bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modeling Electrolytic Conversion of Metabolic CO2 and Optimizing a Microfluidic Electrochemical Reactor for Advanced Closed Loop Life Support Systems
Authors: Dominguez Jesus A , Brown Brittany R , Dennis Brian , Chanmanee Wilaiwan , Curreri Peter 
Published: February 2020

Water electrolysis is required in any life support system intended to be operated in a closed loop system, as metabolic CO2 contains 87% of the O2 consumed by the crew members requiring the generation of the 13% O2 balance (assuming 100% efficiency of O2 recovery from CO2) via water electrolysis. Metabolism of food produces 0.34 kg/day/crewmember more water than consumed leading to having sufficient water to generate the 13% O2 balance via electrolysis. The current state of the art for oxygen recovery onboard the International Space Station (ISS) is the Environmental Control and Life Support System (ECLSS) Atmosphere Revitalization (AR) System. The AR includes four integrated units, which provide critical functions for life support including trace contaminant control (Trace Contaminant Control (TCC) system), CO2 removal (CO2 Removal Assembly (CDRA)), oxygen generation (Oxygen Generation Assembly (OGA)), and oxygen recovery (Carbon Dioxide Reduction System (CDRS)).
CDRS is a Sabatier reactor that reduces CO2 to CH4 and water using H2 from OGA (an electrolysis unit that generates O2 as main product and H2 as byproduct) as reactant. The CDRS limits the feasibility of having a closed loop system, as it requires more water than the water metabolically generated ultimately resulting in a recovery rate of approximately 50%. NASA Marshall Space and Flight Center (MSFC) and University of Texas, Arlington (UTA) are currently developing an Engineering Development Unit (EDU) of a Microfluidic Electro Chemical Reactor (MFECR) to convert a continuous stream of CO2 and water into O2 and C2H4 at standard conditions. The novel design combines CO2 conversion and water electrolysis (currently conducted in OGA and CDRS units respectively) into one compact unit that runs at standard conditions and is theoretically capable of generating metabolic O2 with a maximum metabolic CO2 conversion of 77% while consuming less than metabolic water.
This paper presents a multi-physic 3D model developed at MSFC on CO2 conversion to O2 and C2H4 at standard conditions via MFECR. In the model the electrochemical physics is coupled with all the other physics phenomena involved in the process, such as micro fluid flow, mass and heat transfer, and generation as well as conduction of DC electrical current. This work aims to use this 3D model to build a comprehensive, rigorous, and experimentally validated simulator that will be used as a valuable tool to not only assist the authors on the EDU design but also to optimize its operation.
(Invited) Capillary Electrophoresis Instrumentation and Methods for Spaceflight Missions of Exploration
Authors: Mora Maria Fernanda , Kehl Florian , Tavares da Costa Eric , Bramall Nathan , Creamer Jessica , Noell Aaron C , Willis Peter 
Published: February 2020

The search for evidence of life beyond Earth is among the highest level goals in planetary exploration. However, despite multiple orbiter and landed missions to extraterrestrial bodies in the solar system, we still haven’t found evidence of life. A powerful approach in this search involves seeking biochemical signatures of life at the molecular level, as distributions of organic molecules. The separation techniques capillary electrophoresis (CE) and its miniaturized version, microchip electrophoresis (ME) overcome the limitations of gas-phase techniques and hold unique promise in the search for signatures of life on other worlds. These techniques offers high resolution separations of molecules dissolved in water and are the simplest of all liquid separation methods to implement for flight. Here we describe CE and ME instrumentation developed at JPL and the steps we are taking to someday enable the its implementation on other worlds.
Although multiple detection methods can be coupled to CE and ME, we focus on three detection modes: laser-induced fluorescence (LIF) for state-of-the-art measurements of amino acids, mass spectrometry (MS) for broad detection of ionizable organics, and contactless conductivity detection (C4D) for measurements of inorganic and organic ions. These techniques are complementary of each other and would allow full characterization of the chemical composition of a sample in situ. We are not only developing instrumentation but also analytical methods that could be implemented on a mission scenario.
Here we also describe a system we dub The Chemical Laptop, which would provide the sample processing capabilities required for in situ analysis on extraterrestrial destinations with ultra-high sensitivity in a compact, low-mass, and low-power package. The Chemical Laptop is a truly portable, battery-powered, automated, and reprogrammable microchip electrophoresis instrument coupled to laser-induced fluorescence detection.
This instrument concept could be adapted to the environmental requirements of a variety of astrobiologically interesting targets like Europa, Enceladus, or Titan. This system also serves as a general prototype that could be reprogrammed for terrestrial-based analyses as well.
The Thermodynamic and Kinetic Influence of Solvent, Counter Anion and Salt Concentration on ORR in Li-O2 Batteries
Authors: Leverick Graham , Tatara Ryoichi , Feng Shuting , Crabb Emily , France-Lanord Arthur , Tulodziecki Michal , Stephens Ryan M. , Grossman Jeffrey C. , Shao-Horn Yang 
Published: February 2020

Aprotic Li-O2 batteries have been extensively studied due to their very high theoretical gravimetric energy density; potentially 2-3 times that of commercial Li-ion batteries1. Despite this significant research effort, practical rechargeable Li-O2 batteries remain elusive due to significant issues relating to high overpotential and parasitic side reactions that limit the cycling performance of the battery chemistry. In order to address these issues, a stronger fundamental understanding of the underlying oxygen redox reactions is needed. In this work, the complex influence of the solvent2, counter anion3 and salt concentration4 during the oxygen reduction reaction are unified within a single framework. Ionic coupling between Li+ ions and the superoxide (O2
-) anion formed following the first electron transfer is highlighted as the critical parameter for determining the selectivity between the two competitive discharges pathways. By weakening the Li+-O2
- coupling through interactions with solvent/counter anions with high donor number, or by lowering the Li+ activity, we observe a significant enhancement in the proportion of observed soluble discharge products. Additionally, electrolyte design strategies for suppressing the direct two electron transfer reaction to form an insulating film of Li2O2 will be discussed in their relation to enabling redox mediators during the reduction process, such as DBBQ5 and EV.
References

D. Aurbach, B. D. McCloskey, L. F. Nazar, and P. G. Bruce, Nature Energy, 1, 16128 (2016).

D. G. Kwabi et al., Angewandte Chemie International Edition, 55, 3129–3134 (2016).

C. M. Burke, V. Pande, A. Khetan, V. Viswanathan, and B. D. McCloskey, Proceedings of the National Academy of Sciences, 112, 9293–9298 (2015).

R. Tatara et al., The Journal of Physical Chemistry C, 121, 9162–9172 (2017).

X. Gao, Y. Chen, L. Johnson, and P. G. Bruce, Nature Materials, 15, 882–888 (2016).
Low-Temperature Behavior of Lithium Metal Anodes in Carbonate and Ether Electrolytes
Authors: Thenuwara Akila C , Sandoval Stephanie , Klein Emily J , McDowell Matthew T 
Published: February 2020

The development of energy storage devices that can efficiently operate at temperatures below 0 °C is necessary for both terrestrial and space-based applications. NASA has previously carried out pioneering work that has enabled Li-ion batteries to operate at temperatures down to -30 °C through the development of new carbonate electrolyte formulations. [1-2] However, secondary batteries that utilize lithium metal anodes instead of conventional graphite anodes could significantly boost energy density and specific energy, but the behavior of lithium electrodes at low temperatures are largely unknown. In this work, we investigate the effect of sub-zero temperatures on electrochemical behavior, morphological evolution, and solid-electrolyte interphase (SEI) formation of Li metal anodes in carbonate and ether solvents. Electrolytes made with solvents such as ethylene carbonate and ethyl methyl carbonate with ester co-solvents (e.g., ethyl propionate) exhibit sufficient conductivity and show effective Li deposition/stripping down to -30 °C, but with relatively low average Coulombic efficiencies (CEs) of ~70 % (similar to the room-temperature CE of ~73 %). The introduction of SEI-stabilizing additives such as fluoroethylene carbonate (FEC) boosts the average Coulombic efficiency across a range of temperatures (CE = ~94 %). Ether-based electrolytes, on the other hand, enable Li deposition/stripping down to -70 °C with high CEs (~95 %). Interestingly, investigation of the Li morphology after cycling revealed that distinct Li morphologies form at different temperatures, which may be related to differences in SEI chemistry and structure. These results provide important new information for engineering Li metal anodes for efficient operation under a variety of conditions.
References
[1] Smart, M. C., B. V. Ratnakumar, L. D. Whitcanack, K. B. Chin, S. Surampudi, H. Croft, D. Tice, and R. Staniewicz. "Improved low-temperature performance of lithium-ion cells with quaternary carbonate-based electrolytes." Journal of power sources 119 (2003): 349-358.
[2] Smart, M. C., B. V. Ratnakumar, Larry D. Whitcanack, Kiah A. Smith, Stuart Santee, Robert Gitzendanner, and Vince Yevoli. "Li-Ion Electrolytes Containing Ester Co-Solvents for Wide Operating Temperature Range." ECS Transactions 11 (2008): 99-108.
Development of High-Performance Ion Selective Membranes for Lithium Polysulfide Redox Flow Batteries (Li-PS RFBs)
Authors: Kim Sangil , Wang Tongshuai , Gao Yuechen , Amiri Azadeh , Bae Chulsung 
Published: February 2020

There has been a surge of research interest in the lithium polysulfide (Li-PS) redox flow batteries (RFBs) for large scale energy storage applications because of their high theoretical energy density (~2600 Wh/kg and 2199 Wh/L for elemental Li and S) and low material cost. They also can bring additional advantages, such as design flexibility, easy scalability, and safe operation condition. However, the Li-PS battery systems suffer from polysulfide crossover (polysulfide shuttling) between their two working electrodes which decreases the batteries’ columbic efficiency and shortens their cycle lives. This shuttling effect is more detrimental in Li-PS RFBs which doesn’t have carbon matrix to immobilize the solid-state sulfur. In conventional redox flow batteries (e.g. vanadium redox flow battery), the membrane separators has an important role by suppressing the active species crossover between catholyte and anolyte. However, commercial porous battery separators (e.g. Celgard) cannot be adopted due to their low rejection for polysulfide (PSn-) active species and fast capacity decay. Recent few research works revealed the feasibility of using ion exchange membranes (IEMs) as a barrier layer to selectively transport Li+ ions and block PSn- ions. Unfortunately, most commercial IEMs are unstable in the organic polysulfide electrolyte because of its high swelling ratio which can cause the electrolytes crossover. Hence, there is a critical need to develop high performance membrane materials for the Li-PS RFB applications.
In this work, we will present our recent progress on developing novel ion exchange membrane materials for the Li-PS RFBs which can greatly suppress the polysulfide shuttling while maintaining high Li+ conductivity and mechanical stability. Our biphenyl polymer membrane (BP-SA) presents excellent stability the DOL/DME organic electrolyte solution, exhibiting potential for Li-PS RFBs application. We studied its selective ion transport properties through diffusion and electrochemical measurement. Diffusion test shows that there is close to 100 % rejection of Li-PS ions by the BP-SA membrane, while considerable amount of Li-PS crossover was found for Celgard and Nafion. Moreover, the BP-SA membrane possess comparable Li conductivity (0.13 mS/cm2) to Nafion (0.29 mS/cm2) in organic solvent. As a result, the Li-PS single cell with the IEM/Celgard composite membrane shows better efficiencies in comparison to the cell with Celgard 2325. Our results unambiguously demonstrate that the BP-SA membrane has greater Li+/PS anion selectivity than Nafion and can be a promising base material to make separators for Li-PS RFBs.
High-Rate and Long Cycle-Life of Bulk Na2/3[Ni1/3Mn2/3]O2 Sodium-Ion Battery Cathode Enabled through Structural Inclusion
Authors: Detsi Eric , Fu Jintao , Corsi John S , Li Manni 
Published: February 2020

Recently, sodium-ion batteries (SIB) have been considered a promising alternative to lithium-ion batteries due to the abundance of sodium resources (sodium is the Earth’s 6th most abundant element, while lithium is 33rd) and its low extraction costs. Among various cathode candidates, the layered oxides NaTMO2 (TM=3d transition metal elements and their mixture) can accommodate sodium ions through intercalation mechanism, but suffer from major limitations including poor rate capability and short cycle-life. We have developed a novel bulk Na2/3[Ni1/3Mn2/3]O2 structure containing inclusions, which exhibits an unprecedented rate capability with roughly 50 % capacity retention at 50 C, and a remarkable long-term cycling stability with 95% capacity retention after 1000 cycles at 5 C. During this talk, I will present our new results and elucidate the mechanism through which the cycling performance of the novel materials system is enhanced.
References

Ruiz, M. Cochrane, M. Li, Y. Yan, K. Ma, J. Fu, Z. Wang, SH. Tolbert, VB. Shenoy, E. Detsi, Adv. Energy. Mater., 8 (2018) 1801781.

Li, Z. Wang, J. Fu, K. Ma, E. Detsi, Scripta Materialia, 164 (2019) 52-56.
Oxygen Barrier Composite Membrane for Li-Air Battery Using Cuboid LiAlTiPO4 in Orthogonal Array
Authors: Choi Kyoung Hwan , Choi Wonsung , Im Dongmin 
Published: February 2020

The Li-Air batteries which convert the electrochemical reactions of lithium and O2 into electrical energy have high theoretical gravimetric capacity (3861 mAh/gLi) that is ten times higher than that of lithium ion batteries (372 mAh/gc). Its potential to generate high energy density makes it a promising candidate to replace the lithium ion in the electric vehicle applications. To meet the requirements of the electric vehicle applications, the technical barriers that limit the cycle life such as oxygen permeation, electrolyte and cathode instability and low rate capability need to be overcome. Especially the consumption/de-activation of Li metal is accelerated when oxygen in cathode side moves into Li metal side through the electrolyte, which is one of the most significant factors preventing long-term operation of the system.
Ceramic solid state electrolyte (SSE) separator has a remarkable gas blocking capability, but it should be thick and heavy (~0.3 mm) to be used as a gas barrier of Li-Air battery due to fragile property. This leads to a sharp decrease in energy density. We fabricated composite membrane consisting of micron-sized SSE particles arrayed in matrix shape and polymer grid. Here SSE particles and polymer have functions of lithium ion conduction and gas blocking, respectively. Cuboid particles were synthesized using silicon wafer template with cuboid pattern on it in size of 50 ~ 200um.
Interface energy between particle and polymer was controlled by bimodal surface modification for better mechanical strength of membrane. Compared to amorphous particles, composite membrane using cuboid LATP particle has many benefits in high ionic conductivity, uniform thickness, light weight and flexibility. In this presentation, how to fabricate cuboid SSE particles in matrix shape array and characterization of composite membrane using it will be discussed.
New Nitrile Type Bi-Functional Additive for High-Performance Li-Metal Batteries
Authors: Lee Seon-Hwa , Sun Yang-Kook 
Published: February 2020

Despite the lithium metal has been considered as an ideal anode for boosting the energy density of Li-ion batteries, thermodynamic dendritic lithium growth and aggressive degradation of Ni-rich cathode during charge process hinder the practical application of Li metal/Ni-rich Li[NixCoyMn1-x-y]O2 battery. Herein, we propose an effective multifunctional nitrile type additive. This additive-induced lithium metal anode SEI layer is robust and compact, and thus beneficial to obtain mound-like Li platting morphologies during charge. This uniform and dendrite-free morphology significantly enhanced the safety issues and improved the coulombic efficiency. At the same time, this additive also enhanced the stability of electrolyte/cathode interface by strong coordination between nitrile group (additive) and transition metal (cathode active material) during charge. This coordination effectively hinders decomposition of carbonate solvent on the cathode/electrolyte interface. As a result, Li metal/Ni-rich Li[Ni0.73Co0.10Al0.02Mn0.15]O2 battery is able to achieve an excellent cycle retention even when applying the high current density (1.8 mA cm-2).
[1] S.-J. Park, J.-Y. Hwang, C. S. Yoon, H.-G. Jung, Y.-K. Sun, ACS Appl. Mater. Interfaces
2018, 10, 17985-17993
[2] Zheng, M. H. Engelhard, D. Mei, S. Jiao, B. J. Polzin, J.-G. Zhang, W. Xu, Nat. Energy
2017, 2, 17012.
[3] J.H. Kim, S. J. Kim, T. Yuk, J. Kim, C. S. Yoon, Y. K. Sun, Acs Energy Lett 2018, 3, 3002-3007
[4] S. Kim, T. H. Kim, H. Lee, H. K. Song, Energy Environ. Sci.
2011, 4, 4038-4045.
Von-Alpen Type Nasicon for Seawater Battery Application
Authors: Go Wooseok , Kim Youngsik 
Published: February 2020

For utilization of renewable energy, energy storage systems (ESS) are becoming more important. Seawater battery have attracted attention for large scale ESS system due to high capacity, good cyclability and environment friendly. The seawater battery consists of seawater, cathode current collector, solid electrolyte, organic electrolyte and anode. Among the components, solid electrolyte does critical role for selective transfer of sodium ion. The requirements for the solid electrolyte are high sodium ion conductivity at room temperature, high chemical stability against seawater, wide electrochemical window (0~5V), thermostability (4oC~25oC) and strong mechanical strength. The possible candidates were sodium beta alumina and Hong type NASICON (Na3Zr2Si2PO12). In the previous research, Hong type NASICON has superior seawater stability than sodium beta alumina. So the conventional seawater battery utilizes Hong-type NASICON as solid electrolyte due to applicable properties. Among the NASICON solid electrolytes composition, Na3.1Zr1.55Si2.3P0.7O11 composition was proposed by V. von Alpen et al in 1981. As far as we know, there has no research about Na3.1Zr1.55Si2.3P0.7O11 composition on electrochemical device. In this study, Na3.1Zr1.55Si2.3P0.7O11 composition was used as solid electrolyte for seawater battery application. We investigated on the required properties and compared with Hong-type NASICON. The resulting Na3.1Zr1.55Si2.3P0.7O11 exhibited higher sodium ion conductivity due to bigger grain size and strong mechanical strength. When it applied into the seawater battery, it showed smaller overpotential and higher power with over 1 thousand hours cycling. Thus, Na3.1Zr1.55Si2.3P0.7O11 composition solid electrolyte satisfied the above requirements and exhibited superior properties than previously researched solid electrolytes for seawater battery.
References

Y. Kim, H. Kim, S. Park, I. Seo, and Y. Kim,
Electrochimica Acta
, 191, 1–7 (2016)

V. Von Alpen, M.F. Bell and H.H. Hofer,
Solid State Ionics,
3-4,215-218 (1981).

S.M. Hwang, J. Park, Y.Kim, W.Go, J.Han, Y.Kim and Y.Kim,
Advanced Materials
, 1804936 (2018)
Highly Active Transition Metal Dichalcogenides As Bifunctional Electrocatalysts for Li-Oxygen Batteries
Authors: Majidi Leily , Salehi-Khojin Amin , Curtiss Larry A 
Published: February 2020

Lithium-air (Li-O2) batteries -comprising of an air (O2) cathode and a lithium anode- are able to deliver significantly higher amounts of theoretical energy densities compared to conventional Li-ion batteries. Therefore, these batteries have been extensively investigated lately to become the practical substitution for Li-ion batteries especially in transportation and electric vehicles.
Performance of a Li-O2 battery is fundamentally governed by two main reactions occurring at the cathode: oxygen reduction reaction (ORR) during discharge and oxygen evolution reaction (OER) during charge. In order to improve the performance of Li-O2 batteries, seeking a bifunctional catalyst which operates favorably in both ORR and OER reactions, is a challenging issue. The role of various materials has been investigated in OER-ORR reduction in both aprotic and non-aprotic media, including: noble metals, metal oxides, transition metals, transition metal carbides, and etc. Among these catalysts, transition metal dichalcogenides (TMDCs) such as MoS2 indicated a superior performance towards a bifunctional catalytic activity for ORR and OER in aprotic electrolytes.
Herein we report for the first time the catalytic activity of a number of novel two dimensional TMDCs with transition metals of groups V-IX and the three heavier chalcogens (S, Se, Te) in ORR-OER in an aprotic medium with Li salt. We have synthesized these materials via chemical vapor transport (CVT) and the nanoflakes accompanied by different characterization techniques such as: Raman, XPS, UPS, DLS, AFM and etc. We performed cyclic voltammetry experiements to comparatively study the TMDCs catalytic activity in ORR-OER reactions, their turnover frequency and so on. These catalysts outperformed all of the reported catalysts in aprotic media with Li salts during ORR and OER. A number of them exhibited an excellent bifunctional behavior such as: NbS2, VS2 and VSe2. Density functional theory (DFT) calculations were also performed on a number of these catalysts in order to understand their catalytic activity during ORR and OER in ionic liquid electrolyte. We believe these materials possess great potential to enhance the catalytic activity in core electrochemical reactions especially in Li-O2 battery applications.