bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Engineering Nanocomposite Substrates for Metal Deposition
Authors: Liu Ping 
Published: August 2024

Reversible metal plating is at the heart of aqueous based energy storage. Since virtually all metal anodes, e.g., Fe, and Zn, operate outside the stability window of water, it is thus essential to minimize their surface area by controlling the nucleation and growth during deposition and the pit formation during stripping.
While epitaxial growth has shown promise as exemplified by the horizontal zinc deposition on graphene, an approximate heteroepitaxy, we will focus our effort in developing a nanocomposite substrate that promotes uniform nucleation sites and fast surface transport. The strategy is potentially highly scalable to address the need for large scale storage. Recently, we have shown that a nanocomposite substrate can induce single crystalline Li growth. By reacting FeF3 with Li, a nanocomposite of Fe and LiF is formed which features Fe nanoparticles of < 2 nm in size uniformly distributed in a matrix of LiF. Despite the global lithiophobility of the substrate, nano Fe domains provide energetically uniform nucleation sites for Li deposition while LiF enables rapid surface transport. Corporative merging of neighboring seeds lead to the formation of single crystalline Li. Unlike single crystal substrates, the nanocomposite features uniformly distributed, energetically equivalent sites for nucleation.
We have adopted a similar strategy for Fe and Zn deposition. Preliminary results show that significantly improved macroscopic uniformity is achieved with the nanocomposite substrate. We will discuss materials requirements for operation in an aqueous environment and the general applicability of the approach for other materials.
HE3DA Thick Tablet Electrode Architecture - Large Lithium Cells for Energy Storage
Authors: Prochazka Jan 
Published: August 2024

Large energy storage applications require ultimate safety, economical manufacturing and full recyclability of the batteries. HE3DA lithium battery technology platform with 3-D electrode architecture meets all these demands. The 3D cell construction, together with ceramic composite separator increases battery safety by orders of magnitude. Easy disassembling and separating of the materials after the life end of the battery makes recycling a profitable secondary source of battery materials. Recycling of this type of battery already meets parametres set for 2050.
Main features of this technology and 3D cell parameters produced in the commercial production will be discussed. Advantages of these cells in large energy storage units will be demonstrated.

Figure 1
Diketopyrrolopyrroles As Performance Enhancing Additives for Lithium-Sulfur Batteries
Authors: Searle Joanne , Denison Benjamin , Malagreca Ferdinando , Kibler Alexander , Saywell Alexander , Walsh Darren Anthony , Johnson Lee R , Newton Graham 
Published: August 2024

Although the lithium-ion battery (LIB) has been instrumental in global electrification, more premium applications (such as electrification of aircraft) require capacities and performance beyond the capabilities of traditional LIB chemistries[1]. Lithium-sulfur (Li-S) batteries are a front runner among next generation battery technologies thanks to their very high theoretical capacities (1675 mAh g-1) and impressive gravimetric energy densities (2,700 Wh kg-1) [2,3]. Despite their potential, there are numerous chemical challenges (polysulfide shuttle, dendrite formation etc.) that must be overcome before widespread adoption of the technology [4]. Electrolyte additives have been explored as a means to facilitate the electron transfer reactions that occur within the cell and improve cell capacity and cyclability [5].
Diketopyrrolopyrroles (DPPs) are a class of organic π-conjugated compounds that have garnered significant interest in a variety of electrical applications, including solar cells and sensors [6]. The high electrochemical tunability, made possible through the editable organic structure, makes them suitable candidates for redox active electrolyte additives. Here, we explore DPP derivatives as a novel class of electrolyte additive for improving the cell cycling performance of Li-S batteries. A variety of electrochemical and analytical techniques have been utilised to assess the suitability of DPPs as redox active additives, building an understanding of their interactions with active materials in a Li-S cell. Galvanostatic cycling allows us to connect these electrochemical findings to cell cycling performance, where we observe a large enhancement in capacity. We also present an alternative statistical approach to cell data analysis, providing a more concrete method to assessing cycling enhancement than that shown throughout literature.

Figure 1. A box plot displaying the discharge capacities at specific cycle numbers for standard (light grey) and DPP (dark grey) cells to provide a statistical comparison.
References:
[1] T. Kim, W. Song, D.-Y. Son, L. K. Ono and Y. Qi, J. Mater. Chem. A, 2019, 7, 2942–2964.
[2] A. Fotouhi, D. J. Auger, L. O’Neill, T. Cleaver and S. Walus, Energies , 2017, 10.
[3] S. Gifford and J. Robinson, Faraday Insights, 2020, 1-5.
[4] A. Manthiram, Y. Fu, S.-H. Chung, C. Zu and Y.-S. Su, Chem. Rev., 2014, 114, 11751–11787.
[5] J. M. Cameron, C. Holc, A. J. Kibler, C. L. Peake, D. A. Walsh, G. N. Newton and L. R. Johnson, Chem. Soc. Rev., 2021, 50, 5863–5883.
[6] C. Zhao, Y. Guo, Y. Zhang, N. Yan, S. You and W. Li, J. Mater. Chem. A, 2019, 7, 10174–10199.

Figure 1
Electrochemical CO2 Reduction on Silver – a Perspective through Electrochemical Impedance Spectroscopy
Authors: Sivasankaran Monisha , Sorrentino Antonio , Vidakovic-Koch Tanja 
Published: August 2024

Anthropogenic carbon rise in the earth's atmosphere is the leading cause towards global warming. Electrochemical CO2 reduction (eCO2RR) is one of the most promising sustainable pathways for the utilization and recycling of anthropogenic carbon. The current challenge in eCO2RR is to make the process more energy efficient and to drive the selectivity toward the desired products. eCO2RR normally takes place in parallel with hydrogen evolution reaction (HER). Additionally, dependent on catalyst material and potential different C-products can be obtained. The mechanistic understanding of the interplay between different reactions is still limited, since the involved reactions are characterized by faster kinetics and/or different adsorbed species as well as mass transfer dependences than the other ones. Moreover, we have recently shown that under dynamic conditions eCO2RR product selectivity towards CO can be tuned1. In that study, we developed a simple model and identified key kinetic parameters which govern product selectivity under dynamic conditions. The model included only the electrochemical kinetics of two parallel reactions without consideration of adsorbed species or mass transport limitations. Therefore, some of the experimental observations could not be completely explained. In such complicated cases involving different physicochemical phenomena acting in parallel at different time scales, the use of electrochemical impedance spectroscopy (EIS) to analyse the system could shed light on the understanding of the process.
In this contribution, we have developed a mathematical model which couples micro-kinetics with continuum transport. At first, the model was validated under steady-state conditions. The experiments have been performed under different conditions (mass transport and buffer concentrations) on silver rotating disk electrodes and the product distribution (H2 and CO) has been determined with the help of online gas chromatography. This model was then used to calculate EIS. Based on this approach, we present here a detailed interpretation of the EIS spectrum during eCO2RR and the features obtained at different applied electric potentials. Key insights are drawn about the role of charge and mass transport as well as adsorbed intermediates on the observed features.

References

1.Miličić, T.; Sivasankaran, M.; Blumner, C.; Sorrentino, A.; Vidakovic-Koch, T., Pulsed electrolysis: explained. Faraday Discussions 2023.
Ru Decoration By PEALD for Bifunctional Oxygen Electrocatalysis in Solid Oxide Cells
Authors: Li Haoyu , Kim Hyong June , Garcia ThomasJae , Park Geonwoo , An Jihwan , Lee Min Hwan 
Published: August 2024

Solid oxide cells (SOCs) are electrochemical devices that have garnered significant attention due to their high efficiency, fuel flexibility, and reversibility for operation in both fuel cell and the electrolysis modes. However, the relatively high operating temperature (typically > 800 °C) required presents various challenges such as fast degradation, high operating costs, and slow start-up. To overcome these issues, significant efforts have been made to decrease the operating temperature, but this causes a dramatic decrease in performance due to the low catalytic activity of typical electrode materials. One strategy to increase the catalytic activity is to introduce highly active nanoparticles onto a conventional electrode backbone, but while noble metals such as Ru and Ir have been utilized as oxygen evolution reaction (OER) catalysts, their widespread application in SOECs is hindered by their high cost and limited availability.
In this presentation, we demonstrate a highly effective approach to enhance air electrode performance through the deposition of an ultrathin layer of metallic Ru, as thin as ∼7.5 Å, onto (La0.6Sr0.4)0.95Co0.2Fe0.8O3-δ (LSCF) using plasma-enhanced atomic layer deposition (PEALD). The Ru-decorated cell exhibited a current density of 656 mA cm–2 at 1.3 V, significantly outperforming a bare cell (440 mA cm–2 at 1.3 V). The decorated cell also showed a largely enhanced cell durability, which is ascribed to the beneficial role of SrRuO3 that emerges from the reaction between PEALD-based Ru and surface-segregated Sr species, in suppressing Sr segregation and maintaining favorable oxygen desorption kinetics. Further, the PEALD Ru coating on LSCF also reduces the resistance to the oxygen reduction reaction (ORR), highlighting the bifunctional electrocatalytic activities for reversible fuel cells. When the LSCF electrode of a test cell is decorated with ∼7.5 Å of the Ru overcoat and tested in fuel cell mode at 700 °C, this results in a current density of 656 mA cm-2 at 1.3 V in electrolysis mode and a peak power density of 803 mW cm-2, corresponding to an enhancement of 49.1% and 31.9%, respectively, compared to the pristine cell.
Microtubular Electrodes for Efficient Electrochemical CO2/CO Reduction to Value-Added Products
Authors: Rabiee Hesamoddin , Ge Lei , Zhu John 
Published: August 2024

The conversion of carbon dioxide (CO2) or carbon monoxide (CO) to commodity fuels and chemicals, empowered by low-carbon electricity, has attracted much attention as an alternative to conventional routes of chemical production [1]. Numerous studies have focused on CO2 reduction to CO or formic acid and active/efficient electrocatalysts with high Faradaic efficiencies (FEs) have been developed [2]. However, CO2 reduction to higher value C2+ products needs the critical C-C coupling step, and to date, Cu has been the main electrocatalyst for this conversion [3]. Electrochemical carbon monoxide reduction (CORR) to C2+ products has advantages over electrochemical CO2 conversion (CO2RR) as issues such as carbonation, and CO2 loss during CO2RR are omitted in CORR due to the stability of CO in alkaline solutions. Facing common challenges as CO2RR, CORR suffers more from mass transport resistance and intrinsically lower aqueous CO solubility. Therefore gas-diffusion electrodes (GDEs) are desired to boost the formation of triple phases and active sites to obtain higher reaction rates.
Herein for the first time we design Cu-based HFGDEs for efficient CORR to C2+ products with ethylene as the main product. The pristine Cu HFGDEs showed low selectivity towards C2+ products. Therefore, we tuned the Cu catalyst shape morphology and orientated growth of nanocubes on the outer surface of HFGDEs by electrodeposition. Due to the efficient C-C coupling and high C2+
_selectivity of copper nanocubes with dominant Cu(100), the HFGDEs showed exceptionally high current densities in the 1.0 M KOH electrolyte, outperforming conventional GDEs tested for CORR under similar conditions. Compared with CO2RR in a bicarbonate medium, significantly higher current densities and FEs of C2+ products (>90%) and ethylene (>65%) were achieved when the HFGDE were used for CORR. Moreover, lower partial current densities of C2+ were obtained when using the hollow fibers in the non-GDE mode, confirming the significant performance of HFGDEs for achieving high-rate and selective CO reduction through maximizing triple-phase interfaces and local CO concentration. By increasing the concentration of KOH, an ethylene partial current density of 472 mA cm2- was obtained using the flow-cell reactor, indicating the promises of HFGDEs as an emerging electrode configuration for efficient CORR to C2+ products.

Figure 1
Electrochemical CO2 Reduction in the Presence of Flue Gas Impurities: Effect of NOx, SOx and O2
Authors: Van Daele Sam , Hintjes Lieven , Bohlen Barbara , Daems Nick , Breugelmans Tom 
Published: August 2024

Electrochemically converting CO2 to valuable chemical products using renewable energy sources may present solutions to alter current increasing CO2 emission trends. Currently, electrolyzer research is almost exclusively done with pure CO2 streams that - in practice - would originate from carbon capture units that prevent CO2 release to the atmosphere [1]. The capture and purification steps are cost intensive processes which is why direct usage of flue gases that contain impurities is a highly interesting approach. For this reason, the performance of CO2 electrolyzers equipped with state-of-the-art Bi2O3 or Ag catalysts is investigated in this work with an impure CO2 feed stream containing SO2, NO or O2. The short-term effect of highly concentrated SO2 (10 000 ppm) and NO (8 300 ppm) impurities during CO2 electrolysis was previously described [2,3]. Our work [4] elaborates further on this matter through 20 h experiments with flue gas-like concentrations of 200 ppm SO2 or NO. The results show a stable operation without severe FE losses (remains >90%) and structural adaptations to neither Ag nor Bi2O3 by these impurities. The presence of oxygen in flue gas streams at concentrations of several percent is common and causes a major decrease in FE to the target products (CO or HCOO-) during electrolysis. This is a result of the competition between the ORR and CO2RR with the former occurring more preferentially. To overcome this, we have discovered two possible strategies, which allow high FE’s to CO2RR products even in the presence of oxygen. (1) By operating the electrolyzer at a sufficiently high overall current density, all of the O2 entering and reaching the electrode surface gets reduced, allowing the CO2RR to become the dominant reaction. Although this approach has a higher electricity penalty, the extra cost is negligible compared to the cost otherwise associated with the CO2 purification for CO2 streams with an O2 content below 3%. (2) Given that the ORR is mostly occurring at the carbon-based gas diffusion layers another approach to improve CO2RR efficiency in the presence of oxygen is to replace this conventional support with ultra hydrophobic PTFE membrane filters. Since they are inefficient oxygen reduction catalysts, CO2RR again takes up the major fraction of the applied current density. A downside of using PTFE is that an additional conductive layer is required in case the catalyst itself (e.g. for bismuth oxide) is not conductive enough. These results thus not only offer new insights into the impact of gaseous impurities during CO2 electrolysis, but also suggest a strategy to improve electrolyzer performance with O2-containing feed streams.

Bibliography

[1] Lee M.Y., Environ. Sci. and Technol.; DOI: 10.1080/10643389.2019.1631991
[2] Luc W.; JACS, DOI: 10.1021/jacs.9b03215
[3] Ko B., Nature Comm. DOI : 10.1038/s41467-020-19731-8
[4] Van Daele S ., J. Appl. Catal. B, Environ.; DOI: 10.1016/J.APCATB.2023.123345

Figure 1
Key Factors for Electrochemical Carbon Dioxide Reduction at Ni-N-C Catalysts
Authors: Ko Youngdon , Osmieri Luigi , Zhang Hanguang , Zelenay Piotr 
Published: August 2024

Electrochemical carbon dioxide reduction reaction (CO2RR) has the potential to adequately contribute to addressing the energy and environmental challenges faced by the humanity today. The surplus of CO2 produced by burning fossil fuels can be transformed into valuable products by CO2RR. An effective use of this approach on a large scale requires active, selective, and stable CO2 reduction electrocatalysts. Additionally, insightful understanding of interfacial behavior such as water wetting and carbonate formation at the electrode is required to enhance the performance and durability of CO2RR electrocatalysts.1 Atomically dispersed Ni-N-C materials have attracted attention due to their superior selectivity for CO generation.2 Their activity and selectivity of CO2RR are influenced by the metal center and local atomic defects in M-N-C catalysts.3 In addition to catalyst structures, electrode composition and structure have also substantial impact on the activity and selectivity of CO2RR. Particularly, ionomer compositions and the electrode fabrication process can alter the hydrophobicity of the electrode and the local pH on the catalyst, resulting in considerable changes in CO2RR activity and selectivity.
In this presentation, we will report on the performance of various electrodes fabricated with the Ni-N-C catalyst, using different types of ionomers and measured in a flow cell and zero-gap electrolyzer at > 100 mA/cm2 current densities for CO2RR. We will also introduce an approach that aims at reducing carbonate formation at the CO2RR electrolyzer cathode by the modifications to the electrolyte composition, the CO2 inlet humidity, and the electrochemical cell temperature.

Acknowledgement

Research presented in this work was supported by the Laboratory Directed Research and Development program of Los Alamos National Laboratory under project number 20230065DR.

References

(1) Sa, Y. J.; Lee, C. W.; Lee, S. Y.; Na, J.; Lee, U.; Hwang, Y. J. Catalyst–electrolyte interface chemistry for electrochemical CO2 reduction. Chemical Society Reviews
2020, 49 (18), 6632-6665.
(2) Wu, J.; Sharifi, T.; Gao, Y.; Zhang, T.; Ajayan, P. M. Emerging Carbon-Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value-Added Chemicals. Advanced Materials
2019, 31 (13), 1804257.
(3) Liang, S.; Huang, L.; Gao, Y.; Wang, Q.; Liu, B. Electrochemical Reduction of CO2 to CO over Transition Metal/N-Doped Carbon Catalysts: The Active Sites and Reaction Mechanism. Advanced Science
2021, 8 (24), 2102886.
Carbonate Electrolysis for Energy Efficient Direct Air Capture of CO2
Authors: Tong Emily , Kastelic Matthew , McCatty Steve , Lattimer Judith 
Published: August 2024

Yearly global energy related CO2 emissions continue to increase, reaching a record breaking 37 billion metric tons in 2022. As a major greenhouse gas, CO2 levels need to be reduced by 10s of gigatons to prevent the worst of climate change, something that is no longer feasible with net-zero emissions alone. Removing atmospheric CO2 is therefore of critical importance for the future of our planet. While major improvements have been made in CO2 capture from large point sources, a significant portion of CO2 emitted each year from the United States comes from distributed sources such as cars and smaller factories. Due to the dilute concentrations of CO2 in ambient air, Direct Air Capture (DAC) needs to be highly selective to preferentially absorb CO2 to collect useable amounts. These challenges have made current DAC systems quite costly, both energetically and economically, and require vastly different strategies than carbon capture from concentrated sources.
At Giner, we are developing a novel process for the capture and regeneration of CO2 from air into a purified, concentrated CO2 stream that can be redirected as a feedstock for a wide range of applications, including chemical manufacturing and syngas formation. This process involves the capture of CO2 in a concentrated KOH solution using a high-surface area air contactor to form potassium carbonate. The potassium carbonate is then efficiently electrolyzed in a hydrogen-assisted process to regenerate the CO2 at a low operating potential, increasing the electrical efficiency of the process while producing concentrated and purified CO2. In addition, water, hydrogen, and KOH are also regenerated as byproducts that can be recycled back into the CO2 capture and electrolysis processes, reducing both overall energy and chemical consumption.
Giner has developed a unique 3-compartment carbonate electrolysis flow cell. Using our electrolyzer, we have seen operating voltage as low as 1.2 V at 100 mA/cm2 in a 5 cm2 cell for potassium carbonate conversion to CO2 with H2 assisted electrolysis. Significant improvements in operating voltage have come from optimization of gas-diffusion layers (GDLs), cell geometry, and membrane selection. Furthermore, we have achieved >97% pure CO2 formation in the internal flow-through compartment. Currently, scale-up is in progress to apply these developments to approach comparable conditions in a 50 cm2 multi-cell stack. Further developments will enable pairing with an in-house, carbonate based, air contactor allowing for capture and regeneration of over 1 ton CO2
per year.

Acknowledgement: The project is financially supported by the Department of Energy's ARPA-E Office under the Grant DE-AR0001495