bluuebunny/crossref_metadata_2025 huggingface dataset:
Understanding the Role of Entropy in Promoting Electrocatalytic CO2 Reduction
Authors: Schreier Marcel , Noh Seonmyeong , Zhang Gong , Cho Yoon Jin
Published: August 2024

A global push towards increased sustainability requires technologies that enable the long-term storage of renewable electricity and the sustainable synthesis of chemicals. The electrochemical reduction of CO2 to fuels and chemicals represents a promising avenue to meet these goals. Yet, despite extensive research, many fundamental aspects of the interfacial interactions that enable this reaction remain unclear. One simple question that has not been addressed to date is the mechanism through which the applied potential controls the rate of CO2 reduction. To provide insight, we measured CO2 reduction activation energies on Ag electrodes in the presence of different cations. Building on our earlier work (J. Am. Chem. Soc.
2016, 138, 25, 7820–7823), where some of us demonstrated the important role of structural modifications to imidazolium cations in controlling the rate of CO2 reduction reactions, we expected that these structural modifications impact the reaction rate through changes to the activation energy. However, our findings revealed a much more fascinating picture of the impact of imidazolium cations on CO2 reduction rates.

By measuring the activation energy in the presence of imidazolium cations with different structural features, we find that introducing 1-ethly-3-methylimidazolium (EMIM) results in an apparent activation energy of zero. Under these conditions, the applied potential modifies the reaction rate solely through changes to the pre-exponential factor of the Arrhenius equation.

Based on literature on homogeneous catalysis, we suggest that our finding indicates that the rate of CO2 reduction in the presence of EMIM is entirely controlled by the formation entropy of the CO2 reduction transition state, with the potential likely influencing the rate by modifying the degree of ordering of imidazolium cations at the electrode surface. We further show that proton abstraction from EMIM forms a neutral compound, resulting in the elimination of the rate enhancement. Our results provide important new insight into the mechanism through which the applied potential controls the rate of electrocatalytic reactions and we expect them to be of broad importance to a better understanding of the connection between interface structure and electrocatalytic rates.
Electrosynthesis of Glyoxylic Acid By Electrochemical Reduction of Oxalic Acid and Oxidation of Glyoxal inside Co-Laminar Flow Cells
Authors: Mirzaie Farzad , Goulet Marc-Antoni
Published: August 2024

This study investigates the simultaneous electrosynthesis of glyoxylic acid through electrochemical reduction of oxalic acid and oxidation of glyoxal inside a co-laminar flow reactor. This system offers specific advantages over traditional beaker cells including: continuous operation and controlled mixing of products.

This study involves a systematic exploration of operating conditions such as flow rate, applied potential, current density, electrode gap and influence of specific electrocatalysts. These operating conditions are varied while the yield and current efficiency of the cell are measured. In this way, the optimum conditions for electrosynthesis of glyoxylic acid are determined and insight into the efficiency of other electrosynthesis reactions is obtained.
Metal-Organic Framework-Based Materials for Heavy Metal Sensing in Aqueous Media
Authors: Šljukić Biljana , Milikić Jadranka , Radinović Kristina , Savić Marjetka , Janošević Ležaić Aleksandra , Ćirić-Marjanović Gordana
Published: August 2024

Industrial development leads to an increasing amount of pollutants including heavy metal ions in surface and subsurface waters. For instance, wastewater from battery manufacturing, paint manufacturing or metal plating, contain heavy metals in high concentrations. The heavy metals are typically non-biodegradable and not-easy to excrete. Their presence within the organisms causes damage and failure of different organs. Consequently, the permissible concentrations of heavy metal ions in drinking water set by the World Health Organization are on a ppb level.

In this work, electrode materials based on metal-organic frameworks (MOFs) are prepared and studied for sensing of heavy metals in aqueous media. These involved MOFs in their pristine form, composites of pristine MOFs and conducting polymer polyaniline as well as their carbonized derivatives. Cadmium and lead ions were used as model pollutants. Thorough physico-chemical characterization of the prepared materials was done using scanning electron microscopy, Raman spectroscopy, and dynamic light scattering. Electroanalytical performance was scrutinized using anodic stripping voltammetry and correlated with materials’ structural, morphology and textural properties. Limits of detection and sensitivity were determined upon optimization of the experimental conditions to identify the best material. Moreover, materials proved to be suitable for two heavy metal ions sensing in real river samples.

Acknowledgments

This work was supported by the Science Fund of the Republic of Serbia, grant number 7750219, Advanced Conducting Polymer-Based Materials for Electrochemical Energy Conversion and Storage, Sensors and Environmental Protection-AdConPolyMat (IDEAS programme).
Near Infrared Aggregation Induced Electrogenerated Chemiluminescence Studies of Xanthene Dye
Authors: Motchaalangaram Jesy , Rathnamalala Chathuranga , Scott Colleen N. , Miao Wujian
Published: August 2024

Electrogenerated chemiluminescence (ECL) serves as a versatile electrochemical-spectroscopic tool for rapid sample analysis, offering high sensitivity, good selectivity, and a low detection limit. During electrochemical redox reactions of luminophores and often ECL co-reactants, excited state luminophore species are formed through high energetic electron transfer between oxidized and reduced luminophore radicals or between the radical cation or anion and co-reactant intermediates. This process emits photons, generating ECL. Near infrared (NIR) luminophores represent an emerging class of materials in ECL studies. However, greater vibronic coupling between the ground and excited state in NIR luminophores with a lower band gap promotes nonradiative decay. The aggregation-induced emission (AIE) phenomenon overcomes these challenges, demonstrating enhanced radiative emission. We conducted a study on the photophysical, electrochemical, and ECL behavior of XanthCR-880 dye, which comprises a thienylpiperidine donor and a xanthene core as an acceptor. The central xanthene core provides extended conjugated length and increased charge transfer, resulting in NIR absorption at 880 nm and fluorescence emission at 960 nm, with a stroke shift of 80 nm. Cyclic voltammetry performed at a Pt electrode in MeCN with a scan rate of 50 mVs-1 revealed two oxidation waves and two reduction waves at 0.35 V, 0.70 V, -0.70 V, and -1.55 V vs Ag/Ag+, respectively. Due to the limited potential window of the Pt electrode in MeCN (not exceeding -2.5 V, a boron-doped diamond (BDD) electrode was employed at more negative potentials, uncovering an additional reduction wave at -2.62 V vs Ag/Ag+. The cathodic and anodic ECL behavior of XanthCR-880 dye was investigated using benzoyl peroxide and 2-(dibutylamino)ethanol as cathodic and anodic co-reactants, respectively. For cathodic ECL, XanthCR-880 dye produced two ECL waves at the BDD electrode, with peak potentials of -2.06 V and -2.36 V, respectively. In anodic ECL, relatively weak emission was observed at 1.05 V. ECL spectra were generated using the cathodic ECL pathway and interference filters as wavelength selectors, revealing a maximum emission at ~975 nm. The proposed ECL mechanism, as well as AIE studies, will also be discussed.
Light-Induced Redox Dynamics in Plasmonic Nanostructures and Photosensitizer Transition Metal Compounds
Authors: Sprague-Klein Emily
Published: August 2024

Solar energy harvesting is a nuanced scientific field that involves precise control across energy, time, and nanometer length scales. The understanding of how to harness sunlight to promote chemical reactions is vital for the advancement of renewable energy applications and a sustainable future. Limited knowledge of the precise chemical mechanisms underlying solar energy harvesting restricts widespread technological use and the development of photovoltaic devices that utilize light-harvesting biodegradable materials. My research focuses on developing a fundamental understanding of visible light-activated excited state chemistry that is of great importance in elucidating the mechanisms, structures, and design features for catalysis. In this talk, we will examine excited-state chemical structure dynamics in nanomaterials that use light-matter interactions to drive interfacial or intramolecular charge transfer. Steady-state and time-resolved optical/X-ray spectroscopy allow for the observation of these dynamics across an expansive timescale—from the seconds timescale of oxygen-evolving reactions to the ultrafast timescales of electronic and vibrational motion. Novel light-matter interactions in plasmonic nanostructures, biomimetic metal oxides, and molecular transition metal complexes will be discussed. The talk will conclude with future opportunities for expanding the scope of nanoscale photocatalysis and for designing enhanced localized control over excited-state chemistry.

[1] E. A. Sprague-Klein*, X. He, M. W. Mara, B. J. Reinhart, S. Lee, L. M. Utschig, K. L. Mulfort, L. X. Chen*, D. M. Tiede*. “Photo-Electrochemical Effect in the Water Oxidation Catalyst Cobalt-Phosphate (CoPi),” ACS Energy Letters, 2022, 7, 9, 3129–3138.

[2] N. L. Warren, U. Yunusa, A. B. Singhal, E. A. Sprague-Klein*. "Facilitating Excited-State Plasmonics and Photochemical Reaction Dynamics," Chemical Physics Reviews, (Accepted December 2023).

[3] U. Yunusa, N. Warren, D. Schauer, P. Srivastava, E. Sprague-Klein*. "Plasmon resonance dynamics and enhancement effects in Tris(bipyridine)ruthenium(II) gold nanosphere oligomers," Nanoscale, (Under Review).
Multiphysics Modeling of Electrode Dissolution Under Hydrodynamic Conditions in Low Conductivity Water
Authors: Garcia Fernandez Rogelio Elias , Hicks Phillip Michael , Adam Niklas Miller , Callahan Michael Robert
Published: August 2024

Efficient plug-flow electrochemical reactors are characterized by their ability to effectively convert species with significant ionic strength and/or with the assistance of a well-behaved electrolyte. Because of the classic electroconductivity requirement, electrochemical reactors are not particularly attractive options for applications with low-conductivity conditions, especially for low-pressure feeds. However, these reactors can still find application in dedicated processes such as ultra-clean water conditioning and biological-coupled separation systems. Consequently, a multi-physics model was developed using COMSOL Multiphysics to characterize different reactor-design conditions based on the Tertiary Current Distribution which accounts for the effects of expected variations in electrolyte composition and ionic strength on the electrochemical process, as well as solution resistance and electrode kinetics. The modelling framework presented here employs single-phase laminar fluid flow, the Nernst-Planck equation, the water-based electroneutrality condition, and concentration-dependent overpotentials. This investigation particularly explores the electrolysis process of “anodic dissolution,” in which elemental species dissociate from the solid matrix of the electrode and enter the liquid phase of the electrolyte as soluble ions. The reactor configuration of interest has a rectangular parallel-electrode design and is operated galvanostatically. A series of parametric studies are carried out to inspect the response of the system when hydrodynamic, kinetic, and geometric conditions are changed. The parametric sweep resulted in variable effluent concentrations and system voltage, which reveal underlaying optimization patterns for electrode dissolution in low conductivity water.
(Invited) Computational Models of Proton-Coupled Electron Transfer in Energy Conversion and Storage
Authors: Warburton Robert
Published: August 2024

Proton-coupled electron transfer (PCET) is a fundamental class of chemical reactions that is central to many electrochemical energy conversion and storage processes. In this talk, I will discuss recent theoretical model development for interfacial and intermolecular PCET reactions. First, I will describe a rate constant model for the reaction between reduced anatase TiO2 surfaces and a 4-MeO-TEMPO nitroxyl radical. The rate constants are modeled using vibronically nonadiabatic PCET theory, where the transferring proton and electron are treated quantum mechanically. Hybrid functional periodic density functional theory (DFT) calculations are used to derive model parameters such as driving forces, reorganization energies, and proton vibrational wavefunctions. This modeling strategy highlights the role of inner-sphere bond reorganization and excited vibronic states on the PCET reactivity of metal oxides. Next, I will show how similar computational approaches can be used to predict whether electrochemical PCET is likely to proceed through concerted electron–proton transfer or sequential electron transfer and proton transfer steps. Using PCET reactions between redox-active quinones and functionalized imidazole bases as an example, mechanistic predictions are informed by DFT-calculated potential energy surfaces. These PCET modeling strategies have broad applicability to kinetic studies of electrochemical energy conversion and storage processes.
(Invited) Advances in Modeling Ion Transport in Micropores and Charging Behavior of Porous Electrodes: Merging Molecular Insights with Machine Learning for Energy Storage
Authors: Wu Jianzhong
Published: August 2024

Electric double layer (EDL) charging is a complex process coupling electro-osmotic flow, surface reactions, and ion concentration gradients. The charging dynamics depends on the properties of electrolyte and electrode structure, as well as initial and boundary conditions. While molecular dynamics (MD) simulations and first-principles calculations can encompass all factors, their computational demands are substantial even for simple electrochemical systems such as electrolytes near a planar surface. This presentation explores recent advancements in modeling ion transport in micropores and the charging behavior of porous electrodes with different theoretical and simulation methods. Illustrative examples will be discussed on the integration of molecular modeling and machine-learning techniques to enhance our understanding of complex electrochemical processes and improve the design of energy storage devices.
First-Principle Insight of Synergistic Modification Mechanism in P2-Type Layered Oxide Cathode Material with Anionic Redox Activity for Sodium-Ion Batteries
Authors: CHENG Hsu-Chen , Chen Han-Yi , Chen Hsin-Yi Tiffany
Published: August 2024

Layered oxides exhibiting anionic redox activity have gained attention as a promising material in both Na-ion batteries owing to their additional capacity provided through oxygen redox chemistry. However, unfavorable side effects such as irreversible phase transformation, hysteresis, and gas evolution, usually arise during the stabilization process of the unstable electron holes generated by the redox reaction of oxygen. To address these challenges, we co-dope Cu and Ca in the pristine Nax[Mg0.28Mn0.72]O2 (NMMO) and propose the P2-type NaxCa0.03Mg0.22Cu0.11Mn0.67O2 (NCaMCMO) Na-deficient cathode material which demonstrates high specific capacity with minimal phase change. In this work, we employed the density functional theory (DFT) calculations to investigate the underlying mechanisms of the synergistic modification strategy in both transition metal and alkali metal layers. The substitution of electrochemically active Cu induced variations in the electronic structure near the Fermi level, indicating an inherent change in redox chemistry. The computational results of the local structure provide a deeper understanding of the oxygen-stabilizing effect of Cu. Furthermore, we analyze the nature of the Ca insertion as a pillar in an alkali-metal layer, which mitigates phase transformation to the kinetically unfavorable O2 phase through phase energy comparison. The calculations manifest that Ca doping effectively extends the P2 phase into a deeper charging state. This work elucidates fundamental mechanisms for enhancing cathode materials in future battery design.
(Invited) Insights into Atomistic Processes at Electrified Solid/Liquid Interfaces from Ab Initio Calculations
Authors: Todorova Mira , Yang Jing , Surendralal Sudarsan , Yoo Suhyun , Deissenbeck Florian , Wippermann Stefan , Neugebauer Joerg
Published: August 2024

Many of the challenges we face today towards achieving a greener economy focus on processes occurring at electrified solid/liquid interfaces. Understanding how the interactions between the solid, the liquid and dissolved species are affected by the applied potential will aid our ability to achieve rational design and targeted optimization of relevant processes. Hereby, ab initio molecular dynamic simulations including explicit modelling of the aqueous environment have proven an indispensable tool to gain insights into reaction mechanisms. More approximate choices to modelling the electrolyte, such as implicit solvent models, are however also popular. The talk will discuss the suitability of approximate models for the aqueous environment to study, e.g., the stability of surface phases in the Mg/H2O system and incorporation of impurities in nano-aerogels during synthesis [1,2], by coupling DFT calculations with thermodynamic models. Furthermore, insights into reaction mechanism at electrified solid/liquid interfaces enabled by our recent developments of a thermopotentiostat [3,4] will be presented, using the example of Pt[5].

[1] S.-H. Kim, S.-H. Yoo, S. Shin, A. El-Zoka, O. Kasian, J. Lim, J. Jeong, C. Scheu, J. Neugebauer, H. Lee, M. Todorova, B. Gault, Adv. Mater. 34, 2203030 (2022)

[2] S.-H. Kim, S.-H. Yoo, P. Chakraborty, J. Jeong, J. Lim, A. El-Zoka, L. Stephenson, T. Hickel, J. Neugebauer, C. Scheu, M. Todorova, B. Gault, J. Am. Chem. Soc. 144, 987 (2022)

[3] S. Surendralal, M. Todorova, M. Finnis, and J. Neugebauer, Phys. Rev. Lett. 120, 246801 (2018)

[4] F. Deißenbeck, C. Freysoldt, M. Todorova, J. Neugebauer, and S. Wippermann, Phys. Rev. Lett. 126, 136803 (2021)

[5] S. Surendralal, M. Todorova, and J. Neugebauer, Phys. Rev. Lett. 126,166802 (2021)
Understanding of Anion Effect on Iron Redox Behavior and Oxygen Reduction Activity of Fe-N-C Electrocatalysts
Authors: Xu Jiayi , Wang Xiaoping , Myers Deborah J. , Liu Cong
Published: August 2024

Fe-N-C catalysts are the most promising platinum group metal (PGM) free electrocatalysts for oxygen reduction reaction (ORR). Significant progress has been made in understanding the active site structure and activity and improving the ORR performance. It is generally accepted that the Fe-N-C sites are associated with FeNx centers embedded in a defective nitrogen-doped graphene. As reported in literature, both pyrrolic N and pyridinic N can support Fe single site; however, it is difficult to distinguish between the two. Furthermore, experimental characterization, such as in-situ X-ray absorption spectroscopy (XAS) and Mössbaruer, has elucidated the redox behavior of Fe2+ to Fe3+ during the reaction. Interestingly, in different acidic environments, the ORR activity exhibits differently. For instance, in comparison between H2SO4 and HClO4 solutions at the same pH value, the Fe redox happens at lower potential in H2SO4; however, the right shift of half-wave potential (E1/2) of ORR in H2SO4, compared with HClO4, indicates higher ORR activity. This indicates that the electrolyte systems have a significant impact on ORR activity. To further understand the active site structure and their ORR activity, density functional theory (DFT) calculations utilizing explicit solvation effect are carried out. XANES simulation using FDMNES suggests that as prepared catalysts could consist of Fe single atom sites supported by both pyrrolic and pyridinic N atoms; however, the pyrrolic species are not as stable as pyridinic species in solution. As presented by DFT simulation, the anions in solutions can interact with FeN4 site differently. SO4
2- binds strongly with the FeN4 center, while HSO4- and ClO4- interact rather weakly. Furthermore, the redox potential and limiting potential are evaluated via mechanistic study. By focusing on more stable Fe center supported by pyridinic N, the results suggest that the transformation of Fe2+ to Fe3+ happens at 0.52 V in H2SO4, which is lower than that in HClO4, 0.69V. More interestingly, the limiting potential (activity) of ORR in H2SO4 is higher than that in HClO4 (0.94 vs 0.68 V). DFT simulation indicated that the anions in electrolyte can impact the Fe redox behavior and ORR performance, which agrees well with the experimental investigation. This work also provides significant guidance to further improve ORR activity of Fe-N-C catalysts.
Dual-Ion-Doped Hydrated Vanadium Oxides Nanowires As Cathode Materials for High-Rate Aqueous Zinc Ion Batteries
Authors: Chen Hung-Lin , Chen Hung-Lin
Published: August 2024

Due to environmental-friendliness, high safety and stability, high theoretical capacity as well as low cost, aqueous zinc ion batteries (AZIBs) are budding as attractive alternatives for large-scale energy storage applications. However, the lack of suitable positive electrode materials becomes the main issue for AZIBs to pursue high energy density and excellent rate capability. Herein, the dual-ion-doped hydrated vanadium oxide nanowires (VOH) are synthesized through hydrothermal method, which is suitable to be cathode materials for AZIBs. Through metal ions and crystal water pre-intercalation, the interlayer spacing of (001) becomes larger, which is proposed to have better capability to accommodate Zn2+. Moreover, the pre-intercalated metal ions can serve as structural pillars between layers, providing excellent stability during discharging/charging process. In this study, the novel dual-ion-doped VOH exhibits more than 420 mA h g−1 at 0.1 A g−1 as well as more than 260 mA h g−1 at 5 A g−1. In addition, it can retain more than 80% capacity after 500 cycles at 5 A g−1. The energy storage mechanism of dual-ion-doped VOH is revealed via operando x-ray absorption near edge spectroscopy. This study implies that this dual-ion-doped VOH nanowires can serve as suitable positive electrode materials for high-performance aqueous zinc ion batteries.
(Invited) Battery Manufacturing Needs from the Perspective of DOE's Advanced Materials and Manufacturing Technologies Office
Authors: Suh Changwon
Published: August 2024

The Department of Energy’s Advanced Materials and Manufacturing Technologies Office (AMMTO) continues to invest in energy storage research, development, and demonstration (RD&D) to help stakeholders improve efficiency, cut costs, and make materials, components, and systems with superior performance. Despite recent promising advances, manufacturing capabilities are still necessary to meet the expected demand for batteries as we move toward a clean energy economy. Strengthening the domestic manufacturing supply chains is also another important task to pursue in parallel. A multi-pronged approach is required to strengthen domestic battery manufacturing and reduce time to commercialization and deployment of transformative technologies. AMMTO recognizes a number of unmet needs that need to be addressed including development of manufacturing processes and equipment that take advantage of the most recent technical advances as well as effective utilization of data-driven analysis and experimentation to assist in manufacturing optimization.

In this talk, AMMTO’s perspective on energy storage technology development and manufacturing will be discussed, highlighting current gaps and challenges that need to be addressed. In addition, there will be a robust discussion of a wide variety of DOE’s efforts in the context of technical and manufacturing challenges regarding scale-up and performance that still prevent the electrochemical energy storage community from achieving cost targets and commercial viability.
(Invited) Single Crystal Ni-Rich Cathode Materials: Synthesis, Scaleup and Validation
Authors: Xiao Jie
Published: August 2024

Synthesis of high-performance single crystal Ni-rich NMC, especially when Ni≥0.8, poses a challenge. A conflict exists because as Ni content increase in NMC811, a lower calcination temperature is preferred due to Ni reduction at elevated temperatures, while high temperatures favour single crystal growth.Therefore, molten salt is sometimes employed as the reaction media to promote growth of single crystal NMC811. In general, four approaches for synthesizing of Ni-rich NMC single crystals: molten salt, hydrothermal, direct solid-state synthesis and multi-step lithiation. Molten salt and hydrothermal approaches result in the formation of well-segregated large crystals, but they also increase manufacturing cost. Direct solid-state synthesis, which involves ball milling all precursors together followed by calcination, is a time-saving approach. However, it poses challenge for impurity control due to contamination from milling media, and it can damage the material structure. The calcination of TM(OH)2 precursor with LiOH at very high sintering temperatures forms micron-sized primary particles which, however, still exhibit significantly agglomerated. A post-synthesis milling process is required to break down those NMC811 crystal clusters.

This talk will discuss an innovative nanoscale phase separation approach for synthesis of high-performance single crystal NMC811 that is readily adaptable for industry manufacturing. The reaction mechanism of single crystal growth is investigated to understand the synthesis-morphology-performance relationship in growing single crystal NMC811 in the absence of molten salts. The scaled single crystal NMC811 is then further validated in a 2Ah Li-ion pouch cells, demonstrating 1000 stable cycling, confirming the feasibility of this new synthesis approach. This work provides new insights that are broadly applicable for cost-efficient large-scale synthesis of single crystals for different advanced battery technologies to accelerate deep decarbonization process.
(Invited) Solvent-Free Powder-Based Manufacturing of Electrodes for Lithium-Ion Batteries
Authors: Pan Heng
Published: August 2024

Lithium-ion batteries (LIBs) are one of the most popular energy storage devices due to their high power and energy densities, rechargeability and long service life. LIBs have become the most promising energy storage option for EVs with the advantages in long cycle life and high energy density compared to other secondary batteries. Nevertheless, several challenges need be addressed in order to realize EVs with lower cost, longer driving range, shorter charge time, better safety and longevity. In this presentation, we will discuss a solvent-free manufacturing method aiming at reducing manufacturing cost. The solvent-free manufactured anode and cathode electrodes are investigated by comparing with its counterparts manufactured by conventional slurry casting in terms of bonding strength, electronical properties, and electrochemical performances. The presentation will also discuss fundamental discoveries and engineering challenges associated with solvent-free manufacturing of Li-ion batteries including material handling, calendering, manufacturing scalability and processing-structure-property relationships.
A Novel Approach to Continuous and Scalable Synthesis of Cation-Disordered Rocksalt Cathodes
Authors: Buyuker Isik Su , Zuba Mateusz , Siu Carrie , Kahvecioglu Ozgenur
Published: August 2024

Cation disordered rocksalts (DRX) are an emerging class of high energy density LIB cathodes that can utilize earth-abundant and low-cost redox active transition metals. The DRX cathodes can be synthesized through a rich chemistry of transition metals, where commonly, metal-oxide precursors are combined with lithium source via ball-milling and calcined to achieve cation disordered phase. In this work, we present a new alternative synthesis method to the traditional solid-state synthesis, which provides scalable and continuous production of cathode precursors. A soft synthesis method in aqueous media was adopted to produce Mn-rich cathode precursors in large scale, through which homogenous mixing of the introduced transition metal cations was achieved. Here we report the electrochemical and structural properties of as-synthesized DRX cathodes with various Mn-compositions.
Strategies for Printing Ultra-Thin and Variable Width Lithium Foil
Authors: Cabaniss Joseph Emory , Gao Yuqi , Yakovleva Marina
Published: August 2024

The commercial success of rechargeable lithium-related batteries in electronic devices since the 1990s has been remarkable. Technologies in the field continue to develop to make batteries safer, longer lasting, and more powerful. Emerging lithium-ion battery technologies such as solid-state batteries or high-silicon anode materials utilize, for example, ultra-thin lithium metal foil due to lithium metal high specific capacity (3860 mA h g-1), however; traditional thin lithium foil manufacturing methods have proven challenging at scale due to metal reactivity, poor foil tensile strength, and safety concerns. Additionally, lithium metal foil is needed in a variety of thicknesses, widths, and surface characteristics, which are all crucial for advancing lithium metal based batteries. Fortunately, it can be done via industry standard technologies when using LIOVIX®, Printable Lithium Technology.

LIOVIX formulation has been coated using direct slot die technology at the benchtop scale and tension web slot die technology at the Roll-to-Roll (R2R) scale. Slot die technology facilitates two major elements of this process; particles larger than the theoretical wet film thickness can be deposited, and also the material can be shipped, delivered, and mixed without exposing lithium to air until it leaves the slot die head. This approach allowed us to achieve a uniform coating with heights ranging from 7 µm to 30 µm at a variety of coating widths. This has been done at the benchtop level at speeds up to 200 mm s-1 while maintaining a uniform coating on a copper substrate. R2R coating has done via a tension web coater, with similar theoretical wet film thickness. Specifically, the application of LIOVIX as a coating is particularly noteworthy for offering a strategic advantage in large scale manufacturing while maximizing the electrochemical performance.

LIOVIX formulation enables the R2R production of lithium foil materials, and using a pre-metering system, the coating can be reliably produced at a variety of areal capacity targets.
Scaling and Commercializing Continuous Supercritical Hydrothermal Single Crystal Cathode Active Material Manufacturing
Authors: Lim Jin , Shin Youngho
Published: August 2024

Current polycrystalline cathode active materials (CAMs) in the market face a significant challenge during charge-discharge cycles. The lithiation and de-lithiation processes induce volume changes within the CAMs, leading to strain along grain boundaries. This strain, arising from the expansion of crystals in different orientations, often results in material pulverization, creating void fractions. Such deterioration leads to increased impedance, capacity degradation, and shorter cycle life.

Addressing these challenges, there is an emerging demand for single crystal (SC) CAMs, which promise enhanced performance by eliminating internal void fractions and grain boundaries. The continuous supercritical hydrothermal process, invented at Argonne National Laboratory, offers an innovative and cost-effective method to produce SC CAMs. This method effectively reduces energy consumption and production costs, while also lowering carbon emissions.

In this presentation, we provide a comprehensive overview of the advancements in scaling up and commercializing continuous supercritical hydrothermal process for SC CAM manufacturing. Our focus is on the efforts undertaken by ACT-ion Battery Technologies, the industry commercialization partner, highlighting the significant strides made towards implementing this promising solution on a practical level.
Methods of Producing Disordered Rocksalt Cathode Materials
Authors: Zuba Mateusz , Siu Carrie , Buyuker Isiksu , Kahvecioglu Ozgenur
Published: August 2024

Li-rich cation-disordered rocksalts (DRX) have attracted attention as a promising new class of Co-free Li-ion battery cathodes. Current synthesis and optimization routes of DRX materials often require the use of high-energy ball-milling, which creates inhomogeneous distributions and non-ideal particle morphologies. A new technique to synthesize DRX materials was developed at Materials Engineering Research Facility (MERF) by forming a mixed transition metal hydroxide precursor material through aqueous co-precipitation before calcining the precursor with a Li-source. Such a method enables a controllable and scalable route to synthesize DRX materials.
Bridging the Gap: Scaling up Processes for the Development of Li-Rich Mn-Rich Layered Oxides
Authors: Siu Carrie , Zuba Mateusz , Buyuker Isiksu , Kahvecioglu Ozgenur
Published: August 2024

As the global demand for more powerful and long-lasting energy storage solutions continues to grow, Li-rich Mn-rich layered oxides (LMR) emerges as a promising class of next-generation cathode materials for lithium-ion batteries. The LMR material stands out due to its impressive electrochemical specific capacity, surpassing 280 mAh g–1, along with a high discharge voltage exceeding 3.5 V. It also boasts a remarkable specific energy density close to 1000 Wh kg–1, all while maintaining a relatively lower cost.

Current synthesis methods often rely on batch coprecipitation reactions followed by the calcination of precipitated Mn-rich precursors. However, the inherent challenges of batch reactions, particularly in terms of reproducibility and quality, prompt the exploration of more sophisticated approaches. Moreover, the transition from benchtop experiments to large-scale production introduces a distinct set of challenges. Parameters that work seamlessly on a smaller scale may not translate as effectively when producing the material at the kilogram scale. This scaling-up process involves navigating complexities such as chemical handling risks, and challenges related to reaction heat transfer and mixing efficiency. These factors collectively underscore the difficulties in achieving precise control over critical precursor characteristics, including primary and secondary particle size, morphology, tap density, and stoichiometry.

In response to these challenges, this presentation will discuss an innovative approach. High-quality Li-rich Mn-rich materials are synthesized using continuous coprecipitation, facilitated by a pre-pilot scale Taylor Vortex Reactor (TVR) at the Materials Engineering Research Facility (MERF) in Argonne National Lab (ANL). This emerging synthesis technology offers a scalable solution for the production of high-quality cathode materials. This presentation will delve into the intricacies of the synthesis process, providing valuable insights into the relationship between the characteristics of the synthesized LMR precursors and their subsequent impact on cathode performance.
Electrochemical Reclamation of Lithium-Ion Battery Materials Using SPOT Recycling
Authors: Anderson Nicholas
Published: August 2024

Establishing clean, low-cost methods for recycling lithium-ion batteries is essential for securing a sustainable supply chain for our green energy future. Cool Amps has developed a proprietary electrochemical process for lithium-ion battery recycling that avoids costly and environmentally unsound processing steps such as shredding and pyrometallurgy. Cool Amps uses our prototype laminar flow extraction modules to harvest valuable materials from production scrap or end-of-life batteries with a variety of form factors (cylindrical, pouch, and prismatic cells). The small footprint of our extraction modules allows us to be co-located at gigafactories or end-of-life collection facilities for SPOT recycling, negating the need for complex shipping and transportation logistics and significantly reducing recycling costs. In lab-scale demonstrations, our process recovers >85% of the valuable transition metals harvested from cathode materials and leaves the anode graphite intact and ready for re-use. These materials are characterized by elemental analysis, powder x-ray diffraction, and scanning electron microscopy. We will demonstrate that the reclaimed components are viable components for manufacturing recycled lithium-ion batteries, enabling a secure and circular supply chain for America’s green energy future.
Revealing the Effects of Polymer Additives on Zn Dendrite Suppression in Aqueous Zn Batteries via in-Situ EC-AFM
Authors: Xia Ying , Tao Jinhui , Du Jingshan , Shi Chenyang , Sun Hae Ra Shin , Zhang Mingyi , Orme Christine , Kaiser Mitchell , Thallapally Praveen K , Sushko Maria , De Yoreo James J , Liu Jun
Published: August 2024

Polyethylene glycol (PEO) is a commonly used polymer in the field of batteries for achieving flat and uniform electrodes to enhance the performance of batteries, such as lithium batteries and zinc (Zn) batteries. However, the impact of PEO on the electrochemical deposition of Zn metal on electrodes remains uncertain. In this study, we selected ZnSO4 solution as electrolyte and copper (Cu) substrates as electrodes, which are widely applied in Zn batteries. We used in situ electrochemical atomic force microscopy (EC-AFM) to observe the nucleation and growth of Zn metal plates on the Cu substrate in the presence of different concentrations of ZnSO4 and PEO additives. Our results indicate that PEO biases the crystallographic orientation of the initially deposited Zn metal nuclei, but does not have an obvious influence on subsequent growth. Based on our findings, we hypothesize that PEO primarily interacts with the Cu substrate to adjust the interfacial energy of the Cu-electrolyte interfaces. In contrast, due to the lack of apparent change in the Zn growth rate, we postulate that PEO does not affect the delivery rate of Zn2+ to the electrode surface. The consistent aspect ratio of the Zn plates combined with the lack of an effect on growth rates further suggests that PEO does not interact significantly with the surface of the newly formed Zn plates. The Zn metal will undergo surface reorganization in a mildly acidic aqueous solution as a result of oxidation of Zn, which is not affected by PEO adsorption. Our findings provide both insight into the underlying mechanism by which PEO promotes electrode flattening in Zn batteries and a standardized protocol for elucidating the impact of additives on the morphological evolution of interfaces during electrochemical deposition.

Work by C.O. was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Highly Efficient, Flexible, and Self-Healable Moisture-Driven Energy Harvester Based on 2D Vanadium Pentoxide Nanosheets
Authors: Saha Kundan , Sonkusale Sameer
Published: August 2024

The ubiquitous source of atmospheric moisture brought about a fascinating research avenue of extracting atmospheric water to generate sustainable electricity. Energy may be extracted from ambient moisture with obvious and substantial advantages. This point-of-use technology provides a decentralized alternative to meet the energy needs in isolated off-grid places. Unlike traditional energy generators which predominantly rely upon fossil fuel, moisture-induced energy generators can extract energy from moisture in a sustainable and eco-friendly way. Herein, we demonstrated a self-healable moist electric generator (MEG) based on vanadium pentoxide (V2O5) 2D nanosheet membranes. Lamellar membranes of V2O5 nanosheets have been shown to be excellent cation conductors and excellent materials for harvesting energy from ambient moisture. Ultra-thin 2D nanosheets of V2O5 was obtained by treatment of bulk V2O5 crystals with hydrogen peroxide. V2O5 nanosheet membrane was fabricated by vacuum-assisted filtration of 2D V2O5 nanosheets dispersion over a PTFE support membrane. The V2O5 membrane was easily peeled off from the support membrane on drying to obtain a flexible and freestanding V2O5 membrane. The V2O5 membrane consisting of percolated nanofluidic channels was sandwiched between a bottom solid copper foil and a perforated copper foil as the bottom electrode. The top electrode is perforated for exposure to atmospheric humidity. As the atmospheric water molecules come in contact with the V2O5 surface, an open-circuit voltage of 0.5 Volts and a short-circuit current of 0.3 microamperes is generated. The generated voltage and current is attributed to the preferential flow of cations through the V2O5 nanochannels. The exposed surface and edges of V2O5 nanosheets have a high negative surface charge which results in the splitting of water molecules into H3O+ and OH- ions. An electrical double layer (EDL) is established at the V2O5/water interface which selectively permits H3O+ ions through the channels. The mobile ions of the EDL transport through the nanofluidic channels creating a gradient between the two electrodes, resulting in a constant potential difference between the top and bottom electrodes which is harvested as electric current. The MEGs can be easily connected in parallel or series to enhance the current and voltage respectively. We demonstrate ten MEGs connected in series to power small electronic devices such as calculators and humidity meters. One of the key features of the V2O5 MEG is its ability to repair any physical damage to the active material owing to the water-assisted healing characteristics V2O5 membrane.

Figure 1
Making Nanoporous Metals By Electrochemical Etching without Sacrificing Metals
Authors: Ng Alexander , Koh Hyeongjun , Detsi Eric
Published: August 2024

The creation of nanoporous metals typically involves selective etching of a less noble material from a parent alloy, leaving the etched metal as a waste product. As we aim to achieve a circular economy, recent studies have proposed more sustainable methods to recover some of the sacrificial metals that are lost during the nanoporous metal fabrication process. However, even with these new methods, we still lose up to 35 atomic percent of the sacrificial metal.[1] In this presentation, I will introduce an innovative electrochemical method for creating nanoporous metals that almost entirely eliminates the loss of any sacrificial metals during fabrication. By combining and modifying the etching approach of “reduction-induced decomposition”, introduced in [2],and “electrochemical plating-stripping for nanoporous structures”, introduced in [3], we can create nanoporous metals without losing sacrificial materials. During my presentation, I will demonstrate how a dense silver thin film can be transformed into a fully nanoporous structure through electrochemical plating and reduction. The innovation is that we can create these nanoporous structures by reversibly utilizing ions present in the electrolyte, without consuming them in the reaction. I will also discuss ways to tune the structure size and introduce hierarchical porous morphology in the process. Electrochemistry data, microscopy, and X-ray scattering are used to confirm the porosity and structure size in the sample. Furthermore, in this talk, I will demonstrate the broad generalization of this technique, by showing how we have extended this novel technique to bimetallic alloys to create composite nanoporous metals, consisting of layered dissimilar nanoporous metals.

References

[1] J.S. Corsi, J. Fu, L. Wang, S.S. Welborn, Z. Wang, E. Detsi, Sacrificial Silver Recovery during Nanoporous Gold Formation by Electrolytic Dealloying of Gold-Silver Alloy, J. Electrochem. Soc. 169 (2022) 063501. https://doi.org/10.1149/1945-7111/ac6344.

[2] C. Wang, Q. Chen, Reduction-Induced Decomposition: Spontaneous Formation of Monolithic Nanoporous Metals of Tunable Structural Hierarchy and Porosity, Chem. Mater. 30 (2018) 3894–3900. https://doi.org/10.1021/acs.chemmater.8b01431.

[3] X. Jin, J. Lu, P. Liu, H. Tong, The electrochemical formation and reduction of a thick AgCl deposition layer on a silver substrate, Journal of Electroanalytical Chemistry. 542 (2003) 85–96. https://doi.org/10.1016/S0022-0728(02)01474-2.
Over-Time Stability Evaluation of Fluorinated Self-Assembled Monolayer on Commercial Indium Tin Oxide Electrode on PET Substrate
Authors: Ilhamsyah Rizky , Hesketh Peter J.
Published: August 2024

Motivation: Self-Assembled Monolayer (SAM) modified electrode has a key role in electrochemical biosensor applications to achieve desired sensing properties such as selective interaction with target protein and anti-fouling properties of non-specific protein. However, the degradation of SAM layer on the electrode can cause the electrochemical response to drift over time. This causes adversary effect on the designed biosensor such as limited shelf life and inconsistent electrochemical signal reading between electrodes. For that matter, it is important to understand the signal drift behaviour and ultimately obtain a SAM-modified electrode with good stability over time. In this study, we observed the signal drift of SAM-modified indium tin oxide electrode on PET substrate (ITO-PET). Three-electrode electrochemical impedance spectroscopy (EIS) measurement was carried to evaluate the electrochemical properties of the ITO-PET substrate over time.

Materials and Methods: Commercial ITO-PET (Adafruit, NY, USA) was used as electrode and was modified using Perfluoro-octyltriethoxysilane (Sigma Aldrich, St. Louis, MO, USA) self-assembled monolayer. The ITO-PET substrate was modified by using room temperature RCA-1 silanization process as shown in Figure 1. The modified electrode was rinsed in ethanol and DI water and stored in dark condition with temperature of 5oC. The Electrochemical Impedance Spectroscopy measurements were carried by using Solartron SI1260 impedance analyser tandem with SI1287 potentiostat. with saturated KCl Ag/AgCl (RRPEAGCL2, Pine Research, NC, USA) electrode and Pt wire counter electrode (MW-1032; BASi, West Lafayette, IN, USA). Potassium Ferricyanide (K3Fe(CN)6) (Fischer Scientific, Fair Lawn, NJ, USA) with concentration of 10 mM in 1x PBS was used as redox probe. The EIS run was set at 0.31 Vdc and 10 mV Vac amplitude with frequency ranging from 0.1 – 10000 Hz.

Results: We observed significant increase charge transfer resistance (Rct)increase of SAM-ITO sample (4498 ± 460 Ω.cm2) compared to the bare ITO sample (1348 ± 68 Ω.cm2). The signal also maintains its consistency after one week of storage in enclosed dry and dark environment at 5oC with 3% change in average Rct value (133 Ω.cm2). Ongoing work in this study includes the electrochemical signal evaluation of the ITO-SAM electrode exposed to protein such as casein and BSA.

Figure 1