bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of Carbonate Additive on Cycle Life of Layered Metal Oxide Cathode in Localized High Concentration Electrolyte
Authors: Lucero Marcos , Li Xiaolin
Published: December 2024

Layered metal oxides are the leading cathode materials for high energy Sodium-ion batteries (SIBs). However, some drawbacks include fast capacity fade due to side reactions with the electrolyte, especially with high voltage (>4V vs Na+/Na). Localized high-concentration electrolytes (LHCE) have been shown to mitigate side reactions with the positive electrode due to their unique local structure, which favors the formation of a robust inorganic cathode electrolyte interphase (CEI). This study investigates the role of carbonate additives in LHCE on further extending the cycle life of layered oxide cathodes, specifically O3- NaNi0.6Mn0.2Co0.2O2. Systematic characterization, including galvanostatic cycling, electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, gives insights into the mechanism for extended cycle life.
Optimization and Electrochemical Testing of 3-Electrode Pouch Cell for Insights into Battery Prototyping
Authors: Roberts Alexander John , Greszta Agata , Somyanonthanakun Wuttichai
Published: December 2024

When promising new materials are discovered and assessed for their electrochemical performance in batteries or other energy storage devices, their testing is typically performed initially in small coin cells, progressing to the single layer pouch cell (SLP) and on to commercially relevant prototype devices in various cell formats. As this development process moves from laboratory to commercial reality, the findings at coin cell level and SLP are typically used at an early stage to inform on expected performance. It is often the case that some device performance metrics obtained at SLP scale to those of a final prototype or commercial device, with other metrics from the same cell not giving a true indication.

In this work, we initially look to answer the question ‘what size does my test cell have to be to inform on final device performance?’ This is done through variation of design and size of Li-ion pouch cells, from coin to SLP, through multilayer pouch (MLP) cells of varied numbers of electrodes, and consideration of the relationship of cell parameters such as capacity, rate, resistance, and lifetime relative to those of final MLP prototype device.

A further challenge in the assessment and development of new materials performance and properties as we move from lab to commercially relevant prototype lies in understanding the potentials that individual electrodes experience in larger cell formats. Whilst this is relatively straightforward at the small scale with various methods of constructing coin/ Swagelok test cells with a reference electrode (3-electrode cells), as we move to SLP and MLP, this becomes significantly more challenging. Through the monitoring of individual electrode potentials in the larger format cell, invaluable information can be obtained, for example, for tailoring cell balance for application, helping to develop new algorithms for fast charging and understanding the effects of rate on lifetime.

Having considered the necessary cell size to inform on performance of final prototype device, this information has been used in the development of a 3-electrode cell, with the effect of reference electrode size and position, on anode and cathode potential measurement along with cell performance.
Interplay of Thermal Gradients and C-Rate on Lithium Plating
Authors: Ishtiaque Md Mahdi Ul , Ramamurthy Jayanth , Pint Cary L. , Kingston Todd A.
Published: December 2024

Extreme fast charging (XFC) of lithium-ion batteries is crucial for solving range anxiety and rapid adoption of electric vehicles by significantly reducing charging time [1]. However, one of the key challenges in achieving this goal is lithium plating at the anode during the charging process [2]. Moreover, XFC will induce spatial temperature variations within the battery pack which will translate into thermal gradients inside a cell [3]. Interelectrode thermal gradients were previously found to induce accelerated lithium plating, degrading the battery life drastically [4], [5]. Therefore, it is critical to understand the complex interplay between C-rate and thermal gradients on lithium plating and its governing mechanisms. In this work, we investigate lithium plating under various thermal gradients and C-rates in single-layer NMC/graphite instrumented pouch cells. Thermistors were placed inside the cell at each electrode to precisely measure the magnitude of the thermal gradient conditions being applied. Galvanostatic cycling was performed at different C-rates and interelectrode thermal gradients. A comprehensive analysis was performed, including incremental capacity analysis. Three-electrode cells were utilized to isolate graphite-specific electrochemical processes and decipher the governing mechanisms. Post-mortem analysis was also performed to corroborate the electrochemical behavior.

Acknowledgments

The authors thank Dr. Michele Anderson (Office of Naval Research, grant N00014-22-1-2411) for financial support of this work. The authors also acknowledge Dr. Rachel Carter (U.S. Naval Research Laboratory) for technical discussion of this work.

References

[1] X. G. Yang, T. Liu, Y. Gao, S. Ge, Y. Leng, D. Wang, and C.Y. Wang , “Asymmetric Temperature Modulation for Extreme Fast Charging of Lithium-Ion Batteries,” Joule, vol. 3, no. 12, pp. 3002–3019, 2019, doi: 10.1016/j.joule.2019.09.021.

[2] C. Fear, M. Parmananda, V. Kabra, R. Carter, C. T. Love, and P. P. Mukherjee, “Mechanistic underpinnings of thermal gradient induced inhomogeneity in lithium plating,” Energy Storage Mater., vol. 35, no. July 2020, pp. 500–511, 2021, doi: 10.1016/j.ensm.2020.11.029.

[3] I. A. Hunt, Y. Zhao, Y. Patel, and J. Offer, “Surface Cooling Causes Accelerated Degradation Compared to Tab Cooling for Lithium-Ion Pouch Cells,” J. Electrochem. Soc., vol. 163, no. 9, pp. A1846–A1852, 2016, doi: 10.1149/2.0361609jes.

[4] R. Carter, T.A. Kingston, R.W. Atkinson, M. Parmananda, M. Dubarry, C. Fear, P.P. Mukherjee, and C.T. Love “Directionality of thermal gradients in lithium-ion batteries dictates diverging degradation modes,” Cell Reports Phys. Sci., vol. 2, no. 3, p. 100351, 2021, doi: 10.1016/j.xcrp.2021.100351.

[5] R. Carter and C. T. Love, “Modulation of Lithium Plating in Li-Ion Batteries with External Thermal Gradient,” ACS Appl. Mater. Interfaces, vol. 10, no. 31, pp. 26328–26334, 2018, doi: 10.1021/acsami.8b09131.
Aging and Power Characterization of Graphite-NMC Cells Containing Coal-Derived Graphites
Authors: Wolfe Kody D , Paul Abigail , Magee Regan , Wilczewski Warren , Wichert Nathan , Lowe Jeffrey , Trembly Jason , Staser John A. , Garrick Taylor R.
Published: December 2024

Virtual scale-up of battery cell and pack designs requires detailed information about the thermodynamics and kinetics of lithium storage and transport in the active materials. To investigate lithium transport and kinetics in coal-derived graphites, pouch cells containing three coal-derived anode materials and one control synthetic graphite were prepared and tested with a reference performance test (RPT) followed by hybrid pulse power characterization (HPPC) every 50th cycle. The RPT, performed at a slow rate (C/50) yields pseudo-open circuit voltage behavior that is used to study changes in active material storage mechanisms by comparing to the initial behavior through the lens of the multi-species, multi-reaction (MSMR) model.1,2 HPPC testing at various state-of-charge (SOC) measures the transient resistance and is used to extract kinetic and diffusion parameters.

A comparative study between the three developed coal-derived anode materials will be presented with emphasis on enabling virtual scale-up and studying potential degradation pathways. The overarching goal of this work is to develop a workflow for validating alternative graphite materials to address graphite supply chain issues for applications in electric vehicles and grid storage.

References

1. M. Verbrugge, D. Baker, B. Koch, X. Xiao, and W. Gu, J. Electrochem. Soc., 164, E3243 (2017).

2. A. Paul et al., Journal of The Electrochemical Society, 171, 039001 (2024).
The Dopamine Assisted Synthesis of Integrated MoO3/Carbon Electrodes with Enhanced Charge Storage Properties for Aqueous Zinc-Ion Batteries
Authors: Pomerantseva Ekaterina
Published: December 2024

Molybdenum trioxide (MoO3) emerged as a promising cathode materials for aqueous zinc-ion storage. In our investigation, we explored dopamine assisted synthesis routes to enhance the charge storage properties of MoO3 electrodes in electrochemical cells with aqueous electrolytes containing Zn2+ ions.

We developed a synthesis approach, in which dopamine hydrochloride (Dopa·HCl) was introduced into a hydrogen-peroxide initiated sol-gel reaction, yielding a powder precursor (Dopa)xMoOy, which underwent hydrothermal treatment (HT). Detailed characterization of the HT product revealed crystallization of the MoO3 phase combined with the dopamine carbonization. Therefore, this product was designated as HT-MoO3/C. The light-blue color of HT-MoO3/C, as opposed to the white color of MoO3, suggested presence of oxygen vacancies, however, their presence was not confirmed. The increased specific capacitance delivered by the HT-MoO3/C electrode as compared to the reference MoO3 electrode in 5M ZnCl2 electrolyte can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Building on the developed synthesis method, ethanol was introduced into reacting mixture during HT with the aim to reduce Mo in the forming HT-MoO3/C product. The dark-blue color of the produced powder, indicative of oxygen deficiency in MoO3 structure, was in agreement with XPS, TGA, Raman spectroscopy and XRD analyses confirming the presence of oxygen vacancies in the forming HT-MoO3-δ/C. Compared to the MoO3, four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon. Cyclic voltammetry-based charge storage mechanism analyses of the cells containing HT-MoO3-δ/C cathode, Zn anode and 30m ZnCl2 water-in-salt electrolyte revealed increases in ion transport kinetics attributed to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. With our synthesis method, oxygen vacancy formation can be easily controlled by changing the amount of ethanol during HT step of the synthesis route. Our work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.
Determination of Flash Point in Gel-Polymer Electrolytes for Their Use in Safe Quasi-Solid Batteries
Authors: St-Antoine Caroline , Michaud Paradis Marie-Chloe , Gonnel Pauline , Foran Gabrielle , Prébé Arnaud , Aymé-Perrot David , Dolle Mickael
Published: December 2024

Gel polymer materials have recently gained significant attention for their use as electrolytes in quasi-solid batteries. A gel polymer electrolyte consists of a polymeric matrix in which a solvent is trapped. This composition offers a compromise between high ionic conductivity (facilitated by the solvent) and enhanced safety (provided by the polymeric matrix), making them a promising technology for short-term high-performance batteries. It is widely accepted that the polymeric matrix plays an important role in improving the overall safety of the electrolyte, notably by increasing its mechanical strength.1,2 However, there is a lack of systematic research on the effect of the polymeric matrix on the overall flammability. In the field of battery research, there is no standardized test to define and quantify the flammability of a gel polymer electrolyte.

This work focuses on the development of a flammability test that is adapted for the analysis of gel polymer electrolytes. The flash point temperature represents the lowest temperature at which there is enough vapor to produce a flame with a source of ignition. Flash point measurement is a standardized test extensively studied for liquid chemicals. In our previous work, flash point measurement was adapted for the analysis of gel polymer electrolytes by coupling the flash point instrument with a thermal imaging camera.3 This novel methodology and the subsequent data processing were automated and treated through computer vision to accurately identify the flash point temperature, eliminating potential errors associated with human interpretation on whether the flame is seen or not. The employed deep learning algorithms exhibit high accuracy in detecting the presence of the flash point with a small amount of solvent (15 L), making then suitable for the analysis of gel-polymer electrolytes. Moreover, the effect of intermolecular interactions between the solvent and the salt and between the solvent and the polymeric matrix have been studied by FT-IR and were shown to increase the flash point temperature.

References

Castillo, A. Santiago, X. Judez, I. Garbayo, J. A. C. Clemente, M. C. Morant-Minana, A. Villaverde, J. A. Gonzalez-Marcos, H. Zhang, M. Armand and C. M. Li, Chem Mater, 2021, 33, 8812-8821. 23.

Li, J. Chen, L. Fan, X. Kong and Y. Lu, Green Energy & Environment, 2016, 1, 18-42.

St-Antoine,C., et al., Journal of Materials Chemistry A, 2023. 11(20): p. 10984-10992.

Figure 1
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) Dynamics and Heterogeneity of Particle Network in Composite Electrodes
Authors: Zhao Kejie
Published: December 2024

We use a data-driven approach to assess the heterogeneous electrochemistry and mechanics in composite cathodes. We visualize the morphological defects at multi-scales ranging from the macroscopic composite, particle ensembles, to individual single particles. Particle fracture and interfacial debonding are identified in a large set of tomographic data. The mechanical damage of active particles is highly heterogeneous. The difference originates from the polarization of the electrolyte potential, various local conducting environments, and thus the non-uniform distribution of the activation energy for the charge transfer reaction. We model the kinetics of intergranular fracture and interfacial degradation to assess the heterogeneous mechanical damage in composite electrodes using microstructure-informed mechanics modeling. We quantify the influence of the mechanical damage on the metrics of battery performance. More interestingly, the interfacial failure reconstructs the conductive network and redistribute the electrochemical activities that render a dynamic nature of electrochemistry and mechanics evolving over time in the composite electrodes.
(Invited) The Use of Protected Lithium Metal Electrodes in the Development of High Energy Density Next Generation Batteries
Authors: Visco Steven , Nimon Yevgeniy
Published: December 2024

Li-ion batteries have improved significantly in terms of performance and cost since their introduction in the early 1990’s. Even so, the search for lighter and more compact batteries has continue unabated with a recent focus on lithium metal based chemistries and solid-state batteries. PolyPlus introduced the protected lithium electrode (PLE) in 2004 enabling the development of aqueous Li metal batteries including Li-Water, Li-Air, and Li-(aqueous sulfur). Li-water batteries are in the process of being commercialized now with energy densities of 1600 Wh/kg and 1100 Wh/l. PLEs are enabling for use with highly concentrated aqueous polysulfides for rechargeable Li/S batteries. PolyPlus is also pursuing the use of highly conductive sulfide glass electrolytes to build fully solid-state lithium metal batteries; in this case sulfide glass is drawn down to ultra-thin ribbons (≤ 20 µm) before incorporation into solid-state cells. Battery performance and the complexity (and cost) to manufacture are both critical to the ultimate success of any new battery technology under consideration. These topics will be covered in the presentation.

Figure 1
(Invited) Recent Insights on Conversion Materials for Lithium Batteries
Authors: Takeuchi Esther S. , Marschilok Amy C. , Takeuchi Kenneth J.
Published: December 2024

The use of conversion materials as negative electrodes for lithium based batteries holds appeal due to the opportunity for high electrochemical capacity as the reactions of these materials typically involve multiple electron transfers per active center. However, the material phase changes often accompanied by large volume expansion can negatively impact cycle life due to a variety of degradation methods. Significant insights have been gained in recent years in the understanding of conversion materials and their electrochemistry through the use of multiple characterization methods over various length scales that have allowed investigation at the crystallite, particle, electrode, and systems scales. These insights have motivated deliberate manipulation of the materials and their environment including chemical composition, nanosizing, modification of surface chemistry, controlled aggregation, and electrode design. This presentation will discuss recent findings in the context of the field.
(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
(Invited) Surface-Driven Electrolyte Reactivity
Authors: Cheng Lei , Jeong Heonjae , Xia Dawei , Prabhakaran Venkateshkumar , Lin Feng
Published: December 2024

The quest for next-generation energy storage systems necessitates a deep atomistic level understandings of the interplay and reactivity between the electrode and electrolyte materials. Such understanding is crucial to elucidating the solid electrolyte interphase (SEI) formation mechanism and enhancing ion transport across the interface. Traditionally, the primary SEI formation mechanism is considered to be dictated by the electrochemical decomposition of electrolyte near the interface and the explicit role of the electrode surface in the process has been underexplored in the literature. Our presentation aims to bridge this gap by focusing on our recent computational investigations into electrolyte decomposition reactions at the interface of Mg cathode and graphite anode surfaces. The insights from these studies highlight the critical influence of the electrode surface and chemistry in steering these interface reactions and shed light on the fundamental mechanism driving electrolyte decomposition at the electrode interfaces.
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.
(Invited) New Materials for High-Conductivity Interconnects
Authors: Gall Daniel
Published: December 2024

The resistivity of interconnect lines and vias increases with decreasing dimensions. This is due to diffuse electron scattering at surfaces and grain boundaries and leads to, for example, a 10-fold resistance increase for 10-nm-wide Cu lines, causing power consumption and signal delay. Alternative interconnect materials have the potential to outperform Cu if they have a small electron mean free path to render electron scattering at surfaces and grain boundaries negligible. In addition, high-conductivity is facilitated by engineering metal-liner interfaces which minimize charge transfer, leading to specular surface scattering. This talk presents experimental and computational results to illustrate approaches to minimize the resistivity size effect, including transport measurements on epitaxial layers which quantify the intrinsic resistivity scaling and electron interface scattering. It also discusses new materials solutions for high conductivity interconnects including materials with anisotropic Fermi surfaces with preferential transport along the wire direction and compounds with topologically protected conductive surface states.
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
Electrochemical Studies of Perfluorobutanoic Acid (PFBA) and Perfluorodecanoic Acid (PFDA)
Authors: Ridgeway Madison , Workie Bizuneh
Published: December 2024

Chemically resistant perfluorinated compounds (PFCs) are man-made fluorinated hydrocarbons released into the natural environment and pose a great environmental challenge to humans and wildlife. The decomposition of PFCs using oxidation or reduction methods could produce new treatment approaches. Cyclic voltammetry (CV) studies of per- and poly-fluoroalkyl substances (PFAS), including perfluorobutanoic acid (PFBA) and perfluorodecanoic acid (PFDA) show that the compounds are reducible. The studies were conducted in acetonitrile (CH3CN) with tetrabutylammonium hexafluorophosphate (TBAHFP) as a supporting electrolyte. CV studies of 5.00 mM PFBA and PFDA in the range of 1.20 V and -1.20 V using platinum working and Ag/AgCl, KCl saturated reference electrodes showed the same number of major cathodic and anodic peaks and the same overall appearances with shifts in the peak potentials and variation in the peak heights. The exhaustive electrolysis studies of PFBA and PFDA in TBAHFP–CH3CN showed decomposition of the compounds while forming intermediary products. The information obtained in this study will be used to develop a new electrochemical method for the decomposition of PFAS in general and PFBA and PFDA in particular in wastewater.
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.
Nickel Nanoclusters Embedded in Carbon Flaky Frameworks for Electrochemical Ammonia Oxidation
Authors: Shih Yu-Jen
Published: December 2024

Nitrogenous compounds, such as NH4
+/NH3 and NO3
-, are significant contaminants in water resources. An excess of NH3 leads to eutrophication which poses a threat to aquatic organisms. Electrochemical oxidation has emerged as a promising water treatment technology, offering advantages such as simplicity, small-scale operation, and minimal reliance on additional chemicals. In this study, a nickel-based metal-organic framework (Ni-MOF) was synthesized using 2-aminoterephthalic acid (BDC-NH2) and nickel nitrate. The Ni-MOF was further carbonized to produce nickel oxide and nitrogen-enriched carbon composite, NiOx@NC. Ni ions recrystallized as core-shell nickel oxide/nickel within the 2D mesoporous carbon texture, which served as active sites for ammonia oxidation. Results of characterization showed that the Ni-MOF exhibited a hexagonal and flaky nanoparticle morphology. With increasing pyrolysis temperature, the electrochemical surface area of NiOx@NC significantly increased as to improve the rate of ammonia oxidation. The primary mediator of Ni(OH)2⇌NiOOH phase transition occurred at +1.2 V, compared to oxygen evolution at +1.6 V (vs. Hg/HgO), thereby enhancing the Faradaic efficiency. Batch electrolysis was conducted under parameters, including pyrolysis temperatures, pH, current density, initial concentration, and electrode potential. Among these, NiOx@NC(700), treated at 700 °C, was the best electrode for decomposing ammonium nitrogen of 50 mg-N/L to below 1 ppm within 4 hours at 3 mA/cm2 and pH 10. Oxygenated species, such as nitrate and nitrite, negligibly formed, with N2 nitrogen selectivity surpassing 90% in a paired electrochemical cell assisted with a Cu/Ni cathode.

Figure 1
Commercialization of Posco Lithium Prodcution Technology
Authors: Kim Kyung Hoon , Kim Hyun-Soo , Jeon Sung-il , Kim Jae-Hun , Cho Min-Young
Published: December 2024

The increasing demands for lithium, a vital component in secondary batteries, driven by the rapid growth of the IT and electric vehicle markets, have necessitated innovative approaches to lithium production. Over the past 13 years, Posco has been developing advanced lithium production technology from both ore and brine sources. Recent advancements include the operation of a successful Demo Plant for lithium hydroxide monohydrate (LHM) production for three years, with commercial production plants now operational. This presentation explains the application of Bipolar-electrodialysis (BPED) technology in commercial lithium production processes in South Korea and in Argentina, extracting lithium sulfate solution from ore and brine sources, respectively. Through the BPED process, lithium sulfate solution is converted into lithium hydroxide solution and sulfuric acid. The resulting Lithium Hydroxide monohydrate, the final product, is obtained through the crystallizer, while the sulfuric acid is recycled within the production process. The utilization of BPED technology has significantly reduced chemical usage and waste generation, promoting environmental sustainability and efficiency in lithium production. Posco's dedication to enhancing the economic efficiency of BPED technology has led to the establishment of a robust supply chain for high-performance and cost-effective BPED membranes. These domestically developed membranes, a result of collaborative research efforts, play a crucial role in achieving sustainable and efficient lithium production processes for the evolving energy storage industry.
Electrodeposition for Metal Recovery from Spent Batteries: Strategies for Improving Selectivity
Authors: Choi Seongmin , Kim Kwiyong , Su Xiao
Published: December 2024

Selective recovery of critical metals such as cobalt and nickel at a molecular level is crucial for the sustainable recycling of Li-ion batteries. However, the similarity in reduction potentials between these metals presents a significant challenge for achieving selectivity during electrodeposition, particularly for elements like cobalt and nickel (with E°Co = −0.277 V and E°Ni = −0.250 V vs SHE). In this presentation, we introduce a key strategy aimed at controlling selectivity toward either cobalt or nickel during potential-dependent electrodeposition. Initially, manipulating the electrolyte composition to introduce an excess of chloride ions enables precise control over speciation, leading to the distinct formation of anionic cobalt chloride complexes (CoCl42-) while keeping nickel predominantly in its cationic form ([Ni(H2O)5Cl]+) within an aqueous electrolyte. This forms the basis for potential-dependent selectivity. Additionally, regulating the interfacial charge density through electrode functionalization further fine-tunes selectivity by controlling the diffusion coefficient of the target ions. Moreover, we demonstrate the effectiveness of temperature-dependent control in achieving selectivity, resulting in a Ni/Co ratio exceeding 100. Unlike traditional selective electrodeposition methods, where the extended enrichment of one metal on the solid surface adversely impacts dynamic selectivity due to concentration change in the bulk electrolyte, our innovative approach guarantees high-purity and high-recovery metal extraction even during prolonged electrodeposition. This study presents a hopeful prospect for selective electrodeposition as a proficient separation method in battery recycling procedures.
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.