bluuebunny/crossref_metadata_2025 huggingface dataset:
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).
Understanding the Effects of Forced and Bubble-Induced Convection in Transport-Limited Organic Electrosynthesis
Authors: Bloomquist Casey Kyle , Dogan Melisa , Harris James S , Herzog Benjamin D , Tenn William J , Aydil Eray S , Modestino Miguel A
Published: August 2024

Organic electrosynthesis offers a sustainable path to decarbonize the chemical industry by integrating renewable energy in chemical manufacturing. However, achieving the selectivity and energy efficiency required for industrial applications is challenging due to the inherent mass transport limitations of most electro-organic reactions. Electrochemical reactions rely on transport of reactants to the electrode surface and become mass transport-limited when the reactant diffusion rate is lower than the reaction rate at the electrode. In organic electrosynthesis with several possible products, mass transport limitations can result in decreased selectivity towards the desired product as the various reaction pathways compete. Convection can mitigate mass transport limitations, but fundamental engineering guidelines for selecting and scaling up convection methods in electrochemical systems do not exist. As a result, the impact of convection on industrial-scale complex organic electrochemical processes remain poorly understood. Here we show that the Sherwood number (Sh)—the ratio of convective mass transport to diffusive mass transport—is a crucial metric to characterize mass transport, determine reactor performance, and enable effective scale-up. We investigate the interplay between mass transport and electrochemical reaction rates under convective flows in the context of the electrosynthesis of adiponitrile, one of the largest organic electrochemical processes in the industry. We use experiments and data-driven predictive models to demonstrate that forced liquid convection and bubble-induced convection produce nearly equivalent mass transport conditions when the corresponding Sherwood numbers are equal. This conclusion shows that the Sherwood number characterizes the mass transport condition independent of the underlying convection mechanism. Additionally, we show that the reactor performance scales with the Sherwood number for a given current density and reactant concentration. This scaling enables accurate prediction of performance irrespective of the convection method, and demonstrates that adiponitrile Faradaic efficiencies of >80% can be achieved for current densities of up to 200 mA/cm2 when Sh > 100. Our results provide guidelines for the design and selection of convection methods, from lab to industrial scale, and contribute to the development of more sustainable chemical manufacturing processes.
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.
Vanadium Oxides in Neuromorphic Computing: Unveiling Insights through First Principles Calculations
Authors: Perez Beltran Saul , Balbuena Perla B.
Published: August 2024

Neuromorphic computing represents a revolutionary approach to developing analog non-volatile memory (NVM) devices. This technology relies on electron-correlated materials capable of replicating the functioning of synapses and neurons in the brain, making it ideal for energy-efficient parallel computing applications. Among the myriad of innovative materials suitable for neuromorphic computing, such as conductive polymers, organic semiconductors, and nanowires, among others, electron-correlated transition metal oxides stand out for their ability to undergo metal-insulator transitions either by tuning their oxygen content or the stoichiometry of an intercalating metal ion. In this talk we discuss from a first principles perspective the pivotal role that vanadium oxide has the potential to play in the development neuromorphic computing devices. First, we examine the use of vanadium oxide as a Mott insulator capable of undergoing a stable phase separation process that is suitable for non-volatile electrochemically activated random access memory devices (ECRAM). A stable phase coexistence across multiple segregated vanadium oxides states provides the device the ability express non-volatile memory behavior after precise tunning of oxygen vacancies into VO2. The correlation between these oxides’ formation energies and their oxygen content provides clues on the stable formation of coexisting crystalline phases that provide tunable resistivity based on the relative fraction and distribution of each phase with unusual retention, with an estimated 1% loss over 14 years in ambient conditions. Second, we address the structural and electrical properties of β’-CuxV2O5 based on temperature and Cu content. Ab-initio molecular dynamics calculations provide a close-up view of the correlation between Cu content and mobility and its ability to induce structural distortions to the intercalating β’-CuxV2O5 host that spike close to the insulator-metal transition (IMT).
(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.
Modeling Metal Nitrides for Interface Design in Lithium-Sulfur Batteries with GPUs and CPUs
Authors: Nizami Ameer , Shamekhi Mehdi , Peslherbe Gilles , Li Xia
Published: August 2024

As current batteries reach their limits, finding new battery materials is crucial. Lithium-sulfur batteries are a promising next-generation technology but face three major issues: low active material utilization, cathode pulverization, and limited polysulfide conversion leading to anode corrosion. Nano-deposition of metal nitride (MNx, M = Ti, V, Zr, etc.) layers on the graphene sulfur cathodes could significantly improve conductivity and cycling performance. Nevertheless, the large number of potential metal candidates requires preliminary and efficient computational screening using density-functional theory (DFT). This modeling framework can be used to calculate many properties of the coatings and screen out poor candidates. Firstly, the surface-adsorption ability of metal nitride candidates for lithium polysulfide intermediates involved in the electrochemical cycle (Li2S, Li2S2, Li2S4, Li2S6, Li2S8, S8) must be greater than the adsorption by dioxolane and dimethyl ether electrolytes (>~0.99eV). Secondly, the electronic properties before and after adsorption must feature significant density of states near the Fermi level, as a possible indicator of good electrical conductivity. Lastly, the free-energy profiles for the sulfur reduction reaction (SRR) over the remaining candidates will be estimated to better understand the catalytic properties of the metals. Particular attention will be paid to the Li2S2 reduction to Li2S, the potential limiting step. The top catalyst candidates should allow for an exergonic reaction. Finally, this application serves as a case study for our modeling platform, and the relative merits of standard for CPUs and GPUs in terms of computation time and accuracy will be discussed. Careful analysis of binding energy results, densities of states, and energy profiles for the various metal candidates provides valuable insights into the design of experimentally viable lithium-sulfur batteries, as well as advanced interface design in the broader field of battery research.
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
(Battery Student Slam 8 Award Winner) Enable Processing of Sulfide Solid Electrolytes in Humid Ambient Air
Authors: Liu Mengchen , Sebti Elias , Hong Jessica , Zhou Ke , Wang Shen , Miao Qiushi , Harpak Nimrod , Yu Sicen , Zhou Jianbin , Oh Jeong Woo , Song Min-Sang , Luo Jian , Clement Raphaele J , Liu Ping
Published: August 2024

Sulfide solid-state electrolytes (SSEs) are promising candidates to realize all solid-state batteries (ASSBs) due to their superior ionic conductivity and excellent ductility. However, their hypersensitivity to moisture requires processing environments that are not compatible with today’s lithium-ion battery manufacturing infrastructure. Herein, we present a modification strategy that enables the processability of sulfide SSEs under humid ambient air. We demonstrate that compatible modification with the electrolyte with negligible impact on its ion conductivity. Importantly, the modification extends the amount of time that the sulfide SSE can be exposed to air with limited degradation of its structure while retaining the conductivity for days, a more than 100x improvement in protection time over competing approaches. Experimental and computational results reveal the interaction between modification to the SSE. The modified SSE maintains its function after exposure to ambient humidity when implemented in a Li0.5In/LiNi0.8Co0.1Mn0.1O2 ASSB. The proposed protection strategy represents a major step forward towards cost-competitive and energy-efficient sulfide SSE manufacturing for ASSB applications.
Date Seed-Derived Supercapacitor Electrodes in Aqueous Electrolyte: Unveiling High Capacity and Coulombic Efficiency
Authors: Makanova Nazym , Nurpeissova Arailym , Kalimuldina Gulnur , Bakenov Zhumabay
Published: August 2024

Date seeds, often considered byproducts of date fruit processing, represent a significant bio-waste stream. Despite their abundance, these seeds are underutilized and typically regarded as agricultural waste. Rich in carbon content, date seeds have the inherent potential to serve as precursors for hard carbon electrodes in supercapacitors. Free-standing electrodes were fabricated to enhance cyclic stability and improve Coulombic efficiency, showcasing superior electrochemical performance. The activation process with a 1:3 KOH-to-bio-char ratio yielded a specific capacitance of 204 F/g at 0.2A/g for the symmetric cell with an energy density of 6.5 Wh/kg and a power density of 47.70 W/kg, highlighting the effectiveness of this approach in advancing both structural integrity and electrochemical attributes. To elucidate the electrochemical performance of KOH-activated hard carbon, BET analysis, Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), and Raman Spectroscopy were employed. BET analyses revealed a higher surface area for the hard carbon activated with a 1:3 KOH ratio. This enhancement in structural integrity was further corroborated by cyclic voltammetry (CV) and charge-discharge curves, emphasizing the favorable electrochemical attributes of the proposed method. While previous investigations into date seed supercapacitors revealed promising results, achieving near 100% Coulombic efficiency remained challenging. In this study, the implementation of free-standing electrodes marked a significant advancement, resulting in a remarkable Coulombic efficiency of 99.97%. This nuanced approach underscores the effectiveness of our methodology in addressing and improving the Coulombic efficiency of date seed-derived supercapacitors.
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
In-Situ and in-Operando Li-Ion Batteries for Materials Science Education
Authors: Pal Anirban
Published: August 2024

Electrochemical energy storage systems, particularly Li-ion rechargeable batteries (LiRB), have a key role to play in fortifying US energy generation, decarbonizing the electricity sector, and limiting anthropogenic climate change. LiRBs suffer from limited lifetimes, insufficient energy densities, and fire risks, which are all materials science and engineering challenges stemming from various irreversible degradation processes occurring at nano and micro-scales. These batteries function via the reversible diffusion of Li ions from a Li-rich cathode to a Li-poor anode, each of which undergo various levels of volumetric phase changes, plastic deformation, and microcracking with each charging cycle, thereby compromising subsequent battery performance. Therefore, it is imperative to understand the nano-mechanical processes associated with LiRB degradation and predict transformative material designs that can lead to manufacturing cheaper, denser, and safer LiRBs. Such understanding and design would be instrumental to achieving the US 2050 Net Zero Goal. Additionally, the US lags 10x behind China in terms of Li battery manufacturing capability, and thus a LiRB-aware Research and Development workforce is paramount for continued US energy security. In this context, we propose a new design for in-situ and in-operando Li-ion battery research and education. This battery design will be used in a classroom/lab setting to discuss fundamental materials science concepts such as diffusion, grain-boundaries, and fracture. This activity will be used to broaden "missing millions" student participation in a crucial area of energy research at a minority serving institution.
Tailored Core-Shell Nanostructure Achieved through Atomic Layer Deposition for Superior Energy Storage Performance Application
Authors: NOH Gihyeok , Adhikari Sangeeta , Kim Do-Heyoung
Published: August 2024

A distinctive method was employed to construct ultrathin NiO on phosphorous-doped MnO2 nanosheets, utilizing a straightforward hydrothermal process to form a Mn precursor on Ni-foam followed by phosphorous doping through a simple solid-state annealing process and ALD technique. The impact of phosphorous doping was examined by varying the annealing temperature, resulting in a significant increase in oxygen vacancies and electrochemical performance. Additionally, the atomic layer deposition of NiO not only improved electrochemical performance but also ensured cycling stability without impeding the system. By adjusting the thickness of the NiO thin films over phosphorous-doped MnO2, a notable enhancement in electrochemical performance was achieved, as evidenced by the performance of the solid-state asymmetric device. This hybrid approach is expected to pave the way for novel electrode material designs for high-performance supercapacitors, leveraging electroactive metal oxides through ALD coating.
Solid-State Lithium Batteries with in-Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 ℃
Authors: Sankara Raman Ashwin , Yushin Gleb , Johnson Billy , Chandra Vismay , Dong Sam , Avis Morgan , Jhulki Samik , Fu Wenbin , Narla Aashray , Butcher Riley , Leisen Johannes , Lee Haewon
Published: August 2024

In-situ polymerized acrylate-based polymers are very appealing as solid polymer electrolytes (SPEs) in lithium (Li) batteries due to the drop-in compatibility of such in-situ polymerization with conventional battery production, the ease of acrylate polymerization and their inexpensive, facile SPE chemistry. We identified, however, that such SPEs suffer from either a low cationic transference number with dual ion conducting salts (0.12-0.2) or a low ionic conductivity with single Li-ion conducting (SLIC) salts (6·10-6 S cm-1). In this project we overcame these limitations and developed significantly improved SPE with ionic conductivity of up to 2·10-4 Scm-1 and a relatively high Li-ion transference number of 0.4. With a significantly reduced fraction of mobile anions in the hybrid SPE, in-situ polymerized SPE cells with an LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, the motional narrowing observed in the line-shapes of solid-state nuclear magnetic resonance (SS-NMR) spectra provided additional insights of the differences in Li nucleus environments and revealed a reduced activation energy for the hybrid salt SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer lithium batteries capable of operating at high temperatures using commercial battery fabrication equipment. We expect that further tuning of the acrylate based SPE composition may allow further increases in its conductivity without sacrifices in its electrochemical stability or mechanical properties.
Unravelling the Effect of Sodium Doping on Li2MnO3 nanostructured Cathode Materials
Authors: Ngoepe Phuti Esrom , Malibe Tshidi , Ledwaba Raesibe Sylvia
Published: August 2024

The quest to develop affordable, high-performance electrode materials for lithium-ion batteries in electric vehicles is driving scientific innovation forward. Li2MnO3, as a prospective high-capacity (459 mAh.g-1) cathode, suffers from capacity degradation and voltage decay during the cycling process. Nanostructuring and incorporating sodium ions into lithium sites can mitigate voltage decay by limiting transition metal migration, impeding oxygen loss, and improving lithium diffusion by lowering the activation energy of Li-rich layered host materials. Herein, sodium-incorporated nonospherical structures of the form Li2-xNaxMnO3 (0 ≤ x ≤ 2), generated through the amorphisation and recrystallisation (A+R) technique show remarkable structural stability and enhanced Li-ion mobility owing to the enlarged lithium lattice upon sodium entrance. Specifically, the Li1.95Na0.05NaO3 nanosphere, displays more stable Li+/Mn4+ layers which will greatly contribute to its capacity. The microstructures associated with this configuration show well-ordered layers with high lithium kinetics and lower activation energy compared to pristine Li2MnO3. Characterisation of the x-ray diffraction (XRD) patterns revealed peak broadening along with the shifting of peaks at 2Θ~38 to the right due to the enlarged lithium layers occupied by sodium ions to facilitate lithium diffusion. Moreover, the undesired phase transformation from layered to spinel was observed at a later stage of charge for the sodium-doped systems, suggesting that the presence of sodium stabilizes the structure and minimizes the migration of manganese into lithium layers. These findings may lead to solutions for problems such as structural instability, lattice oxygen loss, and capacity decay in layered lithium oxide materials.
Two-Step Atmospheric RF-Microplasma Synthesis of Lithium-Ion Battery Cathode
Authors: McKalip Nicholas , Brow Ryan , Colclasure Andrew M.
Published: August 2024

To address the increasing demand for lithium-ion batteries for use in energy storage applications, such as electric vehicles, there is a need to make the cathode synthesis process less energy intensive, as the current method requires a sintering temperature of 650 – 950 °C for up to 12 hours. Radiofrequency (RF) microplasma setups provide an avenue to approach this problem by providing a tunable system that can be operated under atmospheric conditions, with a more efficient transfer of energy in the plasma setup as compared to a thermal furnace. Through an RF-microplasma setup, nickel, manganese, and cobalt (NMC) particles were produced from a metal acetate solution under a plasma assisted chemical vapor synthesis. These produced particles were then sintered for less time and under a lower temperature than traditional cathode synthesis methods, to produce a lithiated NMC type cathode. The product was examined physiochemically and electrochemically to examine its structure and functionality. The produced product was reversibly cycled over 60 times with a peak specific capacity around 150 mAh/g, and with future process refinement could meet the current capacity standards set by more established synthetic routes
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.
Development of Bromine Adsorbing Carbon Felt Electrode by Coating of Nitrogen-Doped Mesoporous Carbon Layer for Highly Stable Flowless Zinc-Bromine Battery
Authors: Cho Youngin , Kim Jong Gyeong , Pak Chanho
Published: August 2024

Renewable energy is well known for the extreme volatility of power production, and secondary battery-based energy storage systems (BESS) are the key to the novel and safe energy industry to expand the supply of renewable energy. Currently, lithium-ion battery-based ESS is commonly used, but the frequent ignition accidents from these ESSs rather become an obstacle to the growth of the renewable energy field. Among the redox batteries, the flowless zinc-bromine battery (FLZBB) is studied as the alternative since it uses a non-flammable and cost-effective aqueous Zn- Br2 electrolyte. However, its main challenges are that bromine (Br2) and polybromide anions (), formed at the positive electrode during the charging process, cross over to the negative electrode due to the difference in chemical potential between the electrodes. The diffused Br2 oxidizes the zinc metal, electrodeposited on the negative electrode, and causes a self-discharge reaction that consumes the charging active material and Br2 the battery performance and life. Herein, we present a nitrogen-doped mesoporous carbon coated on the pristine graphite felt fibers (NMC/GF). By uniformly forming a nitrogen-doped porous carbon material on the GF fibers through the evaporation-induced self-assembly (EISA) method, it is a simple and cost-effective method to develop the structural and properties of the GF positive electrode to increase the ability of adsorption and storing the active materials, Br2 and polybromide anions (,, and ) generated during the charging process. In addition, it also improved the bromine redox reaction kinetics by having a strong affinity with the aqueous Zn-Br2 electrolyte. This facilitates long-term charge/discharge cycles, enabling high performance and improved durability for Coulombic efficiency over 95% for 5000 cycles in the FLZBB single-cell platform at a current density of 20 mA cm-2 and a high-rate areal capacity of 2 mAh cm-2.
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.
(Invited) The Role of Carbon in Enabling Stable Solid State Batteries
Authors: Liu Ping
Published: August 2024

Carbonaceous materials are widely used as the anode materials in rechargeable lithium-ion batteries. In that context, they serve as the host for lithium ions. Their structural stability and limited volume changes underpin the long-term stability of the batteries. In solid-state batteries, however, their roles have evolved. With the focus on raising cell energy density and the promise of stable operation of lithium metal due to the absence of organic solvent, carbon has not been widely studied as an anode material. Unfortunately, the promise of lithium metal has encountered significant challenges: it chemical reacts with virtually all known solid state electrolytes; lithium also grows dendrites which can eventually lead to shorting; the stripping of lithium is also often inhomogeneous which had led to void formation at the interface. To address these challenges, carbonaceous materials have been reintroduced.

In this talk, we overview several applications of carbonaceous materials in solid state batteries. We have shown that graphite can be engineered as a 3D host for lithium deposition. Lithiated graphite becomes lithiophilic with low nucleation barrier for lithium metal deposition. The voids between the graphite particles can accomodate lithium metal. As a result, the critical current density and cycling stability of both full cells and symmetric cells have greatly improved. We note that in this context, the anode is essentially a graphite electrode that experiences intentional overlithiation.

In a second application, we show that carbon can serve as an effective interlayer between lithium and the solid electrolyte. This interlayer reduces the side reaction between lithium and the electrolyte, thus greatly improving the cycle life and coulombic efficiency. It is rather surprising that upon lithiation, the interlayer enables lithium transport and preferential lithium deposition at the carbon/lithium interface, rather than the carbon/electrolyte interface. This desirable outcome is observed despite the fact that the interlayer itself is electrically conducting. We studied a wide variety of carbon materials in terms of surface area, crystal structure, and defect density. With the optimized carbon material, critical current densities of over 30 mA/cm2 have been observed. The mechanism of lithium transport will be discussed along with the design criteria for using carbon as an effective mixed electron and ion conductor.
(Invited) 3D Carbon-Based Hierarchical Electrodes for Energy Storage
Authors: Lu Jennifer , Chiovoloni Samuel , Ashworth Austin , Onffroy Philip , Yao Bin , Saccone Max , DeSimone Joseph , Li Yat
Published: August 2024

Abstract: Carbon-based 3D hierarchical electrodes with appropriate spatial distributions of pores are expected to empower rapid and controllable electrochemical reactions. The ability to fabricate such an electrode, with tunable geometries comprised of continuous nano- and micro-conduits, allows simultaneous optimization of conversion capacity as well as reaction rate. Such manufacturability holds great potential to redefine the future of energy storage, electrocatalysis and chemical production for a sustainable future.

In this presentation, I will outline two convergent strategies that involve the integration of additive manufacturing with several decades of advancements in nanomaterials synthesis, coupled with conventional pyrolysis – for creating such electrodes. The primary structure of 3D carbon-based electrodes was fabricated by either direct 3D writing, or the transition metal assisted pyrolysis of 3D-printed polymer templates. The secondary structure was established by employing bottom-up synthesis approaches: (a) SiO2 nanoparticle templates to create nanoscopic porous structures or (b) nanochannels formed through direct growth of carbon nanotubes. We have demonstrated that the primary and secondary structures can be formed by a single step. After monolithic integration of a tertiary structure to reveal sites for electrochemical conversion, these 3D architected electrodes offer impressive charge storage capacities while maintain excellent rate capability.

By exploiting the short mass diffusion lengths, we have demonstrated that the new energy storage devices can operate at temperatures as low as -70°C without the requirement of a heater. Furthermore, the incorporation of a high loading of active materials in our 3D electrodes allows for concurrent enhancement of both energy density and power density. These scalable fabrication protocols address two critical challenges – sluggish mass transfer in 3D and the lack of accessible active sites, thereby offering a pathway to harness electrochemical reactions in 3D. This work offers an adaptable solution across a broad spectrum of industries.
(Invited) Engineering Local Chemical Environments for Efficient Aqueous Energy Storage Systems
Authors: Lukatskaya Maria
Published: August 2024

Electrochemical energy storage is vital as we transition towards sustainable energy sources. Energy storage systems must meet performance criteria related to energy and power density, safety, and cost. Battery metrics optimization depends on the end-application of the energy storage device. Selection of energy storage device components, such as electrode materials and electrolytes, directly affects performance metrics. The local chemical environment of these components can impact the transport of ions, charge transfer reactions, and stability. As such, understanding the role of local chemical environments is vital in developing next-generation energy storage technologies.

This talk will discuss the importance of local chemical environments in sustainable energy technologies. We will explore how optimizing the chemical properties of electrode materials and electrolytes can improve energy storage system performance metrics, and how this can lead to more sustainable and environmentally friendly energy solutions.
Imaging Dopamine Modulation in Brain Acute Slices for Cocaine Addiction Study with Near-Infrared Carbon Nanotube Sensors
Authors: Ouassil Nicholas , Komatsu Natsumi , Landry Markita P
Published: August 2024

Drug addiction is a pressing issue in modern American society that demands thorough research into its mechanisms. Cocaine locomotor sensitization is a well-established model for understanding the physiological effects of cocaine abuse. Previous studies have established loss of dopamine D2 autoreceptors in striatal tissue as a consequence of locomotor sensitization, yet how these differences in autoreceptor expression affect dopamine signaling remains unclear. Herein, we utilized non-genetically encoded near-infrared fluorescent nanosensors based on carbon nanotubes to image dopamine modulation in live acute coronal brain slices. By leveraging dopamine D2 receptor agonists along with the dopamine nanosensor, we developed a method to identify changes in density of functional D2 autoreceptors and dopamine signaling aberrations that accompany addiction, at the level of individual dopamine synapses. We apply the method to compare changes in D2 autoreceptor activity in the Nucleus Accumbens core in cocaine sensitized and saline (control) mice after prolonged cocaine exposure (5 days). Our preliminarily data indicates the decrease in the number of D2 autoreceptor in cocaine sensitized mice, consistent with the previous studies, and suggests that it leads to higher level of dopamine signaling. Furthermore, we confirm dopamine signaling changes by application of D2 Agonists (quinpirole) are from loss of individual dopamine release sites rather than changes in the quantity of dopamine released, or changes in dopamine reuptake kinetics. Our study provides a route to understand the changes in neuromodulation that underlie the neurobiology of addiction and other dopamine-centric neurological conditions.
(Invited) Purification of Enantiomeric Pairs of DNA-Wrapped Carbon Nanotubes and Their Use in Bilateral Chiral Sensing
Authors: Zheng Ming
Published: August 2024

This presentation will focus on our recent progress in purifying enantiomeric pairs of DNA-wrapped carbon nanotubes (DNA-CNTs) via the aqueous two-phase extraction method. We will also discuss a potential application of enantiomeric pairs of DNA-CNTs in bilateral chiral sensing.