[Liu, Chang; Li, Feng; Ma, Lai-Peng; Cheng, Hui-Ming] Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China.;Cheng, HM (reprint author), Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, 72 Wenhua Rd, Shenyang 110016, Peoples R China;cheng@imr.ac.cn

Advanced Materials for Energy Storage

Hollow micro-/nanostructures are of great interest in many current and emerging areas of technology. Perhaps the best-known example of the former is the use of fly-ash hollow particles generated from coal power plants as partial replacement for Portland cement, to produce concrete with enhanced strength and durability. This review is devoted to the progress made in the last decade in synthesis and applications of hollow micro-/nanostructures. We present a comprehensive overview of synthetic strategies for hollow structures. These strategies are broadly categorized into four themes, which include well-established approaches, such as conventional hard-templating and soft-templating methods, as well as newly emerging methods based on sacrificial templating and template-free synthesis. Success in each has inspired multiple variations that continue to drive the rapid evolution of the field. The Review therefore focuses on the fundamentals of each process, pointing out advantages and disadvantages where appropriate. Strategies for generating more complex hollow structures, such as rattle-type and nonspherical hollow structures, are also discussed. Applications of hollow structures in lithium batteries, catalysis and sensing, and biomedical applications are reviewed.

Hollow Micro-/Nanostructures: Synthesis and Applications**

In order to achieve high energy and power densities, we developed a high-voltage asymmetric electrochemical capacitor (EC) based on graphene as negative electrode and a MnO2 nanowire/graphene composite (MGC) as positive electrode in a neutral aqueous Na2SO4 solution as electrolyte. MGC was prepared by solution-phase assembly of graphene sheets and α-MnO2 nanowires. Such aqueous electrolyte-based asymmetric ECs can be cycled reversibly in the high-voltage region of 0−2.0 V and exhibit a superior energy density of 30.4 Wh kg−1, which is much higher than those of symmetric ECs based on graphene//graphene (2.8 Wh kg−1) and MGC//MGC (5.2 Wh kg−1). Moreover, they present a high power density (5000 W kg−1 at 7.0 Wh kg−1) and acceptable cycling performance of ∼79% retention after 1000 cycles. These findings open up the possibility of graphene-based composites for applications in safe aqueous electrolyte-based high-voltage asymmetric ECs with high energy and power densities.

High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors.

In this Review, we aim to provide an updated summary of the research related to hollow micro- and nanostructures, covering both their synthesis and their applications. After a brief introduction to the definition and classification of the hollow micro-/nanostructures, we discuss various synthetic strategies that can be grouped into three major categories, including hard templating, soft templating, and self-templating synthesis. For both hard and soft templating strategies, we focus on how different types of templates are generated and then used for creating hollow structures. At the end of each section, the structural and morphological control over the product is discussed. For the self-templating strategy, we survey a number of unconventional synthetic methods, such as surface-protected etching, Ostwald ripening, the Kirkendall effect, and galvanic replacement. We then discuss the unique properties and niche applications of the hollow structures in diverse fields, including micro-/nanocontainers and rea...

Synthesis, Properties, and Applications of Hollow Micro-/Nanostructures

The search for new electrode materials for lithium-ion batteries (LIBs) has been an important way to satisfy the ever-growing demands for better performance with higher energy/power densities, improved safety and longer cycle life. Nanostructured metal oxides exhibit good electrochemical properties, and they are regarded as promising anode materials for high-performance LIBs. In this feature article, we will focus on three different categories of metal oxides with distinct lithium storage mechanisms: tin dioxide (SnO2), which utilizes alloying/dealloying processes to reversibly store/release lithium ions during charge/discharge; titanium dioxide (TiO2), where lithium ions are inserted/deinserted into/out of the TiO2 crystal framework; and transition metal oxides including iron oxide and cobalt oxide, which react with lithium ions via an unusual conversion reaction. For all three systems, we will emphasize that creating nanomaterials with unique structures could effectively improve the lithium storage properties of these metal oxides. We will also highlight that the lithium storage capability can be further enhanced through designing advanced nanocomposite materials containing metal oxides and other carbonaceous supports. By providing such a rather systematic survey, we aim to stress the importance of proper nanostructuring and advanced compositing that would result in improved physicochemical properties of metal oxides, thus making them promising negative electrodes for next-generation LIBs.

Nanostructured metal oxide-based materials as advanced anodes for lithium-ion batteries.

Novel alpha-MnO2 hollow urchins were synthesized on a large scale by a facile and efficient low-temperature (60 degrees C) mild reduction route, without templates or surfactants in the system. The formation mechanism for the hollow urchins was proved to be the Ostwald ripening process by tracking the crystallization and morphology of the product at different reaction stages. The as-prepared hollow-urchin sample has a high Brunauer-Emmett-Teller surface area of 132 m(2)/g and a mesoporous structure, which were expected to help improve the electrochemical property in Li+ batteries. When the alpha-MnO2 hollow urchins were used as the cathode material in Li batteries, they performed better than the other alpha-MnO2 samples (solid urchins and dispersed nanorods), indicating that the electrochemical performance of the electrode material is sensitive to its morphology. This synthetic procedure is straightforward and inexpensive and thus facilitates mass production of alpha-MnO2 hollow urchins.

Chuanqi Feng

Papers

Low-temperature synthesis of alpha-MnO2 hollow urchins and their application in rechargeable Li+ batteries.