bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of Crystal Structure on Dealloying Behavior in PtCo Alloy and Its Impact on the Oxygen Reduction Reaction
Authors: Kim Miseung 
Published: August 2024

The proton exchange membrane fuel cell (PEMFC) is considered ideal for power generation due to its high energy conversion efficiency, low operating temperature, and environmentally friendly features. However, the performance of PEMFC is limited by the slow oxygen reduction reaction (ORR) at the cathode, necessitating the use of catalysts such as Pt to enhance the reaction. The Pt catalyst, although effective, poses the challenge of high cost. Consequently, numerous studies have been undertaken to develop more cost-effective catalysts that can match the excellent activity of platinum while maintaining high stability. In particular, the development of alloy nano-catalysts has garnered attention, and promising results have been reported for enhancing catalyst performance through dealloying on the surface of the alloy catalyst. Alloy catalysts prepared by the dealloying method offer the advantage of improving performance by selectively dissolving less-noble metal surfaces and constructing a Pt-rich shell layer.
In this study, we synthesized two PtCo alloy catalysts with distinct crystal structures: face-centered cubic (FCC) and face-centered tetragonal (FCT). To prevent particle growth during the transformation from FCC to FCT when subjected to high-temperature heat treatment for an extended duration, we employed the carbon shell encapsulation technique. Subsequently, the synthesized catalyst underwent acid treatment for dealloying. We investigated the variations in dealloying characteristics based on crystal structures and examined their impact on electrochemical performance.
Various characterizations, including X-ray diffraction (XRD), High-Resolution Transmission Electron Microscopy (HR-TEM), Scanning Electron Microscopy (SEM), Thermo-Gravimetric Analysis (TGA), and Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), were conducted to validate the structure of the synthesized PtCo alloy nano-catalyst. Half-cell and unit-cell experiments were carried out to verify electrochemical properties and performance, following the testing protocol suggested by the Department of Energy (DOE) in 2020. Finally, we explored the relationship between the dealloying feature of FCC and FCT and their impact on electrochemical activity and stability.
Efficient Direct Recycling of Spent Cathode Materials in Lithium-Ion Batteries
Authors: Ouaneche Tassadit , Stievano Lorenzo , Monconduit Laure , Guery Claude , Sougrati Moulay Tahar , Recham Nadir 
Published: August 2024

The demand for lithium-ion batteries (LIBs) has surged in recent years, driven by the rapid growth of electric vehicles (EVs) and emerging energy storage technologies. Yet, this surge in demand has also resulted from a significant increase in the number of spent batteries. Given the potential for environment pollution wastage, it is absolutely crucial to prioritize the recovery and recycling of these used lithium-ion batteries.
The common techniques employed in large-scale industrial settings for battery recycling are pyrometallurgy and hydrometallurgy. These are pivotal multi-step processes, particularly suitable for materials containing Cobalt (Co) and Nickel (Ni), such as NMC (LiNixMnyCozO2). Aside from NMC, there has been a surge in the adoption of LFP (LiFePO4) as a cathode material target for lithium-ion batteries in electric vehicles worldwide over the past few decades. However, these established industrial recycling methods are not applicable to LFP due to the comparatively lower value of iron. This necessitates the pursuit of direct recycling approaches.
In order to accomplish this goal, direct recycling stands out as the most suitable technique for regenerating spent batteries1. Unlike processes involving solution-based or high-temperature steps that entail potentially wasteful steps, this
approach aims to reduce energy consumption and costs, all while maintaining environmental integrity through a judicious utilization of resources, materials, and energy. Consequently, our attention is directed towards this specific LFP material, prompting us to detail a direct recycling procedure for spent LFP cathodes via a chemical lithiation process at room temperature in a solution containing lithium iodide (LiI) and various solvents2 (Fig. 1).

References:

(1) Y. Jin, T. Zhang, M. Zhang, Advances in intelligent regeneration of cathode materials for sustainable lithium-ion batteries, Adv. Energy Mater. 12 (2022), 2201526.

(2) Ouaneche, T. et al. Room temperature efficient regeneration of spent LiFePO4 by direct chemical lithiation. 579, J. Power Sources (2023) 233248.

Figure 1
Electrochemical Conversion of Low-Cost Glycerol to Valuable Products
Authors: Yelekli Kirici Ecem , Angizi Shayan , Park Jihyeon , Higgins Drew 
Published: August 2024

Over the last years, biodiesel production, a renewable fuel derived from biomass, has significantly increased, reaching an output of 40 million tons annually. This surge in production has resulted in excessive glycerol production, as a byproduct, accounting for 10 wt.% of biodiesel production. By 2025, it is predicted that glycerol production will amount to 6.3 million tons.1 However, the low demand for glycerol not only causes high disposal costs for this waste byproduct but also poses a threat to the ecosystem. Consequently, the valorization of glycerol is crucial for enhancing the biodiesel industry's economic viability and environmental sustainability.
Among all the techniques for the valorization of glycerol, such as catalytic oxidation, dehydration, and hydrogenolysis, the electrochemical oxidation of glycerol stands out for its cost-effectiveness, simplicity, and eco-friendliness. The glycerol electrooxidation reaction (GOR) can yield a wide range of valuable chemicals, such as C3 products (glyceraldehyde, lactic acid, glyceric acid, tartronic acid), C2 products (glycolic acid, oxalic acid, acetic acid), and C1 products (formic acid). Among all the products, C3 products have notably higher economic value compared to others. In particular, glyceric acid stood out by having a price of over 200 folds of glycerol and having the highest worldwide demand among all the GOR products.2 However, a significant technical challenge lies in developing a highly selective catalyst for C3 products showing high activity, and stability. Thus far, most of the catalyst developed for GOR includes noble metals or their alloys, which limits their usage in realistic systems due to their high cost and scarcity.3 Therefore, developing a cost-effective catalyst with high selectivity, activity, and stability is necessary to make the valorization of glycerol economically viable.
In this work, we demonstrate a bimetallic catalyst that, despite its low noble metal content, achieves high selectivity towards glyceric acid, along with notable catalytic activity and stability. Our analysis focuses on the impact of noble metal amount on activity and stability, and parametric analysis to improve the selectivity of C3 products. Furthermore, we outline the reasons for the discrepancies in the quantification of GOR products, especially in applying H-NMR analysis, and discuss the methods to improve the precision in GOR product analysis.

References:

Attarbachi, T., Kingsley, M. D. & Spallina, V. New trends on crude glycerol purification: A review. Fuel 340, 127485 (2023).

Braun, M., Santana, C. S., Garcia, A. C. & Andronescu, C. From waste to value – Glycerol electrooxidation for energy conversion and chemical production. Curr. Opin. Green Sustain. Chem. 41, 100829 (2023).

Han, X. et al. Electrocatalytic Oxidation of Glycerol to Formic Acid by CuCo2O4Spinel Oxide Nanostructure Catalysts. ACS Catal. 10, 6741–6752 (2020).
Mitigating the HER-Promoted Corrosion of Lead Cathodes during Electrosynthesis
Authors: Achanta Krishna Sai Koushik , Prenzel Tobias , Winter Johannes , Waldvogel Siegfried R , Tessonnier Jean-Philippe 
Published: August 2024

The hydrogen evolution reaction (HER) is a significant side reaction that lowers the faradaic efficiency of electrochemical reductions in aqueous electrolytes. HER has also been identified as a primary contributor to cathodic corrosion for metals like lead, tin, and mercury—commonly employed as cathodes in electrosynthesis. Consequently, the suppression of HER is of paramount importance, not only for enhancing product faradaic efficiencies but also for mitigating corrosion and extending the lifetime of metal cathodes.
In the present study, we demonstrate the suppression of HER over lead electrodes in an acidic electrolyte through the addition of the quaternary ammonium salt N,N,N,N’,N’,N’-hexamethyl-1,12-dodecanediammonium methyl sulfate (H12MS). The quaternary ammonium ions electrostatically interact with the surface of the negatively charged lead electrode, creating a cationic layer that protects the cathode’s surface by repelling hydroniums, thereby suppressing HER. The amount of evolved hydrogen was estimated by conducting chronoamperometry (CA) experiments at a potential of -1.8 V vs. Ag/AgCl (after the onset of HER) for 1 hour in a 0.1 M H2SO4 solution (pH 1). It is observed that the hydrogen produced dropped from ~1.62 mmol/cm2 to ~0.26 mmol/cm2 in the presence of 1 mM H12MS. Further, we notice that the current increased monotonically with time for the blank lead electrode during CA (-43.76 to -114.57 mA/cm2), indicating an increase in the exposed surface area due to corrosion. In contrast, the current remained almost constant (-13.2 to -13.8 mA/cm2) in the presence of 1 mM of H12MS, indicating that cathodic corrosion is mitigated. This mitigation in cathodic corrosion is further supported by the scanning electron microscopy images acquired after 1 hour of vigorous HER process. Without H12MS, the lead coupon exhibited significant surface disintegration, indicative of cathodic corrosion. Conversely, in the presence of 1mM H12MS, the surface of the lead coupon remained intact after HER, affirming the successful mitigation of the corrosion process. Our findings for electrochemical hydrogenation will be extended to electrocatalytic transformations, for example, to favor electro-hydrogenation over HER on PGM catalysts.
(Invited) Analog Computation-in-Memory (CiM) for AI and Neuromorphic Computing
Authors: Takeuchi Ken 
Published: August 2024

[Invited talk]
This paper overviews analog Computation-in-Memory (CiM) with non-volatile memories for AI applications and neuromorphic computing. In the edge IoT/mobile devices, CiM will be heterogeneously integrated with digital processors such as CPUs to realize the inference of AI with high energy efficiency.
This talk also introduces the approximate CiM. Inspired by the approximate computing, by tolerating some degree of memory errors, the trade-off of performance, energy and cost is resolved.
Finally, this paper covers various AI algorithms and neuromorphic computing such as Convolutional Neural Network (CNN), Recurrent Neural Network (RNN), event driven Spiking Neural Network (SNN) and Reservoir Computing.
Effective Lithium Polysulfides Anchoring on Vanadium Disulfide Facets for Lithium-Sulfur Batteries – A Computational Study
Authors: Boteju Welathantrige Thilini Niranga , Abraham Akhil , Ponnurangam Sathish , Thangadurai Venkataraman 
Published: August 2024

The commercialization of Li-S batteries is hindered by the shuttle effects of lithium polysulfides (LiPS) and the sluggish reaction kinetics. Hence, effectively trapping and promoting the conversion rates of LiPSs is of prime importance1. However, the fundamental kinetics of the electrocatalytic charging and discharging of Li-S batteries and the underlying mechanism have not been sufficiently explored yet.2 Therefore, by taking the 2D transition metal sulfide, VS2 as a model, we conducted a systematic investigation using density functional theory to study the ability of dominant exposed crystal planes of VS2 to trap LiPSs from leaching into electrolyte solvents and to act as an electrocatalyst to increase the Sulfur Reduction Reaction (SRR) kinetics3. To reflect a realistic environment of a battery, the effect of electrolyte solvents on the electrocatalytic activity was further investigated.
Our calculations show that VS2 has moderate binding energy toward LiPSs which inhibits LiPS from leaching into electrolytes while fulfilling the key prerequisite to act as an electrocatalyst simultaneously.4 At the discharge, the conversion of S8 to the long chain Li2S8 was facile with a lower energy barrier while the rest of the reactions were sluggish explaining the accumulation of LiPSs. Further, the VS2 (001) facet exhibits excellent electrocatalytic activity for the SRR and Li2S decomposition reaction at charging compared to other dominant crystal planes, which significantly lowers the energy barriers of LiPS conversion during the charging and discharging process, ensuring high-rate performance and longer cycle life4.

References

Manthiram, A., Fu, Y., Chung, S.-H., Zu, C., & Su, Y.-S. (2014). Rechargeable Lithium–Sulfur Batteries. Chemical Reviews, 114(23), 11751–11787.

Abraham, A. M., Thiel, K., Shakouri, M., Xiao, Q., Paterson, A., Schwenzel, J., Ponnurangam, S., & Thangadurai, V. (2022). Ultrahigh Sulfur Loading Tolerant Cathode Architecture with Extended Cycle Life for High Energy Density Lithium–Sulfur Batteries. Advanced Energy Materials, 2201494.

Abraham, A. M., Boteju, T., Ponnurangam, S., & Thangadurai, V. (2022). A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective. Battery Energy, 20220003.

Boteju, T., Abraham, A. M., Ponnurangam, S., & Thangadurai, V. (2023). Theoretical Study on the Role of Solvents in Lithium Polysulfide Anchoring on Vanadium Disulfide Facets for Lithium–Sulfur Batteries. The Journal of Physical Chemistry C.
Ion Conductive High Li+ Transference Number Polymer Composites for Solid-State Batteries
Authors: Tronstad Zachary , McCloskey Bryan D. 
Published: August 2024

Solid-state electrolytes are a promising field of study to improve the safety and energy density of lithium-based batteries. Composite solid electrolytes seek to leverage both the desirable mechanical properties of polymers and the high conductivity of active ceramic fillers; however, Li+ transport through the composite, and especially the extent of Li+ through the ceramic phase, remains an open question.1, 2

Simulations suggest that decreasing interfacial resistance between polymer and ceramic would promote transport through ceramic particles.1 Our work seeks to improve Li+ transport in the ceramic phase by engineering both polymer and ceramic materials that minimize the interfacial resistance between the two.
Traditional polymer electrolytes have a low transference number (~0.15) compared to ceramics (~1), and when combined in composites this mismatch has been suggested as a major contributor to interfacial impedance.3 We explore the effect of the transference number mismatch by using a single-ion conducting polymer poly((trifluoromethane)sulfonamide lithium methacrylate) (PMTFSILi). The Li+ transport in a composite electrolyte with high transference number PMTFSILi is compared with that of a system utilizing a lithium salt.
Contaminants on ceramic surface can also contribute to interfacial resistance. We consider how lithium carbonate (Li2CO3) content on the surface of LLZTO (Li6.4La3Zr2Ta0.6O12) affects Li+ transport. Accompanying this study is a detailed description of washing procedures used to clean the LLZTO surface. Titration Mass Spectrometry (TiMS) is used to quantify Li2CO3 content in our ceramic particles and assess the effectiveness of our cleaning procedures. Inductively-coupled plasma mass spectrometry (ICP-MS) data also assists in measuring the impact (Li+ exchange and transition metal dissolution) of various washing procedures (basic, acidic) on the LLZTO particles.
Solid-state NMR has proven to be a useful tool in deconvoluting Li+ transport in different phases of composite electrolytes2 and is the primary technique we use to quantify transport in our system. These findings will provide a deeper understanding into the relationship between interfacial resistance and Li+ transport in composite electrolyte systems and shed light on how material choices can better utilize the highly conductive ceramic phase for Li+ transport.

Kim, HK., Barai, P., Chavan, K. et al.Transport and mechanical behavior in PEO-LLZO composite electrolytes. J Solid State Electrochem
26, 2059–2075 (2022). https://doi.org/10.1007/s10008-022-05231-w

Zheng J., Hu, Y. New Insights into the Compositional Dependence of Li-Ion transport in polymer-ceramic composite electrolytes. ACS Appl. Mater. Interfaces, 10, 4, 4113–4120 (2018). https://doi.org/10.1021/acsami.7b17301

Mehrotra A. et al. Quantifying Polarization Losses in an Organic Liquid Electrolyte/Single Ion Conductor Interface.
Electrochem. Soc.
161 A1681 (2014). https://doi.org /10.1149/2.0721410jes
Temperature Dependence of SEI Formation and Faradaic Efficiency in Electrochemical Lithium Mediated Nitrogen Reduction to Ammonia
Authors: O'Rafferty Alden , Benedek Peter , Niemann Valerie Anne , Nielander Adam C. , Jaramillo Thomas F. 
Published: August 2024

Lithium-mediated nitrogen reduction (Li-N2R) is a promising electrochemical ammonia production alternative to the Haber Bosch process, a process responsible for 1.3% of CO2 emissions yearly.1 While Haber Bosch requires high temperatures and pressures in large centralized facilities, Li-N2R works at near-ambient temperatures and pressures allowing for decentralized production and can be powered by renewable electricity sources. In Li-N2R, Li ions are plated as Li metal on the working electrode, which then reacts with N2 gas to form lithium nitride (Li3N). Lithium nitride reacts with a proton source to form ammonia (NH3) (Figure left).
Past research indicates that the solid electrolyte interface (SEI) formed in the electrochemical system has a large impact on the NH3 faradaic efficiency (FE) of the cell.2 Variations in the temperature during cell cycling can influence both the thickness and composition of the SEI. This, in turn, alters the kinetics of species transport to and from the electrode. Consequently, SEIs formed at different temperatures lead to varying proportions of products in the reaction, and are a helpful tool to tune the system towards NH3 selectivity. We elucidate temperature effects on SEI formation and FE for electrolytes with 1M LiBF4 in two common solvents, Tetrahydrofuran (THF) and diglyme (DG), with a 1v% ethanol (EtOH) proton source (Figure right). We also confirm the validity of our results with an Ar control. By dissolving SEI species in a D2O rinsate, we can quantify the composition of the SEI formed at different temperatures using a combination of nuclear magnetic resonance (NMR), inductively coupled plasma mass spectrometry (ICP-MS), and ion chromatography (IC). With our strategy, we correlate SEI composition trends with changes in FE, and provide pathways towards engineering the SEI for enhanced Li-N2R FE to NH3 and improved electrolyzer lifetime.

1J. W. Erisman et al., Nat. Geosci 2008, 1, 636–639

2K. Steinberg et al., Nat. Energy 2022, 8 (2), 138

Figure 1
Continuous Direct Air Capture and Electrochemical Conversion of CO2 and H2O into Ethylene and Oxygen in Solid Electrolyte Reactor
Authors: Li Huaping 
Published: August 2024

Chemelectronics LLC has developed economical approach to use solar energy to convert CO2 directly captured from air using carbon dioxide capture conductive sorbent materials coated on carbon foam electrodes into chemical products (ethylene) and oxygen from nick foam electrodes separated with solid polyelectrolytes. We take advantage of commercial off-the-shelf solar panels as electricity to supply the electrochemical reduction of CO2 directly captured from air into chemical products with zero carbon emission.
Based on the life cycle analysis, there is no CO2 emission from CO2 capture and conversion. The energy will be produced from solar panels.
Fabrication of Nano-Carbon-Based Sustainable Perovskite Solar Cells
Authors: Bhattacharjee Jyoti , Roy Subhasis 
Published: August 2024

The rising need for sustainable energy solutions has fuelled considerable research into novel technologies that harness solar energy for efficient and scalable energy storage. Carbon nanotubes (CNTs) have emerged as feasible candidates for these applications due to their unique properties, such as high surface area, better electrical conductivity, and chemical stability.This report focuses on the design and fabrication of cost-effective nano-carbon-based perovskite solar cells (PSCs) and discusses their potential for clean energy generation and storage. This experimental study shows a novel technique to increase the sustainability the conventional fluorine-doped tin oxide (FTO) substrate with an Indium Tin Oxide (ITO) derived from electronic waste and incorporating nanocarbon based-graphene with solution-based techniques. This addition serves as a good basis for the ITO coating, aids charge transport in the perovskite solar cell, and promotes uniform covering maximum electrical conductivity, and transparency. Being the transparent conducting electrode, the CNTs is infused with the upcycled ITO coated glass and was included in the perovskite solar cell architecture, which replaces the traditional ITO electrode, lowering material costs, and improving the circular economy for energy storage devices, and a cleaner energy future.
The ITO extraction process entails recovering indium and tin from mobile phones using an environmentally friendly and economical chemical etching process using hydrochloric acid (HCl) to remove the ITO layer. To ensure the purity and structural integrity of the ITO nanoparticles, they were rigorously characterized using X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. After depositing a perovskite- CNTs precursor solution on the ITO layer glass substrate, the light-absorbing layer was annealed. Electron transport and hole-blocking layers were then deposited utilizing solution processing techniques using the PEDOT: PSS and metal electrodes were deposited to complete the device manufacturing. The current-voltage (J-V) relationship was used to compute the open-circuit voltage, short-circuit current density, fill factor (FF), and power conversion efficiency (PCE) of a solar cell. Electrical characterization allow for the calculation of solar cell performance metrics such as short-circuit current (Isc), short-circuit current density (Jsc), and open-circuit voltage (Voc). These findings imply that employing e-waste-derived ITO on graphene substrates to create high-efficiency perovskite solar cells is a realistic option. This research provides a sustainable and cost-effective method for producing high-performance perovskite solar cells by eco-friendly upcycling e-waste for ITO extraction, addressing the critical issue of e-trash management.

Keywords

Perovskite solar cells, CNTs, sustainable energy, energy conversion.