Publications

Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

Abstract not provided.

Journal of Physical Chemistry C

Spoerke, Erik D.; Small, Leo J.; Foster, Michael E.; Wheeler, Jill S.; Ullman, Andrew M.; Stavila, Vitalie S.; Rodriguez, Mark A.; Allendorf, Mark D.

Metal-organic frameworks (MOFs) are highly ordered, functionally tunable supramolecular materials with the potential to improve dye-sensitized solar cells (DSSCs). Several recent reports have indicated that photocurrent can be generated in Grätzel-type DSSC devices when MOFs are used as the sensitizer. However, the specific role(s) of the incorporated MOFs and the potential influence of residual MOF precursor species on device performance are unclear. Herein, we describe the assembly and characterization of a simplified DSSC platform in which isolated MOF crystals are used as the sensitizer in a planar device architecture. We selected a pillared porphyrin framework (PPF) as the MOF sensitizer, taking particular care to avoid contamination from light-absorbing MOF precursors. Photovoltaic and electrochemical characterization under simulated 1-sun and wavelength-selective illumination revealed photocurrent generation that is clearly ascribable to the PPF MOF. Continued refinement of highly versatile MOF structure and chemistry holds promise for dramatic improvements in emerging photovoltaic technologies. (Figure Presented).

Small, Leo J.; Pratt, Harry P.; Staiger, Chad S.; Martin, Rachel I.; Anderson, Travis M.; Chalamala, Babu C.; Soundappan, Thiagarajan S.; Tiwari, Monika T.; Subarmanian, Venkat R.

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.

Journal of Power Sources

Small, Leo J.; Eccleston, Alexis; Lamb, Joshua H.; Read, Andrew C.; Robins, Matthew; Meaders, Thomas; Ingersoll, David I.; Clem, Paul G.; Bhavaraju, Sai; Spoerke, Erik D.

Robust, safe, and reliable grid-scale energy storage continues to be a priority for improved energy surety, expanded integration of renewable energy, and greater system agility required to meet modern dynamic and evolving electrical energy demands. We describe here a new sodium-based battery based on a molten sodium anode, a sodium iodide/aluminum chloride (NaI/AlCl3) cathode, and a high conductivity NaSICON (Na1+xZr2SixP3−xO12) ceramic separator. This NaI battery operates at intermediate temperatures (120–180 °C) and boasts an energy density of >150 Wh kg−1. The energy-dense NaI-AlCl3 ionic liquid catholyte avoids lifetime-limiting plating and intercalation reactions, and the use of earth-abundant elements minimizes materials costs and eliminates economic uncertainties associated with lithium metal. Moreover, the inherent safety of this system under internal mechanical failure is characterized by negligible heat or gas production and benign reaction products (Al, NaCl). Scalability in design is exemplified through evolution from 0.85 to 10 Ah (28 Wh) form factors, displaying lifetime average Coulombic efficiencies of 99.45% and energy efficiencies of 81.96% over dynamic testing lasting >3000 h. This demonstration promises a safe, cost-effective, and long-lifetime technology as an attractive candidate for grid scale storage.

Spoerke, Erik D.; Small, Leo J.; Wheeler, Jill S.; Clem, Paul G.; Lamb, Joshua H.; Ingersoll, David I.; Eccleston, Alexis E.; Bhavaraju, Sai B.; Kim, Jeongsoo K.

Abstract not provided.

Journal of the Electrochemical Society

Small, Leo J.; Brumbach, Michael T.; Clem, Paul G.; Spoerke, Erik D.

A new multi-step, solution-phase method for the spontaneous deposition of tungsten from a room temperature ethereal solution is reported. This immersion process relies on the deposition of a sacrificial zinc coating which is galvanically displaced by the ethermediated reduction of oxophilic WCl6. Subsequent thermal treatment renders a crystalline, metallic tungsten film. The chemical evolution of the surface and formation of a complex intermediate tungsten species is characterized by X-ray diffraction, infrared spectroscopy, and X-ray photoelectron spectroscopy. Efficient metallic tungsten deposition is first characterized on a graphite substrate and then demonstrated on a functional carbon foam electrode. The resulting electrochemical performance of the modified electrode is interrogated with the canonical aqueous ferricyanide system. A tungsten-coated carbon foam electrode showed that both electrode resistance and overall electrochemical cell resistance were reduced by 50%, resulting in a concomitant decrease in redox peak separation from 1.902 V to 0.783 V. This process promises voltage efficiency gains in electrodes for energy storage technologies and demonstrates the viability of a new route to tungsten coating for technologies and industries where high conductivity and chemical stability are paramount.

Small, Leo J.; Clem, Paul G.; Spoerke, Erik D.

Abstract not provided.

Pratt, Harry P.; Fujimoto, Cy F.; Small, Leo J.

Abstract not provided.

Spoerke, Erik D.; Ingersoll, David I.; Clem, Paul G.; Small, Leo J.; Wheeler, Jill S.; Allcorn, Eric A.; Nagasubramanian, Ganesan N.; Lamb, Joshua H.; Bhavaraju, Sai B.; Eccleston, Alexis E.; Read, Andrew R.

Abstract not provided.

Small, Leo J.; Anderson, Travis M.; Pratt, Harry P.; Fujimoto, Cy F.

Abstract not provided.

Small, Leo J.; Pratt, Harry P.; Fujimoto, Cy F.; Anderson, Travis M.

Abstract not provided.

Anderson, Travis M.; Small, Leo J.; Pratt, Harry P.; Fujimoto, Cy F.

Abstract not provided.

Hess, Ryan F.; Boyle, Timothy J.; Lambert, Timothy N.; Kammler, Daniel K.; Small, Leo J.; Sears, Jeremiah M.

Abstract not provided.

Spoerke, Erik D.; Wheeler, Jill S.; Small, Leo J.; Ihlefeld, Jon I.; Clem, Paul G.; Ingersoll, David I.

Abstract not provided.

Small, Leo J.; Hess, Ryan F.; Lambert, Timothy N.; Vigil, Julian A.; Boyle, Timothy J.; Sears, Jeremiah M.; Kelly, Maria K.

Abstract not provided.

Sears, Jeremiah M.; Boyle, Timothy J.; Hess, Ryan F.; Small, Leo J.

Abstract not provided.

Journal of the Electrochemical Society

Small, Leo J.; Pratt, Harry P.; Fujimoto, Cy F.; Anderson, Travis M.

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. 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.

Boyle, Timothy J.; Hess, Ryan F.; Lambert, Timothy N.; Small, Leo J.; Alam, Todd M.; Sears, Jeremiah M.; Yonemoto, Daniel T.; Fasulo, Francesca F.; Cramer, Roger C.; Neville, Michael L.

Abstract not provided.

RSC Advances

Small, Leo J.; Sears, Jeremiah M.; Lambert, Timothy N.; Boyle, Timothy J.; Hess, Ryan F.

The electroreduction of Er3+ in propylene carbonate, N,N-dimethylformamide, or a variety of quaternary ammonium ionic liquids (ILs) was investigated using [Er(OTf)3] and [Er(NTf2)3]. Systematic variation of the ILs' cation and anion, Er3+ salt, and electrode material revealed a disparity in electrochemical interactions not previously seen. For most ILs at a platinum electrode, cyclic voltammetry exhibits irreversible interactions between Er3+ salts and the electrode at potentials significantly less than the theoretical reduction potential for Er3+. Throughout all solvent-salt systems tested, a deposit could be formed on the electrode, though obtaining a high purity, crystalline Er0 deposit is challenging due to the extreme reactivity of the deposit and resulting chemical interactions, often resulting in the formation of a complex, amorphous solid-electrolyte interface that slowed deposition rates. Comparison of platinum, gold, nickel, and glassy carbon (GC) working electrodes revealed oxidation processes unique to the platinum surface. While no appreciable reduction current was observed on GC at the potentials investigated, deposits were seen on platinum, gold, and nickel electrodes.

Spoerke, Erik D.; Small, Leo J.; Wheeler, David R.; Martinez, Alina M.; Vandelinder, Virginia A.; Bachand, George B.; Rempe, Susan R.

Abstract not provided.

Spoerke, Erik D.; Small, Leo J.; Wheeler, Jill S.; Martinez, Alina M.; Vandelinder, Virginia A.; Bachand, George B.; Rempe, Susan R.

Abstract not provided.

Anderson, Travis M.; Fujimoto, Cy F.; Pratt, Harry P.; Small, Leo J.

Abstract not provided.

Spoerke, Erik D.; Allendorf, Mark D.; Foster, Michael E.; Zarkesh, Ryan A.; Stavila, Vitalie S.; Leong, Kirsty; Small, Leo J.; Wheeler, Jill S.; George, Steven M.; Lancaster, Diane L.

Abstract not provided.

Spoerke, Erik D.; Small, Leo J.; Wheeler, Jill S.; Lambert, Timothy N.; Foster, Michael E.; Stavila, Vitalie S.; Leong, Kirsty; Allendorf, Mark D.

Abstract not provided.

ACS Applied Materials and Interfaces

Vandelinder, Virginia A.; Wheeler, David R.; Small, Leo J.; Brumbach, Michael T.; Spoerke, Erik D.; Henderson, Ian M.; Bachand, George B.

Polycarbonate is a desirable material for many applications due to its favorable mechanical and optical properties. Here, we report a simple, safe, environmentally friendly aqueous method that uses diamines to functionalize a polycarbonate surface with amino groups. The use of water as the solvent for the functionalization ensures that solvent induced swelling does not affect the optical or mechanical properties of the polycarbonate. We characterize the efficacy of the surface amination using X-ray photo spectroscopy, Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and contact angle measurements. Furthermore, we demonstrate the ability of this facile method to serve as a foundation upon which other functionalities may be attached, including antifouling coatings and oriented membrane proteins. (Chemical Presented).