bluuebunny/crossref_metadata_2025_split huggingface dataset:
Charging Mechanism of Lithium-Sulfur Batteries: Insight from Spatially Resolved Operando X-Ray Absorption Spectroscopy
Authors: Gorlin Yelena , Patel Manu U. M. , Freiberg Anna Teresa Sophie , He Qi , Piana Michele , Tromp Moniek , Gasteiger Hubert A. 
Published: February 2020

A major barrier toward to the development of cost-effective lithium-sulfur (Li-S) batteries with sufficient energy densities to meet the requirements of battery electric vehicles is the lack of a mechanistic understanding of the processes occurring inside the battery. Motivated by improving the mechanistic understanding of lithium-sulfur batteries, we focus on the charging process of the Li2S cathode, a possible alternative to the conventional S8 cathode, with a potential to enable batteries with silicon or tin rather than lithium anodes.(1) Li2S presents an interesting system for mechanistic characterization, because the first charge of the cathode requires an application of a high overpotential, while each subsequent charge can be performed at a lower overpotential.(2) The presence of the high overpotential in the first charge has been hypothesized to relate to a charge transfer step that leads to a lithium-deficient surface on the surface of large Li2S particles.(2) This mechanism, however, does not provide a sufficient explanation for how an activation of less than 10% of the volume of the particle could lead to an extraction of the entire capacity.
To clarify the charging process of Li2S cathode, we have performed X-ray absorption spectroscopy (XAS) characterization of Li2S-Li battery using a spectro-electrochemical cell designed in our laboratory (Fig. 1a),(3) which is capable of spatially resolved measurements (Fig. 1b). Our experiments demonstrate which solid and solution phase intermediates are produced in two locations of the cell, the Li2S cathode and the separator, and thus generate a unique set of spatially resolved data, which we use to identify a plausible charging mechanism. Because the intermediates forming during the first charge of Li2S cathode have so far only been characterized using X-ray diffraction (XRD),(2, 4) a technique that is capable of detecting crystalline solids, but cannot provide information about amorphous species, our combination of XAS with spatial resolution facilitates a significantly improved mechanistic understanding of the operation of Li-S batteries.

References

1. J. Hassoun and B. Scrosati, Angew. Chem., 49, 2371 (2010).
2. Y. Yang, G. Zheng, S. Misra, J. Nelson, M. F. Toney and Y. Cui, J. Am. Chem. Soc., 134, 15387 (2012).
3. Y. Gorlin, A. Siebel, M. Piana, T. Huthwelker, H. Jha, G. Monsch, F. Kraus, H. A. Gasteiger and M. Tromp, J. Electrochem. Soc., 162, A1146 (2015).
4. H. Jha, I. Buchberger, X. Cui, S. Meini and H. A. Gasteiger, J. Electrochem. Soc., 162, A1829 (2015).

Figure 1
Direct Visualization of the in-Plane and out-of-Plane Electrostatic Competition in P2 Type Na2/3TMO2
Authors: Qian Danna , Seo Joon Kyo , Xu Jing , More Karren L. , Chi Miaofang , Meng Ying Shirley 
Published: February 2020

Na-ion batteries are important to develop lower cost batteries that deliver safe, reliable storage with long calendar life. Among various studied cathodes, layered P2-NaxTMO2 (TM -- 3d transition metal ions) compounds, exhibiting comparable performance as compared with Li-ion cathodes, are attractive candidates.1-3However, they suffer from capacity loss and poor reversibility upon cycling, which results from two determinative factors structurally: oxygen layer shifts and Na-ion in-plane ordering transitions during Na insertion/extraction. The oxygen layer shifts usually happen at low Na contents and the ordering transitions form at particular Na stoichiometry. A throughout understanding of the Na/Vac ordering is necessary.
Herein we present the first atomic scale visualization of the Na-Na in-plane and out-of-plane distribution variations due to the competitions of the in-plane Nae/f-Nae/f interactions and the out-of-plane Naf-TM-Naf electrostatic forces. An alternative Na concentration distribution along the c axis has been identified in the P2-Na2/3[Ni1/3Mn2/3]O2 where (Ni are all 2+ and Mn are all 4+), while not for P2-Na2/3[Fe1/3Mn2/3]O2(both Fe and Mn are mixture of 3+ and 4+). This study visualizes for the first time the electrostatic-interaction-induced Na ordering in both ab plane and c directions. Our work demonstrates the strong interaction between alkali ordering and electronic, magnetic structure, and underlines the important role that structure plays in determining electronic behavior and electrochemical performance, opening up the new design approach for energy storage materials.
1. J. Electrochem. Soc.
2015, 162, A2589.
2. Functional Materials Letters
2013, 06, 1330001.
3. Nat. Mater.
2012, 11, 512.
One-Dimensional Nanomaterial for Energy Storage
Authors: Mai Liqiang , Tian Xiaocong , Xu Lin , Wei Qiulong 
Published: February 2020

One-Dimensional nanomaterials with large surface area, more surface active sites and better permeability can significantly increase the energy density, power density and cycling performance for the energy storage. Such hierarchical structure can also be used as targeted intracellular recording for its facile synthesis route. In our present work, a series of hierarchical nanomaterials have been obtained, including kinked hierarchical nanowires, hierarchical heterostructured nanowires and hierarchical scrolled nanowires which shows great electrochemical.
To increase the stability of Li-ion battery, V3O7 nanowire templated semi-hollow bicontinous graphene scrolls architecture is designed and constructed through “oriented assembly” and “self-scroll” strategy. The V3O7 nanowire templated semi-hollow bicontinous graphene scrolls with interior cavities provide continuous electron and lithium ion transfer channel and space for free volume expansion of V3O7 nanowires during cycling, thus representing a unique architecture for excellent lithium ion storage capacity and cycling performance. 1 Besides, we have designed and synthesized hierarchical MnMoO4/CoMoO4 heterostructured nanowires by combining "oriented attachment" and "self-assembly". The asymmetric supercapacitors based on the hierarchical heterostructured nanowires show a high specific capacitance and good reversibility with a cycling efficiency of 98% after 1,000 cycles. 2 Recently, we also constructed the hierarchical zigzag Na1.25V3O8 nanowires, 3 K3V2(PO4)3 bundled nanowire, 4 and Li3V2(PO4)3 mesoporous nanotubes 5 with enhanced electrochemical performance. Our work presented here can inspire new thought in constructing novel nanofiber/nanowire structures and accelerate the development of energy storage appilications.
References
(1) Yan, M. Y. et al., J. Am. Chem. Soc. 2013, 135, 18176-18182.
(2) Mai, L. Q. et al., Nature Commun. 2011, 2, 381.
(3) Dong, Y. F. et al., Energy Environ. Sci. 2015, 8, 1267.
(4) Wang, X. P. et al., Adv. Energy Mater. 2015, 5(17).
(5) Niu, C. J. et al., Nature Commun. 2015, 6, 7402.
Development of Novel Noncarbonate Electrolytes for Silicon Alloy Anodes
Authors: Zhu Ye , Cheng Gang , Strand Dee , Yang Johnny 
Published: February 2020

Wildcat Discovery Technologies is developing novel electrolyte additives and noncarbonate solvent formulations that yield improved solid electrolyte interphase (SEI) layers on silicon alloy anodes. The large volumetric changes in silicon during charge/discharge cycles result in mechanical disruption of conventional SEI's leading to rapid capacity fade as the cell cycles. Novel additives are demonstrated to improve cycle life of silicon based materials by forming less brittle, more mechanically robust SEI passivation layers. Since propylene carbonate (PC) is not expected to form an effective SEI layer, the additives are tested with PC to determine their efficacy. Wildcat's high throughput electrolyte formulation, cell assembly, and test capabilities enable the evaluation of hundreds of additives in a very short timeframe.
Once effective SEI additives are identified in a PC-based formulation, other non-SEI forming solvents can be evaluated. Since the additives are effective without solvent participation in SEI formation, solvents can be considered that may not be reductively stable on the anode - and also opens the possibility to more oxidatively stable or less flammable solvents. Wildcat has evaluated hundreds of combinations of noncarbonate solvents with its initial silicon anode SEI additives. This presentation will focus on the results of the additive improvement to cycle life in NMC//Si full cells, and illustrate the opportunities for novel solvent combinations.
Sodium-Ion Polymer Batteries Assembled with Composite Gel Polymer Electrolytes
Authors: Lee Yoon-Sung , G Kannan Aravindaraj , Shin Won-Kyung , Kim Dong-Won , Chung Kyung-Yoon 
Published: February 2020

Rechargeable sodium-ion batteries have become the promising energy storage system due to their high energy density, long cycle life and lower cost. However, safety issues surrounding these batteries must be addressed before they can be widely utilized in large-scale applications such as electric vehicles and grid-scale energy storage devices. Therefore, the quest for safer and more reliable electrolyte system is urgent and polymer electrolytes are promising candidates in this regard. However, they suffer from poor thermal stability and mechanical properties. In order to obtain the gel polymer electrolytes with improved thermal and mechanical properties, ceramic fillers such as SiO2, Al2O3, TiO2 and BaTiO3 have been incorporated into host polymers. In these composite gel polymer electrolytes, the ceramic particles promote electrochemical properties of the polymer electrolytes through physical interactions without directly contributing to the lithium ion transport process. As reported in our previous studies, the ionic conductivity of gel polymer electrolyte was improved by using ceramic fillers covered with poly(styrene sulfonated lithium)(PLSS) containing lithium cation end group [1,2,3]. It is of our interest to synthesize and introduce inorganic materials containing dissociative sodium ions in the electrolyte of sodium-ion batteries to improve the ionic conductivity, thermal stability and mechanical property. In this study, we prepared composite gel polymer electrolytes based on core-shell structured SiO2 nanoparticles containing dissociative sodium ions. The SiO2 particles have unique core-shell morphology with a thin layer of poly(sodium 4-styrene sulfonate) surrounding nano-sized SiO2core particle. The composite gel polymer electrolyte exhibited high ionic conductivity and good mechanical strength. The prepared gel polymer electrolytes were used to assemble sodium-ion polymer batteries, and their cycling performances were evaluated.
References
[1] Y. -S. Lee, S. H. Ju, J. -H. Kim, S. S. Hwang, J. -M. Choi, Y. -K. Sun, H. Kim, B. Scrosati, D. -W.Kim, Electrochem. Commun., 17, 18-21 (2012).
[2] Y. -S. Lee, J. H. Lee, J. A. Choi, W. Y. Yoon, D. -W. Kim, Adv. Funct. Mater., 23, 1019-1027 (2013).
[3] Y. -S. Lee, W. -K. Shin, J. S. Kim, D.-W. Kim, RSC Adv., 5, 18359-18366 (2015).
Investigation of the Degradation of Metallic Lithium Electrode Protected By Bilayer Solid Electrolyte in Lithium-Oxygen Batteries
Authors: Le Hang T.T. , Ngo Duc Tung , Park Chan-Jin 
Published: February 2020

To date, considerable efforts have been made to address the inherent problems of Li metal anode using solid electrolyte or modifying liquid electrolyte including additives, salts and/or solvents. However, despite their own advantage of good processability, the liquid electrolytes can induce the formation of the brittle and unstable enough SEI layer. Further, in order to preclude the Li metal from reacting with poisonous species such as water, O2, and CO2 diffusing from outside atmosphere, the use of lithium ion conducting solid electrolyte are indispensable.
In this work, we report comprehensive investigation of degradation of protected Li electrode (PLE) in the presence of the bilayer solid electrolyte of LiPON/A-LLTO as a typical ceramic solid electrolyte in Li-O2 cell operating in both pure O2 gas and ambient air. The liquid electrolyte employed herein was 1 M LiTFSI in TEGDME. The evaluation includes analysis of structural and morphological change, analysis of surface chemistry change, monitoring electrochemical properties and subsequently exploring the difference in Li electrode’s degradation mechanisms in the cells with and without protection of the ceramic solid electrolyte. Furthermore, this present study supplies the circumstantial view of whole initiation and growth process of Li dendrites using optical microscope (OM). In particular, the formation process of dead Li dendrites that has barely exposed in the previous reports was also recorded.
Obviously, with the presence of the solid electrolyte, the Li dendrites were effectively suppressed by the mechanical strength. The smooth and flat surface of the PLE was easily attained when the symmetric cell was cycled at low current density such as 0.1 mA cm-2. In addition, in the same charge-discharge condition, the symmetric cell without solid electrolyte only operated 15 cycles, much smaller compared with the cell with solid electrolyte, 182 cycles. During the cycling process, the impedance of both cells gradually increased with cycling. However, the degradation of the cell without solid electrolyte was severer than that of the cell with solid electrolyte. XPS spectra confirmed the presence of decomposition products of LiTFSI salt such as LiF, Li3N, Li2S, Li2S2O4 and Sx on both tested Li electrodes after several ten cycles. However, these products of the PLE were detected with the smaller signal intensity than that of the unprotected Li electrode without the solid electrolyte. This suggests the effective suppression of electrolyte decomposition by the solid electrolyte. Hence, with the employment of LiPON/ALLTO, the Li dendrite growth and electrolyte decomposition were effectively suppressed. Accordingly, the Li-O2 cell using the protected Li metal electrode exhibited excellent charge-discharge cycling stability with a long life span of 128 cycles under the limited capacity mode of 1000 mAh g-1 in oxygen atmosphere and 20 cycles in air atmosphere.
Microstructural Investigation of Pulse Electroplated Copper Trenches Deposited with Organic Additives
Authors: Marro James Brandon , Kapat Amrita , Darroudi Taghi , Okoro Chukwudi A. , Obeng Yaw S. , Richardson Kathleen A 
Published: February 2020

Preferential grain orientation of copper (Cu) vias is speculated to result in a decrease in stresses in elastically anisotropic Cu. On the other hand, highly twinned Cu microstructures are known to increase their electromigration resistance and mechanical properties, without significantly degrading electrical performance [1,2]. Therefore, the optimal manipulation of Cu via microstructure could enable the improvement of the reliability of microelectronic devices. In this study, the “tuning” of the microstructure of Cu trenches were achieved by varying the bath’s chemical composition in different trench aspect ratios. The organic additive system comprising of polyethylene glycol (PEG), bis-(sodium sulfopropyl)-disulfide (SPS), and janus green b (JGB) is commonly used in the electroplating of Cu into trenches and higher aspect ratio through-silicon vias (TSV) for microelectronics [3,4]. In this study, copper was pulse-electrochemically deposited (PED) into 500 nm deep trenches of various widths to evaluate the impact of aspect ratio on the evolution of copper microstructure. Trench aspect ratios of 0.25, 1, 2, and 2.78 were investigated. The organic additive concentrations in the PED bath were also adjusted to examine their influence on the Cu microstructure. By metallurgical sample preparation and the focused ion beam (FIB) technique, the sample cross-sections of the Cu filled trenches were revealed for microstructural analysis using electron backscattering diffraction (EBSD). From the EBSD data, the grain orientation and twin boundary distribution of the deposited Cu microstructure were analyzed.
References:
1. L. Lu, X. Chen, X. Huang and K. Lu, Science,
323, 5914 (2009).
2. D. Xu, V. Sriram, V. Ozolins, J. Yang, K. N. Tu, G. R. Stafford, C. Beauchamp, I. Zienert, H. Geisler, P. Hofmann and E. Zschech, Microelectronic Engineering,
85, 10 (2008).
3. K. Kondo, T. Matsumoto and K. Watanabe, Journal of The Electrochemical Society,
151, 4 (2004).
4. M. Jung, Y. Song, T. Yim and J. Lee, Electronic Components and Technology Conference (ECTC), 2011 IEEE 61st, (2011).
Characterization and Metrology of Gold and Copper Electroplated Stylus Ion Traps
Authors: Arrington Christian L. , Hollowell Andrew E , Pillars Jamin Ryan , Singh Varshni , Finnegan Patrick , St. John Christopher R. 
Published: February 2020

Electrochemical fabrication offers unique advantages for nano/microfabrication of 2D and 3D structures. Precise control of deposition molds and thicknesses allows significant challenges to be solved through electrodeposition that are beyond the capabilities of standard silicon methods and conventional machining techniques. One unique application is the study of trapped ions enabling enhanced measurement techniques and reduction of anomalous motional heating 1. The main goal is to correlate the physical features with electric field noise, which can be sensitively measured with the ions. Previous two layer ion taps were created using electroformed gold into high aspect ratio molds, here we further investigate effects of chemistry make-up, applied current density, and pulse plating of gold and copper electrochemical deposition. The effects will then be characterized using scanning electron microscopy, profilometry, energy dispersive spectroscopy, x-ray diffraction, and electron backscatter diffraction to characterize feature height, feature dimensions, surface roughness, stoichiometry, crystal structure, and crystallite size.
1 C. L. Arrington, K. S. McKay, E. D. Baca, J. J. Coleman, Y. Colombe, P. Finnegan, D. A. Hite, A. E. Hollowell, R. Jordens, J. D. Jost, D. Leibfried, A. M. Rowen, U. Warring, M. Weides, A. C. Wilson, D. J. Wineland, and D. P. Pappas, 'Micro-Fabricated Stylus Ion Trap', Review of Scientific Instruments, 84 (2013).
Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. SAND2015-10657A
3D Printing and Electroless Metallization of Microrobots for Biomedical Applications
Authors: Bernasconi Roberto , Credi Caterina , Chatzipirpiridis George , Pané Salvador , Levi Marinella , Magagnin Luca 
Published: February 2020

The manufacture of manipulators able to work wirelessly on a micrometric scale is one of the most interesting topics in microfabrication. Such devices, called microrobots, are expected to deeply change some aspects of modern surgery and to make in particular some medical treatments less invasive. Possible applications include localized drug delivery or confined modification of living tissues. Since motion in fluids at the microscale usually happens in low Reynolds number regime, the shape of microrobots is in general inspired by natural structures like bacterial flagella [1] or other propulsion apparatus of living cells well adapted to such conditions. For this reason shapes like rods, flagella [1] and helixes [2] have been tested in the existing literature. The most used method to control the motion of the devices is the application of a magnetic field [3], and due to this the microswimmers must have at least a part made of a metallic magnetic alloy.
Microrobots are nowadays realized using standard lithographic techniques, with high costs and poor flexibility of the production process. From this point of view the introduction of a manufacturing route based on additive manufacturing can introduce significant advantages. In the present work the possibility to directly 3D print the microrobots employing stereolithography (SLA) as technique is investigated. Typical designs like rods and helixes are employed. Since the SLA printing of metals is problematic, photocurable resins are used to produce the devices and the obtained samples are metallized via electroless plating to obtain the magnetic coating necessary for magnetic actuation. The quality of the 3D printed microrobots is evaluated, while the electroless process is first characterized from the general point of view and subsequently applied to the metallization of the devices. A first layer of a pure metal like copper is applied as flash layer, followed by a thicker layer of a suitable magnetic alloy. Finally the microdevices thus obtained are actuated in a controlled magnetic field and the motion at low Reynold number regime is studied.
[1] R. Mhanna et al.; Small 10, 1953 (2014)
[2] K. E. Peyer et al.; Chem. Eur. J. 19, 28 (2013)
[3] S. Kim et al.; Adv. Mater. 25, 5863 (2013)
Electroless Deposition of Platinum Using Multivalent Metal Ions As Reducing Agents
Authors: Norkus Eugenijus , Jagminiene Aldona , Stankeviciene Ina , Tamasauskaite-Tamasiunaite Loreta , Joi Aniruddha , Dordi Yezdi , Buzas Vytenis , Maciulis Laurynas , Tumonis Liudas 
Published: February 2020

Two new type electroless plating processes for deposition of continuous platinum layer are proposed.
In the presence of different ligands Pt(IV) ions are reduced to the metallic state by means of multivalent metal ions.
In the first case Pt(IV) is reduced by Co(II) forming platinum and Co(III):
4Co(II) + Pt(IV) → Pt + 4Co(III).
In the second type solutions Pt(IV) is reduced by Ti(III) forming platinum and Ti(IV):
4Ti(III) + Pt(IV) → Pt + 4Ti(IV).
The kinetic data of the mentioned reactions are given and discussed.

Acknowledgement

This research was funded by a Grant (No. TEC-06/2015) from the Research Council of Lithuania.
Effect of Different Solvents on Aminosilane-Compound Modification and Its Influence on the Adhesion Between Electroless Nickel/Phosphorous Film and Silicon Wafer
Authors: Wang Wei-Yan , Hsu Chin Wei , Wei Tzu Chien 
Published: February 2020

In semiconductor manufacturer and IC package, electroless deposition (ELD) of nickel/phosphorous (Ni/P) film is a special promising skill [1]. In general, the core of ELD is a catalytic reaction that needs a trace amount of noble metal such as palladium as the activator to lower the activation energy of metal formation [2]. Because the adhesion of ELD Ni/P film relates to the interfacial characteristic of catalyst and silicon surface. In order to enhance the bridging between the silicon substrate and palladium (Pd) catalyst, modifying silicon surface with organo-silane compound such as 3-[2-(2-aminoethylamino)ethylamino] propyl-trimethoxysilane (ETAS) is commonly used. The ETAS treatment then forms a self-assembled monolayer (SAM) which is capable to interact with polymer-capped Pd catalyst and thereby promotes the adsorption of ELD Ni/P film [3]. However, it is known that the SAM formation is very sensitive to process condition such as soaking time and solvent agents.
In this study, various ETAS modification on silicon wafer are investigated. In particular, the ETAS-modified film was done by a wet-soaking method in which the influence of soaking time and solvent agents onto silicon surface were discussed. As shown in Fig 1, the AFM images with various solvent agents of ETAS-modified surface showed significant difference which indicates that the solvent agents does influence SAM formation. The correlation on the solvent effect and the adhesion of ELD Ni/P on ETAS-modified silicon surface are discussed.
REFERENCES
[1] A. Brenner, G.E. Riddell, J. Res. Nat'l Bur. Std. 37 (1946) 31.
[2] L. Li, B. Liu, Mater. Chem. Phys. 128 (2011) 303.
[3] T. C. Wei, T. P. Pan, C. M. Chen, K. C. Lai, C. H. Wu, Electrochem. Commun. 54 (2015) 6

Figure 1