bluuebunny/crossref_metadata_2025_split huggingface dataset:
Flexible Probe for Measuring Local Conductivity Variations in Li-Ion Electrode Films
Authors: Hardy Emilee E , Vogel John E , Clement Derek V , Wheeler Dean R , Mazzeo Brian A 
Published: February 2020

Electrical conductivity is a fundamental characteristic determining the performance of lithium-ion batteries. However, methods to measure the conductivity nondestructively have proven difficult. This is due to the presence of a metallic conductive current collector as well as dominating effect of the contact resistance between the film and the probe. In previous research we developed a micro-four-line probe [1] that can measure thin-film electrodes without removing the current collector. We found that the conductivity of even high-quality electrodes is not homogenous, and has variation on length scales much larger than the size of the active material particles.
Even though the micro-four-line probe worked well, we continue to improve the design. The previous design was fabricated in a clean room on a rigid glass substrate. This limited the geometry of the sample and made adaptation to industrial use difficult. To address this problem, we switched to a flexible polymer substrate, as shown in the figure, which allows for increased sample size and potential low-cost manufacturing. In addition, changes were made to the computer-controlled probe holder and stage, again with an aim toward lowering cost and increasing usability. The stage is used to move the probe over the surface of the sample in order to produce a conductivity map.
We will report conductivity results using the new probe for both anodes and cathodes, including the effect of cycling. Results will also be compared to related work on ionic conductivity of the same electrodes. The hope is that this probe technology can be adapted to manufacturing use as well as to assist other researchers in understanding limiting mechanisms in battery performance.

[1] Lanterman et al., J. Electrochem. Soc. 162, A2145 (2015).

Figure 1
(Invited) P2-Nax(Mn,Fe,Co,Ni) Layered Oxides in Na-Batteries
Authors: Delmas Claude , Yoshida Jun , Mortemard de Boisse Benoit , Guerin Elodie , Carlier Dany , Guignard Marie , Duttine Mathieu , Duttine Mathieu , Wattiaux Alain 
Published: February 2020

In the perspective of the development of electrical vehicles and also of very large scale renewable energy systems the prevailing parameters are the lifetime, the price and the material availability. From these points of view, sodium based batteries have to be investigated. Our research group studied layered oxides as positive electrode for 30 years. Recently, a general investigation was undertaken with a focus on P2-type layered phases.
One of the main interests of this structure is the existence of an ion conduction plane made of face sharing trigonal prims which exhibits a high ionic diffusivity thanks to the existence of a large bottleneck (oxygen rectangle) for sodium diffusion. This structure is able to accommodate a lot of transition metal cations, allowing the optimization of the properties by cationic substitution.
The study will be focused on the P2-Nax(Mn,Fe)O2, P2-Nax(Mn,Co)O2 Nax(Mn,Fe,Co)O2 and Nax(Mn,Fe,Ni)O2 systems with various amounts of transition metal ions. All materials crystallize in the hexagonal system (P63/mmc space group). The structure is made of MO2 slabs built of corner sharing MO6 octahedra. The sodium ions are in trigonal prismatic sites. Half of them share edges (Nae) with the MO6 octahedra while the other one share faces (Naf). As the two types of prisms share a common faces, they cannot be occupied simultaneously. The sodium distribution depends of the cationic charge distribution and of the sodium amount is order to minimize the Na+-Na+ and Na+-Mn+ electrostatic repulsions.
In all systems, the P2 type packing is preserved in the 0.3 < x < 1 range. The fully intercalated phase is difficult to be obtained due to the very low ionic conductivity when the amount of vacancies is very small. For these compositions, only the Naf prisms are occupied. The specific capacity is in the 130-170 mAh.g-1 depending on the voltage range.
In the case of materials with a single transition metal ion like NaxCoO2 and NaxVO2 the shape of the electrochemical curves present a lot of plateau resulting from ordering Na+/Vacancies in the sodium layer. For multi-cations systems, the transition metal disordering is the MO2 slabs prevents from most of the ordering except for the Na.050MO2 composition.
A general overview of the electrochemical behavior of these materials will be presented with a special focus on the relation between the oxidation process and the shape of the electrochemical curve.
Reversible Aqueous Zinc Battery Using Molybdenum-Based Intercalation Cathode
Authors: Xu Wangwang , Cui Xiaodan , Xie Zhiqiang , Wang Ying 
Published: February 2020

As an alternative for lithium ion batteries, aqueous energy storage system has recently attracted tremendous attentions due to the low cost, non-flammable and non-toxic materials.[1] Among various aqueous batteries, aqueous Zn ion batteries are particularly advantageous owing to a high-capacity Zn metal anode (819mAh/g).[2] However, limited cathode materials have been explored for reversible Zn2+-ion intercalation, and most of which exhibit poor rate capabilities and inadequate cycling performance, or limited specific capacity. α-MoO3, as a typical layered transition metal oxide, has been extensively studied as electrode material for lithium batteries due to the advantages of high capacity, low cost, abundant resources and non-toxic.[3] Based on our research, we have found α-MoO3 can be used as host material (cathode) for zinc ions as well owing to the large interlayer space. However, the capacity fading in the initial cycles is still significant and unavoidable. The reason for irreversible capacity fading of MoO3 in the initial cycles can be attributed to its unstable structural prosperity. Recently, pre-intercalation has been demonstrated as an effective way to improve the electrochemical performance for zinc-ion batteries. For example, Linda et.al has reported vanadium oxide bronze pillared by interlayer Zn2+ ions and water can supply the remarkable performance.[2] However, the related research of α-MoO3 as electrode for zinc-ion is still blank.
For the first time, we have studied the electrochemical performance of zinc pre-intercalation α-MoO3 as cathode material for zinc batteries and investigated the electrochemical mechanism during charging and discharging. The zinc pre-intercalation α-MoO3 can supply the initial specific capacity as high as 300 mAh/g, exhibiting great potential for application as high-performance cathode material for zinc-ion batteries.
Reference
1. Pan, H.; Shao, Y.; Yan, P. F.; Cheng, Y. W.; Han, K. S.; Nie, Z. M., Wang, C. M., Yang, J. H.; Li, X. L.; Bhattacharya, P.; Mueller, K. T.; Reversible Aqueous Zinc/Manganese Oxide Energy Storage From Conversion Reactions. Nature Energy, 2016, 1, 16039.
2. Kundu, D.; Adams, B. D.; Duffort, V.; Vajargah, S. H.; Nazar, L. F.; A High-Capacity and Long-life Aqueous Rechargeable Zinc Battery Using a Metal Oxide Intercalation Cathode. Nature Energy. 2016,1,16119.
3. Dong, Y. F.; Xu, X. M.; Li, S., Han, C. H.; Zhao, K. N.; Zhang, L.; Niu, C. J.; Huang, Z.; Mai, L. Q.; Inhibiting Effect of Na+ Pre-Intercalation in MoO3 Nanobelts with Enhanced Electrochemical Performance. Nano Energy. 2015, 15, 145.
Impact of Electrolyte Composition on Seebeck Coefficient of Molten Carbonate Thermocell
Authors: Kandhasamy Sathiyaraj , Burheim Odne Stokke , Solheim Asbjørn , Kjelstrup Signe , Haarberg Geir Martin 
Published: February 2020

A thermocell with molten carbonate electrolyte mixture with two identical gas (CO2|O2) electrodes may be a suitable alternative to the conventional semiconductor thermoelectric converters. Also, it shows the ability to harvest the waste heat at higher temperatures and utilize the available CO­­2 off-gases from metal producing industries for the thermoelectric conversion. Using symmetrical gas electrodes, high Seebeck coefficients in the range of 1 mV/K were measured, whereas the most conventional semiconductor thermoelectric cell shows only 0.2 mV/K.
The inclusion of solid oxide in the electrolyte mixture was found to influence the transported entropy of the carbonate ions and expand the appropriate conditions for thermoelectric conversion. Similarly, the change in the cationic composition of the molten carbonate melt in the electrolyte mixture leads to alter the entropy of the ionic species. Thus, the effect of a compositional change in the electrolyte mixture is studied in detail, towards its contribution to the Seebeck coefficient of the molten carbonate thermocell.
Understanding and Optimizing Ionic Conductivity in Polyborane Solid Electrolytes from Ab Initio molecular Dynamics
Authors: Wood Brandon C. , Varley Joel , Kweon Kyoung , Shea Patrick , Stavila Vitalie , Udovic Terrence John 
Published: February 2020

Polyborane salts based on B12H12
2-, B10H10
2-, CB11H12
- and CB9H10
- demonstrate extraordinary Li and Na superionic conductivity that make them attractive as potential electrolytes in solid-state batteries. The rich chemical and structural diversity of the various cation-anion combinations establishes a diverse design space offering a wide range of superionic transition temperatures and ionic conductivities. Recent synthesis and processing advances have improved ionic conductivity at modest temperatures; however, the origins of these successes are generally poorly understood. Likewise, key questions remain regarding the fundamental mechanisms that drive ionic conductivity, which has impeded the adoption of a more rational design approach.
We have performed extensive ab initio molecular dynamics simulations to broadly explore the dependence of ionic conductivity on cation/anion pair combinations for Li and Na polyborane salts. Additional simulations are used to probe the influence of local modifications to chemistry, stoichiometry, and composition. Carbon doping, anion alloying, and cation off-stoichiometry are found to be favorable because they introduce intrinsic disorder, which facilitates local deviations from the expected cation population. Anion reorientations are also discovered to be critical for conduction. In this case, benefits are traceable the specific chemistry of the cation-anion interaction, which acts to create intrinsic frustration that motivates cation mobility. Our computational studies offer new mechanistic understanding and guidance for future optimization of ionic conductivity in emerging polyborane-based solid electrolytes.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
(Invited) Endohedral Metallofullerene-Based Lewis Acid-Base Pairs
Authors: Lu Xing 
Published: February 2020

Carbon-based Lewis acids are limited merely to trityl cations and some electron-poor allenes.
[1]
Recently, Bazan and coworkers reported that C60 and C70 can behave as all-carbon Lewis acids to form the corresponding Lewis acid–base pairs with a normal NHC structure.
[2]
This work opens a new perspective on the research of carbon-based Lewis acids. Meanwhile, as a novel class of metal-carbon hybrid molecules, endohedral metallofullerenes (EMFs) feature electron transfer from the internal metallic species to the carbon cage, forming zwitterionic compounds.
[3]

Accordingly, it is of special interest to study whether the highly charged carbon cages of EMFs are willing to accept additional electrons to act as Lewis acids or not.
In this representation, taking several kinds of EMFs as a representative, we show that EMFs also exhibit excellent Lewis acidity to form Lewis acid-base pairs with NHCs. Our unambiguous X-ray results reveal that the NHC moiety uses either its normal site or abnormal active center to react with the EMFs under study to form the corresponding adducts with different structures (Scheme 1). It is conformed theoretically the the inherent characteristic of the EMFs is responsible for the addition patterns.

R
eferences：
[1] F. E. Ahn and M. C. Jahnke, Angew. Chem., Int. Ed., 2008, 47, 3122.
[2] H. P. Li, C. Risko, J. H. Seo, C. Campbell, G. Wu, J. Bredas and G. C. Bazan, J. Am. Chem. Soc., 2011, 133, 12410.
[3] X. Lu, L. Echegoyen, A. L. Balch, S. Nagase and T. Akasaka, Endohedral Metallofullerenes: Basics and Applications, CRCPress, New York, 2015.
[4] M. Q. Chen, L. P. Bao, M. Ai, W. Q. Shen and X. Lu. Chem. Sci., 2016, 7, 2331-2334.
Formation and Characterization of Sub-Micron Inert Particle Embedded Nickel Composite Coatings
Authors: Yilmaz Olgun , Erdogan Metehan , Karakaya Ishak 
Published: February 2020

Composite coatings have a wide range of application areas requiring improved mechanical and tribological properties[1,2]. These application areas include aerospace, automotive, chemical and electrical industries. High mechanical and tribological performances can be achieved by incorporation of hard ceramic particles into nickel matrix, which possess anti-corrosion properties. Due to its enhanced properties, Ni-Al2O3 electro-co-deposition rather than pure Ni electrodeposition was investigated. A typical sulfamate bath was used to evaluate the effects of current density, the amount of alumina in the electrolyte and the amount of surfactants. Ammonium lignosulfonate and sodium dodecyl sulfate were used as the surfactants in varying concentrations to arrange the floatation and wetting conditions of Al2O3particles (~300 nm) in the electrolyte. The influences of plating parameters on mechanical and tribological properties of the co-deposits like hardness, friction coefficient and wear were determined.
It was found that Increase in current density increases the hardness and deposited wt.% Al2O3 particles within the parameter ranges covered in this study. A representative cross-sectional view of Al2O3–Ni composite coating is shown in Figure 1.
References
[1] Vitry, V., Kanta, A. F., and Delaunois, F. (2012). Application of nitriding to electroless nickel–boron coatings: Chemical and structural effects; mechanical characterization; corrosion resistance. Materials & Design, 39, 269-278.
[2] Saraloğlu Güler, E., Karakaya, İ. and Konca, E. (2014) Effects of current density, coating thickness, temperature, pH and particle concentration on internal stress during Ni-MoS2 electrocodeposition, Surface Engineering, 30, 109-114.

Figure 1
(Invited) Concepts of the Solid-Electrolyte Phase Boundary: Experimental Evidence and Resulting Devices
Authors: Lewerenz Hans Joachim 
Published: February 2020

The original fundamental concepts at solid-electrolyte interfaces are reviewed including the traditional microcapacitor model of the Helmholtz layer1. Theoretical approaches that expand beyond the classical dielectric model for water and solvation shells are accounted for and recent advanced experiments will be presented that enable a direct profiling of the energetics at this junction by tender x-ray synchrotron radiation photoelectron spectroscopy (TSRPES) 2,3. Combined (photo)electrochemical and surface analytical investigations are presented. For the rectifying semiconductor - solution junction, the space charge behavior of semiconductors in concentrated electrolytes is examined and in dilute solutions, the Galvani potential profiles at metal - electrolyte junctions are followed by TSRPES. The role of truncated profiles for thinner water layers and dilute electrolytes on charge equilibration and build-up of contact potential differences is analyzed. Fig.1 shows an example of the resulting photoelectron spectroscopy tomography.
Fig.1: (left): scheme for tomographic peak sampling; (right): influence of electrostaic potential on peak width
Implications regarding charge transfer and the development of efficient devices for light - induced fuel generation are outlined and optimized structures which show unassisted water splitting are presented, obtained upon modifying the surfaces of III-V tandem absorbers. Application of (photo)electrochemically induced surface transformations 4,5 and of re-directed (photo)corrosion reactions allows passivation of surface and interface states and increased robustness. Details of these procedures will be given. The achieved efficiencies are compared to theoretically achievable limits of solar hydrogen evolution for the respective material combinations6. The influence of the optical properties of the combined catalyst - electrode - solution composite structures is described and routes to more advanced multi-electron and proton transfer reactions are outlined.

References

1. D.C. Grahame, Chem. Rev. 41 (1947) 441-501

2. M.F. Lichtermann, M.H. Richter et al., Energy Environm. Sci. 8 (2015) 2409-2416

3. M.F. Lichtermann, M.H. Richter et al., J. Electrochem. Soc. 163 (2016) H 139-146

4. H.J. Lewerenz, C. Heine et al., Energy Environm. Sci. 3 (2010) 748-760

5. M.M. May, H.J. Lewerenz et al., Nature Comm. 6 (2015) 8286

6. K.T. Fountaine, H.J. Lewerenz, H.A. Atwater, Nature Comm. 7 (2016) 13706

Figure 1
Investigation of Thermal Treatment Processes for Dissimilar Wafer Bonding
Authors: Wang Chenxi , Li Yue , Liu Yannan , Yuan Zhitian , Tian Yanhong , Wang Chunqing , Suga Tadatomo 
Published: February 2020

Wafer bonding, also termed as “direct bonding” or “wafer direct bonding”, has one of the main advantages for its ability to integrate dissimilar materials in various areas of microelelctronics, optoelectronics, micro/nanoelectromechanical systems (M/NEMS). Silicon is the most extensively used material for semiconductor industry. To meet demands on superior electrical, optical and acoustic applications, it is important to combine silicon with appropriate materials, such as GaAs, quartz glass, and LiTaO3. In general, two wafers are brought into contact at room temperature (~25ºC) and followed by thermal treatment processes (>100ºC) enabling reliable bonding strength to withstand subsequent mechanical grinding or polishing processes. During thermal treatments, the major concern in dissimilar bonded wafer pairs is the thermal stress originating from a mismatch in thermal expansion coefficients. Higher thermal stresses above a critical temperature may cause sliding, debonding, cracking or misfit dislocation between two bonded wafers. It is therefore highly desirable to predict the critical temperatures and optimize the thermal steps for dissimilar bonded wafer pairs with various materials and thicknesses.
In this paper, a thermal stress model is developed based on analytical as well as finite element methods. To ensure a good bonding, the thermal stress should be smaller than the critical yield stress of the bonded materials. Meanwhile, the deformation energy should be lower than the bonding energy so that no sliding or debonding occurs during the thermal treatments. Under these two conditions, the critical temperatures for various dissimilar bonded wafer pairs (Si/GaAs, Si/Quartz and Si/LiTaO3) are calculated and predicted. The effects of wafer thickness are also demonstrated. To verify our calculation results, 100-mm silicon wafers are combined to LiTaO3 wafers by plasma activated bonding process. The bonded wafer pairs are heated at different temperatures to strengthen bonding. Experimental results show the critical temperature value is in agreement with our calculation. We believe our model provides a tool to optimize the thermal treatment processes during the dissimilar wafer bonding. It has great potentials to improve the bonding processes for wafer-level hybrid integration.
(Invited) Real-Time, Selective Detection of Lead Ions in Water Using a Graphene-Based Field-Effect Transistor Sensing Platform
Authors: Chen Junhong 
Published: February 2020

Water plays an important role in the economic world; only 3% of available water is potable, and with increasing demand, the need for safe drinking water is rising. The National Academy of Engineering identified “providing access to clean water” as one of the top 10 grand challenges for engineering in the 21st century. Heavy metal ions, e.g., lead, mercury, and arsenic, are widely present in water systems. These heavy metal ions are poisonous and may lead to serious damage to organs, tissues and bones, and nervous systems of humans. Existing water quality monitoring mostly occurs at the water supply intake or water treatment plant, instead of along water distribution lines and at the point of use, which is considered inadequate given potential changes in water quality and associated risks within water distribution systems. Current detection methods for aqueous heavy metal ions are often too expensive or unsuitable for in-situ and real-time detection (an unmet need). A field-effect transistor (FET) device-based sensor is developed to specifically detect Pb2+ ions in an aqueous environment. Reduced graphene oxide (rGO), as the semiconducting channel material, is utilized in the FET device through a self-assembly method. An L-glutathione reduced (GSH) is employed as the capture probe for the label-free detection. By monitoring the electrical characteristics of the FET device, the performance of the sensor is measured and investigated. Compared with conventional detection technologies, this sensor enables real-time detection with a response time of 1-2 seconds. A lower detection limit for Pb2+ ions as low as 10 nM is achieved, which is much lower than the maximum contaminant level (MCL) for Pb2+ ions in drinking water advised by the World Health Organization (WHO). Furthermore, the rGO FET sensor is able to distinguish Pb2+ from other metal ions. Without any sample pretreatment, the platform is user-friendly.
(Invited) Simultaneous Ionic Current and Potential Detection of Biomolecules and Nanoparticles By a Multifunctional Nanopipette
Authors: He Jin 
Published: February 2020

Nanopore sensing based technologies have made significant progress for biomedical applications. In recent years, multimode sensing by multifunctional nanopores shows the potential to greatly improve the sensitivity and selectivity of traditional resistive-pulse sensing method. In this talk, we will show that two label-free electric sensing modes can work cooperatively to detect biological entities, such as biomolecules and biological nanoparticles, in ionic solution by a multifunctional nanopipette. The multifunctional nanopipettes containing both nanopore and nanoelectrode (NE) at the tip are fabricated quickly and cheaply. We will discuss the detection mechanism and demonstrate that the ionic current and local electrical potential changes can be detected simultaneously during the translocation of individual entities. With the combination of ionic current and potential measurements, we are able to detect not only the translocation of single entity but also the motions of entities outside the nanopore entrance, revealing rich information of biological entities.