bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Sr and Mn Doped LaFeO3 Perovskite Oxide As Active Cathode for High Temperature Electrolysis
Authors: Ishihara Tatsumi , Wu Kuan-Ting , Wang Shijing 
Published: February 2020

Solid oxide electrolysis cells (SOECs) for converting CO2 to more useful chemical species are attracting considerable attention because of their high electrolytic efficiency, offering the possibility of direct conversion of CO2 to CO (CO2 → CO + 1/2O2). In addition, recently, high temperature electrolysis of steam to H2 is also attracing much interest. Heat energy supplied to SOECs can maximize electrolysis efficiency, offering both thermodynamic and kinetic advantages. The generated CO can be used as a fuel gas, converted into syngas via reaction with H2, or to reduce iron oxide to pure iron in the iron-making process. The application of SOECs and related technologies can contribute to a more sustainable economy. For the electrolyte in SOECs, ZrO2 doped with 8 mol% of Y2O3 (YSZ) has always been used because of its chemical stability and mechanical strength. However, an electrolyte for CO2 or H2O electrolysis with lower internal resistance and increased efficiency is highly desirable. LaGaO3-based electrolytes have higher oxide-ion conductivities and transport numbers, which can lead to higher energy conversion efficiency; hence, a doped-LaGaO3 electrolyte (La0.9Sr0.1Ga0.8Mg0.2O3, LSGM) has been tested in this study. For CO2 and H2O electrolysis, another drawbacks is durability since electrode is easily aggregated and deactivated.
Although metals, particularly Ni, are widely used as cathodes in CO2 electrolysis cells, we found that a LaFeO3−δ-based perovskite cathode (La0.6Sr0.4Fe0.8Mn0.2O3−δ, LSFM6482) showed the highest activity for CO2 and H2O electrolysis among the examined oxides Among the cells using a La0.6Sr0.4Fe0.9M0.1O3−δ-based oxide cathode (M = Mn, Co, Ni, or Cu) for CO2 electrolysis at 1073K. Mn was the most effective Fe replacement on the B site, and the La0.6Sr0.4Fe0.9Mn0.1O3−δ cathode showed the highest activity and current density for CO2 electrolysis of this set of cathodes. Among the tested dopants, Mn and Co have ionic sizes most similar to Fe and a smaller size mismatch between the host and dopant cations in the perovskite structure, which should suppress dopant segregation and minimize detrimental effects of cation segregation. Overall, among the examined cations, Mn was the best dopant for the B site of the LaFeO3 cathode. A cell consisting of BLC64/LSGM/LSFM6482 exhibited the highest CO2 electrolysis activity (a current density of 0.52 A/cm2 at 1.6 V and 1173 K) of all cathodes investigated in this study and reduced CO2 at a rate of 153 μmol/cm2•min at 1173 K and 1.6 V with negligible carbon formation. In this study, change in internal resistance during electrolysis is also discussed based on impedance measurement.
Influence of the Activation Catalyst on the Polarization Resistance of Electroless Cu Electrodes on BaCe0.1Zr0.8Y0.1O3-δ proton-Conducting Ceramics
Authors: Ricote Sandrine , Patki Neil , Way James Douglas 
Published: February 2020

Copper (Cu) electrodes appear as potential methane dehydroaromatization (MDA) electrodes on BaCexZr0.9-xY0.1O3- δ (BCZY) proton-conducting ceramics [1]. When applied from paste, the electrodes suffer from poor adhesion, and therefore high polarization resistance. In this work, 1 micron thin Cu electrodes were deposited onto BaCe0.1Zr0.8Y0.1O3-d (BCZY18) specimens by electroless plating, using three different activation catalysts: Pd, Ru and Cu [2].
Impedance spectra were recorded on electrolyte based symmetric cells Cu/BCZY/Cu in the temperature range 750-600°C, in dry and moist reducing atmospheres. The area specific resistances (ASR) of these three electrodes were found to be lower in moist gases and were two orders of magnitude lower than that measured on painted Cu electrodes (see figure) . At 700°C, in 3% moist forming gas, ASR of 2.9, 3.8 and 22.7 Ω∙cm2 were calculated on the Cu electrodes with the Pd, Ru and Cu activation catalyst respectively.
The microstructure of the electrodes was evaluated before and after electrochemical testing. In all cases, nano-pores were present on the as-deposited electrodes. After exposure to dry and moist reducing atmosphere at high temperatures, the microstructure of the Pd/Cu and Ru/Cu did not change significantly while major reorganisation was observed for the Cu/Cu electrode.
[1] Morejudo SH, Zanón R, Escolástico S, Yuste-Tirados I, Malerød-Fjeld H, Vestre PK, et al. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor. Science 2016;353:563–566
[2] Patki N, Ricote S, Way JD, Fabrication of reducing atmosphere electrodes (fuel electrodes) by electroless plating of copper on BaZr0.9-xCexY0.1O3-δ – a proton-conducting ceramic, submitted to International Journal of Hydrogen Energy in November 2016

Figure 1
(Invited) An Overview of the Hydrogen Materials - Advanced Research Consortium (HyMARC), a DOE Energy Materials Network Consortium, to Accelerate Development of Hydrogen Storage Materials
Authors: Stetson Ned T , Allendorf Mark D. , Adams Jesse , Hulvey Zeric , Randolph Katie 
Published: February 2020

The DOE launched the Hydrogen Materials – Advance Research Consortium (HyMARC) to address the key barriers impeding the development of hydrogen storage materials that meet the demands of transportation applications. The consortium is composed of a national laboratory core team, and individual materials development projects selected from academia, industry and other Federally Funded Research and Development Centers.
The goal of the DOE Hydrogen Storage Program is to enable the widespread commercialization of hydrogen and fuel cell technologies through the development of advanced hydrogen storage technologies that meet the onboard storage demands. Commercial fuel cell electric vehicles are being released today that use high-pressure 700 bar hydrogen storage onboard, and the hydrogen fuel infrastructure is being installed to support fast fueling of 700 bar onboard hydrogen storage. The high-pressure tanks are significantly more expensive, larger and heavier than conventional gasoline or diesel fuel tanks. Additionally high pressure delivery to the vehicle adds significantly to the cost of fuel and creates reliability issues at the station. Materials-based storage offers an opportunity to enable storage at high density in a compact container at lower pressures, providing the potential to decrease the cost of the onboard hydrogen storage system and the fueling infrastructure.
The HyMARC national laboratory core team, composed of Sandia (SNL) - lead, Lawrence Livermore (LLNL), and Lawrence Berkeley National Laboratories (LBNL), is tasked with carrying out foundational research to understand the interaction of hydrogen with materials in relation to the formation and release of hydrogen from hydrogen storage materials. This effort includes the development of computational material design tools, synthetic and characterization methodologies, and online databases of hydrogen storage materials properties and computational data that will accelerate materials discovery and development for on-board hydrogen storage applications. Individual materials development projects are selected to work with the national laboratory core team to apply the tools and accelerate the development of materials tailored to meet the needs for transportation hydrogen storage applications.
(Invited) Predicting Properties of Complex Interfaces for Photoelectrochemistry: Challenges and Strategies
Authors: Wood Brandon C. , Ogitsu Tadashi , Pham Tuan Anh 
Published: February 2020

Processes occurring at solid-gas, solid-liquid, and solid-solid interfaces are critical to the functionality of most energy storage and conversion devices. However, surfaces and interfaces often exhibit properties that are qualitatively different from their bulk counterparts, preventing straightforward inference of their structural, chemical, and transport characteristics. Moreover, surfaces and interfaces in many operating devices tend to be highly heterogeneous, which introduces additional complexities that must be addressed by diagnostic methods. Predictive modeling based on ab initio simulations offers a unique set of tools for unbiased understanding of interfaces that can operate in tandem with high-fidelity experimental characterization. Indeed, recent advances in hardware, algorithms, and methods have significantly broadened the space of systems accessible to simulations. Nevertheless, accessing the full chemical and structural complexity of interfaces under realistic operating conditions remains a significant challenge for predictive simulations.
In this talk, I will begin by reviewing some of the key difficulties associated with predictive modeling of complex interfaces, with specific reference to solid-liquid and solid-solid interfaces in materials for photoelectrochemical water splitting. Next, I will show how ab initio molecular dynamics can be combined with advanced X-ray spectroscopy (XAS, XES, XPS) and other high-fidelity experimental probes to enable more realistic models of surfaces and interfaces in semiconductor photoelectrodes that go beyond idealized approximations. I will review our recent efforts applying this synergistic approach to study the structural, chemical, and transport properties of III/V semiconductor photoelectrodes under electrochemical and photoelectrochemical operation. I will show how theoretical modeling and experimental characterization operate hand-in-hand in this regard, with experiments aiding the validation and assembly of accurate interface models, and theory aiding the interpretation of complex spectra. The examples will specifically highlight the importance of accounting for structural and chemical changes induced by the presence of the interface under electrochemical conditions, such as surface oxidation and reconstruction, which profoundly alter photoelectrode behavior with consequences for photoelectrochemical durability and efficiency.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
(Invited) The Center for Hierarchical Materials Design: Realizing the Promise of the Materials Genome Initiative
Authors: Voorhees Peter W , DePablo Juan , Olson Greg 
Published: February 2020

The classical materials creation process involves a laborious procedure wherein intuition drives the design of a material that is then created, and tested. In most cases, the design goals are not attained, and this costly procedure is repeated. The Materials Genome Initiative (MGI) seeks to replace this process and thus bring innovative new materials into commercial applications faster and at a lesser expense. The Center for Hierarchical Materials Design (CHiMaD) is the NIST-sponsored Center of Excellence for Advanced Materials Research focusing on developing the next generation of computational tools, databases, and experimental techniques in order to enable the accelerated design of novel materials and their integration into industry. To illustrate the potential of the MGI, we are designing a wide range of materials from Co-superalloys to block co-polymers for nanolithography. Each of these design efforts requires databases and simulation. A discussion of the databases, data mining and materials simulation efforts will be given.
Electrochemical Proximity Assay of Picomolar Platelet-Derived Growth Factor through Combined Surface Plasmon Resonance, Electrochemistry, and Fluorescence Spectroscopy Approach
Authors: Zhou Lang , Chin Bryan A , Simonian Alex 
Published: February 2020

Platelet-derived growth factor (PDGF) is a potential cancer marker, which will play an important role in early detection of cancers. Due to its trace amounts in contrast to abundant proteins and other interfering species in blood sample, it is difficult to be detected. Electrochemical Proximity Assay (ECPA) is an extremely flexible and sensitive technique with high potential for quantitation of a variety of proteins in clinical laboratory settings or at the point-of-care systems. In this study, we applied ECPA strategy on the PDGF recognition to achieve high sensitivity and specificity. Different with previous ECPA approach in which signals are only read out by electrochemical measurement, three characterization techniques including surface plasmon resonance, electrochemistry and fluorescence spectroscopy are combined together here so that these techniques are capable of cross-validating and complementing each other.
With the combined advantages of these techniques, the limit of detection of PDGF quantification reaches as low as picomolar level. More importantly, the cross-validation of signals contributes to identification of the interference from non-specific binding, and further improvement of the detection accuracy. In this research, the influence factors such as concentration of biosensor’s components, injection time and flow rate were studies, the response linear range, sensitivity and selectivity of PDGF detection were obtained. Furthermore, the mechanisms of action and dynamics of sensing and protein recognition in the process of PDGF recognition was investigated. This work not only provides an accurate quantitation information for biomarker PDGF, but allows a fundamental understanding of the biosensor formation with an unprecedented level, which can overcome several key limitations of current, widely-used surface characterization technologies.
Exploring Key Descriptors of Solid Electrolyte Interphase Formation in Lithium Ion Batteries through Atomistic Simulations
Authors: Boyer Mathew J , Hwang Gyeong S 
Published: February 2020

Lithium ion batteries (LIBs) have allowed for a technological revolution in portable electronics, power tools, and electric vehicles. Future improvements, however, require an advancement of existing battery technology to provide for faster charging and larger capacities, while maintaining safety and longevity. This fundamentally represents a knowledge and materials challenge that needs to develop a deeper understanding of electrode and electrolyte materials as well as their interfaces. Electrolyte and electrode materials used in LIBs have been studied separately to a great extent, however the structural and dynamical properties of the electrode/electrolyte interface still remain largely unexplored despite its critical role in governing battery performance. In particular, a key issue restraining the utilization of high-energy density anode materials, such as silicon (Si), is their inability to form a stable interphase during charging which results in continuous capacity fade or even cell failure. The design of better storage devices may be improved through a greater fundamental understanding of the formation of the solid electrolyte interphase (SEI) at the anode/electrolyte interface through atomistic computer simulations. We have utilized molecular dynamics (MD) simulations to correlate the bulk composition of the electrolyte to the interfacial structure and its effect on the transport behavior of key intermediates in the reductive decomposition of this electrolyte at a graphitic carbon electrode. Our study clearly demonstrates that the interfacial structure is sensitive to the molecular geometry and polarity of each solvent molecule as well as the surface structure and charge distribution of the negative electrode. Such quantitative analysis of the molecular arrangements at the electrode/electrolyte interface improves the understanding and description of electrolyte decomposition and SEI formation. Using MD and metadynamics techniques, we have systematically studied how factors such as the bulk composition of mixed carbonate electrolytes, precipitation of lithium fluoride (LiF, a result of the unstable PF6- anion species) onto the anode, and some commonly utilized additives (shown to improve the quality of the SEI layer) influence the transport and accumulation of decomposition products/intermediates. In this talk, we will present some of our recent findings including what we believe to be key descriptors in to predicting the decomposition products arising from the electrochemical reduction of the electrolyte. This improved understanding provides design principles for future investigation into forming a stable SEI on high-energy anodes such as Si.
Developing Cycle-Stable Sn-Based Alloys for Anode Application in Na-Ion Batteries
Authors: Wang Wenhui , Li Quan 
Published: February 2020

Sn is a most promising anode candidate for Na-ion battery, due to its high capacity (847 mAh/g or 1210 Ah/L) and low average operating voltage (~0.25 V vs. Na/Na+). However, its cycle stability is limited by significant volume change, stress built-up, and Sn aggregation during charge/discharge cycles.
The present work attempted to tackle this outstanding problem by introducing other elements to form binary or ternary Sn-based alloys. Although the cycling stability of the Sn-based alloy were significantly improved when compared to pure Sn metal, we found that continuous segregation of Sn from the alloy during the cycling process remained a major problem, causing the deterioration of the alloy anode. We showed that a few other approaches can further enhance the cycling stability of the Sn-based alloys. In many cases, a compromise is needed between the capacity and cycle stability of the alloy anode.
This work is supported by RGC/GRF under project No. 14316716
A Solvent-Free Electrode Coating Technique for All Solid State Lithium Ion Batteries
Authors: Graebe Heiko , Netz Andreas , Kwade Arno 
Published: February 2020

Solid state lithium-ion batteries are one of the promising candidates to power future electric and
hybrid electric vehicles. They offer outstanding safety and power density. The ability to exchange the
liquid electrolyte/separator system by a single component and use a metal lithium anode provides
encouraging advantages for the use of solid state batteries. In general a solid state electrode is
produced by dissolving the polymeric binder in a solvent and disperse the active material and
conductive additives in the solution. Commonly toxic solvents like n-methyl-2-pyrrolidion (NMP),
acetonitrile, methanol etc. are used in this process. Some of these are known to be carcinogenic and
often they have to be removed from the electrode, which results in energy consumption and further
process steps. The challenge is to develop a process which does not require any kind of such a solvent.
The present work investigates a solvent-free mixing and hot pressing technique to prepare both the
solid state lithiumironphosphate (LFP) cathodes and polyethylenoxide (PEO) based electrolytes. The
powder treatment is essential to produce mechanically stable and electrochemically active electrolytes
and electrodes. For the preparation, all ingredients were premixed in a dual asymmetric centrifugal
mixer and filled into a heated pressing die. Ideal process parameters such as pressure and heating time
were investigated. By way of example, figure 1 illustrates a flexible electrolyte film containing
PEO/LiTFSI with a molar ratio of 10:1. It can also be shown that the ionic conductivity of the solid
state electrolytes is in the same range (10-3 S/cm at 80°C) compared to their solvent based coated
counterparts. Additional determination of the electrolyte and electrode performance vs. Li anode is
made with respect to the discharge rate capability.
The lab-scale processing shown below demonstrates a first proof of function of all solid state cathode
and separator and may offer a much simpler method for such cathode and separator manufacturing
overall, with less process steps and potential cost saving and functional advantages. In conclusion, it
seems to be a promising process for further development to demonstrate scalability for future cell
production.
Experimental and Computational Investigation on the Crystal Structure, Stability, and Li Ion Conductivity of Undoped and Doped Garnet-Type Solid Electrolytes
Authors: Jalem Randy , Morishita Yasuyuki , Okajima Takashi , Kondo Yuki , Takeda Hayami , Nakayama Masanobu 
Published: February 2020

Garnet solid electrolytes are regarded as amongst the most promising class of materials for the realization of all-solid-state Li ion batteries, demonstrating good stability vs Li metal (anode) and exhibiting conductivity values that come close to conventional liquid- and/or organic-based electrolytes (on order order of 10-3 S/cm)1,2. These properties are strongly governed by structure stability (thermodynamic and electrochemical), doping effects, and the dominating Li ion conduction mechanism in the garnet framework. In this respect, a clear and fundamental understanding of the garnet material itself is crucial for the formulation of effective strategies for property optimization. Unfortunately, elucidation by experiment alone are met with difficulties. Even conductivity values for the same garnet composition can vary significantly as can be seen in the literature. In the case of electrochemical stability, the decomposition product(s) in the oxidative voltage regime, for example, could be difficult to detect. Meanwhile, ascertaining the actual site preference and distribution of dopants is also not straightforward and could depend on the preparation condition of the garnet powder. When determining bulk and grain boundary conductivity, separating the bulk and grain boundary contributions of resistance in impedance measurements can also become problematic.
By experiment and computational modelling, we attempted to clarify some of the above issues as well as tried to resolve some of the discrepancies existing in the literature. Specifically, we studied the electrochemical stability,3,4 dopant distribution and local structure,5 and Li ion transport properties5,6,7. As an example, for experiment, results will be shown related to the charge process behavior of an air-isolated Li ion battery with a garnet solid electrolyte, and then use modelling to aid in clarifying the origin of capacity fading. Another example, for computation, we employed various techniques such as first-principles density functional theory (DFT), augmented plane-wave method, computational NMR, force-field approach, and molecular dynamics in order to analyze the effects of gallium doping in garnet Li7La3Zr2O12. Our results could provide insights and fresh view, for both experimentalists and computationalists, on the state and the future direction that could be taken for solid electrolyte research.
REFERENCES

1Li et al., J. Mater. Chem. 2012, 22, 15357-15361.

2 Bernuy-Lopez et al., Chem. Mater. 2014, 26, 3610-3617.

3 Nakayama et al., Phys. Chem. Chem. Phys. 2012, 14, 10008-10014.

4 Jalem et al., J. Mater. Chem. A 2016, 4, 14371-14379.

5Jalem et al., Chem. Mater. 2015, 27, 2821-2831.

6 Jalem et al., J. Phys. Chem. C 2015, 119, 20783-20791.

7 Jalem et al., Chem. Mater., 2013, 25, pp 425-430.
Synthesis of Mixed Na2Ti3O7/Na2Ti6O13 Sodium Titanates with Different Phase Ratios and Their Lithium Insertion Properties
Authors: Cech Ondrej , Vanýsek Petr , Částková Klára , Čudek Pavel 
Published: February 2020

Sodium titanate nanorods consisting of two phases were successfully synthesized by microwave assisted hydrothermal synthesis. The electrochemical behavior during lithium ion insertion and deinsertion was studied depending on the different ratio of Na2Ti3O7/Na2Ti6O13 in the sample. Hydrothermally treated precipitates were calcined at temperatures 700°C, 800°C and 900°C. The purity and crystallographic composition of the samples were examined by XRD and the morphology was observed by SEM. Electrochemical behavior was studied by cyclic voltametry and galvanostatic cycling, all measurements were performed in three electrode cells with metallic sodium as counter and reference electrodes. Samples with three phase compositions were prepared: pure trititanate Na2Ti3O7, pure hexatitanate Na2Ti6O13 and mixture of both in the ratio of 42% Na2Ti3O7 to 58% Na2Ti6O13. Best capacity achieved by prepared samples was 145 mAh/g at 0.1C.

Figure 1