A lithium-oxygen battery based on lithium superoxide.

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.

Study on the Catalytic Activity of Noble Metal Nanoparticles on Reduced Graphene Oxide for Oxygen Evolution Reactions in Lithium-Air Batteries.

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.

A physical pulverization strategy for preparing a highly active composite of CoOx and crushed graphite for lithium-oxygen batteries.

A new physical pulverization strategy has been developed to prepare a highly active composite of CoOx and crushed graphite (CG) for the cathode in lithium-oxygen batteries. The effect of CoOx loading on the charge potential in the oxygen evolution reaction (Li(2)O(2) →2 Li(+) +O(2) +2e(-)) was investigated in coin-cell tests. The CoOx (38.9 wt %)/CG composite showed a low charge potential of 3.92 V with a delivered capacity of 2 mAh cm(-2) under a current density of 0.2 mA cm(-2). The charge potential was 4.10 and 4.15 V at a capacity of 5 and 10 mAh cm(-2), respectively, with a current density of 0.5 mA cm(-2). The stability of the electrolyte and discharge product on the gas-diffusion layer after the cycling were preliminarily characterized by (1)H nuclear magnetic resonance spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The high activity of the composite was further analyzed by electrochemical impedance spectroscopy, cyclic voltammetry, and potential-step chronoamperometry. The results indicate that our near-dry milling method is an effective and green approach to preparing a nanocomposite cathode with high surface area and porosity, while using less solvent. Its relative simplicity compared with the traditional solution method could facilitate its widespread application in catalysis, energy storage, and materials science.

Influence of temperature on lithium-oxygen battery behavior.

In this Letter we report an electrochemical and morphological study of the response of lithium-oxygen cells cycled at various temperatures, that is, ranging from -10 to 70 °C. The results show that the electrochemical process of the cells is thermally influenced in an opposite way, that is, by a rate decrease, due to a reduced diffusion of the lithium ions from the electrolyte to the electrode interface, at low temperature and a rate enhancement, due to the decreased electrolyte viscosity and consequent increased oxygen mobility, at high temperature. In addition, we show that the temperature also influences the crystallinity of lithium peroxide, namely of the product formed during cell discharge.

A metal-free, lithium-ion oxygen battery: a step forward to safety in lithium-air batteries.

A preliminary study of the behavior of lithium-ion-air battery where the common, unsafe lithium metal anode is replaced by a lithiated silicon-carbon composite, is reported. The results, based on X-ray diffraction and galvanostatic charge-discharge analyses, demonstrate the basic reversibility of the electrochemical process of the battery that can be promisingly cycled with a rather high specific capacity.

A transmission electron microscopy study of the electrochemical process of lithium-oxygen cells.

The electrochemical reaction of a lithium-oxygen cell using a tetraethylene glycol dimethyl ether-lithium triflate, TEGDME-LiCF(3)SO(3) electrolyte, is investigated by a detailed transmission electron microscopy analysis. The results confirm the reversibility of the process by showing the formation-dissolution of lithium peroxide, Li(2)O(2), upon repeating cell charge and discharge cycles.

Redox Mediators for Li-O2 Batteries: Status and Perspectives.

Li-O2 batteries have received much attention due to their extremely large theoretical energy density. However, the high overpotentials required for charging Li-O2 batteries lower their energy efficiency and degrade the electrolytes and carbon electrodes. This problem is one of the main obstacles in developing practical Li-O2 batteries. To solve this problem, it is important to facilitate the oxidation of Li2 O2 upon charging by using effective electrocatalysis. Using solid catalysts is not too effective for oxidizing the electronically isolating Li-peroxide layers. In turn, for soluble catalysts, red-ox mediators (RMs) are homogeneously dissolved in the electrolyte solutions and can effectively oxidize all of the Li2 O2 precipitated during discharge. RMs can decompose solid Li2 O2 species no matter their size, morphology, or thickness and thus dramatically increase energy efficiency. However, some negative side effects, such as the shuttle reactions of RMs and deterioration of the Li-metal occur. Therefore, it is necessary to study the activity and stability of RMs in Li-O2 batteries in detail. Herein, recent studies related to redox mediators are reviewed and the mechanisms of redox reactions are illustrated. The development opportunities of RMs for this important battery technology are discussed and future directions are suggested.

The lithium/air battery: still an emerging system or a practical reality?

Lithium/air is a fascinating energy storage system. The effective exploitation of air as a battery electrode has been the long-time dream of the battery community. Air is, in principle, a no-cost material characterized by a very high specific capacity value. In the particular case of the lithium/air system, energy levels approaching that of gasoline have been postulated. It is then not surprising that, in the course of the last decade, great attention has been devoted to this battery by various top academic and industrial laboratories worldwide. This intense investigation, however, has soon highlighted a series of issues that prevent a rapid development of the Li/air electrochemical system. Although several breakthroughs have been achieved recently, the question on whether this battery will have an effective economic and societal impact remains. In this review, a critical evaluation of the progress achieved so far is made, together with an attempt to propose future R&D trends. A forecast on whether Li/air may have a role in the next years' battery technology is also postulated.

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium-oxygen batteries.

Lithium-oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium-oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. Here we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium-oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. This dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. The results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium-oxygen cells.

Encapsulation of metal oxide nanocrystals into porous carbon with ultrahigh performances in lithium-ion battery.

A simple and industrial scalable approach was developed to encapsulate metal oxide nanocrystals into porous carbon (PC) with a high distribution. With this method, the composite of PC-metal oxide were prepared in a large amount with a low cost; particularly they exhibit ultrahigh performances in lithium-ion battery applications. For example, the PC-CoOx and PC-FeOx show a high capacity around 1021 mA h g(-1) and 1200 mA h g(-1) at the current density of 100 mA g(-1) respectively, together with an excellent cycling ability (>400 cycles) and rate capacity even at the high current densities of 3 A g(-1) and 5 A g(-1).

Assembling metal oxide nanocrystals into dense, hollow, porous nanoparticles for lithium-ion and lithium-oxygen battery application.

New dense hollow porous (DHP) metal oxide nanoparticles that are smaller than 100 nm and composed of Co3O4, FeOx, NiO and MnOx were prepared by densely assembling metal oxide nanocrystals based on the hard-template method using a carbon colloid as a sacrificial core. These nanoparticles are quite different from the traditional particles as their hollow interior originates from the stacking of nanocrystals rather than a spherical shell. The DHP nanoparticles preserve the intriguing properties of nanocrystals and possess desirable surface area and pore volume that enhance the active surface, which ultimately benefits applications such as lithium-ion batteries. The DHP Co3O4 nanoparticles demonstrated an enhanced capacity of 1168 mA h g(-1) at 100 mA g(-1)vs. 590 mA h g(-1) of powders and stable cycling performance greater than 250 cycles when used as an anode material. Most importantly, the electrochemical performance of DHP Co3O4 nanoparticles in a lithium-O2 battery was also investigated for the first time. A low charge potential of ∼4.0 V, a high discharge voltage near 2.74 V and a long cycle ability greater than 100 cycles at a delivered capacity of 2000 mA h g(-1) (current density, 200 mA g(-1)) were observed. The performances were considerably improved compared to recent results of mesoporous Co3O4, Co3O4 nanoparticles and a composite of Co3O4/RGO and Co3O4/Pd. Therefore, it would be promising to investigate such properties of DHP nanoparticles or other hollow metal (oxide) particles for the popular lithium-air battery.

Ordered mesoporous carbon electrodes for Li-O2 batteries.

Ordered mesoporous carbon (OMC) with highly ordered pore channels was applied as an oxygen-side electrode for a Li-O2 battery. To evaluate the effect of the pore channel size on battery performance, we employed OMCs possessing two different pore sizes (6 and 17 nm). When cycled at a current density of 200 mA g(-1)carbon, the OMC electrodes reduced polarization in the oxygen evolution reaction by 0.1 V compared to those consisting of conventional super P carbon electrode. X-ray diffraction and transmission electron microscopy of the discharged oxygen electrodes provided evidence for the formation of amorphous Li2O2, a product of the oxygen reduction reaction, inside the OMC pores rather than on the electrode surface as in the case of the super P electrode. The OMC electrodes were also effective at high current densities (500 mA g(-1)carbon and 1000 mA g(-1)carbon).

Ruthenium-based electrocatalysts supported on reduced graphene oxide for lithium-air batteries.

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).

An improved high-performance lithium-air battery.

Although dominating the consumer electronics markets as the power source of choice for popular portable devices, the common lithium battery is not yet suited for use in sustainable electrified road transport. The development of advanced, higher-energy lithium batteries is essential in the rapid establishment of the electric car market. Owing to its exceptionally high energy potentiality, the lithium-air battery is a very appealing candidate for fulfilling this role. However, the performance of such batteries has been limited to only a few charge-discharge cycles with low rate capability. Here, by choosing a suitable stable electrolyte and appropriate cell design, we demonstrate a lithium-air battery capable of operating over many cycles with capacity and rate values as high as 5,000 mAh g(carbon)(-1) and 3 A g(carbon)(-1), respectively. For this battery we estimate an energy density value that is much higher than those offered by the currently available lithium-ion battery technology.