bluuebunny/crossref_metadata_2025 huggingface dataset:
Material Dynamics of Nickel (oxy)Hydroxide As an Alcohol Oxidation Electrocatalyst
Authors: Siboonruang Tana , Crago Colin Flynn , Aleman Ashton M. , Ríos Isabela , Schröder Johanna , Jaramillo Thomas F. , Tang Maureen H. , Burke Stevens Michaela
Published: August 2024

Electrochemical alcohol oxidation is an attractive reaction for renewable-energy driven production of value-added chemicals, like precursors for acrylic (acrolein from glycerol) and nylon (adipic acid from cyclohexanol). Implementing selective, earth-abundant catalysts for alcohol oxidation can improve electrolyzer efficiency and economics. For example, replacing the energy intensive oxygen evolution reaction (OER) in CO2 electrolyzers with alcohol oxidation can decrease operating voltage by about 0.85 V and reduce electricity requirements up to 53% while also reducing carbon emissions from chemical production.1 Electrochemical alcohol oxidation catalyzed by as synthesized nickel oxyhydroxide (NiOOH) is hypothesized to proceed through two pathways, a chemical, redox pathway preferred by aldehydes (geminal diols in alkaline electrolyte), and a potential dependent pathway preferred by alcohols.2 Many studies have focused on understanding reaction mechanisms and device performance, however, transition metal alcohol oxidation catalysts, such as NiOOH, are known to undergo reduction/oxidation, phase changes, and even dissolution in the same potential window as alcohol oxidation.3 It is still unclear how these processes affect catalyst material stability and electrochemical performance.

In this work, we probe the performance stability and material stability of Ni(OH)2 for alcohol oxidation in alkaline media through electrochemical cycling and chronoamperometry. We use a rigorously Fe-free environment to mitigate performance impacts from Fe-contamination common in non-purified alkaline electrochemical studies.4 We show that the rate of change of alcohol oxidation current density (mA cm-2) depends on reaction pathway (redox vs. potential dependent), alcohol concentration, and side chain structure. Using EC-MS and NMR, we also probe changes in performance in yield and selectivity by quantifying oxidation products, including oxygen gas. These changes in performance are correlated to material changes through monitoring dissolution with on-line ICP-MS. Furthermore, to disentangle the role of potential and reactant (e.g. alcohol or water) on stability, we elucidate oxidation state and local structural changes using in situ X-ray Absorption Spectroscopy (XAS). Insights from this rigorous model system are directly translatable to the broader goal of developing efficient, long-lasting catalysts for industrial deployment of electrochemical organic reactions powered by clean energy.

References.

Verma, Sumit, Shawn Lu, and Paul JA Kenis. Nature Energy 4.6 (2019): 466-474.2.

Bender, Michael T., and Kyoung‐Shin Choi. ChemSusChem 15.13 (2022): e202200675.

Klaus, Shannon, et al. The Journal of Physical Chemistry C 119.13 (2015): 7243-7254

Wei, Lingze, et al. ACS Catalysis 13.7 (2023): 4272-4282.
Leveraging Flow-Assisted Electrochemistry Toward Decarbonization of Cement Manufacturing
Authors: Chaurasia Shabdiki B. , Luo Dayou , Aravamuthan Sundar Rajan , Wei Jianqiang , Agar Ertan
Published: August 2024

In an effort to decarbonize the global economy by 50% in 2030 and achieve net-zero carbon emissions by 2050, there is a dire need to electrify industrial processes [1]. Approximately 8% of global carbon emissions comes from cement production [2]. Considering the rising demand for cement due to infrastructure expansion, it is critical to develop new concepts for the decarbonization of cement production. With this goal in mind, our work explores the effectiveness of flow-assisted cement electrolysis as a replacement to conventional fossil fuel based high-temperature kilns in cement manufacturing plants [3].

In this study, we employ a scalable 3-channel flow-reactor with acidic anolyte, basic catholyte, and a neutral chemical flush in between to generate calcium hydroxide, Ca(OH)2 [4, 5], which is the key ingredient in cement manufacturing. The central channel is separated from either half cells by a cation exchange and an anion exchange membrane. The electrochemical performance of the proposed cement electrolyzer under a variety of operating conditions is investigated by considering the key variables in reactor design, including flow rate, temperature, catalyst choice and feed concentrations, to shed light into the practical challenges of running a 3-channel flow reactor. Our preliminary study indicates that membranes are possibly responsible for a significant fraction of the limited yields of Ca(OH)2. Specifically, the anion exchange membranes tested are susceptible to degradation in alkaline conditions displaying poor ionic conductance, whereas the cation exchange membranes allow significant water crossover. The findings from this study pave the way in understanding key components for cement electrolysis and other electrochemical systems employing 3-channel flow reactors.

References

DeAngelo, J., et al., Energy systems in scenarios at net-zero CO2 emissions. Nature Communications, 2021. 12(1): p. 6096.

Ellis, L.D., et al., Toward electrochemical synthesis of cement—An electrolyzer-based process for decarbonating CaCO3 while producing useful gas streams. PNAS, 2019. 117(23): p.12584.

Rissman, J., et al., Technologies and policies to decarbonize global industry: Review and assessment of mitigation drivers through 2070. Applied Energy, 2020. 266: p. 114848.

Perego, A., et al., Electrochemical Flow Reactor for Cement Clinker Production. ECS Meeting Abstracts, 2021. MA2021-02(27): p. 840.

Olsson, J.A., S.A. Miller, and M.G. Alexander, Near-term pathways for decarbonizing global concrete production.Nature Communications, 2023. 14(1): p. 4574.
A Combined Insertion-Conversion Process in Graphite: CuO Composite Enhances the Energy of Lithium-Ion Capacitors with Wide Operational Temperatures
Authors: Manohar V Akshay , Subramanyan Krishnan , Lee Yun-Sung , Manohar V Akshay
Published: August 2024

Lithium-ion capacitors (LICs) are prime energy storage devices that meet the limitations of Lithium-ion batteries (LIBs) and Electrical double-layer capacitors, bringing energy and power simultaneously in a single device. Our LIC comprises a combined insertion-conversion mechanism in the battery-type electrode, and the cathode is the commercially available activated carbon. The conversion-type CuO and intercalation-type graphite were mixed uniformly via a mechanical planetary miller and used directly as the anode material. It is noteworthy to mention that the CuO and graphite were regenerated/recovered from the spent LIBs. The copper foil current collector of spent LIB was regenerated as the CuO using simple steps, and the graphite was recycled directly. Five different composites were prepared, and an electrochemical comparative study was performed among these composites. In addition, the performances were compared between two different binders: Polyvinylidene fluoride (PVdF) and Carboxymethylcellulose (CMC), in which the dominance of CMC was significantly observed. The Li-ion storage properties were investigated by pairing the composites with the Li-metal. All the composites exhibited better electrochemical performance in half-cell assembly. The interfacial properties, such as Solid Electrolyte Interface formation/depletion, were studied from the in-situ-impedance. The LIC fabricated, with prior pre-lithiation, exhibited an enhanced energy density of 175 Wh kg–1 with excellent cyclic stability for more than 10,000 cycles. The LIC was also adaptable to different climatic conditions as it was analysed by testing the electrochemical performance at various temperature conditions.

Figure 1
Rational Design of LixSiOy-Based Pre-SEI through Thermal-Evaporated Li-Metal Prelithiated SiOx Anode Enabling Extremely Stable and High-Rate Lithium Microbatteries
Authors: Chen Yi-Xiu , Huang Bing Han , Liu Chuan-Pu
Published: August 2024

Recently, silicon oxides families (SiOx) have been commercialized as high capacity anode materials growing rapidly owing to their natural resource abundance and low-cost.(1) However, both the poor electron/ionic conductivity, and quite low initial coulombic efficiency (ICE) (normally < 60%) limits the further development into next generation SiOx anodes. (2) To address these two critical issues, various pre-lithiation strategies have emerged and systematically investigated with significant progress.(3, 4) Here, we provide a facile approach to prelithiate SiOx films by optimizing RF power and precisely controlling Li-metal deposition to overcome the current challenges of SiOx anodes. We found a strong correlation between the surface chemical state of SiOx and the pre-formation of LixSiOy SEI layers. The optimal prelithiation strategy achieves remarkable rate performance of 72.8% at 20C, and extremely excellent long-term cycling performance of 54.2% over 5000 cycles at 10C. This study significantly promotes SiOx-based anodes development, offering a promising strategy for extreme fast-charging and long-term stability not only overcoming the limitations in microbattery but scalable to practical electrodes.

Reference:

Q. Mai, Chem. Soc. Rev., 48, 285 (2019).

M. L. Jiao, Y. F. Wang, C. L. Ye, C. Y. Wang, W. K. Zhang and C. Liang, J. Alloy. Compd., 842, 21 (2020).

R. M. Zhan, X. C. Wang, Z. H. Chen, Z. W. Seh, L. Wang and Y. M. Sun, Adv. Energy Mater., 11, 20 (2021).

X. Q. Min, G. J. Xu, B. Xie, P. Guan, M. L. Sun and G. L. Cui, Energy Storage Mater., 47, 297 (2022).
(Battery Student Slam 8 Award Winner) Evaluating Electrodeposited Tin and Antimony-Based Anodes for Sodium-Ion Batteries
Authors: Gallawa Jessica Ruby , Ma Jeffrey , Prieto Amy L
Published: August 2024

The widescale adaption of intermittent renewable energy sources, such as wind and solar, must be accompanied by a grid storage network to store energy when it is abundant and redistribute it as needed for on-demand use. Short-term storage in the form of rechargeable batteries is an attractive avenue for meeting these storage needs. The dominant technology in today’s market, the lithium-ion battery (LIB), is cost-prohibitive due to the need for rare-earth materials. Using the same working principle as LIBs, sodium-ion batteries (NIBs) utilize earth-abundant, low-cost sodium compounds instead of lithium compounds. Tin (Sn) and antimony (Sb) alone are promising anode materials for sodium-ion batteries with high theoretical capacities (847 and 660 mAh/g for Sn and Sb with Na, respectively) relative to current LIB anode chemistry (372 mAh/g) [1,2]. When combined, SnSb has shown to have increased stability relative to Sn or Sb alone [3]. Here, we synthesized Sn-Sb thin films with varied Sn and Sb atomic ratios by co-electrodeposition from a deep eutectic solvent by modifying solution stoichiometry and electrodeposition parameters. Using a combination of X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and energy dispersive X-ray spectroscopy (EDS), phases and compositions of Sn-Sb synthesized by electrodeposition were identified. Once synthesized, we sought to determine the influence of morphology, surface chemistry, and composition on the capacity retention and rate capabilities of Sn and Sb-based anodes in NIBs. An optimized electrode composition was identified using a carbonate-based electrolyte, which resulted in stable capacity retention cycling at a rate of C/2 for 270 cycles.

[1] W. T. Jing, C. C. Yang, and Q. Jiang, Journal of Materials Chemistry A, 8, 2913–2933 (2020).

[2] S. Megahed and B. Scrosati, Journal of Power Sources, 51, 79–104 (1994).

[3] W. P. Kalisvaart, H. Xie, B. C. Olsen, E. J. Luber, and J. M. Buriak, ACS Applied Energy Materials, 2, 5133–5139 (2019).
Developing High-Purity Sodium Oxychloride Solid-State Electrolyte for Sodium-Ion Batteries
Authors: Ly Karen , Zheng Fan , Smirnova Alevtina
Published: August 2024

Sodium-ion batteries have attracted significant attention as an alternative energy source to lithium-ion batteries. Solid-state sodium oxyhalides (Na3OX, X = Cl, Br, I) have the advantages of easy synthesis from cheap raw materials. In this study, sodium oxychloride (Na3OCl) antiperovskite was synthesized using a microwave furnace, the first instance in currently available literature. Using the microwave furnace also significantly decreased the reaction time when compared to other published procedures. The ionic conductivity of Na3OCl pellets was determined using electrochemical impedance spectroscopy (EIS). Na3OCl was hot pressed between sodiated hard carbon in a PEEK lined split cell with stainless steel current collectors. The symmetric cell was tested at room temperature with varying external pressures (1 MPa to 12 MPa). Symmetric cells were also tested at constant external pressure (6 MPa) from room temperature to 80˚C.

Arrhenius plots demonstrated linear behavior in the whole temperature range with a calculated activation energy of 0.98 eV. The melting and crystallization temperatures were determined using differential scanning calorimetry (DSC). The purity of as-synthesized Na3OCl was evaluated using x-ray diffraction (XRD). The results on chemical composition and crystal-to-glass phase transformations were produced from in-situ X-ray diffraction (XRD) spectroscopy in the temperature range from 25˚C up to the melting point of Na3OCl. Cross-sectional SEM images of the Na3OCl pellets showed regions that were dense, but also regions with many pores (≤ 5 μm). SEM also showed microcracks that ranged from 1-5 μm. Future work will investigate methods of minimizing pores and microcracks during the cell manufacturing process as these surface features can impede efficient ionic movement.
Mathematical Framework to Model Electrodeposition/Stripping in Li-Metal Batteries during Cycling
Authors: Telmasre Tushar , Jang Taejin , Mishra Lubhani , Subramanian Venkat R.
Published: August 2024

Li-metal batteries, often heralded as the next frontier in energy storage technology, boast remarkable characteristics such as high energy density. Unlike traditional lithium-ion batteries, Li-metal batteries incorporate a lithium-metal anode, which significantly enhances their energy density. This higher energy density translates to a substantial increase in the amount of energy that can be stored in a given volume or weight, paving the way for more powerful and longer-lasting energy solutions[1–3]. However, significant shortcomings do exist, such as uneven Li-Metal deposition, dendrite formation, dead lithium, etc.[4] These phenomena are different than what are usually observed in Li-ion batteries with intercalation chemistry and lead to issues such as poor cycle life, low coulumbic efficiency, and safety concerns.[3]

Mathematical modeling is a promising approach to studying the physicochemical processes involved in the Li-metal batteries to understand the morphology changes during cycling. The plating and stripping of the lithium metal on the anode during cycling can be modeled as a moving boundary problem.[5] Since the process involves a shrinking and expanding electrolyte domain, moving boundary problems call for the fastidious implementation of the model equations and boundary conditions.[6]

In this talk, we will show the general mathematical framework involved in modeling Li-metal batteries in 1D systems. It expands upon the importance of carefully implementing boundary conditions to tackle the mass conservation issue that arises while cycling the model. It will also touch upon the additional complexities associated with expanding the model to 2D systems with convection in the electrolyte phase.

References:

Wang J, Ge B, Li H, et al (2021) Challenges and progresses of lithium-metal batteries. Chem Eng J 420:129739. https://doi.org/10.1016/j.cej.2021.129739

Wang R, Cui W, Chu F, Wu F (2020) Lithium metal anodes: Present and future. J Energy Chem 48:145–159. https://doi.org/10.1016/j.jechem.2019.12.024

Liu J, Bao Z, Cui Y, et al (2019) Pathways for practical high-energy long-cycling lithium metal batteries. Nat Energy 4:180–186. https://doi.org/10.1038/s41560-019-0338-x

Bandhauer TM, Garimella S, Fuller TF (2011) A Critical Review of Thermal Issues in Lithium-Ion Batteries. J Electrochem Soc 158:R1. https://doi.org/10.1149/1.3515880

Mishra L, Subramaniam A, Jang T, et al (2021) Perspective—Mass Conservation in Models for Electrodeposition/Stripping in Lithium Metal Batteries. J Electrochem Soc 168:092502. https://doi.org/10.1149/1945-7111/ac2091

Jang T, Mishra L, Subramaniam A, et al (2023) Addressing Mass Conservation in Two-dimensional Modeling of Lithium Metal Batteries with Electrochemically Plated/Stripped Interfaces. J Electrochem Soc 170:110516. https://doi.org/10.1149/1945-7111/ad0510
(Invited) Thermodynamics of Oxygen Transport in Resistive and Electrochemical Memory
Authors: Li Yiyang
Published: August 2024

Many neuromorphic computing architectures contain emerging memory devices that function through oxygen migration. Examples include resistive memory1 (ReRAM) and electrochemical memory2 (ECRAM), where tuning the distribution of oxygen vacancies enables analog information states. In this presentation, we discuss how oxygen transport in many metal oxides do not obey the drift-diffusion equation, which assumes ideal solution thermodynamics. Instead, the metal oxides undergo composition phase separation into oxygen-rich and oxygen-poor phases. This phase separation explains the long information retention time of ReRAM3. We further use this phase separation to improve the information retention time of oxygen-based ECRAM4,5 by at least ten orders of magnitude, yielding the highest temperature analog nonvolatile memory.

References:

Dittmann, R., Menzel, S. & Waser, R. Nanoionic memristive phenomena in metal oxides: the valence change mechanism. Adv. Phys.
70, 155–349 (2022).

Talin, A. A., Li, Y., Robinson, D. A., Fuller, E. J. & Kumar, S. ECRAM Materials, Devices, Circuits and Architectures: A Perspective. Adv. Mater. (2023) doi:10.1002/adma202204771.

Li, J. et al.
Thermodynamic origin of nonvolatility in resistive switching. https://www.researchsquare.com/article/rs-2365752/v1 (2022) doi:10.21203/rs.3.rs-2365752/v1.

Li, Y. et al. Filament-Free Bulk Resistive Memory Enables Deterministic Analogue Switching. Adv. Mater.
32, 2003984 (2020).

Kim, D. S. et al. Nonvolatile Electrochemical Random-Access Memory under Short Circuit. Adv. Electron. Mater.
9, 2200958 (2023).
(Invited) Engineering the Switching Kinetics of Valence Change-Based Memristive Devices for Neuromorphic Computing
Authors: Sarantopoulos Alexandros , Dittmann Regina
Published: August 2024

Memristive devices based on the valence mechanism are highly interesting candidates for the use as hardware representation of synapses in neuromorphic computing. The memristive model system SrTiO3 exhibit gradual switching and can be tuned between short-term and long-term plasticity. We will discuss the impact of the switching kinetics on the gradual switching mode and provide general guidelines for the design of gradual switching systems. Moreover, we present an approach to accelerate the switching kinetics of SrTiO3 by up to 103 times, or reduce the operating voltage by ≈ 30% to maintain the switching speed.

Our approach is to introduce a low thermal conductivity layer inside the active electrode of the active electrode of the devices, which blocks the heat dissipation caused by Joule heating during switching. Our method leaves the switching layer and its interfaces with the electrodes intact, while the use of HfO2 and TaOx as the heat blocking layers ensures ease of fabrication and CMOS compatibility. We will demonstrate that this approach is transferable to other more common material systems.
(Invited) Understanding Mechanisms of Ion and Electron Transport in Reconfigurable Electrochemical Neuromorphic Components
Authors: Balbuena Perla B. , Perez Beltran Saul , Ghotbi Maryam
Published: August 2024

New materials are emerging as promising components of reconfigurable electrochemical random access memory devices. Among them, transition metal oxides such as those containing vanadium, tantalum, titanium, have shown interesting behaviors regarding their abilities to emulate neuronal behavior, including synapses and other neuronal conductance characteristics, which make them potential candidate components for neuromorphic analog computing devices. In parallel, materials based on molecular complexes appear as another set of promising components that suitably arranged as molecular films may yield artificial neuronal behavior. Here we analyze the ion and electron transport characteristics in these two sets of materials and discuss the fundamental physical and chemical aspects that may drive targeted conductance and memory retention properties. Using first principles theory and simulations we highlight similarities and differences between these two sets of materials regarding their conductance properties and neuromorphic behavior.
Understanding the Non-Volatile Resistive Switching Behavior of Lithium Titanium Oxide during Spinel to Rock Salt Conversion for Neuromorphic Computing
Authors: Sreenarayanan Bhagath , Meng Shirley
Published: August 2024

Lithium based synaptic device research has been a growing new field in the last few years for enabling robust neuromorphic hardware systems. It can realize parallel analogue computation which is beyond the conventional von Neumann computing architecture which is slow, energy inefficient and expensive to execute complex tasks. In this study, we showcase the remarkable potential of Lithium Titanium Oxide (Li4Ti5O12) spinel, both computationally through Density of States (DoS) analysis using Density Functional Theory (DFT), and experimentally via direct current (DC) polarization investigation of electrochemically lithiated Li4Ti5O12 thin film, examining diverse states of discharge (SoD) in both in-plane and out-of-plane configurations. The observed conductivity jump spans up to six orders of magnitude, transitioning from the Li4Ti5O12 spinel phase to the fully lithiated Li7Ti5O12 rock salt phase. Raman Spectroscopy validates the transformation from the Li4Ti5O12 spinel phase to the Li7Ti5O12 rock salt phase. Moreover, the onset of increase in conductivity during this transformation is corroborated by changes in the oxidation state of Titanium (Ti), as explained with the help of X-Ray Photoelectron Spectroscopy. To actualize these findings, we engineered a three-terminal artificial synaptic device integrating Lithium Phosphorous Oxynitride (LiPON) solid-state electrolyte as the lithium ion source and conductor, while employing Lithium Titanium Oxide (Li4Ti5O12) spinel as the channel material. In device testing, we maintained a source-drain voltage (VSD) of 0.5 V, while sweeping the gate voltage (VG) from -3 V to 3 V, resulting in switching spanning up to 4 orders of magnitude, consistently replicable across multiple cycles. Widening the gate voltage window from ±3 V to ±7V induced an increase in conductance. Furthermore, non-volatile testing affirmed the sustained retention of the conductance state across all tested gate voltage windows, showcasing the device's stability over time. These compelling results portray a promising trajectory for the development of a robust synaptic device architecture reliant on lithium-based all solid-state materials, catalyzing the evolution of high-precision analogue neuromorphic computing systems.
(Invited) Electrochemical Random Access Memory for Neuromorphic Computing
Authors: Talin Albert Alec
Published: August 2024

Electrochemical random access memory (ECRAM) is a three terminal device that functions by tuning electronic conductance in functional materials through solid-state electrochemical redox reactions, and is one of several emerging device concepts that are currently being investigated in academic and industrial laboratories for enabling energy efficient brain inspired computing. Early demonstrations of nearly ideal analog switching and the realization that electrochemical ion insertion can be used to tune the electronic properties of many types of materials including transition metal oxides, layered 2D material, organic and coordination polymers, has sparked tremendous interest in ECRAM. Depending on the specific material, the resulting changes in conduction can range from gradual increments needed for analog elements, to large, abrupt changes for dynamically reconfigurable adaptive architectures. At its core, ECRAM shares many fundamental aspects with rechargeable batteries, where ion insertion materials are used extensively for their ability to reversibly store charge and energy. Computing applications, however, present drastically different requirements: systems will require many millions of devices, scaled down to less than 100 nanometers, all while achieving reliable electronic-state tuning at scaled-up rates (~109 Hz) and endurances (>1012 cycles), and with minimal energy dissipation and noise. In my presentation, I will briefly cover the history of ECRAM, the recent progress in devices spanning various types of materials, circuits, architectures, and discuss the rich portfolio of challenging, fundamental questions and how we can harness ECRAM to realize a new paradigm for low power neuromorphic computing.
Enhanced Synaptic Characteristics Under Applied Magnetic Field in V2O5/NiMnIn Based Switching Device for Neuromorphic Computing
Authors: Kaushlendra Kumar , Rahman Habeebur
Published: August 2024

The present study reports a memory structure Al/V2O5/NiMnIn on a flexible stainless-steel (SS) substrate for neuromorphic applications. The fabricated device exhibits gradual SET and RESET switching characteristics with an OFF/ON resistance ratio of ~100, good consistency of 4500, and excellent data retention capability up to 3000 s. The current-voltage (I-V) study supports an Ohmic conduction mechanism in the low resistance state (LRS). In contrast, the trap-controlled modified space charge conduction mechanism demonstrated the high resistance state (HRS). The resistance versus temperature measurement (R-T) in the LRS and HRS of the device signifies that oxygen vacancies form the conduction filament. We further analyze the synaptic functioning by applying identical consecutive voltage pulses, and the device's conductance change has been observed. These characteristics show a good representation of the biological memory synapse in terms of the artificial memory device. Long-term potentiation (LTP) and long-term depression (LTD) show nonlinear and asymmetery behavior, which is substantial for neuromorphic applications. A considerable shift in LTP and LTD was detected by applying external temperature and magnetic field. This is explained via temperature and magnetic field strain in the functional NiMnIn bottom electrode of the fabricated device. The mechanical flexibility of the memory structure was tested by exploring the switching characteristics with various bending angles and bending cycles. Therefore, the present study offers new avenues for flexible devices with high data storage capability for futuristic neuromorphic applications.
Ions Selectively Intrigued Ionologic Devices for Logic Operation
Authors: Zhou Hanfeng , Galek Przemyslaw , Grothe Julia , Kaskel Stefan
Published: August 2024

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy-efficient and nature-inspired next-generation computing devices. Here, we disclose the generalized concept for bias-direction-adjustable n- and p-CAPodes based on selective ion sieving. Controllable-unidirectional ion flux is realized by blocking electrolyte ions from entering sub-nanometer pores. The resulting CAPodes exhibit charge-storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations (‘OR’, ‘AND’). This work demonstrates CAPodes as a generalized concept to achieve p-n and n-p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion-based diodes in ionologic architectures.

Figure 1
Solid Electrolyte Interphase Stabilization via Trace-Level Additives for Ultrafast Charging of Lithium Metal Battery
Authors: An Kihun , Joo Myeong Jun , Tran Yen Hai Thi , Kwak Sehyun , Kim Hyung Gi , Jin Chang-Soo , Suk Jungdon , Kang Yongku , Park Yong Joon , Song Seung-Wan
Published: August 2024

Lithium metal battery (LMB) is a potential next-generation battery that can provide higher energy density than Li-ion batteries. However, during fast charging, lithium dendrites growth occur at the surface of Li metal anode, resulting in short circuiting, thermal runaway, and fire event. Under high-voltages beyond 4.2 V, lithium dendrites growth and structural degradation of cathode active material will be accelerated, leading to faster performance fade and higher risk of short circuiting. Herein, we demonstrate the significant impacts of fluorinated organic additive that enables ultrafast charging 400 cycles performance of Li//Mn-rich LMB under extreme conditions of 20 C (charged in 3 minutes) and charge cut-off voltage of 4.8 V, without lithium dendrites. Stable performance and high tolerance to extreme conditions are ascribed to the additive-derived formation of uniform and robust solid electrolyte interphase (SEI) layers at Li metal anode and Mn-rich cathode. Studies of the correlation between SEI stability, performance, and battery safety will be discussed in the meeting.

Acknowledgements

This research was supported by the Ministry of Trade, Industry & Energy (20007034) and National Research Foundation grant funded by the Ministry of Science and ICT (2019R1A2C1084024 & RS-2023- 00217581) of Korea.
Organic Ionic Plastic Crystal/Polymer Composite Electrolyte Prepared By Solution Casting Method for Solid-State Lithium Batteries
Authors: Wang Yanyu , Rochefort Dominic
Published: August 2024

Solid-state electrolytes have been considered as a promising candidate to address the safety issues for next-generation lithium batteries. Organic ionic plastic crystals (OIPCs) are attracting increasing interests as solid electrolyte materials due to their unique advantages, such as plasticity, nonflammability, good thermal and electrochemical stability. In this study, an OIPC-based composite electrolyte consisting of the OIPC 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr12TFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and the polymer polyvinylidene fluoride (PVDF) has been developed by a facile solution casting strategy. A free-standing and flexible OIPC/polymer composite membrane was fabricated by the solution casting method, which not only provides flexibility and better electrode/electrolyte contact, but also is more compatible with current battery processing methods. The composite membrane used in Li/Li symmetric cell was cycled stably over 900 h at a current density of 0.1 mA cm−2 at 50 °C, demonstrating that the OIPC/polymer composite electrolyte enabled the reversible and stable lithium plating and stripping behaviors. Further tests of the OIPC/polymer composite as solid electrolyte in LiFePO4/Li cell presented a high specific capacity of 149 mAh g−1 at 0.1 C and a long cycle life of over 440 cycles with capacity retention of 89% at 0.5 C at 50 °C, which showed improved rate capability and cycling stability in comparison with the composites with similar compositions but obtained by powder pressing method. This study demonstrated the potential of the OIPC/polymer composite solid electrolyte prepared by solution casting method and will promote the development of high-performance OIPC-based composite electrolytes for solid-state batteries.
Effect of Chemical Doping on Ion Transport in Sulfide Solid Electrolytes
Authors: Shreyas Varun , Gupta Saransh , Chertmanova Sabina Zakhidovna , Halacoglu Selim , Arnold William Richard , Wang Hui , Narayanan Badri
Published: August 2024

Rechargeable solid-state batteries (SSBs) offer tremendous promise as a safe and energy-dense storage technology for use in electric transportation, robotics, and portable electronics. Lithium argyrodites (e.g., Li7PS6, and its halogen-doped derivatives) have emerged as a lucrative class of solid-state electrolytes (SSEs) for SSBs owing to their high Li-ion conductivity (~10-3 S/cm), good elastic stiffness (~30 GPa), and low flammability. Meanwhile, sulfide-based solid electrolytes such as Na3SbS4 (NSS) also showcase substantial potential for SSBs with their high theoretical specific capacity, enhanced safety, and abundance of resources. Despite their promise, both lithium and sodium-based SSBs remain far from commercialization due to lack of atomic-scale understanding of ion-conduction, charge transport, structural evolution, and interfacial reactions (e.g., dendrite growth, electrolyte decomposition etc.). Here we employ a combination of density functional theory calculations, ab initio molecular dynamics simulations, and nudged elastic band calculations to understand ion transport mechanism in chemically doped lithium argyrodites and NSS.

In lithium-based systems, using accurate materials modeling, we design fluorine-containing argyrodite electrolytes that offers enhanced Li-ion conduction facilitated by unique Li-disorder induced by fluorine and other halogen co-dopants. Our results show the opening up of new pathways for Li inter-cage hops in these fluorine -containing argyrodite electrolytes which increases the Li-ion conductivity. In the case of sodium-based systems, we focus on atomic-scale mechanisms underlying Na-ion conduction in the presence of cation dopants. Ab initio molecular dynamics simulations reveal the significant impact of cation dopants on NSS, where the introduction of charge-compensating Na-vacancies enhances Na-ion conduction. The size of the cation dopant is found to be a critical factor, with examples such as Ca-doped NSS (rCa2+
/ rNa+
= 0.98) showing a conductivity approximately 10 times that of pristine NSS, while larger Ba2+ as a dopant (rBa2+
/ rNa+
= 1.35) hinders Na-ion hops due to local strain, resulting in a Na-ion conductivity ~5 times that of NSS. We will discuss these results in the context of accelerating design of novel solid-state electrolytes for long-lived, stable, and high-energy density SSBs.
Operando Tracking the Dissolution and Deposition Dynamics in Aqueous Zn-MnO2 Batteries
Authors: Xia Dawei , Hu Anyang , Zhang Yuxin , Lin Feng
Published: August 2024

Aqueous Zn–MnO2 batteries have received extensive attention for next-generation large-scale energy storage because of their low cost and outstanding safety. Despite efforts to achieve better performances, the charge-storage chemistry of MnO2 cathodes remains controversial. Zn-ion insertion, Zn-ion/proton co-insertion, proton insertion, and electro-dissolution have been proposed as the mechanism of the MnO2 cathodes. More specifically, the pathway of Mn dissolution is debatable: while intercalation chemistry leads to dissolution caused by the Jahn–Teller effect of Mn(III), electro-dissolution relies on a conversion from Mn(IV) to Mn(II). Furthermore, it is recently considered that Mn dissolution/redeposition efficiency is crucial to the reversibility of MnO2 cathodes, depending on pre-added Mn in the electrolyte. The role of trace Mn additive is also confusing. Last but not least, Mn dissolution and deposition is conjectured to be linked to the dissolution/redeposition of Zn‐based species-that is, Zn4SO4·(OH)6·xH2O (ZSH). To understand these key scientific questions that enlighten the further design of materials and electrolytes, it is imperative to develop operando measurements of the MnO2 cathodes. In our study, we utilized synchrotron X-ray fluorescence microscopy with high spatial resolution to probe the evolution of Zn and Mn species during electrochemical cycling. We can quantify the relationship between Zn and Mn concentrations from the electrode level to the single-particle level. We conclude that during the first discharge, MnO2 delivers the capacity by electro-dissolution, accompanied by the rapid precipitation of ZSH due to change of pH. ZSH surrounds the MnO2, which has high reversibility with the pre-added Mn additive in electrolytes. Our work provides in-depth insights into the complex Zn/Mn deposition and deposition near the electrode surface which will guide the further development of aqueous Zn-MnO2 batteries.
Electrochemical Characterization of Non-Aqueous and Aqueous Gel Polymer Electrolytes for Zinc-Ion Fiber Batteries
Authors: Leifer Benjamin Henry , Stavola Alyssa M. , Gallaway Joshua W
Published: August 2024

The increasing miniaturization of integrated circuits has enabled a wide variety of new applications for embedded sensors and smart devices. Miniaturization of their power sources, however, has lagged in comparison. There are many challenges to devising a space-conscious battery, including the power density, mechanical stability, and chemical safety. Batteries made in fiber formats are of interest for use in wearable electronics. Recent studies have shown the feasibility of Li-ion battery chemistries in drawn polymer fibers via thermally induced phase separation (TIPS)1,2 but key performance gaps in safety and reliability of these fiber batteries remain.

In addition to Li-ion, zinc-manganese dioxide (Zn-MnO2) chemistries are particularly good candidates for fiber format batteries due to their relatively low raw material cost, low reactivity, and tolerance of environmental contaminants such as water. Our work has focused on two Zn-MnO2 gel polymer electrolyte (GPE) cell formats: one non-aqueous polyvinylidene fluoride (PVDF) based gel polymer electrolyte, the other an aqueous polyvinyl alcohol (PVA) based GPE. In this work, we synthesize, characterize, and compare these two electrolyte formats head-to-head in both Zn-Zn symmetric cells and Zn-MnO2 full cells.

After the GPEs were synthesized, thermo-gravimetric analysis was used to characterize the gels and evaluate the feasibility of drawing the GPE of interest into fibers. We synthesized zinc salt containing PVDF-based GPEs and characterized them in ionic blocking cells via electrochemical impedance spectroscopy (EIS), achieving conductivities of 1.8 mS/cm2. We also assembled Zn-Zn symmetric cells, investigated key performance characteristics such as the transport number and the electrochemical stability window, and stably cycled them for over 500 hours at 0.5 mA/cm2. Lastly, we assembled Zn-MnO2 full cells to confirm the battery performance.

References:

(1) Lee, J. T.; Jo, C.; De Volder, M. Bicontinuous Phase Separation of Lithium-Ion Battery Electrodes for Ultrahigh Areal Loading. Proc. Natl. Acad. Sci.
2020, 117 (35), 21155–21161. https://doi.org/10.1073/pnas.2007250117.

(2) Khudiyev, T.; Grena, B.; Loke, G.; Hou, C.; Jang, H.; Lee, J.; Noel, G. H.; Alain, J.; Joannopoulos, J.; Xu, K.; Li, J.; Fink, Y.; Lee, J. T. Thermally Drawn Rechargeable Battery Fiber Enables Pervasive Power. Mater. Today
2022, 52, 80–89. https://doi.org/10.1016/j.mattod.2021.11.020.
Microstructure Characterizations of Electrodeposited Magnesium after Discharge/Charge Cycles for Rechargeable Magnesium Battery
Authors: Tsai Wei-Shiang , Wu Ying-Chen , Huang Yu-Shan , Chang Yung-Jen , Chu Peng-Wei
Published: August 2024

Rechargeable magnesium (Mg) batteries attract lots of attention owing to their high theoretical volumetric energy density and low cost from the natural abundance of Mg. Additionally, Mg is less prone to dendrite growth during charging, improving the battery safety. While most studies of rechargeable Mg batteries focus on developing new electrolytes and their performances, the microstructure of the Mg metal anodes during discharge/charge cycles is not fully characterized. Therefore, in this report, we investigated the microstructure evolution of electrodeposited Mg after discharge/charge cycles on both a bulk Mg metal anode and a copper (Cu) current collector in an all phenyl complex (APC) electrolyte.

The electrodeposited Mg on both the Mg anode and the Cu current collector at a current density of 2.25 mA/cm2 with a capacity of 1.5 mAh/cm2 show uniform distributions of Mg grains with an average grain size of about 1 to 2 μm. Subsequent Mg stripping with intermediate current density (0.75 mA/cm2) results in non-uniform discharge holes and possible local exposure of the substrate underneath, which could deteriorate the anode integrity. In contrast, the stripped electrodeposited Mg at relatively large (2.25 mA/cm2) and small (0.25 mA/cm2) discharge current densities show dense and uniform discharged holes on the surface. The microstructure evolution of the electrodeposited Mg on different substrates will be discussed based on the plating/stripping overpotentials and the interfacial impedances of the electrodeposited Mg under different conditions.
Magnetic Field Mapping-Based Battery Management System (BMS) for Lead Acid Application
Authors: Vasconcelos Scarleth , Singh Pritpal , Lee Ross
Published: August 2024

Lead Acid Batteries (LAB) are a widely used technology in Energy Storage Systems (ESS) due to their abundant and low-cost materials, non-flammable water-based electrolyte, and high recyclability rate. The main applications for LABs are in mobility, data centers, and telecommunications. According to the Consortium of Battery Innovation (CBI), the market for lead acid batteries is projected to increase 150 GWh between 2025 and 2030. Therefore, it is fundamental to identify emerging failure modes in LABs in ESS systems to reduce battery degradation and to extend the use life.

An important failure mode in flooded LABs is acid stratification. This research explores H+ concentration changes in H2SO4 (sulfuric acid) electrolyte as a correlation of acid stratification. The objective is to develop a non-invasive, non-destructive, and accurate real-time battery monitoring system. The Magnetic Field Probing (MFP) technique, popular in the medical imaging field, shows a promising solution for ESS performance evaluation. This technique can measure induced magnetic field changes based on variation in H+ concentration in the cell during cycling. See Figure. 1 (a). MFP provides early onset notification of stratification in flooded LABs with capability to discern other failure modes in non-flooded lead batteries.

A set of experimental trials measured pH and magnetic field variation of H2SO4 electrolyte. See Figure. 1 (a). The preliminary results demonstrated changes in electrolyte pH due to possible stratification. See Figure. 1 (b). A correlation between the output voltage resulting from the interaction of the induced magnetic field and the changes in the electrolyte concentration was found. See Figure 1(c) The optimal AC input frequency maximizes the induced magnetic field response. The value found for optimal AC input frequency was 32kHz, which depends on the physical properties of the magnetic field inductors (air core solenoid coils). The experimental results showed and concluded that the induced magnetic field across the tested cell is also inversely proportional to the distance between coils attached to the cell.

Further research involves the use of magneto-resistors to establish a magnetic field mapping in lead acid cells as they are being cycled. Magnetic field response is measured while lead acid cells are cycled from 100% to 20% state of charge range. In the future, this study will provide insights and findings to model and predict cell stratification in lead acid cells with electrochemical computational simulations.

Keywords: Energy storage systems, lead acid batteries, acid stratification, magnetic field, non-invasive method

Figure 1
Enhancing Conductivity and Viscosity in Melt Electrospinning of Biodegradable Polymers through Additive Modification
Authors: Kim Byung-Kwon
Published: August 2024

Biodegradable polymers, derived from renewable sources, have diverse applications spanning biomedical, packaging, textile fibers, and technical fields. Despite their notable attributes, the high viscosity and low electrical conductivity of these polymers present challenges, particularly in melt electrospinning (MES). Thus, this study endeavors to boost the electrical conductivity and viscosity of molten biodegradable polymers for MES nanofiber production through the incorporation of various additives. These additives were chosen based on prior research identifying promising compounds. Subsequently, this investigation compares the efficacy of different additives in enhancing conductivity and viscosity, aiming to optimize polymer solutions for efficient nanofiber manufacturing. The outcomes of this research are anticipated to advance biodegradable polymer-based nanofiber production methods and foster the creation of high-performance, sustainable materials with broad industrial applications.
Chloride Adsorption on Au (111) Electrodes
Authors: Yang Ziyan , Harlow Gary S
Published: August 2024

There are still numerous open questions with regards to adsorption phenomena and partial charge transfer at electrode interfaces. The dynamic nature electrode structure and adsorbate ordering makes an analysis solely based on thermodynamic considerations limited. Here we present recently collected data with such an analysis, using different concentrations of chloride anions in both acidic and neutral electrolytes, for well-defined Au (111) electrodes. Cyclic voltammograms and charge density data is obtained. Then the electrocapillary equation: "-dγ = σMdE + ΓCl-RTdln(cKCl)" is used to get the relative interfacial tension plot and later the electrosorption valency. In the future we will improve on this by more accurately placing the PZC of charge density measurements, using laser induced temperature jump transients and combining our interpretation with state-of-the-art molecular-dynamics using ground state machine learned potentials.

Figure 1
Measuring Double Layer Charging Via Droplet Approach Technique
Authors: Ness Carter , Harlow Gary S
Published: August 2024

The potential of zero-charge (PZC) is an important property of the electrochemical double layer (EDL) that has been shown to correlate with changes in the activities of several important reactions such as the oxygen reduction reaction (ORR) and the hydrogen evolution reaction (HER)1. This property was historically measured on droplet mercury electrodes (DME) where surface tension was measured vs potential, an experiment difficult to perform with other metal electrodes. Electrochemical impedance spectroscopy, cyclic voltammetry and galvanic discharge have been widely used to elucidate double layer capacitance but make several assumptions about the ideality of the double layer, measurement system, physical model employed, and have suffered from irreproducibility. The potential of maximum entropy (PME), where the solvent molecules are most disordered, has been measured via the laser induced temperature jump (LITJ) technique which works well when there is no specific adsorption2. A multiple approach mode of scanning electrochemical cell microscopy (SECCM) has also been used to measure local PZCs of polycrystalline3 and high-entropy alloy electrodes4. The SECCM approach is similar to an older immersion method that is not often used5. In this work we create a simple droplet type cell with a pneumatic sample stage to enable a simplified and less expensive version of the SECCM approach/immersion experiments and compare the results to those obtained via the LITJ method.
Rechargeable Lithium–Chlorine Batteries
Authors: Chen Wei
Published: August 2024

The development of high-energy-density battery systems is crucial. In this poster, I will introduce a new lithium-chlorine secondary battery system. Through the development and optimization of cathode materials, the performance of lithium-chlorine secondary batteries has been greatly improved, but there are still many problems. Further exploration of lithium-chlorine secondary batteries will promote their development in the field of high energy density batteries.