bluuebunny/crossref_metadata_2025 huggingface dataset:
Ultrasound-Assisted Recovery of Cathode Active Materials Using Green Solvents: A Comparative Study
Authors: Shin Hosop , Bhuyan Sajibul Alam , Rahman Mazedur , Hoq Mahmudul
Published: August 2024

The widespread adoption of lithium-ion batteries (LIBs) in various applications has led to an increasing demand for efficient and environmentally sustainable recycling processes. This necessity stems from the broader goal of establishing a sustainable and circular economy for LIBs while simultaneously addressing the challenges within the supply chain.

One of the primary challenges in LIB recycling lies in the retrieval of valuable materials from end-of-life LIBs or electrode scraps in an environmentally benign manner. In particular, reclaiming the high purity of cathode active materials is a critical step to further development of direct recycling. The recovered materials need to be binder- and carbon black-free while retaining their inherent characteristics, including morphology, crystallinity, and electrochemical activity.

Traditional methods for solvent-based cathode recovery involve energy-intensive processes and often employ hazardous solvents, leading to environmental concerns and safety issues. In response, recent studies have proposed several green solvents as environmentally friendly and economically viable alternatives for sustainable cathode recovery processes.

In this study, we conduct a comprehensive comparative analysis of various green solvents to assess their efficiency in recovering cathode materials from electrode scraps. We employ an ultrasound-assisted recovery process using different green solvents to compare the characteristics of the recovered cathode active materials in terms of morphology, purity, surface characteristics, and electrochemical performance. By evaluating the key challenges and advantages of each green solvent, we aim to provide valuable insights into the development of solvent-based cathode recovery.
Highly Stable and Active RuO2/TiOx Electrode for Kolbe Electrolysis of Acetic Acid: An Investigation to Valorize the Pyroligneous Acid
Authors: Lam Jason Chun Ho , Jin Yangxin
Published: August 2024

The efficient utilization of renewable sources based on the simultaneous production of energy fuels and value-added chemicals is an essential tactic of achieving the targets of the circular economy as well as carbon neutrality. As an abundant by-product during the pyrolysis of biomass, pyroligneous acid is rich in acetic acid (AA, CH3COOH) that has been proven to be converted into valuable chemicals and fuels (e.g. methane, ethane, propane). Herein, we fabricate a highly stable and effective ruthenium oxide electrocatalyst (RuO2/TiOx) via using available titanium sheet as the substrate, to highly selectively transform AA to ethane by electrochemical conversion with ~82 (±5)% selectivity. The obtained results demonstrate that RuO2/TiOx exhibits an efficient electrochemical performance at low temperatures (5℃), and can convert AA at various pH, current density, and different concentrations. The catalytic ability of RuO2/TiOx could be maintained even after 200 hours of Kolbe electrolysis. Moreover, we mimicked the complex chemical environment of the pyroligneous acid by adding diverse hydrocarbons (e.g., phenols, aldehydes) in acid solution to evaluate the stability of RuO2/TiOx. The electrolysis was also conducted in original pyroligneous acid solution, in which the RuO2/TiOx exhibits a considerable performance to convert AA to ethane. This work, based on the selective production of ethane from AA by a RuO2/TiOx electrode as an alternative to bulk metals as anodes for oxidative upgrading of carboxylic acids, making it promise to directly turn biomass residual into fuel thus improve the biomass utilization.
(Invited) Energy-Efficient and Impurity-Tolerant Electrochemical Co-Generation of Acid and Base Solutions
Authors: Kanan Matthew
Published: August 2024

The sequential application of acid and base solutions can be used to perform chemical transformations that are of interest for carbon management and sustainable resource utilization, including CO2 capture, CO2 removal, production of slaked lime, and recovery of critical minerals. Electrochemical co-generation of acid and base from salt solutions enables their use in closed-loop processes that could be powered by renewable electricity, wherein acid and base are regenerated from the salt byproduct of their application. To be viable at scale, acid-base co-generating systems need to be energy-efficient and tolerant to impurities that are inevitably released into recycle loops. Conventional electrochemical methods for co-generating acid and base, such as bipolar membrane electrodialysis (BPMED), rely on the use of ion exchange membranes (IEMs) to inhibit H+ and OH– recombination, but IEMs cause large resistive losses that severely limit the energy efficiency and current density of these systems. In addition, cation exchange membranes (CEMs) do not tolerate polyvalent cations (e.g., Ca2+, Mg2+) in the presence of base, yet polyvalent cations are intrinsic to all high-impact applications. In this talk, I will describe our development of acid-base co-generating systems in which H+ and OH– recombination is inhibited by competitive transport of supporting electrolyte and H+ masking, which enables the use of a simple porous diaphragm separator instead of IEMs. We developed an ion transport model to predict the current efficiency for acid-base co-generation as a function of the electrolyte composition and operating parameters. Instead of a bipolar membrane, our systems use the H2 oxidation reaction (HOR) and H2 evolution reaction for H+ and OH– generation, respectively. We demonstrate IEM-free production of acid and base at useful concentrations in the presence of polyvalent cations with much higher energy efficiency and current density than state of the art BPMED systems. Individual cells can be stacked by combining HOR and HER electrodes into bipolar gas diffusion electrodes that recirculate H2 with near-unity efficiency. To demonstrate the utility of the acid and base solutions generated by this system, I will describe their use to extract Mg(OH)2 from ultramafic rocks for application in CO2 removal.
Composite Ion-Exchange Membranes with High Specific Ion Selectivity for Efficient Electro-Membrane Processes
Authors: Lee Ji-Min , Lee Ji-Hyeon , Kang Moon-Sung
Published: August 2024

The advancement of ion-exchange membranes (IEMs) with heightened permselectivity for specific ions is pivotal for improving electro-membrane processes. Achieving targeted ion selectivity necessitates precise control over membrane surface characteristics, including electrostatic forces, ion transport channel size, and hydrophobicity. Utilization of diverse nanostructured materials, particularly metal-organic frameworks (MOFs), offers a pathway to modify these surface properties. MOFs, known for their structural diversity, adjustable pore sizes, and customizable frameworks, are widely applied in separation, catalysis, electrochemical, and biomedical fields. This study presents novel composite membranes, enhanced with various nanostructured materials including MOFs, demonstrating improved specific ion selectivity, robust physical strength, and superior electrochemical properties compared to standard commercial membranes. Notably, these membranes exhibit augmented performance in water-splitting electrodialysis for LiOH production, attributed to enhanced proton-blocking and monovalent ion permeability. This work was supported by the National Research Foundation of Korea (NRF) grants funded by the Korea government (MEST) (NRF-2022M3C1A3081178 and NRF-2022M3H4A4097521).
(Battery Student Slam 8 Award Winner) Multi-Clustered Lithium Diffusion in Single-Crystalline NMC Battery Particles
Authors: Lee Danwon , Nam Chihyun , Kim Juwon , Koo Bonho , Hyun Hyejeong , Chung Jinkyu , Seo Sungjae , Song Munsoo , Song Jaejung , Alsem Daan , Salmon Norman , Lee Suyong , Kim Namdong , Shapiro David , Lim Jongwoo
Published: August 2024

Understanding the diffusion dynamics of lithium within solid-state electrodes is pivotal for developing high-performance batteries. In this context, layered oxides were utilized as a promising cathode material due to their high energy density and fast intraparticle lithium diffusivity. Despite advancements in material composition, coating, and doping, the understanding of intraparticle lithium diffusion has long been described by Fick's law. Conventionally, lithium diffusion is assumed to generate a monotonic lithium concentration gradient within solid-solution single-crystalline battery materials during cycling. This raises fundamental questions about diffusion in layered oxides; (1) Can the diffusion of Li in solids be interpreted as Fickian diffusion, similar to diffusion in gases or liquids, even though it involves structural and phase evolution throughout the battery cycle? and, (2) Does the fast diffusivity (10-11-10-9 cm2/s) support the homogenization of Li?

In this study, we address these questions surrounding lithium diffusion in layered oxide by utilizing operando scanning transmission X-ray microscopy. We revealed the formation of mobile Li-dense/-dilute nano-domains within individual single-crystalline LiNi1/3Mn1/3Co1/3O2 (scNMC) during battery cycles. We term this phenomenon ‘multi-clustered lithium diffusion’, distinguishing our findings from the conventionally suggested Fickian diffusion model in solid-solution materials. These domains persist for at least 4 hours during relaxation, accompanied by locally residing strained domains, as confirmed by Bragg coherent diffraction imaging (BCDI), within a single particle. We believe these domains arise due to the compensation of localized chemical potential gradients that are generated by the sustained presence of strain within the battery particles during cycling.

While maintaining integrity of Li-dense/-dilute domain at various C-rates, STXM result further show that Li-dilute domains maintain during the discharging. Given the lower concentration of Li at insertion boundaries, which could lower the surface charge transfer impedance of the system, Li-dilute domains facilitate lithium transport by functioning as low-resistance pathways. Through a comprehensive analysis of electrical impedance spectroscopy (EIS), STXM imaging and finite element analysis (FEA), we showed that controlling the local domain fraction is crucial for controlling the overpotential during subsequent charging. Our study introduces new insights into nanoscale solid-state diffusion, thereby enabling the fabrication of high-performance batteries.

Figure 1
Scalable Synthesis of Bulk TiO2 Hybrids and Its Li-Storage Properties in “Rocking-Chair” Type Full-Cell Assembly with LiNi0.5Mn1.5O4 Cathode
Authors: S Jyothilakshmi , Subramanyan Krishnan , Lee Yun-Sung , Manohar V Akshay
Published: August 2024

TiO2 as an anode material in lithium-ion batteries (LIB) has abolished hurdles like irreversibility, cycling stability, rate capability, and energy density, which are vital for electrochemical performance. Conventionally, time-consuming and complex techniques like solvothermal methods are employed to synthesize TiO2. We herein open a new avenue towards a simple, scalable, and eco-friendly synthesis of bulk TiO2 anatase/bronze hybrids from sodium meta-titanate through a facile mechano-chemical and ion-exchange process under different temperature conditions (400, 450, and 500 °C). Structural and morphological features are analyzed through various characterization techniques such as XRD, FE-SEM, HR-TEM, and XPS. The bronze phase’s high reversibility, low redox potential, high current rate performance, and high power capability of the anatase phase make the hybrid attractive for fabricating high power and high energy density Li-ion power packs. The Li insertion/extraction properties are studied in half-cell assembly (Li/TiO2), where all three TiO2 hybrids exhibited promising results with an initial discharge capacity >165 mAh g-1 at a current rate of 0.05 A g-1 along with a capacity retention >90% after 100 cycles. A “rocking-chair” type full-cell configuration with high voltage LiNi0.5Mn1.5O4 cathode is fabricated, in which LNMO/TiO2-400 °C displayed a discharge capacity of ~88 mAh g-1 at a current rate of 0.05 A g-1. Moreover, the full cell exhibited a capacity retention of >70% after 100 cycles with a maximum energy density of 192.75 Wh kg-1.

Figure 1
Induced Anion Redox before Full Oxidation of Ru4+/Ru5+ through Local Configuration Modulation in P2-Na0.67[Mg0.33Ru0.67]O2
Authors: Ahn Jinho , Ku Bonyoung , Kim Jongsoon
Published: August 2024

The study of anionic redox in layered-oxide cathodes for Na-ion batteries (NIBs) has been extensive, aiming to attain high-energy density. The involvement of Mn4+ or Ru5+ oxidation states is known to be crucial for the anionic O2
−/O− reaction during Na+ de/intercalation. Nevertheless, our findings indicate that anionic redox can activate in Ru-based layered-oxide cathodes prior to complete Ru4+/Ru5+ oxidation. By employing first-principles calculation and experimental techniques, we disclose that additional Na+ deintercalation from P2-Na0.33[Mg0.33Ru0.67]O2 relies on anionic oxidation after extracting 0.33 mol Na+ from P2-Na0.67[Mg0.33Ru0.67]O2, concomitant with cationic oxidation of Ru4+/Ru4.5+. Specifically, only the oxygen adjacent to 2Mg/1Ru is implicated in anionic redox during Na+ de/intercalation, indicating that the Na–O–Mg arrangement in the P2-Na0.33[Mg0.33Ru0.67]O2 structure significantly reduces the thermodynamic stability of anionic redox compared to cationic redox. Through O anionic and Ru cationic reactions, P2-Na0.67[Mg0.33Ru0.67]O2 demonstrates a substantial specific capacity of ∼172 mA h g−
1 and exceptional power capability, facilitated by facile Na+ diffusion and reversible structural changes during charge/discharge. These findings propose an innovative strategy to enhance anionic redox activity by modifying the local oxygen environment, paving the way for high-energy-density cathode materials in NIBs.
The Impact of Fluoroethylene Carbonate Additive on Charged Sodium Ion Electrodes/Electrolyte Reactivity Studied Using Accelerating Rate Calorimetry
Authors: Shipitsyn Vadim , Jayakumar Rishivandhiga , Zuo Wenhua , Yin Wenbin , Huber Evan , Ma Lin
Published: August 2024

The effects of fluoroethylene carbonate (FEC) electrolyte additive on charged sodium ion electrode/electrolyte reactivity at elevated temperatures were investigated using accelerating rate calorimetry (ARC). The beneficial effect of FEC on cell lifetime was demonstrated using Na0.97Ca0.03[Mn0.39Fe0.31Ni0.22Zn0.08]O2 (NCMFNZO)/hard carbon (HC) pouch cells first prior to ARC measurements. Electrodes from these pouch cells were utilized as sample materials and 1.0 m NaPF6 in propylene carbonate (PC):ethyl methyl carbonate (EMC) (1:1 by vol.) was chosen as control electrolyte. Adding 2wt.% or 5wt.% FEC to the electrolyte does not significantly affect the reactivity of de-sodiated NCMFNZO compared to the control electrolyte (Figure A). However, the addition of FEC obviously changed the reactivity between sodiated HC and electrolytes, especially by showing a suppression on the exothermal behavior between 160°C and 230°C (Figure B). These results give a head to head comparison of the reactivity of FEC additive containing electrolytes with charged sodium ion electrode materials at elevated temperatures and show that the use of FEC at additive levels should not compromise the cell safety when extending cell lifetime.

Figure 1
Investigating Temperature-Dependent Dynamics of SEI Growth and Battery Degradation
Authors: Akhtari Parisa , Shah Krishna
Published: August 2024

Several studies have contributed to the current understanding of the temperature-dependent behavior of solid-electrolyte interphase (SEI) formation in lithium-ion batteries and its impact on battery capacity and lifespan. Liu et al. developed a thermal-electrochemical model that revealed the complex interplay between diffusivity, reaction kinetics, and temperature on SEI growth1. Leng et al. presented an electrochemistry-based electrical model to examine the temperature's effect on battery aging2. Alipour et al. reviewed temperature-dependent electrochemical properties3, while Lubhani Mishra et al. provided a detailed physics-based analysis of battery degradation and temperature inhomogeneities4. These studies collectively indicate higher temperatures accelerating and promoting growth of compact and less permeable SEI structures leading to an increase in capacity loss and cell resistance, and lower temperatures resulting in slow ionic transport through the SEI also causing higher ohmic loss. In the present work, we study SEI growth and resulting effect on battery capacity fade using continuum scale modeling under the assumption of constant battery cell temperature as well as considering actual dynamically changing temperature data from experiments. SEI growth under these two considerations is compared and the comparison is used in determining scenarios where considering dynamically varying temperature is crucial for accuracy. The detailed analysis of the internal states from the simulation results contributes to the understanding of the effect of the thermal dynamics on battery cell degradation due to SEI growth. To achieve these objectives, a physics-based model, specifically the Single Particle Model (SPM), is utilized. The model uses temporal temperature data obtained from past experimental studies as well as temperature dependent properties of SEI provided in the literature as inputs for this investigation. The ultimate aim of this study is to better understand how temperature influences SEI characteristics, thereby contributing to improved battery performance and longevity across diverse thermal environments.

References

Liu, L., Park, J., Lin, X., Sastry, A. M., & Lu, W. (2014). A thermal-electrochemical model that gives spatial-dependent growth of solid electrolyte interphase in a Li-ion battery. Journal of power sources, 268, 482-490.

Leng, F., Tan, C. M., & Pecht, M. (2015). Effect of temperature on the aging rate of Li-ion battery operating above room temperature. Scientific reports, 5(1), 12967.

Alipour, M., Ziebert, C., Conte, F. V., & Kizilel, R. (2020). A review on temperature-dependent electrochemical properties, aging, and performance of lithium-ion cells. Batteries, 6(3), 35.

Mishra, L., Subramaniam, A., Jang, T., Garrick, T. R., & Subramanian, V. R. (2022, October). Model Development for Temperature-Dependent Degradation in Large Format Lithium-Ion Batteries. In Electrochemical Society Meeting Abstracts 242 (No. 28, pp. 1075-1075). The Electrochemical Society, Inc.
Natural Organic Honey-CNT Memristor Based Artificial Synaptic Devices for Sustainable Neuromorphic System
Authors: Templin Zoe , Zhao Feng
Published: August 2024

Neuromorphic computing is considered to have the potential to overcome the limitations of traditional von Neumann architecture due to its high efficiency, low energy consumption, and fault-tolerance. Hardware components that can emulate the synaptic plasticity of neurons, i.e. artificial synaptic devices, are required by neuromorphic systems. New devices have been examined for such components, such as phase-change artificial synapse, ferroelectric artificial synapse, and memristor synapses. Among them, memristor, a two-terminal metal-insulator-metal structure that are analogous to a biological synapse with presynaptic neuron (top electrode), postsynapticneuron (bottom electrode), and synaptic cleft (memristive film), is a promising device technology because of its tunable resistance, scalability, 3D integration compatibility, low power consumption, and relatively high speed. In contrary to inorganic materials such as metal oxides, natural organic materials have attracted interest to form the memristive layer because they are renewable, biodegradable, sustainable, biocompatible, and environmentally friendly. In this paper, honey solution embedded with carbon nanotubes (CNTs) was processed into the memristive layer by a low cost solution-based process, with synaptic plasticity of the final honey-CNT memristors characterized, including forget and relearn, spike-rate-dependent plasticity, spike-voltage-dependent plasticity, short-term to long-term memory transition, paired pulse facilitation, and spatial supra-linear summation behaviors. The successful emulation of these essential biological synaptic behaviors demonstrates the potential of honey-CNT memristors as a viable hardware component in neuromorphic computing systems.
(Invited) Towards an Expanded Palette of Materials and Mechanisms for Neuromorphic Computing
Authors: Banerjee Sarbajit
Published: August 2024

The metal-insulator transitions of electron correlated transition metal oxides provide an attractive vector for achieving large conductance switching with minimal energy dissipation. However, given the sparse and disconnected current knowledge of neuromorphic materials, a fundamental understanding of descriptors of neuromorphic function formulated in terms of intrinsic material properties, and the influence of atomistic defects on mesoscale domain evolution in the presence of external applied fields is currently lacking. Using VO2 and M
x
V2O5 compounds as model systems, I will detail our efforts to develop a systematic understanding of how compositional modifications through substitutional or interstitial doping alter transformation characteristics such as the transition temperature, magnitude of switching, energy dissipation, and hysteresis.

The inclusion of dopant atoms strongly modifies the free energy landscapes in terms of relative phase stabilities, transformation barriers, and pathways; thereby profoundly altering the coupling of lattice, electronic, and spin degrees of freedom in a non-trivial manner. I will particularly focus on the three distinct mechanisms: (a) discovery of diffusive dopants that provide a distinctive new way to alter the dynamics of electronic transitions; (b) cation shuttling and polaron oscillation as a means of engendering metal—insulator transitions; and (c) lattice-anharmonicity-driven mechanisms in compounds with stereochemically active lone pairs.

Acknowledgements: Research supported as part of REMIND, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under DE-SC0023353
(Invited) Sustainable AI and Neuromorphic Computing with Oxide Quantum Materials
Authors: Ramanathan Shriram
Published: August 2024

The presentation will focus on electronic phase transition mechanisms in quantum materials such as correlated perovskite semiconductors that can be used to emulate the characteristics of neurons and synapses in the brain and serve as building blocks for AI hardware as well as sensory interfaces for robotics. We will then discuss how features of intelligence noted in slime molds, insects, birds and mammals can be implemented in electronic devices and circuits for learning and decision-making. The fundamental science enabling such remarkable properties center around understanding ionic-electronic transport and electroneutrality which will form the main theme of the presentation. Strategies for lifelong learning with reconfigurable device platforms will be highlighted. Mouse brain – perovskite interfaces as an example of neural links will then be presented in brief. Approaches towards making sustainable AI hardware will be considered from perspective of materials and physical intelligence.
(Invited) Towards High-Performance Domain-Specific in-Sensor and in-Memory Accelerators
Authors: Angizi Shaahin
Published: August 2024

Internet of Things (IoT) devices are projected to attain an $1100B market by 2025, with a web of interconnection projected to comprise approximately 75+ billion IoT devices. The large number of IoTs consist of sensory systems that enable massive data collection from the environment and people. However, considerable portions of the captured sensory data are redundant and unstructured. Data conversion of such large raw data, storing in volatile memories, transmission, and computation in on-/off-chip processors, impose high energy consumption, latency, and a memory bottleneck at the edge. Therefore, high-speed, low-power, and normally-off computing domain-specific architectures should be explored and developed to overcome these issues. Motivated by the aforementioned concerns, we will be focusing on cross-layer (device/circuit/architecture/application) co-design of energy-efficient and high-performance processing-in-sensor and processing-in-memory platforms for implementing complex AI and machine learning tasks, bioinformatics tasks, graph processing, etc. We explain how to leverage innovations from circuits and architecture to integrate sensors, memory, and logic to break the existing memory and power walls.
Tools for Parameterization of a Single Particle Model with Electrolyte Dynamics (SPMe) with Bayesian Experimental Design to Capture Degradation-Induced Capacity Fade in Lithium-Ion Batteries
Authors: Singh Siddhant , Kwabi David G. , Huan Xun , Coons Thomas , Pathak Yash Vaibhav , Siegel Jason
Published: August 2024

The intelligent design of durable, next-generation lithium-ion batteries can be facilitated through the use of computationally efficient models that capture battery physics. In this work, we demonstrate a single particle model with electrolyte dynamics (SPMe), which accounts for battery capacity fade caused by mechanisms such as solid electrolyte interface (SEI) growth, lithium plating, and stress-induced particle cracking. The model is trained using both experimental data and data generated using a higher-fidelity Doyle-Fuller-Newman model so the ground truth parameters are known. To quantify and reduce the uncertainty in the unknown model parameters, we are developing a Bayesian experimental design approach that, with the aid of multiple models with varying fidelity, can rapidly identify optimal experimental input conditions leading to the greatest expected information gain.
Interleaved Electrode Structures for Enhanced Electrolyte Mass Transport in Li-Ion Batteries : A Numerical Study
Authors: Bhattu Mayuresh , Battiato Ilenia
Published: August 2024

The enhancement of energy and power density in Li-ion batteries remains a focal point in battery research. When Li-ion batteries are operated at high C-rates, mass transport limitations cause large concentration gradients of Lithium ions to form in the electrolyte. The resultant concentration overpotentials and underutilization of active material effectively imply a lower capacity for higher current rates, which creates a tradeoff between energy and power density. The integration of 3D interleaved electrode structures has been proposed to augment power density while preserving energy density. This work comprehensively analyzes the capacity improvement achieved by utilizing a wavy interleaved structure using electrochemical simulations. A pseudo-3D (P3D) model based on the Doyle-Fuller-Newman framework is employed to analyze the performance of various depths and frequencies of the wavy interleaved structure. Galvanostatic simulations are performed for NMC/Graphite-SiOx and LMO/Graphite cells at different C-rates, and the resultant voltage is systematically divided into component overpotentials to delineate the contribution of activation, ohmic, and mass-transfer overpotentials in both solid electrode and electrolyte. With the same amount of active material, simulations indicate a performance improvement of 7% in capacity at high C-rates. It is observed that using a wavy structure significantly reduces electrolyte concentration heterogeneities and resulting concentration gradients when compared to a conventional flat structure. The overpotential breakdown confirms that the improvement in voltage is indeed contributed precisely by the concentration overpotential. Concentration overpotential decreases with deeper interleaved structures as well as for more spatially frequent structures.

Additionally, the impact of the interleaved electrode structure on cell degradation was also assessed. Lithium plating, which is the most prominent side reaction in the anode, was modeled using a Butler-Volmer kinetic equation, with deposition occurring locally when the solid phase potential drops below that of the electrolyte potential. The interleaved structure alleviates plating significantly due to higher uniformity in Li-ion concentration. With this work, we computationally demonstrate that interleaved structure works well for extracting higher capacity with the same active material, and also aids in suppressing Lithium plating.

Figure Caption : Computed Li-ion concentration profile in the solid active material of an interleaved electrode Li-ion cell as a function of location (x, y) and distance from particle center (z)

Figure 1
Combining Solid FePc Immobilized on Py-Functionalized Carbon Matrix with Soluble Redox Mediator FePc As an Efficient Cathode Catalyst for Non-Aqueous Li-O2 Batteries
Authors: Chiu Chen-Lung , Chen Jenn-Shing
Published: August 2024

It is important to develop bifunctional catalysts with high activity and stability for reversible oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) in lithium-oxygen (Li-O2) batteries. Recently, the iron phthalocyanine (FePc) complex has been considered a promising candidate for bifunctional (ORR/OER) O2 catalysts due to its low cost, high catalytic properties, and ease of preparation. In this work, two different structural types of FePc-based solution-phase catalysts as soluble redox mediators (SRMs) and solid FePc immobilized on pyridine-functional carbon supports (multi-walled carbon nanotube, MWCNT and graphene, GR) are investigated to evaluate the influence of FePc structural design on their catalytic activity and kinetics.

Our work demonstrated that FePc(solid)/Py/MWCNT exhibited better bifunctional catalytic activity than FePc(solid)/Py/GR in the same electrolyte because of the stronger axial bonding between FePc(solid) and Py/MWCNT. The combination of FePc(solid)/Py/MWCNT and FePc(sol) displays the best cyclability, which can be attributed to the highly efficient solid-liquid interface. Moreover, FePc(solid)/Py/MWCNT without FePc(sol) shows the lowest overpotential owing to the surface-grown thin film Li2O2 is structurally less order than the solution-grown toroidal Li2O2.
Interfacial Phase Separation Governs the Chemomechanics of Polymer Electrolytes in High-Voltage, Solid-State Lithium Batteries
Authors: Min Jungki , Bak Seongmin , Zhang Yuxin , Yuan Mingyu , Pietra Nicholas , Russell Joshua , Xia Dawei , Du Yonghua , Xiong Claire , Madsen Louis A. , Lin Feng
Published: August 2024

Polymer electrolytes hold great promise for safe and high-energy solid-state batteries. Multiphase polymer electrolytes, consisting of mobile and rigid phases, exhibit fast ion conduction and desired mechanical properties. However, fundamental challenges exist in understanding and regulating intricate chemomechanical interactions at the electrode-electrolyte interface, especially when using a high-voltage layered cathode. Here, we report that depletion of the mobile conductive phase at the interface contributes to battery performance degradation. Molecular ionic composite electrolytes, composed of a rigid-rod ionic polymer with small mobile cations and anions, serve as a multiphase platform to investigate the evolution of conductive domains at the interface. Synchrotron chemical and structural analyses enable the direct visualization of concentration polarization and spatially resolve the interfacial chemical states over a statistically significant field of view for buried interfaces. We discover that concentration and chemical heterogeneities prevail at electrode-electrolyte interfaces, leading to interfacial chemomechanical degradation. We further demonstrate an interphase tailoring strategy based on electrolyte additives to mitigate such interfacial heterogeneity and improve battery stability. While polymer electrolytes have been considered “deformable” for conformal interfaces, our work shows the hidden roles of interfacial chemomechanics in polymer electrolytes and provides an effective mitigation approach.
Heterointerfaces Chemistry of Transition Metal-Shielded Zinc Anode for High-Performance Aqueous Zinc Batteries
Authors: Yu Jingya , Xu Zheng-Long
Published: August 2024

Aqueous zinc metal batteries confront impediments such as severe side reactions and dendrite formation on the zinc metal anode, impeding its commercialization. Although various metals and zinc-metal alloys aim to optimize the zinc anode, the preferential order and reaction mechanisms at the metal/electrolyte interface remain unclear. Here, we utilized magnetron sputtering to create nanolayered metal coatings (Cu, Ti, Ag, Au, Al) on the zinc surface. Notably, the Cu@Zn anode exhibited moderate binding energy with Zn atoms and lower nucleation overpotential than bare Zn, resulting in excellent cycling life (1600 h) and rate performance. Even at a high depth of discharge (80%), the cycling life can still over 200h. In full cells, Cu@Zn//VO2 demonstrated outstanding stability, retaining 95.5% capacity after 600 cycles. Comparison with other metal-coated zinc anodes revealed that Cu@Zn excels due to its moderate binding energy and superior kinetic properties. This study provides valuable insights for optimizing the heterointerface chemistry in zinc anodes, offering general guidelines to regulate various metal anodes suffering the similar challenges.

Keywords: Aqueous Zinc ion battery, Metal-nanolayer, Magnetron sputtering, High Zn utilization
(Battery Student Slam 8 Award Winner) A Simple and Fast Method to Assemble Flexible and Stable Quasi-Solid-State Zn Ion Pouch Cell
Authors: Wang Peng , Andrei Petru
Published: August 2024

Aqueous zinc-ion batteries (AZIBs) have been investigated intensively as effective energy storage devices that are environmentally friendly, safe, and have a lower cost than current Li-ion batteries.[1-5] Being outstandingly safe due to usage of non-organic electrolyte, AZIBs could also be used as power supply for wearable electronics. This also put high standard requirements in terms of flexibility, stability and electrochemical performance to AZIBs. On the other hand, the general challenges, such as the formation of the dendrites on the Zn anodes, hydrogen evolution and side reactions, have been obstructing the practical application of AZIBs. In this presentation, a simple method to assemble quasi-solid-state Zn ion pouch cell with excellent mechanical performance, flexibility and electrochemical performance was developed, combining in-situ electrodeposition of MnO2 cathode and aramid nano fiber-based hydrogel with Zn plate as anode. In-situ and cycling measurements of the electrodeposition of MnO2 on carbon nanotube mat shows excellent capacitance and superior cycling stability. In addition, Kevlar derivatized aramid nanofiber-based hydrogel shows extremely strong strength when combined with polyvinyl alcohol, which prolonged the lifetime of the cell by preventing Zn dendrite growth largely.[5,6] Moreover, the method to assemble the AZIBs pouch cell enables us to optimize the process, decrease the steps, and save time effectively by taking advantage of hydrogel formation stage and avoiding conventional verbose slurry-casting-drying steps. This work paves an efficient path to assemble flexible and stable AZIBs pouch cells with high capacity and cycling stability.

[1] Tang, Boya, et al. "Issues and opportunities facing aqueous zinc-ion batteries." Energy & Environmental Science 12.11 (2019): 3288-3304.

[2] Li, Chang, et al. "Toward practical aqueous zinc-ion batteries for electrochemical energy storage." Joule 6.8 (2022): 1733-1738.

[3] Yu, Feng, et al. "An aqueous rechargeable zinc-ion battery on basis of an organic pigment." Rare Metals 41.7 (2022): 2230-2236.

[4] Lin, Yuexing, et al. "Dendrite-free Zn anode enabled by anionic surfactant-induced horizontal growth for highly-stable aqueous Zn-ion pouch cells." Energy & Environmental Science 16.2 (2023): 687-697.

[5] Wang, Peng, and Petru Andrei. "High Performance Separator and Hydrogel Based on Aramid Fibers for Zn Ion Batteries." Electrochemical Society Meeting Abstracts 242. No. 4. The Electrochemical Society, Inc., 2022.

[6] Xu, Lizhi, et al. "Water‐rich biomimetic composites with abiotic self‐organizing nanofiber network." Advanced Materials 30.1 (2018): 1703343.
A 3D Printed Pumpless Nonaqueous Organic Redox Flow Cell
Authors: Bhuiyan Shaikh Al Mahmud , Kaur Aman Preet , Risko Chad M. , Trinkle Christine A.
Published: August 2024

Redox flow batteries (RFBs) have considerable promise in addressing the ever-increasing demands for robust energy storage devices. The nature of these devices makes it possible to create storage with potential applicability at multiple size scales1. However, conventional RFBs require energy to pump the liquid electrolyte, reducing the overall system efficiency, and limiting its viability to mid- and large-scale operations only2. Eliminating the pumping load can improve overall efficiency and create opportunities for mobile applications. In this work, we demonstrate a 3D printed prototype of a pumpless non-aqueous organic RFB that induces flow in the electrolyte from sinusoidal rocking motion. The body of the flow cell was created using 3D printing, allowing us to modify and adapt geometry easily during testing.

First, the compatibility of the 3D-printed material was studied by testing the chemical stability of widely available additive manufacturing materials under RFB conditions. Then, we evaluated the performance of this pumpless system using an easily scalable, soluble, and stable one electron donor phenothiazine derivative, N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT) which has been widely studied for RFB applications3. We used 0.25 M MEEPT and its bis(trifluoromethanesulfonyl)imide radical cation salt (MEEPT-TFSI) as a redox-active couple in 0.5 M tetraethylammonium bis(trifluoromethanesulfonyl)imide (TEATFSI)/acetonitrile (MeCN). Our results suggest an inversely proportional empirical relationship between limiting current density and the frequency of sinusoidal motion due to varying mass transfer rates. After 100 cycles in this symmetric cell with an area specific resistance of 2.62 Ωcm2, we achieved a capacity retention of 63% and an average Coulombic efficiency of 96%, with minimal sign of decomposition of the redox couple when analyzed post-cell cycling.

The results of this study can be used for 3D printing material selection in numerous electrochemical devices that use organic solvents, including flow cells, supercapacitors, and lithium-ion batteries. Using sinusoidal motion to drive electrolytes instead of a pump can increase the theoretical efficiency and decrease the overall size of a flow cell. This makes it attractive in wearable applications where biomechanical motion can be harnessed.

1 Wang, W. et al. Recent Progress in Redox Flow Battery Research and Development. Advanced Functional Materials
23, 970-986 (2013). https://doi.org:10.1002/adfm.201200694

2 Tian, C. H., Chein, R., Hsueh, K. L., Wu, C. H. & Tsau, F. H. Design and modeling of electrolyte pumping power reduction in redox flow cells. Rare Metals
30, 16-21 (2011). https://doi.org:10.1007/s12598-011-0229-1

3 Milshtein, J. D. et al. High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries. Energy & Environmental Science
9, 3531-3543 (2016). https://doi.org:10.1039/C6EE02027E
Average Voltage Prediction of Battery Electrode Materials Using Transformer Deep Learning Architecture
Authors: Antony Dhason Mary Vinolisha , Soyoye Babatunde , Banik Trapa , Bhattacharya Indranil
Published: August 2024

Batteries are ubiquitous, with their presence ranging from electric vehicles to portable electronics. Research focused on increasing average voltage, improving stability, and extending cycle longevity of batteries is pivotal for the advancement of battery technology. These advancements can be accelerated through research into battery chemistries. The traditional approach, which examines each material combination individually, poses significant challenges in terms of resources and financial investment. Physics-based simulations, while detailed, are both time-consuming and resource-intensive. Researchers are aiming to mitigate these concerns by employing Machine Learning (ML) techniques. We propose the use of a Transformer ML model for predicting the average voltage of battery electrode materials. A Transformer is a Deep Learning (DL) architecture based on the attention mechanism; it dynamically focuses on different parts of the input sequence, thus capturing complex relationships and dependencies among input features. The absence of recurrent units allows the model to require less training time compared to other DL models. We have adapted the Transformer model for tabular data and regression tasks. Our dataset was sourced from the Materials Project Database. To ensure the model's compatibility with our voltage prediction regression task, we successfully trained and tested it using four features across 99 samples. Our ongoing research focuses on incorporating more relevant features and expanding the training and testing of the model to the entire dataset. Our work demonstrates the effectiveness of ML, especially the Transformer model, in predicting the average voltage of battery electrode materials.
Shrinking Lithium-Ion Batteries by Replacing Metal Current Collectors with MXene Films
Authors: Dieng Sokhna , Valurouthu Geetha , Matthews Kyle , Wang Ruocun (John) , Gogotsi Yury
Published: August 2024

The demand for high-performance energy storage devices has been rapidly increasing due to the growing need for renewable energy integration and portable electronics. Traditional lithium-ion batteries have become the preferred choice for numerous applications due to their impressive energy density, but they are reaching limitations of capacity. At the cell level, around 25 w% consists of passive components like current collectors, conductive additives, binders, and separators. Especially, copper (Cu) and aluminum (Al) foils have been commonly used as current collectors for the anode and cathode in lithium-ion batteries (LIBs), contributing around 7 wt% and 8 wt%, respectively, to the overall weight. Despite constituting a considerable portion of the battery, these passive components often receive less attention in the development of high-power batteries. In recent years, the focus has been on decreasing the thickness of these metal current collectors and developing lightweight alternative materials to enhance energy efficiency to potentially boost the performance metrics of a Li-ion battery cell to boost the performance metrics of a Li-ion battery cell. MXenes, a family of two-dimensional transition metal carbides, nitrides, and carbonitrides emerge as a promising solution to address this limitation. In particular, Ti3C2T
x
MXene possesses a 2D morphology with excellent electrical conductivity (up to 20,000 S/cm), high surface area, good mechanical properties, and hydrophilicity. These attributes, coupled with ease of processing, make it very suitable for battery passive components. In this study, we focus on replacing the conventional copper current collector with thinner MXene film current collectors for high-mass loading graphite anode electrodes. Our results show improved capacities and rate performances of electrode materials using Ti3C2T
x
MXene current collectors while also reducing electrode weight and thickness. The electrode-level gravimetric capacity significantly increased by 98.5 mAh g-1 (from 140 mAh g-1 for Cu@graphite to 238.5 mAh g-1 for MXene@graphite). The areal and volumetric capacities increased as well. This study highlights the potential of MXene current collectors in improving the performance of lithium-ion batteries, paving the way for more efficient and lightweight energy storage solutions.
Rechargeable Hydrogen Gas Batteries for Large-Scale Energy Storage
Authors: Chen Wei
Published: August 2024

Large-scale energy storage is of significance to the integration of renewable energy into electric grid. Despite the dominance of pumped hydroelectricity in the market of grid energy storage, it is limited by the suitable site selection and footprint impact. Rechargeable batteries show increasing interests in the large-scale energy storage. However, the challenging requirement of low-cost materials with long cycle and calendar life restricts most battery chemistries for use in the grid storage. Recently we developed a new generation of rechargeable hydrogen gas batteries by exploiting catalytic hydrogen evolution/oxidation reactions as the anode, which offers negligible overpotentials, high rates and stable electrochemical performance. In this poster, I will introduce some exciting rechargeable hydrogen gas battery chemistries, including novel nickel-hydrogen gas, proton-hydrogen gas, chlorine-hydrogen gas, and among others. The excellent stability and low cost of the rechargeable hydrogen gas batteries demonstrate attractive characteristics for large-scale energy storage.
Preparation of Biomass-Derived High Specific Surface Area Carbon with Titanium Nitride Nanoparticles for Lithium-Sulfur Batteries
Authors: Dangaliyeva Akmaral , Sultanov Fail , Urazgaliyeva Aimira , Tatykayev Batukhan , Bakenov Zhumabay , Mentbayeva Almagul
Published: August 2024

The widespread challenges facing lithium-sulfur batteries, including the low electrical conductivity of sulfur and its species, electrode volume fluctuations during cycling, and the lithium polysulfides shuttle effect, have hindered their commercialization and practical utility [1,2].

Our study addresses these issues by incorporating titanium nitride (TiN) nanoparticles onto high specific surface area porous carbon, exploring this composite's potential as both a sulfur cathode host and separator modifier. The synthesis of the carbon/TiN composite involved two key stages: firstly, the in-situ growth of titanium dioxide (TiO2) nanoparticles on the carbon surface utilizing titanium tetrachloride as a precursor; secondly, the conversion of the TiO2 nanoparticles to TiN nanoparticles through carbothermal nitridization (thermal treatment at 1400 ℃ for 4 hours in a nitrogen medium) [3,4].

The lithium-sulfur cell employing the prepared C/TiN-25%@S cathode exhibited an initial discharge capacity of 1155 mAh g-1 at 0.2 C, maintaining a capacity exceeding 700 mAh g-1 after 100 cycles. Notably, the lithium-sulfur cell utilizing the C/TiN-25%@S cathode and a C/TiN-modified separator demonstrated enhanced cycling performance, delivering an initial discharge capacity of 1623 mAh g-1 with retention of over 1126 mAh g-1 after 100 charge/discharge cycles at 0.2 C.

Acknowledgments

This research was funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant No. AP19677708).

References

[1] D.-W. Wang, Q. Zeng, G. Zhou, L. Yin, F. Li, H.-M. Cheng, I.R. Gentle, G.Q.M. Lu, Carbon–sulfur composites for Li–S batteries: status and prospects, J. Mater. Chem. A 1 (2013) 9382. https://doi.org/10.1039/c3ta11045a.

[2] M. Wang, X. Xia, Y. Zhong, J. Wu, R. Xu, Z. Yao, D. Wang, W. Tang, X. Wang, J. Tu, Porous Carbon Hosts for Lithium–Sulfur Batteries, Chem. Eur. J. 25 (2019) 3710–3725. https://doi.org/10.1002/chem.201803153.

[3] S.A. Rezan, G. Zhang, O. Ostrovski, Effect of Gas Atmosphere on Carbothermal Reduction and Nitridation of Titanium Dioxide, Metall Mater Trans B 43 (2012) 73–81. https://doi.org/10.1007/s11663-011-9574-6.

[4] X. Qin, J. Zhang, C. Ke, H. Chen, L. Zhao, Preparation of TiN ultrafine powders from sol-gel by Fe-catalyzed carbothermal reduction nitridation, Inorganic Chemistry Communications 148 (2023) 110278. https://doi.org/10.1016/j.inoche.2022.110278.