluation conditions induced differing behaviors during forced discharge below 0 V. These findings contribute to a better understanding of battery overdischarge behavior and offer fundamental insights for developing an efficient overdischarge process in battery recycling.
Fabrication of High Loading Film Cathode for Thermal Battery
Authors: Ahn Won Jun , Park Mi Seon , Choi Yusong , Ha Sang Hyeon 
Published: December 2024

Thermal batteries are the primary reserve batteries operated at high temperature (350-550 ℃). It has been fabricated by pressing powder mixture without polymer binder to maintain the only pellet shaped electrode. The polymer binder commonly used in tape-casting method has been decomposed into organic gases at the operating temperature. The gas has been enclosed in the battery system, and it could be possible to explore. Moreover, the pressing method for the electrode, especially cathode, in not suitable in aspects of time and cost.
This study aims to fabricate film-type cathode with high loading level by using tape-casting method, which not uses the polymer binder. Through this method, it could be fabricated that the cathode with a thickness of 500 um and more. Also, the fabricated film-type cathode shows the high coulombic efficiency compared with pellet-type cathode. Therefore, the results demonstrate that film-type cathode is replaced for existing pellet-type cathode.
Experimental and Theoretical Study of the Performance of Li-Oxygen Batteries with Multiwall Carbon Nanotube Cathodes
Authors: Andrei Petru , Lobachev Emil 
Published: December 2024

Although Li-oxygen batteries with organic electrolyte have a theoretical energy density of 3505 kWh/kg (which is comparable to the energy density of gasoline), in practice only a fraction of this energy density has been demonstrated. Despite this gap, Li-oxygen batteries remain to have a great potential to replace the current energy storage devices in applications requiring light power sources such as portable electronic devices, unmanned aerial vehicles, and renewable energy storage. There is great interest in seeing if Li-oxygen batteries, which have the potential to have a far higher gravimetric energy storage density than any other battery chemistry, can be developed to power electric vehicles (EVs) and allow for driving ranges that are comparable to those of gasoline-powered cars [1]. In this presentation we make a combined experimental and theoretical investigation of the performance of the Li-oxygen batteries for different cathode structures, assembling technique (that can induce different concentrations of seeds available for precipitation and growth in the cathode) and discharge conditions. The theoretical model is based on the traditional drift-diffusion approach, coupled with a simple model that describes the precipitation and growth of lithium peroxide on the carbon nanotubes. The model also predicts that it is optimum to use variable porosity cathodes (with higher porosity on the oxygen side and lower porosity on the separator side) in order to maximize the energy density of these cells, a fact which is also demonstrated using our experimental data. More details about the mathematical approach and a comparison with the experimental data will be presented at the conference.
[1] N. Imanishi and O. Yamamoto, “Perspectives and challenges of rechargeable lithium–air batteries,” Mater. Today Adv., vol. 4, p. 100031, Dec. 2019, doi: 10.1016/j.mtadv.2019.100031.
Ionic Conductivity Transitions in Sodium Antiperovskite Ionic Conductors
Authors: Zhang Duhan , Li Yiliang 
Published: December 2024

Anti-perovskites (AP) materials have recently attracted great interest as a family of solid-state electrolytes with high ionic conduction. Na3OCl is a well-studied prototypical fast ion conducting compound representative of the AP family. Typical solid-state ionic conductors have temperature-dependent ionic conductivity following Arrhenius behavior over a substantial range of temperatures, corresponding to a constant activation energy Ea. In the Na3OCl antiperovskite, there are regimes of Arrhenius behavior separated by broad transitions, all while the structure remains cubic. So far, no clear explanation has been reported for such non-Arrhenius transition of Na3OCl ionic conductivity.
Here, we observe a two-order-of-magnitude increase in its ionic conductivity (from 10-1 to 10 mS/cm) with increasing temperature at 305°C. Temperature-dependent synchrotron X-ray diffraction (SXRD), differential scanning calorimetry (DSC), quasi-elastic neutron scattering (QENS), and impedance spectroscopy, are used to show that the increase in conductivity is correlated with a transition from tetragonal to cubic symmetry associated with a change in octahedral tilt disorder. While previous work has shown that octahedral tilting in APs can create ion migration pathways with lower migration energies than in the regular cubic structure, this is the first instance where such a large increase (100 times) in ionic conductivity due to a change in octahedral tilt disorder has been observed, the octahedral tilt disorder can be exploited as a pathway to increasing the ionic conductivity of antiperovskites and structurally related compounds.
This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.
Deconvolved First Cycle Capacity Loss Mechanisms in All-Solid-State Batteries
Authors: Kaeli Emma , Jiang Zhelong , Yang Xiaomian , Choy Emma P.K.L , Liang Nicolas , Wang Sunny , Barks Eddie , Kang Stephen D. , Chueh William C. 
Published: December 2024

Deconvolved First Cycle Capacity Loss Mechanisms in All-Solid-State Batteries

All-solid-state batteries (SSBs) fail to compete with their traditional lithium-ion battery (LIB) counterparts due to severe capacity loss in their first cycle. While the key contributors to capacity loss have been identified, it remains unknown the relative contribution of each loss mechanism due to solid electrolyte (SE) redox and worsening kinetics which obscure the measure of capacity. For the chemically abundant sulfur-based composite electrodes in particular, these parallel processes present a formidable challenge to addressing first cycle Coulombic inefficiency.1 Using near-equilibrium electrochemical and X-ray techniques, we demonstrate a full accounting of the sources of capacity loss within our argyrodite SE (Li5PS6Cl) | uncoated Li(Ni0.5Mn0.3Co0.2)O2 (NMC) | carbon composite cathode. By modifying the components of the composite electrode, we differentiate between electrolyte redox at the electronic conductor (current collector + carbon)|SE and NMC|SE interfaces. Using these cell formats we investigate the persistence of electronic conductor interfacial redox across many cycles, as well as the impact of self-discharge on long-term cycling behavior. By modifying the cycling window, we also investigate sluggish discharge kinetics of cathode and oxidation reversibility. Using operando XRD, we compare LIBs and SSBs to track cathode redox throughout cycling, enabling us to differentiate and quantify sources of capacity loss. These findings highlight the need to address overlooked sources of resistance and active material loss in SSBs which are not mitigated by cathode coating solutions.
[1] Janek, J., Zeier, W.G. Challenges in speeding up solid-state battery development. Nat Energy
8, 230–240 (2023).
Interfacial Effects of the Na Metal State on the Electrochemical Behavior on β"-Alumina Solid Electrolyte
Authors: Qiu Jie , Wang Di , Hwang Jinkwang , Matsumoto Kazuhiko 
Published: December 2024

Sodium metal is considered a promising candidate as an anode to maximize the energy density of sodium secondary batteries. The use of β"-alumina solid electrolyte (BASE) is a viable approach to ensure the safe operation of sodium metal batteries.1, 2 Although sodium metal batteries utilizing BASE have gained success at elevated temperatures (e.g. 250 °C), exhibiting stable and efficient cycling performance, even beyond 1000 mA cm−2,3 they are prone to short circuits above certain current densities, which is underscored by a crucial metric referred to the critical current density (CCD). The CCD of BASE typically varies from 0.1 to 10 mA cm−2 at room temperature,1 possibly due to insufficient contact between the rigid surface of BASE and solid sodium metal.
This research focuses on the deposition and dissolution behavior of sodium metal anodes in both liquid and solid states, particularly at slight temperature differences near the melting point of sodium. The CCDs were assessed in a symmetric Na/BASE/Na cell configuration at 90 and 105 °C for solid and liquid sodium (m.p. of sodium 98 °C), respectively. The cell failure was verified by electrochemical impedance spectroscopy after each cycle. Post-test morphological characterizations of the BASE were investigated through scanning electron microscopy. Moreover, rate and cycle performance was assessed using a Na//Na3V2(PO4)3 configuration at two different temperatures. In conclusion, a slight increase in temperature to maintain sodium in the liquid state significantly bolsters the performance of the Na anode, enabling prolonged cycle duration without the dendrite formation causing cell degradation.

References

[1] P. Fertig, K. Skadell, M. Schulz, C. Dirksen, P. Adelhelm and M. Stelter, Batteries Supercaps, 2022, 5, e202100131.
[2] Minnmann, F. Strauss, A. Bielefeld, R. Ruess, P. Adelhelm, S. Burkhardt, S. L. Dreyer, E. Trevisanello, H. Ehrenberg, T. Brezesinski, F. H. Richter, and J. Janek, Adv. Energy Mater., 2022, 12, 2201425.
[3] Landmann, G. Graeber, M. V. F. Heinz, S. Haussener, and C. Battaglia, Mater. Today Energy, 2020, 18, 100515.
In Situ Neutron Diffraction Showing Lithium-Yttrium Chloride Local Structure By Synthesis Method
Authors: Sacci Robert L , Brahmbhatt Teerth , Li Cheng , Guo Liqun , Zheng Jie , Garaga Mounesha N , Greenbaum Steve G , Yao Yan , Nanda Jagjit 
Published: December 2024

Lithium halide-based solid electrolytes have high Li+ conductivity and are mostly synthesized through mechanochemical methods.[1] However, Li3InCl6 can be readily synthesized through low-temperature aqueous solution routes by mere dehydration, presumably due to stable InCl6
3- complexation. [2-4] Replacing In for Y results in partial hydrolysis to form YOCl during dehydration because H2O coordinates more strongly to Y3+ cations. We provide insight into the reaction mechanisms involved in synthesizing halide solid electrolytes, highlighting the importance of synthetic and processing conditions to optimize their performance in all-solid-state batteries. We will describe the synthesis process of Li3YCl6 using three different methods and the evolution thereof using in situ neutron diffraction. Our results show that aqueous-based synthesis requires the formation of an ammonium halide complex intermediate. We found that the synthesis method affects changes in local structure within the lattice, which then affect ionic transport and Li+ diffusivity, as determined through diffusion NMR measurements. We ascribe these changes to the correlative transport of Li+. Synthesis affects particle morphology at the macroscale and relates to cycle life when used in a full cell.
This project was supported by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE) as part of the Battery Materials Research (BMR) program. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.
[1] Park, K.-H.; Kaup, K.; Assoud, A.; Zhang, Q.; Wu, X.; Nazar, L. F. High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries. ACS Energy Lett. 2020, 5, 2, 533–539.
[2] Li, X.; Liang, J.; Luo, J.; Norouzi Banis, M.; Wang, C.; Li, W.; Deng, S.; Yu, C.; Zhao, F.; Hu, Y.; Sham, T.-K.; Zhang, L.; Zhao, S.; Lu, S.; Huang, H.; Li, R.; Adair, K. R.; Sun, X. Air-Stable Li3InCl6 Electrolyte with High Voltage Compatibility for All-Solid-State Batteries. Energy Environ. Sci. 2019, 12, 2665-2671.
[3] Li, W.; Liang, J.; Li, M.; Adair, K. R.; Li, X.; Hu, Y.; Xiao, Q.; Feng, R.; Li, R.; Zhang, L.; Lu, S.; Huang, H.; Zhao, S.; Sham, T.-K.; Sun, X. Unraveling the Origin of Moisture Stability of Halide Solid- State Electrolytes by In Situ and Operando Synchrotron X-Ray Analytical Techniques. Chem. Mater. 2020,32, 16, 7019–7027.
[4] Sacci, R.L.; Bennett, T.H.; Drews, A.R.; Anandan, V.; Kirkham, M.J.; Daemen, L.L.; Nanda, K. Phase evolution during lithium indium halide superionic conductor dehydration. J. Mater. Chem. A, 2021,9, 990-996.
Integrating All-Polymer Solid State Lithium Metal Batteries with High Areal Loading Cathodes
Authors: Ock Jiyoung , Owensby Kyra D'Yana , Ullman Andrew , Chen Xi Chelsea , Sahore Ritu 
Published: December 2024

All solid-state batteries are promising alternative to conventional lithium-ion batteries, because of their high potential in safety, high energy, and power density. However, the induced mechanical stresses from volume changes of electrodes accompanied by electrochemical Li insertion/extraction are a challenge for all solid-state batteries, especially with high loading cathodes (>4 mAh/cm2). In this context, polymer electrolytes are promising candidate due to their flexible features, which may maintain the good contact between the interfaces with sufficient adhesion, upon cycling.
In this study, we present design strategies on integrating polymer electrolytes-based Nickel-rich NMC (LiNixMnyCozO2) composite cathodes in all-polymer solid state lithium metal batteries. We systemically compare three different cell designs focusing on the cathode/electrolyte interface, which is further evaluated by a series of techniques using electrochemical impedance measurement, charge/discharge cycling test, and cryo-microtomed scanning electron microscope. The effect of oxidative stability of the polymer electrolyte on cell performance is discussed as well by comparing two different polymer electrolytes. We present how the polymer electrolyte-integration/cell design protocols link to the cell performance such as capacity, reversibility, and coulombic efficiency.

Acknowledgements

This research was sponsored by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office’s Advanced Battery Materials Research Program (Simon Thompson, Program Manager). A part of this research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. The SEM in this work was performed and supported at the Center for Nanophase Materials Sciences in Oak Ridge National Lab, a DOE Office of Science user facility.