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At least 19 records

Improved Li/TiS2 cell cycling in ether-based electrolytes with synergistic additives

Based on an extensive series of normalized full cell Li/TiS2 cycling studies, open-circuit storage tests, microcalorimetry and AC impedance studies, and chemical precedent, we propose an integrated chemical model consistent with experimental observations concerning the behavior of numerous LiAsF6/cyclic ether electrolytes. The particularly striking potency of certain additives such as 2-methylfuran and the hydroxide action resides in their ability to intercept several different adverse catalytic processes concurrently in the bulk electrolyte as well as the Li anode and TiS2 cathode.

Dominey, L. A.↗

Depolymerization of lignin for biological conversion through sulfonation and a chelator-mediated Fenton reaction

The generating value from lignin through depolymerization and biological conversion to valuable fuels, chemicals, or intermediates has great promise but is limited by several factors including lack of cost-effective depolymerization methods, toxicity within the breakdown products, and low bioconversion of the breakdown products. High yield depolymerization of natural lignins requires cleaving carbon-carbon bonds in addition to ether bonds. To address that need, we report that a chelator-mediated Fenton reaction can efficiently cleave C-C bonds in sulfonated polymers at or near room temperature, and that unwanted repolymerization can be minimized through optimizing reaction conditions. This method was used to depolymerize lignosulfonate from M w = 28,000 g/mol to M w = 800 g/mol. The breakdown products were characterized by SEC, FTIR and NMR and evaluated for bioavailability. The breakdown products are rich in acid, aldehyde, and alcohol functionalities but are largely devoid of aromatics and aliphatic dienes. A panel of nine organisms were tested for the ability to grow on the breakdown products. Growth at a low level was observed for several monocultures on the depolymerized LS in absence of glucose. Much stronger growth was observed in the presence of 0.2% glucose and for one organism we demonstrate doubling of melanin production in the presence of depolymerized LS. The results suggest that this chelator-mediated Fenton method is a promising new approach for biological conversion of lignin into higher value chemicals or intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved Li-TiS2 cell cycling in ether-based electrolytes with synergistic additives

Results of the application of 2-MeF and KOH additives to improve the lithium stability in THF, dioxolane, and THF/2-MeTHF solvent-based electrolytes are presented. The stability of these electrolytes with and without additives is evaluated by microcalorimetry and AC impedance spectroscopy. A novel method, cathode turnover number, is proposed to represent the electrolyte performance in a given system. The lithium cycling efficiency and cathode turnover number of the electrolytes are calculated from the cycle life data in experimental Li-TiS2 cells. Overall, THF/2-MeTHF electrolyte containing 2-MeF and/or KOH exhibited higher stability, lithium cycling efficiency, and cathode turnover number compared to THF and dioxolane electrolytes with and without additives.

Shen, D. H.↗

Synthesis and evaluation of C-ether formulations for use as high temperature lubricants and hydraulic fluids

The formulation and evaluation of C-ether fluids for use in the hydraulic and lubrication systems of the space shuttle and advanced air breathing engines were studied to lower the pour point of a reference C-ether from -29 C to -40 C without changing its evaporation loss. Use of disiloxanes mixed with C-ethers gave a -40 C pour point fluid with little change in the desired evaporation loss or in oxidative stability. A second -40 C pour point fluid containing only C-ethers was also developed. A screening program tested lubrication additives for C-ethers and the new fluids. Six additive packages were chosen for evaluation in 316 C bearing tests, two for evaluation in 260 C pump tests. The goal of the bearing test was a 100 hour run. The rig was a specially designed 80-mm axially loaded ball bearing. The C-ether base fluid ran only one hour at 316 C before cage wear failure occurred. The best additive blends ran 47, 94 and 100 hours. The 96 hour test gave excessive deposits. The 100 hour test had no wear failures; an unexplained loss of cage silver occurred from areas of direct fluid impingement on the cage.

Clark, F. S.↗

12-Crown-4 Ether Improves Rechargeable Lithium Cells

Experiments show addition of 12-crown-4 ether (12Cr4) to thin film of polyethylene oxide (PEO) and LiBF4 reduces charge-transfer resistance of film and enhances performance of electrochemical cell in which film is electrolyte, anode is lithium, and cathode is LixCoO2. By increasing conductivity of the electrolyte, 12Cr4 reduces polarization loss; enabling cell to sustain higher current. Result is new type of rechargeable lithium cell.

Nagasubramanian, Ganesan↗

Toughening reinforced epoxy composites with brominated polymeric additives

Cured polyfunctional epoxy resins including tris (hydroxyphenyl) methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy terminated butadiene acrylonitrile rubber is optionally present in the precure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon reinforced composites, of these resins are disclosed and shown to have improved toughness.

Nir, Z.↗

Toughening reinforced epoxy composites with brominated polymeric additives

Cured polyfunctional epoxy resins including tris(hydroxyphenyl)methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy-terminated butadiene-acrylonitrile rubber is optionally present in the pre-cure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon-reinforced composites, of these resins are disclosed and shown to have improved toughness.

Nir, Z.↗

Boundary lubrication of formulated C-ethers in air to 300 C. 2: Organic acid additives

Friction and wear measurements were made on CVM M-50 steel lubricated with three C-ether (modified polyphenyl ether) formulations in dry and moist air. Results were compared to those obtained with a formulated Type 2 ester and the C-ether base fluid. A ball-on-disk sliding friction apparatus was used. Experimental conditions were a 1-kilogram load, a 17-meter/minute surface speed, and a 25 to 300 C (77 to 572 F) disk temperature range. The three C-ether formulations yielded better boundary lubricating characteristics than the Type 2 ester under most test conditions. All C-ether formulations exhibited higher friction coefficients than the ester from 150 to 300 C (302 to 572 F) and similar or lower values from 25 to 150 C (77 to 302 F).

Jones, W. R., Jr.↗

Catalytic Electrolyte Additive for High-Loading and Lean Electrolyte Li–S Batteries

The cycle life of high-energy Li–S cells is largely constrained by the quick electrolyte depletion. LiNO 3 has been a well-established additive known for protecting the Li metal anode and stabilizing the battery from polysulfide “shuttling”. However, it can be depleted prematurely and can pose safety risks when exposed to carbon, sulfur, or Li metal under harsh conditions. Here, in this study, LiPO 2 F 2 was explored as a safe and durable alternative additive in ether-based electrolytes. LiPO 2 F 2 demonstrates superior performance in Li/S batteries, especially under high sulfur loading (∼4 mg/cm 2 ) and lean electrolyte conditions (E/S = 4), achieving a long-term cycling stability of 40%, compared to 14.7% with LiNO 3 . This additive facilitates the disproportionation of polysulfides, reducing their dissolution and mitigating the shuttle effect. Additionally, LiPO 2 F 2 promotes the formation of a stable solid-electrolyte interphase (SEI) composed of inorganic anion-derived species, improving the battery’s overall stability and functionality. These findings blaze a trail in the design of safer and more durable electrolytes for Li–S batteries.

Li-S batteries↗

Insight Into Sulfur‐Containing Additive to Boost Anti‐Oxidation Ability of the Ether‐Based Electrolyte for Sodium‐Ion Full Batteries

Ether-based electrolytes are considered as promising candidates for sodium-ion batteries (SIBs) due to their high ionic conductivity and good compatibility with hard carbon (HC) anode. However, they suffer from poor anti-oxidative ability with unstable cathode electrolyte interface, inducing successive electrolyte decomposition and rapid capacity fading. Herein, the sulfur-containing additive (1,3-propanediol cyclic sulfate, PCS) is introduced to boost the stability of the electrode-electrolyte interface (EEI) in ether-based electrolyte. PCS largely participates in the inner Na + sheath, causing more diglyme (G2) molecules and fewer PF 6 - anions to occupy the inner Na + solvation sheath, avoiding the decomposition of G2 molecules at high operation voltage. Moreover, PCS is beneficial for simultaneously constructing thin and robust sulfur-containing EEI on both Prussian blue (PB) cathode and HC anode, maintaining the structural stability of PB and alleviating the dissolution of transition metals. These enable PB||HC pouch cells to deliver a capacity retention of 60.3% after 400 cycles, significantly higher than the 32.1% in PCS-free electrolytes. In conclusion, this work discloses the underlying mechanism of PCS to evoke the anti-oxidation ability of ether-based electrolyte and provides a promising method for realizing advanced sodium-ion full cells.

anti-oxidation ability↗

Increased rate of response of the pituitary-adrenal system in rats adapted to chronic stress

The response and adaptation of the pituitary-adrenal system to chronic stresses was investigated. These included individual caging, confinement, and exposure to cold for varying periods of time. Studies were carried out demonstrating that during the period of adaptation when plasma corticosterone concentrations returned toward their prestress level despite continued exposure to the stressor, the animals responded to additional stimuli of ether for 1 min, a saline injection, or release from confinement with a faster increase (within 2.5 min) in plasma corticosterone than controls (10 min). It is concluded that during adaptation to a chronic stress the pituitary-adrenal system is not inhibited by the circulating steroid level but is actually hypersensitive to additional stimuli.

Sakellaris, P. C.↗

Designing High‐Donicity Anions for Rechargeable Potassium Superoxide/Peroxide Batteries

Abstract A battery cathode based on the superoxide/peroxide redox not only inherits the advantage of oxygen (O 2 ) batteries in high capacities and low costs but also overcomes the disadvantages in O 2 storage, electrolyte evaporation, and anode deactivation due to O 2 crossover. Herein, we report an enhanced potassium superoxide (KO 2 )/peroxide (K 2 O 2 ) conversion by adopting a high‐donicity anion additive in the ether‐based electrolyte. Such an anion was synthesized via a “Solvent‐in‐Anion” strategy and validated to enhance the electron donicity of the electrolyte. The use of high‐donicity anion could lead to enhanced KO 2 utilization (≈90.2 %) by retarding electrode passivation and allow the full charging back of K 2 O 2 through the solution‐mediated pathway without electrocatalysts. No apparent cell degradation is observed during the first 120 cycles by controlling the reversible depth‐of‐discharge capacity at 292 mAh g −1 within an O 2 ‐free region. The K−KO 2 cell delivers a high energy efficiency (>84.4 %) and a lifespan of over 1440 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boundary lubrication of formulated C-ether in air to 300 deg C. 1: Phosphorus ester additives

Friction and wear measurements were made on CVM M-50 steel lubricated with three C-ether (modified polyphenyl ether) formulations in dry and wet air. Results were compared to those obtained with a formulated Type 2 ester and the C-ether base fluid. A ball-on-disk sliding friction apparatus was used. Experimental conditions were a 1-kilogram load, a 17-meter-perminute (100-rpm) surface speed, and a 25 to 300 C (77 to 572 F) disk temperature range. The C-ether base fluid and the three formulated C-ether fluids yielded lower wear than the Type 2 ester over the entire temperature range. All C-ether fluids exhibited slightly higher friction coefficients than the ester from 150 to 300 C (302 to 572 F) and similar values from 25 to 150 C (77 to 302 F). In general, lower wear rates were observed with the C-ethers when tested in wet air as compared to a dry air atmosphere.

Jones, W. R., Jr.↗

Designing High‐Donicity Anions for Rechargeable Potassium Superoxide/Peroxide Batteries

Abstract A battery cathode based on the superoxide/peroxide redox not only inherits the advantage of oxygen (O 2 ) batteries in high capacities and low costs but also overcomes the disadvantages in O 2 storage, electrolyte evaporation, and anode deactivation due to O 2 crossover. Herein, we report an enhanced potassium superoxide (KO 2 )/peroxide (K 2 O 2 ) conversion by adopting a high‐donicity anion additive in the ether‐based electrolyte. Such an anion was synthesized via a “Solvent‐in‐Anion” strategy and validated to enhance the electron donicity of the electrolyte. The use of high‐donicity anion could lead to enhanced KO 2 utilization (≈90.2 %) by retarding electrode passivation and allow the full charging back of K 2 O 2 through the solution‐mediated pathway without electrocatalysts. No apparent cell degradation is observed during the first 120 cycles by controlling the reversible depth‐of‐discharge capacity at 292 mAh g −1 within an O 2 ‐free region. The K−KO 2 cell delivers a high energy efficiency (>84.4 %) and a lifespan of over 1440 hours.

Qin, Lei↗

Improved boundary lubrication with formulated C-ethers

A comparison of five recently developed C-ether-formulated fluids with an advanced formulated MIL-L-27502 candidate ester is described. Steady state wear and friction measurements were made with a sliding pin on disk friction apparatus. Conditions included disk temperatures up to 260 C, dry air test atmosphere, 1 kilogram load, 50 rpm disk speed, and test times to 130 minutes. Based on wear rates and coefficients of friction, three of the C-ether formulations as well as the C-ether base fluid gave better boundary lubrication than the ester fluid under all test conditions. The susceptibility of C-ethers to selective additive treatment (phosphinic esters or acids and other antiwear additives) was demonstrated when two of the formulations gave somewhat improved lubrication over the base fluid. The increased operating potential for this fluid was shown in relationship to bulk oil temperature limits for MIL-L-23699 and MIL-L-27502 type esters.

Loomis, W. R.↗