bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elucidating the Solubility and Diffusivity of Atmospheric Gases in a Wide Variation of Liquid Electrolytes for Lithium-Air Batteries
Authors: Haas Ronja , Murat Michael , Janek Jürgen , Natan Amir , Schroeder Daniel 
Published: July 2021

Due to their high theoretical energy density, Li–O2 and Li–air batteries are considered as a promising alternative to Li-ion batteries, especially for mobile applications. However, dissolved gases in the liquid electrolyte, in particular O2, can be involved in detrimental side reactions at the lithium anode. Moreover, CO2 that can form from side reactions with the electrolyte or the cathode material, and N2 from the ambient air might be dissolved in the electrolyte.
In order to evaluate the impact of these dissolved gases on the stability of the anode and to know their concentrations in possible side reactions, the solubility and the diffusion coefficient for each gas in the electrolyte are crucial parameters to know.
In this work, we utilize gas uptake measurements to systematically determine the diffusion coefficients and Henry’s law solubility constants of O2, N2 and CO2 in different ether- and DMSO-based electrolytes and pure solvents. Additionally, we calculate the diffusion coefficient with molecular dynamics simulations and show good qualitative agreement between simulations and experimental results. We discuss the influence of solvent parameters, such as surface tension and viscosity, on the solubility and the diffusivity as well as the impact of different conducting salts. All investigated conducting salts reduce the diffusivity of the gases; however, we observe the solubility can both decrease or increase, depending on the solvent, the gas and the molecular structure of the salt. Therefore, we emphasize that both components, solvent and conducting salt, have to be considered for optimizing the gas transport properties of the electrolyte for Li–O2 and Li–air batteries.
Metal Organic Framework Derived Magnesium Oxide/Carbon Interlayer for Long-Life Lithium-Sulfur Batteries
Authors: Kang Hyeonmuk , Shin Jaewook , Kim Taehee , Lee Yongju , Lee Daehee , Cho EunAe 
Published: July 2021

i-S battery, with abundant S sources and high theoretical capacity, is one of the promising future battery technology. S cathode has a theoretical capacity of 1672 mAhg-1, which is an order of magnitude higher than the transition metal oxides’ of commercial lithium-ion batteries. However, the commercialization of Li-S battery is still struggling due to poor cyclic stability and limited kinetics. These problems come from the low electrical conductivity of S, LiS and Li2S, polysulfide shuttling effect and large volume change during cycling. Polysulfide shuttling effect is a phenomenon that polysulfide intermediate species, generated during charging and discharging of S and Li2S, gets dissolved into electrolyte and cause loss of capacity. Herein, the Mg-MOF-74-derived MgO/carbon interlayer is synthesized. Carbon substrate is known to provide additional electrical conductivity to S cathode, and according to Tao, X., et al, MgO is a good choice to balance between sulfide-adsorption and diffusion on the oxides. Therefore, MOF-derived MgO particles are expected to effectively mitigate polysulfide shuttling and reutilize dissolved polysulfide. Inserting MOF-derived MgO/carbon interlayer, the Li-S cell show excellent cycling stability (87.5% retention within 100 cycles) at 0.2 C with sulfur loading mass 2.6 mg cm-2, whereas the pristine and carbon interlayer sample show 60.0% and 64.3%. The capacity retention still holds at higher loading mass of sulfur electrode. Due to low electrical conductivity and polysulfide dissolution of the sulfur cathode, increasing sulfur content and loading mass of the sulfur electrode, and amount of electrolyte could be detrimental to Li-S cell performance. However, with Mg-MOF-74-derived MgO/carbon interlayer, this limitation could be overcome.
References:
[1] Tao, X., et al., Nat Commun, 2016. 7: p. 11203.
In Situ Stress Evolution on an Au Thin Film Cathode during Charging/Discharging of a Lithium-Oxygen Battery
Authors: Dykes Hannah , Capraz Omer Ozgur 
Published: July 2021

The theoretical energy density of lithium-oxygen batteries is by far the closest competitor to gasoline compared to other battery configurations. Unfortunately, the commercial implementation of this technology is hindered by the poor cycling performance, mostly due to the slow oxygen evolution/reduction kinetics. The sluggish oxygen evolution kinetics are typically more severe and cause the slow oxidation of lithium peroxide. This can cause the irreversible formation of a passivating lithium peroxide layer on the cathode surface. The interfacial dynamics due to the growth of lithium peroxide and the formation of cathode-electrolyte interface (CEI) layers remains largely unknown. It is crucial to elucidate how the nucleation of discharge products on the cathode surface affects the electrochemical performance in order to design new electrolytes and cathodes for lithium-oxygen batteries.
In this study, we propose to investigate the surface stress generation associated with the formation of discharge products and CEI layers on the cathode. Thin Au films were deposited via e-beam evaporation onto a borosilicate glass substrate. These substrates were used as a cathode material. The electrolyte used was 1 M LiTFSI in DMSO, and it was saturated with oxygen prior to performing electrochemical measurements. In situ stress measurements were conducted using a multiple beam optical sensor (MOS). A custom cell was designed to monitor the physical response of the cathode during cycling while enabling optical access to the back of the substrate for stress measurements.
The in situ curvature evolution on an Au coated borosilicate glass cantilever is monitored during one discharge/charge cycle at 10 µA/cm2. Tensile stress generation is observed during the formation of the lithium peroxide discharge product on the Au cathode. A large stress relaxation into the compressive regime is observed at the onset of charging. From our results, the nucleation of lithium peroxide onto the cathode surface causes tensile stress, while the oxidation of lithium peroxide causes compressive stress. Revealing the mechanical response of the charge/discharge products on the cathode will shed light into the formation mechanisms of these products, which is crucial to design both new electrolytes and cathode materials for lithium-oxygen batteries.
Acknowledgement: This work was supported by the Binational Science Foundation (#2018327), and we are thankful to both Dr. Malachi Noked and Rosy for fruitful discussions.
Additive Manufacturing for Rapid Prototyping of Mixed Potential Electrochemical Sensors
Authors: Agi Kamil , Halley Sleight , Tsui Lok-kun , Garzon Fernando H 
Published: July 2021

Natural gas pipeline leaks are responsible methane emissions that amount to over 1.6 x 108 metric tons of CO2 equivalent and more than 2 billion dollars in losses.[1, 2] A widely deployable sensor capable of remotely monitoring pipelines to promptly detect these leaks is needed to curb their environmental and economic impact. YSZ based mixed-potential electrochemical sensors (MPES) fit this need as they are cheap and durable, allowing for wide deployment in the field. Prototyping of these sensors is enhanced by the utilization of additive manufacturing (AM).
The long lead times and high start-up cost of traditional ceramic manufacturing techniques are poorly suited to prototype development of mixed potential electrochemical sensors. Recent advances in AM techniques have opened the possibility for the rapid prototyping of these sensors.[3] We report for the first time a three element mixed potential electrochemical sensor manufactured using direct write syringe extrusion. La0.87Sr0.12CrO3 (LSCO), In2-xSnxO3 (ITO), Au and Pt electrodes bridged with a porous yttria-stabilized zirconia (YSZ) solid electrolyte have been deposited on YSZ substrates. The Pt electrode and leads, as well as the porous YSZ electrolyte and YSZ substrate are deposited by direct write extrusion. The printing parameters for the printing of the YSZ substrate are optimized to achieve desired surface and bulk material characteristics. A density 60% of theoretical of the YSZ substrate is obtained after sintering at 1450 C. The sensors are evaluated for their sensitivity to methane, ethane, ammonia, nitrous oxide, and hydrogen. The sensitivity of the sensors will be compared to that of an industry standard MidIR sensor for natural gas detection.
[1] A.J. Marchese, T. L. Vaugh, D. J. Zimmerle, D. M. Martinez, L. L. Williams, A. L. Robinson, A. L. Mitchell, R. Subramanian, D. S. Tkacik, J. R. Roscioli, S. C. Herndon. Science. 7204 (2018).
[2] Kort, E. A.; Frankenberg, C. Costigan, K.R.; Lindenmaier, R.; Dubey, M. K; Wunch, D. Geophys. Res. Lett, 2014, 41, 19, 6898
[3] Travitzky, N., Bonet, A., Dermeik, B., Fey, T., Filbert‐Demut, I., Schlier, L., Schlordt, T. and Greil, P., 2014. Additive manufacturing of ceramic‐based materials. Advanced engineering materials, 16(6), pp.729-754.
Figure 1. Additively manufactured three electrode pair mixed potential electrochemical sensor.

Figure 1
Enabling High-Rate Plating in Solid-State Li Batteries By Interface Engineering and Pulse Plating
Authors: Flatscher Florian , Reisecker Verena , Chamasemani Fereshteh Falah , Brunner Roland , Ganschow Steffen , Chiang Yet-Ming , Rettenwander Daniel 
Published: July 2021

High power solid-state Li batteries (SSLB) are hindered by the formation of dendritic structures at high current rates. One of the main reasons for their formation are current constriction that arise from inhomogeneous electrical field distributions at the Li metal | solid-electrolyte interface that originates from, e.g., (i) poor contact between Li metal and the solid electrolyte or (ii) the Li metal void formation during Li metal stripping.1,2 Herein, we present a solution achieved via thorough sample preparation consisting of a mixture of polishing steps, heat treatments and the usage of a molten lithium alloy to effectively wet the electrolyte. This reduces the interfacial resistance to negligible values, which enables critical current density (CCD) up to 4 mA/cm². Moreover, we applied different current waveforms (i.e., pulse plating) to homogenize the current distribution at the interface, which increases the CCD significantly to a value of up to 6.3 mA/cm². These results, suggest that the combination of interface engineering in combination with alternative current waveforms are promising strategies to reach the power requirement for future electrical vehicles.
References:
(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 Li 6.25 Al 0.25 La 3 Zr 2 O 12. ACS Appl. Mater. Interfaces
2019, 11 (15), 14463–14477. https://doi.org/10.1021/acsami.9b02537.
(2) Kasemchainan, J.; Zekoll, S.; Spencer Jolly, D.; Ning, Z.; Hartley, G. O.; Marrow, J.; Bruce, P. G. Critical Stripping Current Leads to Dendrite Formation on Plating in Lithium Anode Solid Electrolyte Cells. Nat. Mater.
2019, 1–7. https://doi.org/10.1038/s41563-019-0438-9.
Acknowledgment:
The financial support by the Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development and the Christian Doppler Research Association (Christian Doppler Laboratory for Solid-State Batteries) and the Austrian Science Fund (FWF) (project no. P25702) is gratefully acknowledged.
Electron Leakage through Extended Defects in Inorganic Solid Electrolyte Interphase -- a Non-Equilibrium Green's Function/Density Functional Theory Study
Authors: Smeu Manuel , Leung Kevin 
Published: July 2021

The solid-electrolyte interphase (SEI) that forms on lithium ion battery (LIB) anodes prevents the leakage of electrons to the electrolyte, which causes electrolyte degradation and capacity fade. Grain boundaries (GB) between inorganic SEI components, like LiF/LiF or LiF/Li2CO3 boundaries, have been suggested to accelerate Li+ transport[1]. However, SEI GBs on lithium metal anode surfaces have also been predicted to support the existence of Li atoms and nanoclusters at low voltages[2], potentially leading to nucleus for hazardous lithium plating. In this presentation, we further examine the possibility of electron tunneling from the lithium anode through extended defects in LiF films. Using the non-equilibrium Green's function technique (NEGF-DFT), we find that GBs enhance electron tunneling in thin LiF films by 1-2 orders magnitude, depending on the bias. Extrapolating to 5 nm thick films using the WKB method suggests that GBs may enhance electron leakage by up to 9 orders of magnitude. This emphasizes that GBs in the inorganic SEI film are hotspots with respect to electron leakage. We propose that the further development of NEGF algorithms to enable large scale applications to battery interfaces is crucial for predicting SEI passivating properties.
[1] J. Pan, Q. Zhang, X. Xiao, Y. Cheng, and Y. Qi, Design of Nanostructured Heterogeneous Solid Ionic Coatings through a Multiscale Defect Model, ACS Appl. Mater. Interfaces 8, 5687 (2016).
[2] K. Leung and K. L. Jungjohann, Spatial Heterogeneities and Onset of Passivation Breakdown at Lithium Anode Interfaces, J. Phys. Chem. C 121, 20188 (2017).
Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the document do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

Figure 1
(Invited) Fast Ion Dynamics in Solids As Probed By NMR: Disorder, Dimensionality and Correlation Effects
Authors: Wilkening H. Martin R. 
Published: July 2021

NMR offers plenty of tools to analyze ionic jump processes in crystalline and amorphous solids at atomic scale. Both high-resolution and time-domain 1H(2H), 6,7Li, 19F, 23Na NMR helps shedding light on the origins of rapid self-diffusion in materials being relevant for energy storage.
It is well accepted that in materials with strong site preferences, such as LiAlO2, the Li+ ions are subjected to extremely slow exchange processes. The loss of this site preference, as it is the case in glasses and some nanocrystalline phases, may, however, lead to rapid cation diffusion. Examples that benefit from this effect include cation-mixed, high-entropy fluorides ((Ba,Ca)F2) and LiTi2(PS4)3. In general, in non-equilibrium phases site disorder, polyhedra distortions, strain and the various types of local defects will affect both the migration activation energy and the corresponding Arrhenius pre-factor. Whereas in (Me,Ca)F2 (Me = Ba, Pb) cation mixing influences F anion dynamics, in Li6PS5X (X = Br, Cl, I) the potential landscape can be manipulated by anion site disorder and the introduction of extrinsic defects. In some cases, this leads to rather flat landscapes enabling the ions to have access to concerted displacement processes, as is seen in LLZO-type garnets. On the other hand, in the mixed conductor Li4+x
Ti5O12 cation-cation repulsions immediately lead to a boost in Li+ diffusivity at the early stages of chemical lithiation. For Na-bearing closo-borates, the influence of rotational anion dynamics is usually considered to explain long-range cation transport. Recent examples of our group also include Li- and Na-conducting MOFs, for which, as in the case of the closo-borates and the famous Na-β''-alumina, transitions from correlated to uncorrelated motion are observed at sufficiently high temperature.
Finally, rapid diffusion is also expected for materials that are able to guide the ions along (macroscopic) pathways with confined dimensions, as we have recently observed for layer-structured fluorides such as RbSn2F5 or MeSnF4 with their buried interfaces.
Development of Graphene-Based Nanocomposites for Hydrogen Storage
Authors: Boateng Emamnuel , Chen Aicheng 
Published: July 2021

Hydrogen economy is an envisioned approach with potential to addressing the increasing global energy consumption and emission issues. However, as one of the fundamental elements of the hydrogen economy, storage of hydrogen in a lightweight, compact, and safe manner remains the most serious bottleneck. Gaseous and liquid hydrogen storage methods continue to dominate for commercial usage; however, they have been found to be unsafe and expensive. Consequently, solid-state hydrogen storage has been attracting considerable interests, where hydrogen may be stored via physisorption (carbon-based materials and metal organic frameworks) or chemisorption (metal and complex hydrides) [1-3].
In this presentation, recent advances in graphene-based materials with a high surface area and enhanced storage capacity for solid-state hydrogen storage are highlighted. Specifically, this presentation focuses on the development of uniformly dispersed metal nanoparticles (NPs), for example Pd NPs, on a heteroatom-doped reduced graphene oxide (rGO). Our study has shown that the doping of the heteroatoms (such as boron, nitrogen etc.) effectively suppresses possible metal cluster formation, resulting in uniform distribution of the Pd NPs on the modified rGO. The effect of the doping of different heteroatoms and the decoration with Pd NPs on the hydrogen uptake and release is discussed.
[1] S. K. Konda, and A. Chen, Mater.
Today,
19, 100 (2016).
[2] E. Boateng, and A. Chen, Mater.
Today Adv., 6, 100022 (2020).
[3] E. Boateng, J. S. Dondapati, A. R. Thiruppathi, and A. Chen, Int.
J. Hydrogen Energy, 45, 28951 (2020).
(Invited) Nafion/CNT Passivated Carrier Selective Contacts for Silicon Photovoltaics
Authors: Chen Jianhui , Tune Daniel , Ge Kunpeng , Li Han , Flavel Benjamin S 
Published: July 2021

In the past, the application of carbon nanotube-silicon solar cell technology to industry has been limited by the use of a metallic frame to define the active area in the middle of a silicon wafer. In our work, we use industry standard device geometries with a front- and back-junction design which allow for the entire wafer to be used as the active area. These are enabled by the use of an intermixed Nafion layer which simultaneously acts a passivation, antireflective and physical blocking layer as well as a nanotube dopant. This leads to the formation of a hybrid nanotube/Nafion passivated charge selective contact (PCSC) and solar cells with active areas of 1 – 16 cm2 are fabricated. Record maximum power conversion efficiencies of 15.2% and 18.9% are reported for front- and back-junction devices for 1 cm2 and 3 cm2 active areas, respectively. By placing the nanotube film on the rear of the device in a back-junction architecture many of the design related challenges for carbon nanotube silicon solar cells are addressed and their future application to industrialized processes are discussed.
Additionally, traditional silicon solar cells extract holes and achieve interface passivation with the use of a boron dopant and dielectric thin films such as silicon oxide or hydrogenated amorphous silicon. Without these two key components, few technologies have realized power conversion efficiencies above 20%. We now develop a carbon nanotube/Nafion ink that can be spin coated directly onto a silicon wafer to serve simultaneously as a hole extraction layer, but also to passivate interfacial defects. This enables a low-cost fabrication process that is absent of vacuum equipment and high-temperatures. Power conversion efficiencies of 21.4% on an device area of 4.8 cm2 and 20% on an industrial size (245.71 cm2) wafer are obtained.
[1] D. D. Tune, N. Mallik, H. Fornasier, B. S. Flavel, Adv. Energy Mater. 10, 2020, 1903261. DOI: 10.1002/aenm.201903261
[2] J. Chen, D. D. Tune, K. Ge, H. Li, B. S. Flavel, Adv. Funct. Mater. 2020, 30 2000484. DOI: 10.1002/adfm.202000484
[3] J. Chen, L. Wan, H. Li, J. Yan, J. Ma, B. Sun, F. Li, B. S. Flavel, Adv. Funct. Mater. 30, 2020, 202004476. DOI: 10.1002/adfm.202004476
[4] L. Wieland, H. Li, C. Rust, J. Chen, B. S. Flavel, Adv. Energy Mater. 2020 just accepted manuscript. DOI: 10.1002/aenm.202002880

Figure 1
(Invited) Thermoelectric Performance of Fermi-Level Tuned and Aligned Single Walled Carbon Nanotubes
Authors: Yanagi Kazuhiro 
Published: July 2021

Thermoelectric power generation is one of important technologies for realization of highly efficient energy uses. Improvement of performance of thermoelectric materials is required, and theoretical studies suggest one-dimensional materials have potentials for the realization of the highest performance [1]. However, how 1D materials can really improve the thermoelectric performance has not been experimentally verified yet. In this context, thermoelectric properties of single walled carbon nanotubes attract a lot of attention because of their one-dimensional structure and electronic structures (See a review by Blackburn et al. [2]). Thermoelectric properties significantly depend on the electronic structures of SWCNTs, and relationships among Seebeck coefficient (S), electrical conductivity (σ), power factor, doping levels and their electronic structures have been revealed through various studies [3-5]. As a result, a very unique characteristics on thermoelectric properties of SWCNTs has been clarified [5]. In conventional materials, there is a trade-off between Seebeck coefficient and electrical conductivity, but in the metallic SWCNTs, the trade-off is broken because of the presence of 1D electronic structures, indicating the uniqueness of SWCNTs [5].
For the correct understanding of the thermoelectric performance, zT, in SWCNT thin films, clarification of the relationships among S,
σ, and thermal conductivity κ is very important. Although the relationships between S and σ have been well understood, the relationships among those parameters and κ have not yet. Avery et al. clarified κ is almost constant by the change of σ, and they estimated the zT value is approximately 0.01-0,05 [3]. Recently we developed a technique to clarify the cross-plane thermal conductivity κ
⊥ in SWCNT thin films with tuned Fermi level by a combination of time-domain thermoreflectance method and electrolyte gating technique [6], and then clarified that the κ
⊥ is almost constant even when in-plane σ is changed three order of magnitude from ~10 Sm-1 to 104 Sm-1 [5]. Such constant behavior of κ by the change of σ in SWCNT thin films is interesting in both basic science and application perspectives. Now we can prepare Fermi-level tuned and microscopically aligned SWCNT thin films [7], and the relationships between S and σ in the aligned directions have been clarified [8]. In this talk, I would like to discuss the recent results in our group and the estimated zT values of Fermi-level tuned and aligned SWCNTs.
References:
[1] Hicks& Dresselhaus, Phys. Rev. B 47, 16631 (1993), [2] Blackburn et al., Adv. Mater. 30, 1704386 (2018), [3]Avery et al., Nature energy 1, 1 (2016). [4] Yanagi et al., Nano Lett. 14, 6437 (2014), [5] Ichinose et al., Nano Lett. 19, 7370 (2019). [6] Ueji et al., Appl. Phys. Lett. 117, 133104 (2020). [7] Yanagi et al., Nature Comm. 9, 1121 (2018). [8] Fukuhara et al., Appl. Phys. Lett. 113, 243105 (2018).