Solid-state graft copolymer electrolytes for lithium battery applications

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point ( < 80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed

Calcium-Antimony Alloys as Electrodes for Liquid Metal Batteries

The performance of a calcium-antimony (Ca-Sb) alloy serving as the positive electrode in a Ca∥Sb liquid metal battery was investigated in an electrochemical cell, Ca(in Bi) | LiCl-NaCl-CaCl[subscript 2] | Ca(in Sb). The equilibrium potential of the Ca-Sb electrode was found to lie on the interval, 1.2–0.95 V versus Ca, in good agreement with electromotive force (emf) measurements in the literature. During both alloying and dealloying of Ca at the Sb electrode, the charge transfer and mass transport at the interface are facile enough that the electrode potential varies linearly from 0.95 to 0.75 V vs Ca(s) as current density varies from 50 to 500 mA cm[superscript −2]. The discharge capacity of the Ca∥Sb cells increases as the operating temperature increases due to the higher solubility and diffusivity of Ca in Sb. The cell was successfully cycled with high coulombic efficiency (∼100%) and small fade rate (<0.01% cycle[superscript −1]). These data combined with the favorable costs of these metals and salts make the Ca∥Sb liquid metal battery attractive for grid-scale energy storage.United States. Advanced Research Projects Agency-Energy (Award DE-AR0000047)TOTAL (Firm)Marubun Research Promotion FoundationMurata Overseas Scholarship Foundatio

Electrolysis of a molten semiconductor

Metals cannot be extracted by electrolysis of transition-metal sulfides because as liquids they are semiconductors, which exhibit high levels of electronic conduction and metal dissolution. Herein by introduction of a distinct secondary electrolyte, we reveal a high-throughput electro-desulfurization process that directly converts semiconducting molten stibnite (Sb[subscript 2]S[subscript 3]) into pure (99.9%) liquid antimony and sulfur vapour. At the bottom of the cell liquid antimony pools beneath cathodically polarized molten stibnite. At the top of the cell sulfur issues from a carbon anode immersed in an immiscible secondary molten salt electrolyte disposed above molten stibnite, thereby blocking electronic shorting across the cell. As opposed to conventional extraction practices, direct sulfide electrolysis completely avoids generation of problematic fugitive emissions (CO[subscript 2], CO and SO[subscript 2]), significantly reduces energy consumption, increases productivity in a single-step process (lower capital and operating costs) and is broadly applicable to a host of electronically conductive transition-metal chalcogenides.United States. Advanced Research Projects Agency-Energy (Award DE-AR0000047)TOTAL (Firm

Calcium-based multi-element chemistry for grid-scale electrochemical energy storage

Calcium is an attractive material for the negative electrode in a rechargeable battery due to its low electronegativity (high cell voltage), double valence, earth abundance and low cost; however, the use of calcium has historically eluded researchers due to its high melting temperature, high reactivity and unfavorably high solubility in molten salts. Here we demonstrate a long-cycle-life calcium-metal-based rechargeable battery for grid-scale energy storage. By deploying a multi-cation binary electrolyte in concert with an alloyed negative electrode, calcium solubility in the electrolyte is suppressed and operating temperature is reduced. These chemical mitigation strategies also engage another element in energy storage reactions resulting in a multi-element battery. These initial results demonstrate how the synergistic effects of deploying multiple chemical mitigation strategies coupled with the relaxation of the requirement of a single itinerant ion can unlock calcium-based chemistries and produce a battery with enhanced performance.United States. Advanced Research Projects Agency-EnergyTOTAL (Firm

Genome-wide identification and phenotypic characterization of seizure-associated copy number variations in 741,075 individuals

Copy number variants (CNV) are established risk factors for neurodevelopmental disorders with seizures or epilepsy. With the hypothesis that seizure disorders share genetic risk factors, we pooled CNV data from 10,590 individuals with seizure disorders, 16,109 individuals with clinically validated epilepsy, and 492,324 population controls and identified 25 genome-wide significant loci, 22 of which are novel for seizure disorders, such as deletions at 1p36.33, 1q44, 2p21-p16.3, 3q29, 8p23.3-p23.2, 9p24.3, 10q26.3, 15q11.2, 15q12-q13.1, 16p12.2, 17q21.31, duplications at 2q13, 9q34.3, 16p13.3, 17q12, 19p13.3, 20q13.33, and reciprocal CNVs at 16p11.2, and 22q11.21. Using genetic data from additional 248,751 individuals with 23 neuropsychiatric phenotypes, we explored the pleiotropy of these 25 loci. Finally, in a subset of individuals with epilepsy and detailed clinical data available, we performed phenome-wide association analyses between individual CNVs and clinical annotations categorized through the Human Phenotype Ontology (HPO). For six CNVs, we identified 19 significant associations with specific HPO terms and generated, for all CNVs, phenotype signatures across 17 clinical categories relevant for epileptologists. This is the most comprehensive investigation of CNVs in epilepsy and related seizure disorders, with potential implications for clinical practice

Electrodeposition of crystalline silicon films from silicon dioxide for low-cost photovoltaic applications

Crystalline-silicon solar cells have dominated the photovoltaics market for the past several decades. One of the long standing challenges is the large contribution of silicon wafer cost to the overall module cost. Here, we demonstrate a simple process for making high-purity solar-grade silicon films directly from silicon dioxide via a one-step electrodeposition process in molten salt for possible photovoltaic applications. High-purity silicon films can be deposited with tunable film thickness and doping type by varying the electrodeposition conditions. These electrodeposited silicon films show about 40 to 50% of photocurrent density of a commercial silicon wafer by photoelectrochemical measurements and the highest power conversion efficiency is 3.1% as a solar cell. Compared to the conventional manufacturing process for solar grade silicon wafer production, this approach greatly reduces the capital cost and energy consumption, providing a promising strategy for low-cost silicon solar cells production.Stanford University. Global Climate and Energy Project (Agreement 60853646-118146)Robert A. Welch Foundation (Grant F-0021)National Science Foundation (U.S.) (Grants CBET 1702944, ECCS-1542159

Mixing in a liquid metal electrode

Fluid mixing has first-order importance for many engineering problems in mass transport, including design and optimization of liquid-phase energy storage devices. Liquid metal batteries are currently being commercialized as a promising and economically viable technology for large-scale energy storage on worldwide electrical grids. But because these batteries are entirely liquid, fluid flow and instabilities may affect battery robustness and performance. Here we present estimates of flow magnitude and ultrasound measurements of the flow in a realistic liquid metal electrode. We find that flow does substantially affect mass transport by altering the electrode mixing time. Above a critical electrical current density, the convective flow organizes and gains speed, which promotes transport and would yield improved battery efficiency.United States. Advanced Research Projects Agency-Energy (Award DE-AR0000047)TOTAL (Firm

E-logpO2 diagrams for ironmaking by molten oxide electrolysis

Molten oxide electrolysis is a promising approach to sustainable iron extraction, where direct electrolytic decomposition of iron ore proceeds to yield liquid metallic iron and pure oxygen gas. Here, through fundamental investigations, we constructed thermodynamic E-logpO2 diagrams for systems containing iron and its oxides to elucidate the chemistry of the electrolysis cell at various electric potentials and oxygen partial pressures. Two isotherms, 1473 and 1873K, were investigated, representing the conditions of the frozen electrolyte sidewall and molten oxide electrolyte in the electrolysis cell, respectively. Stability regions of solid and liquid oxides were determined and the effect of electric potential and oxygen partial pressure on their stoichiometry was explored. The results would enable further development of the electrolysis cell through providing a means for improving the design of the electrolyte to maximize current efficiency.Natural Sciences and Engineering Research Council of Canada (Grant number:498382

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (<80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (T[subscript g]) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF[subscript 6] in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.Weatherford International, Inc

Direct Electrolysis of Molten Lunar Regolith for the Production of Oxygen and Metals on the Moon

The feasibility of producing oxygen by direct electrolysis of the molten lunar regolith at 1600 C was investigated and the generation of usable oxygen gas at the anode and concomitant production of iron and silicon at the cathode was successfully achieved from the tightly bound oxide mix. The current efficiency for different melt chemistries, corresponding to different degrees of electrolysis of the regolith, was measured during the course of electrolysis by on steam analysis of oxygen gas and scale-up from thin wire electrodes to plate and disc electrodes was achieved