bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical and Structural Study on PVDF-Based Polymer Electrolytes for Solid-State Batteries
Authors: Yen Dean , Tan Sha , Yang Xiao-Qing , Chen-Wiegart Yu-chen Karen , Hu Enyuan 
Published: November 2022

Lithium-ion batteries are widely used today in powering devices from portable electronics to electric vehicles. Despite their great success, this battery chemistry relies on organic solvent-based liquid electrolytes which are highly flammable, leading to major safety concerns. In contrast, solid-state batteries, which are based on solid-state electrolytes, are regarded to have much better safety characteristics and potentially higher energy density than the conventional lithium-ion batteries. Solid-state electrolytes usually include ceramics, polymers, gels, and composites. Among them, polymer materials have attracted considerable attention due to their great interfacial contact, flexibility, and easy fabrication. In particular, polyvinylidene fluoride (PVDF) polymer electrolyte is a promising candidate as it can potentially provide a high voltage window and enable high energy density solid-state batteries. However, the current PVDF-based polymer electrolyte is still not compatible with high voltage cathodes, such as layered lithium transition metal oxides and the interaction between the salt and PVDF polymer has not been fully elucidated.
We have systematically studied the PVDF-based electrolytes with different salts and salt combinations, including lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI). The optimized electrolyte delivers excellent performance for solid-state Li||LiFePO4 cells, achieving a specific capacity of over 150 mAh/g and lasting more than 50 cycles with over 99% capacity retention. Similar tests have also been applied to lithium nickel manganese cobalt oxides (NMC), and the preliminary results show promising cycling stability and capacity retention. In addition to electrochemical study, we employed a range of synchrotron-based X-ray techniques, including diffraction, pair distribution function analysis, and absorption spectroscopy, to investigate the interactions between the polymer and lithium salt in the polymer electrolytes. This knowledge will provide valuable information for designing new polymer electrolyte systems.
Acknowledgments: The work at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program under contract DE-SC0012704. This research used beamline 23-ID-2 and 28-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.
Development of a Solid-State Ta-Doped Lithium Lanthanum Zirconium Oxide Electrolyte for All-Solid-State Lithium Batteries (ASSLBs)
Authors: Panda Dillip K. , Creager Stephen , Bordia Rajendra Kumar 
Published: November 2022

Large, high-power batteries are necessary for electric vehicles. The safety of batteries is also crucial, as damaged batteries should not be combustible. Moreover, in some cases batteries need to operate a modestly high temperatures in the range of 100 - 150 0C. All-solid-state lithium batteries (ASSLBs) can handle these requirements with ceramic electrolytes, lithium intercalation cathodes, and lithium metal anodes. Although ASSLBs using variations on this material set have been demonstrated, they tend to have low power, in part because of low ionic conductivity, as well as low rates of interfacial reaction between electrodes and electrolytes. Various strategies are being investigated to address the challenge of low power including operating at elevated temperatures, using doped electrolytes, increasing the contact area between the electrodes and the electrolyte, and through engineering of the interfaces between electrodes and electrolytes.
Using tape casting followed by sintering, we are producing thin (~20µm) and dense Ta-doped Lithium Lanthanum Zirconium Oxide (LLZTO) films, and also LLZTO pellets. The challenge of Li-loss during sintering has been addressed by using suitable sintering aids and sacrificial Li source. We have characterized LLZTO films and pellets using techniques such as XRD, SEM, and SEM EXA. The electrochemical properties of the LLZTO electrolyte including ionic conductivity have been measured. This is the first step in the creation of a full cell with engineered electrodes and interfaces. An analytical model has been developed to examine the effect of thickness of anode, cathode, and current collector on energy density.
High Energy Efficiency Rechargeable Li-Air Battery Enabled By Rational Design of Cell Components
Authors: Esmaeilirad Mohammadreza , Kondori Alireza , Asadi Mohammad 
Published: November 2022

Electrical energy storage and conversion is vital to a clean, sustainable, and secure energy future. Among all electrochemical energy storage devices, lithium-air (Li-air) battery is known to offers as high as 5X greater energy density than lithium-ion batteries, representing its promise for electrical vehicles and stationery (micro-grids) applications. However, their practical realization is hindered by their poor rechargeability and rate capability, mostly due to unsuitable design of cell components, i.e., anode, cathode, and the liquid electrolyte.
Here, we are presenting an aprotic Li-air battery cell, enabled by rational design of cell components, that can be cycled over 2400 hours at a capacity of 500 mAh/g (specific energy of about 400 Wh/kg) in an air-like atmosphere consisting of water and other air components. The developed Li-air battery cell leverages a highly active cathode catalyst, a hybrid aprotic electrolyte with two specific redox mediators, and an effective anode protection layer. Our physicochemical and electrochemical characterization of the developed Li-air battery cell indicate that lithium peroxide (Li2O2) is formed as the only discharge product formed via the solution-based mechanism and is reversibly decomposed during the charge processes. Moreover, different electrochemical experiments were performed to find out the rate capability and the deep discharge performance of the developed Li-air battery cell. We found that the designed cell components work well in synergy to deliver the lowest overpotentials reported to date for the discharge and charge (80 and 270 mV, respectively) at the first cycle, resulting in a high energy efficiency of about 90% at the first cycle. This battery design scheme offers significant promise in the advancement of sustainable energy storage systems.
(Invited) FC-Platform and Gen2 Mirai Analysis
Authors: Amemiya Kazuki , Shinohara Kazuhiko , Kawase Motoaki , Imai Hideto , Sodeyama Keitaro 
Published: November 2022

FC-Platform, specialized in PEFC's analysis and evaluation, has been launched as a NEDO's funded project. PF-Platform consists of 5 groups of the electrochemical evaluation, simulation, materials analysis, materials informatics and management, involves 21 institutions. An number of various materials research themes are also running in the NEDO's project. FC-Platform provides better direction of improving for these materials research by analysis and evaluation. Moreover, visualizing and predicting phenomena in the PEFCs are important for realizing high performance and durability at a material level. Therefore, we are focusing on advanced visualization techniques and multi-scale stack modeling development. We conducted analysis and evaluation of Gen2 MIRAI's MEAs and its materials employing developed analytics and modeling in this framework.
This work was supported by a NEDO FC-Platform project commissioned by the New Energy and Industrial Technology Development Organization (NEDO). Toyota Motor Corporation supported for providing MIRAI's MEAs and materials.
High Capacity Lithium-Sulfur Batteries (> 12 mAh cm–2) Enabled By 3D-Compact Sulfur Cathode and Polysulfide Adjoining Interface Engineering
Authors: Kim Hun , Ham Young-Geun , Sun Yang-Kook 
Published: November 2022

Beyond the theoretical limitation of current Li-ion batteries technology, there have been large efforts to develop practical next-generation batteries. Among them, lithium-sulfur (Li-S) batteries have been eagerly studied due to their attractive features; the low cost and expected high energy density. To maximize the energy density of Li−S batteries, it is crucial to increase the loading level of sulfur cathode and minimize the electrolyte content. However, excessive amounts of lithium polysulfides (LiPSs) generated in the high loading Li-S batteries limit the stable cycling. In this study, a high-loading S cathode (15 mg cm−2) with a three-dimensional (3D) network structure is fabricated using a simple pelletizing method, and the exhausting overcharging phenomenon, which occurs in the high loading Li−S cell, is successively prevented by pre-treating the lithium metal anode. Moreover, adding a diluent to the electrolyte containing viscous LiPSs enables the facile conversion between S species during the cycling of high loading Li−S cells under lean electrolyte conditions. Finally, a prototype Li−S pouch cell with high energy density (427 Wh kg−1) was realized by combining a compacted 3D cathode with a high-loading, pretreated thin lithium metal and diluent-modified electrolyte. We believe that the results reported herein will be a good guideline to establish proper strategies to achieve high energy density Li−S batteries.

Reference
s
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[1] J.-Y. Hwang, S. Shin, C. S. Yoon, Y.-K. Sun, ACS Energy Lett. 4 (2019) 2787–2795.
[2] J.-Y. Hwang, S.-J. Park, C. S. Yoon, Y.-K. Sun, Energy Environ. Sci. 12 (2019) 2174–2784.
[3] H. Kim, S. Bang, K.-J. Min, Y.-G. Ham, S.-J. Park and Y.-K. Sun, ACS Appl. Mater. Interfaces 13 (2021) 39435–39445.
Nickel Cobalt Oxide Decorated Cerium Oxide Nanorods for Polysulfide Trapping and Catalytic Conversion in Advanced Lithium Sulfur Batteries
Authors: Azam Sakibul , Wei Zhen , Wang Ruigang 
Published: November 2022

Lithium sulfur batteries (LSBs) are promising candidates for next-generation rechargeable batteries due to the active material sulfur being earth abundant, low cost and environmentally friendly element. But the most important feature of LSBs is that the theoretical capacity of sulfur is ~1645 mAh g-1 which is ~5 times higher than the conventional lithium-ion batteries. However, even with these valuable assets, LSB has not yet been commercialized due to the inherent problems of fast capacity loss resulting in low cycle lifetime. This capacity loss originates from the migration of dissolved sulfur discharge products in the electrolyte known as the notorious polysulfide shuttling effect.
To deal with this issue, several research efforts have been made to trap the high order lithium polysulfides by a) physically encapsulation using high surface area carbonaceous materials and b) chemically binding the lithium polysulfides in its cathode host. Several materials are very popular to efficiently bind the lithium polysulfides such as transition metal oxides, nitrides, sulfides and have helped making significant advances to long cycle life lithium sulfur batteries. However, to make the transition to design next generation LSBs, there is a need for materials that can facilitate fast polysulfide conversion by catalytic reaction that will reduce the diffusion and agglomeration of polysulfides in the liquid organic electrolyte, resulting in high capacity and long cycle lifetime.
With this strategy in mind, we have designed NiCoOx decorated on CeO2 nanorods support as cathode host material for LSBs to provide dual adsorption-catalysis synergy. The CeO2 nanorods with enriched surface defects can effectively bind the lithium polysulfides whereas the NiCoOx nanoclusters can provide highly efficient electrocatalytic sites to improve the conversion kinetics of elemental sulfur to high order lithium polysulfides to finally the lower order polysulfides. As a result, the derived LSBs exhibited excellent electrochemical performance with high capacity of 1236 mAh g-1 at 0.2C with a sulfur loading of 1.33 mg cm-2. Even with high sulfur loading 2.66 mg cm-2 the LSBs exhibits 755 mAh g-1 at 0.2C with a capacity decay of only 0.08% per cycle after 170 cycles. The battery also operates at the sulfur loading of 4 mg cm-2 and 5.33 mg cm-2 for more than 100 which is convincing considering commercialization of LSB.

Key words:
lithium sulfur batteries, lithium polysulfides, shuttle effect, cerium oxide, catalysis.
Microemulsions As Emerging Electrolytes: The Correlation of Structure to Electrochemical Response
Authors: Imel Adam , Barth Brian , Heroux Luke , Hayes Doug , Dadmun Mark , Zawodzinski Thomas A. 
Published: November 2022

Microemulsions are a breakthrough electrolyte for energy storage (BEES) that is emerging as an alternative to traditional RFB electrolytes because of their ability to produce thermodynamically stable, homogeneous solutions of polar and non-polar molecules. The stabilization of oil and water solutions allows microemulsion electrolytes to accommodate organic redox species with fast electron transfer rates that are not soluble in the aqueous phase while still offering the high conductivity of an aqueous salt electrolyte. Microemulsion electrolytes consist of two immiscible phases stabilized by a surfactant, a non-polar phase, solubilizing the redox material—or the redox material can be the entire oil phase—and an aqueous brine phase. Moreover, each component can be environmentally and biologically safe. For example, the aqueous phase only consists of salt and water, the surfactant used in this study, polysorbate-20, is found in many cosmetics and food products, and some of the redox materials investigated in our lab are vitamins such as menadione (vitamin K3) and tocopherol (vitamin E).
Microemulsions form many self-assembled bulk nanoscale structures, such as oil-in-water or water-in-oil droplets and bicontinuous. Furthermore, microemulsions exhibit ordering near surfaces that can be different from the bulk structure. Understanding the bulk and surface structures is critical to understanding a material's properties, such as conductivity and diffusion to an electrode surface. Understanding structural changes with composition variation and surface hydrophobicity provide a path to optimizing the balance between acceptable conductivity levels in the electrolyte and the high volume of an oil phase bearing the redox-active species in a µE. This optimization is critical to achieving high-performing electrochemical systems using µEs.
This talk describes structural studies of microemulsions prepared from water, toluene, butanol, and polysorbate-20. Small-angle neutron scattering was used to monitor the development of the bicontinuous system as a function of the water-to-surfactant mass ratio on a constant oil-to-surfactant dilution line, revealing how the domain size, correlation length, amphiphilicity factor, and bending moduli change with composition. Kratky and Porod analyses are also employed, providing further structural detail of the scattering domains. We demonstrate that controlling the water-to-surfactant ratio with a constant oil-to-surfactant dilution affects the bicontinuous phase, reveals a sizeable compositional region with structural similarities, and provides insight into the correlation of structure to physical properties. Additionally, neutron reflectivity was used to probe the surface ordering of the microemulsions with hydrophilic and amphiphilic surfaces.

Figure 1
(Invited) Anion Conducting Solid Polymer Ionomers Electrolytes for Fuel Cells and Electrolyzers
Authors: Kohl Paul , Mandal Mrinmay , Chen Mengjie , Park Habin , Shah Parin 
Published: November 2022

Ion conducting polymer electrolytes provide an enabling technology for the creation of low temperature fuel cells, hydrogen producing water electrolyzers, and flow batteries. The critical parameters of solid polymer electrolytes include ionic conductivity, ion selectivity, chemical resistance and dimensional stability in the presence of excess water. High pH operation using anion conductive polymer electrolytes has several potential advantages over acid-based polymer devices including low-cost catalysts, hydrocarbon (non-perfluorinated) polymer, and low cost cell components. However, the identification and synthesis of stable, hydroxide conducting solid polymer electrolytes has been elusive.
In this study, a family of hydroxide conducting, poly(norbornene) solid polymer electrolytes were synthesized and used in high-performance, durable membrane electrode assemblies for fuel cells and electrolyzers. In addition to membranes, covalently bonded, self-adherent, hydroxide conducting ionomers were used to form high-performance, durable membrane electrode assembly for water electrolysis. Electrodes made by grind-spray method were compared to electrodes prepared by the solvent-cast method. The self-adhesive ionomers and membranes are based on hydroxide conducting poly(norbornene) polymers. The effect of porous transport layer material and porosity was examined. High performance electrolysis with very low degradation rates was achieved using stainless steel and nickel porous transport layers.
Unusual Cation-Pi Solute Interactions with Deep Eutectic Solvents
Authors: Elgammal Ramez A. , Foister Shane , Zawodzinski Thomas A. 
Published: November 2022

Deep eutectic solvents (DESs) have emerged as an alternative to both common organic solvents and ionic liquids (ILs). DESs share physicochemical properties with ILs such as low vapor pressure, high thermal stability, high viscosity while offering advantages such as low toxicity, lower cost, and ease of preparation. Moreover, DESs are attractive candidates for electrochemical applications due to their large voltage windows and solubility properties. DESs as a solvent class share a general composition of a hydrogen bond donor (HBD), typically a polyol, amide, or acid, and a hydrogen box acceptor (HBA), usually a quaternary ammonium or phosphonium salt. At a specific molar composition of a HBD and HBD, the DES forms a eutectic mixture resulting in a large melting point depression due to extensive hydrogen bonding between the components.
Despite being widely studied, the use and subsequent characterization of DESs as solvents for aromatic phenols and related aromatics has only recently received attention. In this study we have investigated the solubility of a broad class of aromatic solutes as a function of DES composition and solute concentration using 1H, 13C, pulsed field gradient (PFG), and nuclear Overhauser effect (NOE) NMR. The degree to which homogenous mixtures versus heterogeneous and/or multi-phase systems are formed as a function of solute, temperature, and DES composition is examined. Two classes of DESs glyceline (glycerol + choline chloride) and ethaline (ethylene glycol + choline chloride) were investigated.
As many as three distinct phases depending on the nature of the aromatic solute are observed by NMR. {1H-1H}-NOESY measurements show strong correlations between the choline chloride ammonium cation and the aryl protons with cation-pi interactions disrupting the hydrogen bonding network of the DES. We will discuss the implications for these systems as green solvents and comment on how clustering of solutes on the nanoscale may find use in catalysis and self-assembly.
(Invited) Effect of Atomic-Scale Surface Overcoat By Atomic Layer Deposition on Dopant Segregation of Perovskite Cathodes
Authors: Li Haoyu , Garcia ThomasJae , Kang Hung-Sen , Liu Ziqi , Lee Min Hwan 
Published: November 2022

Intense research has been performed to advance the solid oxide cell (SOC) technology because of their excellent efficiency for clean energy conversion and storage, but the lack of long-term durability, particularly of perovskite (ABO3)-based air electrodes, is currently the main technological bottleneck for wider commercial adoption. Long-term durability of SOC air electrodes has been mainly hampered by surface segregation of A-site dopant and morphological agglomeration. Since a deposition of an atomically thin oxide has proven to be highly effective in suppressing electrode agglomeration, a successful suppression of dopant segregation with the same approach will enhance the durability of air electrodes significantly by killing two birds with one stone. In the previous study [1], we demonstrated the effectiveness of an atomic scale overcoat in suppressing particle agglomeration.
In this presentation, we demonstrate that even a few angstroms of metal oxide overcoat by atomic layer deposition (ALD) affects the behavior of Sr segregation in the underlying La0.8Sr0.2MnO3 (LSM) electrode significantly. By leveraging angle-resolved X-ray photoelectron spectroscopy (ARXPS), we provide a quantitative analysis of the relative atomic concentration on both the very surface and bulk of the electrode. Compared to bare LSM electrodes, those with 2 – 3 Å ALD overcoat show relatively high resistivity against Sr segregation when exposed to of 750 °C for 250 h. Particularly, an oxide overcoat with multi-valent cations (CeO2 and TiO2) tends to suppress Sr segregation effectively and even drive Sr species back into the bulk of LSM while an overcoat with single valent cations (ZrO2 and Y2O3) exhibits little effect on Sr segregation. It was further demonstrated that the segregation behavior is nicely aligned with the electrode performance; those coated with CeO2 and TiO2 showed better thermal stability in terms of polarization resistance. Based upon the time evolution of Sr content, cationic valence states, and oxygen defect concentration in the vicinity of surface, we conjecture that the amount of oxygen defects formed by the overcoat and the resulting chemical potential gradient at the interface between the overcoat underlying LSM surface plays a pivotal role in the Sr segregation behavior.
The authors acknowledge the support from National Science Foundation (DMR 1753383) and NASA MIRO program (NNX15AQ01A).
References:

Li, H. et al. J. Mater. Chem. A, 8, 15927–15935, 2020.