Boosting the Performance of Graphene Cathodes in Na-O2 Batteries by Exploiting the Multifunctional Character of Small Biomolecules.

Graphene aerogels derived from a biomolecule-assisted aqueous electrochemical exfoliation route are explored as cathode materials in sodium-oxygen (Na-O2 ) batteries. To this end, the natural nucleotide adenosine monophosphate (AMP) is used in the multiple roles of exfoliating electrolyte, aqueous dispersant, and functionalizing agent to access high quality, electrocatalytically active graphene nanosheets in colloidal suspension (bioinks). The surface phenomena occurring on the electrochemically derived graphene cathode is thoroughly studied to understand and optimize its electrochemical performance, where a cooperative effect between the nitrogen atoms and phosphates from the AMP molecules is demonstrated. Moreover, the role of the nitrogen atoms in the adenine nucleobase of AMP and short-chain phosphate is unraveled. Significantly, the use of such cathodes with a proper amount of AMP molecules adsorbed on the graphene nanosheets delivers a discharge capacity as high as 9.6 mAh cm-2 and performs almost 100 cycles with a considerably reduced cell overpotential and a coulombic efficiency of ≈97% at high current density (0.2 mA cm-2 ). This study opens a path toward the development of environmentally friendly air cathodes by the use of natural nucleotides which offers a great opportunity to explore and manufacture bioinspired cathodes for metal-oxygen batteries.

High Performance Na-O2 Batteries and Printed Microsupercapacitors Based on Water-Processable, Biomolecule-Assisted Anodic Graphene.

Integrated approaches that expedite the production and processing of graphene into useful structures and devices, particularly through simple and environmentally friendly strategies, are highly desirable in the efforts to implement this two-dimensional material in state-of-the-art electrochemical energy storage technologies. Here, we introduce natural nucleotides (e.g., adenosine monophosphate) as bifunctional agents for the electrochemical exfoliation and dispersion of graphene nanosheets in water. Acting both as exfoliating electrolytes and colloidal stabilizers, these biomolecules facilitated access to aqueous graphene bio-inks that could be readily processed into aerogels and inkjet-printed interdigitated patterns. Na-O2 batteries assembled with the graphene-derived aerogels as the cathode and a glyme-based electrolyte exhibited a full discharge capacity of ∼3.8 mAh cm-2 at a current density of 0.2 mA cm-2. Moreover, shallow cycling experiments (0.5 mAh cm-2) boasted a capacity retention of 94% after 50 cycles, which outperformed the cycle life of prior graphene-based cathodes for this type of battery. The positive effect of the nucleotide-adsorbed nanosheets on the battery performance is discussed and related to the presence of the phosphate group in these biomolecules. Microsupercapacitors made from the interdigitated graphene patterns as the electrodes also displayed a competitive performance, affording areal and volumetric energy densities of 0.03 µWh cm-2 and 1.2 mWh cm-3 at power densities of 0.003 mW cm-2 and 0.1 W cm-3, respectively. Taken together, by offering a green and straightforward route to different types of functional graphene-based materials, the present results are expected to ease the development of novel energy storage technologies that exploit the attractions of graphene.

An Overview of Engineered Graphene-Based Cathodes: Boosting Oxygen Reduction and Evolution Reactions in Lithium- and Sodium-Oxygen Batteries.

The depletion of fossil fuels, the rapid evolution of the global economy, and high living standards require the development of new energy-storage systems that can meet the needs of the world's population. Metal-oxygen batteries (M=Li, Na) arise, therefore, as promising alternatives to widely used lithium-ion batteries, due to their high theoretical energy density, which approaches that of gasoline. Although significant progress has been made in recent years, there are still several challenges to overcome to reach the final commercialization of this technology. One of the most limiting and challenging factors is the development of bifunctional cathodes towards oxygen reduction and evolution reactions. In this sense, graphene, which is very promising and tunable, has been widely explored by the research community as a key material for this technology. Herein, a wide literature overview is presented and analyzed with the aim of guiding future research in this field.

Controlling the Three-Phase Boundary in Na-Oxygen Batteries: The Synergy of Carbon Nanofibers and Ionic Liquid.

A series of electrospun binder-free carbon nanofiber (CNF) mats have been studied as air cathodes for Na-oxygen batteries using a pyrrolidinium-based electrolyte and compared with the commercial air cathode Toray 090. A tenfold increase in the discharge capacity is attained when using CNFs in comparison with Toray 090, affording a discharge capacity of 1.53 mAh cm-2 at a high discharge rate of 0.63 mA cm-2 . The good specific discharge and charge capacities of these CNFs are determined by the void space and the highly accessible surface of the carbon fiber. Furthermore, a threefold increase has been attained in terms of specific capacity by controlling the flooding of the air cathode and hence the location of the three-phase boundary within the CNF mat. The enhancement in performance has been correlated to the morphology, composition, distribution, and location of the discharge products. Sodium superoxide and peroxide were identified as the discharge products and, more importantly, the common side reaction discharge products, which are known to be detrimental to battery performance (including sodium fluoride, sodium hydroxide, and formate), were not observed, exemplifying the stability of the pyrrolidinium-based electrolyte and these binder-free CNF air cathodes.

Influence of Multiwalled Carbon Nanotubes as Additives in Biomass-Derived Carbons for Supercapacitor Applications.

Glucose-derived carbon/carbon nanotube (CNT) hybrid materials were prepared by hydrothermal carbonization of glucose in the presence of CNTs and subsequent carbonization, physical activation, or chemical activation. The proportion of CNTs added during the hydrothermal polymerization of glucose was varied to ascertain the optimum dose to maximize the performance of the carbon hybrids in supercapacitor applications. Both the thermal treatment applied and the addition of CNTs lead to changes in the textural and chemical properties of the activated carbons. It was observed that samples bearing CNTs exhibit higher number of nucleation centers for glucose oligomers to polymerize, and consequently, the behavior of the hydrothermal carbon toward activation differs according to the activating agent employed. Moreover, the initial chemical speciation dominated by acidic groups shifts to more basic functionalities (quinones and carbonyl groups) with the addition of CNTs. The effect of the different physicochemical properties of the prepared carbons on their electrochemical behavior was evaluated. The addition of 2 wt % of CNTs and subsequent chemical activation leads to electrode materials yielding 206 F g-1 and 78% of capacitance retention up to 0.8 V and 20 A g-1 and high rate cyclability (97% after 5000 cycles). The outstanding performance is ascribed to the high surface area, narrow mesopores, and phenol/carbonyl surface functionalities, which enhance molecular diffusion, the amount of stored energy, and electronic transportation, respectively.