bluuebunny/crossref_metadata_2025_split huggingface dataset:
Evaluating the Influence of SiOx on the Calendar Lifetime of Li Ion Batteries across Varied Temperatures and State of Charge Conditions
Authors: Qayyum Ahmed Abdul , Niehoff Philip , Winter Martin 
Published: August 2024

Lithium-ion batteries (LIBs) have a wide range of application in various fields, such as automotive and stationary applications. The incorporation of silicon (Si) in the anode is an attractive strategy to increase energy density and enable fast charging. This is due to the excellent theoretical specific capacity of Si, which exceeds 3000 mAh/g. However, due to the alloying behavior of Si, a significant volume change can be observed by Si based anodes when cycled. In literature the rapid cyclic degradation is related to these volume changes. A practical approach is to use silicon oxide (SiOx) as anode material, which undergoes lower volume changes during cycling but still exhibits a specific capacity >2000 mAh/g. Studies on the cycle life of SiOx-containing cells are frequently published in literature, but calendar life studies are scarce.
Here, the calendar life of two different 1 Ah pouch cell configurations, possessing different anode chemistries, were investigated. One cell contained artificial graphite and 10% SiOx (SiO-cell) while the other cell only used artificial graphite as anode material (G-cell). Both cell configurations were built with an NMC811 cathode. 1 M LiPF6 in EC: EMC (3:7 (wt.)) + 2%wt. VC was used as electrolyte. Temperatures of 20 °C, 40 °C and 60 °C and state of charge (SoC) levels of 20%, 40%, 60%, 80% and 100% were investigated in this study. It has been observed that for 20 °C and 40 °C, the degradation rate of both cell types intensifies when stored at 100% SoC. At 60 °C, however, the capacity fade already starts intensifying drastically at around 60% SoC. The capacity fading during storage experiments of the SiO- cells, depending on the parameters tested, is higher by a factor of around 1.1 to 4.1 than the capacity fading of the G- cells. Interestingly, the capacity fade ratio of the SiO-cell to G-cell is at maximum when cells were stored below 40% SoC at 20 °C. When stored at low SoC, SiOx is the anode active material being lithiated majorly. These findings indicate that SiOx indeed causes stronger calendaric degradation compared to graphite. Hence, in future studies on SiOx based anodes calendaric degradation is an interesting topic to address additionally to cyclic degradation.
(Invited) Advanced Processing Science for Low-Cost, High Energy Density Batteries
Authors: Du Zhijia 
Published: August 2024

This project at the DOE Battery Manufacturing R&D Facility (BMF) at Oak Ridge National Laboratory (ORNL) has built research successes on advanced battery processing science and engineering (PSnE), cost reduction, and cell energy and power density improvements. Our goal is to perform the processing science and engineering needed to reduce high-risk, high-payoff technologies to lower risk levels, such that the U.S. industry will consider their integration in future products.
Electron beam curing is demonstrated as a promising method for high speed, low cost and environmentally friendly battery electrode manufacturing. This work reports transfer of this process to pilot scale equipment and evaluation of electrochemical performance in prototype 1.5 Ah pouch cells. Thick NMC composite electrodes with an areal loading of 25 mg cm−2 (∼4 mAh cm−2) are successfully cured at a line speed of 500 feet per minute. This work demonstrates that electron beam curing is a promising method for manufacturing thick battery electrodes at high speeds and low capital/operation cost.
(Digital Presentation) Physical and Chemical Properties of Lithium Tetrachloroaluminate Monosolvate with Sulfur Dioxide
Authors: Garipov Dmitriy , Kuzmina Elena , Golubyatnikova Ludmila , Mishinkin Vadim , Kolosnitsyn Vladimir 
Published: August 2024

In connection with the expansion of the areas of application of lithium-ion batteries and the increase in their energy characteristics, researchers are increasingly paying attention to the problems of battery safety. The use of non-flammable electrolyte systems will significantly improve the safety of lithium-ion batteries.
Electrolyte systems based on solvate complexes of sulfur dioxide have high electrical conductivity and are non-flammable [1]. The most studied composition is LiAlCl4 × 1.6 SO2 [1] and LiAlCl4 × 3 SO2 [2]. The properties of LiAlCl4 x SO2 monosolvate have not been described in the literature.
The presented work summarizes the results of studies of the physicochemical properties (electrical conductivity, viscosity, density) of lithium tetrachloroaluminate monosolvate with sulfur dioxide (table). The temperature dependences of viscosity, density and electrical conductivity are presented in the figure.
This work was performed as part of the Ministry of Science and Higher Education of the Russian Federation [Government Order Theme No. 121111900148-3].

References

Hartl, R., Fleischmann, M., Gschwind, R., Winter, M., & Gores, H. (2013). A Liquid Inorganic Electrolyte Showing an Unusually High Lithium-Ion Transference Number: A Concentrated Solution of LiAlCl4 in Sulfur Dioxide. Energies, 6(9), 4448–4464. DOI:10.3390/en6094448

Chul Wan Park, & Oh, S. M. (1997). Performances of Li/LixCoO2 cells in LiAlCl4 · 3SO2 electrolyte. Journal of Power Sources, 68(2), 338–343. DOI:10.1016/s0378-7753(97)02518-4

Figure 1
(Invited) Electrolysis for Sustainable Ethylene at Dioxycle
Authors: Li Chastity 
Published: August 2024

Industrial emitters are responsible for more than a third of global emissions. The central mission at Dioxycle is to divert industrial carbon emissions from entering the atmosphere and instead transform them into ethylene. Ethylene has a growing annual demand currently in excess of 150 Mton globally, corresponding to a $170 bn market, and is used in a wide range of consumer goods including fabrics, plastics, and construction materials.
Electrified chemical manufacturing is a natural choice for generating sustainable products, but the biggest challenges to its widespread adoption include scalability of production and cost competitivity with fossil-based alternatives. A key difference between academia and industry is the critical focus on the factors that most directly influence the cost of the ultimate product. For electrified chemical manufacturing, this translates to voltage and long-term stability. For example, in a two-electron process such as water electrolysis, an overpotential of 1 V (total voltage 2.23 V) adds an additional 26.6 kWh or roughly $4 to the price of H2 per kg. For comparison, nonrenewable H2 produced from steam methane reforming can be sold for $1/kg H2. Additionally, electrochemical production must scale rapidly to meaningfully compete with their fossil-based alternatives. For a startup in particular, development and research targets must always have these considerations at the forefront and be able to adapt quickly to the latest results. While there are many challenges ahead, the growth of this field and the partnerships between academia and industry will be crucial to achieving our climate goals.
(Invited) CO2-Negative Ethylene Via Electrolysis – Greenerene™, a Green Chemistry Start-up
Authors: Lattimer Judith , Zhang Tianyu , Belt Andy 
Published: August 2024

Reduction of greenhouse gases is vital for the long-term environmental health of the planet. While there has been progress in reducing and capturing CO2 emissions, a vast majority of emissions are not captured, and atmospheric CO2 concentration continues to rise. This creates a large and growing market for CO2 sequestration and utilization, which presents an opportunity to rethink how commodity chemicals, which often come with a large carbon footprint, are produced in the US and globally. C2H4 is a key building block in the chemical industry to produce a wide range of plastics, solvents, cosmetics, etc. On average, the production of 1 MMT of C2H4 generates 1.5 MMT of CO2, from fuel combustion, decoking, and utilities. Globally, C2H4 production by steam cracking is ranked as the second-largest contributor of energy consumption (2.8 EJ/year) and greenhouse gas emissions (300 MMT of CO2-e/year) in the chemical industry. Electrochemical CO2 reduction reaction (CO2RR) to produce C2H4 at ambient conditions, when coupled with renewable electricity, could reduce dependence on fossil fuels and decarbonize the chemical sector associated with C2H4 production.
At Giner, we are developing technology to improve selectivity, productivity, and durability of the CO2 electrolyzer, enabling commercial deployment. This technology is the basis of a spin-out start-up company called Greenerene™ that is currently seeking investment funding to scale up to the pilot plant scale over the next 3-5 years. Currently, our state-of-the-art electrolyzer has achieved 60% C2H4 selectivity at 500 mA cm-2 and 3 V in a 50 cm2 MEA electrolyzer. We are in the process of translating this performance into multi-cell stacks and larger-area cells to enable 1-ton/day production of ethylene at the pilot scale.
We have also developed a detailed Techno-Economic Analysis of our technology, including cost of carbon capture, renewable electricity, and balance of plant including power electronics, recirculation, and purification systems, that demonstrates a pathway to economic competitiveness. With the addition of already implemented and anticipated carbon credits, at scale our technology should be able to produce ethylene at less than current market prices, and with significant environmental and climate benefits compared with current production methods.

Acknowledgement: The project is financially supported by the Department of Energy’s Office of EERE under Grants DE-EE000942l and DE-EE0010836.
Enhanced Mechanical Properties with Ag Addition in Electroplated Ni-Sn Solder Joints: Sub-10 Micron Bond Thickness
Authors: Li Yi-Chen , Lee Yin-Ku , Duh Jenq-Gong 
Published: August 2024

Keywords: Micro-bump; Microstructure; Intermetallic compounds; Mechanical properties; thermocompression bonding
The advancement of electronic devices has garnered more extensive attention towards three-dimensional integrated circuit (3D-IC) technology due to microbump size reduction and increased power density. Microbumps play an important role in driving the development of this technology, especially in 3D chip-stacking involving multiple reflow processes. The reduction in microbump height spotlights the presence of intermetallic compounds (IMCs). In comparison to traditional ball grid array (BGA) solder joints, microbumps with smaller solder volumes exhibit a predominant fraction of IMCs at solder joints, especially with microbump dimensions potentially shrinking to less than 10 micrometers.
The interface reaction within confined spaces has become a critical concern. Mechanical properties will be dominated by IMC properties rather than solder characteristics. In conventional Cu/Sn/Cu solder joints, grain coarsening and prolonged reflowing times, which result in IMC collisions from opposing substrates, forming columnar grains with a uniform orientation, make the solder joint less reliable. Furthermore, the Cu3Sn layer in Cu/Sn/Cu microbumps presents another challenges, indicating the formation of Kirkendall voids, increasing the risk of brittle interface fractures.
This study investigates the mechanical reliability and microstructure of two sub-10um sandwiched structures: Cu/Ni/Sn/Ni/Cu and Cu/Ni/Sn-3.5Ag/Ni/Cu. In the 3D-IC manufacturing process, solder joints will experience multiple reflow processing. Different reflow heat treatment process to achieve different fractions of Ni3Sn4 IMCs were performed on both sandwiched structure. Despite the formation of internal voids due to volume shrinkage in Ni/Sn solder joints, the addition of silver in the solder, forming Ag3Sn, effectively fills these voids. The long-time reflowed sample showed outstanding mechanical properties via the addition of silver in solder. In this study, the influence of silver addition on the microstructure and mechanical properties of the overall joints under identical reflow conditions, the fracture path observation after shear test were investigated. The growth mechanism of Ag3Sn and its distribution in the solder would be further explored and addressed.

Figure 1
Deposition Kinetics and Characteristics of Peald Igzo Films Using Tetrahydrofuran-Adducted in & Ga Precursors
Authors: Lee Samdong , Jeon Sang-Yong , Lee Gyun-Sang , Kwone Yong-Hee , Im Young-Jae , Byun Tae-Seok , Lee Sang-Ick 
Published: August 2024

As the down-scaling of semiconductor materials, silicon compatible emerging materials have extensively researched for next generation display and 3D structured devices. In particular, oxide semiconductors are considered a promising candidate for backplane applications in display. Among them, indium-gallium-zinc oxide (IGZO) using plasma enhanced atomic layer deposition (PEALD) has excellent properties, like high mobility, low leakage current, high transparecy and low temperature processablility. However, conventional precursors for IGZO still have some prolems to solve such as low deposition rate, low thermal stability and high price.
In this study, we developed indium precursor (Trimethylindium Tetrahydrofuran, DIP-4) and gallium precursor (Trimethylgallium Tetrahydrofuran, DGP-2) to overcome the shortcomings of the conventional In & Ga precursors. ALD characteristics of the films deposited using the newly developed the precursors were confirmed through the source feeding time saturation and linearity. Furthermore, the incubation time of In, Ga and Zn oxide films according to the different bottom layer was respectively verified and calculated using the developed DIP-4, DGP-2 and commercially used DEZn. In order form a multilayer IGZO thin film, application of the incubation factors at IGZO process were experimentally demonstrated. Thickness of the IGZO films can be easily controlled through modulation of the incubation factors. The physical and chemical properties of the films were analyzed by X-ray diffraction, X-ray reflectrometer, X-ray photoelectron spectroscopy, transmission electron microscope.

Figure 1
Etch Characteristics of Cobalt Thin Films in High Density Plasma of Cl2/O2/Ar Gas Mixture
Authors: Oh Kyung Ho , Baek Geum Bin , Cho Yoon Jae , Ha Su Myung , Chung Chee Won 
Published: August 2024

Inductively coupled plasma reaction ion etching (ICP-RIE) of cobalt thin films patterned with SiO2 hard masks was performed using Cl2/O2/Ar gas mixture. The etch characteristics of cobalt films in Cl2/Ar gas were examined to determine the roles of Cl2 and O2, respectively. The etch rates and etch profiles of cobalt films were investigated by varying the O2 concentration in Cl2/O2/Ar gas mixture.
In the optimized Cl2/Ar gas mixture, systematic etching of cobalt films was performed by changing the etch parameters including ICP RF power, DC-bias voltage, and process pressure. As the DC-bias voltage and process pressure was increased, the etch rate increased and the etch profile improved. Through the etching parameters variation experiment, the etching properties were investigated by adding O2 to Cl2/Ar under optimized conditions. X-ray photoelectron spectroscopy and optical emission spectroscopy were used to investigate the etch mechanism in the Cl2/O2/Ar gas mixture. In addition, scanning probe microscope was used to observe roughness on the etched cobalt surface. Finally, the etching of cobalt films patterned with nanometer-scale in the optimized Cl2/O2/Ar gas mixture was successfully achieved with good etch profile.
Acknowledgment
This research was supported by the Ministry of Trade, Industry &amp; Energy (MOTIE) (20019504) and Korea Semiconductor Research Consortium (KSRC) support program for the development of future semiconductor devices. This work was supported by Korea Institute for Advancement of Technology (KIAT) grant funded by the Korea Government (MOTIE) (P0008458, HRD Program for Industrial Innovation).
New Hybrid Materials Based on N-Doping Copolymers of Thiophene Derivatives for Electrochemical Energy Storage
Authors: Sadki Said , Gentile Pascal , Marechal Manuel 
Published: August 2024

Over the past decade, electroactive conducting polymers (ECPs) are among the most potential pseudocapacitive materials for the electrodes of microsupercapacitors. ECPs exhibit several advantages, such as good conductivity (up to 103 S cm-1), flexibility, high specific capacitance (values ranging from 300 to 800 F.g-1 depending on synthesis and electrochemical performance conditions), relatively cheap and ease of synthesis [4]. Therefore, the electrochemical deposition of ECPs revealed a new strategy to design a great variety of various polymer morphologies as an innovative pseudocapacitive materials. Based on the different storage mechanism, electrochemical supercapacitors can be divided into three types, namely electrochemical double layer capacitors (EDLCs), pseudosupercapacitors and hybrid supercapacitors in which ECPs and other pseudocapacitive materials such as carbon materials, transition metal oxides, nitride complexes allow to store higher amount of capacitance per gram (faradic reactions) than EDLCs (pure capacitive energy storage reaction).
In this work, we have elaborated new n-doped conducting polymers Poly[3,6-bis(2-thienyl)pyridazine] and Poly[3,6-bis(2-(3-n-hexylthienyl))pyridazine] by making electropolymerization on Pt disk electrode and 3 nm alumina coated silicon nanowires in acetonitrile organic electrolyte. The comonomers 3,6-bis(thienyl)pyridazine and (3,6-bis(2-(3-nhexylthienyl))pyridazine) have been successively synthesized. The produced polymeric materials Poly[3,6-bis(2-thienyl)pyridazine] and Poly[3,6-bis(2-(3-n-hexylthienyl))pyridazine] during n-doping process on Pt working electrode in acetonitrile solution of TBAPF6 (0.1 M) expose very low potential value of -2.23 V and -2.19 V at current density of -0.25 mA.cm-2 and -0.06 mA.cm-2, respectively. The elctropolymerization of synthesized comonomer 3,6-bis(thienyl)pyridazine has been done on Al2O3@SiNWs and resulted in thin layer of polymer film with micropores. The experimental results are compared to electropolymerization study of thiophene monomer on Pt disk and Al2O3@SiNWs electrodes to highlight the similarities and electrochemical advancements.
(Invited) Catalyst and Anode Design for Durable Alkaline-Membrane Electrolysis
Authors: Boettcher Shannon W. 
Published: August 2024

Commercialized membrane electrolyzers use acidic proton exchange membranes (PEMs). These systems offer high performance but require the use of expensive precious-metal catalysts such as IrO2 and Pt that are nominally stable under locally acidic conditions. Alkaline-exchange-membrane (AEM) electrolyzers in principle offer the performance of PEM electrolyzers with the ability to use earth-abundant catalysts and inexpensive bipolar plate materials. I will highlight our fundamental work in understanding the chemical and electrochemical processes in earth-abundant water-oxidation catalysts over the past decade and we are using that understanding to drive progress in high-performance AEM electrolyzers.
Baseline systems operate at 1 A·cm-2 in pure water feed at < 1.9 V at a moderate temperature of ~70 °C using either IrO2 or Co3O4 anode catalyst layers, PiperION alkaline ionomers, and stainless-steel porous transport layers. These devices, however, degrade rapidly compared to PEM electrolyzers which we link to chemical and structural changes in the ionomer-catalyst reactive zone using a combination of integrated reference-electrode device architectures, impedance, and cross-sectional and post-mortem materials analysis. We further discover that dynamic Fe-based OER catalysts – that have world-record performance in traditional liquid alkaline electrolyzer systems – perform poorly with enhanced degradation rates in alkaline membrane electrolysis, illustrating fundamentally different chemical design principles for OER catalysts.
Given this baseline understanding, I will end with new chemical strategies we have developed to mitigate degradation and enhance performance using novel ionomers, passivated electrolyte-catalyst interfacial architectures, and specifically designed multicomponent anode oxygen catalysts to target stable performance without supporting soluble electrolyte: <10 μV/h degradation at currents > 2 A cm-2 and cell voltages < 2V.
(Invited) Electrode Transport Resistance Analysis in Proton Exchange Membrane Water Electrolyzers
Authors: Litster Shawn , Ferner Kara J , Ebbert Mary , Pasmay Fausto N 
Published: August 2024

Decarbonizing sectors that are challenging and economically demanding to electrify, such as heavy-duty ground transportation, aviation, and industries like ammonia, steel, petroleum refining, synthetic fuels, and cement production, is crucial in addressing climate change and environmental pollution. The key strategy for reducing the reliance of these sectors on fossil fuels and cutting emissions involves utilizing hydrogen with low carbon intensity. Proton exchange membrane water electrolyzers (PEMWEs) play a vital role in this transition due to their high efficiency, rapid response time, and capability to electrochemically compress hydrogen. However, despite making encouraging progress, significant improvements in catalyst activity and utilization are necessary to lower loadings to levels that meet ambitious cost targets.
One critical aspect of enhancing catalyst performance for achieving high currents at efficient low voltages is minimizing overpotential losses. These losses result from electron, proton, and water transport to the oxygen evolution catalysts. Additionally, there are secondary current-induced loss mechanisms, including membrane and electrode dry-out and ionic contaminant polarization.
In this presentation, we will delve into the relevant transport mechanisms and the fundamental limits of reducing these overpotentials through modeling. We have evaluated the transport properties of electrodes that are challenging to directly probe due to their micrometer and sub-micrometer length scales using ultra-high-resolution three-dimensional imaging with X-ray computed tomography (nano-CT) and plasma-focused ion beam cross-sectioning with scanning electron microscopy (pFIB-SEM) for image-based simulations. Subsequently, we will briefly review existing methods for experimentally diagnosing transport limitations, as well as highlight new methods currently under development in our laboratory. These new diagnostics include a galvanostatic intermittent titration technique (GITT) for electrolyzers and a limiting-current diagnostic for PEMWEs. The presentation will conclude by highlighting fresh insights into the significance of two-phase transport, electrode and membrane dry-out, all enabled by these diagnostics and modeling.