bluuebunny/crossref_metadata_2025_split huggingface dataset:
Insights into Carbonate Fuel Cell Operation Under Carbon Dioxide Capture Conditions
Authors: Elsen Heather , Sawicki Conrad , Barckholtz Tim , Rosen Jonathan 
Published: February 2020

Providing for increasing global energy needs while managing carbon dioxide emissions is the dual energy challenge the modern world faces. In order to meet this challenge, reliable and dispatchable low carbon energy sources are a likely component. For many scenarios, this suggests that cost effective carbon dioxide capture will be a key technology.[1] Carbon capture with carbonate fuel cells (CFCs) may be one such technology option.[2]
Carbonate fuel cells concentrate carbon dioxide from the cathode to the anode as part of their normal operation, effectively doing both carbon capture and low carbon power generation in a single process. (see Figure 1) When generating power, typical carbon dioxide concentrations fed to the CFC cathode tend to be higher than carbon dioxide emissions of many industrial processes. This means that if we want to capture that carbon dioxide, we need the fuel cell to operate at lower carbon dioxide concentrations than it typically does. For carbon capture operations, cathode inlet carbon dioxide concentrations could be as low as 4%. Additionally, under typical power generation operations, CFCs only capture a fraction of the carbon dioxide (<50%) fed to the cathode, where for carbon capture rates may be as high as 90%. Together these two constraints (low initial concentration and higher capture) results in very low carbon dioxide concentrations in the cell, particularly at the cathode outlet. This may impact the fundamental chemistry of the process.
Carbon dioxide capture at 4% and lower was tested in a fuel cell, specifically designed to minimize mass transport effects external to the active cell components. Carbon capture was demonstrated at a range of carbon dioxide concentrations ranging from standard operation for power generation (>10%) to <1%. Additionally, oxygen concentrations and current densities were varied over likely operational ranges. We demonstrate that under most circumstances, operations under carbon capture conditions proceed via a similar mechanism to those under power generation conditions. However, in harsh or extreme conditions, where carbon dioxide concentrations are low (<0.5%) and/or current densities high, alternative mechanisms appear. We demonstrate how the CFC performs when these alternative mechanisms are present. Additionally, our findings suggest that they appear to utilize water in place of carbon dioxide and allow the cell to operate at conditions beyond theoretical complete carbon capture.
[1] IEA World Energy Outlook 2018; Bloomberg New Energy Finance, New Energy Outlook 2018
[2] Ghezel-Ayagh H., Jolly S., Patel D., Hunt J., Steen W., Richardson C., Marina O., (2013) A Novel System for Carbon Dioxide Capture Utilizing Electrochemical Membrane Technology ECS Transaction Vol 51 (1) 265-272

Figure 1
Role of Li Distribution in High Li Conductivity of Li
x
(Ge,P)3S12
Authors: Hinuma Yoyo , Yajima Takeshi , Hori Satoshi , Iwasaki Rui , Hiroi Zenji , Kanno Ryoji 
Published: February 2020

Li
x
(GeP)2S12 (LGPS) is a lithium superionic conductor with the obvious potential application as an electrolyte for all-solid-state batteries that could be safer and have higher power compared to conventional batteries using liquid electrolytes. Li10GeP2S12 shows an exceptionally high conductivity of 12 mS/cm at room temperature [1], and doubling of the conductivity to 25 mS/cm was attained in the related compound Li9.54Si1.74P1.44S11.7Cl0.3 [2]. LGPS has a complicated structure. The backbone is a framework of GeS4 and PS4 tetrahedra where there are (Ge,P) shared sites and P-only sites. Li is four-folded coordinated with S and occupy four types of sites, Li1 to Li4. (Li1)S4 and (Li3)S4 form a one-dimensional chain and this is considered to be the primary Li diffusion route. The original article [1] claimed that the Li1 site is clearly double-split while the other Li sites are not split. However, in our presentation we show that the Li3 site is actually double-split at room temperature and triple-split at 10K.
Li splitting means that there are more local minima for Li, which in turn results in increased complexity in Li migration paths. Understanding and controlling of Li splitting is important to further enhance Li conductivity. Both Li1 and Li3 sites, which are found to split, take part in the primary Li conduction path and therefore the intriguing high Li conductivity of LGPS should be strongly influenced by fine details of the Li potential. Our first principles calculations show that that neither Li1 nor Li3 sites splits in Li12Ge3S12 where all Li sites are occupied, and reducing the Li concentration, or introducing Li vacancies, was found to be necessary for splitting of these Li sites.

Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A., A lithium superionic conductor. Nat. Mater. 2011, 10 (9), 682.

Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R., High-power all-solid-stae batteries using sulfide superionic conductors. Nature Energy 2016, 1 (4), 16030.
Improving the Ionic Conductivity of Li15P4S16Cl3 By Doping
Authors: Liu Zhantao , He Xingfeng , Xiong Shan , Bai Jianming , Mo Yifei , Indris Sylvio , Chen Hailong 
Published: February 2020

All-solid-state Li-ion batteries are a next generation electrochemical energy storage technology and an emerging alternative to conventional Li-ion batteries owing to higher energy density, wider operation temperature range and better safety properties1. Solid state ionic conductor as the solid electrolyte (SEs) is the key component in all-solid-state Li-ion batteries. Among existing SEs, sulfides SEs attract extensive attentions due to high room temperature ionic conductivity and favorable mechanical properties. However, currently known sulfide SEs only present a few limited types of crystal structures, which limits the materials design and hinders our understanding of ionic conduction mechanisms. Exploring new compound and new crystal structures beyond known groups is much desired in order to expand the ionic conductor database and advances the knowledge about ionic conduction.
Recently, our group successfully synthesized and identified a new lithium chloro-thiophosphate in Li2S-P2S5-LiCl system, namely Li15P4S16Cl3
2. This compound shows a low ionic conductivity of ~10-7 S/cm at room temperature. However, this crystal structure provides abundant choices for composition and unit cell size tuning, which may trigger high ionic conductivity. We successfully substituted P in Li15P4S16Cl3 with aliovalent cations to tune the Li content and the interstitial site occupancy. As a result, high room temperature conductivity of ~10-5 S/cm was achieved. The structure of the doped compounds was examined with using synchrotron X-ray and neutron diffractions. The Li+ diffusion pathway was also theoretically investigated with using ab initio molecular dynamics (AIMD) method and experimentally examined with using 7Li solid state nuclear magnetic resonance (NMR) techniques.

Auvergniot, J.; Cassel, A.; Ledeuil, J.-B.; Viallet, V.; Seznec, V.; Dedryvère, R., Interface Stability of Argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in Bulk All-Solid-State Batteries. Chemistry of Materials
2017,
29 (9), 3883-3890.

Liu, ZT.; Zinkevich, T.; He, XF.; Indris, S.; Xiong, S.; Liu, J.; Xu, W.; Bai, J.; Mo, Yifei; Chen, HL., Li15P4S16Cl3, a new lithium chloro-thiophosphate as a solid state ionic conductor. Submitted.
(Invited) Interface Engineered Lithium Garnets for Lithium-Metal Batteries
Authors: Ramaswamy Murugan 
Published: February 2020

Inorganic solid fast Li+ conductors based batteries are expected to overcome the limitations caused by the safety concerns of flammable organic electrolytes based Li+ batteries. Garnet structured solid electrolytes meet the requirements of being mechanically robust, display high ionic conductivities at room temperature, have large electrochemical window and more importantly few lithium garnets are electrochemically stable when in contact with metallic lithium [1]. However, all-solid-state Li metal batteries based on lithium garnet solid electrolytes have challenges in realizing high practical performances at room temperature due to their high electrode/electrolyte interfacial resistances, formation of reaction product layers at the interfaces and dendrite formation through the grain boundaries.
Onset of lithium dendrite within the electrolyte on repeated cycling at high current densities could be fatal for lithium metal batteries. Homogeneous current distributions at the Li-electrolyte interface along with the synthesis of highly dense solid electrolyte are significantly vital to ensure the safe usage. Hence, it is of utmost importance to provide a favorable contact between Li metal and lithium garnet electrolyte to reduce the interfacial resistance and remove inhomogeneous current distribution. The surface modifications at Li/solid electrolyte interface will be a useful technique to improve the cycle stability and rate capability of charge discharge reaction. However, negating interfacial resistance and the reaction product layer at the cathode-lithium garnet electrolyte interface is still a challenge.
The salient features of various strategies utilized to enhance the room temperature performance of Li metal battery based on garnet structured solid electrolyte will be discussed.

References

[1] R. Murugan, V. Thangadurai, W. Weppner, Fast lithium ion conduction in garnet typeLi7La3Zr2O12, Angew. Chem. Int. Ed. 46 (2007) 7778–7781.
Ab Initio Computation Design for Fast Ionic Conductors
Authors: Mo Yifei 
Published: February 2020

Fast ionic conductor materials are the key component in enabling a variety of electrochemical devices. It is crucial to understand why only a few materials exhibit faster ionic conduction than typical solids and how one can design fast ion conductors following simple principles. Using ab initio modeling techniques, we studied a range of novel fast Li-ion conductor materials and identified the mechanisms leading to fast Li-ion conduction in solid materials. In lithium super-ionic conductors, we show that fast diffusion in super-ionic conductors happens through unique concerted migration mechanism of multiple ions with low energy barrier in contrast to isolated ion hopping in typical solids. We elucidate that low energy barriers of the concerted ionic diffusion are a result of unique mobile-ion configurations and strong mobile-ion interactions in these super-ionic conductor materials. Our theory provides a conceptually simple framework for guiding the design of super-ionic conductor materials. Using first principles computation, we demonstrate this strategy by designing a number of novel fast ion conducting materials. Furthermore, we highlight the design principles for having such crystal structures.
References:
Adelaide Nolan, Yizhou Zhu, Xingfeng He, Qiang Bai, Yifei Mo, “Computation-Accelerated Design of Materials and Interfaces for All-Solid-State Lithium-Ion Batteries”, Joule, 2, 2016-2046 (2018)
Xingfeng He, Yizhou Zhu, Yifei Mo, “Origin of Fast Ion Diffusion in Super-Ionic Conductors” Nature communications, 8, 15893 (2017)
Paradigms of Structural, Chemical, and Dynamical Frustration in Superionic Conductors
Authors: Wood Brandon C. , Kweon Kyoung , Varley Joel Basile , Shea Patrick , Adelstein Nicole 
Published: February 2020

Rationally motivated computational discovery and optimization of solid electrolytes require the development of reliable descriptors for fast ionic conductivity. However, many of the fundamental motivations for superionic behavior in solids remain enigmatic, which has generally slowed progress in screening electrolyte candidates, as well as in tuning existing materials to maximize ionic conductivity. I will discuss our efforts using first-principles molecular dynamics simulations to unravel various mechanisms of ionic conductivity in model classes of solid electrolytes. Using computational “experiments”, our simulations systematically isolate factors such as stoichiometry, strain, composition, and crystal structure in the determination of ionic conductivity. Collectively, the results point to the importance of a frustrated energy landscape in promoting ultrafast diffusion. Different types of frustration in model superionic conductors will be discussed, arising from factors such as off-stoichiometry, competition between interstitial site occupancies, symmetry incompatibilities between local bonding character and lattice geometry, and dynamical frustration coupled to anharmonic processes. Physicochemical origins of the relevance of these factors for cation mobility will be explored, with a view towards developing design rules for engineering faster ionic conductors. Our findings suggest that the relative contributions of the different frustration paradigms depend chiefly on the fundamental nature of the lattice-forming ions, suggesting there may be no single universal descriptor for ionic conductivity, but rather classes of superionic conductors with similar underlying motivations. Specific examples will be drawn from our recent results on superionic materials based on oxides, halides, and polyatomic anions.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Particle Size and Morphology of Carbon Dioxide Reduction Electrocatalysts Fabricated By Pulse/Pulse-Reverse Electrodeposition
Authors: Skinn Brian , Leonard McLain Evan , Wang Dan , Brushett Fikile R. , Taylor E. J. 
Published: February 2020

A variety of techniques for management of carbon dioxide emissions from power generation facilities and other industrial sites have been under active investigation for decades, in an effort to mitigate the environmental impacts of these releases. Once such approach is electrochemical reduction, which treats the waste CO2 as a source material for the production of value-added materials. Currently, the most promising form factor for this electrocatalytic application appears to be a stack-based system, where catalyst is immobilized on porous media that is interfaced with a liquid or solid electrolyte, and the reactant carbon dioxide is delivered to the active region by gaseous diffusion, which is orders of magnitude faster that diffusion though aqueous media. Various carbonaceous reduction products can be created depending on the composition, size, and microstructure of the catalyst particles, including formic acid/formate, carbon monoxide, alcohols, and hydrocarbons. In general, smaller catalyst particles, ideally in the nanoparticulate (« 1 μm) range, tend to yield superior catalytic performance, due to a combination of factors such as a higher density of exposed grain boundaries and a higher fraction of exposed crystalline facets that are uncommon in particles of micron size or larger.
This talk will survey recent work illustrating the ability of pulse/pulse-reverse electrodeposition processes to tune the size of particles applied to gas-diffusion electrode substrates, with a primary focus on two single-metal catalyst materials relevant to carbon dioxide electroreduction: tin and copper. The former is a catalyst primarily for formic acid production, while the latter is unique among single-metal catalysts as the only element known to date to produce significant amounts of hydrocarbons and/or alcohols. Particle morphology and representative particle size will be discussed as a function of pulsed electrodeposition waveform parameters, with the goal of highlighting overarching trends across the waveform space.
(Invited) Pulse Current Currents Transient Curve Study: Hydrogen Discharge and Modeling Attempts
Authors: Hihn Jean-Yves , Lain Amador Lucia , Rolet Jason , Doche Marie-Laure , Gigandet Marie-Pierre , Taborelli Mauro , Ferreira Leonel M.A. , Tardelli Joffrey , Bercot Patrice 
Published: February 2020

Pulse currents and periodic reverse currents have proven to be of great interest for improving plating rate and coatings properties. Virtually all metals are sensitive to this technique. Pulse plating operates a periodically interrupted direct current. [1] Every short (usually a few milliseconds) cathodic pulse is followed by a short time-off, where no current is applied. Reverse plating implements an additional reverse current, periodically applied to the electrode [2]. Nevertheless, the optimum choice of the pulse current sequence parameters requires preliminary studies. Among them, the use of transient curves in response to pulse currents represents an interesting strategy. In the case of electrolytes with high Faradic yields, a succession of characteristic patterns may be observed. Particularly, two typical plateaus are noticeable, the first corresponds to the Faradic reduction of the metallic species involved below the diffusion limit, while the second, at higher potential, is attributed to the local resistance induced by the depletion of the concentration of the concentration of metal close to the interface. This situation called “diffusion limited range” interferes with the metal reduction, promoting the competitive hydrogen production. A recent work performed with copper during electroforming process show a large influence of the various steps on the hydrogen trapping into the coating [3]. On the contrary, electrolytes with low Faradic yields does not exhibit these two patterns, because the hydrogen discharge starts almost immediately with the current increase. In this case, reverse pulse is a possible solution to keep the possibility to modify the coating properties as for example the microstructure. In this case, the strategy for parameters determination is less obvious. In both situations, modeling constitutes a great help to seek for optimization.
[1] J. Cl. Puippe and N. Ibl, J. Appl. Electrochem., 10, (1980)
[2] E. J. Taylor, C. Zhou, and J. J. Sun, USPTO Patent Grants, (2005)
[3] L. Lain Amador, J Rolet, M-L Doche, P. Massuti-Ballester, M-P Gigandet, V. Moutarlier, M. Taborelli, L. M. A. Ferreira, P. Chiggiato, J-Y Hihn, ECS trans. ECS Transactions 85(13): 815-822 (2018)
The Properties of Pulse-Plated Copper Derived from Additive-Bearing, Low-Metal Ion Concentration Electrolytes
Authors: Pena Eden May Dela , Roy Sudipta 
Published: February 2020

In semiconductor devices, copper metallization patterns are created using a combination of photolithography and electroplating. Photolithography, which uses light to transfer geometric patterns from a mask onto a substrate, is a multi-step process that is costly, time-consuming, and entails the use of harmful chemicals.
A recent electrodeposition process called Electrochemical nano and micro Fabrication by flow and Chemistry (EnFACE) was developed to enable single-step, direct, mask-less pattern transfers onto metallic substrates. EnFACE offers the possibility of replacing photolithography and avoid the difficulties associated with the process.
For typical copper electrolytes, the use of pulsed current and plating additives are known to improve deposit properties such as grain structure, mechanical strength, and throwing power. However, EnFACE uses an acid-free, additive-free, low-conductivity plating electrolyte containing low concentrations of metal salts (0.1 M CuSO4), a composition which significantly differs from the conventional copper plating electrolytes. Since the chemistry of this electrolyte is relatively new, a majority of its properties still needs to be discovered and understood. In this work, we report on the influence of current modulation (i.e., pulsed-current) on the properties of Cu electrodeposits obtained from additive-bearing, low metal salt concentration electrolyte.
Copper films were plated from 0.1 M CuSO4 electrolyte containing different concentrations of plating additives (i.e., 0%, 17%, 33%, 50%, 100%, and 200% of the industry recommended concentration) using direct (DC) and pulsed current (PC) modulations. The operating pulse parameters used were θ = 0.25 at a t
p of 100ms and the actual plating time was set for a deposit thickness of 25 um. The mechanical properties of deposits were characterised using the tensile test (UTM), while electrical properties were assessed using the four-point probe. Grain characteristics and morphology was investigated using scanning electron microscope (SEM), electron backscattered diffraction (EBSD), and X-ray diffraction (XRD).
Results of mechanical tests indicate that the PC-plated films possessed higher yield strength, tensile strength and ductility than its DC-plated counterparts (see Fig.1). Similarly, electrical measurements confirmed that pulse plated films have better conductivity than the DC plated ones. These changes in properties were traced to the changes in microstructure induced by the application of pulsed current modulation during plating. Finally, the use of pulsed current offers the added benefit of reducing the required amount of additives to obtain the desired deposit properties. The optimum additive concentration was 50% of the recommended value when using DC plating; while it was only 33% in PC plating.

Figure 1
Modeling of a Gas-Phase, Bipolar Membrane CO2 Electrolyzer
Authors: Star Andrew G. , Deutsch Todd G , Neyerlin K C 
Published: February 2020

Aqueous electrochemical carbon dioxide reduction electrodes encounter prohibitive mass-transport limitations due to the low solubility of CO2 in aqueous electrolyte which limits cells to ~10 mA/cm2 reaction rates (1, 2). While C2+ products are desirable they remain economically challenging with low Faradaic efficiencies and high cell overpotentials (3). Alkaline environments are capable of facilitating preferential C-C bond formation (4); for example, the highest faradaic efficiencies for C2 products (5) and C3 products (6) have been reported under alkaline conditions. Unfortunately, carbon dioxide fouls alkaline reactors through the formation of carbonate species. Bipolar membrane-based CO2 electrolyzers, which combine gas phase acidic reduction and alkaline oxygen evolution, offer a unique opportunity to address the engineering and technological challenges of CO2 reduction. Such a system may preclude large anodic activation overpotentials while avoiding carbonate generation as the cathodic reaction proceeds in acid environment.
In the gas-phase bipolar membrane CO2 reduction reactor, fundamental questions remain regarding optimal choice of cell architecture, catalyst, and operating conditions. A model of the cell was developed and used to explore rate-limiting processes and process parameters effects on reaction kinetics which dictate Faradaic efficiencies and, therefore, economic viability of the reactor. Fundamental benefits and challenges of the reactor were assessed and contrasted with competing cell architectures in context of the ultimate parameter to be optimized, cost per kilogram of averted CO2.

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