bluuebunny/crossref_metadata_2025_split huggingface dataset:
Controlling the Spatial Dimensions of Nanostructured Electrolytes to Stabilize Dendritic Electrodeposition of Silver
Authors: Sharon Daniel , Bennington Peter , Nealey Paul F. , Patel Shrayesh N. 
Published: July 2021

The tendency of metals to form uncontrolled dendritic morphologies during electrodeposition hinders the development of safe and reliable metal batteries. Multiphase nanostructured electrolytes can suppress dendritic growth if the mechanical modulus of the electrolyte is high relative to that of the metal or if the conducting channels are confined to nanoscale dimensions. Direct visualization and analysis of electrodeposition within polymeric nanostructures elucidates the structure−property relationships and mechanisms underlying the suppression of dendrite growth. To overcome these challenges, we introduce here a generalizable platform by which we can directly characterize electrodeposited metal morphologies in well-defined, multiphase nanostructured electrolytes by top-down SEM imaging [1]. This approach requires no destructive sample preparation techniques between electrodeposition and imaging. The platform consists of coplanar electrodes coated by polymeric structures consisting of alternating ion conducting and nonconducting material which are precisely created by lithography and etch techniques. These fabricated polymeric structures are designed to carefully model deposition of metals in nanostructured polymeric separators and electrolytes.
In this study we track the electrodeposition of silver ions (Ag+) dissolved in dry, aprotic poly(ethylene oxide) (PEO) polymer electrolyte confined within channels that are defined by a microfabricated nonconductive polystyrene structures. We find that Ag metal electrodeposition occurs only in the conductive domains with no significant deformation of the adjacent low-modulus nonconductive and confining domains. Moreover, we have shown that the Ag metal deposit morphology was strongly dependent on the dimensions of the conducting domains. When confinement width was similar in scale to the critical length scale for unstable deposition, the metal morphology was dense, unbranched filaments. Gradually increasing the confinement width led to branched dendritic deposition, although the side branch feature size was limited by the size of the confinement. These results demonstrate that in addition to mechanical and transport properties, the nanodimension of the structured electrolyte can also serve to stabilize dendritic morphology growth. This work highlights critical parameters for design of structured battery components such as solid-electrolytes, separators, and current collectors.
[1] Sharon, D.; Bennington, P.; Patel, S.N.; Nealey, P.F.*, “Stabilizing Metal Electrodeposition by Limiting Spatial Dimensions in Nanostructured Electrolytes,” ACS Energy Lett. 2020, 5, 2889−2896.

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Electrochemical Approach to Fabricate Semiconducting 2-D Metal-Organic Frameworks Based Thermoelectric Devices
Authors: Gonzalez-Juarez Maria , Flores Eduardo , Martin-Gonzalez Marisol , Nandhakumar Iris , Bradshaw Darren 
Published: July 2021

In recent years, there has been special interest in developing devices capable to harvest and store energy from natural resources without the generation of pollution. Thermoelectric generator (TEG) is an emergent technology to harvest energy, especially in those environments in which heat waste is involved. These solid-state devices are capable of generating an output voltage as a function of a temperature difference. The conversion of thermal energy into electrical energy in these devices is attributed to the Seebeck effect. The efficiency of a TEG is evaluated through the dimensionless figure of merit, Z. In order to achieve a competitive the figure of merit, a material with a high Seebeck coefficient, electrical conductivity and low thermal conductivity is desirable.
Conductive metal organic frameworks (c-MOFs) are hybrid materials composed of inorganic and organic building blocks, in which metal nodes are coordinated to highly conjugated organic linkers.1,2 The overlap between the metal and ligand frontier orbitals facilitates the charge transport in these materials. Porosity and heterogeneity in atomic species and linkers are features that have led to a predictably low thermal conductivity3, a key aspect to optimize Z, making MOFs potential candidates for TEG. To implement their practical use, the synthesis and study of ultrathin c-MOFs nanosheets have recently been reported4; however, the processing at large scale of these materials is still a challenge.
In this work we present an electrochemical approach to the growth of conducting thin films of the 2D c-MOF Cu3(HHTP)2 (where HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). Bulk Cu3(HHTP)2 was synthesized solvothermally according to the literature5 and we have subsequently fabricated thin films of this important framework by anodic electrochemical synthesis.6 We report the first thermoelectric measurements of this framework both in bulk and thin film form which resulted in Seebeck coefficients of -7.24 μV K-1 and -121.4 μV K-1 with a power factor of 3.15x10-3 μW m-1 for the film respectively. The study of conducting MOFs and their performance as TEG is expected to expand and offer alternatives to non-toxic, scalable and high-efficiency novel TEG materials.
[1] P. Q. Liao, J. Q. Shen, J. P. Zhang, Coord. Chem. Rev.
373, 22, 2018
[2] L. Sun, M. G. Campbell, M. Dincă, Angew. Chem. Int.
55, 3566, 2016
[3] Huang , A. McGaughey , M. Kaviany , Int. J. Heat Mass Transf. 50, 393, 2007
[4] W. Zhaoa, et al., Coord. Chem. Rev.
377, 44, 2018
[5] M. Hmadeh, et al., Chem. Mater.
24, 3511, 2012
[6] Ameloot, R. et al., Chem. Mater. 21, 2580–2582, 2009
(Invited) Copper Electrodeposition for Catalysis and Devices
Authors: Gewirth Andrew A. , Schmidt Ralf , Chen Xinyi 
Published: July 2021

This talk discusses two aspects related to Cu electrodeposition.
In the first area, we discuss our use of Cu electrodeposition to create very active catalysts for the CO2 reduction reaction (CO2RR). We describe how using appropriate additives highly porous Cu and Cu-alloy surfaces can be created. We also show how electrodeposition can be used to incorporate polymers, the addition of which yields exceptionally active catalysts for ethylene production. The activity of these surfaces is interrogated using spectroscopy, which reports on the effect of oxides, pH, and alloy identity on product speciation.
In the second area, we evaluate the effect of chain length for a series of alkyl sulfonic acid additives on Cu electrodeposition by using a combination of electrochemical and Raman spectroscopic methods. The spectroscopy reports on the relative degree of cis and trans character in adsorbed additives, which is correlated with activity.
Comparative Study of Sheet Resistance Stability of Electro-Deposited Ni/Co - Alloy Thin Films
Authors: Rindo Masashi , Okamoto Naoki , Saito Takeyasu , Kitajima Akira 
Published: July 2021

Cu is conventionally used for interconnect material in most of high performance and high integration of logic devices because Cu has low conductivity as 1.7×10－8 Ω･m and also has excellent electromigration resistance. However, Cu requires a barrier layer for eliminating Cu diffusion into SiO2 or Si. Because of the limitation of the barrier layer thickness, the effective resistance of the wiring including the barrier layer greatly increases with decreasing of the width of Cu wiring less than 10 nm. Therefore, many researches have been reported about the development of barrier layer-free wiring technology using Co or Ru with low resistivity compared to Cu wiring system. Ni has similar physical properties e.g. resistivity, thermal expansion coefficient, diffusion coefficient, etc. like Co or Ru, however, few research on electrical properties has been done so far. In this study, Ni, Ni-Co alloys, and Co are deposited by electrodeposition and crystallographic structure and electrical properties were evaluated.
A Ni or W (5 nm) seed layer were deposited onto thermally grown SiO2/Si(001) substrates (10 mm sq.) at R.T. by RF sputtering. After forming the seed layer, Ni or Ni-Co alloy or Co thin film (50 nm) was deposited. Table 1 shows the composition of electrodeposition bath. After the deposition, all samples were annealed in argon atmosphere (0.1 Torr) at 450°C for 30 minutes. Elemental analysis was done by Energy Dispersive X-ray spectrometry (EDX). The crystal structure, Chemical bonding state and electrical properties were evaluated by X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and 2-terminal Method, respectively, before and after annealing.
Figure 1 shows the sheet resistance change of Ni, Ni-Co alloy, or Co films before and after 450°C - 30 minutes annealing using (a) Ni and (b) W as a seed layer. There was no significant difference in sheet resistance between the Ni or W seed layer samples. In the case of Ni or Ni-Co alloy films, the sheet resistance after annealing was very stable for both seed layers, Ni and W. On the other hand, the sheet resistance of Co films increased and they were considered to be oxidized by XPS and XRD results. Co film by electrodeposition was oxidized but Ni and Ni-Co alloy films were not oxidized by annealing, so they are better wiring metal than Co in terms of oxidation resistance.

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PRC Surface Finishing of Additively Manufactured Impellers
Authors: Hall Timothy , Liu Danny , Garich Holly , Taylor E. Jennings , Snyder Stephen 
Published: July 2021

Powder bed methods of additive manufacturing (AM) use either an electron beam (Electron Beam Melting – EBM) to sequentially melt powder, layer by layer, to build up a 3-dimensional object directly from a powder bed according to a computer aided design file. Complexity is free with AM processes, so parts such as the impeller are natural candidates for AM.
With EBM. there are four steps to build each layer in a build. First, the beam is scanned to preheat the powder bed without melting, second, the contours (outer edge) of the area to be melted is traced and powder melted, third, the hatch (area within the contours) is melted and finally any supports that need to be built to support higher layers of the part being built are added. The side face of a part adjacent to powder after an EBM build.
The major concerns for incorporation of AM into structural parts are (1) microstructural anisotropy/inhomogeneity, (2) porosity – open near the surface and closed internally and (3) surface finish that is strongly dependent on the orientation of the surface relative to the build direction. Improving the surface finish is critical for certain applications. While finish machining can be used where surfaces are accessible, one benefit of the complexity of part shape is the possibility of building parts with internal channels, inaccessible to machining.
Therefore, this paper will discuss recent developments toward the demonstration of a process to electrochemically finish the internal passages of grade 5 titanium shrouded impellers produced by additive manufacturing. Specifically, we will discuss developments toward achieving optimal electrochemical processing conditions, surface finish, nominal tooling, and performance through structural spin test evaluations. Unlike conventional surface finishing processes that either use media or machine tools to physically modify the surface, electrochemistry can be used as a non-contact flexible approach, to finish hard to reach surfaces such as the internal channels of shrouded impellers that maybe inaccessible to conventional processes. This paper will focus on pulse/pulse reverse electrofinishing processes developed by Faraday Technology and the technique to scale this approach to functional parts of interest.

Acknowledgements: The financial support of USAF Contract No. FA8814-15-C-0007 is acknowledged.
Techno-Economic Analysis of CO2-to-Fuel with a Proton-Conducting Ceramic Sabatier Electrolyzer
Authors: Pritchard Tyler , Pan Zehua , Braun Rob , Sullivan Neal P. 
Published: July 2021

As intermittent renewable electricity generation achieves higher market penetration, the need for robust storage and dispatch capabilities become more pronounced. In this report, we present a techno-economic analysis based around a levelized cost of storage (LCOS) calculation for a Sabatier Electrolyzer to illustrate the value proposition of electrolyzer technology. The Sabatier Electrolyzer is illustrated in Figure 1A; the CO2 feed to the fuel electrode is upgraded to CH4 through heterogeneous catalysis with hydrogen. The hydrogen is produced through water electrolysis at the steam electrode. When driven by surplus electricity, the Sabatier Electrolyzer presents an energy-storage option with CO2-to-fuels.
The electrolyzer features a proton-conducting ceramic electrolyte (BaCe0.4Zr0.4Y0.1Yb0.1O3-d) that has shown encouraging performance under fuel-cell and H2O-electrolysis applications. The Sabatier chemistry (CO2 + 4 H2 = CH4 + 2 H2O) occurs within the porous fuel electrode, a nickel-ceramic composite, where protons emerging from the ceramic phase react with CO2 or recombine to form H2 over the nickel phase. The exothermic Sabatier reaction can be balanced by the endothermicity of H2O electrolysis improving plant-level thermal balance and higher efficiency.
This report explores the economic potential of a commercial-scale Sabatier electrolyzer plant from the perspective of levelized cost of storage (LCOS). This LCOS is based on similar analyses conducted for lithium-ion batteries, flow batteries, flywheels, and pumped-hydro facilities. The model combines plant-level round-trip efficiency (RTE), overnight capital costs, variable operations and maintenance (O&M) costs, and charging costs into a time value of money (TVM) financial model. The model is exercised to estimate the lifetime cost of energy storage for the plant.
The protonic-ceramic electrolyzer presents a perhaps unusual materials set. While protonic-ceramic fuel cells have demonstrated high performance and encouraging durability at the lab scale, the materials have also shown undesirable electronic conduction that can substantially decrease electrolysis efficiency, boosting costs. The electrochemical model captures the substantial impact of protonic-ceramic electrochemical performance on LCOS, and is validated by lab-scale experimental measurements of protonic-ceramic Sabatier Electrolyzer cells. Results were scaled to yield the commercial-scale LCOS.
Sensitivity analyses demonstrate the primary cost drivers behind the commercial-scale Sabatier Electrolyzer plant. Key cost drivers include Faradaic efficiency, methane yield, utility cost of electricity, and cost of sequestered CO2. Depending on operational parameters, the LCOS of the commercial-scale Sabatier Electrolyzer plant ranges from $4,319 down to $348 per MWh of storage potential.

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Revealing Relationships between Surface Facets and Performance of LiNiO2 Cathodes
Authors: Kim Minkyung , Chen Guoying 
Published: July 2021

Ni-rich layered oxides with a general formula of LiNi1-xMxO2 (M = Mn, Co, Al etc.) are currently considered the most promising cathode materials for lithium-ion batteries (LIBs). In order to further increase energy density, higher Ni content is desirable. Previous studies, however, showed that surface-related degradation reactions become more severe with increasing Ni content, especially at high operating voltages.2 Recent theory work has suggested that surface facets play an important role in the reactivities between LiNiO2 (LNO) and the electrolyte.3 Experimental understanding of the overall relationships between Ni-rich oxide surface and reactivities, on the other hand, is largely missing.
In this study, we synthesized single-crystal LiNiO2 with different shapes and surface orientations, including Cubic with predominately (104)-family surfaces, Octahedron with predominately (012)-family and Truncated-polyhedron with mixed (001)-, (104)- and (012)-family surfaces. Note that synthesis of Ni-rich layered oxides with dominating (104) surfaces was not reported previously. We found that the Cubic-LNO sample consistently outperformed all other samples in terms of cycling stability and thermal stability, confirming (104) surface is preferrable for LNO cathodes with better cycle life and thermal safety. Our study not only identifies the optimal particle surface but also provides design insights for future development of Ni-rich layered oxide cathodes.

References

Bianchini, M.; Roca-Ayats, M.; Hartmann, P.; Brezesinski, T.; Janek, J., There and Back Again -The Journey of LiNiO2 as a Cathode Active Material. Angewandte Chemie International Edition
2019,
58 (31), 10434-10458.

Liang, L.; Zhang, W.; Zhao, F.; Denis, D. K.; Zaman, F. u.; Hou, L.; Yuan, C., Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies. Advanced Materials Interfaces
2019,
7 (3), 1901749.

Cho, E.; Seo, S.-W.; Min, K., Theoretical Prediction of Surface Stability and Morphology of LiNiO2 Cathode for Li Ion Batteries. ACS Applied Materials & Interfaces
2017,
9 (38), 33257-33266.
(Invited) Electro-Chemo-Mechanical Degradation of LiNiO2-Derived High-Ni-Content Cathode Materials
Authors: Xin Huolin , WANG Chunyang , Lin Feng , Mu Linqin 
Published: July 2021

High-Ni and low-Co or Co-free layered cathode materials have become the focus of intense research in the battery community, and have rekindled interest in high-capacity layered lithium nickelate (LiNiO2). Despite increased capacity and reduced cost, LiNiO2 and LiNiO2-based high-Ni cathodes suffer from rapid capacity loss and severe chemomechanical degradation. Specifically, as lithium is deintercalated from LiNiO2, the material undergoes severe oxygen release and phase transformations, and develops cracks at both the nano- and micro-scales, leading to reduced capacity and interfacial instabilities. In this talk, I will report our recent findings on the intricate connection between oxygen loss and LiNiO2 mechanical degradation and a new strategy that can inhibit both effects.
This material is based upon work supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Award Number: DE-EE0008444.
Hard Magnetic Composite: FePt Nanoparticles Grown within Nanostructured Silicon
Authors: Rumpf Klemens , Granitzer Petra , Gonzalez-Rodriguez Roberto , Coffer Jeffery , Reissner Michael 
Published: July 2021

In this work porous silicon (PSi) and silicon nanotubes (SiNTs) are presented as a platform for filling with FePt nanostructures which offer a hard magnetic behavior. The difference of the magnetic characteristics between the two systems is figured out.
The porous silicon is produced by anodization of a highly doped n-type silicon wafer in a 10 wt% HF solution [1]. The morphology offers separated pores of about 60 nm and a mean distance between the pores of 50 nm. The SiNTs are fabricated in using an array of ZO wires as template, subsequent silicon deposition and finally etching off the ZO [2]. The inner diameter of the tubes and also the wall thickness can be tuned by the fabrication process. In this work SiNTs with comparable inner diameter to the PSi structure are used. FePt nanoparticles (NPs) are chemically grown inside the pores and the tubes, respectively whereat the molar ratio of Fe is varied (Pt:Fe 1:1, 1:3 and 1:6). For this purpose a 3 component solution consisting of H2PtCl6, Fe(NO3)3 and citric acid is used, whereas the ratio of the components is modified.
Magnetic characterization of the samples is performed by VSM (Vibrating Sample Magnetometer), the structure is analyzed by SEM, TEM and EDX.
The magnetic response of the two different composite systems is investigated. PSi/FePt shows a higher coercivity and remanence than SiNTs/FePt and thus a higher hard magnetic performance. The variation of the coercivities between SiNTs/FePt and PSi/FePt is about 57%.
Considering the FePt deposits with different molar ratio of Fe the coercivities vary in a range of 5% in the case of both template types. Comparing FePt loaded samples with Co loaded samples in all cases an increase of the coercivity and of the remanence is observed for FePt, whereat in the case of PSi as template material the increase is significantly stronger than in the case of SiNTs samples. Figure 1 shows the comparison of the hysteresis of PSi and SiNTs filled with FePt NPs.
Hard magnetic materials within nanostructured silicon give rise for on-chip applications using 3 dimensional arrays of nanomagnets.
Figure 1: Field dependent magnetization measurements of PSi and SiNTs filled with FePt NPs, respectively showing a higher coercivity in the case of PSi.
[1] K. Rumpf, P. Granitzer, H. Michor, NRL 11, 398 (2016).
[2] X. Huang, R. Gonzalez-Rodriguez, R. Rich, Z. Gryczynski, J.L. Coffer, Chem. Comm. 49, 5760 (2013).

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Application of in-Situ Radiography to Porous Carbon Felt Electrodes in Vanadium Redox Flow Batteries
Authors: Gebhard Marcus , Roth Christina , Schnucklake Maike , Schneider Jonathan , Cheng Ming , Hilger Andre , Manke Ingo 
Published: July 2021

Porous carbon felts are routinely applied as electrodes in vanadium redox flow batteries. They offer several advantages, such as low cost, low weight, good electron conductivity, and chemical inertness. However, due to their comparatively low activity in catalyzing the vanadium reactions at the anode and cathode side of the battery, an activation treatment is required to enhance the kinetics. In the literature, a heat-treatment at 400 °C in air has been reported as sufficient to introduce more oxygen functional groups at the surface, also improving the wettability of the felt and its contact with the electrolyte significantly. In this context, it is however not clear, which mechanisms are responsible for the observed performance increase. In another approach, bismuth is deposited on the carbon felts to enhance the V2+/3+ reaction in the anolyte. While a better battery performance is indeed observed, the bismuth is assumed to be dissolved and re-deposited during the charge-discharge cycles.
The aim of this work is to utilize in-situ X-ray radiography to study both the activation process and the catalytic enhancement effect due to bismuth decoration in more detail. We will highlight the potential of in-situ (synchrotron) radiography for the investigation of electrode/electrolyte interaction, pore filling and electrolyte flow behaviour complementing other more routine characterization techniques nicely [1]. To elucidate the effect of air activation, pristine and heat-treated carbon felts have been brought into contact with water, sulfuric acid and an acidic vanadium solution and ex-situ contact angles determined. This study was complemented by in-situ X-ray radiography, in which an in-house built flow cell served to monitor the electrolyte flow through the porous felt materials (pristine and heat-treated). The effect of the heat-treatment can be clearly discerned in water, see figure 1 (top: pristine felt, bottom: heat-treated felt). In contrast, when the commercial vandium electrolyte was being used, the differences between pristine and heat-treated felt vanished. Consequently, only a negligibly higher pore filling degree was observed for the treated felts, while all felts were flooded in less than 1 minute. [2]
Apart from the phenomena described above, we will also highlight the potential of in-situ radiography with respect to Bi-decorated felts during operation. [3]
[1] L. Eifert, N. Bevilacqua, K. Köble, K. Fahy, L. Xiao, M. Li, K. Duan, A. Bazylak, P.-C. Sui, R. Zeis, ChemSusChem 13 (2020) 3154.
[2] M. Gebhard, M. Schnucklake, A. Hilger, M. Röhe, M. Osenberg, U. Krewer, I. Manke, C. Roth, Energy Technol. 8 (2020) 1901214.
[3] M. Gebhard, T. Tichter, J. Schneider, J. Mayer, A. Hilger, M. Osenberg, M. Rahn, I. Manke, C. Roth J. Power Sources 478 (2020) 228695.

Figure 1