bluuebunny/crossref_metadata_2025_split huggingface dataset:
A New High-Valent Fe Redox Couple in Intercalation Electrodes
Authors: Mu Edward Weian , Ramachandran Hari , Lomeli Eder , Braun Augustin , LIU Jue , Jiang Zhelong , Busse Grace , Park Jungjin , Goto Masato , Shimakawa Yuichi , Solomon Edward I. , Yang Wanli , Devereaux Thomas P. , Gent William E. , Chueh William C. 
Published: August 2024

The overwhelming majority of layered oxide cathode materials are based on the redox activity of expensive and scarce transition metals like Co and Ni. While the Fe-redox based material LiFePO4 has become increasingly attractive due to its low cost, its low gravimetric energy density and relatively low operating voltage limit its use cases. A high-voltage Fe-based layered oxide cathode would provide high energy density utilizing the redox-activity of the most abundant transition metal in Earth’s crust, but such a material that provides stable and reversible electrochemical performance remains elusive. Indeed, high-voltage Fe-redox in oxides is plagued by cation disorder and oxygen dimerization, which leads to capacity fading and large voltage hysteresis (> 1 V).[1]
In contrast, the layered oxide cathode Li4FeSbO6 (equivalently, Li[Li1/3Fe1/3Sb1/3]O2, abbreviated LFSO) exhibits <0.2 V of hysteresis, and a discharge plateau at 4.2 V versus Li/Li+ with two-electron capacity.[2] Both the exceptional electrochemical reversibility of this material and its phase separating nature upon (de)intercalation raise questions about the origin of these properties that are unusual for layered Fe oxide cathodes. In this work, we will discuss our efforts to probe the electronic structure of LFSO with Fe L–edge x–ray absorption (XAS) and 57Fe Mössbauer spectroscopy, as well as O K–edge resonant inelastic x–ray scattering spectroscopy (RIXS). The combination of these element-specific and valence-state sensitive techniques, in conjunction with charge-transfer multiplet and density functional theory calculations, allows us to reveal the electronic structure changes at Fe and O as a function of state of charge for the first time. Correlating these electronic structure changes with synchrotron diffraction measurements, we reveal a unique redox compensation mechanism that readily rationalizes the exceptional electrochemical reversibility, unlocking a new direction for high-voltage, Fe-based redox systems.

References

[1] Kwok, C. Y. et al.
Chem. Mater.
2023. https://doi.org/10.1021/acs.chemmater.3c02111.
[2] McCalla, E. et al.
J. Am. Chem. Soc.
2015, 137 (14), 4804–4814.
Influence of Carbon Types on the Electrochemical Performance of Disordered Rocksalt Cathodes
Authors: Patil Shripad , Koirala Krishna Prasad , Crafton Matthew J , Yang Guang , Tsai Wan-Yu , McCloskey Bryan D. , Wang Chongmin , Nanda Jagjit , Self Ethan 
Published: August 2024

Disordered rocksalt (DRX) materials have recently emerged as a promising class of cobalt-free high-capacity cathodes. However, due to their poor electronic conductivity, they require a high carbon content in the composite cathodes (20-30 wt%) to achieve their full potential, which has a detrimental effect on its cell-level energy density. To assess strategies to mitigate this issue, this study investigates the effect of three types of carbon (Super C65, synthetic graphite, and ketjenblack; chosen based on varying physical properties) and their loadings (10-20 wt%) on the electrochemical performance of DRX cathodes (Patil et al., 2023). Overall, DRX cathodes containing graphite additive demonstrated superior cycling performance (∼260 mA h/g with 85% capacity retention after 50 cycles) and rate capability (∼135 mA h/g at 1000 mA/g) when compared to the traditional carbon blacks. Using a variety of characterization methods such as surface area estimation using BET method, transmission electron microscopy, inductively coupled plasma-optical emission spectroscopy, Raman spectroscopy, and differential electrochemical mass spectrometry, the superior performance of graphite based DRX cathodes is largely attributed to (i) protection of DRX particle surfaces from parasitic reactions owing to a conformal graphitic coating (ii) homogenous distribution of graphite and DRX in the composite electrode providing a robust electronic network. This study provides important insights into how carbon microstructure and processing influences performance of DRX cathodes and paves the path for further development towards reduction of carbon content in composite DRX cathodes.
Reference:
Patil, S., Koirala, K.P., Crafton, M.J., Yang, G., Tsai, W.-Y., McCloskey, B.D., Wang, C., Nanda, J., Self, E.C., 2023. Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes Enabled by a Graphite Conductive Additive. ACS Appl. Mater. Interfaces 15, 39253–39264. https://doi.org/10.1021/acsami.3c05619
Fundamental Understanding of Halide Solid Electrolytes for All-Solid-State Batteries
Authors: Yang Shuhao , Chen Guoying 
Published: August 2024

Due to their superior oxidative stability, high ionic conductivity and excellent chemical compatibility with uncoated 4 V-class cathode active materials, halide compounds, particularly those with a general formula of Li3MCl6 (M = Sc, Zr, In, Y, Er, and Yb etc.), have attracted much attention as solid electrolytes (SEs) for all-solid-state batteries (ASSBs).1,2 While a great deal of effort has been devoted to the discovery of new halide SEs,3–5 fundamental understanding of their properties, such as the mechanism of ionic conductivity, chemical stability, and the interfacial reactivities at the cathode and the anode are still lacking. Here we use Li3YCl6 (LYC) as an example to investigate the key parameters that impact their performances in ASSBs. Hopping frequency analysis is used to understand how synthesis methods and chemical compositions affect mobile carrier concentration and ionic conductivity in the Li–Y–Cl series.6 Synchrotron X-ray absorption (XAS) and diffraction (XRD) are used to investigate electrochemical and interfacial chemistry of LYC in full ASSB cells with an uncoated nickel-rich cathode, a Li metal anode or a lithium-metal alloy anode. Our strategies in developing halide SEs for higher capacity and high energy density ASSBs will be presented.

References:

(1) Manthiram, A.; Yu, X.; Wang, S. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater.
2017, 2, 16103.
(2) Janek, J.; Zeier, W. G.; Challenges in speeding up solid-state battery development. Nat. Energy
2023, 8, 230−240.
(3) Combs, S. R.; Todd, P. K.; Gorai, P.; Maughan, A. E. Designing defects and diffusion through substitutions in metal halide solid electrolytes. J. Electrochem. Soc.
2022, 169, 040551.
(4) Kwak, H.; Wang, S.; Park, J.; Liu, Y.; Kim, K. T.; Choi, Y.; Mo, Y.; Jung, Y. S. Emerging halide superionic conductors for all-solid-state batteries: design, synthesis, and practical applications. ACS Energy Lett.
2022, 7, 1776–1805.
(5) Wang, C.; Liang, J.; Kim, J. T.; Sun, X. Prospects of halide-based all-solid-state batteries: from material design to practical application. Sci. Adv.
2022, 8, eadc9516.
(6) Yang, S.; Kim, S. Y.; Chen, G. Halide superionic conductors for all-solid-state batteries: effects of synthesis and composition on lithium-ion conductivity. Submitted.
(Invited) Nanosecond Electrical Discharges in Liquids: Applications in the Synthesis of Nanoparticles, Including Nanoalloys
Authors: Hamdan Ahmad 
Published: August 2024

In recent decades, the field of nanotechnology has witnessed rapid growth, fueled by the exceptional physical, chemical, mechanical, and electrical properties of nanoscale materials. Nanomaterials have found applications across various domains, including catalysis, drug delivery, microelectronics, and more. Notably, plasma-based methods have emerged as promising avenues for nanomaterial synthesis, offering versatile approaches through both bottom-up and top-down techniques.
One particularly innovative area of research is the plasma-liquid system, which has demonstrated remarkable efficiency in nanomaterial synthesis. This system involves the generation of plasma in a gas phase in contact with a liquid or directly within the liquid, sometimes aided by the introduction of bubbles. This communication has two goals: 1) present an overview of the physics of different discharge mechanisms, with a particular focus on the intriguing phenomena occurring at the interfaces, and 2) show different cases where nanomaterials of interest are produced. For instance, we will show that in-liquid spark discharges prouce nanoparticles through electrode erosion, and notably, the properties of these materials are highly sensitive to both the nature of the electrode and the composition of the liquid. In the second part, we introduce an innovative plasma-liquid system where a discharge can be produced at or close the interface of two immiscible liquids. In specific cases where the system is composed of a conductive solution (e.g. salty water) and a hydrocarbon liquid, spark discharges can be generated between a pin in liquid hydrocarbon and the surface of the conductive solution. This unique configuration facilitates therefore an interaction between a high-density plasma (generated in liquid) and a solution containing metal ions. At this stage, many reactions may occur and lead to the reduction of ions to produce nanomaterials. We found that the particles collected from hydrocarbon liquid are different from those collected from the solution, in terms of composition and size distribution. This finding suggests the triggering of different chemical reactions in each liquid, involving thus species with short- as well as long-lifetime species. Consequently, we adopted this approach to synthesize metal nanoparticles as well as binary and ternary nanoalloys, expanding the scope of possibilities in nanomaterial synthesis.
(Invited) Mixing Elements in 2D Nanostructures Grown by Discharges in Liquids
Authors: Nomine A.V. , Gries Thomas , Noël Cédric , Ghanbaja Jaafar , Bruyère Stéphanie , Nominé Alexandre , Milichko Valentin , Belmonte Thierry 
Published: August 2024

The synthesis of nanosheets through discharges in liquid nitrogen is observed for certain metals when employed as electrodes [1,2]. Various metals have been examined, with bismuth, lead, or zinc showing a propensity to form nanosheets. Other metals, such as silver or indium, also exhibit sheet formation but with smaller aspect ratios (width/thickness). Mixing metals is not only interesting to create alloys with new properties but also to understand how discharges work to enable the synthesis of these objects.
Recently, we demonstrated that these structures can be grown not only in liquid nitrogen but also in water. This is attributed to the discharge primarily originating from the metallic vapor emitted by the electrodes, a consistent process in both liquids, as confirmed by time-resolved optical emission spectroscopy.
We showcased that a pre-treatment, involving chemical etching by a Nital solution, significantly enhances the efficiency of nanosheet production, increasing it from almost zero to nearly 100%. We successfully identified the growth mechanism of nanosheets in the case of bismuth electrodes. These structures grow on the cathode with ion assistance, collecting in the bubble formed during the discharge. Upon the collapse of the bubble, they transfer into the liquid phase. Interestingly, the number density of nanoparticles produced under these conditions is either null or too weak to be evaluated.
It is feasible to incorporate two different elements into 2D nanostructures by utilizing two electrodes. We achieved a mixture of lead and bismuth oxide by using electrodes composed of the respective elements. This capability is likely associated with the similar melting points and miscibility of both elements. Nanosheets exhibit thicknesses around 5-10 nm for widths ranging in the tens of micrometers.
We anticipate that a more comprehensive understanding of the synthesis of these alloys will pave the way for the production of alloyed nanosheets incorporating other elements.
[1] A. Hamdan, H. Kabbara, C. Noël, J. Ghanbaja, A. Redjaimia, T. Belmonte, “Synthesis of two-dimensional lead sheets by spark discharge in liquid nitrogen”, Particuology 40 (2018) 152–159
[2] H. Kabbara, J. Ghanbaja, C. Noël, T. Belmonte, “Nano-objects synthesized from Cu, Ag and Cu28Ag72 electrodes by submerged discharges in liquid nitrogen”, Materials Chemistry and Physics 217 (2018) 371–378
Atmospheric Pressure Plasma Treatment of Glass Surface and Its Influence on the Reliability of Adhesive Bonding
Authors: Kelar Tucekova Zlata , Kelar Jakub , Brodňanský Dávid , Fleischer Michal , Černák Mirko , Boutar Yasmina , Zikmundová Marketa , Sokol Zdeněk , Eliášová Martina 
Published: August 2024

Glass load-bearing structural elements are currently used more often in civil engineering. However, due to the brittle fracture of glass, it is necessary to design these structures with sufficient reliability. Adhesive joints have a number of advantages over mechanical connectors of glass commonly used in construction. Adhesives can eliminate thermal bridges and provide a more uniform stress distribution along the connection without weakening the bonded material.
A variety of chemical methods have been developed for cleaning and activating glass surfaces prior to adhesive bonding. Recently, these methods have been substituted by glass surface cleaning and activation using ambient (humid) air plasma. Such an approach is considered much faster, technically simpler, and more environmentally friendly than the traditional chemical methods. For example, it eliminates the need for the so-called primer interlayer, where the primer is usually considered a heavy chemical with significant environmental impact.
The presented work is focused on the surface activation of glass by atmospheric pressure plasma to improve adhesion using specially selected transparent adhesives. We studied Diffuse Coplanar Surface Barrier Discharge (DCSBD) plasma treatment of different float-glass, heat-treated and tempered glass surfaces in ambient air. The DCSBD plasma effect was evaluated by surface free energy and peel-test adhesion measurements. The morphological changes on the glass surface were investigated by scanning electron and atomic force microscopy. The glass-to-glass adhesion at elevated temperatures was tested with respect to the artificial ageing of adhesive bonding due to the environment.

Acknowledgement: This research was supported by project LM2023039, funded by the Ministry of Education, Youth and Sports of the Czech Republic and supported by project No. GA23-06016S, funded by the Czech Science Foundation (GAČR).
Energy Efficiency of Steady DC and Half Sine Pulsed DC in the High Voltage Pre-Plasma and Plasma Alkaline Water Electrolysis
Authors: Nehra Raviraj SINGH , Kumar Ankit , Lakesar Shyam Sunder , Rajeev KP , Pala Raj Ganesh 
Published: August 2024

The research addresses the contrasting views on the energy efficiency of alkaline water electrolysis using the regular DC vs the pulsed DC. We compare the high voltage steady DC electrolysis with the high voltage half-wave rectified (HWR) AC (or the half Sine pulsed DC, an unexplored form of the pulsed DC) across a wide range of voltage regimes, with a particular focus on the less explored Plasma electrolysis (PE) regime. In addition, the current-voltage characteristics are mapped across the voltage regimes (NE to PE) using a novel high-voltage 3-electrode circuit, which allows better control over the working electrode potential. The experimental design considers critical parameters such as energy efficiency, Faradaic efficiency, and current density, providing a comprehensive evaluation of the regular DC Vs. the half-wave rectified AC electrolysis.
Pulsed electrolysis can facilitate bubble removal and ensure timely replenishment of reactant during the low-bias phase and this is expected to diminish over potential losses due to mass transfer resistance. However, the preliminary energy efficiency assessment suggests that the regular DC is ~13% higher at 33 V bias and ~24% higher at 26.5 V bias than the half sine pulsed DC(50 Hz) electrolysis. This suggests that for these particular reaction conditions, the fluctuations in the current leading to reactive losses in the circuit and other internal losses overwhelm any enhancement in the mass transfer characteristic of pulsed electrolysis. The study also points to regimes where significant thermal decomposition results in a significant increase in the apparent Faradaic efficiency.
Electrocatalytic Conversion of Plasma-Activated CO2 Toward Multicarbon Products
Authors: Kim Ji-Yong , Anderson Kelby , Park Andy , Simon Julia , Winter Lea R 
Published: August 2024

Renewable electricity-powered CO2 reduction reaction (CO2RR) toward chemicals and fuels has been gaining significant attention not only for achieving net-zero carbon emissions but also for enabling long-term energy storage. In electrochemical conversion, CO2 can be upgraded into single- or multicarbon products such as carbon monoxide, formate, and ethylene with remarkable selectivity. However, challenges still exist in terms of high overpotential, limited product range, and low production rates. Moreover, most reported CO2RR to multicarbon products which used Cu as catalysts have predominantly generated C2 products like ethylene or ethanol. However these systems require further performance improvement to target C3+ products which have higher energy density and market price. Another electrified conversion technique involves non-thermal plasma, which can activate CO2 into radical, ionized, and vibrationally excited species at atmospheric pressure and near-ambient temperature. However, plasma processes are non-selective, which poses limitations for controlling reaction pathways and necessitates H2 or light alkanes as co-reactants to produce hydrocarbons.
We synergized plasma and electrocatalytic conversion to demonstrate a combined CO2RR process that overcomes the limitations of each individual method. Through the integration of a dielectric barrier discharge plasma and an electrochemical flow reactor, pre-activated CO2 was electrochemically converted on a Cu electrode to produce multicarbon products. The combination enhanced the faradaic efficiency and reaction rate of desirable products and opened new reaction pathways by increasing the activity of CO2 prior to adsorption. The production rates of ethanol, propanol, and acetaldehyde were significantly increased, and new products such as methanol, acetylene, and ethane that were formed only in the combined reaction were detected. The product distribution was studied according to plasma-activated states of CO2 and the electrochemical applied potential. To elucidate the synergistic effects in the combined system, the selectivity and production rates were compared with those in the plasma-only and electrochemical-only reactions. Further control experiments using ground-state reactants were conducted, and the excited states during plasma activation were identified by optical electron spectroscopy. This work represents not only electrocatalysis of pre-activated reactants for enhanced generation of multicarbon products during electrified conversion of CO2, but also demonstrates synergistic convergence of plasma and electrocatalysis for converting reactants possessing strong chemical bonds.
When and Where Lithium Plating Occurs, Its Correlation with Microstructure Heterogeneity, and the Mechanisms That Initiate and Self-Regulate Electrochemical Heterogeneity
Authors: Usseglio-Viretta Francois L. E. , Colclasure Andrew M. , Allen Jeffery M. , Finegan Donal P. , Graf Peter , Smith Kandler 
Published: August 2024

A microstructure scale electrochemical LIB model was used to investigate lithium plating onset, material non-uniform utilization, and in-plane heterogeneities for an NMC-graphite full cell [1]. Model predicts active material particle surface roughness and size distribution (respectively, non-uniform curvature within and between particles) initiate in-plane heterogeneity, and that particle size heterogeneity at the separator interface controls the lithium plating preferential deposition (“Where”). These in-plane heterogeneities are then exacerbated by through-plane heterogeneities induced at fast charge as electrolyte depletion occurs and concentrates intercalation reaction near the anode-separator interface. Also, overall magnitude and occurrence of lithium plating is controlled by effective, or macroscale, microstructure parameters (“When”).
As local states of charge start to diverge between nearby active material regions, overpotential differences induced by OCP difference kick in and contribute to reduce these SOC local heterogeneities. However, for staged materials such as graphite, with OCP profile alternating between plateaus and varying regions, this balancing mechanism is, respectively, inactive and active. This leads to a dynamic, non-monotonic, in-plane heterogeneity time evolution for state of charge and Faraday current density, for which their respective in-plane heterogeneity magnitude alternates. Such behavior has been modeled both for the whole electrode at the microstructure scale and at the particle scale. In-plane heterogeneities are usually considered to be detrimental, as they result in material non-uniform utilization (i.e., under and over stressed regions) and earlier degradations. However, this work provides a more granular approach as it discriminates between a harmful in-plane heterogeneity (non-uniform curvature) that triggers SOC in-plane heterogeneity, and a beneficial in-plane heterogeneity (Faraday current density) that contributes to reduce SOC in-plane heterogeneity.
This work comprehensively explains the mechanisms that initiate, exacerbate, and regulate heterogeneity at the microstructure scale, while providing some design suggestions to reduce both in-plane and through-plane heterogeneities, as summarized in the graphical abstract.
[1] F. L. E. Usseglio-Viretta, A. M. Colclasure, J. Allen, D. P. Finegan, P. Graf, and K. Smith, Microstructure Scale Lithium-ion Battery Modeling, Part I: on lithium plating prediction and heterogeneity, in preparation.

Figure 1
Numerical Modeling of 3D Printed Structures for Lithium Metal Batteries
Authors: Cross Nicholas R. , Feng Longsheng , Zhu Cheng , Wood Marissa , Bucci Giovanna 
Published: August 2024

The development of lithium metal batteries to enable their use in commercial applications can have a significant impact on the fight against climate change due to the increase in energy density compared to state of art Li-ion batteries. However, technical challenges related to limited cyclability and non-uniformity of Li electroplating need to be addressed. This requires understanding the interplay between nucleation density, solid-electrolyte-interphase (SEI) formation, transport limitations, and unstable growth. 3D printed electrodes are of interest for electrochemical devices for their ability to tailor the electrode shape and structure to minimize system losses through enhanced ion transport and increased surface area for electrochemical reactions. 3D printed structures are constrained by the resolution of the printing method which can limit the feature size of the printed architecture. Numerical modeling of these structures can elucidate the interactions of competing physical phenomena, demonstrate tradeoffs, and estimate critical length scales and design principles that make 3D printed structures outperform traditional planar electrodes. Additionally, simulations can be used to identify failure points, complement experimental results, and deepen the understanding of fundamental questions hindering Li-metal deployment. In this presentation, we will show our recent work using continuum modeling to guide the design and evaluation of 3D printed electrodes for lithium metal batteries.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and was supported by the LLNL-LDRD program under project numbers 22-ERD-043 and 23-SI-002.