bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Plasma-Activated CO2 Reduction at a Plasma-Water Interface
Authors: Simon Julia , Kim Ji-Yong , Winter Lea R 
Published: August 2024

The development of technologies and processes to decarbonize chemical and fuel production is key to reducing global anthropogenic greenhouse gas emissions. Electrochemical carbon dioxide reduction enables a sustainable pathway to circularize carbon-based chemical products by upgrading recovered carbon dioxide using renewable energy sources. Electrochemical CO2 reduction has successfully been employed to produce chemicals such as methanol and ethylene, but it has been hindered by dependence on elevated temperature to achieve high yields and limited ability to generate higher order carbon products. Non-thermal carbon dioxide plasma can be generated at ambient temperature and pressure and contains energetically excited oxygen and carbon species. When introduced to an electrocatalyst, these reactive species could more readily participate in reaction pathways with higher activation barriers towards forming higher order carbon species compared to electrochemical reactions involving ground-state reactants. Further, plasma discharges over water in an electrochemical cell generate plasma-activated water, introducing solvated electrons and secondary reactive oxygen species.
In this work, we investigate how the use of plasma-activated carbon dioxide and a plasma-water interface impacts electrochemical product generation. We design a novel non-thermal plasma electrode to discharge carbon dioxide plasma into water in an electrochemical cell with a Cu nanoparticle electrocatalyst. Results suggest the potential for a plasma-water electrochemical system to generate value-added products that are less commonly generated in electrochemical processes at ambient pressure and temperature.
Plasma Electrochemistry in Non-Aqueous Solvents and Application to Organic Synthesis
Authors: Peyres Sean , Wang Jian , Hollyfield Drew , Confer Matthew Phelan , Uner Necip Berker , Bhargava Rohit , Moore Jeffrey S. , Sankaran Mohan 
Published: August 2024

Low-temperature, atmospheric-pressure plasmas in contact with liquids have attracted interest for various chemical applications including the synthesis of colloidal nanoparticles, degradation of organic pollutants, and conversion of abundant feedstocks. Compared to other chemical approaches, plasma-liquid electrochemical processes do not require a catalyst material, are electrified, and produce unique reactive species such as solvated electrons, one of the strongest chemical reducing species.
Here, we present a study of plasma-liquid electrochemistry in non-aqueous solvents and apply such a system to organic synthesis. The majority of studies to date of plasma-liquid electrochemistry have focused on water. For some applications, including organic synthesis, non-aqueous solvents are required. However, the compatibility of plasmas with these solvents and the chemistry has not been thoroughly investigated. We focused on methanol and the well-known pinacol coupling reaction.1 Parametric studies were performed on methyl-4-formylbenzoate (MFB) as the substrate. The solvent had important effects including the generation of side products through parasitic radical formation. By adding water, the selectivity to the desired pinacol product could be improved. A reaction-diffusion model and thermodynamic calculations at the composite correlated G3(MP2)B3 molecular orbital theory level to support experimental measurements will also be discussed, as well as the potential application of this approach to other organic reactions.

1J. Wang et al., J. Am. Chem. Soc. 2023, 14, 19, 10470-10474.
(Invited) Self-Discharge of Layered Oxide Cathodes Induced by Carbonate-Mediated Hydrogenation
Authors: Wan Gang 
Published: August 2024

Significant efforts have been made to improve the energy and power characteristics of cathodes in Li-ion batteries, while the research into cathode self-discharge has lagged behind. Self-discharge is the voltage drop experienced by all rechargeable batteries while stored in the charged state. The voltage drop becomes more problematic with increased cathode voltage and temperature. The physicochemical nature of internal reactions leading to cathode self-discharge is hardly understood and seldom discussed.
To tackle this challenge, the structure and redox evolution of commercial LiNi0.5Mn0.3Co0.2O2 electrodes and single crystal cathode thin films upon the self-discharge in carbonate-based electrolyte is revealed by surface-sensitive X-ray scattering, spectrometric and electrochemical characterizations in conjunction with thermodynamic analysis. As evidenced by the interfacial toolkits and theoretical calculations, there is an evolution and growth of cathode surface reduction layer in different types of electrolyte after self-discharged from different potentials. Structural and chemical chacterizations as well as the elemental depth profiles within cathode thin film confirms proton-insertion-induced layered cathode hydrogenation. Calculation shows that such process is both thermodynamically and kinetically favorable and is triggered by the interfacial hydrogen atom abstraction of methylene group in carbonate solvent on delithiated cathode surface. A combination of experimental and theoretical studies reveals the carbonate-mediated cathode hydrogenation mechanism accounting for the voltage drop in the self-discharge. This offers additional understanding regarding defect generation and the degradation mechanism in layered cathodes beyond the traditional behaviors of lithium-diffusion-induced self-discharge and rock-salt phase induced cathode degradation. This study offers foundational knowledge of the interfacial degradation of cathode that can be translated to the rational design of improved cathodes and electrolytes, and the self-discharge mechanism studies in other electrochemical ion insertion materials and devices.
Operando Electrochemical Liquid Cell STEM Investigation of the Growth and Evolution of the Mosaic Solid Electrolyte Interphase for Lithium-Ion Batteries
Authors: Walid Dachraoui , Pauer Robin , Battaglia Corsin , Erni Rolf 
Published: August 2024

The solid electrolyte interphase (SEI) is a key component of a lithium-ion battery forming during the first few dis-/charge cycles at the interface between the anode and the electrolyte. The SEI passivates the anode-electrolyte interface by inhibiting further electrolyte decomposition extending the battery's cycle life. Insights into SEI growth and evolution in terms of structure and composition remain difficult to access. To unravel the formation of the SEI layer during the first cycles, operando electrochemical liquid cell scanning transmission electron microscopy (ec-LC-STEM) is employed to monitor in real time the nanoscale processes that occur at the anode-electrolyte interface in their native electrolyte environment [1]. The results show that the formation of the SEI layer is not a one-step process, but comprises multiple steps. The growth of the SEI is initiated at low potential during the first charge by decomposition of electrolyte leading to the nucleation of inorganic nanoparticles. Thereafter, the growth continues during subsequent cycles by forming an island-like layer. Eventually, a thick dense layer is formed with a mosaic structure composed of larger inorganic patches embedded in a matrix of organic compounds. While the mosaic model for the structure of the SEI is generally accepted, our observations document for the first time how the complex structure of the SEI is built up during dis-/charge cycling.
[1] W. Dachraoui, R. Pauer, C. Battaglia, R. Erni, ACS Nano 2023, 17, 20434
Elucidating the Electrochemical Impact of the Calendering Process on Three-Dimensional Designed Electrodes for Lithium-Ion Batteries
Authors: Straßburger Niclas , Zhu Penghui , Pfleging Wilhelm 
Published: August 2024

Significant advancements in battery technology are imperative to meet the ambitious demands for electromobility and stand-alone energy storage devices. This stems from the need to achieve operations with high energy and power density, coupled with stringent safety standards and extended lifespans, while reducing production and material costs. The preferred energy storage technology for the coming decade is anticipated to remain lithium-ion battery (LIB) technology. The focus on researching high-energy active materials to optimize this technology is paramount. In addition to optimizing materials, significant performance enhancements can be achieved by using electrodes with high mass loading and a multiscale tailored electrode design that can be scaled up to production level.
The technological challenges of achieving a breakthrough in gaining simultaneously high energy and power density characteristics while maintaining high process and operational reliability with significant cost savings are the subject of current research and development in the field of LIB technology. To tackle this, the study explores the laser-assisted generation of three-dimensional (3D) electrode architectures and assesses its impact on battery performance and future integration into battery production. The advanced electrode design involves micro and sub-micron structures that can be tailored in various ways, leading to notable improvements in battery lifespan, battery safety, and fast charging and high-power operation capabilities compared to batteries with conventional two-dimensional (2D) electrodes. High-power ultrafast laser ablation emerges as a precise method for introducing such structures.
Coordinating the production of 3D electrodes with laser assistance necessitates synchronization with established manufacturing steps in the battery production process. Notably, the calendering of electrodes holds significance due to its substantial influence on the microstructural properties of the electrode material, encompassing porosity, material density, and layer adhesion. The study investigates the impact of laser-induced structuring, encompassing micro-/nano-porosities and microtopography, on electrodes with varying mass loadings ranging from 2mAh/cm² to 6mAh/cm². Electrochemical characteristics such as high-rate capability, fast charging, and cycle lifetime are evaluated accordingly, employing cells with graphite anodes and lithium-nickel-manganese-cobalt oxide cathodes.
Coupled Electrical – Thermal – Electrochemical Model of a Battery Module
Authors: Tewari Deepti , Rajagopalan Kannan Dhevathi Rajan Rajagopalan , Jeevarajan Judith 
Published: August 2024

A battery module comprises of several lithium-ion cells connected in series and parallel configuration to obtain the desired voltage, current and power specifications. The overall response of a module can be affected by (i) the electrical topology, (ii) the thermal topology and (iii) the cell-to-cell variations. The distribution of current depends on the series/parallel assembly and variation in interconnect resistance in the module. Operation of a cell is accompanied by an increase in temperature. In a module, the thermal environment seen by a cell is different depending on whether it is an interior cell or a cell at the boundary of module exposed to environment. There is additional thermal cross talk between cells through heat conduction in metallic interconnects. Finally, there can be several reasons for cell-to-cell variation in a module. The cells used for building a module can have variable state of charge and internal resistance at the manufacturing level. As the module is cycled, the ageing of cells in a module can differ due to variation in current, evolution of range of lithiation of electrodes and the temperature of the cell.
In this research work, we develop a coupled electrical, thermal, and electrochemical model to simulate the charge and discharge of a battery module with the overall aim of identifying the cell with largest performance degradation and most likelihood of failure. This physics-based modeling approach comprises of a simplified electrochemical and lumped thermal model of an individual cell. At the module level, the modeling framework is extended to include the electrical and thermal connectivity along with the electrochemical response.
(Invited) Using a Chemo-Mechanical Model to Investigate Electrolyte Infiltration and Surface Reconstruction within Cracked Cathode Material
Authors: Allen Jeffery M. , Weddle Peter J , Smith Kandler , Usseglio-Viretta Francois L. E. , Finegan Donal P. 
Published: August 2024

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. To that end, this talk investigates the formation of stress-induced fracture within polycrystalline cathode particles and the impact on capacity loss. The model captures anisotropic Li diffusion within a single polycrystalline particle comprised of hundreds to thousands of randomly oriented grains. Fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains are misaligned, they expand a different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. A previous study showed that small particle with large or single grain geometry tend to crack less and retain the most capacity.
Cracks within the cathode particle that have access to the surface can potentially fill with electrolyte. When this happens, the cracks can be considered new active surface area where the lithium intercalation reaction can occur. Under sufficient conditions, this could lead to better performance because the grains of the cracked particle start to operate more like a network of single-grain particles. However, the newly open surface area is also subject to side reactions and surface reconstruction resulting in diminished transport properties and potentially trapped lithium. The goal of this talk is to investigate this balance between improved lithium transport pathways caused by lithium infiltration and the reduced diffusion due to surface reconstruction.
Engineering Controls for Scaling CO2 Electrolyzers
Authors: Prajapati Aditya , Goldman Maxwell , Krall Eric , Clemens Auston L. , Marufu Michell , Chu An , Gutierrez Laura , Duoss Eric B , Baker Sarah , Hahn Christopher 
Published: August 2024

The electrochemical CO2 reduction (CO2R) to ethylene on copper-based catalysts has garnered significant attention for its potential in sustainable industrial practices. While substantial progress has been achieved in the development of small-scale electrolyzers with geometric areas ranging from 1 to 5 cm2, the imperative to address larger scales for industrial decarbonization necessitates a shift in focus. There are inherent critical risks when scaling a nascent technology like CO2 electrolysis. There can be emergent phenomena observed only at larger scales, that can prevent it from reaching commercialization, such as change in local CO2 concentration, defects in the porous transport layer, and temperature gradients The optimized conditions for operating a 5 cm2 electrolyzer may not work well with a 25 cm2 electrolyzer leading to failures. Therefore, there is a need to develop a systematic way to test for these phenomena to address these challenges to successfully operate a CO2R electrolyzer at an industrially relevant scale. In this work, we highlight the performance of a Cu-based catalyst designed for the selective reduction of CO2 to ethylene across varying scales, ranging from 5 to 100 cm2. This investigation shows the changes in the electrolyzer performance at different scales. Our findings highlight the critical importance of implementing engineering controls to overcome challenges associated with the scaling of electrolyzers. Specifically, we explore the impact of anolyte flow rate, gasket compression, and electrochemical pulsing techniques on maintaining the desired selectivity of the electrocatalyst across different scales. By systematically adjusting these parameters, we demonstrate the ability to mitigate non-linear effects and uphold the efficiency of CO2 reduction to ethylene, even on larger electrode surfaces.
This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
The 2-Propanol Fuel Cell: Direct CO2-Free Electrification with a Liquid Hydrogen Carrier
Authors: Brodt Matthew , Rajendran Menon Rohit , Hübner Christoph , Thiele Simon 
Published: August 2024

Molecular hydrogen is a gas at ambient conditions and requires compression or cryogenic liquefaction for storage and transport, leading to significant losses in efficiency. Therefore, liquid hydrogen carriers are desirable as they are storable without losses. One such fuel that has shown promise recently is 2-propanol (isopropanol), which is converted with high selectivity to acetone in a fuel cell.[1],[2],[3] Power densities over 200 mW/cm2 have been reported for direct isopropanol fuel cells (DIFCs), which rivals the best direct methanol fuel cells (DMFCs), and unlike methanol, isopropanol is non-toxic and it is not fully oxidized to CO2.
[4]

The literature has demonstrated many advantages of DIFCs, yet significant challenges remain.[5] Continuous operation at high current densities can be limited due to anodic catalyst layer network effects: slow removal of acetone from active sites and out of the catalyst layer. Additionally, perfluorinated sulfonic acid (PFSA) ionomers are not fully chemically compatible with 2-propanol and acetone. Operation at higher temperatures with a vaporized 2-propanol feed partially mitigates both of these disadvantages, yet the high energy cost of vaporization reduces the overall efficiency of the system. Future research should focus on stable, high-power operation with a liquid 2-propanol feed.
This contribution chronicles the progress that has been made and discusses the current state-of-the-art and outlook of direct electrification with DIFCs. Recent advances in liquid-fed DIFCs are presented, including design of membrane-electrode-assemblies and operation strategies in full cells. Finally, the concept of using the 2-propanol/acetone couple as an electrochemical liquid organic hydrogen carrier is briefly introduced: a reversible hydrogenation and dehydrogenation cycle for storing and releasing molecular hydrogen on demand.
References
[1] D. Cao, S. H. Bergens, J. Power Sources
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[2] Z. Qi, A. Kaufman, J. Power Sources
2003, 118, 54–60.
[3] M. L. Perry, Z. Yang, J. Electrochem.
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2019, 166, F3268-F3276.
[4] P. Hauenstein, D. Seeberger, P. Wasserscheid, S. Thiele, Electrochemistry Communications
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[5] M. Brodt, K. Müller, J. Kerres, I. Katsounaros, K. Mayrhofer, P. Preuster, P. Wasserscheid, S. Thiele, Energy Technol.
2021, 9, 2100164.
OREATE as a High Yield and Purity Electrochemical Process for Transition and Rare Earth Metal Recovery
Authors: Sansinena Jose-Maria , Braley Sarah E. , Dangel Gabrielle R. , Sykes Kiana S. , Currier Robert P. 
Published: August 2024

Developing a process that can consistently convert transition and rare earth metal oxides to chemically pure metals in near quantitative yield will have significant impact in many levels, from fundamental science to national security-related applications. Traditional separation methods of lanthanides and actinides from aqueous media have been based on liquid-liquid extractions that have proven to be quite efficient, though they are expensive and require complex engineering. Likewise, separation by pyro-chemistry provides a good recovery performance but requires the use of high temperatures that adds technological difficulties to the process. An alternative method that has grown interest in the last few years is the utilization of the difference in the metals’ reduction potentials from ionic state to metallic state. However, this electrochemical approach requires more negative reduction potentials than hydrogen evolution, which requires a very challenging control of their electrolytic deposition onto solid cathodes.
In recent years, our team at LANL has been working on the development of OREATE (Oxide Reduction by Electrochemical Amalgamation and Thermal Extraction). OREATE is a holistic electrochemical approach that involves an initial step wherein the metal oxide is dissolved and chlorinated into an acidic medium. The dissolved metal cation is then electrochemically amalgamated via reduction using a mercury pool cathode. Finally, mercury's high vapor pressure allows an easy thermal extraction process to obtain the metal. From the conceptual perspective and preliminary results, the OREATE process appears easier and simpler than traditional separation methods and is suitable for small- and large-scale preparation of high purity metals.
The results obtained using Cerium (Ce) as a surrogate metal demonstrated near quantitative yield of the electrochemical amalgamation (yield > 99%), almost complete mercury recovery during the thermal extraction (Hg recovery > 99.5%), and high purity of the Ce metal product (purity > 99%). Moreover, a variety of system parameters such as the pH of the buffered solution, concentration of cerium, reduction potential, and temperature were explored to evaluate the effect that the scaling up of the OREATE process may have on reaction rate, current efficiency, process yield, and temperature management.