bluuebunny/crossref_metadata_2025_split huggingface dataset:
Open Circuit Potential Curve Characterization Method for Cathode Active Materials
Authors: Usubelli Camille , Kimura Kevin , Besli Muenir M. , Klein Reinhardt , Ravi Nikhil , Christensen Jake , Gorlin Yelena 
Published: December 2024

The quest to increase battery performance relies on perfecting the components of the batteries as well as improving the battery management system (BMS). As the BMS is responsible for ensuring the safety of the battery, it also governs the optimization of the energy the battery delivers. To improve predictions, classic equivalent circuit models are replaced with physics-based electrochemical models, requiring a deep understanding of the fundamental properties of the battery components. Advanced models not only track the state of charge (SOC) of the cell in the bulk of the materials, but also on the surface. One key parameter for the SOC estimation is the Open Circuit Potential (OCP) of the electrodes as a function of the lithium content, or OCP curve.[1] To provide a highly accurate SOC estimation, the OCP curves need to cover the potential range of the full cell, as well as the potential reached at the surface of the electrodes.
This work focuses on characterizing one overlooked aspect of the characterization of the OCP curve of cathode materials: the low potential region.[2-3] We propose a novel method for characterization of the OCP curve of commonly used active materials, striving to provide a standardized mapping from the gravimetric capacity to the lithium concentration, hence increasing the accuracy of the OCP curve. This method allows to characterize the OCP curve up to the lithium content of 1. This newly set scale is then used to align and compare the extensive characterization work already published on various cathode materials.[4]

Chaturvedi, N. A., Klein, R., Christensen, J., Ahmed, J. & Kojic, A. Algorithms for Advanced battery-Management Systems. IEEE Control Syst. Mag.49–68 (2010).

A. Barai, K. Uddin, M. Dubarry, L. Somerville, A. McGordon, P. Jennings and I. Bloom, Prog. Energy Combust. Sci., 2019, 72, 1–31.

C.-H. Chen, F. Brosa Planella, K. O’Regan, D. Gastol, W. D. Widanage and E. Kendrick, J. Electrochem. Soc., 2020, 167, 080534.

K. Märker, P. J. Reeves, C. Xu, K. J. Griffith and C. P. Grey, Chem. Mater., 2019, 31, 2545–2554.
(Invited) Agricultural Waste Derived Anodes for Lithium and Sodium Ion Batteries
Authors: Laine Richard , Yu Mengjie , Wang Man , Kim Philyoung M , Casey Daniel M , Fernandez Matthew M 
Published: December 2024

Hard or turbostratic carbon anodes are most often derived from thermolysis of biomass in oxygen free environments and considerable data has been accrued to suggest that low specific surface area HC offers the most stable materials for lithiation and sodiation. As part of our efforts to valorize rice hull ash (RHA, 90 wt % SiO2/8 wt % C), produced in 150k ton/yr in the U.S. alone; we learned to first distillatively remove excess SiO2 to produce silica depleted RHA or SDRHA40-70 (40-70 wt.% SiO2).1 The resulting materials are nanocomposites of carbon and SiO2 intermixed at nm length scales.2

The SDRHA carbon can be used as a reductant, and because of the very small diffusion distances, SDRHAxxcan be carbothermally reduced to electronics grade silicon (SiPV, 5’9’s purity)3 or SiC (Ar) or Si2N2O (90N2/10H2) or Si3N4 (N2) at much lower temperatures (1250°-1500 °C)4 than those used to produce the same materials commercially and at higher purities. At certain ratios, HC is a coproduct also intimately mixed with the major silicon containing material.
We have previously found that SiC/HC mixtures can serve as anode materials (coin cells) offering capacities of ≈ 950 mAh/g after long term cycling. This usually is with HC contents of just 10-15 wt. %. In this talk we explore increasing the ratio of HC:SiC via carbothermal reduction of lower wt. % SiO2:C ratios in SDRHA40 to assess the effects on LIB capacity and rates of change and as time permits, sodium ion battery (NIB) properties.

References

(1) Laine, R. M.; Furgal, J. C.; Doan, P.; Pan, D.; Popova, V.; Zhang, X. Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic, Green, and Sustainable Sources. Angew. Chem. Int. Ed.
2016, 55 1065–1069. https://doi.org/10.1002/anie.201506838.
(2) Mengjie Yu; Eleni Temeche; Richard M. Laine. M. Yu, E. Temeche, R. M. Laine, Methods of Adjusting Carbon and Silica Content in Rice Hull Ash (RHA) Byproducts to Control Carbothermal Reduction Forming Nanostructured Silicon Car-Bide, Silicon Nitride, Silicon Oxynitride Nanocomposites,” Provisional Patent Application Filed Sept. 5, 2020.
(3) Marchal, J. C.; Krug III, D. J.; McDonnell, P.; Sun, K.; Laine, R. M. A Low Cost, Low Energy Route to Solar Grade Silicon from Rice Hull Ash (RHA), a Sustainable Source. Green Chem.
2015, 17 (7), 3931–3940. https://doi.org/10.1039/C5GC00622H.
(4) Temeche, Eleni; Yu, Mengjie; Laine, R. M. Silica Depleted Rice Hull Ash (SDRHA), an Agricultural Waste, as a High-Performance Hybrid Lithium-Ion Capacitor. Green Chemistry
2020, 22, 4656–4668.
(Invited) Rational Interfacial Design for Advanced Batteries
Authors: Li Bin 
Published: December 2024

Lithium (Li) metal batteries have attracted world-wide attention due to its low density (0.534 g/cm3), high theoretical capacity (3,860 mAh/g), and low electrochemical potential (-3.04 V vs. SHE), enabling their potential to double the cell-level energy of the state-of-the-art lithium-ion batteries. However, there are still key materials issues that inhibit lithium metal and high-voltage cathodes from being commercialized as the anode and cathode, respectively, for rechargeable battery applications. For Li metal anode, the chemical and morphological (e.g., grain distribution, surface roughness, etc.) non-uniformity, coupled with the high reactivity of lithium drive heterogeneous solid-electrolyte interphase (SEI) formation, poor ionic flux distribution, active material consumption, and rapid dendrite growth. Currently, there are ex-situ and in-situ approaches to address the above issues. For example, one of approaches is to coat artificial SEI layers on Li metal anode surfaces. The component, distribution and structures of SEI layers should be designed and well controlled. The other approach is to exploit advanced electrolyte to in-situ form high-performance SEI layers. At the cathode side, due to instable cathode structure, oxygen evolution and side reaction between electrolyte and cathode materials at high voltage (> 4.3V vs. Li/Li+), the robust and Li ion conductive cathode electrolyte interphase (CEI) layers are required to stabilize the cathode at high voltage. In this talk, we will present our recent work from the three aspects: a) novel closed-host bi-layer porous/dense artificial SEI layers were designed[1]; b) the microstructures of localized high-concentration electrolyte were deeply understood and thus new electrolytes with high-performance SEI layers being formed were discovered;[2] (c) a novel artificial CEI coating was proposed to stabilize the cathode at the high voltage.
References:
[1] Efaw, Corey M., et al. "A closed-host bi-layer dense/porous solid electrolyte interphase for enhanced lithium-metal anode stability." Materials Today 49 (2021): 48-58.
[2] Efaw, Corey M., et al. "Localized High-Concentration Electrolytes Get More Localized Through Micelle-Like Structures." Nature Materials, 2023
Modeling Large Mechanical Deformations in Solid-State Batteries
Authors: Mallarapu Anudeep , Sunderlin Nathaniel , Singh Avtar , Hamilton Dylan , Yang Chuanbo , Smith Kandler , Finegan Donal P. 
Published: December 2024

Interest in all solid-state batteries has been rising due to their potentially safe operation across a wider temperature range and absence of flammable organic solvents. Solid electrolytes are thermally stable up to very high temperatures but their abuse tolerance towards mechanical failure has been debated[1]. It has been reported that thermal runaway kinetics in all solid-state batteries with lithium metal anode can be much faster than conventional lithium-ion batteries[2]. For electric vehicle applications, one of the main failure modes is mechanical abuse during an automotive crash. Deformation and fracture in batteries depend on mechanical properties of materials like active materials, electrolyte, and current collectors. Solid electrolytes can contribute significantly to the mechanical integrity of all solid-state batteries playing an important role in deformation at cell-level. For safety characterization, it is important to understand the deformation thresholds on solid state batteries leading to internal short circuits and compare them to conventional lithium-ion batteries. We develop a finite element microstructure RVE (Representative Volume Element) model to simulate mechanical deformation in solid state batteries to investigate how cell-level mechanical abuse conditions relate to particle-level deformation. We use a cell-level finite element model using representative sandwich (RS) approach to simulate mechanical indentation by a spherical indenter. The RVE model is used to simulate compression, tension, and shear modes to obtain homogenized response of catholyte region while isotropic elastic-plastic properties are used for the solid electrolyte separator and lithium metal. This modeling framework can be used to correlate mechanical abuse tolerance of batteries to properties like particle size and porosity.
Figure 1. (a) Compression simulation on catholyte RVE (b) cell level mechanical model

Figure 1
Observation of Leveler and Accelerator Behaviors in Copper Electroplating Using a Microfluidic Device
Authors: Hayase Masanori , Fukushima Daiki 
Published: December 2024

The high performance of modern integrated circuits is now owing to packaging technologies. Particularly, 3d-packaging using TSVs (Through Silicon Vias) has attracted large attention and entered use in high-end products. To fill conductor in TSVs, copper electroplating is used since extreme bottom-up is available using a combination of additives. Among additives, levelers have an important role, and extreme bottom-up can be seen with single addition of leveler without other additives. But in industry, still combination of leveler, suppressor and accelerator is commonly used. Then, we started to observe interaction of additives using the microfluidic device. In our previous study, interaction between the leveler and suppressors was studied and the leveler showed stronger adsorption compared to suppressors. In this study, mainly interaction between the leveler and the accelerator was mainly studied.
Figure 1 showed a schematic of the experimental setup. Plating solutions containing different additives can be supplied sequentially and in-situ observation of a plating surface through an optical microscope is available. We performed chronoamperometries with sequential supply from the leveler to the accelerator, vice versa, and simultaneous supply. In the sequential supply experiments, it was found that the accelerator can adsorb on the leveler coated surface, and the leveler can also adsorb on the accelerator coated surface. Competitive adsorption between the leveler and the accelerator was suggested. Result with the simultaneous supply of the leveler and the accelerator is shown in figure 2. Initially, the current density with simultaneous addition was larger than the current density obtained with only leveler addition, which we expected. But after that, interestingly, current density with the simultaneous addition maintained lower than the case with only leveler addition. Further study will be needed to understand the phenomenon.
(Invited) Probing the Effect of Molecular Orientation on Cu Deposition Rates at Cu Surfaces
Authors: Gewirth Andrew A. , Lindsay Gavin 
Published: December 2024

Surface enhanced Raman spectroscopy (SERS), electrochemical measurements, and contact angles are used to evaluate the effect of halides on Cu electrodeposition rates in the presence of MPS. The Cu(II) reduction rate is shown to decrease in the order Cl- > Br- > I-. In situ SERS and contact angle measurements show that adsorbed MPS will exhibit decreased gauche to trans (g:t) ratio and decreased hydrophobicity in the same order as the Cu(II) reduction rate. The amount of MPS in the gauche form due to the hydrophobicity of the halide decorated surface is a key factor in the Cu(II) reduction rate in acid sulfate baths containing the accelerator.
We also investigate the effect of amine-based leveler additives on the catalytic function of the accelerator at the Cu-electrolyte interface. In the presence of the bis-(sodium sulfopropyl)-disulfide (SPS) accelerator, chronopotentiometric measurements show the potential changes from inhibition of the levelers increased with molecular weight and were greater to those of glycol-based suppressors. In situ surface-enhanced Raman spectroscopy (SERS) revealed significant conformational changes of the surface-adsorbed SPS in the presence of the amine-based levelers. This leveler-induced conformational perturbation of SPS diminishes the activity of SPS. SERS also revealed decreased coverages of surface-adsorbed SPS in the presence of the high molecular weight amine-based levelers at negative potentials, indicating that the leveler limits direct contact of SPS with the surface. Decreased coverages were also found for adsorbed chloride in the presence of all levelers considered, likely contributing to the deactivation of the accelerative effect of SPS. Secondary-ion mass spectrometry (SIMS) analysis of Cu electrodeposited from solutions comprised of a linear polyethyleneimine (PEI), SPS, and Cl– show increased S, Cl, and C content in the deposit relative to solutions absent PEI, indicating the presence of PEI results in co-incorporation of these additives. This leveler-assisted incorporation of SPS and Cl– also serves to mitigate SPS acceleration.
Hydrogen in Electrolessly Deposited Copper Films -Additive’s Effect on Hydrogen Concentration and Structure of Films-
Authors: Yae Shinji , Hayashi Kazuma , Fukumuro Naoki 
Published: December 2024

Electroless deposition of copper is an important process in manufacturing various electrical connections. In this process, hydrogen is generated concurrently with the deposition of copper atoms by the oxidation of reducing agent (formaldehyde). While most of them are released as molecular hydrogen bubbles, some of them are co-deposited in copper films. Hydrogen co-deposition has been recognized as cause of residual stress generation, ductility loss, and void formation in the films. However, the detailed mechanism of such hydrogen-induced phenomenon has not been clarified. We previously reported that the room-temperature grain growth observed in electrodeposited copper films is caused by hydrogen-induced superabundant vacancy-hydrogen clusters [1,2]. In this study, the atomistic state (interstitial, vacancy-hydrogen clusters, and in nanovoids) and amount of hydrogen in the electrolessly deposited copper films have been analyzed by thermal desorption spectroscopy (TDS) [3]. The hydrogen concentration is much higher than the solubility in bulk copper, and decreased by aging at room temperature. Lattice expansion and compressive residual stress of deposited copper films are decreased with hydrogen concentration, which exists at interstitial sites, by the aging. Additives for electroless deposition reduce the hydrogen concentration and the compressive residual stress of deposited Cu films.
Acknowledgements
The present work was partly supported by JSPS KAKENHI (JP22K04763).
[1] N. Fukumuro, T. Adachi, S. Yae, H. Matsuda, and Y. Fukai, Trans. Inst. Met. Finish., 89, 198 (2011). DOI: 10.1179/174591911X13082997023873
[2] N. Fukumuro, H. Yoshida, T. Yamazaki, Y. Fukai, and S. Yae, J. Japan Inst. Met. Mater., 80, 736 (2016). DOI: 10.2320/jinstmet.JD201608
[3] N. Fukumuro, K. Tohda, and S. Yae, J. Electrochem. Soc., 169, 122505 (2022). DOI: 10.1149/1945-7111/acaa63
Enabling in-Line Silicon Wafer Porosification: An Experimental and Simulation Study
Authors: Petersen Deik , Gronenberg Monja , Carstensen Juergen , Adelung Rainer 
Published: December 2024

Silicon is the dominant material of microelectronic and solar cell devices but also a very promising material for Li-ion battery anodes. For many of these applications thin silicon layers are needed for which a layer transfer is a very efficient way to produce them. In this paper, results of large-scale etched porous silicon wafers using an in-line pilot production tool will be presented. The tool uses a wet chemical front-side contact that periodically changes polarity and thus just needs one side of the wafer in contact to the electrolyte. However, the proportion of the wafer that is exposed to each polarity is a function of its current location, leading to large current density fluctuations. Therefore, multiple electrodes have been positioned within the half-cells of the setup. Voltage and current data were recorded as a function of time, and the respective position of wafer, for all electrodes. A finite element simulation using COMSOL allowed for a very good reproduction of these in-operando measured data. A clear correlation to lateral and vertical porosity variations within the porous layers has been found.
All etching inhomogeneities in the porous layer can be clearly explained by changes in the series resistance and the corresponding voltage losses as the wafer is moving through the setup. These series resistance changes are almost exclusively related to the geometrical shape of the half cells and the positions of the counter electrodes. This means that the passive series resistance network is the reason for non-perfect etching of the porous layers rather than non-linear electrochemical processes. This network also includes the anode and the cathode that are used for contacting the electrochemical half cells. The smart contacting scheme of the in-line etching tool showed up to be fully reliable. The COMSOL studies displayed, that changes of the half-cell geometries can drastically decrease the current fluctuations. Adjustments have shown that a decrease from an initial 40% fluctuation to less than 6% fluctuation are achievable. This allows for the etching of laterally homogeneous porous layers suitable for a layer transfer.
Electrifying PFAS Cleanup: Remediation of per- and Polyfluoroalkyl Substances (PFAS) from Water Using Electrosorption and Electrooxidation Techniques
Authors: Roman Santiago Anaira , Yin Song , Wu Jhen-Cih , Elbert Johannes , Hou Chia-Hung , Shukla Diwakar , Kim Hee-Eun , Su Xiao 
Published: December 2024

Per- and polyfluoroalkyl substances (PFAS) are a class of man-made chemicals extensively utilized in various industrial applications, including the production of waterproof coatings, non-stick surfaces, surfactants, and firefighting agents. The pervasive use of PFAS has led to their widespread dissemination into the environment, where they are commonly detected in soil, groundwater, drinking water sources, and even remote regions such as Antarctic snow. Recent toxicological investigations have elucidated the propensity of PFAS to bioaccumulate within biological systems, thereby posing significant health risks to both humans and wildlife. Despite advancements in water treatment methodologies, the elimination of PFAS remains a formidable challenge due to their resistance to chemical and biological degradation conferred by their strong carbon-fluorine (C-F) bonds, which render traditional degradation approaches energy-intensive (~108 kWh/g). Thus, effective remediation of PFAS from aqueous matrices is a pressing challenge which requires thoughtful design of materials and scalable systems. Electrochemically driven techniques offer promising avenues for modular and energy efficient PFAS capture and destruction.
In this study, we investigated the electrosorption of PFAS using functionalized redox-active copolymer electrodes with 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) groups. Our investigation demonstrated the feasibility of employing oxidizing or reducing potentials to effectuate the capture or release of PFAS via a switch-like mechanism. By tailoring the structural properties of the copolymers to optimize electrostatic and affinity interactions, a notable enhancement in separation efficiency towards hydrophilic short-chain PFAS was achieved. Specifically, the introduction of selective fluorophilic interactions within the redox copolymer structure facilitated the enhanced capture of short-chain PFAS, while the inherent hydrophobicity of the TEMPO copolymer sufficed to drive long-chain PFAS capture via electrostatic interactions. Notably, our research showcases the potential for PFAS capture under environmentally relevant conditions without using additional chemical agents for sorbent regeneration. This was achieved through electro-assisted regeneration upon reduction of the electrode, with a regeneration efficiency of at least 80% observed. Furthermore, we explored the synergistic integration of electrosorption with electrooxidation as a viable strategy for in-situ PFAS eradication from wastewater post-capture.
Robust and Efficient Mechanical Model of High-Volume-Change Silicon Electrodes for Li-Ion Batteries
Authors: Wheeler Dean , Hamedi Amir Sina , Shumway Edmund McKay 
Published: December 2024

This work develops an efficient and accurate pseudo-2D (P2D or Newman-type) model capable of describing the relevant mechanical and electrochemical aspects of porous electrodes where the active material undergoes significant volume change. The model is applied to silicon-based anodes for high-capacity Li-ion batteries. While the standard electrochemical equations in a P2D model are well-known, the mechanical equations are less well-established. This presentation will describe the development of mechanical principles and corresponding equations suitable for use in a P2D model.
While it is common in previous modeling work for much attention to be spent on the mechanics of the active particles themselves, relatively little attention has been spent on understanding the mechanics of the porous composite electrode. As an example, it is common to treat the expansion of the active material as if it affects only electrode thickness and not electrode porosity. Or it is common to neglect plastic deformation and even elastic deformation of the electrode. And yet both are pervasive in the electrode film under the large chemical strains of lithiation and delithiation.
We discuss these and other issues to show complex electrode performance behavior is derived from simple mechanical principles and experimentally derived properties. Shown in the figure below is an example calculation for one set of input parameters, showing how (a,b) porosity, (c,d) film thickness (total strain), and (e,f) tangential (in-plane) stress can change under imposed conditions of external normal stress or lithiation of a pristine electrode. Arrows show direction on a hysteresis loop for a full cycle, caused by plastic deformation of the electrode. Comparison with experiment, where feasible, will also be done.

Figure 1