In situ NMR metrology reveals reaction mechanisms in redox flow batteries.

Large-scale energy storage is becoming increasingly critical to balancing renewable energy production and consumption1. Organic redox flow batteries, made from inexpensive and sustainable redox-active materials, are promising storage technologies that are cheaper and less environmentally hazardous than vanadium-based batteries, but they have shorter lifetimes and lower energy density2,3. Thus, fundamental insight at the molecular level is required to improve performance4,5. Here we report two in situ nuclear magnetic resonance (NMR) methods of studying redox flow batteries, which are applied to two redox-active electrolytes: 2,6-dihydroxyanthraquinone (DHAQ) and 4,4'-((9,10-anthraquinone-2,6-diyl)dioxy) dibutyrate (DBEAQ). In the first method, we monitor the changes in the 1H NMR shift of the liquid electrolyte as it flows out of the electrochemical cell. In the second method, we observe the changes that occur simultaneously in the positive and negative electrodes in the full electrochemical cell. Using the bulk magnetization changes (observed via the 1H NMR shift of the water resonance) and the line broadening of the 1H shifts of the quinone resonances as a function of the state of charge, we measure the potential differences of the two single-electron couples, identify and quantify the rate of electron transfer between the reduced and oxidized species, and determine the extent of electron delocalization of the unpaired spins over the radical anions. These NMR techniques enable electrolyte decomposition and battery self-discharge to be explored in real time, and show that DHAQ is decomposed electrochemically via a reaction that can be minimized by limiting the voltage used on charging. We foresee applications of these NMR methods in understanding a wide range of redox processes in flow and other electrochemical systems.

A Comparative Study on HCN Polymers Synthesized by Polymerization of NH4 CN or Diaminomaleonitrile in Aqueous Media: New Perspectives for Prebiotic Chemistry and Materials Science.

HCN polymers are a group of complex and heterogeneous substances that are widely known in the fields of astrobiology and prebiotic chemistry. In addition, they have recently received considerable attention as potential functional material coatings. However, the real nature and pathways of formation of HCN polymers remain open questions. It is well established that the tuning of macromolecular structures determines the properties and practical applications of a polymeric material. Herein, different synthetic conditions were explored for the production of HCN polymers from NH4 CN or diaminomaleonitrile in aqueous media with different concentrations of the starting reactants and several reaction times. By using a systematic methodology, both series of polymers were shown to exhibit similar, but not identical, spectroscopic and thermal fingerprints, which resulted in a clear differentiation of their morphological and electrochemical properties. New macrostructures are proposed for HCN polymers, and promising insights are discussed for prebiotic chemistry and materials science on the basis of the experimental results.

Organometallic-Derived Carbon (ODC)-Metal Nano-Oxide Composites as Improved Electrode Materials for Supercapacitors.

In the search for the new generation of electrochemical energy storage materials, a novel and straightforward synthetic route for porous carbons and metal oxide nanoparticle composites based on the chlorination of the organometallic compounds Ni(C5H5)2 and Mn(C5H7O2)2 at moderate temperatures, followed by hydrothermal treatment, has been developed. Electrochemical measurements in a three-electrode configuration show that, in both composites NiO@ODC and Mn3O4@ODC, a synergistic effect between the capacitive and pseudocapacitive energy storage mechanisms is observed, thereby improving their electrochemical performance vs pure carbon materials. Electrochemical evaluation of symmetric cells gave gravimetric capacitances of 124 and 130 F g-1 for NiO@ODC and Mn3O4@ODC, respectively. However, the porous structure of the carbon matrix and the higher conductivity of Mn3O4, together, were found to be responsible for the superior electrochemical performance of Mn3O4@ODC.

Polymeric Schiff bases as low-voltage redox centers for sodium-ion batteries.

The redox entity comprising two Schiff base groups attached to a phenyl ring (-N=CH-Ar-HC=N-) is reported to be active for sodium-ion storage (Ar=aromatic group). Electroactive polymeric Schiff bases were produced by reaction between non-conjugated aliphatic or conjugated aromatic diamine block with terephthalaldehyde unit. Crystalline polymeric Schiff bases are able to electrochemically store more than one sodium atom per azomethine group at potentials between 0 and 1.5 V versus Na(+)/Na. The redox potential can be tuned through conjugation of the polymeric chain and by electron injection from donor substituents in the aromatic rings. Reversible capacities of up to 350 mA h g(-1) are achieved when the carbon mixture is optimized with Ketjen Black. Interestingly, the "reverse" configuration (-CH=N-Ar-N=HC-) is not electrochemically active, though isoelectronic.

Fibers of reduced graphene oxide nanoribbons.

Reduced graphene oxide nanoribbon fibers were fabricated by using an electrophoretic self-assembly method without the use of any polymer or surfactant. We report electrical and field emission properties of the fibers as a function of reduction degree. In particular, the thermally annealed fiber showed superior field emission performance with a low potential for field emission (0.7 V µm(-1)) and a giant field emission current density (400 A cm(-2)). Moreover, the fiber maintains a high current level of 300 A cm(-2) corresponding to 1 mA during long-term operation.

Polymeric Redox-Active Electrodes for Sodium-Ion Batteries.

Polymer binding agents are critical for the good performance of the electrodes of Na- and Li-ion batteries during cycling as they hold the electroactive material together to form a cohesive assembly because of their mechanical and chemical stability as well as adhesion to the current collector. New redox-active polymer binders that insert Na+ ions and show adhesion properties were synthesized by adding polyether amine blocks (Jeffamine) based on mixed propylene oxide and ethylene oxide blocks to p-phenylenediamine and terephthalaldehyde units to form electroactive Schiff-base groups along the macromolecule. The synthetic parameters and the electrochemical properties of these terpolymers as Na-ion negative electrodes in half cells were studied. Reversible capacities of 300 mAh g-1 (50 wt % conducting carbon) and 200 mAh g-1 (20 wt % conducting carbon) were achieved in powder and Cu-supported electrodes, respectively, for a polySchiff-polyether terpolymer synthesized by using a poly(ethylene oxide) block of 600 g mol-1 in place of one third of the aniline units. The new redox-active polymers were also used as a binding agent of another anode material (hard carbon), which led to an increase of the total capacity of the electrode compared to that prepared with other standard fluorinated polymer binders such as poly(vinylidene) fluoride.

Response to Comment on "Cycling Li-O2 batteries via LiOH formation and decomposition".

We described a lithium-oxygen (Li-O2) battery comprising a graphene electrode, a dimethoxyethane-based electrolyte, and H2O and lithium iodide (LiI) additives, lithium hydroxide (LiOH) being the predominant discharge product. We demonstrate, in contrast to the work of Shen et al., that the chemical reactivity between LiOH and the triiodide ion (I3 (-)) to form IO3 (-) indicates that LiOH can be removed on charging; the electrodes do not clog, even after multiple cycles, confirming that solid products are reversibly removed.

Response to Comment on "Cycling Li-O2 batteries via LiOH formation and decomposition".

Lithium-oxygen (Li-O2) batteries cycle reversibly with lithium iodide (LiI) additives in dimethoxyethane (DME) to form lithium hydroxide (LiOH). Viswanathan et al. argue that because the standard redox potential of the four-electron (e(-)) reaction, 4OH(-) ↔ 2H2O + O2 + 4e(-), is at 3.34 V versus Li(+)/Li, LiOH cannot be removed by the triiodide ion (I3(-)). However, under nonaqueous conditions, this reaction will occur at a different potential. LiOH also reacts chemically with I3(-) to form IO3(-), further studies being required to determine the relative rates of the two reactions on electrochemical charge.

Oriented graphene nanoribbon yarn and sheet from aligned multi-walled carbon nanotube sheets.

Highly oriented graphene nanoribbons sheets and yarns are produced by chemical unzipping of self-standing multiwalled carbon nanotube (MWNT) sheets. The as-produced yarns - after being chemically and thermally reduced - exhibit a good mechanical, electrical, and electrochemical performance.

Biscrolling nanotube sheets and functional guests into yarns.

Multifunctional applications of textiles have been limited by the inability to spin important materials into yarns. Generically applicable methods are demonstrated for producing weavable yarns comprising up to 95 weight percent of otherwise unspinnable particulate or nanofiber powders that remain highly functional. Scrolled 50-nanometer-thick carbon nanotube sheets confine these powders in the galleries of irregular scroll sacks whose observed complex structures are related to twist-dependent extension of Archimedean spirals, Fermat spirals, or spiral pairs into scrolls. The strength and electronic connectivity of a small weight fraction of scrolled carbon nanotube sheet enables yarn weaving, sewing, knotting, braiding, and charge collection. This technology is used to make yarns of superconductors, lithium-ion battery materials, graphene ribbons, catalytic nanofibers for fuel cells, and titanium dioxide for photocatalysis.