Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries

Despite the imminent commercial introduction of Li-ion batteries in electric drive vehicles and their proposed use as enablers of smart grids based on renewable energy technologies, an intensive quest for new electrode materials that bring about improvements in energy density, cycle life, cost, and safety is still underway. This Progress Report highlights the recent developments and the future prospects of the use of phases that react through conversion reactions as both positive and negative electrode materials in Li-ion batteries. By moving beyond classical intercalation reactions, a variety of low cost compounds with gravimetric specific capacities that are two-to-five times larger than those attained with currently used materials, such as graphite and LiCoO(2), can be achieved. Nonetheless, several factors currently handicap the applicability of electrode materials entailing conversion reactions. These factors, together with the scientific breakthroughs that are necessary to fully assess the practicality of this concept, are reviewed in this report.

Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions

α‐Fe2O3 Nanotubes in Gas Sensor and Lithium‐Ion Battery Applications

Reduced graphene oxide/Fe2O3 composite was prepared using a facile two-step synthesis by homogeneous precipitation and subsequent reduction of the G-O with hydrazine under microwave irradiation to yield reduced graphene oxide (RG-O) platelets decorated with Fe2O3 nanoparticles. As an anode material for Li-ion batteries, the RG-O/Fe2O3 composite exhibited discharge and charge capacities of 1693 and 1227 mAh/g, respectively, normalized to the mass of Fe2O3 in the composite (and ∼1355 and 982 mAh/g, respectively, based on the total mass of the composite), with good cycling performance and rate capability. Characterization shows that the Fe2O3 nanoparticles are uniformly distributed on the surface of the RG-O platelets in the composite. The total specific capacity of RG-O/Fe2O3 is higher than the sum of pure RG-O and nanoparticle Fe2O3, indicating a positive synergistic effect of RG-O and Fe2O3 on the improvement of electrochemical performance. The synthesis approach presents a promising route for a large-sca...

Nanostructured reduced graphene oxide/Fe2O3 composite as a high-performance anode material for lithium ion batteries.

Nanoflakes of α-Fe2O3 were prepared on Cu foil by using a thermal treatment method. The nanoflakes were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. The reversible Li-cycling properties of the α-Fe2O3 nanoflakes have been evaluated by cyclic voltammery, galvanostatic discharge–charge cycling, and impedance spectral measurements on cells with Li metal as the counter and reference electrodes, at ambient temperature. Results show that Fe2O3 nanoflakes exhibit a stable capacity of (680 ± 20) mA h g–1, corresponding to (4.05 ± 0.05) moles of Li per mole of Fe2O3 with no noticeable capacity fading up to 80 cycles when cycled in the voltage range 0.005–3.0 V at 65 mA g–1 (0.1 C rate), and with a coulombic efficiency of > 98 % during cycling (after the 15th cycle). The average discharge and charge voltages are 1.2 and 2.1 V, respectively. The observed cyclic voltammograms and impedance spectra have been analyzed and interpreted in terms of the ‘conversion reaction' involving nanophase Fe0–Li2O. The superior performance of Fe2O3 nanoflakes is clearly established by a comparison of the results with those for Fe2O3 nanoparticles and nanotubes reported in the literature.

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α‐Fe2O3 Nanoflakes as an Anode Material for Li‐Ion Batteries

The electrochemical reduction of hematite with various particle sizes by metallic lithium has been studied by means of X-ray diffraction (XRD) Mossbauer and extended X-ray absorption fine structure (EXAFS) spectroscopy. Previous in situ XRD analysis coupled with electrochemical data showed that lithium can be inserted in the nanosized sample up to 1 Li per Fe2O3 whereas bulk material undergoes an irreversible Li-driven transformation from an hexagonal anionic packing to a close cubic packed framework as soon as 0.03 Li is inserted in the corundum structure. The present data show that only 0.6 Li per formula unit are actually inserted in the structure of small particles. The remaining lithium (0.4) is engaged in irreversible reduction of surface groups, or capacitive behavior. Beyond the solid solution domains, both samples are multiphase, and consist of Li2Fe2O3, Fe0 clusters (10-15 A) and inserted -Fe2O3, which proportions are used to calculate the mean iron oxidation state in the electrode as the reaction proceeds. From these data, we found that electrolyte decomposition can occur at very different steps of the reduction depending on the texture of the active materials. In addition, during the reduction process, we evidenced a reaction of disproportionation (3Fe2+2Fe3+ + Fe0), an intense electrochemical grinding of the hematite particles and the formation of extremely fine metallic surface clusters. For the first time, the EXAFS/X-ray absorption near-edge structure signature of the divalent intermediate Li2Fe2O3 phase is obtained.

R. Cortes

Papers

Combined XRD, EXAFS, and Mössbauer Studies of the Reduction by Lithium of α Fe2 O 3 with Various Particle Sizes

種々の粒子サイズのα-Fe 2 O 3 のLiによる還元についてのXRD,EXAFSおよびMoessbuerの組み合わせによる研究

R. Cortes

Papers

Combined XRD, EXAFS, and Mössbauer Studies of the Reduction by Lithium of α ­ Fe2 O 3 with Various Particle Sizes

種々の粒子サイズのα-Fe 2 O 3 のLiによる還元についてのXRD,EXAFSおよびMoessbuerの組み合わせによる研究

Combined XRD, EXAFS, and Mössbauer Studies of the Reduction by Lithium of α Fe2 O 3 with Various Particle Sizes