bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thermochemical and Techno-Economic Evaluation of Ammonia Synthesis Via Lithium-Molten Salt Processes
Authors: Garzon Fernando H , Matanovic Ivana , Gomez Jamie 
Published: February 2020

Ammonia is an attractive carbon-free energy carrier as it is easily liquified, transported and stored at a lower energy penalty than other non-carbon containing fuels. Anhydrous ammonia production occurs today in large Haber-Bosch (H-B) plants fueled from natural gas. Industrial (H-B) plant techno-economics are poorly suited for remote small-scale ammonia production from renewable energy. Highly efficient ammonia synthesis in small-scale H-B systems does not exist, thus stimulating research towards a low temperature and pressure processes. The thermodynamics of low temperature ammonia synthesis are quite favorable however, the high activation energy for nitrogen reduction requires efficient catalysts and high temperatures. Electrochemistry offers a means to activate the process at lower temperatures however this has proven to be very challenging [1]. Direct electrochemical protonation of nitrogen at low temperatures has produced rates on the order of 10-9 to 10-10 moles/cm2-sec, many orders of magnitude too low for industrial production [2]. Nitrogen reduction on lithium metal occurs spontaneously; hence molten lithium salt processes may prove to be attractive for ammonia generation [3,4,5]. We have evaluated the thermodynamics and techno-economics of intermediate temperature NH3 synthesis processes, based on the spontaneous electro-reduction of nitrogen in lithium ion systems where the potential for lithium is close to metal deposition and the subsequent formation of lithium nitride. The advantage of the molten salt lithium processes is the reaction is autocatalytic however the direct protonation of Li3N with hydrogen yields lithium amide. Protonation with water does yield ammonia however the reaction is very exothermic. The electrolysis of the LiOH product is also a major obstacle as the reaction between LiOH and Li produces Li2O[6]. To overcome this difficulty, we have also evaluated alternative iodide and bromide cycles were lithium electrowinning is known to be viable. The techno-economics of the processes were also considered in a preliminary study.
References:

J. Van der Ham, M. T. Koper , D. G. Hetterscheid , Chem. Soc. Rev., 2014, 43, 5183

T. Gur, E, Energy Environ.
Sci., 2018, 11, 2696

T. Murakami, T. Nishikiori, T. Nohira and Y. Ito, J. Am. Chem. Soc., 2003, 125, 334–335.

A. Joshi, S. Bhavaraju “Ammonia synthesis using lithium ion conductive membrane”, 2012 US Patent, US8916123B2

J. M. McEnaney, et al. Energy
Environ.Sci.,2017,10,1621--1630

O. Takeda, Mi. Li, T. Toma, K. Sugiyama, M. Hoshi, Y. Sato, J.ECS, 2014, 161 (14), D820-D823
Effect of Short Current on the Open Circuit Voltage in a Solid Oxide Fuel Cell
Authors: Lee Choong-Gon , Koomson Samuel , Arthur Ebenzer 
Published: February 2020

The solid oxide fuel cell (SOFC) is a promissing power source with its strong point of solid oxide electrolyte. It allows long time operation without electrolyte supplying. But the electroylte in the SOFC must be very thin to reduce the internal resistance. Thinner electrolyte provides better performance.
In my laboratory, a 100 cm2 class SOFC has been operated. It was supplyed from a SOFC maker in Korea. Since it has several tenth micrometer of electrolyte thickness, it showed voltage behavior of short current when the inert gas step addition (ISA) method [1] was employed. The ISA was firstly used to investigate the flow and partial pressure effect on the performance of molten carbonate fuel cell (MCFC). The method adds nitrogen gas to the anode flow, simultaneously it raises reactant gas flow until the added nitrogen arrives at the cell. Indeed, the nitrogen addition port places about 5 m ahead of the anode cell with 1/4 inch stainless tube, thus several seconds are required to reach to the cell. In the MCFC, there was no voltage change during the period of seveal seconds at open circuit state. Since there was no applied current, it has no doubt. But the SOFC showed clear voltage increase at the tiem period by the nitrogen addition although it was at open circuit state. It is clearly compared with that behavior of MCFC.
In this presentation, the difference will be investigated in terms of short current at the SOFC.
[1] C.-G. Lee, B.-S. Kang, H.-K. Seo, H.-C. Lim, J. Electroanal. Chem., 540, 169–188 (2003).
(Invited) Ionic Conducting Ceramic Membranes – Potential Applications - Materials - Components – Transport in Asymmetric Structures
Authors: Meulenberg Wilhelm A. , Baumann Stefan , Schulze-Küppers Falk , Deibert Wendelin , Guillon Olivier 
Published: February 2020

Ceramic mixed ionic-electronic conducting membranes can be used for the separation of single gases (e.g hydrogen or oxygen) from gas mixtures or in membrane reactors. Ceramic membrane reactors (CMR) offer an opportunity to combine separation processes directly with chemical reactions, leading to process intensification and, hence, benefits with regard to efficiency. This integral coupling of both processes, separation and reaction, generates synergies between them. Current research activities focus on membrane reactors due to their high intrinsic efficiency and great potential for the production of a large variety of commodity chemicals, energy carriers, and synthetic fuels. This includes the reduction of CO2 emissions and the utilisation/valorisation of CO2.
The development of ceramic membrane materials for such devices is focussed on performance and stability (chemical and thermal) in application relevant environment. The operating temperature is between 400-850°C. The presentation covers a series of potential stable materials for oxygen- and hydrogen ion conducting membranes and their characterisation and performance in application oriented conditions. To reach a high performance of the membrane systems thin film membranes, active surface layers and thermochemical and -mechanical stable supports with designed porosity are required.
The production and characterization of membrane structures is explained using the example of sequentially tape cast and laminated supported membranes. Furthermore, the ion and gas transport through such supported thin membranes is described and an example of transport modelling will be given. Finally, the construction of a Proof of Concept membrane reactor for oxygen separation in oxyfuel cement industry or the use in fossil fuelled power plants will be shown. The lecture concludes with an outlook on future development directions.
Electrochemical Characterization of Ion Exchange Composite Membrane with Various Ion Exchange Group Moieties
Authors: Son Tae Yang , Ko Tae Ho , Kim Ki Hyun , Nam Sang Yong 
Published: February 2020

In this study, ion exchange membranes were prepared by sulfonating and aminating the same polymer with different equivalents respectively. Thereafter, the most suitable equivalent amount of the polymer was selected and used for the study. The selected polymer was impregnated into a support in a solution state to prepare a reinforced composite membrane having excellent mechanical strength. The ion exchange capacity tends to decrease with the use of a support. In order to compensate this, the particles are mixed with the polymer solution to maintain the existing performance.
FE-SEM was used to confirm particle dispersion in the membrane, and quantitative analysis was performed using FT-IR. In addition, thermal properties were analyzed using TGA and DSC, and electrochemical characteristics were analyzed through ionic conductivity / membrane resistance / I-V curves.
(Invited) Nano-Structured ORR Catalysts for PEM Fuel Cells
Authors: Lim JeongHoon , Cho EunAe 
Published: February 2020

Polymer electrolyte membrane fuel cells (PEMFCs) are the most attractive power source for zero-emission vehicles owing to their environmental friendliness, high energy efficiency, and high power density. However, their high cost and low durability have prevented PEMFCs from being fully implemented and commercialized, mainly due to the use of platinum as a catalyst to overcome the sluggish kinetics of the oxygen reduction reaction (ORR) in the cathode. To reduce the use of Pt, extensive studies have been conducted and a large variety of ORR catalysts have been developed, such as Pt-M alloys as well as shape-controlled, dealloyed, and structurally ordered catalysts. Although those catalysts exhibited excellent intrinsic activity in aqueous environment, they have been hardly implemented in membrane-electrode assemblies (MEAs) for practical application.
In this talk, we report Pt-M intermetallic catalysts and M-doped PtNi octahedral nanoparticles on a carbon support (M-PtNi/C) that exhibit superior catalytic activity and stability in half-cell and MEA tests as an ORR catalyst for PEMFCs. To prevent agglomeration of Pt-M nanoparticles during heat treatment in which to transform the Pt-M alloy into Pt-M intermetallic structure, a facile synthetic process was conducted at low temperatures. Octahedral PtNi nanoparticles are known as one of the best ORR catalyst with its superior activity toward ORR. However, dissolution of Ni from the surface and collapse of the octahedral shape degrade the activity rapidly under the PEMFC operation conditions. To stabilize Ni and the octahedral shape, small amount of dopant was incorporated into the surface of octahedral PtNi. Electrochemical, chemical, and structural stability was thoroughly investigated through a harsh durability test. The effects of intermetallic structure and doping elements on the surface properties of Pt-based nanoparticles were examined by X-ray absorption fine structure (XAFS) analysis and density functional theory (DFT) calculation.
New Avenues to MOF Derived Cobalt Chalcogenides for Efficient Electrocatalysis
Authors: Das Debanjan , Nanda Karuna 
Published: February 2020

Metal-organic frameworks (MOFs) have emerged as intriguing self-templates for fabricating a plethora of functional materials with excellent activity. Herein, we have developed three different routes useing cobalt imidazolate frameworks (ZIF-67) to design cobalt selenide (CoSe) hybridized with nitrogen doped carbon.
The solid-state strategy involves direct conversion of ZIF-67 into CoSe nanoparticles with an average size of 20-25 nm encapsulated within N-doped graphitic carbon shells with an average size of 300 nm. Interestingly, this method can easily be extended to similarly synthesize CoTe encapsulated N-doped graphitic carbon cages by simply changing the precursor.
The other method involved the self-templated conversion of ZIF-67 into Co nanoparticles encapsulated N-doped carbon polyhedral and their subsequent transformation into vertically aligned CoSe grafted N-doped carbon sheets via a hydrothermal selenization method. Both, these class of materials so synthesized were found to exhibit excellent electrocatalytic activity towards HER and OER in alkaline medium. It is believed that the methods being developed here may be extended to other transition metal chalcogenides for various applications

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(Invited) The Impact of Work By Dr. Gottesfeld and Coworkers on the Commercial Introduction of the Fuel Cell Vehicle -- Calling the Shots in Polymer Electrolyte Fuel Cells
Authors: Mathias Mark F 
Published: February 2020

Dr. Gottesfeld’s entire career has been characterized by developing early stage fuel cell technology using fundamental science and practical engineering intuition and analysis. It is unusual to see fundamental electrochemistry expertise coupled with electrochemical engineering intuition and skills in the same person. This combination has enabled him and his coworkers to identify controlling phenomena that have proven to be focal points for development and the critical points that determine the ultimate capability of the technology and its application outcome. Furthermore, his dedication and passion in these areas guide and inspire the next generation of contributors across four distinct fuel cell families.
In this talk, I will describe how this pairing of fundamental and device level intuition from the group that he led at Los Alamos National Lab (LANL) from 1987-2000 impacted the development of proton exchange membrane fuel cells from initial development stages to readiness for automotive market introduction. For example, the pathway for the reduction of precious metal loadings to commercially viable levels was initially defined by experiments and fundamental models from the LANL group. The LANL work on membrane water transport was critical to understanding why thinner membranes offered performance benefits beyond their ionic resistance impact. Even the contemporary R&D work to push to high current density (>2 A/cm2) for the sake of reduction of fuel cell area is informed by initial LANL developments as well as Dr. Gottesfeld’s work (published in 2008) on the impact of the Pt-oxides on oxygen reduction kinetics. More broadly, this body of work reminds us that the pathway to push any fuel cell technology to its best possible outcome is to systematically apply coupled experiments and models in order to identify and focus R&D attention on the rate processes that are “calling the shots”.
(Invited) Progress Towards High Power Density and Durable PEFCs with PGM-Free Cathodes
Authors: Uddin Md. Aman , Langhorst Lisa , Zhang Hanguang , Guo Yuqi , Xu Xiaomin , Beltran Diana , Wu Gang , Litster Shawn 
Published: February 2020

This presentation will highlight recent advances in achieving high power density with polymer electrolyte fuel cells (PEFCs) that use platinum-group metal-free (PGM-free) catalysts for the cathode’s oxygen reduction reaction (ORR). PGM-free catalysts have the potential to radically reduce the cost of manufacturing PEFC cathodes. However, several technical challenges with PGM-free cathodes need to be addressed, including a need for increased catalyst activity and stability as well as improved catalyst integration into MEAs for higher power density and better durability. Electrode engineering is crucial to achieving high performance with PGM-free catalysts because the lower volumetric activity yields thicker electrodes that cause significant water flooding and large oxygen and proton transport losses. This talk will highlight recent advances in the field as well as our own recent achievements with PGM-free catalysts prepared from chemically-doped metal organic framework (MOF) precursors. The focus of the talk will be on the electrode integration of these catalysts, including a systematic optimization of the catalyst morphology for MEA integration that leverages the ability to carefully tune the size of the MOF-derived catalyst’s primary particles. A key aspect of our study was the control of particle morphology for effective ionomer distribution. Through combined computational simulation, experimental fuel cell characterization, and electron and high resolution X-ray imaging, we show the significant performance improvements that can be achieved. Furthermore, we present the current status of the MEA durability and will discuss current hypotheses regarding the degradation mechanisms and possible mitigation strategies.
The authors gratefully acknowledge research support from the Electrocatalysis Consortium (ElectroCat), established as part of the Energy Materials Network under the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, under Contract Number DE-EE0008076.
(Invited) Limits of Polymer Electrolyte Membranes
Authors: Mittelsteadt Cortney 
Published: February 2020

Since their introduction in the 1960’s polymer electrolyte membranes, PEMS, for fuel cells have been extensively studied. Hundreds if not thousands of polymer systems have been synthesized and characterized to improve the critical properties of conductivity, chemical and mechanical durability as well as the lesser important properties of water and gas transport.
It is well accepted that these properties are highly dependent on the chemistry of the polymer electrolyte backbone as well as the functional groups and how they organize on the molecular scale. Many models have been used to frame these properties to fit experimental data. What is done less-often is to use the models to then establish the limits of these.
Using the conductivity of their small-molecule analogies, triflic acid for PFSA’s and benzene sulfonic acid for hydrocarbons we set limits on conductivity and permeability. Finally we will also look at how the two most common strategies of increasing PEM performance; increasing charge density and acid strength, are limited by mechanical and chemical durability requirements, respectively.
(Invited) Quantitative Understanding of CO2 Behavior in Anion Exchange Membrane Fuel Cells
Authors: Zheng Yiwei , Peng Xiong , Mustain William E. 
Published: February 2020

The past two years have seen a tremendous enhancement in the performance and durability of anion exchange membrane fuel cells (AEMFCs) [1-2]. Multiple AEMFCs have been reported that can achieve 1.5-2.0 W/cm2 peak power, limiting current > 5 A/cm2 and >500 hour operation almost negligible voltage decay. These operation metrics suggest that AEMFCs are well on their way to competing with proton exchange membrane fuel cells (PEMFCs) in terms of performance, with the additional possible benefit of being lower cost. However, one limitation of all of this work is that it has been done with purified O2 or air fed to the cathode in order to avoid exposing the electrolyte to CO2, which leads to carbonation and a loss of cell performance. Most researchers believe that electrolyte carbonation simply leads to a loss of ionic conductivity, but we will show in this presentation that conductivity loss alone is only able to explain ~10% of the voltage loss once the CO2 is fed to the cathode, suggesting a different mechanism that will be explained.
It has also been recently shown theoretically [3] that the level of carbonation in the AEMFC will be a function of the CO2 concentration and current density as the “self-purging” mechanism [4] acts to remove carbonates as they are formed. However, this behavior has not been confirmed experimentally and the carbonation dynamics are poorly understood. This presentation will present an extensive collection of carbonation data as a function of current density and CO2 concentration at the cathode. We will also link the level of carbonation to electrochemical performance, discuss the lower limits for CO2 tolerance in AEMFCs and discuss strategies to reduce make cells more tolerant to cathode CO2.
Finally, one of the most critical items that has been overlooked in AEMFCS to date is the operation of realistic systems where the anode flowrate is preferably very low. In PEMFC systems, the low anode flowrate results in N2 accumulation on that side of the cell from diffusion. In AEMFCs, not only will this happen, but CO2 will accumulate on the anode side of the cell under operation on real air. This means that anodes will operate under very high relative humidity and very high CO2 concentration conditions. Therefore, the final topic discussed in this presentation will be the influence of accumulated anode CO2 on AEMFC performance.

References

Mustain, Current Opinion in Electrochemistry, DOI: 10.1016/j.coelec.2018.11.010

Maurya, S. Noh, I. Matanovic, E.J. Park, C.N. Villarrubia, U. Martinez, J. Han, C. Bae and Y.S. Kim, Energy Environ. Sci., DOI:10.1039/C8EE02192A

Krewer, C. Weinzierl, N. Ziv and D.R. Dekel, Electrochim. Acta, 263 (2018) 433-446.

Ziv, W.E. Mustain and D.D. Dekel, ChemSusChem, 11 (2018) 1136-1150
The Use of a Protein Scaffold to Control the Structure of Electrodes and Ionomer in Proton Exchange Membrane Electrolyzers
Authors: Pramounmat Nuttanit , Kim ChulOong , Renner Julie 
Published: February 2020

Among the frontrunners of hydrogen production technology, proton exchange membrane (PEM) electrolysis is safe, simple, and highly efficient. PEM electrolysis has ability to be integrated in a variety of energy systems and infrastructures such as transportation, renewable electricity, biogas upgrading, as well as ability to address seasonal-variation in long timescales. One of the major challenges that remains is the high cost of noble-metal catalysts in the membrane electrode assembly (MEA). Recent attempts in research and development are directed toward low-loading of platinum group metals.
We engineered a synthetic protein to improve platinum catalyst utilization in the MEA, and control ionomer-catalyst interfaces. The multifunctional protein is engineered to direct ionomer (the electrolyte) towards platinum active sites. With the protein added to catalyst layer, the nanostructure and phase separation were examined and compared with a conventional catalyst layer. The engineered protein additive results in distinct structural changes in the electrode. This work yields a promising model for controlling ionomer catalyst interactions, and could lead low platinum group metal PEM electrolyzers.
Evaluation of Respiratory Activity IMAGE in Normal Human Epidermal Keratinocyte SHEET Using BIO-LSI
Authors: Kasai Shigenobu , Sato Teruya , Prasad Ankush , Inoue Kumi Y. , Ino Kosuke , Shiku Hitoshi , Matsue Tomokazu 
Published: February 2020

Cell sheets have been studied for the purpose of regenerating dysfunctional tissues and it has also been reported that systemic transplantation of autologous cultured epidermis was actually successful. However, there are few simple methods for testing activity after cell sheet preparation. In this study, we aimed to reproduce the state of sunburn on a part of normal human epidermal keratinocyte sheet by UV irradiation and to evaluate the activity using Bio-LSI. The evaluation examined the respiratory bursts in immune cells by monitoring in real-time, the O2 consumption of the epidermal cell sheet. The cell sheet culture kit Lab Cyte EPI-KIT (Japan Tissue Engineering Co., Ltd.) was cultured for 18 days and were cut into a circle of about 5 mm in diameter. The cell sheet was then covered with a mask leaving 1mm × 1mm open surface for irradiation with UV light (365 nm wavelength and an illuminance of 300 mW/cm2 for 10 seconds). Following UV irradiation, it was installed in the measuring device promptly. The experimental conditions were as mentioned below: measurement solution: 11.4 mM glucose in PBS; W.E.: Pt electrode (d= 40 um) ×400 point; R.E.: Ag/AgCl electrode; C.E.: Pt wire; applied voltage: -0.5 V vs. Ag/AgCl and sampling time: 500 ms. In Fig. 3, it can be seen that the area of cell sheet illuminated with UV irradiation shown lower oxygen concentration (reflected by black area) while non-irradiated parts show higher oxygen level. It is due to the fact that UV exposed cells suddenly consumed oxygen.
References:
1) G.G.Gallico III, N.E.O'Connor, C.C.Compton, O.Kehinde, H.Green. (1984). New England Journal of Medicine, 311(7), 448-451.
2) J.G.Rheinwald. (1980). Methods in cell biology (Vol. 21, pp. 229-254). Academic Press.
3) H.Kikuchi, A.Prasad, R.Matsuoka, S.Aoyagi, T.Matsue, S.Kasai. (2016). Frontiers in physiology, 7, 25.

Figure 1