bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) In Situ x-Ray Diffraction Studies of the Atomic Structure and Charge Distribution at the Electrochemical Interface
Authors: Grunder Yvonne , Lucas Christopher A , Joly Yves , Soldo-Olivier Yvonne 
Published: August 2024

The presence of specifically adsorbed anions can significantly affect the electrochemical reactivity of a metal electrode which is of major interest for galvanic deposition, etching, corrosion and electrocatalysis. In-situ surface x-ray diffraction has enabled an atomic/molecular-level understanding of the interface under reactive conditions, including its potential and time dependence, to be developed. While information about the atomic structure of the electrode surface in electrochemical in-situ cells has been widely investigated, insight into the charge distribution and the structure of the electrolyte at the interface is still lacking. Advances in these directions offer possibilities in elucidating atomic scale models of the electrochemical interface and thus will help to establish structure-stability-reactivity relationships.
A fundamental understanding of the nature of the charge transfer, especially the influence of the applied potential and the screening by the electrolyte, is a major goal in electrochemistry to better understand electrochemical processes and charge transfer during adsorption and deposition. [1]
Thus, combining x-ray spectroscopy and x-ray diffraction to gain site specific information about the charge distribution at buried interfaces is a promising tool. [2,3]
Examples of how the use of surface x-ray scattering techniques can help to characterize electrochemical interfaces in-situ in order to link, structure, reactivity and stability will be presented. [4-5] Advances in these directions offer possibilities in elucidating atomic scale models of the electrochemical interface and thus will help to establish structure-stability-reactivity relationships and to understand growth kinetics and electrochemical phase formation.
References:
[1] Y. Gründer and C. A. Lucas, Nano Energy 29, 378 (2016).
[2] Y. Gründer, P. Thompson, A. Brownrigg, M. Darlington, and C. A. Lucas, Journal of Physical Chemistry C 116, 6283 (2012).
[3] Y. Joly et al., Journal of Chemical Theory and Computation 14, 973 (2018).
[4] Y. Grunder et al., Charge Reorganization at the Adsorbate Covered Electrode Surface Probed through in Situ Resonant X-ray Diffraction Combined with ab Initio Modeling; Phys. Chem. C 2022, 126, 9, 4612–4619
[5] Yvonne Soldo-Olivier et al., Unraveling the Charge Distribution at the Metal-Electrolyte Interface Coupling in Situ Surface Resonant X-Ray Diffraction with Ab Initio Calculations, ACS Catal. 2022, 12, 4, 2375–2380
(Invited) Advanced Electrode Processing for Next Generation Batteries
Authors: Kaskel Stefan , Schumm Benjamin , Althues Holger , Hippauf Felix 
Published: August 2024

The development of environmentally friendly processing techniques is a key requisite for future sustainable battery development. The so-called DRYtraec® process is a solvent-free process developed as a viable approach to replace slurry-based binders by fibrous polymers and produce laminated electrodes with a low carbon footprint. It has been demonstrated to work for both, liquid and solid electrolyte batteries. NMC cathodes can be produced in a wide range of loading. For lithium sulfur batteries carbon/sulfur composites can be processed without sulfur loss. In particular in the field of solid state batteries it shows significant advantages. All-solid-state lithium-ion batteries are promising candidates to overcome safety and energy limitations of established lithium-ion batteries (LIBs). Excellent results have been reported for sulfide based electrolytes on a small scale. More and more companies announce their first pilot production lines. Therefore, scalable concepts for material and component development are of crucial need. We evaluate this process for the fabrication of thin argyrodite separator films and compare it with slurry-based separators in ASSBs. To test new cell concepts and components under relevant conditions, it is important to manufacture prototype cells with thin separator layers and flexible housing. Therefore, we prepared slurry-free pouch cells based on Ni-rich NMC cathodes and PVD-synthesized Si anodes.
The presentation highlights recent developments of the DRYtraec® process and its application to ASSBs, LiS and LIBs.
Development of Efficient Ink Dispersion Process for Solid-State Electrolyte and Electrode Manufacturing
Authors: Miller Samuel David , Lee Jungkuk , Xu Shaomao , Chen Mengyuan , Wang Chuanlong , Zhang Yubin , Zhang Yuepeng 
Published: August 2024

All-solid-state lithium batteries (ASSBs) have several advantages over lithium-ion batteries (LIBs) such as higher safety thresholds associated with solid electrolytes (SEs) and the possibility of using lithium metal or silicon anodes to achieve comparatively higher energy and power density. The SE can also prevent chemical interactions with dissolved active materials, and thus solve the issue of long-term instability of LIBs. However, there are also challenges associated with ASSBs manufacturing, such as local stress and contact-loss between SE and active materials in cathodes due to active material “breath”, poor contact and high ionic resistance at the SE-cathode interface, difficulty in fabricating thin SEs, and the absence of scalable and cost-effective manufacturing processes (J. Janek and W.G. Zeier, Nature Energy 8 (2023): 230-240). A key to tackling these issues begins with ink formulation for electrolyte and cathode coating, including ink compositions and rheological properties.
In this study, we report the influence of ink preparation methods and conditions on the solid-state electrolyte and cathode coating qualities, where lithium lanthanum zirconium oxide (LLZO) and lithium nickel manganese cobalt oxide (NMC) are used as model systems. Various mixing methods, such as acoustic wave mixing, high-speed off-axis mixing, and thin film mixing, are compared. Their influence on ink viscosity and particle dispersion, coating thickness and microstructure uniformity, and electrolyte and electrode electrochemical properties will be discussed.
Compression Testing of Individual Battery Electrode Particles
Authors: Barthold-Robinson Jarid , Gabler William , Macey Christopher 
Published: August 2024

The friability of powder materials used to fabricate battery electrodes is an important parameter in determining battery lifetime. Particulate electrode materials are subject to significant stresses during cell fabrication. While in use, battery cyclic charging and discharging induces mechanical stresses in the electrode materials which can significantly impact long-term stability.
Our presentation will describe a novel micro-compression instrument and technique for determining the compression strength of individual particles as small as 1 micron in diameter. Brief examples of the technique used to characterize and compare the hardness of battery anode materials will be discussed. Further in-depth references will also be provided.
Ontology Creation and Database Implementation for Lab-Scale Solid-State Battery Cells
Authors: Albertus Paul , Larson Karl , Schulman Omri , Kattouf Basila , Damatov Delina , Anderson Assaf Y 
Published: August 2024

New developments and publications on alkali metal solid-state batteries are being published at a high rate, with the total number of publications now in the thousands, but the search and analysis of the data in these publications is still largely done using key words and through careful reading of the article and the supporting information. The challenges of efficiently searching and extracting data from thousands of publications in a field are also present in other fields, such as perovskite solar cells, for which a large (>15,000) set of cell data has been entered into a database that continues to be updated.1 A database for alkali metal (e.g., based on Na+ and Li+ conduction) solid-state cells that could be easily searched and that facilitated advanced forms of data analysis could accelerate research progress, and is consistent with efforts such as definition of the “Principles of the Battery Data Genome” and the BIG-MAP project.2 In this talk, we describe our approach to creating an ontology and database for lab-scale solid-state cells, along with results to date. Key areas for the ontology include component material identities, material properties, component properties (e.g., active material loading, mass fractions, thicknesses), processing conditions for materials and the cell itself (e.g., ball milling time, sintering time), and both performance (e.g., rate capability) and degradation (e.g., cycle life). Results based on several hundred solid state cells in our database are presented in terms of histogram plots, violin plots, correlation plots, and other representations. We also describe our efforts to integrate our ontology and tool with broader efforts in the field, and to make it broadly useful to battery researchers.
1. Nature Energy, volume 7, pages 107–115 (2022) and https://www.perovskitedatabase.com/
2. Joule 6, 2253–2271, October 19, 2022 and https://www.big-map.eu/dissemination/battinfo
In Situ Sodium Plating and Stripping at the Aluminum/Nasicon Interface
Authors: Tseng Flora , Lee Kiwoong , Sakamoto Jeff 
Published: August 2024

Solid-state sodium metal batteries have emerged as compelling alternatives to lithium-ion batteries due to their abundance, geopolitical stability, and cost. However, the development of solid-state sodium metal batteries faces challenges such as achieving high ionic conductivity in solid electrolytes, ensuring stable interfaces between the solid electrolyte and sodium metal anode, as well as the complexity of manufacturing due to the air reactivity of sodium metal. To overcome these challenges, the anode-free manufacturing process to fabricate is a promising approach to enable the commercialization of sodium metal batteries.
In this work Na3.4Zr2Si2.4P0.6O12 (NaSICON) was synthesized and densified to >99 % relative density with a total ionic conductivity of 5 mS cm-1 using a solution assisted solid-state reaction process followed by rapid induction hot-pressing, respectively. Using the hot-pressed NaSICON in an anode-free cell design, we demonstrate the feasibility and ease of using commercially available aluminum foil with a sputtered metal layer as the current collector (CC). We show stable sodium plating of several microns at the NaSICON | CC interface with a current density of 0.5 mA cm-2 at room temperature. In addition, this study demonstrates good reversibility after several cycles of plating and stripping.
This study not only explores the electrochemical behavior of in situ sodium plating contributing to the advancement of cost-effective energy storage solutions, but also offers valuable insights into practical manufacturing processes for solid-state sodium metal batteries.
Multiphysics Simulation of Battery Electrode Drying
Authors: Monismith Scott , Roberts Scott A. , Liu Wanjiao , Horner Jeffrey Scott 
Published: August 2024

Scaling Li-ion battery production to meet the demands of increasingly electrified grids and transportation systems will require higher throughput at all levels of the battery cell production process. One of the more energy intensive battery manufacturing steps is the necessary drying of solvents which persist in the electrodes after the initial slurry coating of their current collectors. It is critical to both optimize this drying process to minimize the time and resources required, as well as to understand the effect that the drying has on the electrode microstructure. As it is both expensive and time-intensive to iteratively test different temperatures on multiple initial electrode microstructures, it is necessary to have reliable, high-fidelity simulations which can model the evaporation process. Furthermore, it is easier to control microstructural features such as porosity, and particle size in a simulated environment, Indeed, by simulating evaporation, the design-of-experiments space can be minimized, and process conditions can be established to accelerate the production of high quality, lower cost electrodes.
To that end, we develop a multiphysics model of solvent evaporation using Sandia’s in-house finite element software. By coupling the solvent equations of motion to species conservation equations for the carbon binder material and energy flux driven by evaporative cooling, we demonstrate good agreement between simulation and simple evaporation experiments. This model tackles several difficult aspects of evaporation, namely the evolution of free surfaces and gas-liquid phase-changes. We additionally extend our model to account for mesoscale features (i.e. particle size, porosity, binder distribution) and determine how different temperature profiles and microstructures affect the heating requirements for the electrode. These extensions present a key advantage over conventional 1D models, as these features can have a significant effect on the evaporation process and the final distribution of conductive additive and binder. We leverage this advantage to examine how several design parameters such as porosity, particle size distribution, and heating rate affect the resulting electrode structure and binder distribution. These results demonstrate a pathway to optimizing the electrode drying process and promise to inform the development of improved multiphysics models in the future.
SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525.
(Invited) A Study of the SEI Layer Cross-Talk in Si/C Composite Li-Ion Anodes
Authors: Ihsan-Ul-Haq Muhammad , Larson Jonathan M. , Cha Hyungyeon , Dopilka Andrew , Kostecki Robert 
Published: August 2024

Composite electrodes, especially silicon/carbon (Si/C) anodes, present significant opportunities for advancing the energy density of lithium-ion batteries (LIBs). However, challenges emerge, particularly in performance metrics when a high weight percentage of Si beyond 8-10 wt.% is employed 1. A nuanced understanding of the solid electrolyte interphase (SEI) in Si/C composites is imperative to overcome these limitations and enhance energy density. Conventional techniques such as ex-situ X-ray photoelectron spectroscopy and cryogenic electron microscopy face inherent drawbacks, including exposure to ultrahigh vacuum and the need for solvent washing, potentially altering the SEI layer 2. In contrast, nano-FTIR, utilizing Fourier transform infrared near-field spectroscopy, overcomes these challenges, enabling non-destructive probing of the SEI layer's chemistry and structure at room temperature within an inert atmosphere 3–5.
In this study, we engineer custom-patterned electrodes featuring amorphous Si on atomically flat highly ordered pyrolytic graphite (HOPG) to emulate model composite electrodes. Leveraging nano-FTIR spectroscopy, near-field nanoscale white-light imaging, and atomic force microscopy measurements, our investigation reveals that the SEI on HOPG is enriched in organic lithium ethylene decarbonate (LiEDC), while the SEI on lithiated silicon unveils the presence of inorganic Li2CO3. Notably, we unveil a unique "mixed" SEI layer zone at the Si/HOPG interface, comprising a mixture of dominant SEI species from the surfaces of both the lithiated Si and the HOPG. The coexistence of these species suggests the formation of an SEI layer with presumably unique physicochemical properties, forming along Si-C interfaces in Si/C composite electrodes. These findings provide a comprehensive approach to studying model composite electrodes and offer valuable insights into optimizing the surface passivation of Si/C composite electrodes for high-performance LIBs.

Acknowledgments

This research was supported by the US Department of Energy (DOE)’s Vehicle Technologies Office under the Silicon Consortium Project directed by Brian Cunningham and managed by Anthony Burrell.

References

V. G. Khomenko and V. Z. Barsukov, Electrochim Acta, 52, 2829–2840 (2007).

J. Wu, M. Ihsan-Ul-Haq, Y. Chen, and J. K. Kim, Nano Energy, 89, 106489 (2021).

X. He, J. M. Larson, H. A. Bechtel, and R. Kostecki, Nat Commun, 13, 1398 (2022).

I. Yoon, J. M. Larson, and R. Kostecki, ACS Nano, 17, 6943–6954 (2023).

A. Dopilka, Y. Gu, J. M. Larson, V. Zorba, and R. Kostecki, ACS Appl Mater Interfaces, 15, 6755–6767 (2023).
Elucidating the Interactions between Different Transition Metal Cations and Ti3C2Tx MXene through Intercalation Method for Electrochemical Applications
Authors: Wee Shianlin , Gomez Vazquez Dario , Lian Xiliang , Tayal Akhil , Salanne Mathieu , Lukatskaya Maria R. 
Published: August 2024

MXenes, are a family of two-dimensional (2D) transition metal carbides, nitrides and/ or carbonitrides.[1] The intercalation of different metal cations and organic molecules into MXene for tuning MXenes’ electronic and electrochemical properties have been widely reported.[2]
[3]
[4] However, transition metals (TMs) which have distinct electrochemical behaviors[5]
[6] have not been explored in the literature of MXenes’ intercalation. Therefore, we herein compared the intercalation effects of different TM cations on Ti3C2Tx, for offering a general insight on the influences of multi-valent, redox-active TMs on MXenes. In particular, the changes on the physiochemical and electrochemical properties of MXenes were investigated using different in-situ and ex-situ methods, for a better understanding on the interfacial interactions of TM cations and MXenes in the confined environment of MXenes’ multilayer structures. This work serves as a foundation for the fine-tuning of MXenes’ properties by utilizing a variety of TM cations intercalation for different electrochemical systems.

[1] B. Anasori, M. R. Lukatskaya, Y. Gogotsi, Nature Reviews Materials
2017, 2, 16098.
[2] M. R. Lukatskaya, O. Mashtalir, E. Ren Chang, Y. Dall’Agnese, P. Rozier, L. Taberna Pierre, M. Naguib, P. Simon, M.W. Barsoum, Y. Gogotsi, Science
2013, 341, 1502-1505.
[3] J. Li, H. Wang, X. Xiao, Energy & Environmental Materials
2020, 3, 306-322
[4] M. Ghidiu, S. Kota, J. Halim, A. W. Sherwood, N. Nedfors, J. Rosen, V. N. Mochalin, M. W. Barsoum, Chemistry of Materials
2017, 29, 1099-1106.
[5] D. Göhl, H. Rueß, M. Pander, A. R. Zeradjanin, K. J. J. Mayrhofer, J. M. Schneider, A. Erbe, M. Ledendecker, Journal of The Electrochemical Society
2020, 167, 021501.
[6] M. Esmaeilirad, A. Baskin, A. Kondori, A. Sanz-Matias, J. Qian, B. Song, M. Tamadoni Saray, K. Kucuk, A. R. Belmonte, P. N. M. Delgado, J. Park, R. Azari, C. U. Segre, R. Shahbazian-Yassar, D. Prendergast, M. Asadi, Nature Communications
2021, 12, 5067.
Understanding Reaction Kinetics of Iron Oxide (α- Fe2O3) Reduction with Single Entity Measurements
Authors: Shekhar Raj , Boettcher Shannon W. , Kempler Paul A. 
Published: August 2024

Emitting minimal amount of CO2 during the production of steel is one of the major challenges that can be overcome by producing iron using electrowinning method. The reaction of interest is at the cathode where the direct reduction of Iron oxide (α-Fe2O3) to iron takes place. In this study, we are investigating the electrochemical conversion of hematite (α-Fe2O3) Nanoparticles to iron in an extremely alkaline medium (50 wt% NaOH) using Single Entity Electrochemistry (SEE).
Single Entity Electrochemistry is the study of single atom, molecule or particle colliding with the surface of the electrode usually by diffusion or migration. For these experiments, we are developing alkaline stable carbon-fiber (C)/Nickel (Ni) ultra-microelectrode (UME), prepared using multiple pathways such as plasma-focused ion beam.
A spike in current transient during chronoamperometry (CA) experiments is observed when a hematite particle collides stochastically with the UME and gets reduced in the process. Each spike is the reduction event of one hematite nanoparticle to iron. Individual reduction events, that last 0.2-0.3 s and resulting in 0.1-0.2 nC of charge being passed were observed at Ni and C microelectrodes, this shows good agreement with the average particle radius of 100 nm. The shape of the current transient was distinct from previously reported transients for metal deposition at cathode1-3. However, A. Allanore, et.al. model was used to support a mechanism for the direct oxide reduction process at nanoscale particles4.
The results presented here illustrate the reaction kinetics and the mode of reduction propagation in a single nano-sized hematite particle in alkaline conditions. The kinetics of hematite reduction in alkaline medium is considerably slow as observed from the slope of current spikes in SEE experiments. Furthermore, considering Allanore’s model, the reduction propagation occurs from the outer surface to the inner core.
(1) Luo, L.; White, H. S. Electrogeneration of single nanobubbles at sub-50-nm-radius platinum nanodisk electrodes. Langmuir
2013, 29 (35), 11169-11175.
(2) Xiao, X.; Fan, F.-R. F.; Zhou, J.; Bard, A. J. Current transients in single nanoparticle collision events. Journal of the American Chemical Society
2008, 130 (49), 16669-16677.
(3) Bard, A. J.; Zhou, H.; Kwon, S. J. Electrochemistry of single nanoparticles via electrocatalytic amplification. Israel Journal of Chemistry
2010, 50 (3), 267-276.
(4) Allanore, A.; Lavelaine, H.; Valentin, G.; Birat, J.; Delcroix, P.; Lapicque, F. Observation and modeling of the reduction of hematite particles to metal in alkaline solution by electrolysis. Electrochimica Acta
2010, 55 (12), 4007-4013.
(Invited) Dissolution of Organic Overlayers Modified Platinum Single Crystal Interfaces in Acidic Medium
Authors: Qiu Yunsheng , Briega Valentin , Yang Juntao , Hilpert Felix , Mayrhofer Karl J. J. , Brummel Olaf , Libuda Jörg , Cherevko Serhiy 
Published: August 2024

Electrocatalysts design has been an important researching discipline in the filed of electrochemical energy conversion and storage, among which, surface (organic) modification has becoming an efficient, selective, and flexible approach in electrocatalysis study and applications. In the focus of direct modulation on electrocatalysis interfaces, the functionalization of metallic catalysts with organic ligands (i. e. functional organic molecule, ionomers, ionic liquids) has demonstrated its capacity on improving catalytic activity and selectivity in electrochemical reactions such as ORR, CO2RR, as well as oxidation processes. However the electrocatalysts stability behavior and surface degradation dynamics of such modified systems are still not sufficiently studied.
To fully decipher the potentials of surface/interface modification in electrocatalysis, we focus our studies on the dissolution behavior of functional organics (i. e. melamine, immidazolium ionic liquids) modified model Pt (hkl) single crystal facets, in acidic medium. In regard of the excellent system sensitivity of our inductively coupled plasma mass spectrometer (ICP-MS, detection limit down to 0.1-1 ng/L), we employed a customized scanning flow cell (SFC) coupled on-line monitoring system to probe the potential-resolved surface metal dissolution dynamics. With designed electrochemical system configuration, we acquired results demonstrating the delicate stability behavior changes over transient and accumulative dissolution study on (modified) Pt facets. In combination of other state-of-art operando spectroscopy methods (electrochemical infrared reflection absorption spectroscopy, electrochemical scanning tunneling microscopy, Raman spectroscopy, etc.), we further comprehended the surface oxidation process, surface blockage/modification mechanisms on electrocatalysis interface. Our research conferred a model stability study approach on surface modification of electrodes and electrocatalysts, providing important insights into the dynamic interfacial interaction between functional modifier and electrocatalysts.