bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Reversible Asymmetric Structure Evolution and Battery Performance in Layered Sodium Transition Metal Oxides
Authors: Li Xin 
Published: February 2020

Layered sodium transition metal oxide system of NaMO2 (M = 3d transition metal ions and their mixtures) forms a unique material platform to study the interactions between transition metal, oxygen and sodium sublattices. Specifically, Fe and Mn, which are not stable in layered LiMO2, become much more stable in NaMO2. In this talk, I will show that the interplay between these different sublattices at low Na composition modulates the electrochemical performance of NaxMO2 through the generation of novel high voltage phases. A combined in situ (synchrotron) XRD, X-ray absorption spectroscopy, atomic resolution (scanning) TEM, neutron diffraction and density functional theory (DFT) simulation techniques are used to understand the structural and functional details in crystallographic, electronic and magnetic properties. For the Fe containing mixed transition metal system of Na(FexTM1-x)O2, a rippling phase at high voltage was developed due to the unique electronic property of FeO6­ octahedra, while at low voltage it goes back to the normal flat phase through an asymmetric structural evolution pathway, giving high discharge rate capability. For NaMnO2 a unique phenomenon of super charge separation is reported, where an emergent structural unit of charge superplane related to the collective Jahn-Teller activity of Mn3+ was found to dominate the entire electrochemical evolution, giving asymmetric charge discharge behavior and high discharge capacity. The underlying connection between these reversible asymmetric systems will be discussed to further facilitate the design of advanced cathode materials for sodium ion batteries.
[1]Advanced Functional Materials, 1805105 (2018)
[2]Advanced Functional Materials, 1803896 (2018)
Tailoring Materials Chemistry to Advance Low Temperature Molten Sodium Batteries
Authors: Spoerke Erik D. , Percival Stephen , Peretti Amanda , Small Leo J. 
Published: February 2020

The global implementation of secondary lithium ion (Li-ion) batteries continues to expand rapidly, finding clear utility in portable electronics and vehicle electrification. For large format, grid-scale energy storage however, concerns over the safety, reliability, cost, and lifetime of these batteries has motivated the drive to find alternatives to Li-ion systems. Here we describe the materials-driven development of a low temperature molten sodium-halide battery for grid-scale applications. Molten sodium batteries, such as sodium sulfur (NaS) and sodium nickel chloride (Na-NiCl2or ZEBRA) batteries, continue to show promise for grid-scale applications, valued for their use of earth abundant chemistries, scalability, and the absence of volatile, potentially hazardous organic electrolytes. Widespread implementation of these batteries has been limited, however, by relatively high operating temperatures (~300°C). Potentially impacting both cost and lifetime of these batteries, lowering the battery operating temperature would reduce material degradation, enable the use of lower cost battery components, and facilitate simplified, more cost effective heat management and operating strategies. The promising low temperature system described here comprises a molten sodium anode, a solid state ion-conducting separator, and a sodium iodide (NaI)-based molten salt catholyte. This NaI-based system avoids the hazards of volatile organic electrolytes, employing a fully molten catholyte designed to enable long cycle life while still offering a higher voltage (>3V) than traditional molten sodium batteries. Here, we will describe promising demonstrations of prototype battery cycling at drastically reduced operating temperatures near 100°C. In addition, we will address new materials challenges unique to operating a molten sodium battery at these reduced temperatures. In particular, we will focus on the complex goal of increasing lower temperature separator conductance in mechanically robust solid state electrolytes while minimizing resistances at interfaces between these separators and the molten anode and catholyte. Tuning separator materials chemistry and microstructure, both in the bulk and at separator interfaces, can significantly impact electrolyte wetting, reduce cell resistance, and improve battery cycling performance. Continued development of these emerging molten Na-NaI batteries promises a new route to the type of safe, cost-effective, long-lifetime batteries needed for grid-scale energy storage.
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.
Investigation of the Kinetics of Rechargeable Aqueous Zinc Ion Batteries
Authors: Bischoff Christian , Fitz Oliver , Gentischer Harald , Biro Daniel , Henning Hans-Martin 
Published: February 2020

Rechargeable aqueous zinc ion batteries are currently receiving much attention as large-scale energy storage systems due to their inherent safety, fast ion kinetics, low cost materials and environmental friendliness. Considering the recent literature, the state-of-the-art zinc ion battery combines a manganese oxide cathode, a planar zinc foil anode and an aqueous, mildly acidic electrolyte [1]. Even though the corresponding electrochemical models are subject to recent discussions [2] it is possible to derive basic kinetic parameters allowing a further development of the cell design and electrode composition. For this purpose in this study, zinc foil is used as the anode, a slightly acidic zinc sulphate solution as electrolyte and a stainless steel foil coated with manganese dioxide as the cathode. The coating process of the cathode may greatly influence the kinetics of the battery due to the fact that the cathode thickness, the porosity and the particle size are decisive for the overall performance of the battery. The cathode slurry is a mixture of manganese dioxide, carbon black, binder and distilled water. Previous studies showed that particularly the particle size of the manganese oxide in the cathode has great influence on the capacity of the battery [3]. In order to understand the kinetics of the coated cathode it was investigated if the electrochemical process is mass or charge transfer controlled and corresponding parameters of the Butler-Volmer equation are determined by electrochemical characterization of the samples. These kinetic parameters are identified in order to implement a simulation model allowing a further optimization of the battery cell architecture and the required electrode properties.
References

Liu, J.; Xu, C.; Chen, Z.; Ni, S.; Shen, Z.X. Progress in aqueous rechargeable batteries. Green Energy & Environment
2018, 3, 20–41, doi:10.1016/j.gee.2017.10.001.

Song, M.; Tan, H.; Chao, D.; Fan, H.J. Recent Advances in Zn-Ion Batteries. Adv. Funct. Mater.
2018, 28, 1802564, doi:10.1002/adfm.201802564.

Bischoff, C.; Fitz, O.; Schiller, C.; Gentischer, H.; Biro, D.; Henning, H.-M. Investigating the Impact of Particle Size on the Performance and Internal Resistance of Aqueous Zinc Ion Batteries with a Manganese Sesquioxide Cathode. Batteries
2018, 4, 44, doi:10.3390/batteries4030044.
Lithium-Ion Exchange Polymer Membranes Limit Migration of Dissolved Polysulfide Species in Li-S Batteries
Authors: Xu Hui , Moreira Mario , Laicer Castro , Harrison Katherine 
Published: February 2020

Conventional lithium-ion (Li-ion) batteries dominate development efforts in electrical vehicles due to their high open circuit voltage, desirable power density, and long cycle life. Despite these advantages, state-of-the-art Li-ion batteries barely meet the energy requirement of EV-based power trains due low energy density (180-200 Wh/kg cell) and high cost. Lithium sulfur (Li-S) batteries are promising for EV applications because they address both these barriers. Li-S batteries exploit a redox couple described by the reaction below, which has an open circuit potential of 2.2 V with respect to Li+/Li:
16 Li+ + S8 + 16e-→ 8 Li2S
Assuming full conversion, the theoretical energy density and specific capacity of Li-S batteries is 2500 Wh/kg S and 1675 mAh/g S, respectively.1 In addition, sulfur, the key active cathode material is significantly less expensive than conventional transition metal oxide cathodes used in Li-ion batteries. However, Li-S batteries have not gained acceptance for practical applications because of their poor cycle life. This limitation originates from polysulfide diffusion from the cathode through the electrolyte to the anode which causes parasitic side-reactions and limits capacity and cycle retention.
Our work aims to overcome the challenges of polysulfide diffusion by incorporating lithium-ion exchange (LIE) ionomers as polysulfide blocking barriers in Li-S cells. When exposed to electrolyte solvent, these LIE membranes provide a physical barrier that limits polysulfide diffusion, while also delivering high Li+ ion conductivity through swelling in electrolyte solvent. The LIE ionomers can be applied in a variety of ways including as: binders in the electrode formulation, coatings applied directly to the electrode surface, and as freestanding polymer electrolyte membranes. We have also developed a porous, dimensionally stable membrane (DSM) which can be impregnated with LIE ionomers to improve mechanically stability by limiting in-plane (X-Y direction) swelling. This general approach of incorporating LIE ionomers into Li-S cells has achieved improvements in discharge capacity, cycle life, coulombic efficiency, and energy density.

References:

Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J.-M., Li-O2 and Li-S batteries with high energy storage. Nat Mater
2012,
11 (1), 19-29.
Instigation of Low Cost, Non-Toxic and Environmentally Benign Binders for Mild Aqueous Zn/MnO2 Systems
Authors: Chang Hee Jung , Pan Huilin , Choi Daiwon , Rodríguez-Pérez Ismael , Li Xiaolin , Reed David , Sprenkle Vincent 
Published: February 2020

In recent years, zinc has gained significant attention due to its wide availability (fourth-most mined material on the Earth), low-cost nature and recyclability. Moreover, it allows water-based batteries (i.e. Zn/MnO2) that could compete with LIBs for both transportation and stationary applications without safety issues. However, they are not considered rechargeable in practice yet due to the capacity limitation from the cathode materials and the detrimental zinc dendrite formation.
Most of the electrode preparations are currently based on the use of fluorine-containing polymer binders, such as polyvinylidene difluoride (PVDF) and poly-tetrafluoroethylene (PTFE) with N-methyl-2-pyrrolidone (NMP) as a solvent/dispersant due to its good electrochemical stability and high adhesion to the electrode materials and current collectors. However, the fluorinated binders are relatively expensive and NMP is considered to be a hazardous and toxic substance. Therefore, switching to alternate electrode processing routes with non-toxic binders is crucial to providing a fully sustainable and environmentally friendly electrochemical energy storage device.
In this study, various water-soluble binders have been evaluated in mild aqueous electrolyte conditions for Zn/MnO2 systems and are compared with the conventional MnO2/PVDF systems. We observed water-soluble binders can be stable and offer desirable adhesion at certain pH levels (3.5~5) without any decomposition. Electrochemical data also indicates that higher capacity utilization and lower cell overpotential is achieved in the cells with aqueous binders versus the cells with PVDF binder. In summary, our work suggests that the implementation of water-soluble binders can lead to substantial improvements for efficient and effective aqueous battery systems.
In Situ Formed Li-B-H Complex Enables High-Performance Solid Electrolyte for Li Batteries
Authors: Zheng Shiyou , Pang Yuepeng 
Published: February 2020

All-solid-state Li batteries are considered to be the next-generation high-density energy storage devices. The key material is the solid electrolyte with high Li-ion conductivity and wide electrochemical stability window. LiBH4 is considered as an alternative solid electrolyte due to its high conductivity (10-3 S cm-1 at 120 °C) and good electrochemical stability to Li anode. However, its main disadvantages are the low room temperature conductivity (< 10-7 S cm-1) due to the phase transformation at 110 °C and the poor electrochemical stability at high potential due to the strong reducibility. Searching for new types of Li borohydride beyond LiBH4 with superior Li-ion conducting properties is believed to be an effective strategy to push borohydride-based solid electrolytes towards practical applications. In this work, the Li-B-H complexes are facilely prepared via controllable dehydrogenation of LiBH4 as solid electrolytes for Li batteries. The Li-B-H complex with 7.5 wt% H2 desorption under 3 bar H2 (HP-LiBH2.4) shows exceptionally high Li-ion conductivity (2.7×10-4 S cm-1 at 35 °C) and low activation energy (0.43 eV). The Li-B-H complex possesses the best overall Li-ion conducting properties (in terms of Li-ion conductivity and electrochemical stability) among all borohydride-based solid electrolytes, and thus enables stable cycling of high capacity all-solid-state Li batteries at room temperature. In-depth characterizations demonstrate that the in situ formed interface layer between [Li2B12H11+1/n]n and LiBH4 is believed to be responsible for the high Li-ion conductivity. Moreover, this Li-B-H complex also exhibits excellent electrochemical stability, which enables the stable cycling of Li-TiS2 all-solid-state batteries at room temperature. Our results provide direct evidence for the exceptional Li-ion conductivity and electrochemical stability of Li-B-H complexes. This excellent performance plus the facile fabrication make this class of materials attractive for practical all-solid-state Li battery applications.
References:
[1] H. Maekawa, M. Matsuo, et al. J. Am. Chem. Soc., 2009, 131, 894.
[2] F. Lu, Y. Pang, S. Zheng, et al., Adv. Funct. Mater., 2019, 1809219.

Figure 1
Origin of Low Performance of Lithium-Sulfur Batteries Under Lean Electrolyte Condition
Authors: Zhao Yifan , Guo Juchen 
Published: February 2020

Lithium-sulfur (Li-S) battery is regarded as one of the most promising high-capacity rechargeable batteries, and the research and development on this technology has been active since the late 1960s. Benefiting from the resurrected efforts in the past decade or so, in-depth understanding and technologic know-how of Li-S technology have been accumulated thus leading to tremendous improvement of battery performance. However, wide deployment of Li-S batteries is still hindered by low specific energy and short cycle life. These challenges are dictated by the interplay of the Li anode, sulfur cathode and electrolyte in the battery. Particularly, implementing low mass ratio of electrolyte/sulfur (E/S ratio) is the most critical factor to realize high specific energy at cell level.
In this study, we assembled a 800 mAh Li-S pouch cell with specific energy of 275 Wh/kg and E/S ratio of 2.8. The sulfur loading was 5.4 mg/cm2 on aluminum foil and the specific capacity of sulfur is 1050 mAh/g. With these cell parameters, a 5Ah Li-S pouch cell with 350 Wh/kg specific energy can be delivered by simply incorporating more electrode layers. However, this promising pouch cell could only be cycled for less than 20 cycles. To understand the origin of the low performance under low E/S ratio, the interfacial resistance during the discharge was measured with electrochemical impedance spectroscopy with different E/S ratio. It was found, comparing to relatively high E/S ratio, low E/S ratio at 2.4 induced drastically increasing charge transfer resistance during the first discharge plateau, i.e. generation of high order polysulfides, which terminated the discharge of Li-S cells with low capacity. This observation was also confirmed by the Galvanostatic Intermittent Titration Technique (GITT) experiments. Based the results, we propose that the rate limiting step during the overall charge transfer can either the dissolution (solvation) of polysulfide anions or adsorption of solvated polysulfide anions to the electrode. The potential strategies to address the problem are also discussed.
Thermal Gradients through Sintered Solid State Electrolytes in Lithium-Ion Batteries
Authors: Bock Robert , Onsrud Morten Andreas , Karoliussen Håvard , Pollet Bruno G. , Seland Frode , Burheim Odne Stokke 
Published: February 2020

Recent advancements in research have made solid state electrolytes a strong contender for the previously common liquid electrolytes, as it enables fast charging at very high current densities without flammable liquids. High current in combination with higher ohmic resistance lead to much more heat being dissipated than in conventional Li-ion batteries. As a result, large amounts of ohmic heat are produced inside the battery. As dry electrochemical cells have much lower heat conducting capacity than liquid-containing ones, knowing the thermal conductivity of the cell components plays a crucial role in predicting the heat distribution in such a cell.
Thermal conductivity was measured for three types of solid state electrolyte, Li7La3Zr2O12 (LLZO), Li1.5Al0.5Ge1.5(PO4)3 (LAGP) and Li1.3Al0.3Ti1.7(PO4)3 (LATP) at different compaction pressures. LAGP and LATP were measured in sintered condition, LLZO was measured before and after sintering the sample material. Thermal conductivity for the sintered electrolytes was measured to 0.470 ± 0.009 WK-
1m-
1, 0.5 ± 0.2 WK-
1m-
1 and 0.49 ± 0.02 WK-
1m-
1 at 3 bar compaction pressure for LLZO, LAGP and LATP respectively. Before sintering LLZO showed a thermal conductivity of 0.22 ± 0.02 WK-
1m-
1 at 3 bar compaction pressure.
A simple analytical model of a lithium-ion battery cell stack was constructed to show the impact of the results obtained through the thermal conductivity measurements. It is based on a work by Richter et al. [1]. The resulting temperature profiles are shown in Fig. 1.
The temperature gradients inside the cell stacks need to be considered when assessing lifetime and degradation effects as seen in other electrochemical systems [2-4].
Figure 1: Temperature of the stack center compared to the outer boundary for a) a dry separator and b) a solid state electrolyte, each with two thicknesses.
References
[1] F. Richter, P. J. Vie, S. Kjelstrup, O. S. Burheim, Measurements of ageing and thermal conductivity in a secondary nmc-hard carbon li-ion battery and the impact on internal temperature profiles, Electrochimica Acta 250 (2017) 228 – 237.
[2] R. Bock, A.D. Shum, X. Xiao, H. Karoliussen, F. Seland, I.V. Zenyuk, O.S. Burheim, Thermal conductivity and compaction of GDL-MPL interfacial composite material, J. Electrochem. Soc. 2018 165(7): F514-F525
[3] R. Bock, H. Karoliussen, B. G. Pollet, M. Secanell, F. Seland, D. Stanier, O. S. Burheim, The influence of graphitization on the thermal conductivity of catalyst layers and temperature gradients in proton exchange membrane fuel cells, International Journal of Hydrogen Energy, In-press 2018
[4] O.S.Burheim, M.A. Onsrud, J.G. Pharoah, F. Vullum-Bruer, P.J.S. Vie, Thermal conductivity, heat sources and temperature profiles of Li-ion batteries, ECS Trans., 58 (2013) 145-171.

Figure 1
Deciphering the Structure-Property Relationship in Sulfide-Based Solid Electrolytes for All-Solid-State Na-Ion Batteries
Authors: Xiong Shan , Liu Zhantao , Chen Hailong 
Published: February 2020

Safety concerns on conventional lithium ion batteries are attracting a lot of attention from both academia and industry with the rapid growth of the electric automobile market. Replacing flammable organic liquid electrolytes with nonflammable inorganic solid electrolytes can potentially eliminate the fire hazards. On the other hand, low-cost electrochemical energy storage technologies beyond lithium chemistry are also highly desired for large-scale energy storage applications. All-solid-state Na ion batteries are one of the promising candidates for grid-level energy storage owing to their low cost and outstanding safety properties. The key enabler of this technology is solid electrolyte with sufficiently high ionic conductivity at room temperature and good electrochemical stability. This work presents a group of novel sodium superionic conductors to address the foregoing issues, which is a topic currently receiving extensive attention in the field of electrochemistry and energy storage.
Through a rational design approach and with using facile solid-state reactions, a series of novel Na4SnS4-Na3SbS4 solid-solution-based compounds with cation and anion substitutions were obtained. These sulfides show room temperature conductivities of 0.1~1 mS/cm, which is among the highest values reported for sodium ion conductors to date. The underlying structural factors, including lattice parameters, concentration of defects, local ordering, etc., of these compounds are investigated with a variety of characterization methods, including synchrotron X-ray diffraction, neutron diffraction, and pair distribution function analysis. Interesting structure-property relationships in these compounds were revealed. All-solid-state Na-ion battery cells using these as-synthesized materials as electrolyte was successfully assembled and cycled, demonstrating the promise of this group of sulfide-based compounds as solid electrolytes and implying new opportunities for materials and device development in solid-state batteries.