bluuebunny/crossref_metadata_2025_split huggingface dataset:
Influence of Physicochemical Properties on Gas Transport Properties of Silver-Containing Ionic Liquid Mixtures for Olefin/Paraffin Membrane Separation
Authors: Park Sejoon , Freeman Benny D. , Brennecke Joan F. 
Published: December 2020

Olefin/paraffin separation by cryogenic distillation is one of the most energy-consuming processes not only among the entire chemical processes but also among all the energy-consuming activities by human beings. The purification of propylene and ethylene accounts for 0.3% of global energy use (1). Membrane separation is an attractive alternative, owing to its high energy-efficiency compared to conventional distillation processes. Liquid membranes that utilize gas transport through the liquid phase confined in the pore structures have shown promising performance due to the faster transport compared to solid membrane materials (2).
Since the liquid phase is where the transport of olefin/paraffin molecules occurs, the liquid membrane performance in terms of permeability, selectivity, and stability mainly relies on the properties of the liquid component. Ionic liquids are a suitable material since the liquid component in the membranes provide stable separation performance owing to their extremely low vapor pressure and good thermal/chemical stability. Moreover, the limitless turnability of ionic liquids can be manipulated to enhance the molecular interaction with certain gas molecules to result in better gas solubility. For olefin/paraffin separation, in addition to physical solubility of the olefin in the ionic liquid, silver ions are commonly added to further improve olefin solubility. The silver ions can complex with olefin molecules via interaction between the double bonds of olefins and the orbitals of silver ions.
Here we have investigated the effect of the anion, concentrations of the silver salt, and temperatures on the physicochemical properties of the silver-containing ionic liquid mixtures. The macroscopic physicochemical properties, such as viscosity and density, affect the filling of the membrane pores and stability to transmembrane pressure. However, we show that they are also indicators of ion aggregation in the mixtures, which can be correlated with relevant membrane properties, including solubility, diffusivity and silver ion reactivity with contaminant gases. The physiochemical viewpoint on the silver-containing ionic liquid mixture will provide appropriate insight for understanding the olefin/paraffin gas transport in the ionic liquid mixture, which leads to a design idea for better separation performance.
(1) D. S. Sholl, R. P. Lively, Seven chemical separations: to change the world: purifying mixtures without using heat would lower global energy use, emissions and pollution--and open up new routes to resources. Nature
532, 435 (2016).
(2) C. M. Sanchez, T. Song, J. F. Brennecke, B. D. Freeman, Hydrogen Stable Supported Ionic Liquid Membranes with Silver Carriers: Propylene and Propane Permeability and Solubility. Industrial & Engineering Chemistry Research
59, 5362-5370 (2020).
Synthesis of Li7La3Zr2O12 Li-Ion Conducting Electrolytes By a Rapid Solution-Combustion Method
Authors: Badami Pavan P , Arif M Z , Rettenwander Daniel , Chan Candace K. , Kannan Arunachala Mada 
Published: December 2020

Garnet structured Li-ion conductors (Li7La3Zr2O12, LLZO) have attracted great attention as promising solid electrolytes for all-solid-state batteries, owing to their wide electrochemical window, better thermal stability and high Li-ion conductivity at room temperature [1,2]. Synthesis of cubic phase LLZO using solid state reaction routes requires high reaction temperatures and long reaction time producing unfavorable micron sized particles [3]. In the present study, a rapid and facile synthesis of LLZO in sub-micron size by combustion method using CH6N4O fuel is demonstrated. The effect of fuel to oxidizer ratio, calcination temperature on phase purity, particle size towards formation of LLZO was systematically was examined and the synthesis conditions were optimized to attain high relative densities and conductivities of the pellets. In particular, Al and Ga stabilized LLZO were synthesized as low as 600 °C for duration of 4 h and the pellets showed high Li +conductivity (up to 0.5 mS.cm-1) with relative densities (~ 95 %). Furthermore, studies on critical current densities (CCD) measurements of these pellets would be presented compared to conventional solid-state reaction-based pellets. The presented work is expected to provide insight on producing sub-micron sized LLZO particles at lower synthesis temperatures allowing to explore improved performance of composite-polymer electrolytes and producing thin films.

Keywords
: garnets, solution combustion synthesis, sintering and critical current densities.

References
[1] R. Murugan, V. Thangadurai, and W. Weppner, Angew. Chemie - Int. Ed., 46, 7778–7781 (2007).
[2] R. Pfenninger, M. Struzik, I. Garbayo, E. Stilp, and J. L. M. Rupp, Nat. Energy, 4, 475–483 (2019).
[3] P. Badami, J.M. Weller, A. Wahab, G.J. Redhammer, L. Ladenstein, D. Rettenwander, M. Wilkening, C.K. Chan and A.M. Kannan, ACS Appl. Mater. Interfaces (Under review).

Figure 1
Solid-State Battery Designed for Electric Aviation
Authors: Dornbusch Donald , Viggiano Rocco P. , Kowalski Benjamin A , Lin Yi , Dynys Frederick W. , Connell John W. , Wu James J. 
Published: December 2020

The demand for higher energy density batteries increases as the demand for portable electronic devices and electric automotive increases, as well as a variety of other applications requiring substantially higher power and energy than attainable with current lithium-ion capabilities which includes the areas of high performance vehicles, military applications, and electric aviation. However, the improvement of energy density is insufficient alone for enabling electric aviation when considering the high flammability and risk of thermal runaway inherent in current state-of-the-art liquid electrolytes. The development of high energy, high power, and safe batteries are required to enable hybrid and fully electric aircraft.
Next generation chemistries such as lithium-sulfur provide high theoretical specific energy density suitable for electric aviation without as strict of volumetric requirements observed in the automotive industry. However, due to the phase transition during discharge where sulfur generates a series of soluble intermediate polysulfides, which are lost to the liquid electrolyte, cause detrimental side effects, and severely limit cycle life battery performance is severely reduced. Additionally, the low electrical conductivity of sulfur requires a large amount of inactive carbon dramatically increasing parasitic mass.
The dissolution issue make sulfur a desirable candidate to pair with a solid-state electrolyte in order to avoid polysulfide dissolution and shuttling. In addition, inorganic solid-electrolytes have low flammability providing the improved safety required. Combining this chemistry with a solid-state electrolyte provides a path for achieving the energy and safety required for electric aviation.
The development of scalable thin solid-state electrolytes paired with lithium-sulfur chemistry will be discussed and how their development will aid in enabling a unique application.
Lowering the Interfacial Resistance in LLZTO:PEO Electrolytes By Covalent Surface Modifications
Authors: Kuhnert Eveline , Slugovc Christian , Trimmel Gregor , Wilkening Martin , Rettenwander Daniel 
Published: December 2020

Reducing the high interfacial resistance across the cubic Li7La3Zr2O12 (LLZO) | poly(ethylene oxide) (PEO) interface in LLZO:PEO membranes is one of the key challenges to realize future solid-state lithium batteries.1,2

Recently, several groups presented various approaches to enhance the ionic charge transport across the interface.3,4 As an example, Gupta and Sakamoto showed that heat treatment to remove surface impurities and that an increase in the Li-salt concentration in PEO to match the chemical potential between LLZO and PEO lead to significantly lower interfacial resistance.3

Herein, we present an alternative but complimentary approach to improve the interfacial kinetics by an advance surface modification strategy. For this purpose, we activated the surface terminated oxygen of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles by plasma etching and functionalized the activated oxygen by immersing the LLZTO particles in a (3-glycidyloxypropyl)trimethoxysilane solution to form covalently bonded self-assembled monolayers (SAMs). The SAMs are terminated by an epoxy group that react with the hydroxyl group of the PEO’s according to a ring-opening reaction. This reaction may lead to an ordered arrangement of covalently bonded PEO segments around the LLZO particles enabling the Li ions to easily cross the LLZTO | PEO interface. Indeed, we managed to lower the interfacial resistance by more than four orders of magnitude. Finally, with our approach we realized an area specific resistance of 500 Ω cm2 at 20 °C; to our knowledge, this value is the lowest one reported so far.

Reference
s
:

[1] J. Schwenzel, K. Kun, F. Langer in: R. Murugan, W. Weppner (Eds.), Solid Electrolytes, Springer, Swizerland, 2019, pp. 281–304.
[2] X. Judez, G.G. Eshetu, C. Li, L.M. Rodriguez-Martinez, H. Zhang, M. Armand, Joule 2 (2018) 2208–2224.
[3] A. Gupta, J. Sakamoto, Electrochem. Soc. Interface 28 (2019) 63–69.
[4] Z. Huang, W. Pang, P. Liang, Z. Jin, N. Grundish, Y. Li, C.A. Wang, C.A., J. Mater. Chem. A, 7 (2019) 16425–16436.
Room Temperature to 150 °C Lithium Metal Batteries Enabled By a “Molecular Ionic Composite” Solid Electrolyte
Authors: Yu Deyang , Pan Xiaona , Zanelotti Curt J. , Lin Feng , Madsen Louis A. 
Published: December 2020

Molecular ionic composites (MICs) are a new class of solid electrolyte materials developed recently in our group. These materials are constructed from various ionic liquids and a highly charged rigid rodlike polymer, poly(2,2′-disulfonyl-4,4′-benzideneterephthalamide) (PBDT). MICs demonstrate an unprecedented combination of thermal properties (stability up to 300 °C), mechanical properties (E′ up to ~ 1 GPa), and ion transport properties (ionic conductivity up to 8 mS/cm).[1-3] Here we present preparation and characterization of a MIC membrane based on the PBDT polymer, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI) and LiTFSI. This MIC membrane is robust and flexible, and exhibits ionic conductivity ~ 0.2 mS/cm at room temperature. Due to the electrochemical and mechanical stability of the MIC membrane at elevated temperature, Li/MIC/LiFePO4 coin cells demonstrate excellent cycling performance over a wide temperature range from 20 to 150 °C. This study demonstrates that MIC materials represent a promising electrolyte platform for safe and wide-temperature-range lithium batteries.

References:

[1] Y. Wang, Y. Chen, J. W. Gao, H. G. Yoon, L. Y. Jin, M. Forsyth, T. J. Dingemans, L. A. Madsen, Adv. Mater.
2016, 28, 2571.
[2] J. E. Bostwick, C. J. Zanelotti, C. Iacob, A. G. Korovich, L. A. Madsen, R. H. Colby, Macromolecules
2020, 53, 1405.
[3] R. J. Fox, D. Yu, M. Hegde, A. S. Kumbhar, L. A. Madsen, T. J. Dingemans, ACS Appl. Mater. Interfaces
2019, 11, 40551.

Figure 1. Cycling performance of Li/MIC/LiFePO4 coin cell at 150 °C. Inset image is a MIC membrane.

Figure 1
Highly Sodium-Ion Conductive Sulfide Electrolyte Film Prepared By Pulsed Laser Deposition
Authors: Sakuda Atsushi , Nishimura Masaki , Yubuchi So , Tatsumisago Masahiro , Hayashi Akitoshi 
Published: December 2020

All-solid-state sodium secondary batteries exhibit significant potential for use in next-generation batteries that offer advantages associated with safety and cost. The key material in this battery technology is a solid electrolyte that conducts sodium ions. The most typical solid electrolyte for all-solid-state sodium batteries is Na3PS4 [1]. All-solid-state batteries using Na3PS4 and several electrode active materials operate at room temperature. At their present stage of development, the operation of all-solid-state sodium batteries under high current densities is challenging. It was recently reported that Na3SbS4 solid electrolytes showed a high ionic conductivity that exceeded 10-3 S cm-1 [2-4], which was higher than that of Na3PS4 glass-ceramic [1]. The evaluation of bulk ionic conductivity is important for determining the potential of the electrolytes. However, most previous studies have reported on the ionic conductivities of compressed powder pellets.
Numerous studies have employed pulsed layer deposition (PLD) for fabricating lithium-ion-conducting sulfide electrolyte films. However, PLD has been seldom used for developing sodium-ion-conducting solid electrolyte films thus far. Herein, a thin film of highly dense Na3SbS4 solid electrolyte was prepared by PLD to evaluate its potential sodium-ion conductivity. The as-deposited film was observed to be amorphous, whereas a cubic crystalline phase of Na3SbS4 was formed in the thin film after heat treatment at 190°C. Crystallization of the thin film after heat treatment increased ionic conductivity and decreased activation energy. The heat-treated film showed a conductivity of 1.7×10-2 S cm-1 at 25°C and an activation energy of 15 kJ mol-1 for conduction. Further, it was discovered that the Na3SbS4 solid electrolyte has a high conductivity of more than 10-2 S cm-1 at room temperature. The evaluation of the chemical composition of the film suggested that there are some vacancies in sodium site.

Acknowledgements:

This work was supported by the MEXT program "Elements Strategy Initiative to Form Core Research Center (ESICB)" and JSPS KAKENHI Grant Nos. 18H05255 and 19H05816.

References:

[1] A. Hayashi, K. Noi, A. Sakuda and M. Tatsumisago, Nat. Commun., 3, 856 (2012).
[2] H. Wang, Y. Chen, Z.D. Hood, G. Sahu, A. S. Pandian, J. K. Keum, K. An, C. Liang, Angew.Chem. Int. Ed., 55, 8551 (2016).
[3] A. Banerjee, K. H.Park, J. W. Heo, Y.J. Nam, C. K. Moon, S. M.Oh, S.-T. Hong, Y.S. Jung, Angew. Chem. Int. Ed., 55, 9634 (2016).
[4] L. Zhang, D. Zhang, K. Yang, X. Yan, L. Wang, J. Mi, B. Xu, Y. Li, Adv. Sci.
3, 1600089 (2016).
Lithium Dissolution Using Garnet-Type Solid Electrolyte with a Thin Ionic Liquid Interlayer
Authors: Fuchs Till , Richter Felix H. , Janek Juergen 
Published: December 2020

Currently, all-solid-state batteries enjoy widespread attention in research due to their expected high safety, power and energy density. This stems from their promise of being able to utilize lithium metal as the anode material. As of now, competitive batteries using lithium metal do not exist since most solid electrolytes are not chemically compatible in combination with a lithium anode. As garnets based on the Li7La3Zr2O12 system are stable versus lithium, this solid electrolyte can be used as a model system to study lithium metal stripping and plating.(1,2)
One of the manifold problems regarding lithium metal anodes is based on the morphological changes occurring when stripping and depositing lithium during cycling of a cell.(1) Current densities above a certain threshold lead to pore formation and subsequent contact loss of lithium from the solid electrolyte, as vacancies are not transported away at a sufficient rate. This issue also leads to dendrite formation when depositing lithium due to current constriction on the remaining contact spots. Hence, this work aims to exploit thin ionic liquid interlayers as a means to compensate or attenuate pore formation at the interface. We observed an improvement in dissolution behavior of the lithium metal anode and additionally were able to identify the transport processes when using ionic liquids in combination with Li6.25Al0.25La3Zr2O12 using electrochemical impedance spectroscopy. We underline our conclusions with microscopic morphological studies using scanning electron microscopy. This work acts as a stepping-stone for the assembly of all-solid-state batteries using lithium metal as the anode in hybrid-cell configurations.
(1) Krauskopf, T.; Hartmann, H.; Zeier, W. G.; Janek, J. Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries - An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li6.25Al0.25La3Zr2O12. ACS Appl. Mater. Interfaces
2019, 11 (15), 14463–14477.
(2) Krauskopf, T.; Dippel, R.; Hartmann, H.; Peppler, K.; Mogwitz, B.; Richter, F. H.; Zeier, W. G.; Janek, J. Lithium-Metal Growth Kinetics on LLZO Garnet-Type Solid Electrolytes. Joule
2019, 3 (8), 2030–2049.
4,4'-Bipyridine Adsorption on Sb(111) from Ionic Liquid- in Situ STM and EIS Study
Authors: Pikma Piret , Siimenson Carolin , Siinor Liis , Lust Enn 
Published: December 2020

Room-temperature ionic liquids (RTIL) draw a lot of attention in modern electrochemical research due to their high stability under applied electrode potential, the wide electrochemical window and dual usability as a solvent and an electrolyte RTILs have become very attractive. Molecular self-assembly at solid surfaces, resulting in the formation of nanostructures with well-controlled properties and functionality presents multiple prospective applications in science and technology [2], e.g., the smart tailoring of the structural properties of the functionalized electrodes attracts a lot of attention due to an ability to trigger the specific electrochemical processes.
In this study, the in situ scanning tunnelling microscopy (STM) and impedance spectroscopy methods have been applied to study the structure and adsorption properties of the electrochemically polished Sb(111) single crystal electrode | EMImBF4, and EMImBF4 + X% 4,4'-bipyridine (x= 1; 2; 5), interface.
During the measurements, atomically flat areas have been observed on the in situ STM images of Sb(111) single crystal electrode surface in EMImBF4 and atomic resolution was obtained. The in situ STM data show that there is no quick surface reconstruction process. The surface structure is stable within the potential region investigated (-0.8 — -0.1 vs. Ag/AgCl|EMImBF4) as it has been shown for inactive electrolyte solutions [3].
Additionally, the influence of electrode potential on the adsorption kinetics of 4,4'-bipyridine on Sb(111) has been demonstrated. Within the region of maximal adsorption, the capacitance pits in the differential capacitance vs. electrode potential curves have been observed, depending on the 4,4'-bipyridine concentration [4]. The influence of electrode potential (E) on the adsorption kinetics of 4,4'-BiPy on Sb(111) has been demonstrated. From the in situ STM data it has been found that 4,4’-BP adsorbs in a form of a stripe pattern on antimony single crystal electrodes.
Acknowledgements
This work was supported by Estonian Research Council grants PUT PSG249 and RSG676, and by the EU through the European Regional Development Fund under project TK141 (2014-2020.4.01.15-0011).
References
[1] H. Ohno (Ed.), Electrochemical Aspects of Ionic Liquids, John Wiley & Sons, Inc., New Jersey, 2005, p.1.
[2] T. Wandlowski, Phase Transitions in Two-dimensional Adlayers at Electrode Surfaces: Thermodynamics, Kinetics, and Structural Aspects, A.J. Bard, M. Stratmann (Eds.), Encyclopedia of Electrochemistry, Wiley VCH, Weinheim (2002) p. 383-471.
[3] V. Grozovski, S. Kallip. E. Lust, Surface Science, 613(2013) 108-113.
[4] P. Pikma, L. Siinor, O. Oll, and E. Lust. Electrochemistry Communications, 61 (2015): 61-65.
Controlling of Dispersion State of Particles in Slurry and Electrochemical Properties of Electrodes
Authors: Kuratani Kentaro , Ishibashi Kaoru , Komoda Yoshiyuki , Hidema Ruri , Suzuki Hiroshi , Kobayashi Hironori 
Published: December 2020

The electrode materials which exhibit high capacity have attracted much attention because the capacity of the materials directly commits to the energy density of LIBs and driving miles of EVs. So that, many researchers devote their efforts to find new electrode materials with high capacity such as lithium excess layered oxide, Ni-rich materials and silicon. Electrode manufacturing process, generally consists of (1) preparing slurry, (2) coating the slurry on current collector, (3) drying, (4) pressing steps, is another important issue to achieve LIBs with high energy density.
Compared with numerous reports described with the electrode material development, however, only the limited numbers of papers related to the electrode construction process have been published [1-5]. To shed light the relationship between the electrode construction process and the battery performance is an essential research for obtaining the best performance from electrode materials and assembled LIB cells.
In the present study, we focused our attention on the slurry preparation step among above-mentioned four steps. The slurry preparation is the first step in the electrode construction process, and we recognize the dispersion state of particles achieved during slurry preparation greatly influences the battery performance.
Three different preparation processes were applied to achieve the different dispersion state of particles in slurries, and thus obtained slurries are characterized by rheological measurement. It is found that dispersion process with highly loaded slurry or under high shear flow reduces elastic moduli and that their combination achieved the most dispersed state of the particles among the slurries investigated. X-ray computed tomography unveiled that the electrodes manufactured from these slurries contain the aggregates and the size of aggregates in the electrodes was reduced with the decrease in elastic moduli of slurry. At the discharge current density of 10 mA g–1, these electrodes exhibited 140 mAh g–1 of discharge capacities. At 1000 mA g–1, the electrode prepared from highly loaded slurry maintained 80% of the capacity that obtained at the current density of 10 mA g–1. The capacity of the electrode prepared from the slurry under highly loaded and high shear flow, on the other hand, dropped below 10%, indicated that the electrode from the most dispersed slurry has the worst rate performance.
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