A promising family of mixed transition-metal oxides (MTMOs) (designated as Ax B3-x O4 ; A, B=Co, Ni, Zn, Mn, Fe, etc.) with stoichiometric or even non-stoichiometric compositions, typically in a spinel structure, has recently attracted increasing research interest worldwide. Benefiting from their remarkable electrochemical properties, these MTMOs will play significant roles for low-cost and environmentally friendly energy storage/conversion technologies. In this Review, we summarize recent research advances in the rational design and efficient synthesis of MTMOs with controlled shapes, sizes, compositions, and micro-/nanostructures, along with their applications as electrode materials for lithium-ion batteries and electrochemical capacitors, and efficient electrocatalysts for the oxygen reduction reaction in metal-air batteries and fuel cells. Some future trends and prospects to further develop advanced MTMOs for next-generation electrochemical energy storage/conversion systems are also presented.

Mixed transition-metal oxides: design, synthesis, and energy-related applications.

Several hundred thousands of tons of ZnO are used by per year, e.g. as an additive to concrete or to rubber. In the field of optoelectronics, ZnO holds promises as a material for a blue/UV optoelectronics, alternatively to GaN, as a cheap, transparent, conducting oxide, as a material for electronic circuits, which are transparent in the visible or for semiconductor spintronics. The main problem is presently, however, a high, reproducible and stable p-doping. We review in this contribution partly critically the material growth, fundamental properties of ZnO and of ZnO-based nanostructures, doping as well as present and future applications, with emphasis on the electronic and optical properties including stimulated emission. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

ZnO : From basics towards applications

ZnO is presently experiencing a research boom with more than 2000 ZnO-related publications in 2005. This phenomenon is triggered, for example, by hope to use ZnO as a material for blue/UV optoelectronics as an alternative to GaN, as a cheap, transparent, conducting oxide, as a material for electronic circuits that are transparent in the visible or for semiconductor spintronics. Currently, however, the main problem is to achieve high, reproducible and stable p-doping. Herein, we critically review aspects of the material growth, fundamental properties of ZnO and ZnO-based nanostructures and doping as well as present and future applications with emphasis on the electronic and optical properties including stimulated emission.

ZnO: Material, Physics and Applications

Binary metal oxides has been regarded as a promising class of electrode materials for high-performance energy storage devices since it offers higher electrochemical activity and higher capacity than mono-metal oxide. Besides, rational design of electrode architectures is an effective solution to further enhance electrochemical performance of energy storage devices. Here, the advanced electrode architectures consisting of carbon textiles uniformally covered by mesoporous NiCo2O4 nanowire arrays (NWAs) are successfully fabricated by a simple surfactant-assisted hydrothermal method combined with a short post annealing treatment, which can be directly applied as self-supported electrodes for energy storage devices, such as Li-ion batteries, supercapacitors. The as-prepared mesoporous NiCo2O4 nanowires consist of numerous highly crystalline nanoparticles, leaving a large number of mesopores to alleviate the volume change during the charge/discharge process. Electrode architectures presented here promise fast electron transport by direct connection to the growth substrate and facile ion diffusion path provided by both the abundant mesoporous structure in nanowires and large open spaces between neighboring nanowires, which ensures every nanowire participates in the ultrafast electrochemical reaction. Benefiting from the intrinsic materials and architectures features, the unique binder-free NiCo2O4/carbon textiles exhibit high specific capacity/capacitance, excellent rate capability, and cycling stability.

Mesoporous NiCo2O4 Nanowire Arrays Grown on Carbon Textiles as Binder‐Free Flexible Electrodes for Energy Storage

Mixed transition-metal oxides (MTMOs), including stannates, ferrites, cobaltates, and nickelates, have attracted increased attention in the application of high performance lithium-ion batteries. Compared with traditional metal oxides, MTMOs exhibit enormous potential as electrode materials in lithium-ion batteries originating from higher reversible capacity, better structural stability, and high electronic conductivity. Recent advancements in the rational design of novel MTMO micro/nanostructures for lithium-ion battery anodes are summarized and their energy storage mechanism is compared to transition-metal oxide anodes. In particular, the significant effects of the MTMO morphology, micro/nanostructure, and crystallinity on battery performance are highlighted. Furthermore, the future trends and prospects, as well as potential problems, are presented to further develop advanced MTMO anodes for more promising and large-scale commercial applications of lithium-ion batteries.

Recent Developments and Understanding of Novel Mixed Transition-Metal Oxides as Anodes in Lithium Ion Batteries

Raman scattering has been used to study the influence of manganese, an effective dopant to obtain ZnO diluted magnetic semiconductors, on the lattice dynamics of ZnO. It is found that Mn doping increases the lattice defects and induces two Raman vibration modes of 275 and 526cm−1. On the other hand, high temperature (TC higher than 350K) ferromagnetism is observed in Zn1−xMnxO (x⩽0.02) nanoparticles. It is found that the ferromagnetism of Zn1−xMnxO nanoparticles is strongly related to defects in ZnO.

Raman scattering and high temperature ferromagnetism of Mn-doped ZnO nanoparticles

In this work, we report a mild and cost-effective solution method to directly grow Ni-substituted Co3O4 (ternary NiCo2O4) nanorod arrays on Cu substrates. Electrochemical impedance spectroscopy (EIS) measurements show that the values of the electrolyte resistance Re and charge-transfer resistance Rct of NiCo2O4 are 6.8 and 63.5 Ω, respectively, which are significantly lower than those of binary Co3O4 (10.4 and 122.4 Ω). This EIS characterization strongly confirms that the ternary NiCo2O4 anode has much higher electrical conductivity than that of the binary Co3O4 electrode materials, which should greatly enhance the lithium storage performances. Due to the well-aligned 1D nanorod microstructure and a higher electrical conductivity, these ternary NiCo2O4 nanorod arrays manifest high specific capacity, excellent cycling stability (a high reversible capacity of about 830 mA h g−1 was achieved after 30 cycles at 0.5 C) and high rate capability (787, 695, 512, 254, 127 mA h g−1 at 1 C, 2 C, 6 C 50 C and 110 C, respectively).

Facile synthesis of NiCo2O4 nanorod arrays on Cu conductive substrates as superior anode materials for high-rate Li-ion batteries

Exploring high performance cathode materials is essential to realize the adoption of Li-ion batteries for application in electric vehicles and hybrid electric vehicles. FeF3, as a typical iron-based fluoride, has been attracting considerable interest due to both the high electromotive force value of 2.7 V and the high theoretical capacity of 237 mA h g−1 (1e− transfer). In this study, we report a facile low-temperature solution phase approach for synthesis of uniform iron fluoride nanocrystals on reduced graphene sheets stably suspended in ethanol solution. The resulting hybrid of iron fluoride nanocrystals and graphene sheets showed high specific capacity and high rate performance for iron fluoride type cathode materials. High stable specific capacity of about 210 mA h g−1 at a current density of 0.2 C was achieved, which is much higher than that of LiFePO4 cathode material. Notably, these iron fluoride/nanocomposite cathode materials demonstrated superior rate capability, with discharge capacities of 176, 145 and 113 mA h g−1 at 1, 2 and 5 C, respectively.

Mild and cost-effective synthesis of iron fluoride-graphene nanocomposites for high-rate Li-ion battery cathodes

Multiferroic xBi3.15Nd0.85Ti3O12–(1−x)CoFe2O4 composite thin films with x=0.5, 0.6, and 0.7 were fabricated on Pt∕Ti∕SiO2∕Si(100) substrates by a chemical solution deposition technique. X-ray diffraction shows that there are no other phases but bismuth-layered perovskite Bi3.15Nd0.85Ti3O12 and spinel CoFe2O4 phases in the films. Scanning electron microscopy reveals that CoFe2O4 aggregates locally into nanoparticles and embeds in the Bi3.15Nd0.85Ti3O12 matrix. The composite films exhibit both good ferroelectric and magnetic properties at room temperature, as well as distinct magnetoelectric coupling behaviors, which are comparable with those of multiferroic composite films with conventional Pb-based ferroelectric as a ferroelectric component.

Multiferroic nanoparticulate Bi3.15Nd0.85Ti3O12–CoFe2O4 composite thin films prepared by a chemical solution deposition technique

Mn-doped ZnO nanorods are prepared by a chemical vapor deposition method using zinc and MnO2 powders as source materials of Zn and Mn, respectively. Cathodoluminescence (CL) characterization indicates that the Mn-doped ZnO nanorods grown at different growth temperatures have different oxygen vacancy concentrations. Room temperature ferromagnetism with a saturation magnetization of 0.87μB∕Mn has been observed in Mn-doped ZnO nanorods grown at 650°C, in which moderate oxygen vacancy concentration is observed by CL characterization. It is also found that oxygen vacancies play an important role in the appearance of room temperature ferromagnetism in Mn-doped ZnO nanorods.

J. B. Wang

Papers

Raman scattering and high temperature ferromagnetism of Mn-doped ZnO nanoparticles

Facile synthesis of NiCo2O4 nanorod arrays on Cu conductive substrates as superior anode materials for high-rate Li-ion batteries

Mild and cost-effective synthesis of iron fluoride-graphene nanocomposites for high-rate Li-ion battery cathodes

Multiferroic nanoparticulate Bi3.15Nd0.85Ti3O12–CoFe2O4 composite thin films prepared by a chemical solution deposition technique

Cathodoluminescence and room temperature ferromagnetism of Mn-doped ZnO nanorod arrays grown by chemical vapor deposition