Freestanding Bipolar Membranes with an Electrospun Junction for High Current Density Water Splitting.

Freestanding bipolar membranes (BPMs) with an extended-area water splitting junction were fabricated utilizing electrospinning. The junction layer was composed of a mixed fiber mat that was made by concurrently electrospinning sulfonated poly(ether ether ketone) (SPEEK) and quaternized poly(phenylene oxide) (QPPO), with water splitting catalyst nanoparticles intermittently deposited between the fibers. The mat was sandwiched between solution cast SPEEK and QPPO films and hot-pressed to form a dense trilayer BPM with an extended-area junction of finite thickness, composed of QPPO nanofibers embedded in a SPEEK matrix with the catalyst nanoparticles interspaced between the two polymers. The composition, ion-exchange capacity, and catalyst type/loading in the junction were varied, and the water splitting characteristics of the membranes were assessed. The best BPMs fabricated in this work employed a graphene oxide catalyst and exhibited a low trans-membrane voltage drop of about 0.82 V at 1000 mA/cm2 in water splitting experiments with 0.5 M Na2SO4 and stable water splitting operation for 60 h at 800 mA/cm2.

Investigating dendrites and side reactions in sodium-oxygen batteries for improved cycle lives.

The development of sodium-oxygen batteries with high round-trip efficiencies is hindered by the short cycle lives. Sodium dendrite formation and oxygen crossover are identified as two major issues. By employing an ion selective membrane, the cycle life of sodium-oxygen batteries has been greatly improved.

Understanding side reactions in K-O2 batteries for improved cycle life.

Superoxide based metal-air (or metal-oxygen) batteries, including potassium and sodium-oxygen batteries, have emerged as promising alternative chemistries in the metal-air battery family because of much improved round-trip efficiencies (>90%). In order to improve the cycle life of these batteries, it is crucial to understand and control the side reactions between the electrodes and the electrolyte. For potassium-oxygen batteries using ether-based electrolytes, the side reactions on the potassium anode have been identified as the main cause of battery failure. The composition of the side products formed on the anode, including some reaction intermediates, have been identified and quantified. Combined experimental studies and density functional theory (DFT) calculations show the side reactions are likely driven by the interaction of potassium with ether molecules and the crossover of oxygen from the cathode. To inhibit these side reactions, the incorporation of a polymeric potassium ion selective membrane (Nafion-K(+)) as a battery separator is demonstrated that significantly improves the battery cycle life. The K-O2 battery with the Nafion-K(+) separator can be discharged and charged for more than 40 cycles without increases in charging overpotential.

Combinatorial screening of PtTiMe ternary alloys for oxygen electroreduction.

The catalytic oxygen electroreduction properties of PtTiMe (Me = Co, Cr, Cu, Fe, Mn, Mo, Ni, Pd, Ta, V, W and Zr) ternary alloys were studied using an in-house developed thin film based combinatorial high throughput method. Libraries containing discrete alloy compositions were fabricated by plasma co-sputtering and the resulting alloys were electrochemically screened by the hydrodynamic rotating disk electrode technique. Candidate catalysts were identified by comparing the activity-stability-composition relationships between the platinum titanium alloys and pure platinum standard. Among the PtTiMe alloys studied, PtTiNi, PtTiCu and PtTiV, respectively, displayed the highest catalytic oxygen electroreduction activities with a tenfold, an eightfold and a sixfold enhancement as compared to the pure platinum standard and good chemical stabilities.