bluuebunny/crossref_metadata_2025_split huggingface dataset:
Criteria for Lithium “Dendrite” Propagation Evaluated in Single Crystal Solid Electrolytes
Authors: Park Richard , Swamy Tushar , Sheldon Brian W. , Rettenwander Daniel , Porz Lukas , Berendts Stefan , Uecker Reinhard , Carter W. Craig , Chiang Yet-Ming 
Published: February 2020

Lithium is both the most electropositive and lightest metal, making it the ideal anode material. Non-flammable ceramic electrolytes paired with Li metal anodes could potentially result in safe, energy dense batteries surpassing state-of-the-art lithium ion batteries. Oxide solid electrolytes typically have high shear moduli, far beyond that of Li metal, which one criterion [1] suggests should suppress lithium metal dendrites. However, our group has recently shown that fracture of the solid electrolyte initiating at surface defects can create pathways for dendritic growth of metallic Li that short-circuit the device. [2]
In this work, in-situ optical microscopy has been conducted to characterize the propagation of Li dendrites through single crystal solid electrolytes under a variety of electrochemical conditions. The complete absence of grain boundaries excludes that class of internal defects as paths for propagation. A unique morphological structure of the lithium dendrite observed within the single crystal support a Griffith flaw based fracture model, and in addition, suggest a local field-intensification mechanism of dendrite growth within the solid. Results for the single crystals compared to those from polycrystalline solid electrolytes, in literature and from our own work.
Additionally, it is shown that the initiation of Li propagation through single crystals may be affected by the electrode geometry. Under certain circumstances, Li infiltration is observed to initiate at the perimeter of the electronic conductor contact with the electrolyte – especially at corners with high local curvature. This behavior suggests that localized field and current concentration is also important, and may determine which supercritical surface sites dominate Li metal propagation during electrodeposition.

Reference
s
:

[1] Monroe, C. & Newman, J. The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces. J. Electrochem. Soc. 152, 396–404 (2005).
[2] Porz, L. et al. Mechanism of Lithium Metal Penetration through Inorganic Solid Electrolytes. Adv. Energy Mater. 1701003, 1–12 (2017).

Figure 1
Wire-Shaped Li-Ion Battery Based on Iron Sulfide Nanostructures on Carbon Based Electrode
Authors: Gibertini Eugenio , Panzeri Gabriele , Accogli Alessandra , Magagnin Luca 
Published: February 2020

In recent years, the development of new materials, electrode architectures and manufacturing strategies has opened Li-ion batteries to new application areas. In particular, the implementation of high-performances and reliable energy storage devices is a challenging task in the sector of smart-fabrics and wearable electronics. Wire-shaped batteries (WSBs) are one of the most active and rapidly growing research fields, because of their flexibility and easy integration in fabrics. The development of a suitable technique for the production of graphene fibers as electrodes boosted the interest in WSBs [1]. Typically, Li-ion WSBs rely on self-supported all-carbon electrodes made of reduced graphene oxide (RGO) and/or carbon nanotubes (CNTs) fibers [2], synthesized through the wet-spinning process. The incorporation of higher capacity active materials in carbon fibers like TiO2 nanosheets [3], SiO2 [4] and S nanoparticles [5,6] has already been demonstrated as a successful strategy to further increase battery performances. However, the incorporation of active material during the wet-spinning of the carbon-based fibers limits this technique to 2D materials only. Here, we propose Li-ion WSB based on RGO fibers electrode and iron sulfide. Iron nanostructures have been deposited on RGO fibers by an easy electrochemical route and converted in iron sulfide as active material through sulfurization process by thermal treatment in presence of sulfur. Half-cell configuration with Li wire as cathode has been evaluated as well as a full-cell configuration. Electrochemical stability of the active materials were investigated through cyclic voltammetries while capacity, efficiency and cycle stability were evaluated for both half-cell and full-cell configurations. Morphological and structural investigations were performed on the electrodes by means of SEM, XRD and Raman analysis.

References

[1] Z. Xu, C. Gao, Nat. Commun. 2 (2011) 571
[2] Zhang, Ye, et al. "Super-stretchy lithium-ion battery based on carbon nanotube fiber." Journal of Materials Chemistry A 2.29 (2014): 11054-11059.
[3] Hoshide, Tatsumasa, et al. "Flexible Lithium-Ion Fiber Battery by the Regular Stacking of Two-Dimensional Titanium Oxide Nanosheets Hybridized with Reduced Graphene Oxide." Nano letters 17.6 (2017): 3543-3549.
[4] Rao, Jiangyu, et al. "A high performance wire-shaped flexible lithium-ion battery based on silicon nanoparticles within polypyrrole/twisted carbon fibers." RSC Advances 7.43 (2017): 26601-26607.
[5] Liu, Ruiqing, et al. "Flexible wire-shaped lithium-sulfur batteries with fibrous cathodes assembled via capillary action." Nano Energy 33 (2017): 325-333.
[6] Chong, Woon Gie, et al. "Lithium–Sulfur Battery Cable Made from Ultralight, Flexible Graphene/Carbon Nanotube/Sulfur Composite Fibers." Advanced Functional Materials 27.4 (2017).
In-Situ AFM Measurements on Lithium Metal Anodes
Authors: Benning Svenja , Hausen Florian 
Published: February 2020

Using lithium metal electrode for the next generation of Lithium Ion Batteries (LIB) possesses the advantage of high energy around 300 Wh/kg coupled with progressed cathode material [1]. However, the formation of lithium dendrites and mossy lithium under electrochemical load (cycling) are currently the major hindrance of a wider use of such material and commercialization of the concept. Recently, the aforementioned challenges have been analyzed by means of nuclear magnetic resonance and found [2]. Those formations lead to degradation processes which are not yet understood at the micro- and nanometer scale. Therefore, experiments with high spatial resolution under realistic conditions gaining a better understanding of such phenomena are of utmost importance. Based on the practical significance for various applications the in-situ atomic force microscopy (AFM) characterization under electrochemical load is a key to develop new devices with improved functionality. Within this contribution we present combined atomic force microscopy and cyclic voltammetry (CV) measurements of the electrode-electrolyte interface between lithium anode and LP 30 (LiPF6 in EC/DMC), a common electrolyte in conventional energy storage. Therefore, the simultaneous investigation of structural, electrochemical and mechanical properties under electrochemical conditions is demonstrated. We will discuss the formation of mossy lithium as well as the formation of dendrites within the in-situ AFM results. Our results shed light onto the small scale processes on lithium metal anodes for LIBs and path the way towards applicability of bare lithium as anode material.

References:

[1] J. Wandt et al, Energy Environ. Sci., 2015, 8, 1358
[2] S. Kayser et al., arXiv: 1710.02577, 2017
https://arxiv.org/ftp/arxiv/papers/1710/1710.02577.pdf
Comparison of Battery Degradations Induced By Different Synthetic Driving Cycles and Real-World Traffic Conditions
Authors: Baure George , Dubarry Matthieu 
Published: February 2020

Advances in lithium ion battery pack technology have led to significant market penetration for electric vehicles (EVs), but there is still a need to develop new battery technologies, better control algorithms, and faster charging strategies to enhance further the ownership experience. Once developed, these advances must be validated. Unfortunately, fleet testing is not often an option because of the associated cost.
To address this issue and permit the validation of new technologies in the laboratory quickly, many studies are relying on synthetic driving cycles to mimic the usage cells would experience under actual utilization. Among the more popular ones are the Federal Urban Driving Schedule (FUDS), a US standard; the Dynamic Stress Test (DST) which is a simplified version of the FUDS cycle; and the New European Driving Cycle (NEDC), a European standard. The ability of these cycles to replicate EV usage is usually taken for granted; whereas, to the best of our knowledge, no study has scrutinized these cycles to establish if the induced degradation is indeed comparable with what is observed from real driving data.
It is proposed here to investigate the impact of the most-used, standardized driving cycles on state-of-the art lithium-ion cells and evaluate them against the impact of real driving in a laboratory-controlled environment. Different analysis techniques and metrics, such as voltage response, capacity, rate capability, and resistance, are employed to compare the most common synthetic driving cycles (FUDS, DST and NEDC) with scaled-down real driving data selected from the Hawai'i Natural Energy Institute (HNEI) in-house database. Two different sets of real driving data was used, one using a single commute in a loop and one using 25 similar commutes in a loop, to reveal any effect of traffic.
This study aimed to elucidate any significant discrepancies between simulated and real driving outcomes, determine the effect of traffic conditions, and propose possible improvements.
Controlled Synthesis of Mos­2 Microparticles for Lithium Ion Batteries
Authors: Schuppert Nicholas David , Bates Alex , Lee Sang C. , Park Sam 
Published: February 2020

Introduction – MoS2 is promising as alternative to traditional graphite anodes. MoS2 possesses a low redox potential relative to lithium and approximately 3x the theoretical capacity of graphite, making it an ideal candidate for lithium ion battery anodes [1, 2]. To achieve high storage capacities and stable capacities over many charge/discharge cycles, high electrochemically active surface areas and access to layer edge intercalation sites is required. Controlled growth of MoS2 microspheres, whose robust morphology should provide a stable structure and abundant access to intercalation sites also allows for the control of particle surface area to volume ratios, a key component to determining electrochemical activity of the anode particles. In this work, experimental parameters such as precursor materials, temperature and pressure are varied for the hydrothermal synthesis of MoS2 microparticles, giving control over particle morphology and size. The influence of surface area to volume ratios are then examined with respect to material stability and capacity. Fabrication procedures and preliminary results are shown in the following sections.

Fabrication procedures – Synthesis of MoS2 microspheres is accomplished by a hydrothermal procedure under high pressure. In a typical procedure hexammonium heptamolybdate tetrahydrate and thiourea are vigorously in a solution of deionized water. The solution is then transferred to a Teflon lined autoclave reactor vessel and heated to 220 °C for an extended period of time. The resulting black MoS2 precipitate is collected by centrifugation and washed with ethanol and deionized water several times to remove impurities. Lingering solvent is then removed by drying the material at low temperatures in atmosphere overnight.

Preliminary results – X-ray diffraction spectra of MoS2 microspheres taken at different reaction times are shown in Figure 1(a). Material crystallinity is observed to be dependent on reaction time. An SEM image typical of the fabricated MoS2 microspheres is shown in Figure 1(b), showing that the microspheres are composed of conglomerations of MoS2 sheets. Figure 1(c) shows particle size distributions of the three reaction times. All resulted in two size distributions per reaction time, with an increase in reaction time yielding an increase in both particle size distributions. Figure 1(d) shows surface area to volume ratios (S.V.R.) of the measured particle size distributions plotted against the S.V.R. function for a sphere.

References –

[1] T. Stephenson, Z. Li, B. Olsen, D. Mitlin, Energy & Environmental Science, 7 (2014) 209-231.
[2] N. Yabuuchi, K. Kubota, Y. Aoki, S. Komaba, The Journal of Physical Chemistry C, 120.

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(Invited) Safe, High-Energy-Density, Solid-State Li Batteries
Authors: Wachsman Eric D. 
Published: February 2020

We have developed transformational, and intrinsically safe, all-solid-state Li-ion batteries (SSLiBs), by incorporating high conductivity garnet-type solid Li-ion electrolytes into tailored tri-layer microstructures, by low-cost solid oxide fuel cell (SOFC) fabrication techniques to form electrode supported dense thin-film (~10μm) solid-state electrolytes. The microstrucurally tailored porous garnet scaffold support increases electrode/electrolyte interfacial area, overcoming the high impedance typical of planar geometry SSLiBs resulting in an area specific resistance (ASR) of only ~2 to 7 Ωcm-2 at room temperature. The unique garnet scaffold/electrolyte/scaffold structure further allows for charge/discharge of the Li-metal anode and cathode scaffolds by pore-filling, thus providing high depth of discharge ability without mechanical cycling fatigue seen with typical electrodes. Moreover, these scalable multilayer ceramic fabrication techniques, without need for dry rooms or vacuum equipment, provide for dramatically reduced manufacturing cost.
Fabrication of supported dense thin-film garnet electrolytes, their ability to cycle Li-metal at high current densities with no dendrite formation, and results for Li-metal anode/garnet-electrolyte based batteries with a number of different cathode chemistries will be presented.
Zero Degradation in Power Density over Long-Term SOFC Operation Based on a Novel Interlayer
Authors: Wang Yudong , Dogdibegovic Emir , Zhou Xiao-Dong 
Published: February 2020

Doped ceria interlayer is ubiquitously used between the cathode and electrolyte in solid oxide fuel cells to prevent the cathode/electrolyte interaction and offer a better thermal expansion match. The mechanism on how the interlayer influences the durability and activity of the cathode still remains elusive. This is particularly true in the nickelate cathode (e.g. Pr2NiO4) since the nickelate does go through a phase transition during operation. Traditional Gd-doped ceria was found to substantially accelerate the phase transition in Pr2NiO4 cathode, leading to faster cell degradation in performance. In this work, several new designs of the interlayer are adopted, including various approaches to add Pr into ceria. The addition of Pr in the ceria layer can suppress the phase decomposition of nickelate cathode and increase the performance. As a result, the cell performance exhibits zero degradation over 500 hours. Electrochemical impedance spectroscopy data and its distribution of relation times were obtained to understand the mechanism for this unique observation.
Key words: Doped ceria, interlayer, zero degradation, nickelate
Plating and Stripping Calcium at Room Temperature
Authors: Gao Xiangwen , Wang Da , Bruce Peter G. 
Published: February 2020

Multivalent-ion batteries are receiving significant attention as potential post-lithium ion energy storage devices, such as Mg, Ca, etc.1-6 Among them, calcium has a potential much closer to Li (0.17 V vs. Li) and its natural abundance in the Earth’s crust make calcium cells potentially attractive. However, the major problem of calcium anodes is their tendency to reduce the organic electrolyte solvents forming passivating surface films such as CaO and CaCO3 that inhibit further plating.2,8-9 Recent studies showed calcium deposition under elevated temperatures, 75 to 100 °C, however with significant side reactions.5

Here, our recent studies show that calcium can be plated and stripped at room temperature with capacities of 1 mAh cm-2 at a rate of 1 mA cm-2, with low polarization (100 mV), in excess of 50 cycles and with low side reactions, Fig.1. The key role of the electrolyte, Ca(BH4)2 in tetrahydrofuran (THF), will be discussed.
Figure 1. Galvanostatic Ca plating/stripping load curves in Ca(BH4)2 in THF at the rate of 1 mA cm-2. Inset shows variation of coulombic efficiency with cycle number.

References:

Aurbach D., Lu Z., Schechter A., Gofer Y., Gizbar H., Turgeman R., et al. Prototype systems for rechargeable magnesium batteries. Nature, 407, 724-727 (2000).

Aurbach D., Skaletsky R., Gofer Y. The Electrochemical-Behavior of Calcium Electrodes in a Few Organic Electrolytes. J Electrochem Soc, 138, 3536-3545 (1991).

Lin M. C., Gong M., Lu B. G., Wu Y. P., Wang D. Y., Guan M. Y., et al. An ultrafast rechargeable aluminium-ion battery. Nature, 520, 324-328 (2015).

Muldoon J., Bucur C. B., Gregory T. Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond. Chem Rev, 114, 11683-11720 (2014).

Ponrouch A., Frontera C., Barde F., Palacin M. R. Towards a calcium-based rechargeable battery. Nat Mater, 15, 169-172 (2016).

Yoo H. D., Shterenberg I., Gofer Y., Gershinsky G., Pour N., Aurbach D. Mg rechargeable batteries: an on-going challenge. Energ Environ Sci, 6, 2265-2279 (2013).

Muldoon J., Bucur C. B., Oliver A. G., Sugimoto T., Matsui M., Kim H. S., et al. Electrolyte roadblocks to a magnesium rechargeable battery. Energ Environ Sci, 5, 5941-5950 (2012).

Hayashi M., Arai H., Ohtsuka H., Sakurai Y. Electrochemical characteristics of calcium in organic electrolyte solutions and vanadium oxides as calcium hosts. J Power Sources, 119, 617-620 (2003).

Canepa P., Gautam G. S., Hannah D. C., Malik R., Liu M., Gallagher K. G., et al. Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges. Chem Rev, 117, 4287-4341 (2017).

Figure 1
Screen-Printed Electrodes As EC-SERS Active Surfaces for Quantitative Raman Spectroelectrochemical Detection of Biologically-Related Species
Authors: Fanjul Bolado Pablo , Junquera Pérez Alejandro , González García María Begoña , Hernández Santos David 
Published: February 2020

Surface-Enhanced Raman Scattering (SERS) is a very interesting technique for the detection of analytes at ultra-low concentrations. In recent years, it has been applied to the detection of species with biological or medical interest [1]. However, one of the key issues of SERS-based assays is the low reproducibility between different substrates and measurements due to the low control of hot spots and the strong influence of the surface features on the SERS activity. Therefore, there is a strong scientific interest for increasing the applicability of SERS assays for quantitative studies with reproducible and simple methods. Electrochemically roughened electrodes have been widely employed for SERS-based assays. Recently, we have demonstrated that the utilization of screen-printed electrodes with in situ dynamic simultaneous roughening and detection could improve the precision of these assays [2]. Furthermore, the dynamic and in situ electrogeneration of SERS substrates allows to obtain a strongly active metallic surface for increasing detection sensitivity. Screen-printed electrodes due to their versatility, precise mass-fabrication, disposability and low-cost could be promising SERS substrates.
In this work, the evaluation of electrochemical SERS (EC-SERS) for the detection of biologically-related species at very low concentrations is performed using metallic screen-printed electrodes. Several species with a possible biological interest were tested such as Ruthenium-bipyridine, Naratriptan or Nicotinamide. Ruthenium-bipyridine is a very interesting molecule because it is the most common detection label in electrochemiluminescence bioassays due to its exceptional performance and sensitivity. Naratriptan is a pharmaceutical active ingredient used for the treatment of migraine headaches in human beings. Nicotinamide is an essential B-vitamin necessary to support the function of many biological enzymes. EC-SERS using screen-printed electrodes allows the detection of these species at very low concentrations.
[1] L.A. Lane, X. Qian, S. Nie, “SERS Nanoparticles in Medicine: From Label-Free Detection to Spectroscopic Tagging”, Chem. Rev. 115 (2015), 10489-10529.
[2] D. Martín-Yerga, A. Pérez-Junquera, M.B. González-García, J.V. Perales, A. Heras, A. Colina, D. Hernández-Santos, P. Fanjul-Bolado, “Quantitative Raman Spectroelectrochemistry using silver screen-printed electrodes”, Electrochim. Acta 264 (2018), 183-190.
Oxidation of Antioxidant Species with Superoxide Radicals Produced By the Xanthine-Xanthine Oxidase System
Authors: Juarez-Gomez Jorge , Ramírez-Silva María Teresa , Palomar Manuel , Romero-Romo Mario 
Published: February 2020

Free radicals have become very important in recent years due to the damage they cause to biological molecules. The superoxide radical (O2•-) is the primary species of reactive oxygen species (ROS) that plays a major role in physiological processes. This radical normally is produced physiologically at such a rate that the human body is able to catabolize it. However, when the production of O2•- radicals exceeds the capacity of the human body, physiological imbalances become harmful.
In this work the xanthine oxidase enzyme is proposed to catalyze the oxidation of xanthine and take advantage of the production of O2•- radicals. The O2•- formed in the enzymatic reaction are reacted with different antioxidant compounds (caffeic acid, gallic acid, ascorbic acid) and the oxidized species are quantified by cyclic voltammetry in an electrochemical cell thermostatted at 30 °C in a medium buffered with phosphate buffer 0.1 mol L−
1 pH 7.0. A carbon paste electrode was the working electrode, Ag/AgCl the reference and platinum the counter electrode. All antioxidants have an oxidation process between 200 and 600 mV, as well as a reduction process between −200 and 200 mV. The enzyme and the substrate do not present redox processes in the work potentials. However, uric acid has an oxidation process around 400 mV, but does not present reduction processes.