bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Mixed Protonic-Electronic Membrane Reactors; Converting Hydrocarbon Resources and CO2 to Fuels
Authors: Wachsman Eric 
Published: December 2020

Membrane reactor technology holds the promise to circumvent thermodynamic equilibrium limitations by in-situremoval of product species, resulting in improved chemical yields. Recent advances in mixed-conducting oxide-membrane technology present the possibility for a dramatic reduction in the cost of converting petroleum, coal and biomass derived feed stocks to hydrogen and other “value added” hydrocarbons. We have developed novel membrane reactor technology, based on high temperature proton conductors, that can convert a wide range of hydrocarbons to pure H2, and syngas for synthesis of liquid fuels and chemical feed stocks. By simultaneous H2 permeation and catalysis, we have demonstrated the ability to increase water gas shift yields >70% over thermodynamic limitations. Similarly, we have demonstrated increases in steam reforming yields, and the ability to reform CH4 with CO2.
More recently we have developed single-step gas to liquid reactors that convert natural gas to C2+ products with high yields and no unwanted oxidation byproducts. The direct utilization of CH4 and CO2 to simultaneously produce C2+hydrocarbons (C2 and aromatics) and syngas (CO and H2) on opposite sides of a mixed protonic-electronic conducting SrCe0.7Zr0.2Eu0.1O3-δ membrane reactor is demonstrated. On one side (interior) of the membrane reactor, direct non-oxidative methane conversion (DNMC) over an iron/silica catalyst produces C2+ hydrocarbons and H2. On the other side (outer surface) of the membrane, permeated H2 (driving the DNMC reaction) reacts with a CO2 sweep gas to form CO and water via the reverse water gas shift (RWGS) reaction. This novel single H2-permeable membrane reactor simultaneously addresses both reduction of greenhouse gas (CO2 and CH4) emissions as well as production of value-added hydrocarbon products (C2+, CO, and H2) with in situ gas separation.
Performance and Stability Enhancement of Ni-Based Cermet Anode Using Atomic Layer Deposited Ruthenium for Direct Methane-Fueled Low-Temperature Solid Oxide Fuel Cell
Authors: GO Dohyun , Kye Seunghyeon , Yang Byung Chan , Kim Hyong June , Shin Jeong Woo , Lee Sungje , An Jihwan 
Published: December 2020

Nickel (Ni) based cermet, e.g., Ni-doped zirconia(e.g., YSZ) and Ni-doped ceria(e.g., GDC), is the most widely used anode material for solid oxide fuel cell (SOFC). SOFC has been considered as a promising energy converter because of its high efficiency, eco-friendliness, and fuel flexibility. However, recently, SOFC operating below 500°C with more conventional fuels such as hydrocarbon or alcohol are actively studied for overcoming the limitations of high temperature SOFC, e.g., durability, cost, and limited application. Therefore, the necessity of improving the performance and stability of Ni-based anode is aroused because it shows relatively slow hydrocarbon and alcohol oxidation kinetics in the low-temperature regime and vulnerable to carbon deposition. To improve kinetics and stability of Ni-based anode upon hydrocarbon fuel-based operation, various kinds of metal catalysts, e.g., copper, palladium, iron, etc., have been applied using fabrication techniques such as wet synthesis, infiltration, vapor deposition, etc.
In this study, ruthenium (Ru) having high catalytic activity and carbon coking toleration is applied to Ni-based cermet anode used in methane-fueled low-temperature SOFC. In particular, atomic layer deposition (ALD), which can deposit nanoparticles conformally on porous structures, is used for depositing Ru nanoparticles on nano-structured Ni-based cermet anode. ALD Ru nanoparticles fabricated in such a way are well-dispersed on the surface of Ni-based cermet anode and effectively improve the performance and stability of the anode when it is operated with methane-fuel. Especially, Ni-based anode with optimal ALD Ru thickness, i.e., 10nm in thickness, shows 40% higher maximum power density than those without ALD Ru overcoating when operated with methane fuel.
Development of Various Solid Oxide Cell Technology and Stack Platforms at Nexceris, LCC
Authors: Dogdibegovic Emir , Lockhart Cody , Kopechek David , Sellers Chad , Arkenberg Gene , Swartz Scott , Kidner Neil J. 
Published: December 2020

With over 25 years of experience in solid oxide fuel cell (SOFC) materials, components and stack development, Nexceris has been rapidly expanding the technology portfolio. Development in Fuel Cell Materials, FlexCell and ChromLok technology are only a few examples. Stack testing capability up to 5 kW has been developed. Modular high-performance stack platforms that accommodate cells from 40 cm2 to 250 cm2 are being utilized, depending on customer requirements and system needs.
Recently, Nexceris expanded its R&D efforts into solid oxide electrolysis cell (SOEC) technology. Initial performance of -1.5 A/cm2 and 500-hour durability tests at 1.3-1.4 V and 800 °C in short stacks show promising platform for further SOEC performance and durability improvements. Besides anode- and electrolyte- supported cell development, metal-supported cells (MSCs) have also been successfully developed at Nexceris and scaled to 250 cm2. The structure, performance and durability of MSCs are being continuously improved. Short 5-cell stacks are currently being demonstrated and the results will guide further stack development. A wide range of cell and stack technology developed at Nexceris provides capability to tailor cells and stacks based on user applications, whether those include continuous non-interrupted stationary operation or dynamic operation such as rapid thermal and redox cycling in mobile applications.
Redox Re-Activation of Steel-Supported Solid Oxide Cells
Authors: Skafte Theis Løye , Tucker Mike C , Graves Christopher 
Published: December 2020

Wide-spread commercial application of the solid oxide cell (SOC) technology is hindered by limited lifetime and high fabrication cost. Development has largely been focused on material choice and manufacturing techniques to improve performance and mitigate degradation mechanisms.
Here we instead present an innovative approach to prolonging device lifetime, namely by re-activating the electrodes periodically during operation. This can counteract steady degradation, and thereby avoid expensive replacement of the damaged stack. With the right procedure and materials, this can be accomplished by simple redox cycling.
First, a comprehensive overview of several known re-activation methods for different electrodes is given, including the current mechanistic understanding of each one. Second, we demonstrate the process on model electrodes for proof-of-concept. Third, we optimize the procedure for next-generation metal-supported SOCs, which have the potential to substantially lower manufacturing costs. For these specific cells it is investigated what the optimal procedure is, whether both electrodes can be re-activated, whether the effect is long-lasting, and how the effectiveness compares to all-ceramic electrodes. Lastly, we examine the underlying mechanism.
Figure 1. Electrochemical impedance spectra of a steel-supported SOC being re-activated with a redox cycle after 500 h of aging at open-circuit voltage, 650 °C and H2:H2O 0.8:0.2.

Figure 1
Voltammetric and Spectroscopic Investigations of L-Cysteine Interactions with Bismuth Ions
Authors: Cheek Graham , Pena Dominik V 
Published: December 2020

Bismuth compounds have been widely used for many years as treatments for gastric conditions.1 The electrochemical activity of bismuth suggests that voltammetric studies can provide some insights into interactions of bismuth with naturally occurring ligands found in the digestive system. Of particular interest is L-cysteine, the sulfhydryl side chain of which can interact with bismuth(III) ions.1 Previous work in this laboratory has characterized the electrochemical behavior of L-cysteine in aqueous systems,2 and the present work involves the effect of L-cysteine on the voltammetric behavior of bismuth(III) nitrate, bismuth(III) citrate, and bismuth(III) salicylate. In order to simulate the pH level of gastric contents, studies have been carried out in 0.100 M HCl and 0.100 M HNO3 using the techniques of cyclic voltammetry and square wave voltammetry. Voltammetric scans have been carried out at both glassy carbon and boron-doped diamond electrodes in order to avoid the reduction of protons, which would occur at platinum and gold electrodes. It was found that L-cysteine addition greatly increases the solubility of bismuth(III) nitrate in 0.100 M HNO3, as seen by an increase in the bismuth reduction current and also in the subsequent stripping current of the bismuth deposit. Bismuth(III) salicylate was found to be soluble at the 1 mM level in 0.100 HNO3, and L-cysteine additions produced potential shifts in the voltammetric processes for the bismuth(III) system. These results support the complexation of bismuth(III) salicylate by L-cysteine, even under these very acidic conditions. Similar studies for bismuth(III) citrate were also carried out. Finally, the electrochemical behavior of bismuth(III) nitrate in pH 7.4 MOPS3 buffer was also investigated. It was found that bismuth(III) nitrate (nominal 1.0 mM) was essentially insoluble in this medium; however, additions of L-cysteine produced voltammetric currents typical of the 1 mM concentration level. Initial reduction of bismuth(III) was followed by bismuth stripping peaks at more positive potentials. This behavior supports the complexation of bismuth(III) ion by L-cysteine at pH 7.4. Further evidence of this complexation was found by UV-VIS studies of bismuth(III) nitrate in pH 7.4 MOPS buffer with incremental additions of L-cysteine. An absorbance band at 325 nm appeared as L-cysteine was added, the absorbance of which remained constant after the 1:2 Bi3+: L-cysteine point. These results indicate formation of Bi(Cys)2 under these conditions. As a whole, the present studies indicate the ability of bismuth(III) compounds to interact with L-cysteine over a range of pH levels.
References
1. H. Li, R. Wang, and H. Sun, Acc. Chem. Res., 52, 216 (2019).
2. G. T. Cheek and M. A. Worosz, ECS Trans., 164(12), D707 (2016).
3. C. M. H. Ferreira, I. S. S. Pinto, E. V. Soares, and H. M. V. M Soares, RSC Advances, 5(39), 30989 (2015).
Improvement of Total Capacity of a Lactate/Oxygen Biofuel Cell Based on a Three-Enzyme-Modified Carbon Cloth Electrode
Authors: Tsunaga Motoki , Hoshi Yoshinao , Watanabe Hikari , Shitanda Isao , Mikawa Tsutomu , Tsujimura Seiya , Itagaki Masayuki 
Published: December 2020

A biofuel cell using MgO-templated carbon (MgOC) is highly attention as a wearable power source1). A lactate/oxygen biofuel cell, in which lactate oxidase (LOx) is normally used, utilize two-electron oxidation of lactate to pyruvate 2). On the other hand, it is possible to improve the total capacity of the lactate/oxygen biofuel cells by using an enzyme cascadereaction3
).
In the present study, we developed a new biofuel cell that modifies pyruvate decarboxylase (PDC) and acetaldehyde dehydrogenase (ALDH) with LOx in anode. A total of four-electron oxidation reaction can be occurred from lactate to acetic acid via acetaldehyde. In this study, we examined the relationship between the battery capacity and the current density by enzyme cascade in detail.
A carbon cloth was used as anode. 1,2-naphthoquinone, ALDH (20 units), PDC (40 units) and LOx (20 units) were dropped on the anode surface, successively. On the other hand, a MgO-templated carbon (MgOC)-coated carbon cloth was used as cathode. A bilirubin oxidase (BOD, 9 units) was immobilized on the MgOC-coated carbon cloth surface. The performance of the biofuel cell was evaluated by performing chronopotentiometry at a current density of 1 mA cm-2 and 2 mA cm-2. The electrolyte (50 mL) used was 1 mol dm-3 phosphate buffer (pH 7.0) containing 100 mmol dm-3 lactic acid.
Figure 1 shows the chlonopotentiogram of the biofuel cell. It was confirmed that the open-circuit potential of the multi-enzyme-modified biofuel cell was increased compared with that of a conventional lactic acid biofuel cell [2]. The voltage of multi-enzyme-modified biofuel cell was firstly about 0.6 V and then gradually decreased to 0.4 V. Finally, the voltage was drastically dropped at 0 V after 330 s. On the other hand, a voltage of a biofuel cell, which only LOx was modified on the anode, was dropped at 150 s at 1 mA cm-2. The time to reach 0 V was shorter at 2 mA cm-2 at each anode, due to the drastically decrease of the substrate concentration of the electrode surface. From these results, it was indicated that the capacity of the biofuel cell was improved by the enzymatic cascade reactions.
(1) A. Niiyama et al., Journal of Power Sources, 427, (2019), 49.
(2) I. Shitanda et al., Journal of Power Sources, 436, (2019), 226844.
(3) D. Sokic-Lazic et al., Electrochimica Acta, 56, (2011), 10772.
Acknowledgements This work was partially supported by JST-ASTEP Grant Number JPMJTS1513, JSPS Grant Number 17H02162 and Private University Research Branding Project (2017-2019) from Ministry of Education, Culture, Sports, Science and Technology, and Tokyo University of Science Grant for President's Research Promotion．

Figure 1
Microelectrode Arrays for Present and Future Electrophysiological Applications
Authors: Wanzenboeck Heinz , Schuller Patrick , Mika Johann , Taus Philipp , Pribyl Markus 
Published: December 2020

In vitro diagnostic devices have highly esteemed platforms for toxicological testing, drug screening and even for theranostics. An extremely promising device type are microstructured devices, often referred to as biochips, that can be coupled with in vitro cell cultures. Employing microfluidic structures devices such as cell-chips and organ-on-a-chip devices have been developed to mimic the microenvironment of the human body. By implementing microelectrodes on the chip it is facile to utilize the benefits of microelectronics - the label-free, non-destructive, permanent real-time measurement of cellular processes.
With electretic cells the action potential of cells can be directly measured, while other non-electrically cells can be measureds via their impedance. We will present devices on both concepts from our research. We will present sophisticated biomedical devices, were used to record the electrophysiological activity the neurite part of nerve cells of in real-time. With an axon isolation device a delicate microfluidics system is combined with microelectrodes inside of microchannels just large enough for axonal and dendritic structures.
Also the biocompatibility of electrode materials is essential, and the relevance of cyclic voltammetry for checking the safe voltage range of microelecrtrodes will be explained with practical examples. Fabrication routes, benefits and limitations of microelectrode arrays. interdigitated electrode sensors and even 3D nanoelectrodedes will be discussed.
An outlook on future devices featuring arrays 3D nanoelectrodes and microstructured guidance structures will be given.
Crystalline-to-Amorphous Phase Transformations As a Key Ingredient to Enhanced Rate Performance and Cycle Life in Mg- and Na-Ion Battery Anodes: Operando x-Ray Scattering Studies
Authors: Welborn Samuel S. , Wang Lin , Li Manni , Qiu Tian , Foucher Alexandre , Stach Eric A. , Rappe Andrew , Detsi Eric 
Published: December 2020

The increasing popularity of Li-ion batteries in new applications such as electric vehicles is expected to cause the key resources (Li, Ni and Co) used in these batteries to become scarce. Alternative battery technologies, including Mg-ion, Na-ion, and metal-air batteries are therefore desirable. In this talk, I will discuss the use of operando wide-angle X-ray scattering (WAXS) to study the crystalline to amorphous phase transformations that are key to the outstanding performance of state-of-the-art alloy-type Mg- and Na-ion anodes. The 1st part of the talk will be on the impact of the crystalline-to-amorphous transformation on batteries cycle life. Here I will discuss our novel self-healing Ga/Mg anode, which holds the current record for cycle performance and rate capability in alloy-type Mg-ion battery anodes, owing to a crystalline Mg2Ga5 to amorphous liquid Ga phase transformation occurring near room temperature, preventing the well-known pulverization issue in alloy-type anodes.[1] The 2nd part of the talk will detail the impact of the crystalline-to-amorphous transformation on the rate capabilities of batteries. Here, I will present our nanoporous Sb/Na system, which transforms from crystalline Na3Sb to crystalline Sb, going through an amorphous intermediate. It will be shown using a combination of WAXS, electrochemical characterization, and computational study based on ab initio grand canonical (aiGCMC) simulations that the amorphous intermediate phase favors high rate Na storage in Sb.[2]
[1] Wang, L., Welborn, S. S., Kumar, H., Li, M., Wang, Z., Shenoy, V. B., Detsi, E.: High‐Rate and Long Cycle‐Life Alloy‐Type Magnesium‐Ion Battery Anode Enabled Through (De)magnesiation‐Induced Near‐Room‐Temperature Solid–Liquid Phase Transformation.
Adv. Energy Mater. 2019, 1902086. https://doi.org/10.1002/aenm.201902086

[2] M. Li, T. Qiu, S. Welborn, A. Foucher, B. Lesel, E. Stach, A. M. Rappe, E. Detsi: Understanding the Fast Kinetics of Sodium Storage in Antimony (unpublished)
Towards an Understanding of the SEI Formation and Lithium Preferential Plating on Copper
Authors: Menkin Svetlana , O'Keefe Christopher A. , Gunnarsdottir Anna B. , Dey Sunita , Pesci Federico , Shen Zonghao , Aguadero Ainara , Grey Clare P. 
Published: December 2020

‘Anode-free’ batteries present a significant advantage due to their substantially higher energy density and ease of assembly in a dry air atmosphere. However, potential safety issues due to lithium (Li) dendrite growth rather than smooth Li metal plating on the Cu current collector, and low cycling coulombic efficiency during their operation are delaying their practical implementation. To understand the interplay between Cu surface chemistry and the morphology of the plated Li, we studied the SEI formation on Cu and the preferential plating of Li using ssNMR, insitu NMR, XPS, ToF-SIMS, SEM and EIS.
A native interphase layer (N-SEI) is formed instantaneously on copper current collectors upon their immersion in LiPF6-based electrolyte. The nature of the N-SEI is affected by the copper interface composition, homogeneity and formation time. In addition to the typical SEI components, it contains CuxO and its reaction products. Parasitic semi-reversible electrochemical reactions were observed with in-situ NMR measurements of Li plating efficiency during the first five cycles. The morphology of the plated lithium is affected by the SEI homogeneity, current density and rest time in the electrolyte before the plating. The preferential plating of Li is governed by the distribution of ionic conducting compounds rather than electronic conducting compounds.[i]

[i] Menkin, Svetlana; O'Keefe, Christopher A.; Gunnarsdottir, Anna B.; Dey, Sunita; Pesci, Federico; Shen, Zonghao; et al. (2020): Towards an Understanding of the SEI Formation and Lithium Preferential Plating on Copper. ChemRxiv. Preprint. https://doi.org/10.26434/chemrxiv.12839792.v1
Study of Li Metal/C Paper Electrodes for Li/S Batteries By Operando Dilatometry
Authors: Fatahine Mohamed , Guay Daniel , Roue Lionel 
Published: December 2020

The use of Li metal anode in rechargeable batteries such as Li-S and Li-air is challenging due to the uncontrolled formation of lithium dendrites during repeated charge/discharge cycling, which induces various issues such as cell short circuit, aggravated adverse reactions, dead Li formation, polarization increase and large volume changes, resulting in safety concerns and low coulombic efficiencies [1]. Different characterization techniques have been used to study Li metal electrode morphological changes associated with Li dendrite formation such as scanning electron microscopy, transmission electron microscopy, atomic force microscopy and optical microscopy [2]. A large part of these characterizations were performed ex situ or in situ but under static conditions (no cycling) or operando using open cell requiring none volatile electrolyte, giving limited information on the Li growth dynamics in real systems. Recently, operando synchrotron X-ray tomography has been used to visualize the morphological evolution of Li metal electrodes in various cell configurations (e.g. Li-S cell [3]). However, the limited access to beamtime at synchrotron X-ray sources and challenges with data processing (image segmentation, volume reconstruction, artefact minimization, etc.) are major drawbacks.
In the present study, a simple and low-cost method is used to monitor the electrode thickness variation associated with the Li plating/stripping process. This technique, named ‘’electrochemical dilatometry’’, consists in integrating a gap sensor or a displacement transducer within the electrochemical cell for measuring the vertical displacement of the working electrode during its cycling. It has been successfully applied for studying the volume expansion/contraction of Si-based electrodes for Li-ion batteries [4]. To the best of our knowledge, electrochemical dilatometry has never been applied to the study of Li metal electrodes. In the present study, this technique is used for studying the expansion/contraction behavior of electrodes integrating commercial porous C papers as 3D matrices for Li electrodeposition and compared to what is observed on a 2D Cu foil substrate (Figure 1).

References

[1] X.B. Cheng, R. Zhang, C.Z. Zhao, Q. Zhang, Toward safe lithium metal anode in rechargeable batteries: a review, Chem. Rev 117 (2017) 10403-10473.

[2] D. Lin, Y. Liu, Y. Cui, Reviving the lithium metal anode for high-energy batteries, Nat. Nanotechnol. 12 (2017) 194-206.

[3] G. Torin, G. Vaughan, R. Boucher, F. Alloin, M. Di Michiel, L. Boutafa, J.F. Colin, C. Barchasz, Multiscale characterization of lithium/sulfur battery coupling operando X-ray tomography and spatially-resolved diffraction, Sci. Rep. 7 (2017) 2755.

[4] A. Tranchot, P-X. Thivel, H. Idrissi, L. Roué, Impact of the slurry pH on the expansion/contraction behavior of silicon/carbon/carboxymethylcellulose electrodes for Li-ion batteries. J. Electrochem. Soc. 163 (2016).

Figure 1
New Class of Electrodes to Minimize Tortuosity and Enable Fast Charging
Authors: Roumi Farshid 
Published: December 2020

The major problem with fast charging is that high charge rates are restricted by ionic transport and polarization, addressed today by thinner electrodes at the expense of energy density. The goal is to increase electrode utilization such that a thicker electrode can deliver both high energy density and high charge rates.
We are developing a novel electrode design, called PLE, which enables up to double the rate of electrode utilization, at high charge/discharge rates. It is chemistry agnostic and applicable to today’s anode and cathode chemistries such as Graphite and lithium oxide materials, as well to future chemistries such as silicon and sulfur materials. PLE enables 2X higher rate of discharge, compared to conventional electrodes, at 5m Ah/cm2 at C/3. Originally developed by our team at Caltech in 2015, PLE is a laminated electrode structure, based on laminating 2 layers of unit electrodes to make a thicker electrode

Figure 1