Publications

The cis- form of diaminodibenzocyclooctane (DADBCO, C16H18N2) is of interest as a negative coefficient of thermal expansion (CTE) material. The crystal structure was determined through single-crystal X-ray diffraction at 100 K and is presented herein.

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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.

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The energy density of nonaqueous redox flow batteries is often limited by the concentration of the redox active species soluble in solution. A possible route to increasing the this energy density is through the use of energy-dense solid materials such as polyoxometalates, LiFePO₄, or Li_xTi0₂. These solid materials can be contained in canisters through which an electrolyte with dissolved redox-active species is flowed. The redox potentials for the flowing species are chosen specifically such that they mediate the chemical reduction and oxidation of the solid components. This strategy is advantageous in that it allows for independent optimization of the flow electrolyte (e.g. for low viscosity, high charging rate) and the solid energy storing media (e.g. high energy density). This report summarizes results using a variety of redox active organic and metalorganic species to mediate the oxidation and reduction of polyoxometalate and Li-ion battery chemistries in a redox flow battery system.

A systematic approach is presented 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.

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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.

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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.

Anion receptors that bind strongly to fluoride anions in organic solvents can help dissolve the lithium fluoride discharge products of primary carbon monofluoride (CFx) batteries, thereby preventing the clogging of cathode surfaces and improving ion conductivity. The receptors are also potentially beneficial to rechargeable lithium ion and lithium air batteries.We apply Density Functional Theory (DFT) to show that an oxalate-based pentafluorophenyl-boron anion receptor binds as strongly, or more strongly, to fluoride anions than many phenyl-boron anion receptors proposed in the literature. Experimental data shows marked improvement in electrolyte conductivity when this oxalate anion receptor is present. The receptor is sufficiently electrophilic that organic solvent molecules compete with F^- for boron-site binding, and specific solvent effects must be considered when predicting its F^- affinity. To further illustrate the last point, we also perform computational studies on a geometrically constrained boron ester that exhibits much stronger gas-phase affinity for both F^- and organic solvent molecules. After accounting for specific solvent effects, however, its net F^- affinity is about the same as the simple oxalate-based anion receptor. Finally, we propose that LiF dissolution in cyclic carbonate organic solvents, in the absence of anion receptors, is due mostly to the formation of ionic aggregates, not isolated F^- ions.

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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.