Fine control over the thermal expansion and contraction behavior of polymer materials is challenging. Most polymers have large coefficients of thermal expansion (CTEs), which preclude long performance lifetimes of composite materials. Herein, we report the design and synthesis of epoxy thermosets with low CTE values below their Tg and large contraction behavior above Tg by incorporating thermally contractile dibenzocyclooctane (DBCO) motifs within the thermoset network. This atypical thermomechanical behavior was rationalized in terms of a twist-boat to chair conformational equilibrium of the DBCO linkages. We anticipate these findings to be generally useful in the preparation of materials with designed CTE values.
This communication describes a novel series of linear and crosslinked polyurethanes (PUs) and their selective depolymerization under mild conditions. Two unique polyols are synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis (RCM) to five- and six-membered cycloalkenes. These polyols are co-polymerized with toluene diisocyanate to generate linear PUs and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked PUs. The polyol design is such that the RCM reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs’ catalyst under ambient conditions, the PUs are rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enable further re-polymerization by traditional strategies for polymerization of double bonds. It is anticipated that this general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.
We present a systematic approach for increasing the concentration of redox-active species in electrolytes for nonaqueous redox flow batteries (RFBs). Starting with an ionic liquid consisting of a metal coordination cation (MetIL), ferrocene-containing ligands and iodide anions are substituted incrementally into the structure. While chemical structures can be drawn for molecules with 10 m redox-active electrons (RAE), practical limitations such as melting point and phase stability constrain the structures to 4.2 m RAE, a 2.3× improvement over the original MetIL. Dubbed “MetILs3,” these ionic liquids possess redox activity in the cation core, ligands, and anions. Throughout all compositions, infrared spectroscopy shows the ethanolamine-based ligands primarily coordinate to the Fe2+ core via hydroxyl groups. Calorimetry conveys a profound change in thermophysical properties, not only in melting temperature but also in suppression of a cold crystallization only observed in the original MetIL. Square wave voltammetry reveals redox processes characteristic of each molecular location. Testing a laboratory-scale RFB demonstrates Coulombic efficiencies >95% and increased voltage efficiencies due to more facile redox kinetics, effectively increasing capacity 4×. Application of this strategy to other chemistries, optimizing melting point and conductivity, can yield >10 m RAE, making nonaqueous RFB a viable technology for grid scale storage.
We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.
This report describes advances in electrolytes for lithium primary battery systems. Electrolytes were synthesized that utilize organosilane materials that include anion binding agent functionality. Numerous materials were synthesized and tested in lithium carbon monofluoride battery systems for conductivity, impedance, and capacity. Resulting electrolytes were shown to be completely non-flammable and showed promise as co-solvents for electrolyte systems, due to low dielectric strength.
The overall Project objective is to develop a portable, non-cryogenic oxygen generator capable of supplying medical grade oxygen at sufficient flow rates to allow the field application of the Topical Hyperbaric Oxygen Therapy (THOT{reg_sign}) developed by Numotech, Inc. This project was sponsored by the U.S. Department of Energy Global Initiatives for Proliferation Prevention (GIPP) and is managed by collaboration between Sandia National Laboratories (SNL), Numotech, Inc, and LLC SPE 'Spektr-Conversion.' The project had two phases, with the objective of Phase I being to develop, build and test a laboratory prototype of the membrane-pressure swing adsorber (PSA) system producing at 15 L/min of oxygen with a minimum of 98% oxygen purity. Phase II objectives were to further refine and identify the pre-requisites needed for a commercial product and to determine the feasibility of producing 15 L/min of oxygen with a minimum oxygen purity of 99%. In Phase I, Spektr built up the necessary infrastructure to perform experimental work and proceeded to build and demonstrate a membrane-PSA laboratory prototype capable of producing 98% purity oxygen at a flow rate of 5 L/min. Spektr offered a plausible path to scale up the process for 15 L/min. Based on the success and experimental results obtained in Phase I, Spektr performed work in three areas for Phase II: construction of a 15 L/min PSA; investigation of compressor requirements for the front end of the membrane/PSA system; and performing modeling and simulation of assess the feasibility of producing oxygen with a purity greater than 99%. Spektr successfully completed all of the tasks under Phase II. A prototype 15 L/min PSA was constructed and operated. Spektr determined that no 'off the shelf' air compressors met all of the specifications required for the membrane-PSA, so a custom compressor will likely need to be built. Modeling and simulation concluded that production of oxygen with purities greater than 99% was possible using a Membrane-PSA system.
Two of the most daunting problems facing humankind in the twenty-first century are energy security and climate change. This report summarizes work accomplished towards addressing these problems through the execution of a Grand Challenge LDRD project (FY09-11). The vision of Sunshine to Petrol is captured in one deceptively simple chemical equation: Solar Energy + xCO{sub 2} + (x+1)H{sub 2}O {yields} C{sub x}H{sub 2x+2}(liquid fuel) + (1.5x+.5)O{sub 2} Practical implementation of this equation may seem far-fetched, since it effectively describes the use of solar energy to reverse combustion. However, it is also representative of the photosynthetic processes responsible for much of life on earth and, as such, summarizes the biomass approach to fuels production. It is our contention that an alternative approach, one that is not limited by efficiency of photosynthesis and more directly leads to a liquid fuel, is desirable. The development of a process that efficiently, cost effectively, and sustainably reenergizes thermodynamically spent feedstocks to create reactive fuel intermediates would be an unparalleled achievement and is the key challenge that must be surmounted to solve the intertwined problems of accelerating energy demand and climate change. We proposed that the direct thermochemical conversion of CO{sub 2} and H{sub 2}O to CO and H{sub 2}, which are the universal building blocks for synthetic fuels, serve as the basis for this revolutionary process. To realize this concept, we addressed complex chemical, materials science, and engineering problems associated with thermochemical heat engines and the crucial metal-oxide working-materials deployed therein. By project's end, we had demonstrated solar-driven conversion of CO{sub 2} to CO, a key energetic synthetic fuel intermediate, at 1.7% efficiency.
Concentrating solar power (CSP) systems use solar absorbers to convert the heat from sunlight to electric power. Increased operating temperatures are necessary to lower the cost of solar-generated electricity by improving efficiencies and reducing thermal energy storage costs. Durable new materials are needed to cope with operating temperatures >600 C. The current coating technology (Pyromark High Temperature paint) has a solar absorptance in excess of 0.95 but a thermal emittance greater than 0.8, which results in large thermal losses at high temperatures. In addition, because solar receivers operate in air, these coatings have long term stability issues that add to the operating costs of CSP facilities. Ideal absorbers must have high solar absorptance (>0.95) and low thermal emittance (<0.05) in the IR region, be stable in air, and be low-cost and readily manufacturable. We propose to utilize solution-based synthesis techniques to prepare intrinsic absorbers for use in central receiver applications.