Batteries based on sodium superoxide and on potassium superoxide have recently been reported. However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research into the lithium-oxygen (Li-O2) battery because of its potential high energy density. Several studies of Li-O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime. These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li-O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

Ruthenium-based nanomaterials supported on reduced graphene oxide (rGO) have been investigated as air cathodes in non-aqueous electrolyte Li-air cells using a TEGDME-LiCF3SO3 electrolyte. Homogeneously distributed metallic ruthenium and hydrated ruthenium oxide (RuO2·0.64H2O), deposited exclusively on rGO, have been synthesized with average size below 2.5 nm. The synthesized hybrid materials of Ru-based nanoparticles supported on rGO efficiently functioned as electrocatalysts for Li2O2 oxidation reactions, maintaining cycling stability for 30 cycles without sign of TEGDME-LiCF3SO3 electrolyte decomposition. Specifically, RuO2·0.64H2O-rGO hybrids were superior to Ru-rGO hybrids in catalyzing the OER reaction, significantly reducing the average charge potential to ∼3.7 V at the high current density of 500 mA g(-1) and high specific capacity of 5000 mAh g(-1).

Among many challenges present in Li-air batteries, one of the main reasons of low efficiency is the high charge overpotential due to the slow oxygen evolution reaction (OER). Here, we present systematic evaluation of Pt, Pd, and Ru nanoparticles supported on rGO as OER electrocatalysts in Li-air cell cathodes with LiCF3SO3-tetra(ethylene glycol) dimethyl ether (TEGDME) salt-electrolyte system. All of the noble metals explored could lower the charge overpotentials, and among them, Ru-rGO hybrids exhibited the most stable cycling performance and the lowest charge overpotentials. Role of Ru nanoparticles in boosting oxidation kinetics of the discharge products were investigated. Apparent behavior of Ru nanoparticles was different from the conventional electrocatalysts that lower activation barrier through electron transfer, because the major contribution of Ru nanoparticles in lowering charge overpotential is to control the nature of the discharge products. Ru nanoparticles facilitated thin film-like or nanoparticulate Li2O2 formation during oxygen reduction reaction (ORR), which decomposes at lower potentials during charge, although the conventional role as electrocatalysts during OER cannot be ruled out. Pt-and Pd-rGO hybrids showed fluctuating potential profiles during the cycling. Although Pt- and Pd-rGO decomposed the electrolyte after electrochemical cycling, no electrolyte instability was observed with Ru-rGO hybrids. This study provides the possibility of screening selective electrocatalysts for Li-air cells while maintaining electrolyte stability.

We report the fabrication and electrochemical activity of free-standing reduced graphene oxide (RGO) films as cathode materials for lithium ion batteries. The conducting additive and binder-free RGO electrodes with different oxygen contents were assembled by a simple vacuum filtration process from aqueous RGO colloids prepared with the aid of cationic surfactants. The gravimetric capacity of RGO film cathodes showed clear dependence on the oxygen contents controlled by the thermal reduction process. The capacity increased with the increase of the amount of oxygen functional groups, indicating that the main lithium capturing mechanism of RGO cathodes is Li(+) ion interaction with the surface oxygen functionalities. The hydroxyl groups (C-OH) as well as carbon-oxygen double bonds have been identified as the lithiation-active species. The RGO cathodes achieved excellent rate capability due to the fast surface Faradaic reaction, suggesting that self-supported RGO films are promising cathodes for high power application. The graphene oxide (GO)/RGO composite films showed inferior performance to those of RGO only. The poor electronic conductivity of GO might result in inefficient utilization of redox active oxygen functional groups despite the higher oxygen content and higher theoretical capacity of GO/RGO composite films. Further optimization on the amount of oxygen functional groups for higher capacity and better electronic conductivity would lead to the development of RGO based high energy-high power cathodes.

Membranes that differentiate ions are being actively developed to meet the needs in separation, sensing, biomedical, and water treatment technologies. Biomimetic approaches that combine bioinspired functional molecules with solid state supports offer great potential for imitating the functions and principles of biological ion channels. Here we report the design and fabrication of biomimetic graphene oxide (GO) based membranes functionalized with a peptide motif that has the capabilities for selective recognition and transport. The peptide, which has ion binding affinity to Co2+ ions, was adopted to enable the ion selective filtration capability and was then anchored on a GO surface. The resulting GO-based membranes show remarkable ion selectivity toward the specific ion of interest, for the transport across the membranes as in the biological ion channels. Ion recognition capability of this peptide motif successfully translates into ion specificity for selective transport. This study provides a new avenue for developing artificial ion channels via a synergistic combination of biomimetic recognition chemistry, with a novel nanoplatform such as GO.