Publications

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Here, we report a simple method to synthesize V⁴⁺(VO²⁺) electrolytes as feedstock for all vanadium redox flow batteries (RFB). By dissolving V₂O₅ in aqueous HCl and subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V⁴⁺ (VO²⁺). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65°C) for V⁴⁺(VO²⁺) electrolytes in HCl compared to in H₂SO₄ electrolytes.

High-temperature X-ray diffraction with concurrent gas chromatography (GC) was used to study cobalt disulfide cathode pellets disassembled from thermal batteries. When CoS2 cathode materials were analyzed in an air environment, oxidation of the K(Br, Cl) salt phase in the cathode led to the formation of K2SO4 that subsequently reacted with the pyrite-type CoS2 phase leading to cathode decomposition between ∼260 and 450 °C. Independent thermal analysis experiments, i.e. simultaneous thermogravimetric analysis/differential scanning calorimetry/mass spectrometry (MS), augmented the diffraction results and support the overall picture of CoS2 decomposition. Both gas analysis measurements (i.e. GC and MS) from the independent experiments confirmed the formation of SO2 off-gas species during breakdown of the CoS2. In contrast, characterization of the same cathode material under inert conditions showed the presence of CoS2 throughout the entire temperature range of analysis.

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In situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques are applied to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarly coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. We suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediate ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.

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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.

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In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductance values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.

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SNL has developed a series of ionic-liquid electrolytes with accompanying non- Aqueous compatible membranes and flow cell designs for improved energy density redox flow batteries targeted to support increasing demands for stationary energy storage. The new electrolytes yield a higher energy density by chemically incorporating an electro- Active transition metal element into the solvent's molecular formula. Although ionic liquids have higher viscosities than conventional non- Aqueous electrolytes, they are promising for higher energy densities due to higher metal concentrations and wider voltage windows. We have addressed high viscosity by developing new materials through careful ligand and anion selection. We have also developed tunable membranes for non- Aqueous compatibility and rapid laboratory-scale prototyping to quickly screen materials and cell designs. We are projecting a four-fold improvement in energy density over the next two years.

SNL has developed a series of ionic-liquid electrolytes with accompanying non- Aqueous compatible membranes and flow cell designs for improved energy density redox flow batteries targeted to support increasing demands for stationary energy storage. The new electrolytes yield a higher energy density by chemically incorporating an electro- Active transition metal element into the solvent's molecular formula. Although ionic liquids have higher viscosities than conventional non- Aqueous electrolytes, they are promising for higher energy densities due to higher metal concentrations and wider voltage windows. We have addressed high viscosity by developing new materials through careful ligand and anion selection. We have also developed tunable membranes for non- Aqueous compatibility and rapid laboratory-scale prototyping to quickly screen materials and cell designs. We are projecting a four-fold improvement in energy density over the next two years.

A pair of redox flow batteries containing polyoxometalates was tested as part of an ongoing program in stationary energy storage. The iron-containing dimer, (SiFe3W9(OH)3O34) 2(OH)311-, cycled between (SiFe 3W9(OH)3O34)2(OH) 311-/(SiFe3W9(OH)3O 34)2(OH)314-and (SiFe 3W9(OH)3O34)2(OH) 317-/(SiFe3W9(OH)3O 34)2(OH)314- for the positive and negative electrode, respectively. This compound demonstrated a coulombic efficiency of 83% after 20 cycles with an electrochemical yield (measured discharge capacity as a percentage of theoretical capacity) of 55%. Cyclic voltammetry on the Lindqvist ion, cis-V2W4O 194-, showed quasi-reversible vanadium electrochemistry, but tungsten reduction was mostly irreversible. In a flow cell configuration, cis-V2W4O194-had a coulombic efficiency of 45% (for a two-electron process) and an electrochemical yield of 16% after 20 cycles. The poor performance of cis-V2W 4O194-was attributed primarily to its higher charge density. Collectively, the results showed that both polyoxometalate size and charge density are both important parameters to consider in battery material performance.

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